JP6808831B2 - Photosensitive resin compositions, cured films, laminates, methods for producing cured films, semiconductor devices and compounds - Google Patents

Description

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

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, mechanical properties, etc. has been used as a protective film and an interlayer insulating film of a semiconductor element. However, with the increasing integration and size of semiconductor devices in recent years, there is a demand for thinner and smaller encapsulant resin packages, and methods such as surface mounting using LOC (read-on-chip) and solder reflow method have been adopted. It has been taken.

A photosensitive resin composition in which photosensitive is imparted to the polyimide resin itself has been used for manufacturing such a semiconductor element. This is because the pattern forming step can be simplified by using the photosensitive resin composition. For example, Patent Document 1 describes (a) a polyimide precursor having a predetermined structure, (b) a compound that generates radicals by irradiation with active light, and (c) the following formula (4a) or (4b). A resin composition containing the compound and (d) a solvent is disclosed.
(In formula (4a), na is an integer of 3 or less. In formula (4b), R ¹⁰¹ and R ¹⁰² are independently hydrogen atoms or monovalent groups. Mb is an integer of 9 or less. .)
Specific examples of the compound represented by the formula (4a) or (4b) include tripropylene glycol diacrylate and tripropylene glycol.

Japanese Unexamined Patent Publication No. 2014-201695

However, it has been found that the composition described in Patent Document 1 is not necessarily highly sensitive to light. Further, when the photosensitive resin composition is stored for a certain period of time and then used as a cured film, the storage stability of the photosensitive resin composition is also required.
An object of the present invention is to solve the above problems, a photosensitive resin composition having excellent storage stability and high sensitivity, and a cured film, a laminate, and a cured film using the same. It is an object of the present invention to provide a manufacturing method and a semiconductor device. Another object of the present invention is to provide a compound for producing the above-mentioned photosensitive resin composition.

As a result of diligent studies by the present inventor based on the above problems, it has been found that the above problems can be solved by blending a radically polymerizable compound having a sulfur atom in the photosensitive resin composition. Specifically, the above-mentioned problems were solved by the following means <1>, preferably by <2> to <22>.
<1> A photosensitive resin composition containing a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a radically polymerizable compound having a sulfur atom, a photoradical polymerization initiator, and a solvent.
<2> The photosensitive resin composition according to <1>, wherein the polymer precursor contains a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, respectively.
R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group;
In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. Represent.
<3> The photosensitive resin composition according to <2>, wherein the polymer precursor contains 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);
In formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom, and X ¹¹ and X ¹² each independently represent a single bond or a divalent linking group, and R ¹¹ And R ¹² each independently represent a hydrogen atom or a monovalent organic group; however, at least one of R ¹¹ and R ¹² represents a monovalent organic group containing at least one radically polymerizable group; R ¹¹ And R ¹² may be combined with each other to form a ring.
<5> The photosensitive resin composition according to <4>, wherein the above formula (3-1) is represented by the following formula (3-2);
Wherein (3-2), ^{L 1} is, -S -, - S-S -, - S (= O) -, or, -S (= _{O) 2} - represents, ^{X 1} and ^{X 2,} Single bond independently, -O-, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O) _2- or -NR ³ CO −, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radically polymerizable group, and La ^{1 to} La ⁴ independently represent a single bond. Represents either a group consisting of one or more combinations of an alkylene group and a phenylene group, and a group consisting of a combination of one or more of an alkylene group and a phenylene group and -O-; R ³ Represents a hydrogen atom or an alkyl group; however, at least one of R ¹ and R ² is a radically polymerizable group.
<6> The photosensitive resin composition according to <5>, wherein both R ¹ and R ² are independently radically polymerizable groups.
<7> The photosensitive resin composition according to <5> or <6>, wherein X ¹ and X ² are −O−.
<8> The photosensitive resin composition according to any one of <5> to <7>, wherein L ¹ is −S (= O) −.
<9> The photosensitive resin composition according to any one of <5> to <8>, wherein R ¹ and R ² are monovalent organic groups each independently having an acryloyl group or a methacryloyl group.
<10> The photosensitive resin composition according to <4>, wherein the above formula (3-1) is represented by the following formula (4);
In formula (4), R is a hydrogen atom or a methyl group.
<11> One of <1> to <10> containing the radically polymerizable compound having a sulfur atom in a proportion of 0.001% by mass or more of the solid content contained in the photosensitive resin composition. The photosensitive resin composition according to the above.
<12> The photosensitive resin composition according to any one of <1> to <11>, further comprising a radically polymerizable compound other than the radically polymerizable compound having a sulfur atom.
<13> The photosensitive resin composition according to any one of <1> to <12>, which further contains 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 developing with a developing solution 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 rewiring layer.
<17> A cured film formed from the photosensitive resin composition according to any one of <1> to <16>.
<18> A laminated body having two or more layers of the cured film according to <17>.
<19> The laminate according to <18>, which has a metal layer between the cured films.
<20> A method for producing a cured film, which comprises using the photosensitive resin composition according to any one of <1> to <16>.
<21> 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 the exposed photosensitive resin. The method for producing a cured film according to <20>, which comprises a developing treatment step of performing a developing treatment on the composition layer.
<22> A semiconductor device having the cured film according to <17> or the laminate according to <18> or <19>.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition having excellent storage stability and high sensitivity, and an excellent cured film, laminate, cured film manufacturing method and semiconductor device using the above photosensitive resin composition. became. In addition, it has become possible to provide a novel compound used in the above-mentioned photosensitive resin composition.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Further, examples of the light used for exposure generally include an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacryloyl", or either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
As used herein, the solid content is the mass percentage of other components excluding the solvent with respect to the total mass of the composition. Further, the solid content concentration refers to the concentration at 25 ° C. unless otherwise specified.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Unless otherwise specified, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) is used for detection.

The photosensitive resin composition of the present invention (hereinafter, may be simply referred to as “the composition of the present invention”) is a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a radical having a sulfur atom. It is characterized by containing a polymerizable compound, a photoradical polymerization initiator, and a solvent. With such a configuration, a photosensitive resin composition having excellent storage stability and high sensitivity can be obtained. It is presumed that the reason for this is that the radically polymerizable compound having a sulfur atom is less likely to cause a polymerization reaction at room temperature and enhances the radical polymerizable property of the composition.

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

<< Polyimide precursor >>
The polyimide precursor preferably contains a repeating unit represented by the following formula (1).
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² in the formula (1) are oxygen atoms or NH, and oxygen atoms are preferable.
R ¹¹¹ in the formula (1) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, which are a linear aliphatic group having 2 to 20 carbon atoms and 3 to 20 carbon atoms. A 20-branched aliphatic group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable. A group consisting of is more preferred.

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

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −S. (= O) _2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O- , -C (= O)-, -S-, -S (= O) _2- , more preferably a group selected from -CH _2- , -O-, -S-, -S (= It is more preferably a divalent group selected from the group consisting of O) _2- , -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- .

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenylsulfone , 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexa Fluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , 4,4'-Diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] Sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl- 4,4'-Diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino Octafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-) Aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone , 3,3-Dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetra Methyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis ( 4-Aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis ( 4-Aminophenyl) Octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3) -Aminophenoxy) Phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-Aminophenoxy) -3,5-dimethyl Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethylphenoxy) Benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-4'-bis) Amino-3-trifluoromethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) Diphenylsulfone, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, Choose from 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl At least one diamine is mentioned.

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

Further, a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) −Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, etc., but are limited to these. Not done.
Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

R ¹¹¹ is preferably represented by −Ar ⁰ −L−Ar ⁰⁻ from the viewpoint of the flexibility of the obtained cured film. However, Ar ⁰ is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L is substituted with a fluorine atom. An aliphatic hydrocarbon group having 1 to 10 carbon atoms, −O−, −C (= O) −, −S−, −S (= O) _2- or −NHCO−, and the above 2 It is a group consisting of one or more combinations. Ar ⁰ is preferably a phenylene group, and L is 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 -is more preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
Equation (51)
In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R ^{50 to} R ⁵⁷ is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group or a trifluoromethyl group.
As a monovalent organic group of R ^{50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.
Equation (61)
In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

R ¹¹⁵ in the formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
Equation (5)
In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S. -, -S (= O) _2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom. , -O-, -C (= O)-, -S- and -S (= O) _2- , more preferably -CH _2- , -C (CF ₃ ) _{2- , -C (CH 3) 2 -} , - O -, - C (= O) -, - S- and -S (= _{O) 2} - ₂ divalent radical selected from the group consisting of is more preferable.

Equation (6)

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
Equation (O)
In formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 , 4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedian Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,54-tetracarboxylic dianhydride, 1, 4,5,6-naphthalenetetracarboxylic dianhydride, 2,2', 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-phenanthenetetracarboxylic dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and / or alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

R ¹¹³ and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and both of them are radically polymerized. It is more preferable to include a sex group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III). The (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.

In formula (III), ^R200 represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ − or a polyoxyalkylene group having 4 to 30 carbon atoms (as an alkylene group, 1 to 12 carbon atoms). 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3).
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2- .
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
As the monovalent organic group represented by R ¹¹³ or R ^114, a substituent that improves the solubility of the developing solution is preferably used.

When R ¹¹³ or R ¹¹⁴ is a monovalent organic group, examples thereof include an aromatic group and an aralkyl group having one, two or three, preferably one acidic group bonded to the carbon constituting the aryl group. Be done. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.

In the formula (1), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. Good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

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

The repeating unit represented by the formula (1) is preferably the repeating unit represented by the formula (1-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (1-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (1-A)
In formula (1-A), A ¹¹ and A ¹² represent oxygen atoms or NH, R ¹¹¹ and R ¹¹² independently represent divalent organic radicals, and R ¹¹³ and R ¹¹⁴ are independent, respectively. In addition, it represents a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a radically polymerizable group, and is preferably a radically polymerizable group.

A ¹¹ , A ¹² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are independently synonymous with A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (1), respectively, and so are the preferred ranges. is there.
R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

In the polyimide precursor, the repeating structural unit represented by the formula (1) may be one kind, or two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (1). Further, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the repeating unit represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 1,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The dispersity of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

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

It is preferable to include a step of precipitating a solid in the production of the polyimide precursor. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

<< Polybenzoxazole precursor >>
The polybenzoxazole precursor used in the present invention preferably contains a repeating unit represented by the following formula (2).
In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. Represent.

In formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of 6 to 10) is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, which are synonymous with R ¹¹³ and R ¹¹⁴ in the above formula (1), and the preferable range is also the same.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of the above formula (2).
It is preferable to include the diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

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

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, it remains after removal of the acid dianhydride group from the tetracarboxylic dianhydride in terms of improving alkali solubility. It is preferable to include a tetracarboxylic acid residue as a repeating structural unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 1,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The dispersity 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, based on the total solid content of the composition. It is further preferably ~ 98% by mass, further preferably 50 to 95% by mass, even more preferably 60 to 95% by mass, and even more preferably 70 to 95% by mass.
The polymer precursor may contain only one type, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Radical polymerizable compound with sulfur atom>
The photosensitive resin composition of the present invention contains a radically polymerizable compound having a sulfur atom. One embodiment of a radically polymerizable compound having a sulfur atom is a radical having a sulfur atom having two or more radically polymerizable groups (preferably 2 to 4, more preferably 2 to 3 and even more preferably 2). It is a polymerizable compound.
The radically polymerizable compound having a sulfur atom is preferably a compound represented by the following formula (3-1).
In formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom, and X ¹¹ and X ¹² each independently represent a single bond or a divalent linking group, and R ¹¹ And R ¹² each independently represent a hydrogen atom or a monovalent organic group; however, at least one of R ¹¹ and R ¹² represents a monovalent organic group containing at least one radically polymerizable group; R ¹¹ And R ¹² may be combined with each other to form a ring.

In formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom. It is preferably a linking group having one or two sulfur atoms, and more preferably a linking group having one or two sulfur atoms and having an oxygen atom and having 2 to 6 atoms. More preferably, it has the same meaning as L ¹ of the formula (3-2) described later, and the preferable range is also the same.

In formula (3-1), X ¹¹ and X ¹² each independently represent a single bond or a divalent linking group. As the divalent linking group, a linear or branched alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms). , 6-14 is more preferred, 6-10 is particularly preferred), -O-, -S-, -C (= O)-, -NR ^3- , -NR ³ CO-, and concatenations relating to their combinations. The group is mentioned. R ³ is synonymous with R ³ in the formula (3-2) described later. Further, the linking group may be a hydrocarbon group. The hydrocarbon group may be an oligo hydrocarbon group, and the number of repetitions at that time is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6. The hydrocarbon group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. When the number of atoms of the linking group is other than the oligohydrocarbon group, the number of atoms is preferably 1 to 24, more preferably 1 to 12, and 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, and particularly preferably 2 to 18. The divalent linking group represented by X ¹¹ and X ¹² is a divalent linking group containing an oxygen atom, a sulfur atom, or a nitrogen atom (preferably 1 to 12 atoms, more preferably 1 to 6 atoms, 1 to 3). Is particularly preferable), and more preferably a divalent linking group containing an oxygen atom.

In formula (3-1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a monovalent organic group containing a radically polymerizable group, a substituent T described later, and the like. Examples of the radically polymerizable group include a group having a carbon-carbon unsaturated double bond. Among them, as the radically polymerizable group, a group having a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group is preferable, and a group having an acryloyl group or a methacryloyl group is more preferable. More specifically, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, vinyl group, vinylphenyl group (o, m, p), vinylphenyloxy group (o, m). , P), vinylphenylmethyl group (o, m, p) are preferable, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group are more preferable, acryloyloxy group, methacryloyloxy group. Is even more preferable.
The monovalent organic group containing a radically polymerizable group may be a group having only one radically polymerizable group or a group having two or more radically polymerizable groups. When a monovalent organic group containing a radically polymerizable group has two or more radically polymerizable groups, the plurality of radically polymerizable groups may be the same as or different from each other. Further, the monovalent organic group containing a radically polymerizable group may further have a substituent described later as long as the effect of the present invention is not impaired. Examples of the substituent include the Substituent T described later. The number of radically polymerizable groups contained in one monovalent organic group is preferably 3 or less, and more preferably 2 or less. In the present invention, a mode in which the monovalent organic group containing a radically polymerizable group does not have a substituent is preferably exemplified.

In formula (3-1), at least one of R ¹¹ and R ¹² represents a monovalent organic group containing at least one radically polymerizable group. Among them, it is preferable that both R ¹¹ and R ¹² are monovalent organic groups each independently containing a radically polymerizable group.
Further, in the formula (3-1), the number of radically polymerizable groups in one molecule is preferably 2 or more, preferably 4 or less, and more preferably 3 or less. It is preferable, and more preferably two.

In formula (3-1), R ¹¹ and R ¹² may be coupled to each other to form a ring. When R ¹¹ and R ¹² form a ring, R ¹¹ and R ¹² may be directly linked or may be linked via a linking group L described later. Further, the formed ring may be condensed. As the linking group L, a linear or branched alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), −O−, −S−, −C (= O). )-, -NR ^3- , -NR ³ CO-, and linking groups for combinations thereof. R ³ has the same meaning as R ³ in the formula (3-2) described later, and the preferable range is also the same.

The radically polymerizable compound having a sulfur atom is more preferably represented by the following formula (3-2).
Wherein (3-2), ^{L 1} is, -S -, - S-S -, - S (= O) -, or, -S (= _{O) 2} - represents, ^{X 1} and ^{X 2,} Single bond independently, -O-, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O) _2- or -NR ³ CO −, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radically polymerizable group, and La ^{1 to} La ⁴ independently represent a single bond. Represents either a group consisting of one or more combinations of an alkylene group and a phenylene group, and a group consisting of a combination of one or more of an alkylene group and a phenylene group and -O-; R ³ Represents a hydrogen atom or an alkyl group; however, at least one of R ¹ and R ² is a radically polymerizable group.

In equation (3-2), L ¹ represents −S−, −SS−, −S (= O) −, or −S (= O) ₂₋ , and −S (= O) − Is preferable.
X ¹ and X ² are independently single-bonded, -O-, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (=). O) Represents ₂ − or −NR ³ CO−, preferably single bond or −O−, more preferably −O−. R ³ is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , 2-3 are particularly preferred), alkynyl groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are particularly preferred), aryl groups (6-22 carbon atoms are preferred, 6-18 are preferred). More preferably, 6 to 10 is particularly preferable), and a hydrogen atom or an alkyl group having the above carbon number is preferable.
R ¹ and R ² are independently radical-polymerizable groups, hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), and cycloalkyl groups (carbon atoms). It represents 3 to 24, more preferably 3 to 12, more preferably 3 to 6) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 and particularly preferably 6 to 10).
When R ¹ and R ² are an alkyl group, a cycloalkyl group, or an aryl group, they may have an arbitrary substituent T as long as the effects of the present invention are not impaired. As the optional substituent T, a branched or linear alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), a cycloalkyl group (preferably 3 to 24 carbon atoms). 3, 12 is more preferred, 3 to 6 are particularly preferred), hydroxyl groups, hydroxylalkyl groups (1 to 24 carbon atoms are preferred, 1 to 12 are more preferred, 1 to 6 are particularly preferred; the number of hydroxyl groups is 1 to 6 are preferable, 1 to 3 are more preferable), an amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and particularly preferably 0 to 6), an aminoalkyl group (1 to 24 carbon atoms are preferable). Preferably, 1 to 12 are more preferable, 1 to 6 are particularly preferable; the number of amino groups is preferably 1 to 6 and more preferably 1 to 3), a thiol group and a thiolalkyl group (preferably 1 to 24 carbon atoms). 1 to 12 are more preferable, 1 to 6 are particularly preferable; the number of thiol groups is preferably 1 to 6 and 1 to 3 is more preferable), a carboxyl group and a carboxyalkyl group (preferably 1 to 24 carbon atoms, 1 to 1). 12 is more preferable, 1 to 6 is particularly preferable; the number of carboxyl groups is preferably 1 to 6, 1 to 3 is more preferable), and an acyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 ~ 3 is particularly preferable), an acyloxy group (1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, 1 to 3 are particularly preferable), and an aryloyl group (7 to 23 carbon atoms are preferable, 7 to 19 are more preferable). , 7-11 is particularly preferable), an aryloyloxy group (7 to 23 carbon atoms are preferable, 7 to 19 is more preferable, 7 to 11 is particularly preferable), an oxo group (= O), an imino group (= NR ^3). ), Alkylidene group (= C (R ³ ) ₂ ) and the like.
However, at least one of R ¹ and R ² represents a radically polymerizable group.

Examples of the radically polymerizable groups represented by R ¹ and R ² include groups having the same meaning as those exemplified by the above-mentioned formula (3-1). It is preferable that both R ¹ and R ² are independently radically polymerizable groups, and more preferably the same radically polymerizable groups.

In the formula (3-2), La ^{1 to} La ⁴ are independently a single bond, a group consisting of one or more combinations of an alkylene group and a phenylene group, and one of an alkylene group and a phenylene group. Alternatively, it represents any of the groups consisting of a combination of two or more and −O−. La ^{1 to} La ⁴ are independently a single bond, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms), a phenylene group, and a (oligo) oxyalkylene group (preferably 1 to 6 carbon atoms). The alkylene group preferably has 1 to 24 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6, and the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). (Oligo) alkyleneoxy group (alkylene group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6; the number of repetitions is preferably 1 to 12, more preferably 1 to 6 and 1 to 1 3 is particularly preferable), or may have a linking group by a combination thereof. The (oligo) oxyalkylene group means an oxyalkylene group or an oligooxyalkylene group. The same applies to other groups containing the description "(oligo)".
The alkylene group, phenylene group, (oligo) oxyalkylene group, and (oligo) alkyleneoxy group may further have the above-mentioned arbitrary substituent T as long as the effects of the present invention are not impaired.
La ^{1 to} La ⁴ are more preferably single bonds or alkylene groups, respectively, more preferably La ² and La ³ are single bonds, and La ¹ and La ⁴ are alkylene groups. ..

R ¹ and R ² may be combined with each other to form a ring. When R ¹ and R ² form a ring, R ¹ and R ² may be directly linked or may be linked via the linking group L. Further, the formed ring may be condensed.
The radically polymerizable compound having a sulfur atom used in the present invention may be a small molecule (for example, a molecular weight of less than 2000 or even less than 1000) or a polymer, but is preferably a small molecule.

Examples of the radically polymerizable compound having a sulfur atom include the following exemplified compounds, but the present invention is not limited to these. Among the exemplified compounds, the following compounds 301, 302, 303, 304, 312, 222 are preferable, 301 and 302 (compounds represented by the formula (4)) are more preferable, and 302 is particularly preferable.

In the above exemplified compounds, m is 1 to 30 and n is 1 to 30.
The content of the radically polymerizable compound having a sulfur atom in the photosensitive resin composition of the present invention is preferably 0.001% by mass or more as a lower limit value with respect to the total solid content of the composition, preferably 0.005% by mass. % Or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and 0. It is even more preferably 3% by mass or more. The upper limit value is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and further preferably 7% by mass or less and 5% by mass or less. It may be 2% by mass or less and 1% by mass or less.
The total amount of the radically polymerizable compound having a sulfur atom with respect to 100 parts by mass of the polymer precursor is preferably 70 parts by mass or less as the polymerizable compound in total with other polymerizable compounds described later, and is preferably 60 parts by mass or less. It is more preferably 55 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less. The polymerizable compound is preferably 0.1 part by mass or more, and may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, and 10 parts by mass or more.
The ratio of the radically polymerizable compound having a sulfur atom in the total polymerizable compound including other polymerizable compounds described later is preferably 0.01% by mass or more, more preferably 0.02% by mass or more as the lower limit value. 0.1% by mass or more is further preferable, 0.3% by mass or more is further preferable, and 0.5% by mass or more is even more preferable. The upper limit is preferably 100% by mass or less, and is 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 7% by mass or less, 5% by mass or less, 2% by mass or less, and 1% by mass or less. It may be.
By incorporating the radically polymerizable compound having a sulfur atom in the composition in the above ratio, higher stability and higher exposure sensitivity can be achieved.
Only one type of radically polymerizable compound having a sulfur atom may be contained, or two or more types may be contained. When two or more types are included, the total amount is preferably in the above range.

<Photoradical polymerization initiator>
The photosensitive resin composition of the present invention contains a photoradical polymerization initiator.
The photoradical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

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

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photobase generator.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminovtan-2-one, and 2-acetoxy. Iminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use this oxime-based photopolymerization initiator. Oxime-based photopolymerization initiators have a> C = N—O—C (= O) − linking group in the molecule.
As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02 (above, manufactured by BASF), and ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Photoradical Polymerization Initiator 2 described in JP2012-14052) are also suitable. Used for. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Corp.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound are described in Compounds described in JP-A-2010-262028, Compounds 24 described in paragraph 0345 of JP-A-2014-500852, and paragraphs 0347-0348. Examples thereof include compounds 36 to 40, and the compound (C-3) described in paragraph 0101 of JP2013-164471A.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-aromatic ketones such as propanone-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.
In the formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a ^{biphenylyl,, R I01} is a group represented by formula ^(II), the same as ^{R I00} It is a group, and R ^{I02 to} R ^I04 are independently alkyl having 1 to 12 carbon atoms and alkoxy or halogen having 1 to 12 carbon atoms, respectively.
In the formula, R ^{I05 to} R ^I07 are the same as R I ^{02 to} R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015 / 125469 can also be used.

The content of the photoradical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photoradical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photoradical polymerization initiators are contained, the total 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 as long as it does not deviate from the gist of the present invention.
A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be allowed to proceed as well as the cyclization of the polymer precursor, so that a higher degree of heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

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

<Solvent>
The photosensitive resin composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include 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, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-Alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the properties of the coated surface.
In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable, the amount is more preferably 10 to 70% by mass, and further preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.
Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<Other polymerizable compounds>
<< Radical polymerizable compound containing no sulfur atom >>
The photosensitive resin composition of the present invention also contains a radically polymerizable compound containing no sulfur atom (hereinafter, also referred to as "polymerizable monomer containing no sulfur atom") in addition to the above-mentioned radically polymerizable compound containing a sulfur atom. Is preferable. With such a configuration, a cured film having excellent heat resistance can be formed.

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

The number of radically polymerizable groups contained in the polymerizable monomer containing no sulfur atom may be one or two or more, but the polymerizable monomer containing no sulfur atom may have two or more radically polymerizable groups. It is preferable to have three 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 even more 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 preferably contains at least one polymerizable monomer containing two or more polymerizable groups and not containing a bifunctional or higher functional sulfur atom, and is preferably trifunctional or higher functional sulfur. It is more preferable to contain at least one atom-free polymerizable monomer. Further, it may be a mixture of a polymerizable monomer containing no bifunctional sulfur atom and a polymerizable monomer containing no trifunctional or higher functional sulfur atom. The number of functional groups of the polymerizable monomer containing no sulfur atom means the number of radically polymerizable groups in one molecule.

Specific examples of the polymerizable monomer containing no sulfur atom include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. , Preferably esters of unsaturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group or an amino group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional carboxylic acid. A dehydration condensation reaction product with an acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol or an amine, and a halogen group or the like are removed. Substitution reactions of unsaturated carboxylic acid esters or amides having a dissipative substituent with monofunctional or polyfunctional alcohols and amines are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the polymerizable monomer containing no sulfur atom, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-41708, JP-A-50-6034, and JP-A-51-37193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) acrylics described in JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
Further, as a polymerizable monomer containing no preferable sulfur atom other than the above, it has a fluorene ring and is ethylenically described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups having unsaturated bonds and cardo resins can also be used.
Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-4537, and Japanese Patent Publication No. 1-4536, and JP-A-2-25493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, the journal of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and their contents are incorporated in the present specification.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-62986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a polymerizable monomer containing no sulfur atom.

Further, the compounds described in paragraphs 0104 to 0131 of JP2015-187211A can also be used as other polymerizable monomers, and their contents are incorporated in the present specification.

As polymerizable monomers containing no sulfur atom, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320;) Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd., Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nihon Kayaku Co., Ltd.), Di Pentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol and propylene. Structures linked via glycol residues are preferred. These oligomer types can also be used.

Commercially available products of the polymerizable monomer containing no sulfur atom include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. SR-209, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA- 40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Nichiyu Co., Ltd.) ) Made) and so on.

Examples of other polymerizable monomers include urethane acrylates as described in JP-A-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Further, urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, as a 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 phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The polymerizable monomer having the above is more preferable. Particularly preferably, in a polymerizable monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to have an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or di. It is a compound that is pentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toa Synthetic Co., Ltd.
As the polymerizable monomer having an acid group, one type may be used alone, or two or more types may be mixed and used. Further, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used in combination.
The preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is within the above range, it is excellent in manufacture and handling, and further excellent in developability. Moreover, the polymerizable property is good.

In the photosensitive resin composition of the present invention, a monofunctional polymerizable monomer can be preferably used as the polymerizable monomer containing no sulfur atom from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the cured film. Examples of the monofunctional polymerizable monomer include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

<< Polymerizable compounds other than the radically polymerizable compounds mentioned above >>
The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the radically polymerizable compound described above. Examples of polymerizable compounds other than the above-mentioned radically polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; and benzoxazine compounds.

(Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ is a group represented by -OR ⁶ or -OCO-R ^7. R ⁶ indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁷ indicates an organic group having 1 to 10 carbon atoms.)

(In the formula, R ⁴⁰⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁴⁰⁵ represents a group represented by -OR ⁴⁰⁶ or -OCO-R ⁴⁰⁷ , and R ⁴⁰⁶ is a hydrogen atom or carbon. It represents an organic group having a number of 1 to 10, and R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

(In the formula, u represents an integer of 3 to 8, R ⁵⁰⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ^507. , R ⁵⁰⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R ⁵⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

By using the above-mentioned compound having a hydroxymethyl group or the like, the occurrence of cracks can be more effectively suppressed when the photosensitive resin composition is applied on an uneven substrate. Further, it is possible to form a cured film having excellent pattern processability and high heat resistance having a 5% by mass reduction temperature of 350 ° C. or higher, more preferably 380 ° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-. PC, DML-PTBP, DML-34X, 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-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacethoxymethyl-p-cresol and the like. ..

Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like. HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC Examples thereof include MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

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

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

Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; and epoxy group-containing silicone such as polymethyl (glycidyloxypropyl) siloxane. However, it is not limited to these. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.) and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable because it suppresses warpage and is excellent in heat resistance. For example, Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.

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

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

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

The content of the polymerizable compound other than the radically polymerizable compound having a sulfur atom is preferably 0 to 60% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass, and further preferably 30% by mass or less.
As the other polymerizable compounds, one type may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Migration inhibitor>
The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds, hindered phenolic compounds , Pyrazole acid derivative compound, hydrazide derivative compound and the like. 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.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-15701, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-59656A. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520 can be used.

Specific examples of the migration inhibitor include the following compounds.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, and is 0. .05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.
The migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, 1,4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4, 4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N- Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline , 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium Salts, bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication WO2015 / 125469 can also be used.
In addition, the following compounds can be used (Me is a methyl group).
When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is particularly preferable.
The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication WO2011 / 080992A1, JP-A-2014-191252. Examples thereof include the compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

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

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly preferably 0, based on 100 parts by mass of the polymer precursor. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Base 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.

<< Thermal base generator >>
The type of thermal base generator is not particularly specified, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having pKa1 of 0 to 4 and an ammonium cation. It is preferable to contain a thermobase generator containing at least one of these. Here, pKa1 indicates a logarithmic representation (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid.
By blending such a compound, the cyclization reaction of the polymer precursor can be carried out at a low temperature, and a composition having more excellent stability can be obtained. Further, since the thermobase generator does not generate a base unless it is heated, it can suppress the cyclization of the polymer precursor during storage even when coexisting with the polymer precursor, and is excellent in storage stability.

The thermobase generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. Is preferably included.
Since the acidic compound (A1) and the ammonium salt (A2) generate bases when heated, the bases generated from these compounds can promote the cyclization reaction of the polymer precursor and cyclize the polymer precursor. It can be done at low temperature. Further, even if these compounds coexist with a polymer precursor that is cyclized and cured by a base, the cyclization of the polymer precursor hardly proceeds unless it is heated, so that a polymer precursor having excellent stability is prepared. be able to.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added, and the compound is added at room temperature for 1 hour. Stir. It means a compound having a value of less than 7 measured at 20 ° C. using a pH meter for the solution.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C. or higher, more preferably 135 ° C. or higher.
When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, bases are less likely to be generated during storage, so that a polymer precursor having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polymer precursor can be lowered. For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated to 250 ° C. in a pressure resistant capsule at 5 ° C./min, the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine is highly basic, the cyclization temperature of the polymer precursor can be further lowered. The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 140 ° C. or higher. The molecular weight of the generated 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 value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.

The ammonium salt used as the thermobase generator is preferably a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, or may be held outside the molecule of the ammonium cation, but may be held outside the molecule of the ammonium cation. preferable. The fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the non-molecular anion of the cation part is also referred to as a counter anion.
Wherein ^R N1 ^{to R N6} are independently a hydrogen atom or a hydrocarbon group (preferably 1 to 36 carbon atoms, more preferably 1 to 24, particularly preferably 1 to 12) represents, an alkyl group (carbon number 1-36 is preferable, 1 to 24 is more preferable, 1 to 23 is particularly preferable), an alkenyl group (2 to 36 carbon atoms is preferable, 2 to 24 is more preferable, 2 to 23 is particularly preferable), and an alkynyl group (is preferable. The number of carbon atoms is preferably 1 to 36, more preferably 1 to 24, particularly preferably 1 to 23), and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms). ..
^RN7 represents a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), and an alkylidene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms).
R ^N1 and ^{R N2, R N3} and ^{R N4, R N5} and ^{R N6, R N5} and ^{R N7} may be bonded to each other to form a ring. When forming the ring, the above-mentioned linking group L or the hetero-linking group Lh described later may be interposed in the middle thereof. R ^N1 to R ^N7, to the extent that does not impair the effects of the present invention, may have a substituent group T described above.

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

In Formula ^{(Y1-1) ~ (Y1-6),} R N101 is Nn number (Nn is an integer of 1 to 12) represents an organic group, Nn-valent group (carbon number 1 based upon alkane 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable), and an alkene-based Nn-valent group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable. ), Nn-valent groups based on aromatic hydrocarbons (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), or combinations thereof. Among them, ^RN101 is preferably an aromatic hydrocarbon group. ^RN101 may have the above-mentioned substituent T as long as the effect of the present invention is not impaired. When ^RN101 is an alkane-based group or an alkene-based group, the following heterolinking group Lh may be interposed.
R ^N1 and ^{R N7} are the same meaning as ^{R N1} and ^{R N7} in formula (101) or formula (102).
^RN8 is an alkyl group (preferably 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, particularly preferably 4 to 18 carbon atoms), an alkenyl group (preferably 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, 4 to 18 carbon atoms). Is particularly preferred), an alkynyl group (preferably 2-36 carbons, more preferably 2-24, particularly preferably 4-18), an aryl group (preferably 6-22 carbons, more preferably 6-18, 6). 10 is particularly preferable). At this time, the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may have a linking group Lh having a heteroatom interposed in the middle of the chain or in the connection with the mother nucleus. Examples of the linking group Lh having a heteroatom include -O-, -S-, -C (= O)-, -NR ^3- , or a linking group related to a combination thereof. The number of linking groups Lh having a hetero atom is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. R ³ is a hydrogen atom or an alkyl group (preferably a methyl group). ^RN8 may further have the above-mentioned substituent T as long as the effect of the present invention is not impaired.
R ^N9 is preferably a group synonymous with R ^N8 . Among them, an aryl group-containing group is preferable, an aryloyl group-containing group is more preferable, and an aryloyl alkyl group (alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). preferable. At this time, a substituent T may be further introduced into the aromatic ring of the aryl group or the aryloyl group as long as the effect of the present invention is not impaired.
In the formula (Y1-4), Ar ^N101 and Ar ^N102 each independently represent an aryl group (preferably 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 or more and 12 or less. Nm represents an integer from 0 to 5. No is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.
And if R ^{N1, R N1} and ^{R N8, R N1} and ^{R N7, R N1} and ^{R N9, R N1} and ^{Ar N101, R N1} and ^{Ar N102, Ar N101} and ^{Ar N102} are bonded to each other to form a ring May be good. When forming the ring, the above-mentioned linking group L or the hetero-linking group Lh described later may be interposed in the middle thereof.

In the present embodiment, the ammonium salt preferably 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 even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and the stability of the composition can be improved. When pKa1 is 4 or less, the stability of the thermobase generator is good, the generation of bases can be suppressed without heating, and the stability of the composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polymer precursor or the like is good.
The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphate anion and sulfate anion, and more preferably carboxylic acid anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to obtain a thermobase generator capable of further improving the stability, curability and developability of the composition. In particular, the use of a divalent carboxylic acid anion can further improve the stability, curability and developability of the composition.
In the present 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 even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
Here, pKa1 indicates a logarithmic representation (-Log10Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid, and is Determination of Organic Structures by Physical Methods (author: Brown, HC, Mc. , D.H., Hafliger, O., Nachod, F.C .; Compilation: Braude, E.A., Nachod, F.C .; Academic Press, New York, 1955), and Data : Dawson, RMC et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that the substituent constant σm of Hammett shows a positive value. Here, σm is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value include CF ₃ groups (σm = 0.43), CF ₃ CO groups (σm = 0.63), HC≡C groups (σm = 0.21), and the like. CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = _0.34), H ₂ NCOCH 2 group (σm = 0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 independently contain a hydrogen atom and an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3). Especially preferable), alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6 to 6). 10 is particularly preferable), or represents a hydroxyl group, or a carboxyl group. However, ^{R X1} of formula (EWG-1), is not ^{R X1} of formula (EWG-4) is a carboxyl group. Ar represents an aromatic group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms). When R ^{x1 to} R ^x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and when the ring is formed, the above-mentioned linking group L or the heterolinking group Lh described later is interposed in the middle. May be. When R ^{x1 to} R ^x3 are an alkyl group, an alkenyl group, or an aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired. Among them, Ar preferably has a carboxyl group (preferably 1 to 3).
Np is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

In the present embodiment, the carboxylic acid anion is preferably represented by the following formula (XA).
Equation (XA)
In the formula (XA), L ¹⁰ is a single bond, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 6 carbon atoms), an alkenylene group (2 to 12 carbon atoms are preferable). Preferably, 2 to 6 are more preferred, 2-3 are particularly preferred), aromatic groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 10 are particularly preferred), -NR ^X- and these. represents a divalent linking group selected from the combination of, ^{R X} is a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms, more preferably 1-6, particularly preferably 1 to 3), an alkenyl group (carbon The number 2 to 12 is preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable) or an aryl group (carbon number 6 to 22 is preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable).

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
Details of the thermobase generator can be referred to in paragraphs 0021 to 0077 of JP-A-2016-0273557, and these contents are incorporated in the present specification.
Examples of the thermobase generator include the following compounds.

When a thermobase generator is used, the content of the thermobase generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.25% by mass or more, and further preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less.
As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
Further, as one embodiment of the present invention, a configuration that does not substantially contain a thermal base generator can be used. The term "substantially free" means that the total solid content of the composition is less than 0.1% by mass, and further, it may be 0.01% by mass or less, particularly 0.001% by mass or less. it can.

<< Photobase generator >>
The photosensitive resin composition used in the present invention may contain a photobase generator. A photobase generator is a substance that generates a base by exposure and does not show activity under normal conditions of normal temperature and pressure, but when it is irradiated with electromagnetic waves and heated as an external stimulus, it is a base (basic substance). ) Is not particularly limited as long as it occurs. Since the base generated by exposure acts as a catalyst when the polymer precursor is cured by heating, it can be suitably used when performing a developing process.

In the present invention, known photobase generators can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A.M. Sarker, and D. Neckers, Chem. Mater. , 11, 170 (1999); Tachi, M. et al. Shirai, and M. Tsunooka, J. Mol. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J. et al. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H. et al. Araki, M. et al. Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those in which the amidin moiety is latent by forming a salt with a carboxylic acid. , Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
The generated basic substance is preferably a compound having an amino group having a higher degree of basicity. This is because such a compound has a strong catalytic action on the dehydration condensation reaction and the like in the imidization of the polymer precursor, and the addition of a smaller amount makes it possible to exhibit the catalytic effect in the dehydration condensation reaction and the like at a lower temperature. .. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the photosensitive resin composition is improved.
From the viewpoint of the above catalytic effect, the basic substance is preferably amidine or an aliphatic amine.
The photobase generator used in the present invention preferably contains an aromatic ring and the generated basic substance is a compound having an amino group.

Examples of the photobase generator according to the present invention include a photobase generator having a katsura acid amide structure as disclosed in JP-A-2009-80452 and International Publication No. 2009/123122, JP-A-2006-. Photobase generators having a carbamate structure as disclosed in JP-A-189591 and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581. Examples thereof include a photobase generator having a carbamoyloxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.

Other examples of the photobase generator include the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples include the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204319 and the compounds described in paragraphs 0052 of International Publication WO2010 / 064631.

Commercially available photobase generators include WPBG-266, WPBG-300, WPBG-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.
Moreover, the following compounds are exemplified as a photobase generator. Et represents an ethyl group and Me represents a methyl group.

When a photobase generator is used, the content of the photobase generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
As the photobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
Further, as one embodiment of the present invention, a configuration that does not substantially contain a photobase generator can be used. The term "substantially free" means that the total solid content of the composition is less than 0.1% by mass, and further, it may be 0.01% by mass or less, particularly 0.001% by mass or less. it can.

<Other additives>
The photosensitive resin composition of the present invention contains various additives such as a thermoacid generator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher grade, if necessary, as long as the effects of the present invention are not impaired. Fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<< Thermal Acid Generator >>
The photosensitive resin composition of the present invention may contain a thermoacid generator. The thermoacid generator generates an acid by heating, promotes the cyclization of the polymer precursor, and further improves the mechanical properties of the cured film. Examples of the thermoacid generator include the compounds described in paragraph 0059 of JP2013-167742A.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymer precursor. By containing 0.01 part by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical 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.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<< Sensitive Dye >>
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 the electron-excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes actions such as electron transfer, energy transfer, and heat generation. As a result, the thermal base generator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye may be 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. 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 the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

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

<< Surfactant >>
Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.

<< Higher fatty acid derivatives >>
In the photosensitive resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the surface of the composition is dried in the process of drying after application. It may be unevenly distributed in.
When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative shall be 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<Restrictions on other contained substances>
The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 parts by mass (parts per million), more preferably less than 1 parts by mass, and particularly preferably less than 0.5 parts by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

The photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm, from the viewpoint of wiring corrosiveness. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

As a storage container for the photosensitive resin composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into the raw materials and compositions, the inner wall of the container is made of a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are formed into a 7-layer structure. It is also preferable to use a bottle of plastic. Examples of such a container include the container 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 a conventionally known method can be used.
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. 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 filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Cured film, laminate, semiconductor device, and manufacturing method thereof>
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
The cured film of the present invention is 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 can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

Two or more layers of the cured film of the present invention may be laminated to form a laminated body. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

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

The cured film in the present invention can also be used for producing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Preferably, 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 the exposed photosensitivity Examples thereof include a method for producing a cured film, which comprises a developing treatment step of performing a developing treatment on the sex resin composition layer (resin layer). The photosensitive resin composition of the present invention is preferably used when developing.

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, after forming the cured film according to the method for producing a cured film of the present invention, the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are further performed. It is preferable to repeat the procedure in order. In particular, it is preferable that the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are further performed 2 to 5 times (that is, 3 to 6 times in total) in the above order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion that has been developed and removed after the cured film is provided and developed.
These details will be described below.

<< Photosensitive resin composition layer forming step >>
The production method according to a preferred embodiment of the laminate of the present invention includes a step of forming a photosensitive resin composition layer by applying the photosensitive resin composition to a substrate to form a layer.
The type of substrate can be appropriately determined according to the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited. In the present invention, a semiconductor-made substrate is particularly preferable, and a silicon substrate is more preferable.
When the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
Coating is preferable as a means for applying the photosensitive resin composition to the substrate.
Specifically, as the means to apply, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, the spin coating method, the slit coating method, etc. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. The coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method, spray coating method, inkjet, etc. The method or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<< Drying process >>
The method for producing a laminate of the present invention may include a step of forming a photosensitive resin composition layer and then drying it to remove a solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<< Exposure process >>
The method for producing a laminate of the present invention may include an exposure step of exposing the photosensitive resin composition layer. Exposure is not particularly limited so long as it can be cured photosensitive resin composition, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365nm, 200~8000mJ / cm ² irradiated Is more preferable.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.
In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. Regarding the photosensitive resin composition according to the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with an i-line is particularly preferable. As a result, particularly high exposure sensitivity can be obtained.

<< Development process >>
The method for producing a laminate of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By performing the development, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted. Development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is 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, and more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acid acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. As the sulfoxides, dimethyl sulfoxide is preferably mentioned.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The developing time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly specified, but is usually 20 to 40 ° C.
After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition. 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, the cyclization reaction of the polymer precursor proceeds. Further, although the composition of the present invention contains a radically polymerizable compound other than the polymer precursor, curing of the radically polymerizable compound other than the unreacted polymer precursor also proceeds. The heating temperature (maximum heating temperature) is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and even more preferably 160 to 350 ° C.
The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature after drying is, for example, a temperature 30 to 200 ° C. lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from.
The heating time (heating time at the maximum 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 multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US 91595947. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<< Metal layer forming process >>
The method for producing a laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer (cured film) after the development treatment.
As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<< Laminating process >>
The production method of the present invention preferably further includes a laminating step.
The laminating step is a series of steps including performing the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step again in the above order. Needless to say, the laminating step may further include the drying step, the heating step, and the like.
When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the exposure step or the metal layer forming step. An example of the surface activation treatment is plasma treatment.
The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a structure in which the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step are performed in the above order so as to cover the metal layer. Is preferable. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin layer) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be laminated alternately.

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

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(Synthesis Example 1)
[Synthesis of polyimide precursor A-1 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below]
21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and heated to a temperature of 60 ° C. Diester of 4,4'-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was prepared by stirring with the mixture for 4 hours. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCL ₂ was added over 60 minutes while keeping the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution prepared by dissolving 38.0 g of the hydroxyl group-containing diamine (a) shown below in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ° C. over 60 minutes. Then, after stirring the mixture for 2 hours, 20 mL of ethyl alcohol was added. The polyimide precursor was then precipitated in 6 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes. The solid polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate the polyimide precursor in water, filtered, and dried under reduced pressure at 45 ° C. for 3 days. This polyimide precursor had a weight average molecular weight of 27400 and a number average molecular weight of 10100.

Diamine (a)

(Synthesis Example 2)
[Synthesis of polyimide precursor A-2 from pyromellitic acid dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl]
14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed, stirred at a temperature of 60 ° C. for 4 hours, and pyromellitic. Diesters of merit acid dianhydride and 2-hydroxyethyl methacrylate were produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCL ₂ was added over 60 minutes while keeping the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 20.1 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl in 100 mL of N-methylpyrrolidone was dissolved at -10 ° C. The mixture was added dropwise to the reaction mixture over 60 minutes, the mixture was stirred for 2 hours, and then 20 mL of ethyl alcohol was added. The polyimide precursor was then precipitated in 6 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes. The solid polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate the polyimide precursor in water, filtered, and dried under reduced pressure at 45 ° C. for 3 days. This 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 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl]
21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Then, a diester of 4,4'-oxydiphthalic acid dianhydride and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCL ₂ was added over 60 minutes while keeping the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 20.1 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl in 100 mL of N-methylpyrrolidone was dissolved at -10 ° C. The mixture was added dropwise to the reaction mixture over 60 minutes, the mixture was stirred for 2 hours, and then 20 mL of ethyl alcohol was added. The polyimide precursor was then precipitated in 6 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes. The solid polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate the polyimide precursor in water, filtered, and dried under reduced pressure at 45 ° C. for 3 days. This 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 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether]
21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Then, a diester of 4,4'-oxydiphthalic acid dianhydride and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCL ₂ was added over 60 minutes while keeping the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 25.1 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ° C. over 60 minutes. After stirring the mixture for 2 hours, 20 mL of ethyl alcohol was added. The polyimide precursor was then precipitated in 6 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes. The solid polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate the polyimide precursor in water, filtered, and dried under reduced pressure at 45 ° C. for 3 days. This 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 from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Subsequently, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate the polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C. for 2 days. This polybenzoxazole precursor had a weight average molecular weight of 25,800 and a number average molecular weight of 9,300.

(Synthesis Example 6)
[Synthesis of radically polymerizable compound B1-1 having a sulfur atom]
109.4 g of 2-hydroxyethyl methacrylate, 70.0 g of pyridine and 500 mL of tetrahydrofuran were mixed. The mixed solution was cooled to 0 ° C., 50.0 g of SOCL ₂ was added dropwise over 60 minutes while keeping the temperature below 5 ° C., and then the mixture was stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. The obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed by an evaporator to obtain 220.1 g of the radically polymerizable compound B1-1. The obtained compound is the above-mentioned exemplary compound 302 of the radically polymerizable compound having a sulfur atom.
^{1 1} H NMR (400 MHz, 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 a sulfur atom]
101.8 g of 4-vinylbenzyl alcohol, 70.0 g of pyridine and 500 mL of tetrahydrofuran were mixed. The mixed solution was cooled to 0 ° C., 50.0 g of SOCL ₂ was added dropwise over 60 minutes while keeping the temperature below 5 ° C., and then the mixture was stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. The obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed by an evaporator to obtain 200.2 g of a radically polymerizable compound B1-2. The obtained compound is the above-mentioned exemplary compound 312 of a radically polymerizable compound having a sulfur atom.

(Synthesis Example 8)
[Synthesis of radically polymerizable compound B1-3 having a sulfur atom]
19.0 g of bis (4-hydroxyphenyl) sulfone, 7.0 g of pyridine and 100 mL of tetrahydrofuran were mixed. The mixed solution was cooled to 0 ° C., 19.0 g of methacrylic acid chloride was added dropwise over 60 minutes while keeping the temperature below 5 ° C., and then the mixture was stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. The obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed by an evaporator to obtain 220.1 g of a radically polymerizable compound B1-3. The obtained compound is the above-mentioned exemplary compound 322 of a radically polymerizable compound having a sulfur atom.

<Measurement method of molecular weight>
The molecular weights (weight average molecular weight, number average molecular weight) of the above polymer precursors were defined as polystyrene-equivalent values according to gel permeation chromatography (GPC method). Specifically, HLC-8220 (trade name: manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (trade name) are used as columns. : Obtained by using Tosoh Corporation). The eluate was measured using THF (tetrahydrofuran). In addition, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) was used for detection. Unless otherwise specified, the molecular weights specified in the present specification are all values measured according to the above-mentioned measuring method.

<Examples 1 to 16 and Comparative Examples 1 to 3>
<< Preparation of photosensitive resin composition >>
Each component shown in Table 1 below was mixed to prepare a uniform solution. The obtained solution was pressure-filtered at a pressure of 0.3 MPa through a filter having a pore width of 0.8 μm to obtain a photosensitive resin composition.

<< Storage stability >>
10 g of the above photosensitive resin composition was sealed in a container (container material: light-shielding glass, capacity: 100 mL) and allowed to stand in an environment of 25 ° C. and a relative humidity of 65%. The stability was evaluated by the time from the photosensitive resin composition to the precipitation of the solid. The longer the time until precipitation, the higher the stability of the photosensitive resin composition, which is a preferable result. For the precipitation of solids, three samples stored in a container were prepared for one type of photosensitive resin composition, and one sample container was opened after 30, 60, and 120 days had passed. Then, the entire amount of the photosensitive resin composition as the content was pressure-filtered with a mesh having a pore size of 0.8 μm, the presence or absence of foreign matter on the mesh was visually observed, and the presence or absence of precipitates was determined as follows.
A: No solid precipitation was observed even after 120 days.
B: The solid was precipitated within 120 days, exceeding 60 days.
C: A solid was precipitated within 60 days beyond 30 days.
D: Solids precipitated within 30 days.

<< Measurement of exposure energy >>
The photosensitive resin composition was spun and applied onto a silicon wafer. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform film having a thickness of 10 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using an aligner (Karl-Sus MA150 [trade name] manufactured by SUSS MICROTEC AG). The exposure was carried out with a high-pressure mercury lamp, and the exposure energy required to cure the above-mentioned 10 μm uniform film at a wavelength of 365 nm was measured. The lower the exposure energy, the higher the sensitivity, which is a preferable result.

(A) Polymer precursors A-1 to A-5: Polymer precursors produced in Synthesis Examples 1 to 5

(B1) Radical polymerizable compound having a sulfur atom B1-1 to B1-3: Radical polymerizable compound having a sulfur atom produced in Synthesis Examples 6 to 8.

(B2) Radical polymerizable compounds (both trade names)
B2-1: NK Ester M-40G (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
B2-2: SR-209 (manufactured by Sartmer)
B2-3: NK Ester A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
B2-4: A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

(C) Photoradical polymerization initiator (both are trade names)
C-1: IRGACURE OXE 01 (manufactured by BASF)
C-2: IRGACURE OXE 02 (manufactured by BASF)
C-3: IRGACURE OXE 04 (manufactured by BASF)
C-4: IRGACURE-784 (manufactured by BASF)
C-5: NCI-831 (manufactured by ADEKA Corporation)

(D) Base generator D-1: The following compound D-2: The following compound D-3: The following compound

(E) Polymerization inhibitor E-1: 1,4-benzoquinone E-2: 1,4-methoxyphenol

(F) Additive (migration inhibitor)
F-1: 1,2,4-triazole F-2: 1H-tetrazole

(G) Silane coupling agent G-1: The following compound G-2: The following compound G-3: The following compound

Et represents an ethyl group.

(H) Solvent H-1: γ-Butyrolactone H-2: Dimethyl sulfoxide H-3: N-methyl-2-pyrrolidone H-4: Ethyl lactate Regarding the solvent in Table 1, for example, the type column is "H". When "-1 / H-2" and the column of parts by mass are "48 + 12", it means that H-1 is contained by 48 parts by mass and H-2 is contained by 12 parts by mass.

As is clear from the results in Table 1 above, it was found that when a radically polymerizable compound having a sulfur atom was used, the storage stability was excellent and the sensitivity was high (Examples 1 to 16). In particular, as shown in Example 20, the superiority of the present invention can be seen in that excellent storage stability and high sensitivity are achieved even when a radically polymerizable compound having a trace amount of sulfur atoms is blended.
On the other hand, when the radically polymerizable compound having a sulfur atom was not blended, the sensitivity became low (Comparative Examples 1 to 3).

<Example 100>
Using the photosensitive resin composition of Example 1, the photosensitive resin composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm ² using a stepper (NSR 2005 i9C [trade name] manufactured by Nikon Corporation), and the exposed photosensitive resin composition layer was exposed. (Resin layer) was developed with cyclopentanone for 60 seconds to form holes having a diameter of 10 μm. Then, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours. After cooling to room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer so as to cover the hole portion. Further, on the surfaces of the metal layer and the photosensitive resin composition layer, the same type of photosensitive resin composition is used again, and the photosensitive resin composition is filtered in the same manner as described above, and the patterned film is heated for 3 hours. The procedure up to the above was carried out again to prepare a laminate composed of a resin layer / metal layer / resin layer.
The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using this interlayer insulating film for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (15)

Polymer precursors selected from polyimide precursors and polybenzoxazole precursors,
Radical-polymerizable compounds with sulfur atoms and
Photoradical polymerization initiator and
And a solvent seen including,
A photosensitive resin composition in which the radically polymerizable compound having a sulfur atom is a compound represented by the following formula (4) .
In formula (4), R is a hydrogen atom or a methyl group. The photosensitive resin composition according to claim 1, wherein the polymer precursor contains a repeating unit represented by the following formula (1) or a repeating unit represented by the following formula (2);
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, respectively.
R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group;
In formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. Represent. The photosensitive resin composition according to claim 2, wherein the polymer precursor contains a repeating unit represented by the formula (1). The photosensitive resin according to any one of claims 1 to 3 , wherein the radically polymerizable compound having a sulfur atom is contained in a proportion of 0.001% by mass or more of the solid content contained in the photosensitive resin composition. Composition. The photosensitive resin composition according to any one of claims 1 to 4 , further comprising a radically polymerizable compound other than the radically polymerizable compound having a sulfur atom. The photosensitive resin composition according to any one of claims 1 to 5 , further comprising a base generator. The photosensitive resin composition according to any one of claims 1 to 6 , which is used for development. The photosensitive resin composition according to any one of claims 1 to 7 , which is used for developing with a developing solution containing an organic solvent. The photosensitive resin composition according to any one of claims 1 to 8 , which is used for forming an interlayer insulating film for a rewiring layer. A cured film formed from the photosensitive resin composition according to any one of claims 1 to 9 . A laminated body having two or more layers of the cured film according to claim 10 . The laminate according to claim 11 , which has a metal layer between the cured films. A method for producing a cured film, which comprises using the photosensitive resin composition according to any one of claims 1 to 9 . A step of forming a photosensitive resin composition layer by applying the photosensitive resin composition to a substrate to form a layer,
An exposure step for exposing the photosensitive resin composition layer and
The method for producing a cured film according to claim 13 , further comprising a developing treatment step of performing a developing treatment on the exposed photosensitive resin composition layer. A semiconductor device having the cured film according to claim 10 or the laminate according to claim 11 or 12 .