WO2021235469A1

WO2021235469A1 - Curable resin composition, cured film, laminate, cured film production method and semiconductor device

Info

Publication number: WO2021235469A1
Application number: PCT/JP2021/018920
Authority: WO
Inventors: 大輔浅川
Original assignee: 富士フイルム株式会社
Priority date: 2020-05-20
Filing date: 2021-05-19
Publication date: 2021-11-25
Also published as: JP7573026B2; TW202208507A; KR102727376B1; JPWO2021235469A1; KR20230008114A

Abstract

This curable resin composition contains: at least one type of resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, polyamide-imide, and polyamide-imide precursors; a compound B having at least one group selected from an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group and an N-hydroxyimide group; and an organometallic complex.

Description

Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Resins such as polyimide, polybenzoxazole, and polyamide-imide have excellent heat resistance and insulating properties, and are therefore applied to various applications. The application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, the resin such as polyimide, polybenzoxazole, and polyamideimide is selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, polyimide precursor, polybenzoxazole precursor, and polyamideimide precursor. It is used in the form of a curable resin composition containing at least one resin.
Such a curable resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then exposed, developed, heated or the like as necessary to apply the cured product onto the substrate. Can be formed.
The polyimide precursor, the polybenzoxazole precursor, and the polyamide-imide precursor are cyclized by, for example, heating, and become polyimide, polybenzoxazole, and polyamide-imide in the cured product, respectively.
Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, polybenzoxazole, polyamide-imide, etc., from the viewpoint of excellent manufacturing adaptability, the above-mentioned curable resin composition is expected to be increasingly applied in industry.

For example, Patent Document 1 describes a negative photosensitive resin composition containing (A) a polyimide precursor, (B) an imide compound having a specific structure, and (C) a photopolymerization initiator. ..

Japanese Unexamined Patent Publication No. 2019-185031

In the formation of a pattern made of a curable resin composition, improvement in resolution is required.

The present invention relates to a curable resin composition having excellent resolution at the time of pattern formation, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film. It is an object of the present invention to provide a semiconductor device including the cured film or the laminated body.

Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor.
Compound B having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group, and
A curable resin composition containing an organometallic complex.
<2> The curable resin composition according to <1>, further comprising a photopolymerization initiator.
<3> The curable resin composition according to <1> or <2>, further comprising a cross-linking agent.
<4> The curable resin composition according to any one of <1> to <3>, wherein the organometallic complex is a metallocene compound.
<5> The curable resin composition according to any one of <1> to <4>, wherein the organometallic complex is a titanium compound.
<6> The curable resin composition according to any one of <1> to <5>, wherein the organometallic complex has a photoradical polymerization initiation ability.
<7> The compound B is a compound having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, and an N-hydroxyamide group, <1> to <. 6> The curable resin composition according to any one of.
<8> The compound B includes a compound having an N-hydroxyimide group, and is represented by the formula (1-1), the compound represented by the formula (1-2), and the formula (1-3). The curable resin composition according to any one of <1> to <6>, further comprising at least one compound selected from the group consisting of the compounds represented by).

In the formula (1-1), the formula (1-2) or the formula (1-3), R ¹¹ and R ¹² are independently used as unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms and as substituents, respectively. At least one selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group. An aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent of, or 2 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. Representing an aliphatic hydrocarbon group of ~ 7, R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³¹ and R ³² respectively. Independently, it represents an aliphatic hydrocarbon group ^{having 1 to 7 carbon atoms which may have a substituent, and R 33} represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
<9> The curable resin composition according to any one of <1> to <8>, wherein the ratio of the molar content of the compound B to the molar content of the organometallic complex is 30 to 500%. thing.
<10> The curable resin composition according to any one of <1> to <9>, which is used for forming a photosensitive film to be subjected to negative development.
<11> The curable resin composition according to any one of <1> to <10>, which is used for forming an interlayer insulating film for a rewiring layer.
<12> A cured film obtained by curing the curable resin composition according to any one of <1> to <11>.
<13> A laminate containing two or more layers of the cured film according to <12> and containing a metal layer between any of the cured films.
<14> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <11> to a substrate to form a film.
<15> The method for producing a cured film according to <14>, which comprises an exposure step for exposing the film and a developing step for developing the film.
<16> The method for producing a cured film according to <15>, wherein the exposure light used for the above exposure includes light having a wavelength of 405 nm.
<17> The method for producing a cured film according to <15> or <16>, wherein the exposure is an exposure by a laser direct imaging method.
<18> The method for producing a cured film according to any one of <14> to <17>, which comprises a heating step of heating the film at 50 to 450 ° C.
<19> A semiconductor device comprising the cured film according to <12> or the laminate according to <13>.

According to the present invention, a curable resin composition having excellent resolution at the time of pattern formation, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and the like. And a semiconductor device including the cured film or the laminate is provided.

Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
As used herein, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive film, the direction from the base material to the photosensitive film is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.

(Curable resin composition)
The curable resin composition of the present invention (also simply referred to as "the composition of the present invention") comprises a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, a polyamideimide, and a polyamideimide precursor. It has at least one group selected from the group consisting of at least one resin selected from the group, an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group. It contains compound B and an organic metal complex.
Hereinafter, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor is also referred to as "specific resin" and is referred to as N-hydroxy. Compound B having at least one group selected from the group consisting of an amino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group is also referred to as a "specific compound".

The curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is used for exposure and formation of a film to be subjected to development using a developing solution containing an organic solvent. Is preferable.
Further, the curable resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
In the present invention, negative-type development refers to development in which a non-exposed portion is removed by development in exposure and development, and positive-type development refers to development in which an exposed portion is removed by development.
The exposure method, the developer, and the developing method include, for example, the exposure method described in the exposure step in the description of the method for producing a cured film described later, the developer and the developing method described in the developing step. Is used.

The curable resin composition of the present invention is excellent in the resolution of the obtained pattern.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

Conventionally, an organic titanium compound or the like has been added to a curable resin composition for the purpose of improving chemical resistance.
However, when patterning is performed using a curable resin composition containing an organometallic complex, the organometallic complex may aggregate in the film and the resolution may be deteriorated.
The curable resin composition of the present invention further contains a specific compound in addition to the organometallic complex.
It is considered that the organometallic complex contained in the curable resin composition is dispersed in the film in a nearly uniform state due to the strong interaction between the specific compound and the organometallic complex. As a result, it is presumed that the curable resin composition of the present invention has excellent resolution.
Here, Patent Document 1 does not describe or suggest the technical idea of improving the resolution by using a specific compound and a metal complex in combination.

Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

<Specific resin>
The curable resin composition of the present invention is at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. )including.
The curable resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described later as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described below, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative photosensitive film is formed.
Further, the specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitive agent. From such a curable resin composition, for example, a chemically amplified positive type photosensitive film or a negative type photosensitive film is formed.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).

In formula (2), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ^113. And R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
^{R 111} in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by —L—Ar— is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —C (= O) −, —S—, —SO. ₂ -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - C ( = O) -, - S-, or, -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 ) _2- or -C (CH ₃ ) _2- is more preferable.
In the formula, * represents a binding site with another structure.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane , Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octa Fluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-Bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4, 4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluo) Lomethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2, 2-Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'- At least one selected from diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl. Diamine can be mentioned.

Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.

Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.

R ¹¹¹ is preferably represented by −Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO ₂ - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.

Further, ^{from the viewpoint of i-ray transmittance, R 111} is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group or trifluoro. It is a methyl group.
The ^{monovalent organic group of R 50} to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used.

^{R 115} in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * independently represents a binding site with another structure.

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —CO—, —S—, —SO. _2- , And NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO _2- _{, -CH 2-} , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2-, -O-, -CO.} -, - and more preferably a divalent radical selected from the group consisting of _- S-, and SO 2.

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).

In formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferred range of R ¹¹⁵ has the same meaning as ^{R 115} in formula (2), and preferred ranges are also the same.

Specific examples of tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3'. , 4,4'-Diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 7-Naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5, 6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4 5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrentetracarboxylic acid dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and these. Examples thereof include an alkyl having 1 to 6 carbon atoms and an alkoxy derivative having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

It is also preferable that at least one of R ¹¹¹ and R ^{115 has an OH group.} More specifically, ^{as R 111} , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both contain a polymerizable group. preferable. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino. The group is mentioned. As the radically polymerizable group of the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- or a polyalkylene oxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group are more preferable, and polyalkylene group. Oxy groups are more preferred.
In the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the cyclic alkyl group of the monocycle include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, It is a thianthrene ring, a chromen ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

At ^{least one of R 113} and R ¹¹⁴ may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.

The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. Representing a hydrogen atom or a monovalent organic group ^{, at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} each independently have the same meaning as ^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} in formula (2), and preferred ranges are also the same ..
R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

The polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As an embodiment of the polyimide precursor in the present invention, there is an embodiment in which the content of the repeating unit represented by the formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal may be the repeating unit represented by the formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern formability. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
As used herein, the "main chain" refers to the relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bound chains.

-Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later, or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group ^{in R 132} in the repeating unit represented by 4) ^{or in R 131} in the repeating unit represented by the formula (4) described later.
The amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.

-Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is ^{preferably contained in R 131} in the repeating unit represented by the formula (4) described later, and is organically modified (poly ^{) in R 131} in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have it in the side chain, but it is preferable to have it in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is ^{preferably contained in R 132} in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later. ^{It is more preferable that R 132} in the repeating unit represented by (4) ^{or R 131} in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
Of these, ethylenically unsaturated bond, ethylene R ¹³¹ in the repeating unit represented by the preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).

Wherein ^{(IV), R 20} represents a hydrogen atom or a methyl group, a methyl group is preferable.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, —O—CH ₂ CH (OH) CH _2- , −C (= O) O−, —O (C = O) NH−. , (Poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1). ~ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.

Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group having two or more bonds thereof, and is X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which ^{R 201 in the formula (III) is bonded.}
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R ²¹ having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the alkylene group of 12 or the (poly) alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In the formulas (R1) to (R3), * is synonymous with * in the formula (IV), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.

The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.

-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 131} in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.

-Polar conversion group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving developability. Is more preferable.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In the present specification, pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
Further, when the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained ^{in, for example, R 132} ^{in the repeating unit represented by the formula (4) described later or R 131} in the repeating unit represented by the formula (4) described later.
The amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4).

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When having a polymerizable group, the polymerizable group ^{may be located at at least one of R 131} and R ¹³² , and may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)

In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)

At ^{least one of R 134} and R ¹³⁵ is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. As the divalent organic group, the same group as R ¹¹¹ in the formula (2) is exemplified, and the preferred range is also the same.
In addition, ^{examples of R 131} include diamine residues remaining after removal of the amino group of diamine. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. ^{Specific examples include the example of R 111} in the formula (2) of the polyimide precursor.

It is preferable that R ¹³¹ is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the generation of warpage during firing. A diamine residue containing two or more of an ethylene glycol chain and / or a propylene glycol chain in one molecule is more preferable, and a diamine residue containing no aromatic ring is more preferable.

Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine.

R ¹³² represents a tetravalent organic group. As the tetravalent organic group, the same group as R ¹¹⁵ in the formula (2) is exemplified, and the preferable range is also the same.
For example, ^{four conjugates of a tetravalent organic group exemplified as R 115} combine with four —C (= O) − moieties in the above formula (4) to form a fused ring.

In addition, ^{examples of R 132} include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. ^{Specific examples include the example of R 115} in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable to have an OH group in at least one of R ¹³¹ and R ^132. More specifically, ^{as R 131} , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. As R ¹³² , the above-mentioned (DAA-1) to (DAA-5) are more preferable examples.

It is also preferable that the polyimide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

Further, in order to improve the storage stability of the composition, the main chain end of the polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Examples thereof include aminothiophenol and 4-aminothiophenol. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited and may be 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near ^{1377 cm -1, which is the absorption peak derived from the imide structure.} Next, the polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain the peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

The polyimide may contain a repeating unit represented by the above formula (4), all containing one type of R ¹³¹ or R ^132, ^{and the above formula including two or more different types of R 131} or R ^132. It may include a repeating unit represented by 4). Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit represented by the above formula (4). Examples of other types of repeating units include repeating units represented by the above formula (2).

The polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is a monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) to obtain a diester with a tetracarboxylic acid dianhydride and an alcohol, and then diamine (partly monoamine). A method of reacting in the presence of a condensing agent (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with a terminal encapsulant (replacement with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrix5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. show.

In the formula (3), R ¹²³ and R ¹²⁴ ^{are synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid consisting of is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosandioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Tria Examples thereof include contandioic acid, hentoria-contandioic acid, dotoria-contanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.

In the formula, A is -CH _2- , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (2), and the preferable range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bis-aminophenols may be used alone or in combination.

Of the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferable.

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, ^{it is also preferable that R 122} has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the four * and # in total are the bonding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded, and} preferably R ¹²² in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R ¹²² are attached in the formula (3) ^{, And two # are the bonding sites with the nitrogen atom to which R 122} in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded.} ^{It is more preferable that the site is a site and the two #s} are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which ^{the R 122 in the formula (3) is bonded.} It is more preferable that it is a bond site with an atom and the ^{two #s} are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.

In the formula (As), R ₁ is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (A-s), the ortho position of the phenolic hydroxy groups, i.e., to have also substituent R ₃ is believed to closer the distance of the carbonyl carbon and hydroxy group of the amide bond, at a low temperature It is particularly preferable in that the effect of increasing the cyclization rate when cured is further enhanced.

Further, in the above formula (As), _{it is said that the fact that R 2} is an alkyl group and R ₃ is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.

Further, in the above formula (As), _{it is more preferable that R 1} is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene according to R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH _{2- and} -CH (CH ₃ ). -, -C (CH ₃ ) ₂ -has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.

As a method for producing the bis-aminophenol derivative represented by the above formula (As), for example, paragraph numbers 805 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.

Specific examples of the structure of the bis-aminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506, and the contents thereof are described in the present specification. Will be incorporated into. Of course, it goes without saying that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the generation of warpage associated with ring closure can be suppressed.

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group ^{having 1 to 10 carbon atoms, and R 2s} is a hydrocarbon group having 1 to 10 carbon atoms. ^Yes , at least one of R 3s, R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to achieve both the effect of suppressing warpage and the effect of improving solvent solubility.

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, It is 000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-degradable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group ^{may be located at at least one of R 133} and R ¹³⁴ , and may be located at least one of the following. It may be located at the terminal of polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)

In the formula (X-2), R ¹³⁷ is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).

A polar converting group such as a polymerizable group or an acid-degradable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include aliphatic or aromatic groups. ^{Specific examples include the example of R 121} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 121.}

R ¹³⁴ represents a tetravalent organic group. Examples of the ^{tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 122.}
For example, ^{four conjugates of a tetravalent organic group exemplified as R 122} combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a fused ring. For example, when R ¹³⁴ is the following organic group, it forms the following structure.

Polybenzoxazole preferably has an oxazole formation rate of 85% or more, more preferably 90% or more. When the oxazole formation rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

The polybenzoxazole may contain a repeating structural unit of the above formula (X), all comprising one R ¹³¹ or R ¹³² ^{, the above formula comprising two or more different types of R 131} or R ^132. It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R ^133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This can be obtained by oxazole using a known oxazole reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative that has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

[Polyamide-imide precursor]
The polyamide-imide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or monovalent. Represents an organic group of.

In formula (PAI-2), R ¹¹⁷ is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. The above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.

Further, it ^{is preferable that R 117} is derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound.
Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
Examples of the tricarboxylic acid compound that may be halogenated used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds.
Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.

Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms. A tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable. A tricarboxylic acid compound containing a group in which two or more aromatic groups of the number 6 to 20 are combined is more preferable.

Specific examples of the tricarboxylic acid compound include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (Or phthalic acid anhydride) and benzoic acid are single-bonded, -O-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or a phenylene group. Examples thereof include linked compounds.
These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride), or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid chloride). There may be.

Wherein ^(PAI-2), each R ^111, A ^{2, R 113,} have the same meaning as ^R ^111, A ^{2, R 113} in formula (2) described above, preferable embodiments are also the same.

The polyamide-imide precursor may further contain other repeating units.
Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group and R ¹¹¹ represents a divalent organic group.
In formula (PAI-1), R ¹¹⁶ is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. The above-mentioned linked groups are exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms are exemplified. The aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable. A group in which two or more of the above are combined is more preferable.
The linking group includes -O-, -S-, -C (= O)-, -S (= O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a link in which two or more of these are bonded. A group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable. The halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom. Examples of preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.

Further, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxy groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds.
Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.

Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms. A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable. , Or a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.

Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid, 2,2-. Didimethyl succinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, suberic acid, Dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosanedioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Triacanthani Acid, Hentria Contanedioic Acid, Dotoria Contanedioic Acid, Diglycolic Acid, phthalic Acid, Isophthalic Acid, Telephthalic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'-biphenylcarboxylic Acid, 4,4'- Examples thereof include dicarboxydiphenyl ether and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxy groups are halogenated in the above-mentioned specific examples of the dicarboxylic acid compound.

Wherein ^{(PAI-1), R 111} has the same meaning as ^{R 111} in the above equation (2), preferable embodiments thereof are also the same.

It is also preferable that the polyamide-imide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, an embodiment using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like can be mentioned.

As one embodiment of the polyamide-imide precursor in the present invention, a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2). An embodiment in which the total content is 50 mol% or more of all repeating units can be mentioned. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) and the formula (PAI-1). It may be either a repeating unit or a repeating unit represented by the formula (2).
Further, as another embodiment of the polyamide-imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is all repeated. Examples thereof include an embodiment in which the unit is 50 mol% or more. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamide-imide precursor except the terminal are represented by the repeating unit represented by the formula (PAI-2) or the formula (PAI-1). It may be any of the repeating units to be used.

The weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.

The degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

[Polyamide-imide]
The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide or may be a polyamide-imide soluble in a developer containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyamide-imide means a polyamide-imide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and is 0. It is preferably a polyamide-imide that dissolves 5 g or more, and more preferably a polyamide-imide that dissolves 1.0 g or more. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
Further, the polyamide-imide is preferably a polyamide-imide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.

-Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyamide-imide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and in the repeating unit represented by the formula (PAI-3) described later. It is more preferable that it is contained in R ¹¹⁷ or R ^{111 as an alkyl fluoride group.}
The amount of fluorine atoms with respect to the total mass of the polyamide-imide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.

-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyamide-imide may have an ethylenically unsaturated bond.
The polyamide-imide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferable to have it at the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is ^{preferably contained in R 117} or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and the repeating unit represented by the formula (PAI-3) described later. It is more preferable that it is contained as a group having an ethylenically unsaturated bond in R ¹¹⁷ or R ^{111 in the above.}
The preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

The amount of the ethylenically unsaturated bond with respect to the total mass of the polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyamide-imide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond in the polyamide-imide include the same group as the crosslinkable group other than the ethylenically unsaturated bond in the above-mentioned polyimide.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 111} in the repeating unit represented by the formula (PAI-3) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyamide-imide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.

-Polar conversion group-
Polyamideimide may have a polar conversion group such as an acid-degradable group. The acid-degradable group in the polyamide-imide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value-
When the polyamide-imide is subjected to alkaline development, the acid value of the polyamide-imide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g, from the viewpoint of improving developability. It is more preferably g or more.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyamide-imide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mgKOH / g, 3 ~ 30 mgKOH / g is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyamide-imide, the same group as the acid group in the above-mentioned polyimide can be mentioned, and the preferred embodiment is also the same.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyamide-imide preferably has a phenolic hydroxy group.
The polyamide-imide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained ^{in, for example, R 117} or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later.
The amount of the phenolic hydroxy group with respect to the total mass of the polyamide-imide is preferably 0.1 to 30 mol / g, more preferably 1 to 20 mol / g.

The polyamide-imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but preferably contains a repeating unit represented by the following formula (PAI-3).

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ ^{are synonymous with R 111} and R ¹¹⁷ in formula (PAI-2), respectively, and so are preferred embodiments.
When having a polymerizable group, the polymerizable group ^{may be located at at least one of R 111} and R ¹¹⁷ , or may be located at the end of the polyamide-imide.

Further, in order to improve the storage stability of the composition, the main chain end of polyamide-imide should be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. Is preferable. The preferred embodiment of the terminal encapsulant is the same as the preferred embodiment of the terminal encapsulant in the above-mentioned polyimide.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyamide-imide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. , 90% or more is more preferable.
The upper limit of the imidization rate is not particularly limited and may be 100% or less.
The imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

The polyamide-imide may include repeating units of the above formula (PAI-3) ^{, all comprising one R 111} or R ¹¹⁷ ^{, including two or more different types of R 131} or R ¹³² . It may include a repeating unit represented by the above formula (PAI-3). Further, the polyamide-imide may contain other types of repeating units in addition to the repeating unit represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above-mentioned formula (PAI-1) or formula (PAI-2).

For the polyamide-imide, for example, a polyamide-imide precursor is obtained by a known method, and the polyamide-imide precursor is completely imidized by using a known imidization reaction method, or the imidization reaction is stopped in the middle and a partial imide structure is obtained. By blending the completely imidized polymer with the polyamide-imide precursor thereof, it can be synthesized by utilizing the method of introducing a partially imidized structure.

The weight average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyamide-imides are contained, the weight average molecular weight of at least one kind of polyamide-imide is preferably in the above range.

[Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

It is also preferable to synthesize using a non-halogen catalyst without using the above-mentioned halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

-End sealant-
In order to further improve the storage stability in the manufacturing method of the polyimide precursor, etc., the end of the polyimide precursor, etc. is used with an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound. It is preferable to seal it. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.

-Solid precipitation-
A step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more with respect to the total solid content of the composition. It is more preferably 50% by mass or more, and even more preferably 50% by mass or more. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

Further, it is also preferable that the curable resin composition of the present invention contains at least two kinds of resins.
Specifically, the curable resin composition of the present invention may contain two or more kinds of a specific resin and another resin described later in total, or may contain two or more kinds of a specific resin, but is specific. It is preferable to contain two or more kinds of resins.
When the curable resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R ^{115 in the above formula (2)).} It is preferable to contain the polyimide precursor of.

<Specific compound>
The curable resin composition of the present invention is a compound having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group. Contains B (specific compound).
The specific compound may have at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group in total. It may have two or more, but it is preferable to have only one.

[N-hydroxyamino group]
In the present invention, the N-hydroxyamino group means a group represented by the following formula (N-1).
However, the structure corresponding to the N-hydroxyamide group or the N-hydroxyimide group described later does not correspond to the N-hydroxyamino group.

In the formula (N-1), * independently represents a binding site with another structure, and is preferably a binding site with a hydrogen atom, a nitrogen atom or a carbon atom.

Further, in the present invention, when the specific compound contains an N-hydroxyamino group, the specific compound preferably contains a structure represented by the following formula (N1-1) or formula (N1-2).

In the formula (N1-1) or the formula (N1-2), * independently represents a binding site with another structure, and is preferably a binding site with a carbon atom.

Further, in the present invention, when the specific compound contains a structure represented by the formula (N1-1), the specific compound is represented by the following formula (N1-3) as the structure represented by the above formula (N1-1). It preferably contains the structure represented.

In the formula (N1-3), * independently represents a binding site with another structure, preferably a binding site with a hydrogen atom or a carbon atom, and more preferably a binding site with a carbon atom. preferable.

When the specific compound contains an N-hydroxyamino group, the specific compound is preferably a compound represented by any of the following formulas (N-1-1) and (N-1-2).

In the formula (N-1-1), ^RN11 and ^RN12 each independently represent a hydrogen atom or a monovalent substituent, and ^RN11 ^{and RN12} may be bonded to form a ring structure.
In the formula (N-1-2), ^RN13 and ^RN14 each independently represent a hydrogen atom or a monovalent substituent, and ^RN13 ^{and RN14} may be bonded to form a ring structure.

In the formula (N-1-1), ^RN11 and ^RN12 independently have a hydrogen atom, a hydrocarbon group, or a hydrocarbon group, and -O-, -C (= O)-, -S-, respectively. -S (= O) 2 _- and -NR N - ^(an R ^N represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom) represented by a combination of at least one group selected from the group consisting of It is preferable to represent a group, and it is preferable to represent a hydrocarbon group.
Further, in the formula (N-1-1), ^{an embodiment in which RN11} and ^RN12 are bonded to form a ring structure is also one of the preferred embodiments of the present invention, and the formed ring structure is an alicyclic structure. It may have an aromatic ring structure, a heterocyclic structure, or a hydrocarbon ring structure. Examples of the hetero atom in the hetero ring structure include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a silicon atom.
Further, the ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 6-membered ring structure.
Among these, as the ring structure, an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure is preferable, a benzene ring structure or a pyridine ring structure is more preferable, and a benzene ring structure is further preferable. As the hetero atom in the aromatic hetero ring structure, a nitrogen atom is preferable. Further, the ring structure is known as a hydrocarbon group, a halogen atom, a carboxy group, an amide group, a nitro group or the like which may be substituted with a halogen atom. It may be substituted with a substituent of.

In the formula (N-1-2), ^{it is preferable that one of RN13} and ^RN14 represents a hydrogen atom and the other represents a monovalent substituent.
As the ^{monovalent substituent in RN13} and ^RN14 , a hydrocarbon group is preferable, a hydrocarbon group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Alkyl groups of are more preferred.
When the number of carbon atoms is 3 or more, the alkyl group may contain a branched structure or a ring structure, or may be a cyclic alkyl group.

[N-hydroxyimino group]
In the present invention, the N-hydroxyimino group means a group represented by the following formula (N-2).

In the formula (N-2), * independently represents a binding site with another structure, and is preferably a binding site with a carbon atom.

Further, in the present invention, when the specific compound contains an N-hydroxyimino group, the specific compound preferably contains a structure represented by the following formula (N2-1) or formula (N2-2).

In the formula (N2-1) or the formula (N2-2), * represents a binding site with another structure, and is preferably a binding site with a carbon atom.
Wherein (N2-2), R ^N2 represents an optionally substituted alkyl group or an aromatic hydrocarbon group, an alkyl group, haloalkyl group or a phenyl group are more preferable. As used herein, the haloalkyl group means an alkyl group in which a part of the hydrogen atom of the alkyl group is substituted with a halogen atom, and an alkyl group in which all the hydrogen atoms of the alkyl group are substituted with a halogen atom is preferable.
When ^RN2 is an optionally substituted alkyl group, ^{the carbon number of RN2} is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
When ^RN2 is an aromatic hydrocarbon group, ^{the carbon number of RN2} is preferably 6 to 20, more preferably 6 to 12.

Further, in the present invention, when the specific compound contains a structure represented by the formula (N2-1), the specific compound is represented by the following formula (N2-3) as the structure represented by the above formula (N2-1). It preferably contains the structure represented.

In the formula (N2-3), * independently represents a binding site with another structure, and is preferably a binding site with a carbon atom.

When the specific compound contains an N-hydroxyimino group, the specific compound is preferably a compound represented by the following formula (N-2-1).

In formula (N-2-1), ^RN21 and ^RN22 each independently represent a monovalent organic group.

In the formula (N-2-1), ^RN21 and ^RN22 are independently cyano group, hydrocarbon group, or hydrocarbon group, and —O—, −C (= O) −, —S—, respectively. -S (= O) ₂ and -NR ^N - ^(R N represents a hydrogen atom or a hydrocarbon group, a hydrogen atom is preferred) groups represented by the combination with at least one group selected from the group consisting of It is more preferable that it is a cyano group, a hydrocarbon group, or a group represented by —C (= O) OR (R is a hydrocarbon group).
When ^RN21 and ^RN22 are hydrocarbon groups, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be an alkyl group, an alkenyl group, or an aromatic hydrocarbon. Groups are preferred. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. When the number of carbon atoms is 3 or more, the alkyl group may contain a branched structure or a ring structure, or may be a cyclic alkyl group. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 4 carbon atoms is more preferable. As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Further, the hydrocarbon group may be substituted with a known substituent such as a halogen atom.
As R in the group represented by the above-C (= O) OR, an alkyl group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable. When the number of carbon atoms is 3 or more, the alkyl group may contain a branched structure or a ring structure, or may be a cyclic alkyl group.
As a preferred embodiment of the present invention, one of ^RN21 and ^RN22 is a cyano group and the other is represented by a group represented by —C (= O) ^OR , or RN21 and ^RN22. Examples thereof include an embodiment in which both of the above are alkyl groups.

[N-Hydroxyamide group]
In the present invention, the N-hydroxyamide group means a group represented by the following formula (N-3).
However, the structure corresponding to the N-hydroxyimide group described later does not correspond to the N-hydroxyamide group.

In the formula (N-3), * independently represents a binding site with another structure, and is preferably a binding site with a hydrogen atom, a nitrogen atom or a carbon atom.

Further, in the present invention, when the specific compound contains an N-hydroxyamide group, the specific compound includes a structure represented by the following formula (N3-1), formula (N3-2) or formula (N3-3). Is preferable.

In the formulas (N3-1) to (N3-3), * represents a binding site with another structure, preferably a binding site with a hydrogen atom or a carbon atom, and is a binding site with a carbon atom. Is more preferable.

Further, in the present invention, when the specific compound contains a structure represented by the formula (N3-1), the specific compound is represented by the following formula (N3-4) as the structure represented by the above formula (N3-1). It preferably contains the structure represented.

In the formula (N3-4), * independently represents a binding site with another structure, preferably a binding site with a hydrogen atom or a carbon atom, and more preferably a binding site with a carbon atom. preferable.

When the specific compound contains an N-hydroxyamide group, the specific compound is preferably a compound represented by the following formula (N-3-1).

Wherein ^{(N-3-1), R N31} represents a monovalent organic ^{group, R N32} represents a hydrogen atom or a monovalent organic ^{group, R N31} and ^{R N32} are bonded to form a cyclic structure May be good.

In the formula (N-3-1), ^RN31 is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable. The alkyl group may contain a branched structure or a ring structure when the number of carbon atoms is 3 or more, and may be a cyclic alkyl group. In the formula (N-3-1), ^RN31 is a hydrogen atom or a hydrocarbon. It is preferably a group, more preferably a hydrogen atom. ^{The preferred embodiment when RN31} is a hydrocarbon group is the same as the preferred embodiment of ^RN31 .
In the formula (N-3-1), embodiments for forming the R ^N31 and R ^N32 are bonded to the ring structure is also one of the preferred embodiments of the present invention, as the ring structure formed, saturated ring structure However, it may have an unsaturated ring structure, but an unsaturated ring structure is preferable.
Further, the ring structure is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 6-membered ring structure.
Another ring structure may be further condensed in the ring structure to form a condensed ring structure. Examples of the other ring structure include a benzene ring.
Further, the ring structure may be substituted with a known substituent such as a hydrocarbon group, a halogen atom, a carboxy group, an amide group or a nitro group which may be substituted with a halogen atom.
When ^RN31 and ^RN32 are combined to form a ring structure, the compound represented by the formula (N-3-1) is the following formula (N-3-2) or the following formula (N-3-3). It is preferably a compound represented by.

In the formula (N-3-2), ^RN33 independently represents a hydrogen atom or a monovalent substituent, and ^RN34 independently represents a hydrogen atom or a monovalent substituent.
In the formula (N-3-2), ^RN33 is preferably a hydrogen atom. When ^RN33 is a monovalent substituent, ^RN33 may be a known substituent, and examples thereof include an alkyl group, an aryl group, a halogen atom, a carboxy group, and an amino group.
In the formula (N-3-3), ^RN34 is preferably a hydrogen atom. When ^RN34 is a monovalent substituent, the same substituents as ^{RN33 can be mentioned.}

[N-hydroxyimide group]
In the present invention, the N-hydroxyimide group means a group represented by the following formula (N-4).

In the formula (N-4), * independently represents a binding site with another structure, and is preferably a binding site with a carbon atom.

Further, in the present invention, when the specific compound contains an N-hydroxyimide group, the specific compound includes a structure represented by the following formula (N4-1), formula (N4-2) or formula (N4-3). Is preferable.

In the formulas (N4-1) to (N4-3), * represents a binding site with another structure, and is preferably a binding site with a hydrogen atom or a carbon atom.

When the specific compound contains an N-hydroxyimide group, the specific compound is preferably a compound represented by the following formula (N-4-1).

In the formula (N-4-1), ^RN41 and ^RN42 each independently represent a monovalent organic group, and ^RN41 and ^RN42 may be combined to form a ring structure.

^RN41 and ^RN42 each independently represent a monovalent organic group, preferably a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 10 carbon atoms.
^{An embodiment in which RN41} and ^RN42 are combined to form a ring structure is also one of the preferred embodiments of the present invention.
The ring structure to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.
Another ring structure may be further condensed in the ring structure to form a condensed ring structure. Examples of the other ring structure include a benzene ring.
Further, the ring structure may be substituted with a known substituent such as a hydrocarbon group, a halogen atom, a carboxy group, an amide group or a nitro group which may be substituted with a halogen atom.
When ^RN41 and ^RN42 are bonded to form a ring structure, the specific compound is one of the following formulas (N-4-2), (N-4-3) and (N-4-4). It is preferably a compound represented by.

In the formula (N-4-2), the formula (N-4-3) and the formula (N-4-4), ^RN43 independently represents a hydrogen atom or a monovalent organic group, and ^RN44 respectively. Independently, a hydrogen atom or a monovalent organic group is represented, and ^RN45 independently represents a hydrogen atom or a monovalent organic group.

In the formula (N-4-2), ^RN43 is preferably a hydrogen atom. When ^RN43 is a monovalent substituent, ^RN43 may be a known substituent, and examples thereof include an alkyl group, an aryl group, a halogen atom, a carboxy group, and an amino group.
In the formula (N-4-3), ^RN44 is preferably a hydrogen atom. When ^RN44 is a monovalent substituent, the same substituents as ^{RN43 can be mentioned.}
In the formula (N-4-4), ^RN45 is preferably a hydrogen atom. When ^RN45 is a monovalent substituent, the same substituents as ^{RN43 can be mentioned.}

[Preferable embodiment]
Among these, from the viewpoint of resolution, the specific compound is a compound having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, and an N-hydroxyamide group. Is preferable.
Since the N-hydroxyamino group, the N-hydroxyimino group, and the N-hydroxyamide group have lower electron attracting properties than the N-hydroxyimide group, they have a strong interaction with the organic metal complex and are organic metal complexes. It is considered that the resolution is likely to be improved because the aggregation of the minerals is easily suppressed.
Further, from the viewpoint of chemical resistance, the specific compound is preferably a compound having an N-hydroxyimide group.
The N-hydroxyimide group is hydrophilic because it has a large number of carbonyl groups as compared with other structures. Therefore, it is presumed that the hydrophilicity of the cured film is improved, the solubility in an organic solvent is lowered, and the chemical resistance is improved.
Further, from the viewpoint of achieving both chemical resistance and resolution, an embodiment containing a compound having an N-hydroxyimide group and the compound C described later is also one of the preferred embodiments of the present invention.

[Molecular weight]
The molecular weight of the specific compound is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 47 or more, and more preferably 75 or more.

〔Concrete example〕
Hereinafter, specific examples of the specific compound will be shown, but the specific compound is not limited thereto.

〔Content〕
The content of the specific compound in the composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and 0.1 to 5% by mass, based on the total solid content of the composition. Is more preferable.
The ratio of the molar content of the specific compound to the molar content of the organometallic complex is preferably 30 to 500%, more preferably 50 to 450%, and further preferably 80 to 400. preferable.
The composition of the present invention may contain a specific compound alone or in combination of two or more. When two or more kinds of specific compounds are used in combination, it is preferable that the total content mass or the total content molar amount is within the above range.

<Organometallic complex>
The curable resin composition of the present invention contains an organometallic complex.
The organic metal complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is a complex compound in which an organic group is coordinated with respect to the metal atom. Is more preferable, and a metallocene compound is further preferable.
In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have a substituent as η5-ligands.
The organic group is not particularly limited, but a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferable. As the hetero atom, an oxygen atom, a sulfur atom and a nitrogen atom are preferable.
In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferably cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
As the cyclic group of the 5-membered ring, a cyclopentadienyl group is preferable.
Further, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The organic metal complex is not particularly limited, but is preferably a compound containing a metal corresponding to a Group 4 element, and is at least one compound selected from the group consisting of a titanium compound, a zirconium compound and a hafnium compound. More preferably, it is more preferably at least one compound selected from the group consisting of a titanium compound and a zirconium compound, and particularly preferably a titanium compound.

The organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organic metal complex contains two or more metal atoms, it may contain only one kind of metal atom or may contain two or more kinds of metal atoms.

The organic metal complex is preferably a ferrocene compound, a titanosen compound, a zirconocene compound or a hafunosen compound, more preferably a titanosen compound, a zirconosen compound or a hafunosen compound, and further preferably a titanosen compound or a zirconosen compound. , Titanosen compounds are particularly preferred.

An embodiment in which the organometallic complex has an ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
According to the present invention, it is considered that the organometallic complex is dispersed in the membrane in a nearly uniform state by using the specific compound.
Therefore, when the organic metal complex has the ability to initiate photoradical polymerization, it is considered that the local aggregation of the radical polymerization initiator due to the aggregation of the organic metal complex is suppressed.
It is considered that the degree of polymerization of the specific resin or the cross-linking agent tends to be almost uniform in the film by suppressing the aggregation of the radical polymerization initiator. Therefore, it is considered that the generation of development residue and the disconnection of the pattern are unlikely to occur, and the exposure sensitivity and the resolvability are likely to be improved.
In the present invention, having the ability to initiate photoradical polymerization means that free radicals capable of initiating radical polymerization can be generated by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organic metal complex is irradiated with light in a wavelength range in which the organic metal complex absorbs light and the radical cross-linking agent does not absorb light, radicals are generated. By confirming the presence or absence of the disappearance of the cross-linking agent, the presence or absence of the photoradical polymerization initiation ability can be confirmed. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of the radical cross-linking agent, and for example, it may be confirmed by IR measurement (infrared spectroscopy measurement) or HPLC measurement (high performance liquid chromatography).
When the organometallic complex has a photoradical polymerization initiating ability, the organometallic complex is preferably a metallocene compound, more preferably a titanosen compound, a zirconocene compound or a hafnosen compound, and more preferably a titanosen compound or a zirconocene compound. Is more preferable, and a titanosen compound is particularly preferable.
When the organic metal complex does not have the ability to initiate photoradical polymerization, the organic metal complex is selected from the group consisting of a titanosen compound, a tetraalkoxytitanium compound, a titanium acylate compound, a titanium chelate compound, a zirconocene compound and a hafnosen compound. It is preferably a compound of a species, more preferably at least one compound selected from the group consisting of a titanosen compound, a zirconocene compound and a hafnosen compound, and more preferably at least one selected from the group consisting of a titanosen compound and a zirconosen compound. It is more preferably a species compound, and particularly preferably a titanosen compound.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

As the organometallic complex, a compound represented by the following formula (P) is preferably mentioned.

In formula (P), M is a metal atom and R is an independent substituent.
It is preferable that the R is independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, a titanium atom or a zirconium atom is further preferable, and titanium. Atoms are particularly preferred.
Examples of the aromatic group in R in the formula (P) include an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a phenyl group, a 1-naphthyl group, or an aromatic group. , 2-naphthyl group and the like.
As the alkyl group in R in the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group and an isopropyl group. , T-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
Examples of the halogen atom in R include F, Cl, Br, and I.
As the alkyl group constituting the alkylsulfonyloxy group in R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, an octyl group, and the like. Examples thereof include an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclopentyl group and the like.
The above R may further have a substituent. Examples of substituents are halogen atom (F, Cl, Br, I), hydroxy group, carboxy group, amino group, cyano group, aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxy. Examples thereof include a carbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group and a diarylamino group.

Specific examples of the organic metal complex are not particularly limited, but are tetraisopropoxytitanium, tetrakis (2-ethylhexyloxy) titanium, diisopropoxybis (ethylacetacetate) titanium, and diisopropoxybis (acetylacetate). Nato) Titanium, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, pentamethylcyclopentadiene titanium tri Examples thereof include methoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, and the following compounds.

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but the present invention is not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more. The upper limit is more preferably 25% by mass or less.
As the organometallic complex, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin and the like.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition may be prepared by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the cross-linking agent described later or in addition to the cross-linking agent described later. It is possible to improve the coatability, the solvent resistance of the organic film, and the like.

When the composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, still more preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the composition. Further, it is more preferably 5% by mass or less, further preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Compound C>
The curable resin composition of the present invention is a group consisting of a compound represented by the formula (1-1), a compound represented by the formula (1-2), and a compound represented by the formula (1-3). May contain at least one compound selected from (also referred to as "Compound C").
Compound C is considered to suppress the aggregation of the organometallic complex by interacting with the specific compound and the organometallic complex. Therefore, it is considered that the inclusion of the compound C in the composition improves the resolution at the time of pattern formation.
In particular, when the curable resin composition contains a compound having an N-hydroxyimide group as a specific compound, the curable resin composition further contains compound C from the viewpoint of improving resolution and achieving both chemical resistance. Is preferable.

In the formula (1-1), the formula (1-2) or the formula (1-3), R ¹¹ and R ¹² are independently used as unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms and as substituents, respectively. At least one selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group. An aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent of, or 2 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. Representing an aliphatic hydrocarbon group of ~ 7, R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R ³¹ and R ³² respectively. Independently, it represents an aliphatic hydrocarbon group ^{having 1 to 7 carbon atoms which may have a substituent, and R 33} represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

[R ¹¹ and R ¹² ]
In formula (1-1), R ¹¹ and R ¹² are independently unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or primary amine salt structures and secondary amine salts as substituents. An aliphatic hydrocarbon group having 1 to 7 carbon atoms having at least one substituent selected from the group consisting of a structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group is preferable. , An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
As the ^{unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 11} and R ¹² , an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferable, and an unsubstituted aliphatic hydrocarbon group having 2 to 7 carbon atoms is preferable. Saturated aliphatic hydrocarbon groups are more preferable, and ethyl groups, isopropyl groups, t-butyl groups or cyclohexyl groups are more preferable.

From a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group as substituents in ^{R 11} and R ^12. As the aliphatic hydrocarbon group having 1 to 7 carbon atoms having at least one substituent selected from the above group, a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituent is preferable.
Further, the aliphatic hydrocarbon group may have a plurality of the above-mentioned substituents, but it is preferable to have only one of the above-mentioned substituents.

The primary amine salt structure in the above substituent means a salt structure composed of a primary amino group (-NH ₂ ) and an acid, and a salt structure of a primary amino group and an inorganic acid is preferable, and a hydrochloride structure is preferable. And so on.
The secondary amine salt structure in the above substituent means a salt structure composed of a secondary amino group (-NRH, R represents an organic group) and an acid, and is a salt of a secondary amino group and an inorganic acid. The structure is preferable, and examples thereof include a hydrochloride structure.
Examples of the secondary amino group constituting the secondary amine salt structure in the substituent include a monoalkylamino group, a monoarylamino group and the like, and a monoalkylamino group having 1 to 4 carbon atoms is preferable.
The tertiary amine salt structure in the above substituent means a salt structure _{consisting of a tertiary amino group (-NR 2} and R each independently represent an organic group) and an acid, and is a tertiary amino group and an inorganic substance. A salt structure with an acid is preferable, and a hydrochloride structure and the like can be mentioned.
As the tertiary amino group constituting the tertiary amino group or the tertiary amine in the above substituent, a dialkylamino group is preferable, and the carbon numbers of the two alkyl groups are independently 1 to 4, respectively. A dialkylamino group is more preferred, and a dimethylamino group is more preferred.
When one of R ¹¹ and R ¹² has any one of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, and a tertiary amine salt structure as a substituent, R ¹¹ and R are used. ^{The other of 12} is preferably the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
A fat having 1 to 7 carbon atoms having at least one selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, and a tertiary amine salt structure as a substituent. The group hydrocarbon group is preferably a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms having these substituents at the terminal, and has these substituents at the terminal. It is more preferably a linear or branched saturated aliphatic hydrocarbon group of 3 to 5, and a linear saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms having these substituents at the terminal. It is more preferable to have.

As the quaternary ammonium group in the above substituent, a group represented by the following formula (A-1) is preferable.

In the formula (A-1), ^RA1 to ^RA3 each independently represent a hydrocarbon group, and ^{at least two of RA1} to ^RA3 may be bonded to form a ring structure, and X is a counter anion. , And * represents a bonding site with an aliphatic hydrocarbon group having 1 to 7 carbon atoms.
In the formula (A-1), ^RA1 to ^RA3 are independently, more preferably an aromatic hydrocarbon group or an alkyl group, more preferably a phenyl group or an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Alkyl groups are more preferred, and methyl groups are particularly preferred.
An ^{embodiment in which all of RA1} to ^RA3 are methyl groups is also one of the preferred embodiments of the present invention.
The ring structure at least two which is formed by bonding of R ^{A1 ~} R ^A3, saturated aliphatic hydrocarbon rings such as cyclohexane ring, unsaturated aliphatic hydrocarbon rings such as cyclohexene ring, saturated fat, such as morpholino ring Group heterocycles and the like can be mentioned.
In the formula (A-1), X represents a counter anion and may be a monovalent anion or a divalent or higher anion, but a monovalent anion is preferable.
Further, X is not particularly limited, but is preferably a halide ion or a tosylate anion, and more preferably a halide ion.
Examples of the halide ion include fluoride ion, chloride ion, bromide ion, iodide ion and the like, and chloride ion is preferable.
When one of R ¹¹ and R ^{12 has} a quaternary ammonium group as a substituent, ^{the other of R 11} and R ¹² may be the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. preferable.
The aliphatic hydrocarbon group having 1 to 7 carbon atoms having a quaternary ammonium group as a substituent is a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms having a quaternary ammonium group at the terminal. It is preferably a hydrogen group, more preferably a linear or branched saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms having a quaternary ammonium group at the terminal, and a quaternary ammonium at the terminal. It is more preferably a linear saturated aliphatic hydrocarbon group having a group and having 3 to 5 carbon atoms.

Examples of the hetero atom in the aliphatic hetero ring group in the above substituent include an oxygen atom, a nitrogen atom, a sulfur atom and the like, and an oxygen atom is preferable.
The aliphatic heterocyclic group may have only one heteroatom or may have two or more heteroatoms.
The aliphatic heterocyclic group preferably has a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure.
The aliphatic heterocyclic group may further have a known substituent such as an alkyl group.
As the aliphatic heterocyclic group, a 2,2-dimethyl-1,3-dioxolane-4-yl group is preferable.
When one of R ¹¹ and R ¹² has an aliphatic heterocyclic group as a substituent, it is preferable that the other of ^{R 11} and R ^{12 also has an aliphatic heterocyclic group as a substituent.}
The aliphatic hydrocarbon group having 1 to 7 carbon atoms having an aliphatic heterocyclic group as a substituent is preferably a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms having an aliphatic heterocyclic group at the terminal. It is more preferably a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms having an aliphatic heterocyclic group at the terminal, and further preferably a methyl group having an aliphatic heterocyclic group. preferable.

R ¹¹ and R ¹² are independently aliphatic hydrocarbon groups having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. There may be.
The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the substituents, but an embodiment having only one substituent is also one of the preferred embodiments of the present invention.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 4 carbon atoms is more preferable.
As the alkylthio group, an alkylthio group having 1 to 10 carbon atoms is preferable, and an alkylthio group having 1 to 4 carbon atoms is more preferable.
As the aliphatic hydrocarbon group having 2 to 7 carbon atoms, a saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 2 to 4 carbon atoms is more preferable.
Examples of an aliphatic hydrocarbon group having 2 to 7 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group and an alkylthio group include a hydroxyethyl group and a hydroxypropyl group. , Methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group and the like, but the present invention is not limited thereto.

[R ²¹ and R ²² ]
R ²¹ and R ²² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
R ²¹ and R ²² are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent. , An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
Aliphatic hydrocarbon group R ²¹ and the unsubstituted C 1-7 at R ^22, or, a preferred embodiment of the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the above substituents, respectively, R ¹¹ and it is similar to that shown in the description of R ^12.

[R ³¹ and R ³² ]
R ³¹ and R ³² each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
As R ³¹ and R ³² , an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent is preferable. , An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferable.
Preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R ³¹ and R ³² or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the substituent are R ¹¹ and R 32, respectively. it is similar to that shown in the description of R ^12.

[R ³³ ]
R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, and has an unsubstituted carbon number. It is more preferably a saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
As R ³³ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group is preferable, and an ethyl group is more preferable.

Further, the compound C is a compound that does not contain a radically polymerizable group such as a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an alkoxyalkyl group, a hydroxyalkyl group, an alkoxysilyl group, and a silanol group. Is preferable.

Specific examples of the compound C include, but are not limited to, the following compounds (1) to (27).
Further, among these compounds, the compounds (1) to (12) are particularly preferable from the viewpoint of resolution.

From the viewpoint of resolvability, the content mass of the compound C is preferably 10 to 50,000 ppm, more preferably 30 to 20,000 ppm, and more preferably 70 to 20,000 ppm with respect to the total mass of the curable resin composition. It is more preferably 15,000 ppm.
When the curable resin composition contains two or more kinds of compounds C, the above-mentioned content mass is the total mass of all the compounds C.

<Solvent>
The curable resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.

Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples thereof include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.

As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.

As the sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Suitable examples include dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Further, a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

The solvent may be contained in only one kind, or may be contained in two or more kinds. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Photosensitizer>
The composition of the present invention preferably contains a photosensitive agent.
It is assumed that the photosensitive agent does not contain the above-mentioned organometallic complex and a compound having a photoradical polymerization initiation ability.
The composition of the present invention preferably contains a photopolymerization initiator.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitive agent.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.

In the present invention, the compound corresponding to the organometallic complex does not correspond to the photosensitizer and the photoradical polymerization initiator.

When the organic metal complex has a photoradical polymerization initiator ability, it is also preferable that the composition of the present invention does not substantially contain a radical polymerization initiator other than the above organic metal complex. The fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the organometallic complex means that the content of the radical polymerization initiator other than the organometallic complex is based on the total mass of the organometallic complex. 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass.
Further, when the composition of the present invention contains an organometallic complex having a radical polymerization initiating ability, it is also preferable that the composition of the present invention contains the above-mentioned organometallic complex and a photoradical polymerization initiator. According to such an embodiment, as described above, the generation of development residue, the disconnection of the pattern, and the like can be suppressed, and the exposure sensitivity can be improved.
When the composition of the present invention contains an organic metal complex having no photoradical polymerization initiator ability, the composition of the present invention preferably contains a photoradical polymerization initiator. Since the composition of the present invention contains a specific resin, it is considered that aggregation of the organometallic complex is suppressed. It is speculated that by suppressing the aggregation of organometallic complexes that do not have the ability to initiate photoradical polymerization, the local increase in plasticity of the membrane due to aggregation is suppressed, and the increase in local degree of polymerization at the aggregation site is also suppressed. Will be done. As a result, it is presumed that the occurrence of variation in sensitivity depending on the part of the film is suppressed and the resolution is improved.
When the composition of the present invention contains an organometallic complex and a photoradical polymerization initiator, the content of the organometallic complex with respect to the total content of the organometallic complex and the photoradical polymerization initiator is 20 to 80% by mass. It is preferably 30 to 70% by mass, and more preferably 30 to 70% by mass.
Further, as the photoradical polymerization initiator, the oxime compound described later is preferable.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient ^{of at least about 50 L · mol -1} · cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, organic boron compounds and the like can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, and 2-acetoxy. Iminopentane-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = N—O—C (= O)-in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA ARCULDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Further, an oxime compound having the following structure can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

Further preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms. 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R ^I01 is a group represented by formula (II), the same as R ^I00 The groups, R ^I02 to R I ^04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.

In the formula, R ^I05 to R I ⁰⁷ are the same as ^{R I 02} to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

[Photoacid generator]
Further, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitive agent.
By containing the photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part is removed by the developing solution. A positive pattern can be obtained.
Further, when the composition contains a photoacid generator and a cross-linking agent other than the radical cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by the acid generated in the exposed part, and the exposed part becomes It is also possible to make it more difficult to be removed by the developing solution than the non-exposed portion. According to such an embodiment, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.

The quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded and a sulfonamide bond. Examples include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazido sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).

Wherein (OS-1), ^{X 3} is an alkyl group, an alkoxyl group, or a halogen atom. If X ³ there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X ³ may have a substituent. The alkyl group in the above X ^3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X ^3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X ^3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.
In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

Wherein (OS-1), m3 is 3, ^{X 3} is a methyl group, the substitution position of ^{X 3} is ^{ortho, R 34} is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and R ^{s2, which may be present in a plurality of R s2,} independently represents a hydrogen atom, an alkyl group and an aryl group. ^{R s6} , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), ^{an alkyl group represented by R s1} (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.

In the formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. ^{Of the Rs2} that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by ^{R s2 may have a substituent T.}
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the ^{alkyl group represented by R s6} (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.

Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R ^t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R ^t2 represents a hydrogen atom or a methyl group.
In the formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.

In the formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.

Other suitable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In the formula (OS-101) or the formula (OS-102), ^Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group. The ^{embodiment in which R u9} is a cyano group or an aryl group is more preferable, and the embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), ^Ru2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, ^-NH- , -NR u5-, -CH _2- , -CR ^u6 H- or CR ^u6 R ^u7. -, R ^u5 to R ^u7 independently represent an alkyl group or an aryl group, respectively.

In the formula (OS-101) or the formula (OS-102), ^Ru1 to ^Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the ^R ^u1 ~ R ^u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring. The R ^u1 ~ ^{R u4,} a hydrogen atom, preferably a halogen atom or an alkyl group, ^also aspects to form the at least two aryl groups bonded to each other of R u1 ^{~ R u4} preferred. Above all, it is preferable that all of ^Ru1 to ^{Ru4 are hydrogen atoms.} Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.

In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-690 (any of which). Also Fujifilm Wako Pure Chemical Industries, Ltd., Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF). (Made by Midori Chemical Industries, Ltd.) and the like.

Further, a compound represented by the following structural formula is also mentioned as a preferable example.

As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, JP-A-55-3207, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, JP-A-63-70243, JP-A-63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like can be mentioned, and in particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

As a photoacid generator, an organic borate compound can also be applied. Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding Compound 19-22, 1998, Chicago", etc. Organic borate, organic boron sulfonium complex or organic boron oxosulfonium complex described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554. Japanese Patent Laid-Open No. 6-175553, Organic Boron Iodonium Complex, Japanese Patent Application Laid-Open No. 9-188710, Organic Boron Phosphorium Complex, Japanese Patent Application Laid-Open No. 6-348011, JP-A-7-128785, JP-A. Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.

A disulfone compound can also be applied as a photoacid generator. Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.

Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069, Phosphonium salts described in 055 and 4,069,056, European Patents 104 and 143, US Patents 339,049 and 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent. No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, The sulfonium salt according to each specification of German Patent No. 2,904,626, 3,604,580, and 3,604,581. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as the arsonium salt and the pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988).

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

In the formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. 12 alkenyl groups, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, allyloxy groups with 1 to 12 carbon atoms, halogen atoms, 1 to 12 carbon atoms Alkylamino group, dialkylamino group with 1 to 12 carbon atoms, alkylamide or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group with 1 to 12 carbon atoms, carbon Examples thereof include thioaryl groups having the number 1 to 12. Z11 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar21 and Ar22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and a preferable substituent is an alkyl group having 1 to 12 carbon atoms. , An alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, and carbon. Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 to 12 carbon atoms Examples thereof include a thioalkyl group of 1 to 12 and a thioaryl group having 1 to 12 carbon atoms. Z21 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In the formula (RI-III), R31, R32, and R33 each represent an aryl group or an alkyl group having 20 or less carbon atoms, an alkenyl group, and an alkynyl group, which may independently have 1 to 6 substituents, and are preferable. From the viewpoint of reactivity and stability, an aryl group is desirable. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group with 1 to 12 carbon atoms, halogen atom, alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.

Specific examples include the following.

When the photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.

[Photobase generator]
The curable resin composition of the present invention may contain a photobase generator as a photosensitive agent.
When the curable resin composition contains a photobase generator and a cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by promoting the cyclization of the specific resin by the base generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.

The photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); H. Tachi, M. et al. Shirai, and M. Tsunooka, J.M. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.M. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); K.K. Suyama, H. et al. Araki, M. et al. Shirai, J.M. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those latent by salt formation of an amidin moiety with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
In the present invention, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples of the photobase generator.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but is preferably 20 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) shall be used as pKa.

From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator is preferable. It is preferable that there is no charge on the top. As the photobase generator, it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Further, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in the structure.

Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamon acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as the photobase generator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.

In addition, a commercially available product may be used as the photobase generator. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-207, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.

When the photobase generator is contained, the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.

<Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the cross-linking agent can be promoted in the heating step described later, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

<Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and at the time of final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935.

Among them, those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) Methyl ((2-Methylphenyl) Methyl) Sulfonium, 3-(5-(((propylsulfonyl) Oxy) Imino) Thiophen-2 (5H) -Ilidene) -2- (o-Trill) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as the thermal acid generator.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermal acid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

Further, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermal base generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Thermal base generator>
The curable resin composition of the present invention may further contain a thermosetting agent.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermobase generator.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermal base generator include compounds represented by the formula (B1) or the formula (B2).

In the formula (B1) and the formula (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In the formulas (B1) and (B2), ^{it is preferable that at least one of Rb 1} , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have a substituent as long as the effect of the present invention is exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. Maybe cyclohexyl groups are more preferred.

Examples of Rb ³ include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18). ~ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24). 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). Among them, a cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), and arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.

Rb ³⁵ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.

The content of the other thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermal base generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<Crosslinking agent>
The curable resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.

<Radical cross-linking agent>
The curable resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.

The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the ethylenically unsaturated bond.
Further, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
Further, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable.

The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.

Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate group or an epoxy group, or a monofunctional or polymorphic acid group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0379193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) acrylics described in JP-A-48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.

Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, Japanese Square Root 01-040336, and Japanese Patent Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.

As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded to each other is preferable. These oligomer types can also be used.

Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The radical cross-linking agent provided with the above is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. On the other hand, from the viewpoint of the development speed in the case of alkaline development, the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.

In the curable resin composition of the present invention, it is preferable to use a bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene. Glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethyrol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimetallylate of bisphenol A, PO adduct diacrylate of bisphenol A, EO addition of bisphenol A Dimetalylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylate having a urethane bond, and bifunctional methacrylate having a urethane bond can be used. If necessary, two or more of these can be mixed and used.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern, a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

When a radical cross-linking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

The radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.

<Other cross-linking agents>
The curable resin composition of the present invention preferably contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule that promote the formation reaction, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of the acid or the base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable. A compound having a structure directly bonded to a nitrogen atom is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycol-uryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.

In addition, as the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which the group of the species is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.

Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.

Further, it is also preferable that the curable resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, contained silicone. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E (the above products) Name, manufactured by DIC Co., Ltd., Rica Resin (registered trademark) BEO-60E, Rica Resin (registered trademark) HBE-100, Rica Resin (registered trademark) DME-100, Rica Resin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolyde GT400, Servinus B0134, B0177 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000 -L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201 , BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

[Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.

[Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (hereinafter, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly. Examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.

<Compounds having a sulfonamide structure, compounds having a thiourea structure>
From the viewpoint of improving the adhesion of the obtained pattern to the substrate, the curable resin composition of the present invention is at least one selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain the compound.

[Compound having a sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).

In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * may independently form a binding site with another structure. show.
The R is preferably the same group as ^{R 2} in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but is preferably a compound having one sulfonamide structure.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ are bonded to each other. It may form a ring structure.
It is preferable that R ¹ , R ² and R ³ are independently monovalent organic groups.
Examples of R ¹ , R ² and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group and a carboxy group. Examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.

Among these, ^{compounds in which R 1} is an aryl group and R ² and R ³ are independently hydrogen atoms or alkyl groups are preferable.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1. -Sulfonamide, Naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethyl Examples thereof include methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide and the like.

[Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ⁴ and R ⁵ may be combined to form a ring structure, where R ⁴ is. * it is may form a ring structure and other structures that bind, R ⁵ may form a ring structure and other structures that bind *, * is independently other Represents the site of connection with the structure of.

It is preferable that R ⁴ and R ⁵ are independently hydrogen atoms.
Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxy group, and a carbonyl group. Examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
As the cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
As the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
Examples of the heterocyclic group include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).

In the formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and ^{at least two of R 4} to R ⁷ are bonded to each other to form a ring structure. You may.

Wherein (T-2), ^{R 4} and ^{R 5} have the same meanings as ^{R 4} and ^{R 5} in formula (T-1), a preferable embodiment thereof is also the same.
In the formula (T-2), ^{it is preferable that R 6} and R ⁷ are independently monovalent organic groups.
In the formula (T-2), the preferred embodiment of the monovalent organic group in ^{R 6} and R ⁷ is the same as the preferred embodiment of the monovalent organic group in ^{R 4} and R ^{5 in the formula (T-1).} ..

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoylthiourea, N, N'-. Diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydrantin.

〔Content〕
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the curable resin composition of the present invention. %, More preferably 0.2 to 3% by mass.
The curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more of them. When only one kind is contained, the content of the compound is preferably in the above range, and when two or more kinds are contained, the total amount thereof is preferably in the above range.

<Migration inhibitor>
The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive film.

The migration inhibitor is not particularly limited, but has a heterocyclic ring (pyran ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, etc. Compounds having a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidin ring, piperazin ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered Examples thereof include phenol-based compounds, salicylic acid derivative-based compounds, and hydrazide derivative-based compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trap agent that traps anions such as halogen ions can also be used.

Examples of other migration inhibitors include the rust preventive agent described in paragraph 0094 of JP2013-015701, the compound described in paragraphs 0073 to 0076 of JP2009-283711, and JP-A-2011-059656. The compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compound described in paragraph 0166 of International Publication No. 2015/199219 and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

The migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-sulfopropylamino) phenol, N- Nitrosophenyl hydroxyamine first cerium salt, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane, 1,3,5-tris ( 4-t-Butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2,2, 6,6-Tetramethylpiperidin 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt , N-nitroso-N-phenylhydroxylamine ammonium salt, N, N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, etc. It is preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used.

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.

The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include a silane coupling agent, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, an amino compound and the like. And so on.

Examples of the silane coupling agent include the compound described in paragraph 0167 of International Publication No. 2015/199219, the compound described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraph of International Publication No. 2011/080992. The compounds described in 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanule, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Examples thereof include propyltriethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.

Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..

The content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. As the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocycle-containing polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern after the heating step and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured product after the heating step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, to the extent that the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, antiaggregating agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzilidenindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Surfactant]
A surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the composition.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.

Examples of the hydrocarbon-based surfactant include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic® L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd. (Nissin Chemical Industry Co., Ltd.) Made by Co., Ltd.).

Specifically, as a cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Specific examples of the anion-type surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

[Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and may particularly contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be promoted by adding the thermal radical polymerization initiator, the solvent resistance can be further improved.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to the scattering of the exposure light.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Further, as an example of the triazine-based ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-Triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) )-1,3,5-Triazine, 2,4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-Triazine, 2,4,6-Tris [2-Hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-Triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.

In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. .. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).

In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R6 represents an alkylene group having 2 or more carbon atoms. R7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.

Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. Examples of R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of interaction with a resin and metal adhesion due to metal complex formation. preferable.

Examples of the compound represented by the general formula (3) include the following, but the compound is not limited to the following structure.

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. When the addition amount is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation property after reliability and the adhesion to the metal material, and when the addition amount is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of reducing the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.6% by mass, from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

The metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as the raw material constituting the curable resin composition of the present invention. Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible are mentioned. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass by mass, from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing impurities from being mixed into the raw materials and the curable resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 7 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Use of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

<Preparation of curable resin composition>
The curable resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is a cured film obtained by curing the curable resin composition of the present invention. The cured film is preferably a patterned cured film. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminated body of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. An embodiment in which the resin composition is a cured film is preferable. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be present or it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

Further, the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the method for producing the present invention”) is a film forming in which the curable resin composition of the present invention is applied to a substrate to form a film (resin film). It is preferable to include a step.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film. By the above exposure step and development step, a pattern of a cured film can be obtained.
Further, it is more preferable that the method for producing a cured film of the present invention includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying a curable resin composition to a substrate to form a film (resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) Exposed Development step for developing the film (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed, and sufficient curability is obtained.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. In the method for producing the laminated body of the present embodiment, after forming the cured film according to the above-mentioned method for producing the cured film, the steps (a), the steps (a) to (c), or (a) are further performed. )-(D). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).

The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film film) array substrate, plasma display panel (PDP) electrode plate, and the like. Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Further, when the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.

Coating is preferable as a means for applying the curable resin composition to the base material.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Further, depending on the viscosity of the resin composition and the film thickness to be set, it is also preferable to apply the resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain uniformity of the film thickness, it is also possible to apply a combination of a plurality of rotation speeds.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end portion of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wet step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.

<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step). The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (resin composition layer). The exposure amount is not particularly determined as long as the curable resin composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm ^2.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
Further, the exposure light preferably contains light having a wavelength of 365 nm or 405 nm, and more preferably contains light having a wavelength of 405 nm.

The exposure wavelengths are as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

The exposure method is not particularly limited as long as it is a method in which at least a part of the film (photosensitive film) made of the curable resin composition is exposed, but an exposure using a photomask or a laser direct imaging method is used. Exposure and the like can be mentioned.
In the present invention, an aspect in which the exposure in the exposure step is an exposure by a laser direct imaging method is also one of the preferred embodiments.

<Development process>
The production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a substrate, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a combination thereof. Processes can be adopted.

Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
As the developing solution, a developing solution containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

When the developing solution is a developing solution containing an organic solvent, the organic solvent may be, for example, as esters such as ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, 2-alkyloxypropionate) Methyl, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2) -Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol. Dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol mono As propyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example, toluene. , Xylene, anisole, limonene and the like, dimethyl sulfoxide is preferably mentioned as a sulfoxide, and a mixture of these organic solvents is also preferably mentioned.

When the developer is a developer containing an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.

When the developer is a developer containing an organic solvent, 50% by mass or more of the developer is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is organic. It is more preferably a solvent. Further, the developer may be 100% by mass of an organic solvent.

The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. .. When TMAH is used, for example, the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.

[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and a method of immersing the base material in the developer, a method of supplying the developer on the base material using a nozzle and paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly determined, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.

After the treatment with the developer, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed using the solvent contained in the curable resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

When the rinsing solution contains an organic solvent, the ethers include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid). Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran. , Ethyl Glycol Monomethyl Ether, Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene and the like, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols. Glycols and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

When the rinsing liquid contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.

When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.

The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

[Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and is a method of immersing the base material in the rinsing liquid, a method of supplying the base material by filling, a method of supplying the base material with the rinsing liquid by a shower, and the like. There is a method of continuously supplying the rinse liquid onto the base material by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the film after exposure by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sonic or the like and a process of combining them can be adopted.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured membrane can be prevented from excessive volatilization. Residual stress can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.

The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and even more preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, it is the temperature of the film (layer) after drying, and is, for example, higher than the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and the temperature is kept at 200 ° C. for 120 minutes. , Such as a pretreatment step may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

<Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (resin composition layer).

As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified. The alloy containing the above is more preferable, and copper is further preferable.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, still more preferably 1 to 10 μm in the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

In the laminating step, (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, it may be an embodiment in which only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated resin composition layers all at once. Further, the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.

When the laminating step is further performed, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.

The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

For example, a configuration in which the resin layer is 2 or more and 20 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration of 3 or more and 7 or less is more preferable. More preferably, it has 3 or more layers and 5 or less layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the resin composition layer (resin layer) and the metal layer forming step, the resin composition layer (resin layer) and the metal layer can be alternately laminated.

(Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer forming step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then the metal layer forming step. good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer that forms the photosensitive resin composition layer on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. As described above, by performing the surface activating treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF ₄ / O _2. Etching treatment with NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment with ultraviolet (UV) ozone method, soaking in a hydrochloric acid aqueous solution to remove the oxide film, and then removing amino and thiol groups. It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / ^{m 2,} more preferably 1000 ~ 100,000J / ^{m 2,} and most preferably 10,000 ~ 50,000J / ^{m 2.}

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 of JP-A-2016-0273557 and the description in FIG. 1 are referred to. Yes, these contents are incorporated herein.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis Example 1: Synthesis of Polymer A-1>
23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of 4,4'-biphthalic acid dianhydride (BPDA) were placed in a separable flask and 2-hydroxyethyl methacrylate (HEMA) 39. 69 g and 136.83 g of γ-butyrolactone were added and stirred at room temperature, and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( 27.42 g of DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyimide precursor A-1). When the molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2: Synthesis of Polymer A-2>
Polymer A-2 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA.

<Synthesis Example 3: Synthesis of Polymer A-3>
By the same method as in Synthesis Example 1, except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA and 39.69 g of HEMA was changed to 19.85 g of HEMA and 18.32 g of diethylene glycol monomethyl ether. , Polymer A-3 was synthesized.

<Synthesis Example 4: Synthesis of Polymer A-4>
10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. It was dissolved in 85.8 g of N-methylpyrrolidone (NMP). Next, 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was added dropwise over 1 hour, and the mixture was stirred at 25 ° C. for 2 hours.
After stirring, the precipitate was precipitated in 2 liters of water / methanol = 75/25 (volume ratio), and the mixture was stirred at a rate of 2,000 rpm for 30 minutes. The precipitated polybenzoxazole precursor resin was filtered off and washed with 1.5 liters of water. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain A-4.

<Synthesis Example 5: Synthesis of Polymer A-5>
Put 29.08 g of trimellitic acid anhydride in a separable flask, add 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone, and stir at room temperature to add 24.66 g of pyridine while stirring. In addition, a reaction mixture was obtained. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left at room temperature for 16 hours.
Next, under ice-cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether ( 27.42 g of DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, the obtained precipitate was filtered off, and then vacuum dried to obtain a powdered polymer (polyamideimide precursor) A-5. Obtained.

<Synthesis Example 6: Synthesis of Polymer A-6>
Polymer A-6 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 44.54 g of BPDA.

<Synthesis Example 7: Synthesis of Polymer A-7>
With the exception of Synthetic Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA and 39.69 g of HEMA was changed to 52.52 g of the compound represented by the following formula (7-1). Polymer A-7 was synthesized by the same method.

<Synthesis Example 8: Synthesis of Polymer A-8>
Place 44.42 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and 20.02 g of 4,4'-diaminodiphenyl ether in a separable flask, and add 322.20 g of γ-butyrolactone for 6 hours at 130 ° C. Stirred.
The obtained reaction solution was added dropwise to 2706.48 g of methanol to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-8.

<Synthesis Example 9: Synthesis of Polymer A-9>
29.51 g of 4,4'-oxybis (benzoyl chloride) was placed in a separable flask, 220.47 g of γ-butyrolactone was added, and the mixture was stirred at -5 ° C. After 17.40 g of pyridine was added thereto, a mixed solution of 36.63 g of 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 110.23 g of γ-butyrolactone was added dropwise. After the dropping, the mixture was stirred at −5 ° C. for 1 hour, then heated to room temperature and stirred for 2 hours. Then, the reaction solution was stirred at 130 ° C. for 6 hours.
The obtained reaction solution was added dropwise to 2899.68 g of methanol to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-9.

<Synthesis Example 10: Synthesis of Polymer A-10>
4- (2- (1,3-Dioxo-1,3-dihydroisobenzofuran-5-yl) -1,1,1,3,3,3-hexafluoropropane-2-yl) benzenecarboxylic acid 41. 82 g and 20.02 g of 4,4'-diaminodiphenyl ether were placed in a separable flask, 310.30 g of γ-butyrolactone was added, and the mixture was stirred at 130 ° C. for 6 hours.
The obtained reaction solution was added dropwise to 2604.98 g of methanol to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-10.

<Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.
Specifically, the content of each component shown in Tables 1 to 7 is the amount (parts by mass) shown in parentheses in each column of Tables 1 to 7.
However, the content of the specific compound was the amount (parts by mass) described in the column of "content (parts by mass)" of the "specific compound".
In addition, the description in the column of "mmol" of "organic metal complex" and "specific compound" in the table represents the molar portion (mmol portion) of each compound.
The description in the column of "amount (mol%) with respect to the organic metal complex" of "specific compound" in the table represents the ratio (%) of the molar content of the specific compound to the molar content of the organic metal complex.
The obtained curable resin composition and comparative composition were pressure-filtered using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 1 to 5, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 1 to 5 are as follows.

〔resin〕
A-1 to A-10: Polymers A-1 to A-10 obtained by the above synthetic example.

[Photosensitizer (photoradical polymerization initiator)]
B-1 to B-3: Compounds with the following structure

[Organometallic complex]
-X-1: Bis (η5-2,4-cyclopentadiene-1-yl) Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) Titanium-X-2: Pentamethylcyclo Pentazienyl Titanium Trimethoxide ・ X-3: Bis (η5-2,4-Cyclopentadiene-1-yl) Bis (2,6-difluorophenyl) Titanium ・ X-4: Tetraisopropoxytitanium (Matsumoto Fine Chemical Co., Ltd.) Made)
-X-5: Diisopropoxybis (acetylacetonato) titanium (manufactured by Matsumoto Fine Chemical Co., Ltd.)
X-6 to X-8: Compounds having the following structure.

The above X-1 and X-3 are compounds having an ability to initiate photoradical polymerization.

[Crosslinking agent (radical crosslinking agent)]
C-1 to C-2: Compounds with the following structure

[Polymerization inhibitors, etc.]
-D-1 to D-7: Compounds having the following structure D-1 is a compound corresponding to the above-mentioned migration inhibitor.
D-2 to D-7 are compounds corresponding to the above-mentioned polymerization inhibitors.

〔Additive〕
E-1 to E-10: Compounds with the following structure

[Metal adhesion improver]
-F-1 to F-6: Compounds with the following structure

In the above structural formula, Me represents a methyl group and Et represents an ethyl group.

[Specific compound]
G-1 to G-10: Compounds having the following structure

[Solvent (solvent)]
-NMP: N-methyl-2-pyrrolidone-EL: Ethyl lactate-DMSO: Dimethyl sulfoxide

<Evaluation>
[Resolution evaluation]
In each Example or Comparative Example, the prepared curable resin composition or comparative composition was applied onto a silicon wafer by a spin coating method. The silicon wafer was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 20 μm on the silicon wafer.
In the example described as "M" in the exposure condition, the curable resin composition layer on the silicon wafer was exposed using a stepper. The exposure was performed using light having the wavelength described in "Exposure wavelength nm" in the table, and using a fuse box photomask from 5 μm to 25 μm in 1 μm increments. The exposure amount was the exposure amount that minimizes the minimum line width described later.
In the example described as "D" in the exposure condition, the exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure was performed by laser direct imaging exposure at a wavelength of 405 nm so that the exposed portion became a line portion in a line and space pattern in 1 μm increments from 5 μm to 25 μm. The exposure amount was the exposure amount that minimizes the minimum line width described later.
The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds and then rinsed with PGMEA (propylene glycol monomethyl ether acetate).
In the pattern obtained after development, the line width of the line pattern in which the silicon wafer was exposed between the line patterns and the line width was the smallest was defined as the "minimum line width" and evaluated according to the following evaluation criteria. It can be said that the smaller the line width is, the better the resolution is, and for example, it means that the metal wiring width formed in the subsequent plating step can be miniaturized, which is a preferable result. The measurement limit is 5 μm. The evaluation results are described in the "Resolution" column in the table.
-Evaluation criteria-
A: The minimum line width was 5 μm or more and less than 8 μm.
B: The minimum line width was 8 μm or more and less than 10 μm.
C: The minimum line width was 10 μm or more and less than 12 μm.
D: The minimum line width was 12 μm or more and less than 15 μm.
E: The minimum line width was 15 μm or more.

[Exposure sensitivity evaluation]
A curable resin composition layer having a uniform thickness of 20 μm was formed on a silicon wafer by the same method as in the above resolution evaluation.
In the example described as "M" in the exposure condition, the curable resin composition layer on the silicon wafer is described as "negative" in the mask portion having a diameter of 15.0 μm by a stepper (in the column of development conditions in the table). An example) or a photomask having a non-masked portion (an example described as "positive" in the column of current conditions in the table) was used for exposure. The exposure wavelength is described in "Exposure wavelength (nm)" in the table. The exposure amount was varied in 50 mJ / cm ² increments in the range of 50 ~ 500mJ / cm ^2.
In the example described as "D" in the exposure condition, laser direct imaging exposure was performed using a direct exposure apparatus (Adtech DE-6UH III). The exposure wavelength was 405 nm, and exposure was made so that an unexposed portion having a diameter of 15.0 μm was formed. The exposure amount was varied in 50 mJ / cm ² increments in the range of 50 ~ 500mJ / cm ^2.
The sensitivity was evaluated according to the following evaluation criteria from the minimum exposure amount at which a hole pattern having a bottom diameter of 15.0 μm was formed. The smaller the minimum exposure amount (the higher the sensitivity), the more preferable, and it can be said that the exposure sensitivity is excellent. The evaluation results are described in the "Sensitivity" column in the table.
-Evaluation criteria-
A: The minimum exposure amount was less than ^{100 mJ / cm 2.}
B: the minimum exposure amount is less than 100 mJ / cm ² or more 150 mJ / cm ^2.
C: The minimum exposure amount was 150 mJ / cm ² or more.

[Evaluation of elongation at break]
The curable resin composition or the comparative composition prepared in each Example and each Comparative Example was applied onto a silicon wafer by a spin coating method to form a resin layer.
The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer.
In the example described as "negative" in the column of current conditions in the table, the entire surface of the curable resin composition layer on the silicon wafer was exposed with an exposure energy of ^{500 mJ / cm 2.} The exposure wavelength is described in "Exposure wavelength (nm)" in the table. No exposure was performed in the example described as "Positive" in the column of current conditions in the table.
The temperature of the curable resin composition layer after the exposure was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, reached 230 ° C., and then maintained at 230 ° C. for 3 hours. The cured resin composition layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation rate of the obtained test piece in the longitudinal direction was measured in JIS-K6251 in an environment of a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity) using a tensile tester (Tensilon). Measured in compliance. The measurement was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece was broken in each of the 5 measurements was used as an index value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "elongation at break" in the table. It can be said that the larger the index value, the better the film strength of the cured film.
-Evaluation criteria-
A: The above index value was 60% or more.
B: The index value was 55% or more and less than 60%.
C: The above index value was less than 55%.

[Evaluation of chemical resistance]
-Calculation of dissolution rate-
In each Example or Comparative Example, the curable resin composition layer was formed on the silicon wafer by the same method as the formation of the curable resin composition layer in the above-mentioned resolution evaluation.
After that, in each Example or Comparative Example, for the example described as "M" in the "Exposure condition" column, the entire surface of the curable resin composition layer was exposed without using a photomask, and "exposure" was performed. For the example described as "D" in the "Conditions" column, exposure was performed by the same method as the exposure method in the above-mentioned evaluation of pattern formability, except that the entire surface of the curable resin composition layer was exposed to laser. This was performed to obtain a resin film.
Next, the resin film obtained in each Example or Comparative Example was heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained for 3 hours to maintain the cured film. Formed.
The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
Chemicals: Mixture of dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the cured membrane in the chemicals at 75 ° C. for 15 minutes. The thicknesses of the cured films before and after were compared, and the dissolution rate (nm / min) was calculated.
The obtained dissolution rate values were evaluated according to the following evaluation criteria and described in the "Chemical resistance" column. It can be said that the smaller the dissolution rate, the better the chemical resistance.
-Evaluation criteria-
A: The dissolution rate is less than 250 nm / min.
B: The dissolution rate is 250 nm / min or more and less than 500 nm / min.
C: The dissolution rate is 500 nm / min or more.

From the above results, it can be seen that the curable resin composition of the present invention has excellent resolution.
The comparative composition according to Comparative Example 1 does not contain a specific compound.
Further, the comparative composition according to Comparative Example 2 does not contain an organometallic complex.
It can be seen that when these comparative compositions are used, the resolution is inferior.

<Example 101>
The curable resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a photosensitive film having a film thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 120 minutes to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor.
Compound B having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, an N-hydroxyamide group, and an N-hydroxyimide group, and
A curable resin composition containing an organometallic complex.
The curable resin composition according to claim 1, further comprising a photopolymerization initiator.
The curable resin composition according to claim 1 or 2, further comprising a cross-linking agent.
The curable resin composition according to any one of claims 1 to 3, wherein the organometallic complex is a metallocene compound.
The curable resin composition according to any one of claims 1 to 4, wherein the organometallic complex is a titanium compound.
The curable resin composition according to any one of claims 1 to 5, wherein the organometallic complex has an ability to initiate photoradical polymerization.
Any of claims 1 to 6, wherein the compound B is a compound having at least one group selected from the group consisting of an N-hydroxyamino group, an N-hydroxyimino group, and an N-hydroxyamide group. The curable resin composition according to item 1.
The compound B includes a compound having an N-hydroxyimide group, is represented by the formula (1-1), the compound represented by the formula (1-2), and the compound represented by the formula (1-3). The curable resin composition according to any one of claims 1 to 6, further comprising at least one compound selected from the group consisting of the following compounds.

In the formula (1-1), the formula (1-2) or the formula (1-3), R 11 and R 12 are independently used as unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms and as substituents, respectively. At least one selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group. An aliphatic hydrocarbon group having 1 to 7 carbon atoms having a substituent of, or 2 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group. Representing an aliphatic hydrocarbon group of ~ 7, R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 31 and R 32 respectively. Independently, it represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
The curable resin composition according to any one of claims 1 to 8, wherein the ratio of the molar content of the compound B to the molar content of the organometallic complex is 30 to 500%.
The curable resin composition according to any one of claims 1 to 9, which is used for forming a photosensitive film to be used for negative development.
The curable resin composition according to any one of claims 1 to 10, which is used for forming an interlayer insulating film for a rewiring layer.
A cured film obtained by curing the curable resin composition according to any one of claims 1 to 11.
A laminated body containing two or more layers of the cured film according to claim 12, and containing a metal layer between any of the cured films.
A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 11 to a substrate to form a film.
The method for producing a cured film according to claim 14, further comprising an exposure step for exposing the film and a developing step for developing the film.
The method for producing a cured film according to claim 15, wherein the exposure light used for the exposure includes light having a wavelength of 405 nm.
The method for producing a cured film according to claim 15 or 16, wherein the exposure is an exposure by a laser direct imaging method.
The method for producing a cured film according to any one of claims 14 to 17, which comprises a heating step of heating the film at 50 to 450 ° C.
A semiconductor device comprising the cured film according to claim 12 or the laminate according to claim 13.