CN110741318A

CN110741318A - Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device, and compound

Info

Publication number: CN110741318A
Application number: CN201880037130.9A
Authority: CN
Inventors: 川端健志; 吉田健太; 岩井悠; 涩谷明规
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2017-06-06
Filing date: 2018-06-04
Publication date: 2020-01-31
Anticipated expiration: 2038-06-04
Also published as: CN110741318B; KR20190137942A; JPWO2018225676A1; KR102279447B1; TWI742285B; WO2018225676A1; JP6808831B2; TW201902991A

Abstract

The present invention provides photosensitive resin compositions having excellent storage stability and high sensitivity, and a cured film, a laminate, a method for producing a cured film, and a semiconductor device using the photosensitive resin compositions, and also provides novel compounds for forming a photosensitive resin composition, photosensitive resin compositions comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a radical polymerizable compound having a sulfur atom, a photo radical polymerization initiator, and a solvent.

Description

Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device, and compound

Technical Field

The invention relates to kinds of photosensitive resin compositions, cured films, laminates, methods for producing cured films, semiconductor devices and compounds.

Background

Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for protective films and interlayer insulating films of semiconductor devices. However, in recent years, with the progress of high integration and large-scale growth of semiconductor elements, thinning and miniaturization of sealing resin packages have been required, and surface mounting using LOC (lead on chip) or reflow has been adopted.

For example, patent document 1 discloses resin compositions containing (a) a polyimide precursor having a predetermined structure, (b) a compound that generates radicals by irradiation with active light, (c) a compound represented by the following formula (4a) or (4b), and (d) a solvent.

[ chemical formula 1]

(in the formula (4a), na is an integer of 3 or less; in the formula (4b), R is¹⁰¹And R¹⁰²Each independently is a hydrogen atom or a 1-valent group. mb is an integer of 9 or less. )

Specifically, as the compound represented by formula (4a) or (4b), tripropylene glycol diacrylate, tripropylene glycol, and the like are disclosed.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2014-201695

Disclosure of Invention

Technical problem to be solved by the invention

However, it is known that the composition described in the above patent document 1 is not necessarily high in sensitivity to light, and that storage stability of the photosensitive resin composition is also required when the photosensitive resin composition is held for hours and then used as a cured film.

The present invention has an object to solve the above problems, and an object of the present invention is to provide photosensitive resin compositions having excellent storage stability and high sensitivity, and a cured film, a laminate, a method for producing a cured film, and a semiconductor device each using the same, and to provide compounds for producing the photosensitive resin compositions.

Means for solving the technical problem

As a result of intensive studies based on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a radical polymerizable compound having a sulfur atom into a photosensitive resin composition. Specifically, the above problem is solved by the following means <1>, preferably <2> to <22 >.

<1> photosensitive resin compositions comprising a polymer precursor selected from polyimide precursors and polybenzoxazole precursors, a radical polymerizable compound having a sulfur atom, a photo radical polymerization initiator, and a solvent.

<2> the photosensitive resin composition according to <1>, wherein the polymer precursor comprises a repeating unit represented by the following formula (1) or a repeating unit represented by the following formula (2);

[ chemical formula 2]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH,

R¹¹¹represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group;

[ chemical formula 3]

In the formula (2), R¹²¹Represents a 2-valent organic group, R¹²²Represents a 4-valent organic group, R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group.

<3> the photosensitive resin composition according to <2>, wherein the polymer precursor comprises a repeating unit represented by formula (1).

<4> the photosensitive resin composition according to any of < > in <1> to <3>, wherein the radical polymerizable compound having a sulfur atom is represented by the following formula (3-1);

[ chemical formula 4]

R¹²-X¹²-L¹¹-X¹¹-R¹¹(3-1)

In the formula (3-1), L¹¹Represents a 2-valent linking group containing a sulfur atom, X¹¹And X¹²Each independently represents a single bond or a 2-valent linking group, R¹¹And R¹²Each independently represents a hydrogen atom or a 1-valent organic group; wherein R is¹¹And R¹²At least of the groups represent a 1-valent organic group containing at least radically polymerizable groups, R¹¹And R¹²Optionally bonded to each other to form a ring.

<5> the photosensitive resin composition according to <4>, wherein the formula (3-1) is represented by the following formula (3-2);

[ chemical formula 5]

R²-La¹-X²-La²-L¹-La³-X¹-La⁴-R¹(3-2)

In the formula (3-2), L¹represents-S-, -S-, -S (═ O) -or-S (═ O)₂-，X¹And X²Each independently represents a single bond, -O-, -C (O) O-, -OC (O) -, -S (O)₂-or-NR³CO-，R¹And R²Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical polymerizable group, La¹～La⁴Each independently represents of a single bond, a group composed of 1 or 2 or more of alkylene and phenylene, and a group composed of 1 or 2 or more of alkylene and phenylene and-O-)³Represents a hydrogen atom or an alkyl group; wherein R is¹And R²At least of the groups are radical polymerizable groups.

<6>According to<5>The photosensitive resin composition, the above R¹And R²These two groups are each independently a radical polymerizable group.

<7>According to<5>Or<6>The photosensitive resin composition, the above X¹And X²is-O-.

<8>According to<5>～<7>The photosensitive resin composition of any one of items , wherein L is¹is-S (═ O) -.

<9>According to<5>～<8>The photosensitive resin composition of any one of items , wherein R is¹And R²Each independently is a 1-valent organic group having an acryloyl group or a methacryloyl group.

<10> the photosensitive resin composition according to <4>, wherein the formula (3-1) is represented by the following formula (4);

[ chemical formula 6]

In the formula (4), R is a hydrogen atom or a methyl group.

<11> the photosensitive resin composition according to any one of <1> to <10> at , wherein the radical polymerizable compound having a sulfur atom is contained at a ratio of 0.001 mass% or more of a solid content contained in the photosensitive resin composition.

<12> the photosensitive resin composition according to any one of <1> to <11> of , further comprising a radical polymerizable compound other than the radical polymerizable compound having a sulfur atom.

<13> the photosensitive resin composition according to any one of <1> to <12> of , further comprising an alkali generator.

<14> the photosensitive resin composition according to any one of <1> to <13> of , which is used for development.

<15> the photosensitive resin composition according to any one of <1> to <14> of , for use in development using a developer containing an organic solvent.

<16> the photosensitive resin composition according to any one of <1> to <15> of , for use in forming an interlayer insulating film for a rewiring layer.

<17> kinds of cured films formed from the photosensitive resin composition of any of <1> to <16> item .

<18> laminate comprising 2 or more layers of the cured film of <17 >.

<19> the laminate according to <18>, which comprises a metal layer between the cured films.

<20> cured film manufacturing methods, which includes the use of <1> to <16> of any of the photosensitive resin composition process.

<21> the method for producing a cured film according to <20>, comprising:

a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer; an exposure step of exposing the photosensitive resin composition layer; and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer.

<22> kinds of semiconductor devices, which have the cured film <17> or the laminate <18> or <19 >.

Effects of the invention

The present invention can provide photosensitive resin compositions having excellent storage stability and high sensitivity, and excellent cured films, laminates, cured film manufacturing methods, and semiconductor devices using the photosensitive resin compositions, and can provide novel compounds for the photosensitive resin compositions.

Detailed Description

The present invention will be described below. In the present specification, "to" means that numerical values described before and after the "to" are included as a lower limit value and an upper limit value.

The following description of the constituent elements of the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

In the expression of the group (atomic group) in the present specification, the expression that substitution and non-substitution are not described includes both the case where the group has no substituent and the case where the group has a substituent. For example, "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).

In the present specification, "exposure" is not particularly limited, and in addition to exposure using light, drawing using a particle beam such as an electron beam or an ion beam is also included in exposure. Examples of the light used for exposure include active light such as far ultraviolet light, extreme ultraviolet light (EUV light), X-ray, and electron beam, which are typically represented by a bright line spectrum of a mercury lamp or an excimer laser, and radiation.

In the present specification, the numerical range represented by "to" means a range in which the numerical values before and after "to" are included as the lower limit value and the upper limit value.

In the present specification, "(meth) acrylate" means of two or any of "acrylate" and "methacrylate", "meth (acrylic acid)" means of two or any of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means of two or any of "acryl" and "methacryl".

In the present specification, the term "step" is included in the term not only as an independent step but also as long as the action expected for the step can be achieved even when the step cannot be clearly distinguished from other steps.

In the present specification, the solid component is a mass percentage of the component other than the solvent in the total mass of the composition. The solid content concentration is a concentration at 25 ℃ unless otherwise specified.

In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as styrene equivalent values based on gel permeation chromatography (GPC measurement). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the eluent was measured with THF (tetrahydrofuran). Unless otherwise stated, detection is performed using a 254nm wavelength detector for UV rays (ultraviolet rays).

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "the composition of the present invention") is characterized by containing a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a radical polymerizable compound having a sulfur atom, a photo radical polymerization initiator, and a solvent. With this configuration, a photosensitive resin composition having excellent storage stability and high sensitivity can be obtained. The reason is presumed to be that the radical polymerizable compound having a sulfur atom is less likely to cause a polymerization reaction at room temperature under heat, and is based on the improvement of the radical polymerizability of the composition.

< Polymer precursor >

The photosensitive resin composition of the present invention contains a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and the polymer precursor is preferably a polyimide precursor or a polybenzoxazole precursor, more preferably a polyimide precursor, and further is preferably a polyimide precursor containing a repeating unit represented by formula (1) described later.

Polyimide precursor

The polyimide precursor preferably contains a repeating unit represented by the following formula (1).

[ chemical formula 7]

In the formula (1), A¹And A²Each independently represents an oxygen atom or NH, R¹¹¹Represents a 2-valent organic group, R¹¹⁵Represents a 4-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group.

A in the formula (1)¹And A²Is an oxygen atom or NH, preferably an oxygen atom.

R in the formula (1)¹¹¹Represents a 2-valent organic group. Examples of the 2-valent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably 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, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms.

R¹¹¹The diamine used for producing the polyimide precursor is preferably derived from a diamine, and examples thereof include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines, and only kinds of diamines may be used, or two or more kinds thereof may be used.

Specifically, the diamine preferably contains a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof, and more preferably contains a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 8]

In the formula, A is preferably a single bond or selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, -S (-O)₂The radical-further to step is preferably selected from the group consisting of-CH₂-、-O-、-S-、-S(＝O)₂-、-C(CF₃)₂-and-C (CH)₃)₂-a 2-valent radical of the group consisting.

Specific examples of the diamine include at least one selected from the group consisting of 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane, 1, 2-diaminocyclopentane or 1, 3-diaminocyclopentane, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane or 1, 4-diaminocyclohexane, 1, 2-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4 ' -diamino-3, 3 ' -dimethylcyclohexylmethane and isophoronediamine, m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4 ' -diaminobiphenyl and 3,3 ' -diaminobiphenyl, 4,4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 4,4 ' -diaminodiphenyl methane and 3,3 ' -diaminodiphenyl methane, 4,4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfone, 2-diaminodiphenyl sulfone, 4,4 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl, 4 ' -diaminodiphenyl sulfone, 2-diaminodiphenyl, 4 ' -diaminodiphenyl, 4-diaminodiphenyl-bis (3,4 ' -diamino-4-tetrafluoro-2-4-2-tetrafluoro-2-4-2-tetrafluoro-2-tetrafluoro-2-4-2-tetrafluoro-2-3-tetrafluoro-2-3-p-2-tetrafluoro-2-tetrafluoro-2-3-2-1, 3-2-tetrafluoro-1, 3-2-1, 4-1, 3-diaminodiphenyl-2-1, 3-diaminodiphenyl-4-tetrafluoro-4-1, 3-diamino-2-4-diamino-1, 3-4-1, 3-diamino-4-tetrafluoro-2-tetrafluoro-2-diamino-1, 3-2-1, 3-diamino-tetrafluoro-1, 3-2-diamino-2-1-4-tetrafluoro-bis (diamino-tetrafluoro-4-diamino-4-2-1, 3-4-1-2-1-diamino-4-1-diamino-2-1, 4-1, 3-2-1, 3-2-diamino-1-2-diamino-tetrafluoro-diamino-2-diamino-2-1, 3-2-diamino-2-tetrafluoro-2-1, 3-2-tetrafluoro-4-2-1, 3-2-tetrafluoro-2-1, 3-2-1, 4-1, 3-2-tetrafluoro-2-diamino-tetrafluoro-diamino-2-4-2-tetrafluoro-2-1, 3-1, 3-diamino-bis (diamino-2-tetrafluoro-2-1, 3-tetrafluoro-diamino-1, 3-tetrafluoro-2-4-1, 4-1, 3-1-2-diamino-1, 3-diamino-tetrafluoro-diamino-1-2-diamino-bis (diamino-2-diamino-2-cyclohexane, 3-2-diamino-2-diphenyl-2-diamino-tetrafluoro-1, 3-diamino-diphenyl-2-diamino-diphenyl-diamino-2-diamino-1, 3-diamino-diphenyl-2-diamino-2-diamino-diphenyl-2-diamino-.

Also, diamines (DA-1) to (DA-18) shown below are also preferable.

[ chemical formula 9]

[ chemical formula 10]

Further, as a preferable example, a diamine having at least 2 or more alkylene glycol units in the main chain, a diamine containing or two ethylene glycol chains and propylene glycol chains in total in molecules, and more preferably a diamine containing no aromatic ring, may be mentioned, for example, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (product name, product name of above, manufactured by HUSMAN Co., Ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (2-aminopropoxy) propan-2-oxy) propan-2-amine, and the like, but not limited thereto.

The following shows the structures of JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, and JEFFAMINE (registered trademark) EDR-176.

[ chemical formula 11]

In the above, x, y and z are average values.

From the viewpoint of flexibility of the obtained cured film, R¹¹¹Preferably represented by-Ar⁰-L-Ar⁰-represents. Wherein Ar is⁰Each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-or-NHCO-, and groups comprising a combination of 2 or more of the foregoing. Ar (Ar)⁰Preferably a phenylene group, and L in step is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-or-S (═ O)₂-. Among them, the aliphatic hydrocarbon group is preferably an alkylene group.

From the viewpoint of i-ray transmittance, R¹¹¹Preferred is a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and ready availability, the 2-valent organic group represented by formula (61) is more preferable.

Formula (51)

[ chemical formula 12]

In the formula (51), R⁵⁰～R⁵⁷Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R⁵⁰～R⁵⁷At least of which are fluorine atoms, methyl groups, fluoromethyl groups, difluoromethyl groups or trifluoromethyl groups.

When R is⁵⁰～R⁵⁷When the group is a 1-valent organic group, examples thereof include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like。

Formula (61)

[ chemical formula 13]

In the formula (61), R⁵⁸And R⁵⁹Each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound to which the structure of formula (51) or (61) is imparted include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4, 4' -diaminooctafluorobiphenyl, and kinds of these may be used, or two or more kinds may be used in combination.

R in the formula (1)¹¹⁵Represents a 4-valent organic group. The 4-valent organic group is preferably a 4-valent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).

Formula (5)

[ chemical formula 14]

In the formula (5), R¹¹²Preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (═ O) -, -S-, -S (═ O)₂-, -NHCO-and combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (-O) -, -S-, and-S (-O)₂The radical-further to step is preferably selected from the group consisting of-CH₂-、-C(CF₃)₂-、-C(CH₃)₂-, -O-, -C (═ O) -, -S-and-S (═ O)₂-a 2-valent radical of the group consisting.

Formula (6)

[ chemical formula 15]

With respect to R in the formula (1)¹¹⁵Specific examples of the 4-valent organic group include tetracarboxylic acid residues remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride, and kinds of tetracarboxylic acid dianhydrides may be used alone or two or more kinds of tetracarboxylic acid dianhydrides may be used.

Formula (O)

[ chemical formula 16]

In the formula (O), R¹¹⁵Represents a 4-valent organic group. R¹¹⁵Is defined as in formula (1) and R¹¹⁵The same is true.

Specific examples of the tetracarboxylic dianhydride include at least one derivative selected from the group consisting of pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylsulfide tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylmethane tetracarboxylic dianhydride, 2 ', 3,3 ' -diphenylmethane tetracarboxylic dianhydride, 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic dianhydride, 4,4 ' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5, 7-naphthalenetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-hexafluoropropane dianhydride, 3, 4-hexafluoroethane dianhydride, 1,3, 4-and 1,3, 4,5, 8-carbon atoms of 1,3, 3, 4-and 10-and 1, 4-and 1, 5-carbon atoms of 1,3, 3, 5-and 1, 5-and 10-biphenyltetracarboxylic dianhydride, 5-and 1-to 10-benzenetetracarboxylic dianhydride.

Preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.

[ chemical formula 17]

In the formula (1), R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, R¹¹³And R¹¹⁴At least of the above-mentioned groups are preferably repeating units containing a radical polymerizable group, and more preferably both of them contain a radical polymerizable group.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like. Further, the (meth) acryloyl group is a generic name of acryloyl group and methacryloyl group.

[ chemical formula 18]

In the formula (III), R²⁰⁰Represents a hydrogen atom or a methyl group, and more preferably a methyl group.

In the formula (III), R²⁰¹An alkylene group having 2 to 12 carbon atoms, -CH₂CH(OH)CH₂Or a C4-30 polyoxyalkylene group (as an alkylene group, preferably C1-12, more preferably C1-6, and particularly preferably C1-3; the number of repetitions is preferably 1-12, more preferably C1-6, and particularly preferably C1-3).

Preferred R²⁰¹Examples of (3) include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH₂CH(OH)CH₂-, more preferably ethylene, propylene, trimethylene, -CH₂CH(OH)CH₂-。

Particularly preferably R²⁰⁰Is a firstRadical, R²⁰¹Is an ethylene group.

As a group consisting of R¹¹³Or R¹¹⁴The 1-valent organic group represented may preferably be a substituent which improves the solubility of the developer.

When R is¹¹³Or R¹¹⁴In the case of a 1-valent organic group, there may be mentioned an aromatic group or an alkyl group having 1,2 or 3 acidic groups, preferably 1 acidic group, bonded to the carbon constituting the aryl group. Specifically, the aromatic group has 6 to 20 carbon atoms and has an acidic group, and the aralkyl group has 7 to 25 carbon atoms and has an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group.

From the viewpoint of solubility in an aqueous developer, R¹¹³Or R¹¹⁴More preferred are a hydrogen atom, 2-hydroxybenzyl group, 3-hydroxybenzyl group and 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R¹¹³Or R¹¹⁴Preferably a 1-valent organic group. The 1-valent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and more preferably an alkyl group substituted with an aromatic group.

The number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group), the alkyl group may be any of a linear, branched or cyclic group, 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, an octadecyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group and a 2-ethylhexyl group, examples of the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.

As the aromatic group, there may be mentioned a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indene ring, perylene ring, condensed pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, condensed tetrabenzene ring, perylene ring, phenanthrene ring, perylene ring, condensed tetrabenzene ring, perylene ring, phenanthrene ring, anthracene ring, condensed tetrabenzene ring, perylene ring,

A ring, a triphenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, an morpholine ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxazine ring or a phenoxazine ring. Most preferred is a benzene ring.

In the formula (1), when R is¹¹³Is a hydrogen atom or R¹¹⁴When the atom is a hydrogen atom, the polyimide precursor may form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. Examples of the tertiary amine compound having these ethylenically unsaturated bonds include N, N-dimethylaminopropyl methacrylate.

In the polyimide precursor, it is also preferable that the constituent unit has a fluorine atom. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less. The upper limit is not particularly limited, and is actually 50% by mass or less.

Further, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1) for the purpose of improving adhesion to a substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). that is, at least of the polyimide precursors used in the present invention are preferably precursors having a repeating unit represented by the formula (1-A). by these structures, the width of exposure latitude can be increased further steps.

Formula (1-A)

[ chemical formula 19]

In the formula (1-A), A¹¹And A¹²Represents an oxygen atom or NH, R¹¹¹And R¹¹²Each independently represents a 2-valent organic group, R¹¹³And R¹¹⁴Each independently represents a hydrogen atom or a 1-valent organic group, R¹¹³And R¹¹⁴At least of them are groups containing a radical polymerizable group, and preferably radical polymerizable groups.

A¹¹、A¹²、R¹¹¹、R¹¹³And R¹¹⁴Are each independently defined as A in the formula (1)¹、A²、R¹¹¹、R¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

R¹¹²Is defined with R in formula (5)¹¹²Similarly, the preferred ranges are also the same.

The polyimide precursor may contain kinds of repeating units represented by the formula (1), or two or more kinds of repeating units, and may contain structural isomers of the repeating units represented by the formula (1).

An embodiment of the polyimide precursor in the present invention is exemplified by a polyimide precursor in which 50 mol% or more, more preferably 70 mol% or more, particularly 90 mol% or more of the total repeating units are repeating units represented by the formula (1), and the upper limit is actually 100 mol% or less.

The polyimide precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, further steps preferably 10000 to 50000, and a number average molecular weight (Mn) of 800 to 250000, more preferably 2000 to 50000, further steps preferably 4000 to 25000.

The dispersion degree of the polyimide precursor is preferably 1.5 to 3.5, and the step is preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a diamine.

In the method for producing a polyimide precursor, it is preferable to use an organic solvent for the reaction, and the number of the organic solvents may be or two or more.

The organic solvent can be appropriately set according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

The production of the polyimide precursor preferably includes a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid deposition can be performed.

Precursor of polybenzoxazole

The polybenzoxazole precursor used in the present invention preferably contains a repeating unit represented by the following formula (2).

[ chemical formula 20]

In the formula (2), R¹²¹The 2-valent organic group is preferably a group containing at least of aliphatic groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms) and aromatic groups (preferably 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms). As the aliphatic group, a linear organic group is preferably usedAn aliphatic group. R¹²¹Preferably from 4, 4' -oxodibenzoyl chloride.

In the formula (2), R¹²²Represents a 4-valent organic group. As the 4-valent organic group, R in the above formula (1) is defined¹¹⁵Similarly, the preferred ranges are also the same. R¹²²Preferably from 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R¹²³And R¹²⁴Each independently represents a hydrogen atom or a 1-valent organic group, and is as defined for R in the above formula (1)¹¹³And R¹¹⁴Similarly, the preferred ranges are also the same.

The polybenzoxazole precursor may contain other kinds of repeating structural units in addition to the repeating unit of the above formula (2).

From the viewpoint of suppressing the occurrence of warpage in the cured film accompanying ring closure, it is preferable that the diamine residue represented by the following formula (SL) is contained as another type of repeating structural unit.

[ chemical formula 21]

In the formula (SL), Z has a structure a and a structure b, R^1sIs a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R^2sIs a C1-10 hydrocarbon group (preferably C1-6, more preferably C1-3), R^3s、R^4s、R^5s、R^6sAt least of the groups are aromatic groups (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and particularly preferably having 6 to 10 carbon atoms), and the balance is hydrogen atoms or organic groups having 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 6 carbon atoms), and the groups may be the same or different from each other, and the polymerization of the a structure and the b structure may be block polymerization or random polymerization, and in the Z moiety, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and a + b is 100 mol%.

Formula (SL)) Among them, preferable Z is R in the structure of b^5sAnd R^6sZ being phenyl. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is generally used. By setting the molecular weight in the above range, the elasticity of the polybenzoxazole precursor after dehydration ring closure can be reduced, and the effects of suppressing warpage and improving solubility can be achieved at the same time.

When the diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, it is more preferable to contain a tetracarboxylic acid residue remaining after removing the acid dianhydride from the tetracarboxylic acid dianhydride as the repeating structural unit, from the viewpoint of improving the alkali solubility. Examples of such tetracarboxylic acid residues include R in the formula (1)¹¹⁵Examples of (3).

The polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 2000 to 500000, more preferably 5000 to 100000, further steps preferably 10000 to 50000, and a number average molecular weight (Mn) of 800 to 250000, more preferably 2000 to 50000, further steps preferably 4000 to 25000.

The dispersion degree of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, more preferably 30 to 99% by mass, further preferably 40 to 98% by mass in the step , further preferably 50 to 95% by mass in the step , further preferably 60 to 95% by mass in the step , and further preferably 70 to 95% by mass in the step , based on the total solid content of the composition.

The polymer precursor may contain only species, or may contain two or more species, and when two or more species are contained, the total amount is preferably within the above range.

< radically polymerizable Compound having Sulfur atom >

The embodiment of the radical polymerizable compound having a sulfur atom is a radical polymerizable compound having a sulfur atom and having 2 or more (preferably 2 to 4, more preferably 2 to 3, and further steps are preferably 2) radical polymerizable groups.

The radical polymerizable compound having a sulfur atom is preferably a compound represented by the following formula (3-1).

[ chemical formula 22]

R¹²-X¹²-L¹¹-X¹¹-R¹¹(3-1)

In the formula (3-1), L¹¹Represents a 2-valent linking group containing a sulfur atom, X¹¹And X¹²Each independently represents a single bond or a 2-valent linking group, R¹¹And R¹²Each independently represents a hydrogen atom or a 1-valent organic group; wherein R is¹¹And R¹²At least of the groups represent a 1-valent organic group containing at least radically polymerizable groups, R¹¹And R¹²May be bonded to each other to form a ring.

In the formula (3-1), L¹¹Preferably a 2-valent linking group containing a sulfur atom, more preferably a linking group having 1 or 2 sulfur atoms, still more preferably a linking group having 1 or 2 sulfur atoms and having 2 to 6 atoms of oxygen atom, and further is preferably L in the formula (3-2) defined below¹Similarly, the preferred ranges are also the same.

In the formula (3-1), X¹¹And X¹²Each independently represents a single bond or a 2-valent linking group. Examples of the 2-valent linking group include a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms), -O-, -S-, -C (═ O) -, -NR, and the like³-、-NR³CO-and combinations of these. R³The definition of (3) and R in the formula (3-2) described later³The same is true. The linking group may be a hydrocarbon group. The hydrocarbon group may be an oligohydrocarbon group, and the number of repetitions in this case is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6. The number of carbon atoms of the hydrocarbon group is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6. When the number of atoms of the linking group is other than the number of atoms of the oligohydrocarbyl group, the number of atoms is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 241 to 6. In the case of an (oligo) hydrocarbyl group, the number of atoms is preferably 2 to 64, more preferably 2 to 32, and particularly preferably 2 to 18. X¹¹And X¹²The 2-valent linking group is preferably an oxygen atom, a sulfur atom, or a 2-valent linking group containing a nitrogen atom (preferably 1 to 12 atoms, more preferably 1 to 6 atoms, and particularly preferably 1 to 3 atoms), and more preferably a 2-valent linking group containing an oxygen atom.

In the formula (3-1), R¹¹And R¹²The 1-valent organic group may include a 1-valent organic group containing a radically polymerizable group, a substituent T described later, and the like, and the radically polymerizable group may include a group having a carbon-carbon unsaturated double bond, wherein the radically polymerizable group is preferably a group having a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and more preferably a group having an acryloyl group or a methacryloyl group, and more specifically, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamido group, a methacrylamido group, a vinyl group, a vinylphenyl group (o, m, p), a vinylphenoxy group (o, m, p), a vinylphenylmethyl group (o, m, p), and more preferably an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamido group, a methacrylamido group, and the step is preferably an acryloyloxy group or a methacryloyloxy group.

The 1-valent organic group containing a radically polymerizable group may be a group having only 1 radically polymerizable group, or may be a group having 2 or more radically polymerizable groups. When the 1-valent organic group containing a radically polymerizable group has 2 or more radically polymerizable groups, the plurality of radically polymerizable groups may be the same as or different from each other. The 1-valent organic group containing a radical polymerizable group may further have a substituent described later within a range not to impair the effects of the present invention. Examples of the substituent include a substituent T described later. The number of radical polymerizable groups contained in 1 valent organic group is preferably 3 or less, and more preferably 2 or less. In the present invention, a mode in which a 1-valent organic group containing a radical polymerizable group has no substituent can be preferably exemplified.

In the formula (3-1), R¹¹And R¹²At least of the above groups represent a 1-valent organic group containing at least radically polymerizable groups, wherein R represents¹¹And R¹²These two groups are preferably each independently a 1-valent organic group containing a radical polymerizable group.

In the formula (3-1), the number of radical polymerizable groups in the molecule of is preferably 2 or more, and preferably 4 or less, more preferably 3 or less, and further steps are preferably 2.

In the formula (3-1), R¹¹And R¹²May be bonded to each other to form a ring. R¹¹And R¹²When forming a ring, R¹¹And R¹²The linkage may be direct or via a linker L described later. Also, the rings formed may be fused rings. Examples of the linking group L include a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), -O-, -S-, -C (═ O) -, -NR-³-、-NR³CO-and the linking groups associated with combinations of these. R³The definition of (3) and R in (3-2) described later³Similarly, the preferred ranges are also the same.

The radical polymerizable compound having a sulfur atom is more preferably represented by the following formula (3-2).

[ chemical formula 23]

R²-la¹-X²-La²-L¹-La³-X¹-La⁴-R¹(3-2)

In the formula (3-2), L¹represents-S-, -S (═ O) -, or-S (═ O)₂-，X¹And X²Each independently represents a single bond, -O-, -C (O) O-, -OC (O) -, -S (O)₂-or-NR³CO-，R¹And R²Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical polymerizable group, La¹～La⁴Each independently represents a single bond, a group of 1 or 2 or more of alkylene and phenyleneAny of the group formed by combination and the group formed by the combination of 1 or more than 2 of alkylene and phenylene and-O-)³Represents a hydrogen atom or an alkyl group; wherein R is¹And R²At least of the groups are radical polymerizable groups.

In the formula (3-2), L¹Preferably represents-S-, -S (═ O) -or-S (═ O)₂-，-S(＝O)-。

X¹And X²Each independently represents a single bond, -O-, -C (O) O-, -OC (O) -, -S (O)₂-or-NR³CO-is preferably a single bond or-O-, and more preferably-O-. R³Represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), preferably a hydrogen atom or an alkyl group having the above-mentioned carbon atoms.

R¹And R²Each independently represents a radical polymerizable group, a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 6 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms).

R¹And R²When it is an alkyl group, a cycloalkyl group or an aryl group, it may have any substituent T within a range not impairing the effects of the present invention. Examples of the optional substituent T include a branched or straight-chain alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms), a hydroxyl group, a hydroxyalkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), an amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, and particularly preferably 0 to 6 carbon atoms), an aminoalkyl group (preferably having 1 to 6 carbon atoms), and the likeThe number of the subunits is 1-24, more preferably 1-12, and particularly preferably 1-6; the number of amino groups is preferably 1 to 6, more preferably 1 to 3), mercapto groups, mercaptoalkyl groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6; the number of mercapto groups is preferably 1 to 6, more preferably 1 to 3), carboxyl groups, and carboxyalkyl groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 6; the number of carboxyl groups is preferably 1 to 6, more preferably 1 to 3), acyl (preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), acyloxy (preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), aroyl (preferably 7 to 23, more preferably 7 to 19, and particularly preferably 7 to 11), aroyloxy (preferably 7 to 23, more preferably 7 to 19, and particularly preferably 7 to 11), oxy (═ O), imino (═ NR), or the like³) Alkylene (═ C (R)³)₂) And the like.

Wherein R is¹And R²At least of them represent radical polymerizable groups.

With respect to R¹And R²Examples of the radical polymerizable group include those having the same definitions as those of the compound represented by the above formula (3-1). R¹And R²These two groups are preferably each independently a radical polymerizable group, and more preferably the same radical polymerizable group.

In the formula (3-2), La¹～La⁴Each independently represents of a single bond, a group composed of 1 or 2 or more of alkylene and phenylene, and a group composed of 1 or 2 or more of alkylene and phenylene and-O-¹～La⁴May independently have a single bond, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 carbon atoms), a phenylene group, an (oligo) alkyleneoxy group (the alkylene group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 repeating numbers are preferably 1 to 12, even more preferably 1 to 6, even more preferably 1 to 3.), and an (oligo) alkyleneoxy group (the alkylene group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more preferably 1 to 6 repeating numbers are preferably 1 to 12, even more preferably 1 to 6 repeating numbers are 1 to 6Particularly preferably 1 to 3), or a combination thereof, (oligo) alkyleneoxy means alkyleneoxy or oligo alkyleneoxy, and it is considered that the -described group including other "(oligo)" is also the same.

The alkylene group, phenylene group, (oligo) alkyleneoxy group, and (oligo) alkyleneoxy group may further have the optional substituent T as described above within a range not to impair the effects of the present invention.

La¹～La⁴More preferably, each independently is a single bond or an alkylene group, and further is preferably La²And La³Is a single bond, La¹And La⁴Is an alkylene group.

R¹And R²May be bonded to each other to form a ring. R¹And R²When forming a ring, R¹And R²The linking group may be directly linked or may be linked via the linking group L. Also, the rings formed may be fused rings.

The radical polymerizable compound having a sulfur atom used in the present invention may be a low molecule (for example, a molecular weight of less than 2000, and further less than 1000), or may be a high molecule, and is preferably a low molecule.

Examples of the radical polymerizable compound having a sulfur atom include the following exemplified compounds, but the present invention should not be construed as being limited thereto. Among these exemplified compounds, the following compounds 301, 302, 303, 304, 312 and 322 are preferable, and compound 301 and 302 (compounds represented by formula (4)) are more preferable, and compound 302 is particularly preferable.

[ chemical formula 24]

[ chemical formula 25]

In the above exemplary compounds, m is 1 to 30 and n is 1 to 30.

The content of the radical polymerizable compound having a sulfur atom in the photosensitive resin composition of the present invention is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, further steps preferably 0.01 mass% or more, further steps preferably 0.05 mass% or more, further steps preferably 0.1 mass% or more, further steps preferably 0.3 mass% or more, and the upper limit is preferably 20 mass% or less, more preferably 15 mass% or less, further steps preferably 10 mass% or less, and further may be 7 mass% or less, 5 mass% or less, 2 mass% or less, and 1 mass% or less, based on the total solid content of the composition.

The amount of the radical polymerizable compound having a sulfur atom blended with 100 parts by mass of the polymer precursor is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, further steps are preferably 55 parts by mass or less, further steps are preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less, in total with other polymerizable compounds described later, and the polymerizable compound is preferably 0.1 part by mass or more, and may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, and 10 parts by mass or more.

The lower limit of the proportion of the radical polymerizable compound having a sulfur atom in the total polymerizable compounds including other polymerizable compounds described later is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, further steps are preferably 0.1% by mass or more, further steps are preferably 0.3% by mass or more, and further steps are preferably 0.5% by mass or more, and the upper limit is preferably 100% by mass or less, and may be 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 7% by mass or less, 5% by mass or less, 2% by mass or less, and 1% by mass or less.

By containing the radical polymerizable compound having a sulfur atom in the composition in the above-mentioned ratio, -step higher stability and -step higher exposure sensitivity can be achieved.

The radical polymerizable compound having a sulfur atom may contain only species, or may contain two or more species.

< photo radical polymerization initiator >

The photosensitive resin composition of the present invention contains a photo radical polymerization initiator.

The photo radical polymerization initiator that can be used in the present invention is not particularly limited, and can be suitably selected from known photo radical polymerization initiators, and for example, a photo radical polymerization initiator that is photosensitive to light from an ultraviolet region to a visible region is preferable, and an active agent that generates an active radical by acting on with a photo-excited sensitizer may be used.

The photo radical polymerization initiator preferably contains at least kinds of compounds having an absorption coefficient of at least about 50 mol in the range of about 300 to 800nm (preferably 330 to 500 nm). the mol absorption coefficient of the compounds can be measured by a known method, for example, preferably by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian corporation) at a concentration of 0.01g/L using an ethyl acetate solvent.

When the photosensitive resin composition of the present invention contains a photo radical polymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light, whereby curing by radicals occurs and the solubility in a light irradiated portion can be reduced. Therefore, for example, there is an advantage that regions having different solubilities can be easily produced according to the electrode pattern by exposing the photosensitive resin composition layer through a photomask having a pattern for shielding only the electrode portion.

As the photo radical polymerization initiator, known compounds can be arbitrarily used, and examples thereof include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference may be made to the descriptions in paragraphs 0165 to 0182 of japanese patent application laid-open No. 2016-027357, which are incorporated herein by reference.

Examples of the ketone compound include those described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which are incorporated herein by reference. Among commercially available products, KAYACURE DETX (nippon kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese patent laid-open No. 10-291969 and an 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 (product names: both manufactured by BASF Corp.) were used.

As the aminoacetophenone initiator, commercially available IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: manufactured by BASF) were used.

As the aminoacetophenone-based initiator, a compound described in Japanese patent laid-open publication No. 2009-191179, which has a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm, can also be used.

Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: manufactured by BASF) can be used as a commercially available product.

Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF corporation).

The use of an oxime compound is particularly preferable because the exposure latitude (exposure margin) can be further increased effectively by , and the oxime compound is less tolerant to exposure (exposure margin) than and also functions as a photobase generator.

Specific examples of the oxime compound include compounds described in Japanese patent application laid-open Nos. 2001-233842, 2000-080068, and 2006-342166.

Preferred examples of the oxime compounds include compounds having the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. The oxime-based photopolymerization initiator is preferably used for the photosensitive resin composition of the present invention. The oxime-based photopolymerization initiator has a linking group having > C — N — O — C (═ O) -in the molecule.

[ chemical formula 26]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02(BASF CORPORATION), and ADEKA OPTOMER N-1919 (the photo radical polymerization initiator 2 described in ADEKA CORPORATION, Japanese patent laid-open publication No. 2012 and 014052) can also be preferably used. Also, TR-PBG-304 (manufactured by Changzhou powerful electronic New Material Co., Ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

Further, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include the compounds described in Japanese patent application laid-open No. 2010-262028, the compounds 24 described in section 0345 of Japanese patent application laid-open No. 2014-500852, the compounds 36 to 40 described in sections 0347 to 0348, and the compound (C-3) described in section 0101 of Japanese patent application laid-open No. 2013-164471.

As the most preferable oxime compound, an oxime compound having a specific substituent as shown in Japanese patent laid-open Nos. 2007-269779 and an oxime compound having a thioaryl group as shown in Japanese patent laid-open No. 2009-191061 are mentioned.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is a compound selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred photo radical polymerization initiators are trihalomethyl triazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, preferably at least compounds selected from the group consisting of trihalomethyl triazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, more preferably the metallocene compounds or oxime compounds are used in the further step , and more preferably the oxime compounds in the further step .

Further, as the photo radical polymerization initiator, N ' -tetraalkyl-4, 4 ' -diaminobenzophenone such as benzophenone and N, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Michler's ketone)), aromatic ketones such as 2-benzyl-2-dimethylamino-1- (4-kou-inolinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-kou-inolinyl-acetone-1 and the like, quinones such as alkylanthraquinone and the like condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ethers and the like, benzoin compounds such as benzoin and alkyl benzoin and the like, benzyl derivatives such as benzyl dimethyl ketal and the like can be used. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 27]

In the formula (I), R^I00Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms and interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group substituted with at least of 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, an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms interrupted by 1 or more oxygen atoms, or a biphenyl group, R^I01Is a group represented by the formula (II), or with R^I00Same radicals, R^I02～R^I04Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[ chemical formula 28]

In the formula, R^I05～R^I07With R of the above formula (I)^I02～R^I04The same is true.

Further, as the photo radical polymerization initiator, a compound described in paragraphs 0048 to 0055 of International publication WO2015/125469 can be used.

The content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further is preferably 0.5 to 15% by mass, further is preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention, the photo radical polymerization initiator may contain species alone, or may contain two or more species.

< thermal radical polymerization initiator >

The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator within a range not departing from the gist of the present invention.

The thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding the thermal radical polymerization initiator, cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed, so that higher heat resistance can be achieved.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and further is preferably 5 to 15% by mass, based on the total solid content of the photosensitive resin composition of the present invention, the thermal radical polymerization initiator may contain only kinds, or two or more kinds, and when two or more kinds of thermal radical polymerization initiators are contained, the total amount thereof is preferably in the above range.

< solvent >

The photosensitive resin composition of the present invention contains a solvent. The solvent can be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.

Examples of the esters include preferred esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.) (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl esters of 2-alkoxypropionic acid (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc, Ethyl 2-oxobutyrate, and the like.

Examples of the 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 acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

Preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

As the aromatic hydrocarbons, for example, preferable aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.

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

Preferable examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.

The solvent is preferably mixed with two or more kinds of solvents from the viewpoint of improvement of the coating surface shape or the like.

In the present invention, kinds of solvents selected from the group consisting of methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent of two or more thereof is preferable, and dimethyl sulfoxide and γ -butyrolactone are particularly preferably used together.

The solvent content is preferably set to an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably , even more preferably , even more preferably 40 to 70% by mass, from the viewpoint of coatability.

The solvent may contain only kinds, or two or more kinds, and when two or more kinds are contained, the total amount is preferably in the above range.

< other polymerizable Compound >

Polymerizable Compound containing no Sulfur atom

The photosensitive resin composition of the present invention preferably contains a radical polymerizable compound containing no sulfur atom (hereinafter referred to as "polymerizable monomer containing no sulfur atom") in addition to the radical polymerizable compound containing the sulfur atom. With such a configuration, a cured film having excellent heat resistance can be formed.

As the polymerizable monomer containing no sulfur atom, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

The number of radical polymerizable groups of the polymerizable monomer containing no sulfur atom may be or 2 or more, but the polymerizable monomer containing no sulfur atom preferably has 2 or more radical polymerizable groups, more preferably 3 or more, and the upper limit is preferably 15 or less, more preferably 10 or less, and further steps are preferably 8 or less.

The molecular weight of the polymerizable monomer containing no sulfur atom is preferably 2000 or less, more preferably 1500 or less, and further preferably 900 or less in the step, and the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least polymerizable monomers containing 2 or more polymerizable groups and not containing a sulfur atom, more preferably contains at least polymerizable monomers containing 3 or more polymerizable groups and not containing a sulfur atom, and may be a mixture of polymerizable monomers containing 2 functional groups and not containing a sulfur atom and polymerizable monomers containing 3 or more polymerizable groups.

Specific examples of the polymerizable compound not containing a sulfur atom include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters and amides thereof, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds, and further, addition products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group or an amino group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation products with monofunctional or polyfunctional carboxylic acids, and the like are preferably used, and further, substitution products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, addition products of amines, and unsaturated carboxylic acid esters or amides having a releasable substituent such as a halogen group with monofunctional or polyfunctional alcohol, amines, and substitution products of amines with monofunctional or polyfunctional alcohol, amines are also preferable, and, as another example, instead of the above-mentioned unsaturated carboxylic acids, a group of compounds substituted with vinyl benzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ethers, allyl ethers, etc. can be used, and japanese patent laid-open publication No. 2016 (kokai) 2) and 357, published by the contents of the same.

The polymerizable monomer containing no sulfur atom is also preferably a compound having a boiling point of 100 ℃ or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the mixture, JP-B-48-041708, JP-B-50-006034, carbamates of (meth) acrylic acid disclosed in JP-B-51-037193, esters of (meth) acrylic acid disclosed in JP-B-50-006034, JP-51-037193, esters of (meth) acrylic acid, and mixtures thereof, The polyester acrylates described in JP-A-48-064183, JP-A-49-043191 and JP-A-52-030490, and the polyfunctional acrylates or methacrylates such as epoxy acrylates as a reaction product of an epoxy resin and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of Japanese patent laid-open No. 2008-292970 are also suitable. Further, there can be mentioned a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate.

Further, as a preferable polymerizable monomer not containing a sulfur atom other than the above, compounds having a fluorene ring and having 2 or more ethylenically unsaturated bond-containing groups or cardo (cardo) resins described in japanese patent application laid-open No. 2010-160418, japanese patent application laid-open No. 2010-129825, japanese patent application laid-open No. 4364216, and the like can be used.

Further, as other examples, specific unsaturated compounds described in Japanese patent publication No. 46-043946, Japanese patent publication No. 1-040337, and Japanese patent publication No. 1-040336, vinylphosphonic acid-based compounds described in Japanese patent publication No. 2-025493, and the like can be cited. Furthermore, a compound containing a perfluoroalkyl group as described in Japanese patent application laid-open No. 61-022048 can also be used. Further, those described as photocurable monomers and oligomers in Journal of the Society of Japan, vol.20, No.7, pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 can be preferably used, and these contents are incorporated in the present specification.

Further, the following compounds described as the formula (1) and the formula (2) in jp-a-10-062986 and the specific example thereof, which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resulting mixture, can also be used as a polymerizable monomer containing no sulfur atom.

Further, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can be used as other polymerizable monomers, and these contents are incorporated in the present specification.

As the polymerizable monomer containing no sulfur atom, dipentaerythritol triacrylate (KAYARAD-330; Nippon Kayaku Co., manufactured by Ltd.) and dipentaerythritol tetraacrylate (KAYARAD-320; Nippon Kayaku Co., manufactured by Ltd., manufactured by A-TMMT: Shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD-310; Nippon Kayaku Co., manufactured by Ltd.) and dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; Nippon Kayaku Co., manufactured by Ltd., manufactured by A-DPH; Shin-Nakamura Chemical Co., manufactured by Ltd.) and structures in which the (meth) acryloyl groups thereof are bonded to each other via ethylene glycol residues and propylene glycol residues are preferable. Oligomer types of these can also be used.

Commercially available products of polymerizable monomers containing no sulfur atom include, for example, SR-494 made by Sartomer Company, Inc. as a 4-functional acrylate having 4 oxyethylene chains, SR-209 made by Inc. as a 2-functional acrylate having 4 vinyloxy chains, Nippon Kayaku Co., DPCA-60 made by Ltd. as a 6-functional acrylate having 6 pentyloxy chains, TPA-330 made by 3-functional acrylate having 3 isobutoxy chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (PPONDANDSUS ES CO., LTD. made by LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200(Shin-Nakamura Co., Ltd., DPHA-40K Co., LTD. made by Chemical Co., LTD., LTP Co., Nippon Co., LTH) UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600(Kyoeisha chemical Co., manufactured by Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As the other polymerizable monomer, urethane acrylates such as those disclosed in JP-B-48-041708, JP-B-51-037193, JP-B-2-032293 and JP-B-2-016765, urethane compounds having an ethylene oxide skeleton as disclosed in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also preferable. Further, as the polymerizable monomer containing no sulfur atom, compounds having an amino group structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 1-105238 can be used.

The polymerizable monomer containing no sulfur atom may be a polymerizable monomer having an acid group such as a carboxyl group or a phosphoric acid group. Among the polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a polymerizable monomer having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride is more preferable. In particular, among the polymerizable monomers having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydric compound with a non-aromatic carboxylic acid anhydride, the aliphatic polyhydric compound is preferably a compound of pentaerythritol and/or dipentaerythritol. Examples of commercially available products include a polybasic acid-modified acrylic oligomer made by TOAGOSEI CO., Ltd., M-510, M-520, and the like.

The acid group-containing polymerizable monomers may be used singly in the form of types, or two or more types may be used in combination.

The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and the developability is excellent. Also, the polymerizability was good.

The photosensitive resin composition of the present invention can preferably use a monofunctional polymerizable monomer as a polymerizable monomer containing no sulfur atom from the viewpoint of suppressing warpage accompanying control of the elastic modulus of a cured film. As the monofunctional polymerizable monomer, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylic acid derivatives such as glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allyl glycidyl ether, diallyl phthalate and triallyl trimellitate. The monofunctional polymerizable monomer is preferably a compound having a boiling point of 100 ℃ or higher under normal pressure in order to suppress volatilization before exposure.

Polymerizable compounds other than the above-mentioned radical polymerizable compounds

The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the above radical polymerizable compound. Examples of the polymerizable compound other than the above-mentioned radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; a benzoxazine compound.

(Compound having hydroxymethyl group, alkoxymethyl group or acyloxymethyl group)

The compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group is preferably a compound represented by the following formula (AM1), (AM4) or (AM 5).

[ chemical formula 29]

(wherein t represents an integer of 1 to 20, R⁴Represents a t-valent organic group having 1 to 200 carbon atoms, R⁵Is represented by-OR⁶or-OCO-R⁷A group represented by R⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 30]

(in the formula, R⁴⁰⁴Represents a 2-valent organic group having 1 to 200 carbon atoms, R⁴⁰⁵Is represented by-OR⁴⁰⁶or-OCO-R⁴⁰⁷A group represented by R⁴⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁴⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

[ chemical formula 31]

(wherein u represents an integer of 3 to 8, R⁵⁰⁴Represents a u-valent organic group having 1 to 200 carbon atoms, R⁵⁰⁵Is represented by-OR⁵⁰⁶Or, -OCO-R⁵⁰⁷A group represented by R⁵⁰⁶R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms⁵⁰⁷Represents an organic group having 1 to 10 carbon atoms. )

By using the compound having a methylol group or the like, the occurrence of cracks can be more effectively suppressed when the photosensitive resin composition is applied to a substrate having irregularities. Further, a cured film having excellent pattern processability and high heat resistance, in which the temperature decreased by 5 mass% is 350 ℃ or higher, more preferably 380 ℃ or higher, can be formed. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name: ASAHI YUKIZAICORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylBISOC-P, DML-PFP, DML-PSBP, DML-MTPC (trade name: Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name: Sanwa Chemical Co., Ltd.), 2, 6-dimethylymethyl-4-t-butylphenyl (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylymethyl-2-dimethoxycresol (2, 6-dimethoxymethyl-2-cresol), 6-diacetoxymethyl-p-cresol), and the like.

Specific examples of the compound represented by the formulｃA (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHIYUKIZAI CORATION), NIKALAMX-280, NIKALAC MX-270, and NIKALAC MW-100LM (trade name, manufactured by SanwｃA Chemical Co., Ltd.).

(epoxy Compound (Compound having epoxy group))

The epoxy compound is preferably a compound having molecules with 2 or more epoxy groups, epoxy resin is based on 200 ℃ or less of the crosslinking reaction, and because it does not cause crosslinking dehydration reaction and hardly causes film shrinkage, therefore, by containing the epoxy compound, the low temperature curing and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group, whereby the elastic modulus is further decreased by and warpage is suppressed, and the number of repeating units of ethylene oxide is preferably 2 to 15.

Examples of the epoxy compound include, but are not limited to, bisphenol a type epoxy resins, bisphenol F type epoxy resins, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, and the like. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (trade names of DIC, DIC-S, EP, EPICLON) EXA-4822 (registered trademark), RIKARESIN (registered trademark) BEO-60E (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-40052, EPICLON, manufactured by ADEKACORPORATION), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and are therefore preferable.

(Oxetane Compound (Compound having an Oxetanyl group))

Examples of the OXETANE compound include compounds having molecules with 2 or more OXETANE rings, 3-ethyl-3-hydroxyoxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexylmethyl) OXETANE, 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester, and specific examples thereof include TOAGOSEI CO.

(benzoxazine Compound (Compound having polybenzoxazole group))

The benzoxazine compound is preferable because the crosslinking reaction due to the ring-opening addition reaction does not generate degassing during curing, and further, the heat shrinkage is reduced to suppress the generation of warpage.

Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (hereinafter, trade name: Shikoku Chemicals Corporation), benzoxazine adduct of polyhydroxystyrene resin, and novolak type dihydrobenzoxazine compound. These may be used alone, or two or more kinds may be mixed.

The content of the polymerizable compound other than the radical polymerizable compound having a sulfur atom is preferably 0 to 60% by mass relative to the total solid content of the photosensitive 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, and the step is preferably 30% by mass or less.

The other polymerizable compounds may be used singly in the form of kinds, or in the form of a mixture of two or more kinds.

< migration inhibitor >

Preferably, the photosensitive resin composition of the present invention further comprises a migration inhibitor. By including the migration inhibitor, it is possible to effectively inhibit the metal ions originating from the metal layer (metal wiring) from migrating into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, and triazine ring), compounds having a thiourea group and a mercapto group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole-based compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and benzotriazole can be preferably used.

Further, an ion scavenger that scavenges anions such as halogen ions can also be used.

As other migration inhibitors, there can be used rust inhibitors described in paragraph 0094 of Japanese patent application laid-open No. 2013-015701, compounds described in paragraphs 0073-0076 of Japanese patent application laid-open No. 2009-283711, compounds described in paragraph 0052 of Japanese patent application laid-open No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese patent application laid-open No. 2012-194520, and the like.

Specific examples of the migration inhibitor include the following compounds.

[ chemical formula 32]

When the photosensitive resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass in the step , based on the total solid content of the photosensitive resin composition.

The number of migration inhibitors may be or two or more, and when two or more migration inhibitors are used, the total amount is preferably in the above range.

< polymerization inhibitor >

The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, 1, 4-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, glycoletherdiamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, di-t-butylphenol, p-t-butylcatechol, p-butylcatechol, 1, 4-thiobis (3-methyl-6-t-butylphenol), N, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-tert-butyl) phenylmethane and the like. Further, the polymerization inhibitor described in paragraph 0060 of Japanese patent laid-open publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International publication WO2015/125469 can also be used.

Further, the following compound (Me is methyl) can also be used.

[ chemical formula 33]

When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and particularly preferably 0.05 to 2.5% by mass, relative to the total solid content of the photosensitive resin composition of the present invention.

The polymerization inhibitor may be kinds only, or two or more kinds, and when two or more kinds are used, the total amount is preferably in the above range.

< Metal adhesion improver >

The photosensitive resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to a metal material used for an electrode, a wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.

Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International publication No. WO2011/080992A1, compounds described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-041264, and compounds described in paragraphs 0055 of International publication No. WO 2014/097594. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358. Further, the following compounds are also preferably used as the silane coupling agent. In the following formula, Et represents an ethyl group.

[ chemical formula 34]

The metal adhesion improver can also be a compound described in paragraphs 0046 to 0049 of Japanese patent application laid-open No. 2014-186186 or a sulfide described in paragraphs 0032 to 0043 of Japanese patent application laid-open No. 2013-072935.

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 particularly preferably 0.5 to 5 parts by mass per 100 parts by mass of the polymer precursor, and by setting the lower limit or more, the adhesion between the cured film and the metal layer after the curing step is good, and by setting the upper limit or less, the heat resistance and mechanical properties of the cured film after the curing step become good.

< agent for generating alkali >

The photosensitive resin composition of the present invention may contain an alkali generator. The alkali generator may be a thermal alkali generator or a photoalkali generator.

Thermokalite generating agent

The kind of the thermokalite generator is not particularly limited, and is preferably a thermokalite generator containing at least kinds selected from an acidic compound generating a base when heated to 40 ℃ or higher and an ammonium salt having an anion with a pKa1 of 0-4 and an ammonium cation, wherein pKa1 represents a logarithmic sign (-Log) of a dissociation constant (Ka) of th proton of a polybasic acid₁₀Ka)。

By blending these compounds, the cyclization reaction of the polymer precursor can be performed at a low temperature, and a composition having further excellent stability can be obtained. Further, since the thermal alkali generator does not generate an alkali unless heated, the thermal alkali generator can suppress cyclization of the polymer precursor during storage even in the presence of the polymer precursor, and has excellent storage stability.

The thermal base generator in the present invention preferably contains at least kinds selected from an acidic compound (A1) which generates a base when heated to 40 ℃ or higher, and an ammonium salt (A2) having an anion with a pKa1 of 0 to 4 and an ammonium cation.

Since the acidic compound (a1) and the ammonium salt (a2) generate a base upon heating, the base generated from these compounds can promote the cyclization reaction of the polymer precursor and can cause the cyclization of the polymer precursor at a low temperature. Further, even if these compounds coexist with a polymer precursor cyclized and cured by an alkali, since cyclization of the polymer precursor hardly proceeds unless heated, a polymer precursor having excellent stability can be produced.

In the present specification, the term "acidic compound" means that 1g of the compound is collected in a container, and 50mL of a mixed solution of ion-exchanged water and tetrahydrofuran (water/tetrahydrofuran: 1/4 by mass) is added thereto. Stirred at room temperature for 1 hour. A compound having a value of less than 7 as measured on the solution at 20 ℃ with a pH meter.

In the present invention, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ℃ or higher, more preferably 120 to 200 ℃, the upper limit of the alkali generation temperature is preferably 190 ℃ or lower, more preferably 180 ℃ or lower, and further is preferably 165 ℃ or lower, and the lower limit of the alkali generation temperature is preferably 130 ℃ or higher, more preferably 135 ℃ or higher.

Since the alkali generation temperature of the acidic compound (a1) and the ammonium salt (a2) is 120 ℃ or higher, the alkali is not easily generated during storage, and thus a polymer precursor having excellent stability can be produced. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ℃ or lower, the cyclization temperature of the polymer precursor and the like can be lowered. The alkali generation temperature can be measured, for example, by heating the compound to 250 ℃ at 5 ℃/min in a pressure-resistant capsule by differential scanning calorimetry, reading the peak temperature of the lowest-temperature exothermic peak, and determining the peak temperature as the alkali generation temperature.

In the present invention, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine, the tertiary amine is highly basic and therefore can lower the cyclization temperature of the polymer precursor, and the boiling point of the base generated by the hot base generator is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and further steps are preferably 140 ℃ or higher, and the molecular weight of the generated base is preferably 80 to 2000, the lower limit is more preferably 100 or higher, the upper limit is more preferably 500 or lower, and the value of the molecular weight is a theoretical value determined from the structural formula.

In the present invention, the acidic compound (a1) preferably contains or more selected from ammonium salts and compounds represented by the formula (101) or (102) described later.

In the present invention, the ammonium salt (a2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃) or a compound other than an acidic compound which generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃).

The ammonium salt used as the hot alkali generator is preferably a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion, and the anion may be bonded to any portion of the ammonium cation by a covalent bond, or may be present outside the molecule of the ammonium cation, but is preferably present outside the molecule of the ammonium cation.

[ chemical formula 35]

In the formula, R^N1～R^N6Each independently represents a hydrogen atom or a hydrocarbon group (preferably 1 to 36, more preferably 1 to 24, and particularly preferably 1 to 12 carbon atoms), preferably an alkyl group (preferably 1 to 36, more preferably 1 to 24, and particularly preferably 1 to 23 carbon atoms), an alkenyl group (preferably 2 to 36, more preferably 2 to 24, and particularly preferably 2 to 23 carbon atoms), an alkynyl group (preferably 1 to 36, more preferably 1 to 24, and particularly preferably 1 to 23 carbon atoms), and an aryl group (preferably 6 to 22, more preferably 6 to 18, and particularly preferably 6 to 10 carbon atoms).

R^N7The alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and preferably an alkylene group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms.

R^N1And R^N2、R^N3And R^N4、R^N5And R^N6、R^N5And R^N7May be bonded to each other to form a ring. The above-mentioned linker L or a hetero-linker Lh described later may be interposed in the middle of the ring formation. Within a range not impairing the effects of the present invention, R^N1～R^N7May have the aforementioned substituent T.

The ammonium cation is preferably represented by any of the following formulae (Y1-1) to (Y1-6).

[ chemical formula 36]

In the formulae (Y1-1) to (Y1-6), R^N101Examples of the organic group having a valence of Nn (Nn is an integer of 1 to 12) include a group having a valence of Nn based on an alkane (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 3), a group having a valence of Nn based on an olefin (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and particularly preferably 2 to 3), a group having a valence of Nn based on an aromatic hydrocarbon (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and particularly preferably 6 to 10), and a combination thereof. R^N101Among them, aromatic hydrocarbon groups are preferable. Within a range not impairing the effects of the present invention, R^N101May have the aforementioned substituent T. When R is^N101In the case of an alkane-based group or an alkene-based group, the following hetero-linking group Lh may be interposed.

R^N1And R^N7Is defined with R in formula (101) or formula (102)^N1And R^N7The same is true.

R^N8The compound is an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and even more preferably 4 to 18 carbon atoms), an alkenyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and even more preferably 4 to 18 carbon atoms), an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and even more preferably 4 to 18 carbon atoms), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms). In this case, a linker Lh having a hetero atom may be interposed in the alkyl group, the alkenyl group, the alkynyl group, or the aryl group in the middle of the chain or in the connection with the parent nucleus. As the linking group Lh having a hetero atom, there may be mentionedTo produce-O-, -S-, -C (-O) -, -NR³-or a combination of these. The number of the hetero atom-containing linking groups Lh is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. R³Is a hydrogen atom or an alkyl group (preferably a methyl group). Within a range not impairing the effects of the present invention, R^N8And may further have the substituent T described above.

Preferably R^N9Is defined as^N8The same groups. Among them, preferred is an aryl-containing group, more preferred is an aroyl-containing group, and particularly preferred is an aroylalkyl group (the alkyl group is preferably a group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In this case, the substituent T may be further introduced into the aromatic ring of the aryl group to the aroyl group within a range not to impair the effects of the present invention.

In the formula (Y1-4), Ar^N101And Ar^N102Each independently represents an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms).

Nn represents an integer of 1 to 12 inclusive. Nm represents an integer of 0 to 5. No is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

R^N1Each other, R^N1And R^N8、R^N1And R^N7、R^N1And R^N9、R^N1And Ar^N101、R^N1And Ar^N102、Ar^N101And Ar^N102May be bonded to form a ring. The above-mentioned linker L or a hetero-linker Lh described later may be interposed in the middle of the ring formation.

In the present embodiment, it is preferable that the ammonium salt has an anion having a pKa1 of 0 to 4 and an ammonium cation, the upper limit of pKa1 of the anion is more preferably 3.5 or less, the further step is preferably 3.2 or less, the lower limit is preferably 0.5 or more, and more preferably 1.0 or more, and when the pKa1 of the anion is in the above range, the polymer precursor and the like can be cyclized at a lower temperature, and further, the stability of the composition can be improved.

The kind of anion is preferably kinds selected from the group consisting of carboxylic acid anion, phenol anion, phosphoric acid anion and sulfuric acid anion, and carboxylic acid anion is more preferable from the viewpoint of compatibility between salt stability and thermal decomposability.

The carboxylic acid anion is preferably an anion of a carboxylic acid having 2 or more carboxyl groups and a valence of 2 or more, and more preferably an anion of a carboxylic acid having a valence of 2 according to this embodiment, a thermobase generator capable of further improving the stability, curability, and developability of the composition at step can be provided, and particularly, the stability, curability, and developability of the composition can be further improved at step by using an anion of a carboxylic acid having a valence of 2.

In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less, pKa1 is more preferably 3.5 or less, and a further step is preferably 3.2 or less, and according to this embodiment, the stability of the composition can be further improved .

Here, pKa1 represents the logarithmic representation (-Log) of the dissociation constant (ka) of the th proton of the polybasic acid₁₀Ka), and can refer to the Determination of Organic Structures by Physical Methods (authors: brown, h.c., McDaniel, d.h., hawiiger, o., nacho, f.c.; editing: braude, e.a., nacho, f.c.; academycpress, New York, 1955), Data for Biochemical Research (author: dawson, r.m.c.et al; oxford, Clarendon Press, 1959). As for the compounds not described in these documents, values calculated from the structural formulae using software using ACD/pKa (manufactured by ACD/Labs) were used.

The carboxylic acid anion is preferably represented by the following formula (X1).

[ chemical formula 37]

In the formula (X1), EWG represents an electron withdrawing group.

The electron-withdrawing group in this embodiment is a group having a positive Hammett substituent constant σ m. Among them, σ m is described in detail in general, Journal of Synthetic Organic Chemistry, Japan, Vol.23, No. 8 (1965), p.631-642. The electron-withdrawing group in the present embodiment is not limited to the substituents described in the above documents.

Examples of the substituent having a positive σ m include CF₃Base (. sigma.m.0.43), CF₃CO group (σ m ═ 0.63), HC ≡ C group (σ m ≡ 0.21), CH group₂CH (σ m) group 0.06, Ac (σ m) group 0.38, MeOCO (σ m) group 0.37, MeCOCH (σ m) CH group 0.21, PhCO (σ m) group 0.34, H₂NCOCH₂And a group (σ m ═ 0.06). In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6).

[ chemical formula 38]

In the formulae (EWG-1) to (EWG-6), R^x1～R^x3Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), a hydroxyl group, or a carboxyl group. Wherein R of the formula (EWG-1)^x1R of formula (EWG-4)^x1Not a carboxyl group. Ar represents an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms). When R is^x1～R^x3When the group is an alkyl group, an alkenyl group or an aryl group, a ring may be formed, and the above-mentioned linking group L or the hetero-linking group Lh described later may be interposed in the ring formation. When R is^x1～R^x3In the case of an alkyl group, an alkenyl group, or an aryl group, Ar may have a substituent T within a range not impairing the effects of the present invention. Among them, Ar is preferably a carboxyl group (preferably 1 to 3).

Np is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

In the present embodiment, the carboxylate anion is preferably represented by the following formula (XA).

Formula (XA)

[ chemical formula 39]

In the formula (XA), L¹⁰Represents a single bond or is selected from the group consisting of an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), -NR^X-and 2-valent linking groups in combinations of these, R^XRepresents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms).

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenyliminodiacetic acid anion, and oxalic acid anion.

The details of the hot alkali generator can be found in paragraphs 0021 to 0077 of Japanese patent application laid-open No. 2016-027357, which are incorporated herein.

The following compounds are exemplified as the thermokalite generator.

[ chemical formula 40]

[ chemical formula 41]

[ chemical formula 42]

[ chemical formula 43]

When a hot alkali generator is used, the content of the hot alkali generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition, the lower limit is more preferably 0.25% by mass or more, the step is preferably 0.5% by mass or more, the upper limit is more preferably 20% by mass or less, and the step is preferably 10% by mass or less.

kinds or two or more of the hot alkali generators can be used, and when two or more are used, the total amount is preferably in the above range.

The embodiment of the present invention may be configured to contain substantially no thermokalite generator, and substantially no means less than 0.1% by mass, more preferably 0.01% by mass or less, and particularly preferably 0.001% by mass or less of the total solid content of the composition.

Photobase generating agent

The photosensitive resin composition used in the present invention may contain a photobase generator. The photobase generator is a substance that generates a base by exposure, and does not exhibit activity under normal temperature and pressure conditions, but is not particularly limited as long as it generates a base (basic substance) when electromagnetic waves are irradiated and heated as an external stimulus. The base generated by exposure acts as a catalyst when the polymer precursor is cured by heating, and therefore can be preferably used when a development treatment is performed.

In the present invention, a photobase generator known as a photobase generator can be used. For example, as m.shirai, and m.tsunooka, prog.polym.sci.,21,1 (1996); jiaokang Zhenghong, polymer processing, 46,2 (1997); c.kutal, coord.chem.rev.,211,353 (2001); y.kaneko, a.sarker, and d.neckers, chem.mater.,11,170 (1999); h.tachi, m.shirai, and m.tsunooka, j.photopolym.sci.technol.,13,153 (2000); m.winkle, and k.graziano, j.photopolym.sci.technol.,3,419 (1990); m.tsunooka, h.tachi, and s.yoshitaka, j.phopolym.sci.technol., 9,13 (1996); examples of the alkali-latent nonionic compound include transition metal compound complexes, substances having a structure such as ammonium salts, ionic compounds in which an amidino moiety is latent by formation of a carboxylic acid or a salt, and carbamate or oxime ester compounds in which an alkali component is latent by formation of a salt, as described in k.suyama, h.araki, m.shirai, j.photopolym.sci.technol.,19,81 (2006).

The basic substance generated by the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly polyamines such as monoamines and diamines, and amidines.

The generated basic substance is preferably a compound having an amino group with higher basicity. The reason for this is that these compounds have a strong catalytic action against a dehydration condensation reaction or the like in imidization of a polymer precursor, and can exhibit a catalytic effect in a dehydration condensation reaction or the like at a lower temperature with a smaller amount of addition. That is, the generated basic substance has a large catalytic effect, and thus the sensitivity of the appearance as a photosensitive resin composition is improved.

From the viewpoint of the catalytic effect, the basic substance is preferably amidine or aliphatic amine.

The photobase generator used in the present invention is preferably a compound containing an aromatic ring and generating a basic substance having an amino group.

Examples of the photobase generators according to the present invention include photobase generators having a cinnamamide structure as disclosed in japanese patent laid-open nos. 2009-080452 and 2009/123122, photobase generators having a carbamate structure as disclosed in japanese patent laid-open nos. 2006-189591 and 2008-247747, and photobase generators having an oxime structure or a carbamoyl oxime structure as disclosed in japanese patent laid-open nos. 2007-249013 and 2008-003581, but the photobase generators are not limited thereto and known photobase generators can be used.

Examples of the photobase-generating agent include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese patent laid-open No. 2012 and 093746, compounds described in paragraphs 0022 to 0069 of Japanese patent laid-open No. 2013 and 194205, compounds described in paragraphs 0026 to 0074 of Japanese patent laid-open No. 2013 and 204019, and compounds described in paragraph 0052 of International publication No. WO 2010/064631.

As commercially available photobase generators, there can be used WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the photobase generator include the following compounds. Et represents ethyl and Me represents methyl.

[ chemical formula 44]

When the photobase generator is used, the content of the photobase generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition, the lower limit is more preferably 0.5% by mass or more, the step is preferably 1% by mass or more, the upper limit is more preferably 30% by mass or less, and the step is preferably 20% by mass or less.

kinds or two or more of photobase generators can be used, and when two or more are used, the total amount is preferably in the above range.

The embodiment of the present invention may be configured to contain substantially no photobase generator, and substantially no containing means less than 0.1% by mass, more preferably 0.01% by mass or less, and particularly preferably 0.001% by mass or less of the total solid content of the composition.

< other additives >

The photosensitive resin composition of the present invention can contain, as necessary, various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like, as long as the effects of the present invention are not impaired. When these additives are blended, the total blending amount thereof is preferably 3% by mass or less of the solid content of the composition.

Thermal acid generators

The photosensitive resin composition of the present invention may contain a thermal acid generator which generates an acid by heating and promotes cyclization of the polymer precursor to further improve mechanical properties of the cured film, and examples of the thermal acid generator include compounds described in paragraph 0059 of Japanese patent laid-open publication No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more per 100 parts by mass of the polymer precursor, and the mechanical properties and the resistance to the use of vegetables can be further improved by step by including 0.01 parts by mass or more of the thermal acid generator to promote the crosslinking reaction and the cyclization of the polymer precursor, and the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of the electrical insulation property of the cured film.

The thermal acid generator may be used alone in kinds, or two or more kinds may be used.

Sensitizing pigment

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation to become an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermokalite generator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and functions such as electron transfer, energy transfer, heat generation, and the like are generated. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. The details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further is preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention, types of sensitizing dye may be used alone, or two or more types of sensitizing dye may be used simultaneously.

Chain transfer agent

The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in page 683-684 of The third edition of The Polymer dictionary (The Society of Polymer Science, Japan, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These radicals can be generated by supplying hydrogen to a low-activity radical to generate a radical, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, and the like) can be preferably used.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 1 to 5 parts by mass in the step, per 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention.

Surface active agent

From the viewpoint of further improving the coatability of , various surfactants can be added to the photosensitive resin composition of the present invention, and as the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

[ chemical formula 45]

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the photosensitive resin composition of the present invention, and the surfactant may be or two or more surfactants.

Higher fatty acid derivatives

In order to prevent inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the photosensitive resin composition of the present invention so as to be locally present on the surface of the composition during drying after application.

When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the photosensitive resin composition of the present invention, the number of the higher fatty acid derivatives may be or two or more, and when the number of the higher fatty acid derivatives is two or more, the total range is preferably in the above range.

< restrictions on other contained substances >

From the viewpoint of coating surface shape, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass.

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

As a method for reducing metal impurities unexpectedly contained in the photosensitive resin composition of the present invention, there can be mentioned a method in which a raw material having a small metal content is selected as a raw material constituting the photosensitive resin composition of the present invention, the raw material constituting the photosensitive resin composition of the present invention is subjected to filter filtration, and the raw material is lined with polytetrafluoroethylene or the like in an apparatus to distill under conditions in which contamination is suppressed as much as possible.

In view of the corrosion of wiring, the content of the halogen atom in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm, wherein the content of the substance existing in the state of the halogen ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further is preferably less than 0.5 mass ppm.

As the container for the photosensitive resin composition of the present invention, a conventionally known container can be used. Further, for the purpose of suppressing the contamination of impurities into the raw materials or the composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such containers include those described in Japanese patent laid-open publication No. 2015-123351.

< preparation of composition >

The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be carried out by a conventionally known method.

In addition, for the purpose of removing foreign matters such as dust and fine particles in the composition, it is preferable to perform filtration using a filter, the pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and further steps are preferably 0.1 μm or less, the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon, and a filter previously cleaned with an organic solvent can be used.

In addition to filtration using a filter, an impurity removal treatment using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. 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 methods for producing these >

Next, the cured film, the laminate, the semiconductor device, and the methods for producing these will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more and 1 μm or more. The upper limit value may be 100 μm or less, and may be 30 μm or less.

The cured film of the present invention may be laminated in 2 or more layers to form a laminate. The laminate having 2 or more layers of the cured films of the present invention preferably has a metal layer between the cured films. These metal layers can be preferably used as metal wirings such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer or the like in a three-dimensional mounting device.

The cured film of the present invention can also be used for the production of printing plates such as offset printing plates and screen printing plates, the use of molded parts, and the production of protective paints and dielectric layers for electronics, particularly microelectronics.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Preferably, the method for producing a cured film comprises: a photosensitive resin composition layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a layer; an exposure step of exposing the photosensitive resin composition layer; and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer (resin layer). The photosensitive resin composition of the present invention can be preferably used when development is performed.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, according to the method for producing a cured film of the present invention, after the cured film is formed, it is more preferable to perform the photosensitive resin composition layer forming step, the exposure step, and the development treatment step again in this order. In particular, it is more preferable to perform the photosensitive resin composition layer forming step, the exposure step, and the development treatment step 2 to 5 times (i.e., 3 to 6 times in total) in this order. By laminating the cured films in this manner, a laminate can be obtained. In the present invention, particularly after the cured film is provided and developed, it is preferable to provide a metal layer at a portion removed by development.

The details of these will be described below.

Photosensitive resin composition layer Forming Process

The method for producing a laminate according to a preferred embodiment of the present invention includes a photosensitive resin composition layer forming step of applying a photosensitive resin composition to a substrate to form a layer.

The type of the substrate may be appropriately set according to the application, but is not particularly limited, and examples thereof include a semiconductor substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, a semiconductor substrate such as quartz, glass, an optical film, a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe, paper, sog (spin On glass), a TFT (thin film transistor) array substrate, and an electrode plate of a Plasma Display Panel (PDP). In the present invention, a semiconductor substrate is particularly preferable, and a silicon substrate is more preferable.

When the photosensitive 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 serves as a substrate.

The method of applying the photosensitive resin composition to a substrate is preferably coating.

Specifically, examples of suitable methods 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, a slit coating method, and an ink jet method. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. By adjusting the solid content concentration and the coating conditions appropriately according to the method, a resin layer having a desired thickness can be obtained. The coating method can be appropriately selected according to the shape of the substrate, and is preferably a spin coating method, a spray coating method, an ink jet method, or the like as long as it is a circular substrate such as a wafer, and is preferably a slit coating method, a spray coating method, an ink jet method, or the like as long as it is a rectangular substrate. In the case of the spin coating method, the method can be applied at a rotation speed of, for example, 500 to 2000rpm for about 10 seconds to 1 minute.

Drying Process

The method for producing a laminate of the present invention may further comprise a step of drying the photosensitive resin composition layer to remove the solvent, preferably at a drying temperature of 50 to 150 ℃, more preferably 70 to 130 ℃, and further preferably at a drying temperature of 90 to 110 ℃ in the step . 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 method for producing a laminate of the present invention may include an exposure step of exposing the photosensitive resin composition layer. The exposure dose is not particularly limited in the range capable of curing the photosensitive resin composition, and for example, the exposure dose is preferably 100 to 10000mJ/cm in terms of exposure energy at a wavelength of 365nm²More preferably, the irradiation is 200 to 8000mJ/cm²。

The exposure wavelength can be set within a range of 190 to 1000nm, preferably 240 to 550 nm.

The exposure wavelength is described in relation to a light source, and examples thereof include (1) a semiconductor laser (having a wavelength of 830nm, 532nm, 488nm, 405nm etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, a g-ray (having a wavelength of 436nm), an h-ray (having a wavelength of 405nm), an i-ray (having a wavelength of 365nm), a broad (3 wavelengths of g, h, and i-rays), (4) an excimer laser, a KrF excimer laser (having a wavelength of 248nm), an ArF excimer laser (having a wavelength of 193nm), an F2 excimer laser (having a wavelength of 157nm), and (5) extreme ultraviolet rays; EUV (wavelength 13.6nm), (6) electron beam, and the like. In the present invention, the photosensitive resin composition is particularly preferably exposed to light by a high-pressure mercury lamp, and particularly preferably exposed to light by i-rays. This makes it possible to obtain particularly high exposure sensitivity.

(developing treatment Process)

The method for producing the laminate of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By performing development, an unexposed portion (unexposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as spin immersion, spraying, dipping, or ultrasonic waves can be used. The development is performed using a developer. The developing solution can be used without particular limitation as long as the unexposed portion (unexposed portion) can be removed. The developer preferably comprises an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP of-1 to 5, and more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be calculated as a calculated value by inputting the structural formula by chembidraw (chemibiological diagram).

As the organic solvent, there may be suitably mentioned, 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 alkoxyacetates (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) and alkyl 3-alkoxypropionates (for example, methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.), Ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate (example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like, and ethers such as diethylene glycol dimethyl ether, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, toluene, xylene, anise ether, limonene, etc., and as sulfoxides, dimethyl sulfoxide, etc., may be suitably cited.

In the present invention, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.

Preferably, 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more of the developer is an organic solvent, and further preferably 90% by mass or more of the developer is an organic solvent in the step .

The developing time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and can be usually carried out at 20 to 40 ℃.

After the treatment with the developer, rinsing may be further performed. Preferably, the rinsing is performed with a different solvent than the developer. For example, the solvent contained in the photosensitive resin composition can be used for rinsing. The rinsing time is preferably 5 seconds to 1 minute.

Heating Process

The method for producing the laminate of the present invention preferably includes a step of heating after development, in the heating step, a cyclization reaction of the polymer precursor is performed, and the photosensitive resin composition of the present invention contains a radical polymerizable compound other than the polymer precursor, and also cures a radical polymerizable compound other than an unreacted polymer precursor, and the heating temperature (maximum heating temperature) is preferably 50 to 450 ℃, more preferably 140 to 400 ℃, and further is preferably 160 to 350 ℃.

The heating is preferably performed at a temperature rise rate of 1 to 12 ℃/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ℃/min, and further preferably 3 to 10 ℃/min in the step , and by setting the temperature rise rate to 2 ℃/min or more, excessive volatilization of the amine can be prevented while ensuring the productivity, and by setting the temperature rise rate to 12 ℃/min or less, the residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, and further preferably 25 to 120 ℃ in the step . the temperature at the start of heating means the temperature at the start of the step of heating to the maximum heating temperature, for example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature after drying is, for example, preferably increased gradually from a temperature 30 to 200 ℃ lower than the boiling point of the solvent contained in the photosensitive resin composition.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, and further steps are preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.

In particular, in the case of forming a multilayer laminate, the heating is preferably performed at a heating temperature of 180 to 320 ℃ and more preferably at 180 to 260 ℃ from the viewpoint of the adhesiveness between the layers of the cured film. The reason is not clear, but is considered to be because the ethynyl groups of the polymer precursors between the layers are crosslinked with each other by setting the temperature to this temperature.

The heating may be performed in stages, for example, by a pretreatment step of raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min, holding the temperature at 180 ℃ for 60 minutes, raising the temperature from 180 ℃ to 200 ℃ at 2 ℃/min, and holding the temperature at 200 ℃ for 120 minutes, the heating temperature as the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and further steps are preferably 120 to 185 ℃.

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

In the heating step, it is preferable to perform the heating step in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (by volume) or less, more preferably 20ppm (by volume) or less.

Metal layer Forming Process

The method for producing a laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer (cured film) after the development treatment.

The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, more preferably copper and aluminum, and further steps preferably copper.

The method for forming the metal layer is not particularly limited, and conventional methods can be applied. For example, the methods described in Japanese patent laid-open Nos. 2007-157879, 2001-521288, 2004-214501 and 2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like are conceivable. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are given.

The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

(lamination Process)

The production method of the present invention preferably further comprises a lamination step.

The laminating step is an series step including a case where the photosensitive resin composition layer forming step, the exposure step, and the development treatment step are performed in this order, and may include the drying step, the heating step, or the like.

When the lamination step is performed after the lamination step, the surface activation treatment step may be further performed after the exposure step or after the metal layer formation step. As the surface activation treatment, plasma treatment is exemplified.

The laminating step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.

For example, the resin layer such as resin layer/metal layer/resin layer/metal layer is preferably 3 layers or more and 7 layers or less, and further steps are preferably 3 layers or more and 5 layers or less.

That is, in the present invention, particularly after the metal layer is provided, it is more preferable to sequentially perform the photosensitive resin composition layer forming step, the exposure step, and the development treatment step so as to cover the metal layer. The photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated by alternately performing the laminating step of laminating the photosensitive resin composition layer (resin layer) and the metal layer forming step.

A semiconductor device having the cured film or the laminate of the present invention is also disclosed. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer, reference can be made to the descriptions in paragraphs 0213 to 0218 of Japanese patent laid-open No. 2016-027357 and the description of FIG. 1, and these contents are incorporated in the present specification.

Examples

The present invention will be described in further detail below in with reference to examples, and materials, amounts of use, ratios, treatment details, treatment steps and the like shown in the following examples can be modified as appropriate without departing from the spirit of the present invention.

(Synthesis example 1)

[ Synthesis of polyimide precursor A-1 derived from 4, 4' -oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below ]

21.2g of 4,4 '-oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme (diglyme) were mixed and stirred at 60 ℃ for 4 hours to prepare a diester of 4, 4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate, and then the reaction mixture was cooled to-10 ℃ to ℃ and 17.0g of SOCl was added to for 60 minutes while maintaining the temperature at-10 ℃₂. After diluting with 50mL of N-methylpyrrolidone, 38.0g of a solution obtained by dissolving the hydroxyl group-containing diamine (a) shown below in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 2 hours, followed by addition of 20mL of ethanol. Subsequently, the polyimide precursor was precipitated in water by pouring 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was put into 6 liters of water to precipitate a polyimide precursor in water, filtered, and dried at 45 ℃ for 3 days under reduced pressure. The polyimide precursor is heavyThe average molecular weight is 27400 and the number average molecular weight is 10100.

Diamine (a)

[ chemical formula 46]

(Synthesis example 2)

[ Synthesis of polyimide precursor A-2 derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl ]

14.9g of pyromellitic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme were mixed and stirred at 60 ℃ for 4 hours to prepare a diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate, and then the reaction mixture was cooled to-10 ℃ to ℃ while maintaining the temperature at-10 ℃ and , 17.0g of SOCl was added over 60 minutes₂. After diluting with 50mL of N-methylpyrrolidone, a solution prepared by dissolving 20.1g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 2 hours, followed by addition of 20mL of ethanol. Subsequently, the polyimide precursor was precipitated in water by pouring 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was put into 6 liters of water to precipitate a polyimide precursor in water, filtered, and dried at 45 ℃ for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 23100 and the number average molecular weight was 9700.

(Synthesis example 3)

[ Synthesis of polyimide precursor A-3 derived from 4,4 ' -oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl ]

21.2g of 4, 4' -oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme were mixedAnd then stirred at 60 ℃ for 4 hours to produce a diester of 4, 4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate, and then the reaction mixture was cooled to-10 ℃ to ℃ while maintaining the temperature at-10 ℃ and to which 17.0g of SOCl was added over 60 minutes₂. After diluting with 50mL of N-methylpyrrolidone, a solution prepared by dissolving 20.1g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 2 hours, followed by addition of 20mL of ethanol. Subsequently, the polyimide precursor was precipitated in water by pouring 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380g of tetrahydrofuran. The obtained solution was put into 6 liters of water to precipitate a polyimide precursor in water, filtered, and dried at 45 ℃ for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 23500 and the number average molecular weight was 9400.

(Synthesis example 4)

[ Synthesis of polyimide precursor A-4 derived from 4,4 '-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4, 4' -diaminodiphenyl ether ]

21.2g of 4,4 '-oxydiphthalic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme were mixed and stirred at 60 ℃ for 4 hours to prepare a diester of 4, 4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate, and then the reaction mixture was cooled to-10 ℃ to ℃ while maintaining the temperature at-10 ℃ and to which 17.0g of SOCl was added over 60 minutes₂. After diluting with 50mL of N-methylpyrrolidone, a solution prepared by dissolving 25.1g of 4, 4' -diaminodiphenyl ether in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10 ℃ over 60 minutes, and the mixture was stirred for 2 hours, followed by addition of 20mL of ethanol. Subsequently, the polyimide precursor was precipitated in water by pouring 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered to dissolve it in tetraAnd 380g of tetrahydrofuran. The obtained solution was put into 6 liters of water to precipitate a polyimide precursor in water, filtered, and dried at 45 ℃ for 3 days under reduced pressure. The weight average molecular weight of the polyimide precursor was 23200, and the number average molecular weight was 9600.

(Synthesis example 5)

[ Synthesis of polybenzoxazole precursor composition A-5 derived from 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4, 4' -oxydibenzoyl chloride ]

28.0g of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200mL of N-methylpyrrolidone. Then, 25.0g of 4, 4' -oxybenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ℃, and then stirring was continued for 60 minutes. To the obtained reaction solution, 6L of water was poured to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45 ℃ for 2 days under reduced pressure. The weight average molecular weight of the polybenzoxazole precursor is 25800 and the number average molecular weight is 9300.

(Synthesis example 6)

[ Synthesis of radically polymerizable Compound B1-1 having Sulfur atom ]

109.4g of 2-hydroxyethyl methacrylate, 70.0g of pyridine and 500mL of tetrahydrofuran were mixed, the mixture was cooled to 0 ℃ and was added dropwise 50.0g of SOCl over 60 minutes while keeping the temperature below 5 ℃ and ℃₂And then stirred for 1 hour. The reaction was stopped by adding 200mL of distilled water, and 500mL of ethyl acetate was added. The obtained organic layer was washed 5 times with distilled water, and then the low-boiling point solvent was removed by an evaporator, whereby 220.1g of a radically polymerizable compound B1-1 was obtained. The compound obtained is an exemplary compound 302 of the radical polymerizable compound having a sulfur atom described above.

¹H NMR(400MHz,CDCl₃)δ(ppm)：6.15(t,2H)、5.62(t,2H)、4.37(m,4H)、4.30(m,2H)、4.21(m,2H)、1.95(dd,6H)。

(Synthesis example 7)

[ Synthesis of radically polymerizable Compound B1-2 having Sulfur atom ]

101.8g of 4-vinylbenzyl alcohol70.0g of pyridine and 500mL of tetrahydrofuran were mixed, the mixture was cooled to 0 ℃ and was added dropwise 50.0g of SOCl over 60 minutes while keeping the temperature below 5 ℃ and ₂And then stirred for 1 hour. The reaction was stopped by adding 200mL of distilled water, and 500mL of ethyl acetate was added. The obtained organic layer was washed 5 times with distilled water, and then the low-boiling solvent was removed by an evaporator, thereby obtaining 200.2g of a radically polymerizable compound B1-2. The compound obtained is an exemplary compound 312 of the radical polymerizable compound having a sulfur atom.

(Synthesis example 8)

[ Synthesis of radically polymerizable Compound B1-3 having a Sulfur atom ]

19.0g of bis (4-hydroxyphenyl) sulfone, 7.0g of pyridine and 100mL of tetrahydrofuran were mixed, the mixture was cooled to 0 ℃ and , ℃ was maintained at 5 ℃ or lower, 19.0g of methacryloyl chloride was added dropwise over 60 minutes while stirring for 1 hour, 200mL of distilled water was added to stop the reaction, 500mL of ethyl acetate was added, the resulting organic layer was washed 5 times with distilled water, and then the low-boiling point solvent was removed by an evaporator to obtain 220.1g of a radically polymerizable compound B1-3, which was an exemplary compound 322 of the radically polymerizable compound having a sulfur atom.

< method for measuring molecular weight >

The molecular weight (weight average molecular weight, number average molecular weight) of the polymer precursor is defined as a polystyrene equivalent value by gel permeation chromatography (GPC method). Specifically, HLC-8220 (trade name: TosohCuration) was used, and the protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (trade name: Tosoh Corporation) were used as columns. The eluate was measured using THF (tetrahydrofuran). In addition, a 254nm wavelength detector of UV rays (ultraviolet rays) was used for the detection. The molecular weight specified in the present specification is not particularly limited, and is a value measured by the above-described measurement method.

< examples 1 to 16, comparative examples 1 to 3>

Preparation of photosensitive resin composition

Each component described in table 1 below was mixed to prepare a homogeneous solution. The obtained solution was passed through a filter having a pore width of 0.8 μm and pressure-filtered at a pressure of 0.3MPa to obtain a photosensitive resin composition.

Storage stability

The photosensitive resin composition 10g into a container (container material: light-shielding glass, volume: 100mL) and sealed, at 25 degrees C, relative humidity 65% environment under static, in the photosensitive resin composition precipitation of solid time to the time evaluation, until precipitation of time, the photosensitive resin composition stability is higher, and become the preferred result, in the solid precipitation, for kinds of photosensitive resin composition, preparation of 3 samples stored in the container, in 30 days, 60 days, 120 days after the time of 1 sample container, with a 0.8 u m mesh for the content of the photosensitive resin composition total pressure filtration, visual observation of the mesh on the foreign matter, and the following determination of whether there is precipitate.

A: no solid was precipitated even after 120 days.

B: over 60 days, and within 120 days, solids are precipitated.

C: over 30 days, and within 60 days, solids are precipitated.

D: solid is separated out within 30 days.

Measurement of Exposure energy

The photosensitive resin composition was coated on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ℃ for 5 minutes, thereby forming a uniform film having a thickness of 10 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a aligner (product name of Karl-SUSS MA150, manufactured by SUSS MICROTEC AG). The exposure was carried out using a high-pressure mercury lamp, and the exposure energy required for curing the 10 μm uniform film at a wavelength of 365nm was measured. A lower exposure energy indicates higher sensitivity, and is a preferable result.

(A) Polymer precursor

A-1 to A-5: polymer precursors produced in Synthesis examples 1 to 5

(B1) Radically polymerizable compound having sulfur atom

B1-1 to B1-3: the radical polymerizable Compound having a Sulfur atom produced in Synthesis examples 6 to 8

(B2) Radical polymerizable Compound (all trade names)

B2-1: NK ester M-40G (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

B2-2: SR-209 (manufactured by Sartomer Company, Inc.)

B2-3: NK ester A-9300(Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

B2-4: A-TMMT (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

(C) Photo radical polymerization initiator (all trade names)

C-1: IRGACURE OXE 01 (manufactured by BASF corporation)

C-2: IRGACURE OXE 02 (manufactured by BASF corporation)

C-3: IRGACURE OXE 04 (manufactured by BASF corporation)

C-4: IRGACURE-784 (manufactured by BASF corporation)

C-5: NCI-831 (manufactured by ADEKA CORPORATION)

(D) Alkali generating agent

D-1: the following compounds

D-2: the following compounds

D-3: the following compounds

[ chemical formula 47]

(E) Polymerization inhibitor

E-1: 1, 4-p-benzoquinone

E-2: 1, 4-methoxyphenol

(F) Additive (migration inhibitor)

F-1: 1,2, 4-triazoles

F-2: 1H-tetrazole

(G) Silane coupling agent

G-1: the following compounds

G-2: the following compounds

G-3: the following compounds

[ chemical formula 48]

Et represents an ethyl group.

(H) Solvent(s)

H-1: gamma-butyrolactone

H-2: dimethyl sulfoxide

H-3: n-methyl-2-pyrrolidone

H-4: lactic acid ethyl ester

In addition, in Table 1 solvent, for example, when the type column is "H-1/H-2", the part by mass column is "48 + 12", means that 48 parts by mass of H-1, 12 parts by mass of H-2.

As is clear from the results in table 1, when a radical polymerizable compound having a sulfur atom is used, the storage stability is excellent and the sensitivity is high (examples 1 to 16). In particular, as shown in example 20, even when a small amount of a radical polymerizable compound having a sulfur atom is blended, the advantage of the present invention can be seen from the viewpoint of achieving excellent storage stability and high sensitivity.

On the other hand, when the radical polymerizable compound having a sulfur atom is not blended, the sensitivity becomes low (comparative examples 1 to 3).

< example 100>

The photosensitive resin composition of example 1 was applied to a silicon wafer by a spin coating method. Drying the silicon wafer coated with the photosensitive resin composition layer on a hot plate at 100 deg.C for 5 minA uniform photosensitive resin composition layer having a thickness of 15 μm was formed on the silicon wafer. Use stepper (Nikon NSR 2005i9C [ trade name [ ]]) At 500mJ/cm²The exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds to form holes having a diameter of 10 μm by exposing the photosensitive resin composition layer on the silicon wafer to light, then, the temperature was raised at a rate of 10 ℃/minute to 250 ℃ in a nitrogen atmosphere, and then, the layer was heated for 3 hours, and after cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed by vapor deposition at parts of the surface of the photosensitive resin composition layer so as to cover the hole parts, and further, the same kind of photosensitive resin composition was used again for the surfaces of the metal layer and the photosensitive resin composition layer, and the step of filtering the photosensitive resin composition to the patterned film for 3 hours was performed again in the same manner as described above to produce a laminate composed of a resin layer/metal layer/resin layer.

The interlayer insulating film for a rewiring layer has excellent insulating properties.

Then, it was confirmed that the semiconductor device was normally operated as a result of manufacturing the semiconductor device using the interlayer insulating film for a rewiring layer.

Claims

1, photosensitive resin compositions comprising:

a polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors;

a radical polymerizable compound having a sulfur atom;

a photo radical polymerization initiator; and

a solvent.

2. The photosensitive resin composition according to claim 1,

the polymer precursor comprises the following repeating unit represented by formula (1) or repeating unit represented by formula (2);

3. The photosensitive resin composition according to claim 2,

the polymer precursor comprises a repeating unit represented by formula (1).

4. The photosensitive resin composition according to any of claims 1 to 3, wherein,

the radical polymerizable compound having a sulfur atom is represented by the following formula (3-1);

R¹²-X¹²-L¹¹-X¹¹-R¹¹(3-1)

5. The photosensitive resin composition according to claim 4,

the formula (3-1) is represented by the following formula (3-2);

R²-La¹-X²-La²-L¹-La³-X¹-La⁴-R¹(3-2)

in the formula (3-2), L¹represents-S-, -S-, -S (═ 0) -or-S (═ 0)₂-，X¹And X²Each independently represents a single bond, -0-, -C (═ 0) -, -C (═ O)0-, -OC (═ 0) -, -S (═ 0)₂-or-NR³CO-，R¹And R²Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical polymerizable group, La¹～La⁴Each independently represents of a single bond, a group composed of 1 or 2 or more of alkylene and phenylene, and a group composed of 1 or 2 or more of alkylene and phenylene and-0-³Represents a hydrogen atom or an alkyl group; wherein R is¹And R²At least of the groups are radical polymerizable groups.

6. The photosensitive resin composition according to claim 5,

the R is¹And R²These two groups are each independently a radical polymerizable group.

7. The photosensitive resin composition according to claim 5 or 6,

said X¹And X²Is-0-.

8. The photosensitive resin composition according to any of claims 5 to 7, wherein,

said L¹is-S (═ 0) -.

9. The photosensitive resin composition according to any of claims 5 to 8, wherein,

the R is¹And R²Each independently is a 1-valent organic group having an acryloyl group or a methacryloyl group.

10. The photosensitive resin composition according to claim 4,

the formula (3-1) is represented by the following formula (4);

in the formula (4), R is a hydrogen atom or a methyl group.

11. The photosensitive resin composition according to any of claims 1 to 10, wherein,

the radical polymerizable compound having a sulfur atom is contained at a ratio of 0.001 mass% or more of a solid content contained in the photosensitive resin composition.

12. The photosensitive resin composition of any of claims 1 to 11, further comprising a radically polymerizable compound other than the radically polymerizable compound having a sulfur atom.

13. The photosensitive resin composition of any of claims 1-12, further comprising a base generator.

14. The photosensitive resin composition according to any of claims 1 to 13, which is used for development.

15. The photosensitive resin composition according to any of claims 1 to 14, for use in development using a developer containing an organic solvent.

16. The photosensitive resin composition according to any of claims 1 to 15, which is used for forming an interlayer insulating film for a rewiring layer.

17, kinds of cured films formed from the photosensitive resin composition described in any of claims 1 to 16.

A laminate of 18, having 2 or more layers of the cured film of claim 17.

19. The laminate according to claim 18,

a metal layer is provided between the cured films.

20, kinds of cured film manufacturing method, which includes the use of claim 1 to 16 any of the photosensitive resin composition process.

21. The method for manufacturing a cured film according to claim 20, comprising:

a photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer;

an exposure step of exposing the photosensitive resin composition layer; and

and a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer.

22, semiconductor devices having the cured film of claim 17 or the laminate of claim 18 or 19.