CN110741318B - Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The invention provides a photosensitive resin composition with excellent storage stability and high sensitivity, a cured film, a laminated body, a manufacturing method of the cured film and a semiconductor device using the photosensitive resin composition. Also provided is a novel compound for forming a photosensitive resin composition. A photosensitive resin composition comprises 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, and semiconductor device

Technical Field

The invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing the cured film, a semiconductor device and a compound.

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 for semiconductor devices. However, in recent years, with the progress of high integration and large-sized semiconductor devices, there has been a demand for a thin and compact sealing resin package, and a surface mount method using LOC (wire on chip) or reflow method has been adopted.

In the production of such a semiconductor element, a photosensitive resin composition that imparts photosensitivity to the polyimide resin itself is used. This is because the use of the photosensitive resin composition can simplify the patterning process. For example, patent document 1 discloses a resin composition comprising (a) a polyimide precursor having a predetermined structure, (b) a compound that generates a radical upon irradiation with an active light, (c) a compound represented by the following formula (4 a) or (4 b), and (d) a solvent.

[ chemical formula 1]

(in formula (4 a), na is an integer of 3 or less in formula (4 b), R ¹⁰¹ R is R ¹⁰² Each independently is a hydrogen atom or a 1-valent group. mb is an integer of 9 or less. )

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

Technical literature of the prior art

Patent literature

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

Disclosure of Invention

Technical problem to be solved by the invention

However, it is known that the composition described in patent document 1 does not necessarily have high sensitivity to light. When the photosensitive resin composition is left for a certain period of time and then used as a cured film, the storage stability of the photosensitive resin composition is also required.

The present invention has been made to solve the above problems, and an object thereof is to provide a photosensitive resin composition 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 same. Further, an object is to provide a compound for producing the photosensitive resin composition.

Means for solving the technical problems

Based on the above-described problems, the present inventors have conducted intensive studies and found that the above-described problems can be solved by blending a radical polymerizable compound having a sulfur atom into a photosensitive resin composition. Specifically, the above problems are solved by the following means <1>, preferably <2> to <22 >.

<1> a photosensitive resin composition comprising: a polymer precursor selected from polyimide precursors and polybenzoxazole precursors; a radically polymerizable compound having a sulfur atom; a photo radical polymerization initiator; and (3) 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 formula (2);

[ chemical formula 2]

In the formula (1), A ¹ A is a ² Each independently represents an oxygen atom or NH,

R ¹¹¹ Represents a 2-valent organic group, R ¹¹⁵ Represents a 4-valent organic group, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group;

[ chemical formula 3]

In the formula (2), R ¹²¹ Represents a 2-valent organic group, R ¹²² Represents a 4-valent organic group, R ¹²³ R is R ¹²⁴ Independently represent a hydrogen atom or a 1-valent organic compoundA group.

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

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

[ chemical formula 4]

R ¹² -X ¹² -L ¹¹ -X ¹¹ -R ¹¹ (3-1)

In the formula (3-1), L ¹¹ Represents a 2-valent linking group containing a sulfur atom, X ¹¹ X is X ¹² Each independently represents a single bond or a 2-valent linking group, R ¹¹ R is R ¹² Each independently represents a hydrogen atom or a 1-valent organic group; wherein R is ¹¹ R is R ¹² Represents a 1-valent organic group comprising at least one free radically polymerizable group; r is R ¹¹ R is R ¹² Optionally 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]

R ² -La ¹ -X ² -La ² -L ¹ -La ³ -X ¹ -La ⁴ -R ¹ (3-2)

In the formula (3-2), L ¹ representing-S-, -S (=O) -or-S (=O) ₂ -，X ¹ X is X ² Each independently represents a single bond, -O-, -C (=o) O-, -OC (=o) -, -S (=o) ₂ -or-NR ³ CO-，R ¹ R is R ² Independently of one another, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical-polymerizable group, la ¹ ～La ⁴ Each independently represents any one of a single bond, a group consisting of a combination of 1 or more of an alkylene group and a phenylene group, and a group consisting of a combination of 1 or more of an alkylene group and a phenylene group and-O-; r is R ³ Represents a hydrogen atom or an alkyl group; wherein R is ¹ R is R ² Is to of (a)At least one of which is a radical polymerizable group.

<6>According to<5>The photosensitive resin composition, R is as follows ¹ R is R ² These two are each independently a radical polymerizable group.

<7>According to<5>Or (b)<6>The photosensitive resin composition, X ¹ X is X ² is-O-.

<8>According to<5>～<7>The photosensitive resin composition according to any one of the above L ¹ is-S (=o) -.

<9>According to<5>～<8>The photosensitive resin composition according to any one of the above R ¹ R is R ² Each independently is a 1-valent organic group having an acryl group or a methacryl 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>, wherein the radically polymerizable compound having a sulfur atom is contained in a proportion of 0.001 mass% or more of the solid content contained in the photosensitive resin composition.

<12> the photosensitive resin composition according to any one of <1> to <11>, 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>, further comprising a base generator.

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

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

<16> the photosensitive resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a re-wiring layer.

<17> a cured film formed from the photosensitive resin composition of any one of <1> to <16 >.

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

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

<20> a method for producing a cured film, comprising the step of using the photosensitive resin composition according to any one of <1> to <16 >.

<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 development treatment step of developing the exposed photosensitive resin composition layer.

<22> a semiconductor device having the cured film <17> or the laminate <18> or <19 >.

Effects of the invention

The present invention can provide a photosensitive resin composition having excellent storage stability and high sensitivity, and an excellent cured film, a laminate, a method for producing a cured film, and a semiconductor device using the photosensitive resin composition. Further, a novel compound used for the photosensitive resin composition can be provided.

Detailed Description

The following describes the content of the present invention. In the present specification, "to" means that numerical values described before and after "are used as meanings included in the lower limit value and the upper limit value.

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

The expression "substituted" and "unsubstituted" in this specification means that the expression "unsubstituted" includes both the case where the substituent is absent and the case where the substituent is present. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "exposure" in the present specification is not particularly limited, and includes exposure by a particle beam such as an electron beam or an ion beam, as well as exposure by light. The light used for exposure is usually an active ray or radiation such as extreme ultraviolet (EUV light), X-ray, electron beam, etc. represented by an open-line spectrum of a mercury lamp or an excimer laser.

In the present specification, the numerical range indicated by "to" refers to a range including numerical values before and after "to" as a lower limit value and an upper limit value.

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

In the present specification, the term "process" is not limited to a single process, but is also included in the term if the desired action of the process can be achieved even if the process cannot be clearly distinguished from other processes.

In the present specification, the solid component is a mass percentage of components other than the solvent with respect to the total mass of the composition. Unless otherwise specified, the solid content concentration means a concentration at 25 ℃.

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 obtained by using HLC-8220 (manufactured by TOSOH CORPORATION), and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as the column. Unless otherwise specified, the eluent was determined by THF (tetrahydrofuran). Further, unless otherwise specified, detection is performed using a 254nm wavelength detector of UV rays (ultraviolet rays).

The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention") is characterized by comprising a polymer precursor selected from the group consisting of 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 for this is presumably that the radical polymerizable compound having a sulfur atom is not likely to cause polymerization reaction at room temperature and is also based on improvement of radical polymerizability of the composition.

< Polymer precursor >

The photosensitive resin composition of the present invention comprises a polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors. The polymer precursor is preferably a polyimide precursor or a polybenzoxazole precursor, more preferably a polyimide precursor, and even more preferably a polyimide precursor containing a repeating unit represented by the formula (1) described below.

Polyimide precursor

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

[ chemical formula 7]

In the formula (1), A ¹ A is a ² Each independently represents an oxygen atom or NH, R ¹¹¹ Represents a 2-valent organic group, R ¹¹⁵ Represents a 4-valent organic group, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group.

A in formula (1) ¹ A is a ² Is an oxygen atom or NH, preferably an oxygen atom.

R in formula (1) ¹¹¹ Represents 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, and a group containing 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 is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.

R ¹¹¹ Preferably derived from diamines. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. The diamine may be used alone or in combination of two or more.

Specifically, the diamine is preferably a diamine containing 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 a diamine containing a group having 6 to 20 carbon atoms. Examples of the aromatic group include the following aromatic groups.

[ chemical formula 8]

Wherein A is preferably 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 (=O) ₂ -, -NHCO-and combinations of these, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C (=O) -, -S (=O) ₂ The radicals in are further preferably selected from the group consisting of-CH ₂ -、-O-、-S-、-S(＝O) ₂ -、-C(CF ₃ ) ₂ -and-C (CH) ₃ ) ₂ -a valence 2 group of the group consisting of.

Specific examples of the diamine include 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 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4 '-diaminobiphenyl and 3,3' -diaminobiphenyl, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane and 3,3' -diaminodiphenylmethane 4,4 '-diaminodiphenyl sulfone and 3,3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide and 3,3' -diaminodiphenyl sulfide, 4 '-diaminobenzophenone and 3,3' -diaminobenzophenone, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethyl-4, 4' -diaminobiphenyl 3,3 '-dimethoxy-4, 4' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4 '-diamino p-diphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, and, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene 3,3 '-diethyl-4, 4' -diaminodiphenylmethane, 3 '-dimethyl-4, 4' -diaminodiphenylmethane, 4 '-diaminooctafluorobiphenyl 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydro-anthracene, 3',4,4 '-tetraminobiphenyl, 3',4,4 '-tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9 '-bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3 '-diaminodiphenyl sulfone, 3',5,5 '-tetramethyl-4, 4' -diaminodiphenylmethane, 2, 4-diaminocumene and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzoylanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzotrifluoride, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecyl heptanes 2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-dimethylphenyl ] hexafluoropropane, 2-bis [4- (4-aminophenoxy) -3, 5-bis (trifluoromethyl) phenyl ] hexafluoropropane for bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4 '-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3', at least one diamine selected from the group consisting of 5,5 '-tetramethyl-4, 4' -diaminobiphenyl, 4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5',6 '-hexafluoro-biphenylamine and 4,4' -diaminotetrabiphenyl.

Further, 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 can be mentioned. The diamine preferably contains 2 or more ethylene glycol chains or propylene glycol chains in total in one molecule, and more preferably contains no aromatic ring. Specific examples thereof include 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 (the above are product names, manufactured by HUNTSMAN corporation), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (2-aminopropoxy) propane-2-yl) oxy) propane-2-amine, and the like, but are not limited thereto.

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, JEFFAMINE (registered trademark) EDR-176 are shown below.

[ chemical formula 11]

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

From the viewpoint of flexibility of the obtained cured film, R ¹¹¹ Preferably from-Ar ⁰ -L-Ar ⁰ -a representation. Wherein Ar is ⁰ Each independently is an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L is an aliphatic hydrocarbon group containing 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S (=O) ₂ -or-NHCO-,And groups comprising a combination of 2 or more of the foregoing. Ar (Ar) ⁰ Preferably phenylene, L is further 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 the i-ray transmittance, R ¹¹¹ The 2-valent organic group represented by the following formula (51) or (61) is preferable. In particular, from the viewpoint of the i-ray transmittance and availability, the 2-valent organic group represented by formula (61) is more preferable.

(51)

[ chemical formula 12]

In the formula (51), R ⁵⁰ ～R ⁵⁷ Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R ⁵⁰ ～R ⁵⁷ At least one of which is a fluorine atom, methyl group, fluoromethyl group, difluoromethyl group or trifluoromethyl group.

When R is ⁵⁰ ～R ⁵⁷ When the organic 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.

(61)

[ chemical formula 13]

In the formula (61), R ⁵⁸ R is R ⁵⁹ Each independently is a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

Examples of the diamine compound having a structure represented by the formula (51) or (61) include dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. One of these may be used, or two or more of them may be used in combination.

R in formula (1) ¹¹⁵ Represents 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).

(5)

[ chemical formula 14]

In the formula (5), R ¹¹² Preferably a single bond or an aliphatic hydrocarbon group selected from the group consisting of 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=o) -, -S (=o) ₂ -, -NHCO-and combinations of these, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C (=O) -, -S-and-S (=O) ₂ The radicals in are further preferably selected from the group consisting of-CH ₂ -、-C(CF ₃ ) ₂ -、-C(CH ₃ ) ₂ -, -O-, -C (=O) -, -S-and-S (=o) ₂ -a valence 2 group of the group consisting of.

(6)

[ chemical formula 15]

With respect to R in formula (1) ¹¹⁵ Specific examples of the 4-valent organic group include a tetracarboxylic acid residue remaining after removal of an acid dianhydride group from a tetracarboxylic acid dianhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).

(O)

[ chemical formula 16]

In the formula (O), R ¹¹⁵ Represents a 4-valent organic group. R is R ¹¹⁵ Definition of (1) and R of formula (1) ¹¹⁵ The same applies.

Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 3',4' -diphenylmethane tetracarboxylic dianhydride, 2',3,3' -diphenylmethane tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2', at least one of 3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 1,2,4, 5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzenetetracarboxylic dianhydride, and alkyl derivatives having 1 to 6 carbon atoms and/or alkoxy derivatives having 1 to 6 carbon atoms.

Further, preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.

[ chemical formula 17]

In the formula (1), R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group, R ¹¹³ R is R ¹¹⁴ At least one of them is preferably a repeating unit containing a radical polymerizable group, more preferably both of them contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and is preferably exemplified byExamples of the group having an ethylenic unsaturated bond are.

Examples of the group having an ethylenic unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III). In addition, (meth) acryl is a generic term for acryl and methacryl.

[ chemical formula 18]

In the formula (III), R ²⁰⁰ Represents a hydrogen atom or a methyl group, more preferably a methyl group.

In the formula (III), R ²⁰¹ Represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ Or polyoxyalkylene having 4 to 30 carbon atoms (alkylene group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and repetition number is preferably 1 to 12, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms).

Preferred R ²⁰¹ Examples of (C) include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butylene, 1, 3-butylene, pentamethylene, hexamethylene, octamethylene, dodecamethylene and-CH ₂ CH(OH)CH ₂ -, more preferably ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -。

R is particularly preferred ²⁰⁰ Is methyl, R ²⁰¹ Is ethylene.

As represented by R ¹¹³ Or R is ¹¹⁴ The 1-valent organic group represented may preferably be a substituent that improves the solubility of the developer.

When R is ¹¹³ Or R is ¹¹⁴ When the organic group is 1-valent, it may be an aromatic group having 1,2 or 3 acidic groups bonded to carbon constituting the aryl group, preferably 1 acidic group, an alkyl group, or the like. Specifically, examples thereof include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, benzene having an acidic group can be exemplifiedA group and a benzyl group having an acidic group. The acidic groups are preferably OH groups.

From the viewpoint of solubility in an aqueous developer, R ¹¹³ Or R is ¹¹⁴ More preferred are a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group.

From the viewpoint of solubility to organic solvents, R ¹¹³ Or R is ¹¹⁴ Preferably a 1-valent organic group. The 1-valent organic group is preferably an alkyl group containing a linear or branched alkyl group, a cyclic alkyl group, or 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 ring). The alkyl group may be any of straight chain, branched chain, and cyclic. Examples of the straight-chain or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl and 2-ethylhexyl groups. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, camphene (camphenyl), decalin, tricyclodecyl, tetracyclodecyl, camphordiacyl, dicyclohexyl and pinenyl (pinenyl). Among them, cyclohexyl is most preferable from the viewpoint of both high sensitivity and high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described later.

Examples of the aromatic group include a substituted or unsubstituted benzene ring, naphthalene ring, pentylene ring, indene ring, azulene ring, heptylene ring, indene ring, perylene ring, fused pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetracene ring, and,

Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ringA pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a keadine ring, an acridine ring, a keolin ring, a thianthrene ring, a chromene ring, a xanthene ring, a keoxathiazide ring, a keothiazine ring, or a keizine ring. Most preferably a benzene ring.

In the formula (1), when R ¹¹³ When it is a hydrogen atom or R ¹¹⁴ When the hydrogen atom is a hydrogen atom, the polyimide precursor may form a conjugate base with a tertiary amine compound having an ethylenic unsaturated bond. Examples of tertiary amine compounds having these ethylenic unsaturated bonds include N, N-dimethylaminopropyl methacrylate.

In addition, the polyimide precursor preferably has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less. The upper limit is not particularly limited, but is practically 50 mass% or less.

In order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the repeating unit represented by formula (1). Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like can be exemplified.

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

(1-A)

[ chemical formula 19]

In the formula (1-A), A ¹¹ A is a ¹² Represents an oxygen atom or NH, R ¹¹¹ R is R ¹¹² Each independently represents a 2-valent organic group, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group, R ¹¹³ R is R ¹¹⁴ At least one of them is a radical-polymerizable group-containing group, preferably a radical-polymerizable group.

A ¹¹ 、A ¹² 、R ¹¹¹ 、R ¹¹³ R is R ¹¹⁴ Are defined independently of A in formula (1) ¹ 、A ² 、R ¹¹¹ 、R ¹¹³ R is R ¹¹⁴ The same applies to the preferred ranges.

R ¹¹² And R in formula (5) ¹¹² The same is preferable.

In the polyimide precursor, the repeating unit represented by the formula (1) may be one kind or two or more kinds. And, structural isomers of the repeating unit represented by formula (1) may be included. In addition to the repeating unit of the above formula (1), the polyimide precursor may contain other types of repeating structural units.

As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, and further 70 mol% or more, and particularly 90 mol% or more of the repeating units represented by the formula (1) are total repeating units can be exemplified. The upper limit is practically 100 mol% or less.

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

The dispersibility of the polyimide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

Polyimide precursors can be obtained by reacting a dicarboxylic acid or dicarboxylic acid derivative with a diamine. Preferably, the acid is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting the resultant with a diamine.

In the method for producing a polyimide precursor, an organic solvent is preferably used in the reaction. The organic solvent may be one kind or two or more kinds.

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

In the production of the polyimide precursor, the step of precipitating solids is preferably included. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be performed.

Polybenzoxazole precursors

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), R ¹²¹ Represents a 2-valent organic group, R ¹²² Represents a 4-valent organic group, R ¹²³ R is R ¹²⁴ Each independently represents a hydrogen atom or a 1-valent organic group.

In the formula (2), R ¹²¹ Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms). The aliphatic group is preferably a straight chain aliphatic group. R is R ¹²¹ Preferably derived from 4,4' -oxo-dibenzoyl chloride.

In the formula (2), R ¹²² Represents a 4-valent organic group. R in the above formula (1) is defined as a 4-valent organic group ¹¹⁵ The same applies to the preferred ranges. R is R ¹²² Preferably 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

R ¹²³ R is R ¹²⁴ Each independently represents a hydrogen atom or a 1-valent organic group, and R is defined as in formula (1) ¹¹³ R is R ¹¹⁴ The same applies to the preferred ranges.

In addition to the repeating units of formula (2) described above, the polybenzoxazole precursors may also contain other types of repeating structural units.

From the viewpoint of suppressing the occurrence of warpage of a cured film accompanied by closed-loop, it is preferable to include a diamine residue represented by the following formula (SL) as another kind of repeating structural unit.

[ chemical formula 21]

In the formula (SL), Z has a structure a and a structure b, R ^1s Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms), R ^2s Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), R ^3s 、R ^4s 、R ^5s 、R ^6s At least one of them is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, particularly preferably having 6 to 10 carbon atoms), and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 6 carbon atoms), and may be the same or different. The polymerization of the a and b structures may be block polymerization or random polymerization. In the Z moiety, the a structure is preferably 5 to 95 mol%, the b structure is preferably 95 to 5 mol%, and the a+b is preferably 100 mol%.

In the formula (SL), preferable Z is R in the b structure ^5s R is R ^6s Z is phenyl. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, 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 and ring closure can be reduced, and the effect of suppressing warpage and the effect of improving solubility can be achieved.

Comprises, as other kinds of repeating structural units, a diamine residue represented by the formula (SL)In this case, it is preferable that the repeating structural unit contains a tetracarboxylic acid residue remaining after the acid dianhydride is removed from the tetracarboxylic acid dianhydride, in order to improve the alkali solubility. Examples of the tetracarboxylic acid residues include R in the formula (1) ¹¹⁵ Is an example of (a).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100000, still more preferably 10000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.

The degree of dispersion of the polybenzoxazole precursor is preferably 1.5 to 3.5, 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, still more preferably 40 to 98% by mass, still more preferably 50 to 95% by mass, still more preferably 60 to 95% by mass, and still more preferably 70 to 95% by mass, based on the total solid content of the composition.

The polymer precursor may be contained in one kind or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

< radical polymerizable Compound having Sulfur atom >

The photosensitive resin composition of the present invention contains a radically polymerizable compound having a sulfur atom. One embodiment of the radically polymerizable compound having a sulfur atom is a radically polymerizable compound having a sulfur atom and having 2 or more (preferably 2 to 4, more preferably 2 to 3, still more preferably 2) radically polymerizable groups.

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

[ chemical formula 22]

R ¹² -X ¹² -L ¹¹ -X ¹¹ -R ¹¹ (3-1)

In the formula (3-1), L ¹¹ Represents a 2-valent linking group containing a sulfur atom, X ¹¹ X is X ¹² Respectively and independently representA single bond or a 2-valent linking group, R ¹¹ R is R ¹² Each independently represents a hydrogen atom or a 1-valent organic group; wherein R is ¹¹ R is R ¹² Represents a 1-valent organic group comprising at least one free radically polymerizable group; r is R ¹¹ R is R ¹² May bond to each other to form a ring.

In the formula (3-1), L ¹¹ Represents a 2-valent linking group containing a sulfur atom. The linking group is preferably a linking group having 1 or 2 sulfur atoms, more preferably a linking group having 1 or 2 sulfur atoms and having 2 to 6 atoms of oxygen atoms. Further preferably, L is defined as the formula (3-2) described later ¹ The same applies to the preferred ranges.

In the formula (3-1), X ¹¹ X is X ¹² Each 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, particularly preferably 1 to 6 carbon atoms), an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), -O-, -S-, -C (=o) -, -NR ³ -、-NR ³ CO-and combinations of these. R is R ³ R in the formula (3-2) described below ³ The same applies. Further, the linking group may be a hydrocarbon group. The hydrocarbon group may be an oligomeric hydrocarbon group, and in this case, the number of repetition 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, particularly preferably 1 to 6. When the number of atoms of the linking group is other than the oligomeric hydrocarbon group, the number of atoms is preferably 1 to 24, more preferably 1 to 12, particularly preferably 1 to 6. In the case of a (oligo) hydrocarbon group, the number of atoms is preferably 2 to 64, more preferably 2 to 32, particularly preferably 2 to 18.X is X ¹¹ X is X ¹² The represented 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, particularly preferably 1 to 3 atoms), and more preferably a 2-valent linking group containing an oxygen atom.

In the formula (3-1), R ¹¹ R is R ¹² Each independently represents a hydrogen atom or a 1-valent organic group. Examples of the 1-valent organic group include radical polymerizable groupsA 1-valent organic group, a substituent T described below, and the like. Examples of the radical polymerizable group include a group having a carbon-carbon unsaturated double bond. Among them, the radical polymerizable group is preferably a group having a vinyl group, an allyl group, an acryl group or a methacryl group, and more preferably a group having an acryl group or a methacryl group. More specifically, it is preferably an acryl group, a methacryl group, an acryloyloxy group, a methacryloyloxy group, an acrylamido group, a methacryloylamino group, a vinyl group, a vinylphenyl group (o, m, p), a vinylphenoxy group (o, m, p), a vinylphenylmethyl group (o, m, p), more preferably an acryl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamido group, a methacryloylamino group, and further preferably an acryloyloxy group, a methacryloyloxy group.

The 1-valent organic group containing a radical polymerizable group may be a group having only 1 radical polymerizable group, or may be a group having 2 or more radical polymerizable groups. When the 1-valent organic group containing a radical polymerizable group has 2 or more radical polymerizable groups, the plurality of radical 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 below within a range that does not impair the effects of the present invention. As the substituent, a substituent T described below can be exemplified. The number of radical polymerizable groups contained in 1-valent organic group is preferably 3 or less, more preferably 2 or less. In the present invention, a mode in which a 1-valent organic group containing a radical polymerizable group does not have a substituent may be preferably exemplified.

In the formula (3-1), R ¹¹ R is R ¹² Represents a 1-valent organic group comprising at least one free radically polymerizable group. Wherein R is ¹¹ R is R ¹² These two are preferably each independently a 1-valent organic group comprising a free radically polymerizable group.

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

In the formula (3-1), R ¹¹ R is R ¹² May bond to each other to form a ring. R is R ¹¹ R is R ¹² R when forming a ring ¹¹ R is R ¹² May be directly connected or connected via a linker L described below. And, the ring formed may be a condensed ring. As the linking group L, there may be mentioned a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6), -O-, -S-, -C (=O) -, -NR ³ -、-NR ³ CO-and linkers related to combinations of these. R is R ³ R in the following (3-2) ³ The same applies to the preferred ranges.

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

[ chemical formula 23]

R ² -la ¹ -X ² -La ² -L ¹ -La ³ -X ¹ -La ⁴ -R ¹ (3-2)

In the formula (3-2), L ¹ representing-S-, -S (=O) -, or-S (=O) ₂ -，X ¹ X is X ² Each independently represents a single bond, -O-, -C (=o) O-, -OC (=o) -, -S (=o) ₂ -or-NR ³ CO-，R ¹ R is R ² Independently of one another, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical-polymerizable group, la ¹ ～La ⁴ Each independently represents any one of a single bond, a group consisting of a combination of 1 or more of an alkylene group and a phenylene group, and a group consisting of a combination of 1 or more of an alkylene group and a phenylene group and-O-; r is R ³ Represents a hydrogen atom or an alkyl group; wherein R is ¹ R is R ² At least one of them is a radical polymerizable group.

In the formula (3-2), L ¹ Preferably represents-S-, -S-S-, -S (=o) -or-S (=o) ₂ -，-S(＝O)-。

X ¹ X is X ² Each independently represents a single bond, -O-, -C (=o) O-, -OC (=o) -, -S (=O) ₂ -or-NR ³ CO-, is preferably a single bond or-O-, more preferably-O-. R is R ³ Represents 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), or an alkyl group having the above carbon atoms.

R ¹ R is R ² Each 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, particularly preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms), or an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms).

R ¹ R is R ² When the substituent is an alkyl group, a cycloalkyl group or an aryl group, the substituent may have any substituent T within a range that does not impair the effect 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, particularly preferably 1 to 6), a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6), a hydroxyl group, a hydroxyalkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, a hydroxyl group having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms), an aminoalkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, a amino group having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), a mercapto group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, a mercapto group having preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), a carboxyl group, a carboxyalkyl group (preferably having 1 to 24 carbon atoms, particularly preferably 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 12 carbon atoms), an acyl group having 1 to 12 carbon atoms, particularly preferably 1 to 12 carbon atoms, Particularly preferably 1 to 3), aroyl (preferably 7 to 23, more preferably 7 to 19, particularly preferably 7 to 11) aroyloxy (preferably 7 to 23, more preferably 7 to 19, particularly preferably 7 to 11), oxy (=o), imino (=nr) ³ ) Alkylene (=c (R) ³ ) ₂ ) Etc.

Wherein R is ¹ R is R ² At least one of them represents a radical polymerizable group.

With respect to R ¹ R is R ² Examples of the radical polymerizable group represented by the formula (3-1) include those having the same definition as those of the compound exemplified by the formula. R is R ¹ R is R ² The two groups are preferably each independently a radical polymerizable group, more preferably the same radical polymerizable group.

In the formula (3-2), la ¹ ～La ⁴ Each independently represents any one of a single bond, a group consisting of a combination of 1 or more of an alkylene group and a phenylene group, and a group consisting of a combination of 1 or more of an alkylene group and a phenylene group and-O-. La (La) ¹ ～La ⁴ The linking groups may each independently have a single bond, an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6), a phenylene group, an (oligo) alkyleneoxy group (alkylene group is preferably having 1 to 24 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6, repeating number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3.), (oligo) alkyleneoxy group (alkylene group is preferably having 1 to 24 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6, repeating number is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3.) or a combination thereof. (oligo) alkyleneoxy means alkyleneoxy or oligoalkyleneoxy. The same holds true for the inclusion of other groups described under "(oligomeric)".

The alkylene group, phenylene group, the (oligo) alkyleneoxy group, and the optional substituent T may be further contained within a range not impairing the effect of the present invention.

La ¹ ～La ⁴ More preferably, each independently is a single bond or an alkylene group, still more preferably La ² La and La ³ Is a single bond, la ¹ La and La ⁴ Is an alkylene group.

R ¹ R is R ² May bond to each other to form a ring. R is R ¹ R is R ² R when forming a ring ¹ R is R ² May be directly connected or connected via the above-mentioned linking group L. And, the ring formed may be a condensed ring.

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

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

[ chemical formula 24]

[ chemical formula 25]

In the above exemplified 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, still more preferably 0.01 mass% or more, still more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and still more preferably 0.3 mass% or more, based on the total solid content of the composition. The upper limit value is preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, and further may be 7 mass% or less, 5 mass% or less, 2 mass% or less, or 1 mass% or less.

The amount of the radically polymerizable compound having a sulfur atom to be 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, still more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less, based on the total of the radically polymerizable compound and other polymerizable compounds described later. The polymerizable compound is preferably 0.1 part by mass or more, but may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more.

The lower limit of the ratio of the radical polymerizable compound having a sulfur atom in the total polymerizable compounds including other polymerizable compounds described later is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, still more preferably 0.1 mass% or more, still more preferably 0.3 mass% or more, and still more preferably 0.5 mass% or more. 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, or 1% by mass or less.

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

The radical polymerizable compound having a sulfur atom may be contained in one kind or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

< 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 may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. And, may be an active agent that exerts some effect with the photoexcited sensitizer and generates active radicals.

The photo radical polymerization initiator preferably contains at least one compound having an absorbance of at least about 50 moles in the range of about 300 to 800nm (preferably 330 to 500 nm). The molar absorptivity of the compounds can be determined by known methods. For example, it is preferable to measure the content by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

The photosensitive resin composition of the present invention contains a photo radical polymerization initiator, and after 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, light is irradiated, whereby curing due to radicals occurs and the solubility in a light irradiation section can be reduced. Therefore, for example, there is an advantage that the photosensitive resin composition layer is exposed to light through a photomask having a pattern that shields only the electrode portion, whereby the regions having different solubilities can be easily produced according to the pattern of the electrode.

As the photo radical polymerization initiator, known compounds can be arbitrarily used, and examples thereof include halogenated hydrocarbon derivatives (for example, 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, iron aromatic hydrocarbon complexes, and the like. For details of these, reference is made to paragraphs 0165 to 0182 of Japanese unexamined patent publication No. 2016-027357, which is incorporated herein by reference.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, which is incorporated herein by reference. Among the commercial products, KAYACURE DETX (Nippon Kayaku co., ltd.) is also preferably used.

As the photo radical polymerization initiator, it is also possible to preferably use hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in JP-A-4225898 can also be used.

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

As the aminoacetophenone initiator, IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade name: all manufactured by BASF corporation) which are commercially available products can be used.

As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179 having a maximum absorption wavelength matching a light source having a wavelength of 365nm or 405nm or the like can be used.

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

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

As the photo radical polymerization initiator, an oxime compound is more preferably exemplified. By using an oxime compound, the exposure latitude can be further effectively improved. Among oxime compounds, an oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photobase generator.

Specific examples of the oxime compound include a compound described in JP-A-2001-233836, a compound described in JP-A-2000-080068, and a compound described in JP-A-2006-342166.

Preferable oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxyimino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino1-phenylpropane-1-one having the following structures. The oxime photopolymerization initiator is preferably used in the photosensitive resin composition of the present invention. The oxime-based photopolymerization initiator has a linking group of > c=n-O-C (=o) -in the molecule.

[ chemical formula 26]

Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02 (the above is manufactured by BASF corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) may be preferably used. In addition, TR-PBG-304 (manufactured by Hezhou powerful electronic New materials Co., ltd.), ADEKAARKLS NCI-831 and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Further, DFI-091 (DAITO CHEMIX Co., ltd.) can be used.

Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of these oxime compounds include a compound described in JP 2010-26261028A, a compound 24 described in paragraph 0345 of JP 2014-500852A, a compound 36-40 described in paragraphs 0347-0348, a compound (C-3) described in paragraph 0101 of JP 2013-164471, and the like.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like.

From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl 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, 3-aryl substituted coumarin compounds.

More preferred photo-radical polymerization initiator is a trihalomethyltriazine compound, an α -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, preferably at least one compound selected from the group consisting of trihalomethyltriazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, still more preferably a metallocene compound or oxime compound, still more preferably an oxime compound.

The photo radical polymerization initiator may be a benzoin ether compound such as a benzoin ketone, an N, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), a benzoin ether compound such as benzoin, an alkyl benzoin, a benzyl derivative such as benzyl dimethyl ketal, or the like. Further, a compound represented by the following formula (I) can also be used.

[ chemical formula 27]

In the formula (I), R ^I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atomsAt least one substituted phenyl or biphenyl group selected from 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 interrupted by 1 or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, R ^I01 Is a group represented by formula (II), or is a group represented by formula (II) and R ^I00 The same radicals R ^I02 ～R ^I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[ chemical formula 28]

Wherein R is ^I05 ～R ^I07 R is the same as the R of the formula (I) ^I02 ～R ^I04 The same applies.

The photo radical polymerization initiator may be any of the compounds described in paragraphs 0048 to 0055 of International publication WO 2015/125469.

The content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The photo radical polymerization initiator may be contained in one kind or two or more kinds. When two or more photo radical polymerization initiators are contained, the total thereof is preferably in the above range.

< 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 starts or accelerates the polymerization reaction of a compound having polymerizability. By adding a thermal radical polymerization initiator, cyclization of the polymer precursor can be performed and 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. 2008-063254.

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 even more preferably 5 to 15% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The thermal radical polymerization initiator may be contained in one kind or two or more kinds. When two or more thermal radical polymerization initiators are contained, the total thereof is preferably within 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 preferable 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 alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-alkoxy-2-methylpropionate, methyl 2-alkoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-ethoxypropionate, etc. Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 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.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone.

Examples of the aromatic hydrocarbon include toluene, xylene, anisole, and limonene.

Examples of sulfoxides include dimethyl sulfoxide, which is a preferred sulfoxide.

As the amides, preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, and the like.

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

In the present invention, it is preferable that the solvent be one or a mixture of two or more 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. It is particularly preferred to use dimethyl sulfoxide and gamma-butyrolactone simultaneously.

The content of the solvent is preferably 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 an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 75% by mass, still more preferably an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 10 to 70% by mass, and still more preferably an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 40 to 70% by mass, from the viewpoint of coatability. The content of the solvent may be adjusted according to the desired thickness and coating method.

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

< other polymerizable Compound >

Polymerizable Compound containing no Sulfur atom

The photosensitive resin composition of the present invention preferably contains a radically polymerizable compound containing no sulfur atom (hereinafter referred to as "sulfur atom-free polymerizable monomer") in addition to the radically polymerizable compound containing a sulfur atom. By adopting these configurations, a cured film excellent in 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 ethylenic 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 in the polymerizable monomer containing no sulfur atom may be one or 2 or more, but the polymerizable monomer containing no sulfur atom is preferably a radical polymerizable group having 2 or more, more preferably 3 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and even more 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. 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 is preferably a polymerizable monomer containing at least one sulfur atom-free monomer having 2 or more functions containing 2 or more polymerizable groups, and more preferably a polymerizable monomer containing at least one sulfur atom-free monomer having 3 or more functions. Further, the polymerizable monomer may be a mixture of a polymerizable monomer having no sulfur atom having 2 functions and a polymerizable monomer having no sulfur atom having 3 functions or more. The number of functional groups of the polymerizable monomer containing no sulfur atom means the number of radical polymerizable groups in 1 molecule.

Specific examples of the polymerizable compound not containing a sulfur atom include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids with a polyhydric alcohol compound and amides of unsaturated carboxylic acids with a polyhydric amine compound. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an affinity substituent such as a hydroxyl group or an amino group with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Also, a substitution reactant of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol or amine and a substitution reactant of an unsaturated carboxylic acid ester or amide having a dissociative substituent such as a halogen group with a monofunctional or polyfunctional alcohol or amine is preferable. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like can be used. For a specific example, reference is made to paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, and these are incorporated herein by reference.

The polymerizable monomer containing no sulfur atom is preferably a compound having a boiling point of 100 ℃ or higher at 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, tri (acryloxyethyl) isocyanato, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerol or trimethylolethane and then subjecting the resultant mixture to (meth) acrylation, and functional acrylates such as those described in Japanese patent application publication No. 48-041708, japanese patent application publication No. 50-006034, the (meth) acrylic acid carbamates described in Japanese patent application publication No. 51-037193, japanese patent application publication No. 48-064183, japanese patent application publication No. 49-043191, and Japanese patent application publication No. 52-030490. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenic unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can be also mentioned.

Further, as a preferable polymerizable monomer containing no sulfur atom other than the above, a compound having a fluorene ring and having 2 or more groups containing ethylenic unsaturated bonds or a cardo resin described in japanese patent application laid-open publication No. 2010-160418, japanese patent application laid-open publication No. 2010-129825, japanese patent application No. 4364216, and the like can also be used.

Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 1-040337 and Japanese patent publication No. 1-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 2-025493. Furthermore, a perfluoroalkyl group-containing compound described in Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, those described as photocurable monomers and oligomers in "Journal of the Adhesion 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 are incorporated herein.

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

Furthermore, 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 are incorporated herein.

The polymerizable monomer containing no sulfur atom is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by Ltd.), A-TMMT: shin-Nakamura Chemical Co., manufactured by Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD-310;Nippon Kayaku Co, manufactured by Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; nippon Kayaku Co., manufactured by Ltd., A-DPH; shin-Nakamura Chemical Co., manufactured by Ltd.), or a structure in which the (meth) acryloyl groups are bonded via a glycol residue and a propylene glycol residue. These oligomer types can also be used.

Examples of the commercially available polymerizable monomer not containing sulfur atom include SR-494 which is a 4-functional acrylate having 4 ethyleneoxy chains, sartomer Company, inc, SR-209 which is a 2-functional methyl acrylate having 4 ethyleneoxy chains, nippon Kayaku Co., ltd., DPCA-60 which is a 6-functional acrylate having 6 ethyleneoxy chains, TPA-330 which is a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, urethane oligomer UAB-140 (NIPPON PAPER INDUSTRIES CO., LTD), NK ester M-40G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin-Nakamura Chemical, ltd.), DPHA-40H (ppkayaku, td., 306-306, UAS-35, and UK.600, WO 35-600, and so on, and the like, which are manufactured by the same.

As the other polymerizable monomer, urethane acrylate compounds having an ethylene oxide skeleton as described in Japanese patent publication No. Sho 48-041708, japanese patent application laid-open No. Sho 51-037193, japanese patent application laid-open No. Hei 2-032293 and Japanese patent application laid-open No. Hei 2-016765, japanese patent application laid-open No. Sho 58-049860, japanese patent application laid-open No. Sho 56-017654, japanese patent application laid-open No. Sho 62-039417 and Japanese patent application laid-open No. Sho 62-039418 are also preferred. Further, as the polymerizable monomer containing no sulfur atom, a compound having an amino structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 can also 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 phosphate 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. Particularly, among the polymerizable monomers having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, the aliphatic polyhydroxy compound is preferably a compound which is pentaerythritol and/or dipentaerythritol. Examples of the commercially available products include polyacid-modified acrylic oligomers produced by TOAGOSEI CO., ltd. Include M-510 and M-520.

The polymerizable monomer having an acid group may be used alone or in combination of two or more. Further, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used together as required.

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

From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional polymerizable monomer as the polymerizable monomer containing no sulfur atom. 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-hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and the like can be preferably used. The monofunctional polymerizable monomer is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure in order to suppress volatilization before exposure.

Polymerizable Compound other than the radically polymerizable Compound described above

The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radical polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; an epoxy compound; oxetane compounds; 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 (AM 1), (AM 4) or (AM 5).

[ chemical formula 29]

(wherein t represents an integer of 1 to 20, R ⁴ A t-valent organic group having 1 to 200 carbon atoms, R ⁵ Represented by-OR ⁶ or-OCO-R ⁷ A group represented by R ⁶ R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms ⁷ An organic group having 1 to 10 carbon atoms. )

[ chemical formula 30]

(wherein R is ⁴⁰⁴ A 2-valent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ Represented by-OR ⁴⁰⁶ or-OCO-R ⁴⁰⁷ A group represented by R ⁴⁰⁶ R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms ⁴⁰⁷ An organic group having 1 to 10 carbon atoms. )

[ chemical formula 31]

(wherein u represents an integer of 3 to 8, R ⁵⁰⁴ A u-valent organic group having 1 to 200 carbon atoms, R ⁵⁰⁵ Represented by-OR ⁵⁰⁶ Or, -OCO-R ⁵⁰⁷ A group represented by R ⁵⁰⁶ R represents a hydrogen atom or an organic group having 1 to 10 carbon atoms ⁵⁰⁷ An organic group having 1 to 10 carbon atoms. )

When the photosensitive resin composition is applied to a substrate having irregularities, the occurrence of cracks can be more effectively suppressed by using the compound having a hydroxymethyl group or the like. Further, a cured film having high heat resistance, which is excellent in patterning property and has a temperature reduced by 5 mass% to 350 ℃ or higher, more preferably 380 ℃ or higher, can be formed. Specific examples of the compound represented by the formula (AM 4) include 46DMOC, 46DMOEP (trade name, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34-X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., ltd.), 2, 6-dimethylmethyl-4-t-buthylphenol (2, 6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethylmethyl-p-cresol (2, 6-dimethoxymethyl-p-cresol), 2, 6-dimethylmethyl-p-diacetoxycresol, and the like.

Specific examples of the compound represented by the formula (AM 5) 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 above, honshu Chemical Industry Co., ltd.), TM-BIP-A (trade name, ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name above, sanwa Chemical Co., ltd.).

(epoxy Compound (Compound having epoxy group))

The epoxy compound is preferably a compound having 2 or more epoxy groups in one molecule. The epoxy undergoes a crosslinking reaction based on 200 ℃ or less, and hardly causes film shrinkage since it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing the epoxy compound, low-temperature curing and warpage of the composition can be effectively suppressed.

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

Examples of 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, and epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane. Specifically, 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 name, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, new Japan Chemical, 35 Co. 35, manufactured by Ltds 4000, etc. are exemplified. Among these, polyethylene oxide group-containing epoxy resins are preferable in view of suppression of warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, RIKARESIN (registered trademark) BEO-60E contains a polyethylene oxide group, and is preferable.

(oxetane Compound (Compound having an oxetanyl group))

Examples of oxetane compounds include compounds having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. As specific examples, TOAGOSEI co.ltd. ARON oxide series (e.g., next-121, next-221, next-191, next-223) can be preferably used, and these may be used alone or two or more kinds may be used in combination.

(benzoxazine Compound (Compound having polybenzoxazole group))

The benzoxazine compound is preferable because it does not generate outgas during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.

Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and novolak type dihydrobenzoxazine compounds. 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 mass% or more. The upper limit is more preferably 50 mass%, and still more preferably 30 mass% or less.

The other polymerizable compounds may be used alone or in combination of two or more. When two or more kinds are used simultaneously, the total amount thereof is preferably within the above range.

< migration inhibitor >

Preferably, the photosensitive resin composition of the present invention further comprises a migration inhibitor. By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively inhibited.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocycle (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 thiourea and mercapto groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and benzotriazole can be preferably used.

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

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

Specific examples of migration inhibitors include the following compounds.

[ chemical formula 32]

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the photosensitive resin composition.

The migration inhibitor may be one kind or two or more kinds. When the migration inhibitor is two or more, the total thereof 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, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso-N- (1-naphtyl) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl) phenylmethane and the like can be preferably used. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International publication WO2015/125469 can also be used.

In addition, 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 one kind or two or more kinds. When the polymerization inhibitor is two or more, the total amount thereof is preferably in the above range.

< Metal adhesion improver >

The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. As the metal adhesion improver, a silane coupling agent and the like can be exemplified.

Examples of the silane coupling agent include a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International publication WO2011/080992A1, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-04264, and a compound described in paragraph 0055 of International publication WO 2014/097594. 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. The following compounds are also preferably used as the silane coupling agent. In the following formula, et represents ethyl.

[ 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 in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and particularly preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor. By setting the lower limit value or more, the adhesion between the cured film after the curing step and the metal layer is improved, and by setting the upper limit value or less, the heat resistance and mechanical properties of the cured film after the curing step are improved. The metal adhesion improver may be one or two or more. When two or more kinds are used, the total thereof is preferably in the above range.

< alkali Generator >

The photosensitive resin composition of the present invention may contain a base generator. The base generator may be a thermal base generator or a photobase generator.

Hot alkali producing agent

The type of the thermal base generator is not particularly limited, but is preferably a thermal base generator containing at least one selected from the group consisting of an acidic compound that generates a base when heated to 40 ℃ or higher and an ammonium salt having an anion with pKa1 of 0 to 4 and an ammonium cation. Wherein pKa1 represents a logarithmic sign (-Log) of the dissociation constant (Ka) of the first proton of the polyacid ₁₀ Ka)。

By blending these compounds, the cyclization reaction of the polymer precursor can be performed at a low temperature, and a composition having more excellent stability can be obtained. Further, since the thermal base generator does not generate a base unless it is heated, cyclization of the polymer precursor during storage can be suppressed and the storage stability is excellent even if it is coexistent with the polymer precursor.

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

Since the acid compound (A1) and the ammonium salt (A2) form a base when heated, the base formed from these compounds can promote the cyclization reaction of the polymer precursor and can cyclize the polymer precursor at a low temperature. In addition, even if these compounds coexist with a polymer precursor which is cyclized and cured by a base, the cyclization of the polymer precursor hardly proceeds unless heating is performed, and therefore, a polymer precursor excellent in stability can be produced.

In the present specification, the 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 (mass ratio of water/tetrahydrofuran=1/4) is added. Stir at room temperature for 1 hour. Compounds having a value of less than 7 were measured at 20 ℃ using 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 base generation temperature is preferably 190℃or lower, more preferably 180℃or lower, and still more preferably 165℃or lower. The lower limit of the base generation temperature is preferably 130℃or higher, more preferably 135℃or higher.

The alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ℃ or higher, and thus, alkali is not easily generated during storage, and a polymer precursor having excellent stability can be produced. The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) can be reduced by the cyclization temperature of the polymer precursor or the like as long as it is 200 ℃. As for the base generation temperature, for example, a compound can be measured by heating the compound to 250 ℃ at 5 ℃/min in a pressure-resistant capsule by differential scanning calorimetric measurement, reading the peak temperature of the lowest heat generation peak, and measuring the peak temperature as the base generation temperature.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Tertiary amines are highly basic and therefore lower the cyclization temperature of the polymer precursor. The boiling point of the base generated by the thermal base generator is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and even more preferably 140 ℃ or higher. The molecular weight of the produced base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains at least one compound selected from ammonium salts and compounds represented by the following formula (101) or (102).

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 that generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃), or may be a compound other than an acidic compound that generates a base when heated to 40 ℃ or higher (preferably 120 to 200 ℃).

The ammonium salt used as the thermal base generator is preferably a salt of an ammonium cation represented by the following formula (101) or formula (102) with an anion. The anion may be bonded to any part 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. In addition, the fact that the anion is outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded by covalent bonds. Hereinafter, anions outside the molecule of the cation portion are also referred to as anions.

[ chemical formula 35]

Wherein R is ^N1 ～R ^N6 Each independently represents a hydrogen atom or a hydrocarbon group (preferably 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 12 carbon atoms), preferably an alkyl group (preferably 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 23 carbon atoms), an alkenyl group (preferably 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, particularly preferably 2 to 23 carbon atoms), an alkynyl group (preferably 1 to 36 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 23 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms).

R ^N7 Represents a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), preferably an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms).

R ^N1 And R is R ^N2 、R ^N3 And R is R ^N4 、R ^N5 And R is R ^N6 、R ^N5 And R is R ^N7 May bond to each other to form a ring. The above-mentioned linker L or a hetero-linker Lh described later may be incorporated in the middle of the ring when forming the ring. Within the range that does not impair the effect of the present invention, R ^N1 ～R ^N7 May haveThe aforementioned substituent T.

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

[ chemical formula 36]

In the formulae (Y1-1) to (Y1-6), R ^N101 Examples of the organic group having a valence of Nn (Nn is an integer of 1 to 12) include an alkane-based valence of Nn (preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), an olefin-based valence of Nn (preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 to 3), an aromatic hydrocarbon-based valence of Nn (preferably 6 to 22, more preferably 6 to 18, and particularly preferably 6 to 10), and a combination of these. R is R ^N101 Among them, aromatic hydrocarbon groups are preferable. Within the range that does not impair the effect of the present invention, R ^N101 May have the aforementioned substituent T. When R is ^N101 When an alkane-based group or an alkene-based group is used, the following hetero-linking group Lh may be incorporated.

R ^N1 R is R ^N7 R in the formula (101) or (102) ^N1 R is R ^N7 The same applies.

R ^N8 Alkyl (preferably having 1 to 36 carbon atoms, more preferably having 2 to 24 carbon atoms, particularly preferably having 4 to 18 carbon atoms), alkenyl (preferably having 2 to 36 carbon atoms, more preferably having 2 to 24 carbon atoms, particularly preferably having 4 to 18 carbon atoms), alkynyl (preferably having 2 to 36 carbon atoms, more preferably having 2 to 24 carbon atoms, particularly preferably having 4 to 18 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, particularly preferably having 6 to 10 carbon atoms). In this case, a linking group Lh having a heteroatom may be incorporated in the alkyl group, alkenyl group, alkynyl group, or 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, examples thereof include-O-, -S-; -C (=o) -NR ³ -a linker of a combination of these. The number of the linking groups Lh having a hetero atom is preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3.R is R ³ Is a hydrogen atom or an alkyl group (preferably methyl group)). Within the range that does not impair the effect of the present invention, R ^N8 Further, the above substituent T may be present.

Preferably R ^N9 To define and R ^N8 The same groups. Among them, an aryl group-containing group is preferable, an aroyl group-containing group is more preferable, and an aroylalkyl group (an alkyl group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3) is particularly preferable. 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 that does not impair the effect of the present invention.

Ar in the formula (Y1-4) ^N101 Ar and Ar ^N102 Each independently represents an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 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, particularly preferably an integer of 1 to 3.

R ^N1 Each other, R ^N1 And R is R ^N8 、R ^N1 And R is R ^N7 、R ^N1 And R is R ^N9 、R ^N1 With Ar ^N101 、R ^N1 With Ar ^N102 、Ar ^N101 With Ar ^N102 May be bonded separately to form a ring. The above-mentioned linker L or a hetero-linker Lh described later may be incorporated in the middle of the ring when forming the ring.

In this 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, and still more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. If the pKa1 of the anion is within 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. If pKa1 is 4 or less, the thermal base generator has good stability, and the generation of base is suppressed without heating, and the composition has good stability. If the pKa1 is 0 or more, the produced base is not easily neutralized, and the cyclization efficiency of the polymer precursor or the like is good.

The type of the anion is preferably one selected from the group consisting of a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion, and is more preferably a carboxylic acid anion from the viewpoint of achieving both stability of the salt and thermal decomposition property. That is, the ammonium salt is more preferably a salt of an ammonium cation with a carboxylic acid anion.

The carboxylic acid anion is preferably an anion of a carboxylic acid having 2 or more carboxyl groups and having 2 or more valences, more preferably an anion of a carboxylic acid having 2 or more valences. According to this aspect, the composition can be further improved in stability, curability, and developability. In particular, by using an anion of a 2-valent carboxylic acid, the stability, curability, and developability of the composition can be further improved.

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

Here, pKa1 represents the logarithmic expression (-Log) of the dissociation constant (ka) of the first proton of the polyacid ₁₀ Ka), and can refer to Determination of Organic Structures by Physical Methods (author: brown, H.C., mcDaniel, D.H., haflinger, o., nacmod, f.c.; editing: braude, e.a., nacmod, f.c.; academic Press, new York, 1955), data for Biochemical Research (author: dawson, r.m.c.et al; oxford, clarendon Press, 1959). For the compounds not described in these documents, values calculated by the structural formula using software of 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.

In the present embodiment, the electron withdrawing group is a group in which the hamite substituent constant σm represents a positive value. Among them, σm is described in detail in Dou Yexiong, journal of Synthetic Organic Chemistry, japanese 23, volume 8 (1965) p.631-642. The electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents.

Examples of substituents in which σm represents a positive value include CF ₃ Base (σm=0.43), CF ₃ CO group (σm=0.63), hc≡c group (σm=0.21), CH ₂ The group=ch (σm=0.06), ac (σm=0.38), meOCO (σm=0.37), mecoch=ch (σm=0.21), phCO (σm=0.34), H ₂ NCOCH ₂ Base (σm=0.06), and the like. In addition, me represents methyl, ac represents acetyl, and Ph represents phenyl (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 ^x3 Each independently represents 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 aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), a hydroxyl group or a carboxyl group. Wherein R of the formula (EWG-1) ^x1 R of formula (EWG-4) ^x1 Not a carboxyl group. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms). When R is ^x1 ～R ^x3 When the alkyl group, alkenyl group or aryl group is used, a ring may be formed, and the above-mentioned linker L or a hetero-linker Lh described later may be incorporated in the middle of the ring formation. When R is ^x1 ～R ^x3 In the case of an alkyl group, an alkenyl group or an aryl group, ar may have a substituent T within a range that does not impair the effect 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, particularly preferably 1 or 2.

In this embodiment, the carboxylic acid anion is preferably represented by the following formula (XA).

(XA)

[ chemical formula 39]

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

Details of the thermal base generator can be referred to in paragraphs 0021 to 0077 of Japanese patent application laid-open No. 2016-027357, and these are incorporated herein by reference.

As the thermal base generator, the following compounds are exemplified.

[ chemical formula 40]

[ chemical formula 41]

[ chemical formula 42]

[ chemical formula 43]

When a thermal base generator is used, the content of the thermal base 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 mass% or more, and still more preferably 0.5 mass% or more. The upper limit is more preferably 20 mass% or less, and still more preferably 10 mass% or less.

One or two or more kinds of thermal alkali generators can be used. When two or more kinds are used, the total amount is preferably in the above range.

In addition, as an embodiment of the present invention, the composition may be configured to substantially not include a thermal alkali generator. Substantially not included means that the content is less than 0.1 mass% of the total solid content of the composition, and further, may be 0.01 mass% or less, and particularly, may be 0.001 mass% or less.

Photobase generator

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 show activity under normal temperature and pressure conditions, but is not particularly limited as long as it generates a base (alkaline substance) when irradiated with electromagnetic waves and heated as external stimulus. The base generated by exposure functions as a catalyst when curing by heating the polymer precursor, and therefore can be preferably used when performing the development treatment.

In the present invention, a known photobase generator can be used as the photobase generator. For example, as in M.Shirai, and M.Tsunooka, prog.Polym.Sci.,21,1 (1996); the red sage root is forward grown, and macromolecule processing is carried out, 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); winkle, and K.Graziano, J.Photopolym.Sci.Technol.,3,419 (1990); M.Tsunooka, H.Tachi, and S.Yoshitaka, J.Photopolym.Sci.Technol.,9,13 (1996); K.Suyama, H.Araki, M.Shirai, J.Photopolym.Sci.Technol.,19,81 (2006) describes a transition metal compound complex, a substance having a structure such as an ammonium salt, or a nonionic compound in which an amidine moiety is a compound that is potentially rendered by formation of a carboxylic acid or a salt, an ionic compound in which a base component is neutralized by formation of a salt, a urethane bond or an oxime bond such as a urethane derivative, an oxime ester derivative, or an acyl compound, and the base component is potentially rendered by formation of a salt.

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

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

From the viewpoint of the above-mentioned catalyst effect, the basic substance is preferably an amidine or an aliphatic amine.

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

Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in japanese patent application laid-open publication No. 2009-080452 and international publication No. 2009/123122, a photobase generator having a urethane structure as disclosed in japanese patent application laid-open publication No. 2006-189591 and japanese patent application laid-open publication No. 2008-247747, a photobase generator having an oxime structure and a carbamoyl oxime structure as disclosed in japanese patent application laid-open publication No. 2007-249013 and japanese patent application laid-open publication No. 2008-003581, but the present invention is not limited to these, and other known photobase generators may be used.

Examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP-A2012-093746, compounds described in paragraphs 0022 to 0069 of JP-A2013-194205, compounds described in paragraphs 0026 to 0074 of JP-A2013-204019, and compounds described in paragraph 0052 of International publication WO 2010/064631.

As commercial products of the photobase generator, 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.) can also be used.

The following compounds are exemplified as the photobase generator. Et represents ethyl, 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 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less.

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

In addition, as an embodiment of the present invention, the composition may be configured to substantially not include the photobase generator. Substantially not included means that the content is less than 0.1 mass% of the total solid content of the composition, and further, may be 0.01 mass% or less, and particularly, may be 0.001 mass% or less.

< other additives >

The photosensitive resin composition of the present invention can be blended with 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, a coagulation inhibitor, and the like as needed, within a range that does not impair the effects of the present invention. When these additives are blended, the total blending amount 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. The thermal acid generator generates an acid by heating and promotes cyclization of the polymer precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include the compounds described in paragraph 0059 of JP-A2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymer precursor. Since the crosslinking reaction and cyclization of the polymer precursor are promoted by containing 0.01 parts by mass or more of the thermal acid generator, the mechanical properties and drug resistance of the cured film can be further improved. 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 electrical insulation of the cured film.

The thermal acid generator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

Sensitization pigment

The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron excited state. The sensitizing dye in an electron excited state is brought into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like, and thereby causes an effect such as electron transfer, energy transfer, heat generation, or the like. Thus, the thermal base generator, the thermal radical polymerization initiator, and the photo radical polymerization initiator chemically change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, reference is made to 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 sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the photosensitive resin composition of the present invention. The sensitizing dye may be used alone or in combination of two or more.

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 pages 683-684 of the third edition of the Polymer dictionary (society of Polymer (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 supply hydrogen to the low-activity radicals to generate radicals, or after oxidation, the radicals can be generated by deprotonation. In particular, thiol compounds (e.g., 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) 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 even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. The chain transfer agent may be one kind or two or more kinds. When the chain transfer agent is two or more, the total range is preferably the above range.

Surfactant(s)

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

[ chemical formula 45]

When the photosensitive resin composition of the present invention has 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. The surfactant may be one kind or two or more kinds. When the number of the surfactants is two or more, the total range is preferably the above range.

Higher fatty acid derivative

In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide 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 higher fatty acid derivative may be one kind or two or more kinds. When the number of higher fatty acid derivatives is two or more, the total range is preferably the above range.

< restriction on other substances contained >

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

The metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million (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 total 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 is 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 filtered by a filter, and the raw material is lined in a device with polytetrafluoroethylene or the like to carry out distillation or the like under a condition in which contamination is suppressed as much as possible.

From the viewpoint of wiring corrosiveness, the content of halogen atoms 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. Among them, the halogen ion is preferably present in an amount of less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is in the above range.

As the container for containing the photosensitive resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6 layers of resins constituting the inner wall of the container and a bottle having 6 types of resins in a 7-layer structure are also preferably used for the purpose of suppressing the mixing of impurities into the raw material or the composition. Examples of the container include those described in Japanese patent application laid-open 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 performed by a conventionally known method.

In order to remove foreign matters such as garbage and fine particles in the composition, filtration using a filter is preferable. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be a filter previously washed with an organic solvent. In the filtration step of the filter, a plurality of filters may be used in parallel or in series. When a plurality of filters are used, filters having different pore diameters and/or materials may be used in combination. And, various materials may be filtered multiple times. When the filtration is performed a plurality of times, the filtration may be a cyclic filtration. And, filtration may be performed after pressurization. When filtration is performed after pressurization, the pressure at which pressurization is performed is preferably 0.05MPa or more and 0.3MPa or less.

In addition to filtration using a filter, 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. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon are mentioned.

< cured film, laminate, semiconductor device, and method for producing the same >

Next, a cured film, a laminate, a semiconductor device, and methods for manufacturing these will be described.

The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, 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 as a laminate. The laminate of the cured film of the present invention having 2 or more layers preferably has a metal layer between the cured films. These metal layers may 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, the present invention can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.

The cured film of the present invention can also be used for the production of a plate surface such as an offset plate surface or a screen plate surface, the use of molded parts, the production of protective paint and dielectric layers in electronics, particularly microelectronics, and the like.

The method for producing a cured film of the present invention comprises using the photosensitive resin composition of the present invention. The following method for producing a cured film is preferable, and the method comprises the steps of: 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 development treatment step of developing 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 preferable that the photosensitive resin composition layer forming step, the exposure step and the development treatment step are further sequentially performed again. In particular, it is preferable that the photosensitive resin composition layer forming step, the exposure step and the development treatment step are sequentially performed 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be obtained. In the present invention, particularly after providing the cured film for development, it is preferable to provide a metal layer at the portion removed by development.

Details of these are 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 can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc., metal substrates such as quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, ni, cu, cr, fe, etc., papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of Plasma Display Panels (PDP), etc. In the present invention, a semiconductor production 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 becomes a substrate.

As a method for applying the photosensitive resin composition to a substrate, coating is preferable.

Specifically, examples of the application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of thickness of the photosensitive resin composition layer, spin coating, slit coating, spray coating, and inkjet method are more preferable. By adjusting the appropriate solid content concentration and coating conditions 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 spin coating, spray coating, ink jet method, or the like is preferable as long as the substrate is a circular substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable as long as the substrate is a rectangular substrate. In the case of spin coating, the spin speed of 500 to 2000rpm can be used for about 10 seconds to 1 minute.

Drying Process

The method for producing a laminate of the present invention may further include a step of drying the photosensitive resin composition layer after forming the photosensitive resin composition layer to remove the solvent. The drying temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, still more preferably 90 to 110 ℃. 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 amount is not particularly limited in a range where the photosensitive resin composition can be cured, and for example, the exposure energy at 365nm is preferably 100 to 10000mJ/cm in terms of irradiation ² More preferably 200 to 8000mJ/cm ² 。

The exposure wavelength can be appropriately set in the range of 190 to 1000nm, preferably 240 to 550nm.

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

Development treatment Process

The method for producing a laminate of the present invention may include a development treatment step of developing the exposed photosensitive resin composition layer. By performing development, an unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, spin-coating immersion, spraying, dipping, ultrasonic wave, or other developing methods can be employed. The development is performed using a developer. The developer is not particularly limited as long as the unexposed portion (non-exposed portion) can be removed. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP of-1 to 5, more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be calculated by inputting structural formula by chembio draw (chemical biological map).

As the organic solvent, for example, ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxymethyl, ethyl 2-ethoxypropionate), ethyl 2-alkoxy-2-methyl 2-methoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc. may be suitably cited Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like, and as sulfoxides, dimethyl sulfoxide, and the like, can be suitably cited.

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

The organic solvent is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more of the developing solution. Further, 100 mass% of the developer may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly limited, and can be usually set at 20 to 40 ℃.

After the treatment with the developer, further washing can be performed. The rinsing is preferably performed with a solvent different from the developer. For example, the photosensitive resin composition may be rinsed with a solvent contained therein. The rinsing time is preferably 5 seconds to 1 minute.

Heating Process

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

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

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

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

In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180 to 320 ℃, and more preferable to heat at 180 to 260 ℃ from the viewpoint of adhesion between layers of the cured film. The reason for this is not necessarily clear, but it is considered that the acetylene groups of the polymer precursors between the layers undergo a crosslinking reaction by setting the temperature.

The heating may be performed in stages. As an example, a pretreatment process may be performed in which the temperature is raised from 25 ℃ to 180 ℃ at 3 ℃/min, and kept at 180 ℃ for 60 minutes, and the temperature is raised from 180 ℃ to 200 ℃ at 2 ℃/min, and kept at 200 ℃ for 120 minutes. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. The film characteristics can be improved by these pretreatment steps. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more step, and for example, the pretreatment step 1 may be performed at 100 to 150 ℃ and the pretreatment step 2 may be performed at 150 to 200 ℃.

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

The heating step is preferably performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, for example, in order to prevent decomposition of the polymer precursor. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.

Metal layer forming step

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 a 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 still more preferably copper.

The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, and Japanese patent application laid-open No. 2004-101850 can be used. For example, photolithography, peeling, electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method using a combination of sputtering, photolithography, and etching, and a patterning method using a combination of photolithography and electrolytic plating can be cited.

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

Lamination Process

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

The lamination step is a series of steps including the step of forming the photosensitive resin composition layer, the exposure step, and the development step again in this order. Of course, the lamination step may include the drying step, the heating step, and the like.

When the lamination step is further 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, a plasma treatment is exemplified.

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

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

That is, in the present invention, in particular, after the metal layer is provided, it is preferable that the photosensitive resin composition layer forming step, the exposure step, and the development treatment step be performed in this order so as to cover the metal layer. By alternately performing the lamination step of laminating the photosensitive resin composition layers (resin layers) and the metal layer formation step, the photosensitive resin composition layers (resin layers) and the metal layers can be alternately laminated.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the photosensitive resin composition of the present invention is used for formation of an interlayer insulating film for a re-wiring layer, reference is made to paragraphs 0213 to 0218 of japanese patent application laid-open publication No. 2016-027357 and to the description of fig. 1, and these are incorporated herein by reference.

Examples

The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment steps and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

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 produce a diester of 4,4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to-10℃and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃ ₂ . After dilution with 50mL of N-methylpyrrolidone, 38.0g of a solution of a hydroxyl group-containing diamine (a) shown below in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10℃for 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Then, the polyimide precursor was precipitated in water by pouring it into 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The polyimide precursor solid was filtered and dissolved in 380g of tetrahydrofuran. The resulting solution was poured into 6 liters of water to precipitate a polyimide precursor in water and filtered, and dried at 45℃under reduced pressure for 3 days. The polyimide precursor has a weight average molecular weight of 27400 and a number average molecular weight of 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 ]

A diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate was produced by mixing 14.9g of pyromellitic dianhydride, 18.0g of 2-hydroxyethyl methacrylate, 23.9g of pyridine and 250mL of diglyme and stirring at 60℃for 4 hours. Next, the reaction mixture was cooled to-10℃and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃ ₂ . After dilution with 50mL of N-methylpyrrolidone, a solution of 20.1g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10℃for 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Then, the polyimide precursor was precipitated in water by pouring it into 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The polyimide precursor solid was filtered and dissolved in 380g of tetrahydrofuran. The resulting solution was poured into 6 liters of water to precipitate a polyimide precursor in water and filtered, and dried at 45℃under reduced pressure for 3 days. The polyimide precursor had a weight average molecular weight of 23100 and a number average molecular weight of 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 are introducedMixing was carried out and stirred at a temperature of 60℃for 4 hours to produce a diester of 4,4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to-10℃and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃ ₂ . After dilution with 50mL of N-methylpyrrolidone, a solution of 20.1g of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10℃for 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Then, the polyimide precursor was precipitated in water by pouring it into 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. The polyimide precursor solid was filtered and dissolved in 380g of tetrahydrofuran. The resulting solution was poured into 6 liters of water to precipitate a polyimide precursor in water and filtered, and dried at 45℃under reduced pressure for 3 days. The polyimide precursor had a weight average molecular weight of 23500 and a number average molecular weight of 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 produce a diester of 4,4' -oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to-10℃and 17.0g of SOCl was added over 60 minutes while maintaining the temperature at-10 ℃ ₂ . After dilution with 50mL of N-methylpyrrolidone, a solution of 25.1g of 4,4' -diaminodiphenyl ether dissolved in 100mL of N-methylpyrrolidone was added dropwise to the reaction mixture at-10℃for 60 minutes, and after stirring the mixture for 2 hours, 20mL of ethanol was added. Then, the polyimide precursor was precipitated in water by pouring it into 6 liters of water, and the water-polyimide precursor mixture was stirred for 15 minutes. Filtering and dissolving the polyimide precursor solid380g in tetrahydrofuran. The resulting solution was poured into 6 liters of water to precipitate a polyimide precursor in water and filtered, and dried at 45℃under reduced pressure for 3 days. The polyimide precursor had a weight average molecular weight of 23200 and a number average molecular weight of 9600.

Synthesis example 5

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

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

Synthesis example 6

[ Synthesis of radically polymerizable Compound B1-1 having a 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 50.0g of SOCl was added dropwise over 60 minutes while keeping the temperature below 5 ℃ ₂ Then stirred for 1 hour. 200mL of distilled water was added to stop the reaction, and 500mL of ethyl acetate was added. After the obtained organic layer was washed 5 times with distilled water, the low boiling point solvent was removed by an evaporator, thereby obtaining 220.1g of radical polymerizable compound B1-1. The obtained compound is an exemplary compound 302 of the radical polymerizable compound having a sulfur atom described above.

¹ H NMR(400MHz,CDCl ₃ )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-ethyl acetateAlkenyl benzyl alcohol, 70.0g of pyridine, and 500mL of tetrahydrofuran were mixed. The mixture was cooled to 0℃and 50.0g of SOCl was added dropwise over 60 minutes while keeping the temperature below 5 ℃ ₂ Then stirred for 1 hour. 200mL of distilled water was added to stop the reaction, and 500mL of ethyl acetate was added. After the obtained organic layer was washed 5 times with distilled water, the low boiling point solvent was removed by an evaporator, whereby 200.2g of radical polymerizable compound B1-2 was obtained. The obtained compound is exemplified by the above-mentioned radical polymerizable compound 312 having a sulfur atom.

Synthesis example 8

[ Synthesis of radically polymerizable Compound B1-3 having 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 19.0g of methacryloyl chloride was added dropwise over 60 minutes while keeping the temperature below 5℃and then stirred for 1 hour. 200mL of distilled water was added to stop the reaction, and 500mL of ethyl acetate was added. After the obtained organic layer was washed 5 times with distilled water, the low boiling point solvent was removed by an evaporator, thereby obtaining 220.1g of radical polymerizable compound B1-3. The obtained compound is exemplified by the compound 322 of the radical 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 according to gel permeation chromatography (GPC method). Specifically, HLC-8220 (trade name: manufactured by Tosoh Corporation) was used, and the column was obtained using a column composed of protection columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (trade name: manufactured by Tosoh Corporation). The eluent was measured using THF (tetrahydrofuran). In addition, a 254nm wavelength detector of UV (ultraviolet) was used for the detection. The molecular weight specified in the present specification is not particularly limited, and is a value measured according to the above measurement method.

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

Preparation of photosensitive resin composition

The components described in table 1 below were mixed to prepare a homogeneous solution. The obtained solution was passed through a filter having a pore width of 0.8 μm and was subjected to pressure filtration under a pressure of 0.3MPa, whereby a photosensitive resin composition was obtained.

Storage stability

10g of the photosensitive resin composition was placed in a container (material of the container: light shielding glass, capacity: 100 mL), sealed, and allowed to stand in an atmosphere of 65% relative humidity at 25 ℃. Stability was evaluated during the time from precipitation of the solid from the photosensitive resin composition. The longer the time until precipitation, the higher the stability of the photosensitive resin composition, and the preferable result. In the precipitation of solids, 3 samples stored in containers were prepared for one photosensitive resin composition, the containers of 1 sample were opened at the time of 30 days, 60 days, and 120 days, the total amount of the photosensitive resin composition as the content was pressure-filtered through a mesh having a pore diameter of 0.8 μm, and the presence or absence of foreign matters on the mesh was observed with naked eyes, and the presence or absence of the precipitate was determined as follows.

A: no precipitation of solids was observed even over 120 days.

B: over 60 days, and within 120 days, solid is precipitated.

C: over 30 days, and within 60 days, solid precipitated.

D: within 30 days, solid is precipitated.

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 to light using a aligner (manufactured by SUSS MICROTEC AG, karl-Suss MA150[ trade name ]). The exposure was performed by a high-pressure mercury lamp, and the exposure energy required for curing the above-mentioned 10 μm uniform film at 365nm was measured. The lower the exposure energy, the higher the sensitivity, and the preferred result.

(A) Polymer precursors

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: radically polymerizable Compounds having Sulfur atom produced in Synthesis examples 6 to 8

(B2) Radical polymerizable compounds (trade names)

B2-1: NK esters M-40G (Shin-Nakamura Chemical Co., ltd.)

B2-2: SR-209 (Sartomer Company, inc.)

B2-3: NK esters A-9300 (Shin-Nakamura Chemical Co., ltd.)

B2-4: A-TMMT (Shin-Nakamura Chemical Co., 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 (ADEKA CORPORATION system)

(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) Additives (migration inhibitor)

F-1:1,2, 4-triazole

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 ethyl.

(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, the solvents in Table 1, for example, when the column of the type is "H-1/H-2" and the column of the mass part is "48+12", refer to 48 parts by mass of H-1 and 12 parts by mass of H-2.

From the results of table 1, it is clear that 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 trace amount of a radical polymerizable compound having a sulfur atom is blended, the advantages of the present invention are seen from the viewpoint of achieving excellent storage stability and high sensitivity.

In contrast, 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. Will be coated withThe silicon wafer of the photosensitive resin composition layer was dried on a hot plate at 100℃for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15. Mu.m. Using a stepper (Nikon NSR 2005i9C trade name]) At 500mJ/cm ² The photosensitive resin composition layer on the silicon wafer was exposed to light with exposure energy, and the exposed photosensitive resin composition layer (resin layer) was developed with cyclopentanone for 60 seconds to form holes having a diameter of 10 μm. Then, the temperature was raised to 250℃at a temperature rise rate of 10℃per minute in a nitrogen atmosphere, and then the mixture was heated for 3 hours. After cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Further, the same type of photosensitive resin composition was used again on 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 and heating for 3 hours was performed again in the same manner as described above, to produce a laminate composed of the resin layer/metal layer/resin layer.

The interlayer insulating film for a rewiring layer is excellent in insulation properties.

Further, as a result of manufacturing a semiconductor device using the interlayer insulating film for a rewiring layer, it was confirmed that the operation was normal.

Claims (20)

1. A photosensitive resin composition comprising:

a polymer precursor selected from polyimide precursors and polybenzoxazole precursors;

a radically polymerizable compound having a sulfur atom;

a photo radical polymerization initiator; and

The solvent is used for the preparation of the aqueous solution,

the radically polymerizable compound having a sulfur atom is represented by the following formula (3-2):

R ² -La ¹ -X ² -La ² -L ¹ -La ³ -X ¹ -La ⁴ -R ¹ (3-2)

in the formula (3-2), L ¹ representing-S-, -S (=O) -or-S＝O) ₂ -，X ¹ X is X ² Each independently represents a single bond, -O-, -C (=o) O-, -OC (=o) -, -S (=o) ₂ -or-NR ³ CO-，R ¹ R is R ² Independently of one another, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical-polymerizable group, la ¹ ～La ⁴ Each independently represents any one of a single bond, a group consisting of a combination of 1 or more of an alkylene group and a phenylene group, and a group consisting of a combination of 1 or more of an alkylene group and a phenylene group and-O-; r is R ³ Represents a hydrogen atom or an alkyl group; wherein R is ¹ R is R ² At least one of them is a radical polymerizable group.

2. The photosensitive resin composition according to claim 1, wherein,

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

in the formula (1), A ¹ A is a ² Each independently represents an oxygen atom or NH,

R ¹¹¹ represents a 2-valent organic group, R ¹¹⁵ Represents a 4-valent organic group, R ¹¹³ R is R ¹¹⁴ Each independently represents a hydrogen atom or a 1-valent organic group;

in the formula (2), R ¹²¹ Represents a 2-valent organic group, R ¹²² Represents a 4-valent organic group, R ¹²³ R is R ¹²⁴ Each independently represents a hydrogen atom or a 1-valent organic group.

3. The photosensitive resin composition according to claim 2, wherein,

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

4. The photosensitive resin composition according to claim 1, wherein,

the R is ¹ R is R ² These two are each independently a radical polymerizable group.

5. The photosensitive resin composition according to claim 1, wherein,

the X is ¹ X is X ² is-O-.

6. The photosensitive resin composition according to claim 1, wherein,

the L is ¹ is-S (=o) -.

7. The photosensitive resin composition according to claim 1, wherein,

the R is ¹ R is R ² Each independently is a 1-valent organic group having an acryl group or a methacryl group.

8. The photosensitive resin composition according to claim 1, wherein,

The formula (3-2) is represented by the following formula (4);

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

9. The photosensitive resin composition according to any one of claim 1 to 3, wherein,

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

10. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a radical polymerizable compound other than the radical polymerizable compound having a sulfur atom.

11. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a base generator.

12. A photosensitive resin composition according to any one of claims 1 to 3 for development.

13. A photosensitive resin composition according to any one of claims 1 to 3 for use in development using a developer containing an organic solvent.

14. The photosensitive resin composition according to any one of claims 1 to 3, which is used for forming an interlayer insulating film for a rewiring layer.

15. A cured film formed from the photosensitive resin composition of any one of claims 1 to 14.

16. A laminate having 2 or more layers of the cured film of claim 15.

17. The laminate according to claim 16, wherein,

with a metal layer between the cured films.

18. A method for producing a cured film, comprising the step of using the photosensitive resin composition according to any one of claims 1 to 14.

19. The method for producing a cured film according to claim 18, 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 development treatment step of developing the exposed photosensitive resin composition layer.

20. A semiconductor device having the cured film according to claim 15 or the laminate according to claim 16 or 17.