TW201902991A - Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device and compound - Google Patents

Abstract

Provided are: a photosensitive resin composition which has excellent storage stability, while exhibiting high sensitivity; and a cured film, a laminate, a method for producing a cured film, and a semiconductor device, each of which uses this photosensitive resin composition. Also provided is a novel compound which is used for the purpose of forming a photosensitive resin composition. A photosensitive resin composition which contains: a polymer precursor that is selected from among polyimide precursors and polybenzoxazole precursors; a radically polymerizable compound having a sulfur atom; a radical photopolymerization initiator; and a solvent.

Description

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

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, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical properties have been used as protective films and interlayer insulating films of semiconductor devices. However, in recent years, with the development of high integration and large-scale development of semiconductor devices, it is required to reduce the thickness and size of sealing resin packages, and adopt surface mount methods using LOC (lead-on-chip) or reflow methods. .

In the production of such a semiconductor device, a photosensitive resin composition that imparts sensitivity to a polyimide resin itself is used. The reason is that by using a photosensitive resin composition, the pattern forming step can be simplified. For example, Patent Document 1 discloses a resin composition including (a) a polyimide precursor having a predetermined structure, (b) a compound that generates radicals upon irradiation with active light, and (c) the following: A compound represented by formula (4a) or (4b) and (d) a solvent. [Chemical Formula 1] (In formula (4a), na is an integer of 3 or less. In formula (4b), R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a monovalent group. Mb is an integer of 9 or less.) Specifically, as The compound represented by the formula (4a) or (4b) discloses tripropylene glycol diacrylate or tripropylene glycol. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2014-201695

However, it was found that the composition described in Patent Document 1 is not necessarily high in light sensitivity. In addition, when the photosensitive resin composition is held for a certain period of time and 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, and to provide a photosensitive resin composition having excellent storage stability and high sensitivity, a method for manufacturing a cured film, a laminate, a cured film using the same, and a semiconductor device. Another object is to provide a compound for producing the above-mentioned photosensitive resin composition.

Based on the above problems, as a result of intensive studies, the inventors have found that the above problems can be solved by blending a photosensitive polymer composition with a radical polymerizable compound having a sulfur atom. Specifically, the above-mentioned problem is solved by the following mechanism <1>, preferably by <2> to <22>. <1> A photosensitive resin composition comprising: a polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; a radical polymerizable compound having a sulfur atom; a photoradical polymerization Initiators; and solvents. <2> The photosensitive resin composition according to <1>, wherein the polymer precursor includes a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2); [Chemical Formula 2] In Formula (1), A ¹ and A ² each 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 each independently represent a hydrogen atom or a monovalent group. Organic group; [Chemical Formula 3] In the formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. <3> The photosensitive resin composition according to <2>, wherein the polymer precursor includes a repeating unit represented by formula (1). <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the radical polymerizable compound having a sulfur atom is represented by the following formula (3-1); [Chemical Formula 4] In formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom, 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 1 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 bonded to 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); [Chemical Formula 5] In formula (3-2), L ¹ represents -S-, -SS-, -S (= O)-or -S (= O) _2- , and X ¹ and X ² each independently represent a single bond, -O -, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O) ₂ -or -NR ³ CO-, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a radical polymerizable group, and La ¹ to La ⁴ each independently represent a single bond, one or two or more of an alkylene group and a phenylene group. Any one of a group consisting of a combination of R 2 and a combination of 1 or more of alkylene and phenylene with -O-; R ³ represents a hydrogen atom or an alkyl group; wherein R ¹ And at least one of R ² is a radical polymerizable group. <6> The photosensitive resin composition according to <5>, wherein the two R ¹ and R ² are each independently a radical polymerizable group. <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 the 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 each independently a monovalent organic group having an acrylfluorenyl group or a methacrylfluorenyl group. <10> The photosensitive resin composition according to <4>, wherein the formula (3-1) is represented by the following formula (4); [Chemical Formula 6] In formula (4), R is a hydrogen atom or a methyl group. <11> The photosensitive resin composition according to any one of <1> to <10>, which contains the sulfur atom in a proportion of 0.001% by mass or more of the solid content contained in the photosensitive resin composition. Radical polymerizable compounds. <12> The photosensitive resin composition according to any one of <1> to <11>, further comprising a radical polymerizable compound other than a radical polymerizable compound having a sulfur atom. <13> The photosensitive resin composition according to any one of <1> to <12>, further comprising an alkali generator. <14> The photosensitive resin composition according to any one of <1> to <13>, which is used for development. <15> The photosensitive resin composition according to any one of <1> to <14>, which is used for development using a developer containing an organic solvent. <16> The photosensitive resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a redistribution layer. <17> A cured film formed from the photosensitive resin composition according to any one of <1> to <16>. <18> A laminated body comprising the hardened film according to <17> in two or more layers. <19> The laminated body according to <18>, which has a metal layer between the cured films. <20> A method for producing a cured film, including the case where the photosensitive resin composition according to any one of <1> to <16> is used. <21> The method for producing a cured film according to <20>, comprising: a step of forming a photosensitive resin composition layer, applying the photosensitive resin composition to a substrate to form a layer; The photosensitive resin composition layer is subjected to exposure; and a development process step, where the exposed photosensitive resin composition layer is subjected to a development treatment. <22> A semiconductor device comprising the cured film according to <17> or the laminated body according to <18> or <19>. [Inventive effect]

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, a laminated body, a method for producing a cured film, and a semiconductor device using the photosensitive resin composition. In addition, it is possible to provide a novel compound for use in the photosensitive resin composition.

The content of the present invention will be described below. In addition, in this specification, "~" means the meaning which uses the numerical value described before and after that as a lower limit and an upper limit.

The description of the constituent elements in the present invention described below may be made based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the label of a group (atomic group) in this specification, the descriptions of the substituted and unsubstituted labels include both those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) having no substituents, but also alkyl groups (substituted alkyl groups) having substituents. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for exposure, active light rays such as bright line spectrum of a mercury lamp and excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In the present specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth) acrylic" means "acrylic" and "methacrylic" Either or both, "(meth) acrylfluorenyl" means either or both of "acrylfluorenyl" and "methacrylfluorenyl". In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the desired effect on the step can be achieved, it is also included in this term. In the present specification, the solid content refers to the mass percentage of components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25 ° C. In this specification, unless otherwise stated, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined based on gel permeation chromatography (GPC measurement), and are defined as styrene conversion values. In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.

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

<Polymer Precursor> The photosensitive resin composition of the present invention includes a polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. As the polymer precursor, a polyfluorene imide precursor or a polybenzoxazole precursor is preferable, and a polyfluorine imide precursor is more preferable. The polymer including a repeating unit represented by the formula (1) described later is more preferable. The fluorene imine precursor is further preferred.

<<< Polyimine precursor> It is preferable that the polyfluorene imide precursor contains a repeating unit represented by the following formula (1). [Chemical Formula 7] In Formula (1), A ¹ and A ² each 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 each independently represent a hydrogen atom or a monovalent Organic.

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

It is preferred that R ¹¹¹ is derived from a diamine. Examples of the diamine used in the production of the polyfluorene imide precursor include a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine. The diamine may be used alone or in combination of two or more. Specifically, the diamine includes 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. A group is more preferable, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following aromatic groups.

[Chemical Formula 8] In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C (= O)-, -S-, -S (= O) ₂ -which may be substituted with a fluorine atom. , -NHCO- and groups in combinations thereof are preferred, single bond, selected from alkylene having 1 to 3 carbon atoms which may be substituted by fluorine atom, -O-, -C (= O)-, The groups in -S-, -S (= O) ₂ -are more preferably selected from the group consisting of -CH _2- , -O-, -S-, -S (= O) _2- , -C (CF ₃ ) ₂ -and -C (CH ₃ ) ₂ -are more preferably divalent groups.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclo Hexane or 1,4-diaminocyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis ( Aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4, 4'-diaminodiphenylphosphonium and 3,3-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4 , 4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'- Aminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amine Phenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl ) 碸, bis (4-amino-3-hydroxyphenyl) 碸, 4,4'-diamino p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) phenyl] Hydrazone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diamine Diphenylphosphonium, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) Benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4 ' -Diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) benzene ] 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'-diamine Diphenylphosphonium, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene Ene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-xylylenediamine Amine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) Ethane, diaminobenzidineaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis (4-aminophenyl) hexafluoro Propane, 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-dimethylphenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2- Trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-tri Fluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5 -Trifluoromethylphenoxy) diphenylphosphonium, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5 At least one diamine among 5,5 ', 6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl.

Diamines (DA-1) to (DA-18) shown below are also preferred.

[Chemical Formula 9]

[Chemical Formula 10]

In addition, as a preferable example, a diamine having at least two or more alkylene glycol units in the main chain may be mentioned. A diamine containing one or more of two or more ethylene glycol chains and propylene glycol chains in one molecule is preferred, and a diamine containing no aromatic ring is more preferred. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are the product names, manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropyl) Oxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropyloxy) propane-2-yl) oxy) propane-2-amine, etc., But it is not limited to these. JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( (Registered trademark) EDR-176 structure.

[Chemical Formula 11]

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

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ is preferably represented by -Ar ⁰ -L-Ar ^0- . Among them, Ar ^{0 is} each independently an aromatic hydrocarbon group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, and 6 to 10 is particularly preferred), and L is a carbon number 1 to 10 including fluorine atoms which may be substituted. Aliphatic hydrocarbon group, -O-, -C (= O)-, -S-, -S (= O) ₂ -or -NHCO-, and a group containing a combination of two or more of the above. Ar ⁰ is preferably a phenylene group, and L is an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C (= O)-, -S-, or -S (= O) ₂ -is further preferred. Among them, an aliphatic hydrocarbon-based alkylene group is preferred.

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, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and ease of availability. Formula (51) [Chemical Formula 12] In Formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or a difluoromethyl group. Or trifluoromethyl. When R ⁵⁰ to R ⁵⁷ are monovalent organic groups, unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and 1 to 10 carbon atoms (preferably carbon number 1) may be mentioned. ~ 6) Fluorinated alkyl and the like. Formula (61) [Chemical Formula 13] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group. Examples of the diamine compound imparting a structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4 '-Diaminobiphenyl, 2,2'-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. One of these may be used, or two or more of them may be used in combination.

R ¹¹⁵ in 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. Formula (5) [Chemical Formula 14] In Formula (5), R ¹¹² is a single bond or selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted by a fluorine atom, -O-, -C (= O)-, -S-, -S (= O) _2- , -NHCO- and groups thereof are preferred, and are single bonds, selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C ( = O)-, -S- and -S (= O) ₂ -are more preferably selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- Divalent groups in the group of -O-, -C (= O)-, -S- and -S (= O) ₂ -are further preferred.

Formula (6) [Chemical Formula 15]

Specific examples of the tetravalent organic group represented by R ¹¹⁵ in formula (1) include a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride. Tetracarboxylic dianhydride may be used alone, or two or more of them may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 16] In the formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same as defined in formula (1) is R ^115.

Specific examples of the tetracarboxylic dianhydride include those selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3 ', 4,4'-Diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonium tetracarboxylic dianhydride, 3,3 ', 4,4'-dibenzoyl Ketotetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3 , 3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane- 3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3, 4,9,10-fluorenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-di Phenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives of 1 to 6 carbon and / or alkoxy derivatives of 1 to 6 carbon At least one of them.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are mentioned. [Chemical Formula 17]

In the formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is preferably a repeating unit containing a radical polymerizable group, and both of them contain Radical polymerizable groups are more preferred. The radical polymerizable group is a group capable of performing a cross-linking reaction by the action of a radical, and a preferable example includes 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) acrylfluorenyl group, and a group represented by the following formula (III). In addition, (meth) acrylfluorenyl is a general term for acrylfluorenyl and methacrylfluorenyl.

[Chemical Formula 18]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents 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, carbon number 1 -12 is more preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred; repeating numbers 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred). Examples of preferred R ²⁰¹ include ethylene, propyl, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. methylene, octamethylene, _{dodecamethylene, -CH 2 CH (OH) CH} 2 - , ethyl stretching, stretch propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is more good. Particularly preferred are R ^200- based methyl groups and R ^201- based ethylene groups. As the monovalent organic group represented by R ¹¹³ or R ¹¹⁴ , a substituent that improves the solubility of the developing solution can be preferably used.

When R ¹¹³ or R ¹¹⁴ is a monovalent organic group, there may be mentioned one, two or three acid groups bonded to a carbon constituting an aryl group, and an aromatic group and an alkyl group having one acid group are preferred. Wait. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group, and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. From the viewpoint of solubility in an aqueous developer, R ¹¹³ or R ¹¹⁴ is more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are more preferable, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1 to 30 (in the case of a cyclic group, it is 3 or more). The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecane Octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, fluorenyl, camphenyl, decalinyl, tricyclodecyl, tetracyclodecyl, and fluorenyl. Fluorenyl, dicyclohexyl and pinenyl. Among them, cyclohexyl is the most preferable from the viewpoints of both the balance and high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described later. Examples of the aromatic group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentenene ring, an indene ring, a fluorene ring, a heptene ring, an indenene ring, a fluorene ring, a fused pentaphenyl ring, and pinene Ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, fluorene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, Pyridine ring, pyrimidine ring, pyridyl ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinone ring, quinoline ring, phthaloline ring, naphthyridine ring, quinoxaline Ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiathracene ring, chromene ring, kouyamaguchi ring, morphine ring, phenothialine ring or Brown ring. The benzene ring is the best.

In formula (1), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyfluorene imide precursor may form a conjugate base with a third amine compound having an ethylenically unsaturated bond. Examples of the third amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropylmethacrylate.

It is also preferred that the polyfluorene imide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but it is actually 50% by mass or less.

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

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, it is preferred that at least one of the polyimide precursors used in the present invention has a repeating unit precursor represented by the formula (1-A). With these structures, the width of exposure latitude can be further increased. Formula (1-A) [Chemical Formula 19] In Formula (1-A), A ¹¹ and A ¹² represent an oxygen atom or NH, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. At least one of R ¹¹³ and R ¹¹⁴ is a group containing a radical polymerizable group, and a radical polymerizable group is preferred.

The definitions of A ¹¹ , A ¹² , R ¹¹¹ , R ^113, and R ¹¹⁴ are independently the same as A ¹ , A ² , R ¹¹¹ , R ^113, and R ^{114 in} Formula (1), and the preferred ranges are also the same. The same as R (5) R ¹¹² is as defined in Formula ^112, the preferred range is also the same.

In the polyimide precursor, the repeating 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 formula (1). In addition to the repeating unit of the formula (1), the polyfluorene imide precursor may contain other kinds of repeating structural units.

As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total repeating unit may be exemplified, and furthermore, 70 mol% or more, and particularly 90 mol% or more may be represented by formula (1). Polyimide precursors of repeating units. The upper limit is actually 100 mol% or less.

The weight average molecular weight (Mw) of the polyfluorene imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The dispersion degree of the polyfluorene imide precursor is preferably 1.5 to 3.5, and 2 to 3 is more preferable.

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

In the production of a polyimide precursor, it is preferred to include a step of precipitating a solid. Specifically, a polyfluorene imide precursor in the reaction solution is precipitated in water, and a polyfluorene imide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solids can be precipitated.

<< Polybenzoxazole precursor> The polybenzoxazole precursor used in the present invention preferably includes a repeating unit represented by the following formula (2). [Chemical Formula 20] In the formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In the formula (2), R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is particularly preferred) and an aromatic group (carbon number 6 to 22 is preferred, 6 to 6) 14 is more preferred, and 6 to 10 are particularly preferred. As the aliphatic group, a linear aliphatic group is preferred. More preferably, R ^{121 is} derived from 4,4'-oxodibenzoyl chloride. In formula (2), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, the definition is the same as that of R ¹¹⁵ in the formula (1), and the preferred range is also the same. R ¹²² is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R ¹¹³ and R ¹¹⁴ in the formula (1), and preferred ranges are also the same.

In addition to the repeating unit of formula (2) described above, the polybenzoxazole precursor may also contain other kinds of repeating structural units. From the viewpoint of suppressing the occurrence of warping of the cured film accompanying the ring closure, it is preferable to include a diamine residue represented by the following formula (SL) as another kind of repeating structural unit.

[Chemical Formula 21] In the formula (SL), Z has an a structure and a b structure, 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 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group (preferably 6 to 22 carbons, more preferably 6 to 18 carbons, particularly preferably 6 to 10 carbons, the remainder is a hydrogen atom or 1 to 30 carbons (preferably 1 to 18 carbons, more preferably carbons) The number is 1 to 12, and an organic group having 1 to 6 carbon atoms is particularly preferred, and may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mole%, the b structure is 95 to 5 mole%, and a + b is 100 mole%.

In the formula (SL), examples of preferred Z include 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, and more preferably 500 to 3,000. The molecular weight can be determined by gel permeation chromatography generally used. By setting the molecular weight to the above range, it is possible to have both the effect of reducing the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, and the effect of suppressing warpage and the effect of improving solubility.

When the diamine residue represented by the formula (SL) is included as another kind of repeating structural unit, from the viewpoint of improving the alkali solubility, the tetracarboxylic acid residue remaining after removing the acid dianhydride from the tetracarboxylic dianhydride is also included. It is preferred that it is based on repeating structural units. Examples of such a tetracarboxylic acid residue include an example of R ¹¹⁵ in formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The dispersion degree of the polybenzoxazole precursor is preferably 1.5 to 3.5, and more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20 to 100% by mass, more preferably 30 to 99% by mass, and 40 to 98% by mass based on the total solid content of the composition. Preferably, 50 to 95% by mass is further preferred, 60 to 95% by mass is further preferred, and 70 to 95% by mass is further preferred. The polymer precursor may contain only one kind, or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably in the above range.

<A radical polymerizable compound having a sulfur atom> The photosensitive resin composition of the present invention contains a radical polymerizable compound having a sulfur atom. One embodiment of the radically polymerizable compound having a sulfur atom is a radically polymerizable group having two or more (preferably 2 to 4, more preferably 2 to 3, and even more preferably 2) Free radical polymerizable compound of sulfur atom. The radical polymerizable compound having a sulfur atom is preferably a compound represented by the following formula (3-1). [Chemical Formula 22] In formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom, 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 1 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 bonded to each other to form a ring.

In the formula (3-1), L ¹¹ represents a divalent linking group containing a sulfur atom. A linker having one or two sulfur atoms is preferred, and a linker having one to two sulfur atoms and two to six atoms of oxygen atoms is more preferred. More preferably, the definition is the same as that of L ^{1 in} the formula (3-2) described later, and the preferred 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. Examples of the divalent linking group include a linear or branched alkylene group (carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are particularly preferred), and aromatic groups (carbon number 6 ～ 22 is preferred, 6 ～ 14 is more preferred, and 6 ～ 10 is particularly preferred), -O-, -S-, -C (= O)-, -NR ^3- , -NR ³ CO- and others Linker of the combination. The same as R (3-2) as defined in the formula R ^{3 3} described after. The linking group may be a hydrocarbon group. The hydrocarbon group may be an oligomeric hydrocarbon group. In this case, the repeating number is preferably 1 to 24, 1 to 12 is more preferable, and 1 to 6 is particularly preferable. The carbon number of the hydrocarbon group is preferably from 1 to 24, more preferably from 1 to 12, and particularly preferably from 1 to 6. When the number of atoms of the linking group is other than an oligomeric hydrocarbon group, the number of atoms is preferably from 1 to 24, more preferably from 1 to 12, and particularly preferably from 1 to 6. When it is a (oligomeric) hydrocarbon group, 2 to 64 atoms are preferred, 2 to 32 are more preferred, and 2 to 18 are particularly preferred. The divalent linking group represented by X ¹¹ and X ¹² is an oxygen atom, a sulfur atom, or a divalent linking group containing a nitrogen atom (the number of atoms is 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred ) Is more preferred, and a divalent linking group containing an oxygen atom is more preferred.

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 radical polymerizable group, a substituent T described later, and the like. Examples of the radical polymerizable group include a group having a carbon-carbon unsaturated double bond. Among them, as the radical polymerizable group, a group having a vinyl group, an allyl group, an acryl group, or a methacryl group is more preferable, and a group having an acryl group or a methacryl group is more preferable. More specifically, propenyl, methacryl, propyl, methacryl, methacryl, methacryl, methacryl, vinyl, vinylphenyl (ortho, m , P), vinyl phenoxy (o, m, p), vinylphenylmethyl (o, m, p) are preferred, acrylfluorenyl, methacrylfluorenyl, acryloxy, methyl Acrylic acid groups, acrylic acid groups, and methacrylic acid groups are more preferable, and acrylic acid groups and methacrylic acid groups are more preferable. The monovalent organic group containing a radical polymerizable group may be a group having only one radical polymerizable group, or a group having two or more radical polymerizable groups. When the 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. Moreover, as long as the effect of this invention is not impaired, the monovalent organic group containing a radically polymerizable group may further have the substituent mentioned later. Examples of the substituent include a substituent T described later. The number of radical polymerizable groups contained in one monovalent organic group is preferably 3 or less, and more preferably 2 or less. In the present invention, a state in which a monovalent organic group containing a radical polymerizable group does not have a substituent can be preferably exemplified.

In formula (3-1), at least one of R ¹¹ and R ¹² represents a monovalent organic group containing at least one radical polymerizable group. Among them, R ¹¹ and R ¹² are each independently a monovalent organic group containing a radical polymerizable group. In formula (3-1), the number of radical polymerizable groups in one molecule is preferably two or more, more preferably four or less, more preferably three or less, and two more good.

In formula (3-1), R ¹¹ and R ¹² may be bonded to each other to form a ring. When R ¹¹ and R ¹² form a ring, R ¹¹ and R ¹² may be directly connected or may be connected through a linking group L described later. The formed ring may be a condensed ring. Examples of the linking group L include a linear or branched alkylene group (carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are particularly preferred), -O-, -S-, -C (= O)-, -NR ^3- , -NR ³ CO- and combinations of these. Defined the same as R ³ of the above (3-2) in R ^3, the preferred ranges are also the same.

The radical polymerizable compound having a sulfur atom is more preferably represented by the following formula (3-2). [Chemical Formula 23] In Formula (3-2), L ¹ represents -S-, -SS-, -S (= O)-, or -S (= O) _2- , and X ¹ and X ² each independently represent a single bond, -O-, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O) ₂ -or -NR ³ CO-, R ¹ And R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a radical polymerizable group, and La ¹ to La ⁴ each independently represent a single bond, one or two of an alkylene group and a phenylene group. Any one of a group consisting of a combination of two or more, and a group consisting of one or two or more of an alkylene group and a phenylene group and -O-; R ³ represents a hydrogen atom or an alkyl group; At least one of R ¹ and R ² is a radical polymerizable group.

In the formula (3-2), L ¹ represents -S-, -SS-, -S (= O)-or -S (= O) _2- , and -S (= O)-is more preferred. X ¹ and X ² each independently represent a single bond, -O-, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O ) ₂ -or -NR ³ CO-, single bond or -O- is preferred, and -O- is more preferred. R ³ represents a hydrogen atom, an alkyl group (1 to 12 carbons is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), an alkenyl (2 to 12 carbons is preferred, 2 to 6 is more preferred) 2 to 3 are particularly preferred), alkynyl (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), and aryl (6 to 22 carbons are preferred, 6 -18 is more preferred, 6-10 is particularly preferred), and a hydrogen atom or an alkyl group having the above carbon number is more preferred. R ¹ and R ² each independently represent a radical polymerizable group, a hydrogen atom, an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is particularly preferred), cycloalkyl (carbon The number 3 to 24 is preferred, 3 to 12 is more preferred, 3 to 6 is particularly preferred) or aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, and 6 to 10 is particularly preferred). When R ¹ and R ² are an alkyl group, a cycloalkyl group, or an aryl group, they may have any substituent T as long as the effect of the present invention is not impaired. Examples of the optional substituent T include a branched or straight-chain alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 are particularly preferred), and a cycloalkyl group (carbon number 3 ～ 24 is preferred, 3-12 is more preferred, 3-6 is particularly preferred), hydroxyl and hydroxyalkyl (carbon number 1-24 is preferred, 1-12 is more preferred, and 1-6 is particularly preferred; The number system of hydroxyl groups is preferably 1 to 6, more preferably 1 to 3), amino groups (carbon numbers of 0 to 24 are preferred, 0 to 12 are more preferred, 0 to 6 are particularly preferred), and amine alkyl groups ( Carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are particularly preferred; the number of amine groups is 1 to 6 and 1 to 3 are more preferred), mercapto, mercaptoalkyl (carbon Numbers 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 6 are particularly preferred; the number of mercapto groups is 1 to 6 is preferred, and 1 to 3 is more preferred; carboxyl and carboxyalkyl groups (carbon number 1 -24 is preferred, 1-12 is more preferred, and 1-6 is particularly preferred; the number of carboxyl groups is 1-6 is preferred, and 1-3 is more preferred; fluorenyl (carbon numbers of 1-12 are preferred) 1 to 6 are more preferred, 1 to 3 are particularly preferred), alkoxy (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 are particularly preferred), arylfluorenyl (carbon number 7 to 23 are preferable, 7 to 19 are more preferable, and 7 to 11 are special ), Aromatic acyl group (having 7 to 23 carbon atoms are preferred, more preferably 7 to 19, particularly preferably 7 to 11), oxy (= O), extending amine (= NR ^3), alkylene (= C (R ³ ) ₂ ) and so on. However, at least one of R ¹ and R ² represents a radical polymerizable group.

Regarding the radical polymerizable group represented by R ¹ and R ² , a group having the same definition as that exemplified by the above formula (3-1) can be mentioned. It is preferable that R ¹ and R ² are each independently a radical polymerizable group, and the same radical polymerizable group is more preferable.

In the formula (3-2), La ¹ to La ⁴ each independently represent a single bond, a group consisting of one or more combinations of alkylene and phenylene, and a group consisting of alkylene and phenylene. Any one of the groups consisting of one or two or more in combination with -O-. La ¹ to La ⁴ may each independently have a single bond, an alkylene group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, 1 to 6 is particularly preferred), phenylene group, and (oligomeric) ethylene group Alkoxy (alkylene-based carbons 1 to 24 are preferred, 1 to 12 are more preferred, 1 to 6 are particularly preferred. Repeating numbers 1 to 12 are preferred, 1 to 6 are more preferred, 1 to 6 3 is particularly preferred.), (Oligomeric) alkoxyl (alkylene-based carbon numbers 1 to 24 are preferred, 1 to 12 are more preferred, 1 to 6 are particularly preferred. Repeating numbers 1 to 12 are Preferably, 1 to 6 are more preferred, and 1 to 3 are particularly preferred.) Or a linker based on a combination of these. (Oligomeric) alkoxy means alkoxy or oligoalkoxy. It is considered that the group including other records of "(oligomerization)" is also the same. As long as the effect of the present invention is not impaired, the above-mentioned alkylene group, phenylene group, (oligomeric) alkyleneoxy group, and (oligomeric) alkyleneoxy group may further have any of the aforementioned substituents T. La ¹ to La ⁴ are each more preferably a single bond or an alkylene group independently, 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 bonded to each other to form a ring. When R ¹ and R ² form a ring, R ¹ and R ² may be directly connected or may be connected through the above-mentioned linking group L. The formed ring may be a condensed ring. The radical polymerizable compound having a sulfur atom used in the present invention may be a low molecule (for example, a molecular weight of less than 2000, and then less than 1,000), or may be a high molecule, preferably a low molecule.

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

[Chemical Formula 24]

[Chemical Formula 25]

In the above-mentioned exemplary 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, and 0.005% by mass or more with respect to the total solid content of the composition. More preferably, 0.01% by mass or more is further preferred, 0.05% by mass or more is further preferred, 0.1% by mass or more is further preferred, and 0.3% by mass or more is further preferred. As the upper limit value, 20% by mass or less is preferred, 15% by mass or less is more preferred, and 10% by mass or less is more preferred, and further 7% by mass or less, 5% by mass or less, 2% by mass or less, and 1% by mass may be further preferred. %the following. The blending amount of the radical polymerizable compound having a sulfur atom to 100 parts by mass of the polymer precursor is preferably 70 parts by mass or less of the polymerizable compound system based on the total amount with other polymerizable compounds described later, and 60 parts by mass It is more preferable that it is less than or equal to 55 parts by mass, it is more preferable that it is less than 55 parts by mass, it is even more preferable that it is less than 50 parts by mass, and it is particularly preferable that it is less than 45 parts by mass. The polymerizable compound may preferably be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, and 10 parts by mass or more. The lower limit of the proportion of the radically polymerizable compound having a sulfur atom in the total polymerizable compound containing other polymerizable compounds described later is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and 0.1% by mass. % Or more is further preferred, 0.3% by mass or more is further preferred, and 0.5% by mass or more is further preferred. The upper limit value is preferably 100% by mass or less, and may be 50% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 7% by mass or less, 5% by mass or less, 2% by mass or less, 1 mass% or less. By including a radically polymerizable compound having a sulfur atom in the composition in such a ratio as described above, it is possible to achieve further high stability and further high exposure sensitivity. The radical polymerizable compound having a sulfur atom may contain only one kind, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<Photo radical polymerization initiator> The photosensitive resin composition of this invention contains a photo radical polymerization initiator. The photo-radical polymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photo-radical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that generates some action with a light-excited sensitizer and generates an active radical. The photoradical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to perform measurement at a concentration of 0.01 g / L by using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Corporation) and using an ethyl acetate solvent.

When the photosensitive resin composition of the present invention 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 the light is irradiated to thereby generate light. It is hardened by free radicals and can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that, by exposing the photosensitive resin composition layer through a light mask having a pattern that shields only the electrode portion, regions having different solubility can be easily produced according to the pattern of the electrode.

As the photo-radical polymerization initiator, a known compound can be arbitrarily used, and examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a tri-skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), Fluorenyl phosphine compounds such as fluorenylphosphine oxide, oxime compounds such as hexaarylbisimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, Hydroxyacetophenone, azo-based compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic compounds, and the like. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

As the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a fluorenylphosphine 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 (product names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 with a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm can also be used. Examples of the fluorenylphosphine-based initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

As a photoradical polymerization initiator, an oxime compound is more preferably mentioned. By using an oxime compound, exposure latitude can be further effectively improved. Among the oxime compounds, exposure latitude (exposure margin) is wide, and it also functions as a photobase generator, so it is particularly preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. . Preferred examples of the oxime compound include compounds having the following structure, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3 -Propanyloxyiminobutane-2-one, 2-Ethyloxyiminopentane-3-one, 2-Ethyloxyimino-1-phenylpropane-1-one , 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Imino-1-phenylpropane-1-one and the like. In the photosensitive resin composition of the present invention, it is particularly preferable to use the oxime-based photopolymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = NOC (= O)-in the molecule. [Chemical Formula 26] Among commercially available products, the light freedom described in IRGACURE OXE 01, IRGACURE OXE 02 (above manufactured by BASF), and ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Application Publication No. 2012-14052) can also be preferably used Radical polymerization initiator 2). In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKAARKLS NCI-831, and ADEKAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, and compounds described in Japanese Patent Application No. 2014-500852, paragraph 0345, and compounds 24, 0347 to 0348. Compounds 36 to 40, Compound (C-3) described in paragraph 0101 of Japanese Patent Application Laid-Open No. 2013-164471, and the like. Examples of the preferred oxime compound include an oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, and an oxime compound having a sulfur aryl group shown in Japanese Patent Application Laid-Open No. 2009-191061. Wait.

From the standpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl tri compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and fluorenylphosphines. Compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl- Compounds in the group of benzene-iron complexes and their salts, halomethylpyridazole compounds, and 3-aryl substituted coumarin compounds. More preferred photoradical polymerization initiators are trihalomethyl tri compounds, α-amino ketone compounds, fluorenyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salts. Compound, benzophenone compound, acetophenone compound, at least selected from the group consisting of trihalomethyl tri compounds, α-amino ketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds One compound is further preferred, the use of a metallocene compound or an oxime compound is further preferred, and the oxime compound is further preferred. In addition, as the photoradical polymerization initiator, benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), and other N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-portolinylphenyl) -butanone-1 Aromatic ketones such as 2,2-methyl-1- [4- (methylthio) phenyl] -2-portalolinyl-acetone-1, alkyl anthraquinones, and other quinones that are condensed with aromatic rings Compounds, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin, alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. A compound represented by the following formula (I) can also be used. [Chemical Formula 27] In formula (I), R ^{I 00} 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, and a phenyl group , Interrupted by an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, cyclopentyl, cyclohexyl, an alkenyl group having 2 to 12 carbon atoms, interrupted by one or more oxygen atoms R ^{1 01} is a phenyl or biphenyl substituted with at least one of an alkyl group having 2 to 18 carbons and an alkyl group having 1 to 4 carbons, and R ^{I 01} is a group represented by formula (II), or R ^{I 00} The same group, R ^{I 02} to R ^{I 04} are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 28] In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^{I04 in} the formula (I).

As the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

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

<Thermal radical polymerization initiator> The photosensitive resin composition of this invention may contain a thermal radical polymerization initiator in the range which does not deviate from the meaning of this invention. A thermal radical polymerization initiator is a compound that generates radicals by the energy of heat and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can be performed, and the polymerization reaction of the polymer precursor can be performed. Therefore, higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-63554.

When a thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably, relative to the total solid content of the photosensitive resin composition of the present invention. 5 to 15 mass%. The thermal radical polymerization initiator may contain only one kind, or may contain two or more kinds. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.

<Solvent> The photosensitive resin composition of this invention contains a solvent. The solvent can be any known one. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, fluorenes, and amidines. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, alkyl Ethoxyacetate, butyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), Alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., 2-alkane Methyloxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2 -Methyl alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, 2 -Ethyl oxobutyrate and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve B. Acid ester, 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. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As a fluorene, for example, dimethyl fluorene is preferable. As preferred amines, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamidine are mentioned as preferable. Amine, etc.

Regarding the solvent, it is also preferable to mix two or more forms from the viewpoint of improving the coating surface shape. In the present invention, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, and butyl acetate. Esters, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbidine One solvent or a mixed solvent composed of two or more kinds of alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferred to use both dimethyl sulfene and γ-butyrolactone.

The content of the solvent is preferably from 5 to 80% by mass of the total solid content concentration of the photosensitive resin composition of the present invention from the viewpoint of coating properties. The photosensitive resin composition of the present invention is preferably used. A total solid content concentration of 5 to 75% by mass is more preferred, and a total solid content concentration of the photosensitive resin composition of the present invention is more preferably set to an amount of 10 to 70% by mass. The total solid content concentration of the photosensitive resin composition is more preferably 40 to 70% by mass. The content of the solvent may be adjusted according to the desired thickness and coating method. The solvent may contain only one kind or two or more kinds. When two or more solvents are contained, the total is preferably in the above range.

<Other polymerizable compounds> <<< Sulfur atom-free polymerizable compound> The photosensitive resin composition of the present invention contains a radical polymerization compound containing no sulfur atom in addition to the radical polymerizable compound containing the sulfur atom. A chemical compound (hereinafter, referred to as a "polymerizable monomer containing no sulfur atom") is preferred. With such a configuration, a cured film having excellent heat resistance can be formed.

As the polymerizable monomer not containing a sulfur atom, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acrylfluorenyl group, and an allyl group. The radical polymerizable group (meth) acrylfluorenyl is preferred.

The number of radical 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 has two or more radical polymerizable groups. It is more 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 not containing a sulfur atom is preferably 2000 or less, more preferably 1500 or less, and still 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, it is preferable that the photosensitive resin composition of the present invention contains at least one kind of a bifunctional or more polymerizable monomer containing no sulfur atom containing two or more polymerizable groups, and contains at least one kind of a trifunctional or more polymerizable monomer. Polymerizable monomers which do not contain a sulfur atom are more preferred. Furthermore, it may be a mixture of a bifunctional polymerizable monomer not containing a sulfur atom and a trifunctional polymerizable monomer not containing a sulfur atom. The number of functional groups of the polymerizable monomer that does not contain a sulfur atom means the number of radical polymerizable groups in one molecule.

Specific examples of the polymerizable compound not containing a sulfur atom include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid) or esters thereof, and The amines are preferably esters of an unsaturated carboxylic acid and a polyhydric alcohol compound, and amidines of an unsaturated carboxylic acid and a polyamine compound. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an affinity substituent such as a hydroxyl group or an amine group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or Dehydration condensation reactants of polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and monofunctional or polyfunctional alcohols, addition reactions of amines, and halogen groups have detachable substituents Substituted reactants of unsaturated carboxylic acid esters or amidines with monofunctional or polyfunctional alcohols and amines are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

A polymerizable monomer that does not contain a sulfur atom is also a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and neopentaerythritol tri ( (Meth) acrylates, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, hexanediol (methyl ) Acrylates, trimethylolpropane tris (propylene ethoxypropyl) ether, tris (propylene ethoxyethyl) isotricyanate, glycerol or trimethylolethane, etc. in polyfunctional alcohols (Meth) acrylate compound after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Publication No. 51-37193 (Meth) acrylic acid urethanes described in Japanese Patent Application Publication No. 48-64183, Japanese Patent Application Publication No. 49-43191, and Japanese Patent Application Publication No. 52-30490 Polyesters, epoxy acrylates, etc., which are reaction products of epoxy resins and (meth) acrylic acid Acrylate or methacrylate esters, and mixtures of these. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Furthermore, polyfunctional carboxylic acid etc. which are obtained by making a polyfunctional carboxylic acid react with the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth) acrylate, etc. are mentioned. Moreover, as a polymerizable monomer which does not contain a sulfur atom other than the above, it is also possible to use those described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like. A compound or a cardo resin having a fluorene ring and having two or more ethylenically unsaturated bond-containing groups. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-43946, Japanese Unexamined Patent Publication No. 1-40337, Japanese Unexamined Patent Publication No. 1-40336, and specific unsaturated compounds described in Japanese Unexamined Patent Publication No. Hei 2-200 can be cited. A vinylphosphonic acid-based compound described in Japanese Patent No. 25493 and the like. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photocurable monomer and oligomer.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 can be preferably used and incorporated into this specification.

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-62986 as formulas (1) and (2) together with specific examples thereof can also be used as polymerizable monomers that do not contain a sulfur atom. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylicating it.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as other polymerizable monomers, and these contents can be incorporated into this specification.

As a polymerizable monomer which does not contain a sulfur atom, dineopentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dinepentaerythritol tetraacrylate (as Commercially available products are KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available Products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH ; Manufactured by Shin-Nakamura Chemical Co., Ltd.) and such (meth) acrylfluorenyl groups are preferably bonded via ethylene glycol residues and propylene glycol residues. These types of oligomers can also be used.

Examples of commercially available polymerizable monomers that do not contain a sulfur atom include SR-494, which is a four-functional acrylate having four ethoxyl chains, and four vinyloxy groups, which are manufactured by Sartomer Company, Inc. SR-209 made by Sartomer Company, Inc., a bifunctional methyl acrylate with a chain, DPCA-60, a 6-functional acrylate with 6 pentyloxy chains, and 3 different isopropyl acrylates, made by Nippon Kayaku Co., Ltd. TPA-330 trifunctional acrylate with extended butoxy chain, urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical 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 (manufactured by NOF CORPORATION.), Etc.

Other polymerizable monomers are described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Urethane acrylates are 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. Oxyethane-based urethane compounds are also preferred. Furthermore, as the polymerizable monomer not containing a sulfur atom, the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238 can also be used. Compounds with an amine structure inside.

The polymerizable monomer not containing a sulfur atom may be a polymerizable monomer having an acid group such as a carboxyl group and a phosphate group. Among the polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to polymerize the acid group. Sexual monomers are more preferred. Particularly preferred is a polymerizable monomer having an acid group in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride, and the aliphatic polyhydroxy compound is used as neopentyl tetraol and / or dipentaerythritol. Of compounds. As a commercial item, M-510, M-520, etc. are mentioned as a polyacid modified acrylic oligomer by TOAGOSEI CO., Ltd., for example. The polymerizable monomer having an acid group may be used singly or in combination of two or more kinds. If necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group may be used simultaneously. 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. As long as the acid value of the polymerizable monomer is within the above range, it is excellent in manufacturing or handling properties, and further, it is excellent in developability. The polymerizability was also good.

From the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film, the photosensitive resin composition of the present invention can preferably use a monofunctional polymerizable monomer as the polymerizable monomer not containing a sulfur atom. As the monofunctional polymerizable monomer, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxy can be preferably used. Ethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N -Derivatives of (meth) acrylic acid, such as methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. Compounds, N-vinyl compounds such as N-vinylpyrrolidone, N-vinyl caprolactam, alkenyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Propyl compounds and so on. As the monofunctional polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.

<<< Polymerizable compound other than the above-mentioned radically polymerizable compound >> The photosensitive resin composition of this invention can contain the polymerizable compound other than the said radically polymerizable compound. Examples of the polymerizable compound other than the radical polymerizable compound include compounds having a methylol group, an alkoxymethyl group, or a fluorenylmethyl group; epoxy compounds; oxetane compounds; and benzofluorene compounds.

(Compounds having methylol, alkoxymethyl, or methyloxymethyl) Compounds having methylol, alkoxymethyl, or methyloxymethyl are represented by the following formulae (AM1), (AM4), or (AM5) The compound represented by) is more preferable.

[Chemical Formula 29] (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, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical Formula 30] (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 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. , R ⁴⁰⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical Formula 31] (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, R ⁵⁰⁵ represents a group represented by -OR ⁵⁰⁶ or -OCO-R ⁵⁰⁷ , and 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 a compound having the aforementioned methylol group or the like, when a photosensitive resin composition is applied to an uneven substrate, the occurrence of cracks can be more effectively suppressed. In addition, it is possible to form a cured film which is excellent in pattern workability and has a high heat resistance of 350 ° C. or higher at a temperature reduced by 5 mass%. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), 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 (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diethoxymethyl-p-cresol) Phenol) and so on.

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, and HML-TPPHBA. , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

(Epoxy compound (compound having an epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferable. The epoxy undergoes a crosslinking reaction based on a temperature of 200 ° C or lower, and it is difficult to cause film shrinkage because it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing an epoxy compound, low-temperature hardening and warping of a composition can be suppressed effectively.

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

Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl) Group), but not limited to epoxy-containing silicones and the like. Specific examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, and EPICLON (registered trademark) HP-4700. , EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) ) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA CORPORATION), and the like. Among these, a polyethylene oxide-based epoxy resin is preferred from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E are preferred because they contain polyethylene oxide groups.

(Oxetane compound (compound having oxetanyl group)) Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, and 3-ethyl group -3-hydroxymethoxybutane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- (2 -Ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester, and the like. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. Can be preferably used, and these can be used alone or in combination. More than two.

(Benzofluorene compound (compound with polybenzoxazolyl group)) The benzofluorene compound does not generate outgassing during hardening due to the cross-linking reaction originating from the ring-opening addition reaction, thereby reducing heat shrinkage and suppressing warpage. It is better.

Preferred examples of the benzofluorene compound include Ba-type benzofluorene, Bm-type benzofluorene (the above are trade names, manufactured by Shikoku Chemicals Corporation), benzofluorene adducts of polyhydroxystyrene resins, and phenolaldehydes. Varnish-type dihydrobenzofluorene compound. These may be used alone, or two or more kinds may be mixed.

The content of the polymerizable compound other than the radical polymerizable compound having a sulfur atom is preferably 0 to 60% by mass based on the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50% by mass, and even more preferably 30% by mass or less. Other polymerizable compounds may be used singly or in combination of two or more. When two or more kinds are used at the same time, the total amount thereof is preferably within the above range.

<Migration inhibitor> The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive resin composition layer can be effectively suppressed. The migration inhibitor is not particularly limited, and examples thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, and tetrazole). Ring, pyridine ring, pyridyl ring, pyrimidine ring, pyrimidine ring, piperidine ring, piperidine ring, terminal moxaline ring, 2H-pyran ring, 6H-pyran ring, tricyclic ring) compounds, having thioureas and mercapto groups Compounds, hindered phenol compounds, salicylic acid derivative compounds, hydrazine derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and benzotetrazole can be preferably used.

Moreover, an ion trapping agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, rust inhibitors described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-15701, compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-open No. 2009-283711, and Japanese Patent Laid-Open No. 2011 can be used. -59656, the compounds described in paragraph 0052, Japanese Patent Laid-Open No. 2012-194520, the compounds described in paragraphs 0114, 0116, and 0118, and the like.

Specific examples of the migration inhibitor include the following compounds. [Chemical Formula 32]

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0 relative to the total solid content of the photosensitive resin composition. The mass% is more preferable. The migration inhibitor may be only one type, or may be two or more types. When two or more migration inhibitors are used, the total is preferably in the above range.

<Polymerization inhibitor> It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 1,4-methoxyphenol, di-third-butyl-p-cresol, catechol, and p-third-butylphthalate can be preferably used. Phenol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis ( 4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylene Diamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-butyl-4-methylphenol, 5-nitroso-8 -Hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol , N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-third butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used. The following compounds (Me is methyl) can also be used. [Chemical Formula 33] When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass, and 0.02 to 3% by mass relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 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 kinds 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 adhesion improver for improving adhesion with a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent.

Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Laid-Open No. 2014 The compounds described in paragraphs 0060 to 0061 of Japanese Patent Publication No. -191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of International Publication No. WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Et represents an ethyl group. [Chemical Formula 34]

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and sulfides described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can 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 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer precursor. By making it more than the said lower limit value, the adhesiveness of the hardened film after a hardening process and a metal layer becomes favorable, and by making it below the said upper limit value, the heat resistance and mechanical characteristics of the hardened film after a hardening process become favorable. The metal adhesion improving agent may be only one type, or may be two or more types. When two or more kinds are used, it is preferable that the total is in the above range.

<Alkali generator> The photosensitive resin composition of this invention may contain an alkali generator. The alkali generator may be a hot alkali generator or a light alkali generator.

<<< Thermal alkali generator> There is no particular limitation on the type of the hot alkali generator, and it contains an acidic compound selected from the group consisting of an acidic compound that generates an alkali when heated to 40 ° C or higher, and an ammonium having an anion and ammonium cation having a pKa1 of 0 to 4 A hot base generator of at least one of the salts is preferred. Here, pKa1 represents the logarithmic label (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyacid. By blending these compounds, a cyclization reaction of a polymer precursor can be performed at a low temperature, and a composition having more excellent stability can be obtained. In addition, since the hot alkali generator does not generate an alkali unless it is heated, it can suppress the cyclization of the polymer precursor during storage even with the polymer precursor, and has excellent storage stability.

The hot alkali generator in the present invention preferably contains at least one selected from the group consisting of an acidic compound (A1) which generates an alkali when heated to 40 ° C or higher, and an ammonium salt (A2) having an anion and an ammonium cation having a pKa1 of 0 to 4 . The acidic compound (A1) and the ammonium salt (A2) generate a base when heated. Therefore, the base generated from these compounds can promote the cyclization reaction of the polymer precursor and can be polymerized at a low temperature. Cyclization of precursors. In addition, even if these compounds coexist with a polymer precursor cyclized and hardened by a base, the polymer precursor is hardly cyclized unless heated, so that a polymer precursor having excellent stability can be prepared. In addition, in the present specification, an acidic compound means that 1 g of the compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added. Stir at room temperature for 1 hour. A compound having a value of less than 7 when measured with a pH meter at 20 ° C.

In the present invention, the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 to 200 ° C. The upper limit of the alkali 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 alkali generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. As long as the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, alkali is not easily generated during storage, so a polymer precursor having excellent stability can be prepared. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the polymer precursor and the like can be reduced. Regarding the alkali generation temperature, for example, differential scanning calorimetry can be used to heat the compound in a pressure-resistant capsule to 250 ° C at 5 ° C / min, read the peak temperature of the lowest exothermic peak, and use the peak temperature as the alkali. The temperature was measured.

In the present invention, the alkali-based second amine or the third amine generated by the hot alkali generator is more preferable, and the third amine is more preferable. Since the tertiary amine is highly basic, the cyclization temperature of the polymer precursor can be reduced. The boiling point of the alkali generated by the hot alkali 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 base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. The molecular weight value is a theoretical value obtained from a structural formula.

In this invention, it is preferable that the said acidic compound (A1) contains 1 or more types chosen from the group which consists of an ammonium salt and the compound represented by Formula (101) or (102) mentioned later.

In the present invention, the aforementioned ammonium salt (A2) -based acidic compound is preferred. In addition, the above-mentioned 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 it may be other than to be heated to 40 ° C or higher (preferably 120 to 200) ℃) to produce compounds other than the acidic compounds of the base.

The ammonium salt used as the hot alkali generator is preferably a salt of an ammonium cation and an anion represented by the following formula (101) or (102). The anion may be bonded to any part of the ammonium cation through a covalent bond, and may also be provided outside the molecule of the ammonium cation, but it is preferably provided outside the molecule of the ammonium cation. In addition, an anion having an ammonium cation outside the molecule means a case where the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is also referred to as an anion. [Chemical Formula 35] In the formula, R ^N1 to R ^N6 each independently represent a hydrogen atom or a hydrocarbon group (carbon number 1 to 36 is preferred, 1 to 24 is more preferred, 1 to 12 is particularly preferred), and alkyl (carbon number 1 to 36 is Preferably, 1 to 24 are more preferred, 1 to 23 are particularly preferred), alkenyl (2 to 36 carbons are preferred, 2 to 24 are more preferred, 2 to 23 are particularly preferred), alkynyl (carbon number 1 to 36 is preferable, 1 to 24 is more preferable, 1 to 23 is particularly preferable), and aryl (carbon number 6 to 22 is more preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable). good. R ^N7 represents a hydrocarbon group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred), and an alkylene group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred) is more preferred. 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 a ring, the aforementioned linker L or a later-mentioned hetero linker Lh may be interposed. As long as the effect of the present invention is not impaired, R ^N1 to R ^N7 may have the aforementioned substituent T.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-6). [Chemical Formula 36]

In the formulae (Y1-1) to (Y1-6), R ^N101 represents an organic group having a valence of Nn (Nn is an integer of 1 to 12), and examples include an alkane-based Nn-valent group (carbon number 1 to 12) Preferably, 1 to 6 are more preferred, and 1 to 3 are particularly preferred. Nn-valent groups based on olefins (2 to 12 carbons are preferred, 2 to 6 are more preferred, and 2 to 3 are particularly preferred. Good), Nn-valent group based on aromatic hydrocarbons (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is particularly preferred), or combinations thereof. Among them, the aromatic hydrocarbon group of the R ^N101 system is preferable. As long as the effect of the present invention is not impaired, R ^N101 may have the aforementioned substituent T. When R ^N101 is an alkane-based group or an olefin-based group, the following hetero linking group Lh may be included. The definitions of R ^N1 and R ^{N7 are the} same as those of R ^N1 and R ^N7 in formula (101) or formula (102). R ^N8 is alkyl (carbon number 1 to 36 is preferred, 2 to 24 is more preferred, 4 to 18 is particularly preferred), alkenyl (carbon number 2 to 36 is preferred, 2 to 24 is more preferred, 4 -18 is particularly preferred), alkynyl (2 to 36 carbons is preferred, 2 to 24 is more preferred, 4 to 18 is particularly preferred), aryl (6 to 22 is preferred, 6 to 18 is preferred) More preferably, 6-10 are particularly preferred). At this time, in the alkyl group, alkenyl group, alkynyl group, and aryl group, a linking group having a hetero atom Lh may be interposed in the middle of the chain or in the connection with the mother core. Examples of the linking group Lh having a hetero atom include a linking group of -O-, -S-, -C (= O)-, -NR ^3- , or a combination thereof. The number system of the linking group Lh having a hetero atom is preferably 1 to 12, 1 to 6 is more preferred, and 1 to 3 is particularly preferred. R ³ is a hydrogen atom or an alkyl group (preferably a methyl group). As long as the effect of the present invention is not impaired, R ^N8 may further have the aforementioned substituent T. R ^N9 is preferably the same as R ^N8 . Among them, a group containing an aryl group is more preferred, a group containing an arylfluorenyl group is more preferred, and an arylfluorenyl group (an alkyl-based carbon number of 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 For the best) For the best. In this case, a substituent T may be introduced into the aromatic ring of the aryl group to the arylfluorenyl group within a range that does not impair the effect of the present invention. In the formula (Y1-4), Ar ^N101 and Ar ^N102 each independently represent an aryl group (carbon number 6 to 22 is more preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable). Nn represents an integer of 1 to 12. Nm represents an integer of 0 to 5. No is preferably an integer of 1 to 12, an integer of 1 to 6 is more preferred, an integer of 1 to 3 is particularly preferred. 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 may be bonded to form a ring, respectively. When forming a ring, the aforementioned linker L or a later-mentioned hetero linker Lh may be interposed.

In this embodiment, it is preferable that the ammonium salt has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the 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. As long as the pKa1 of the anion is within the above range, the polymer precursor and the like can be cyclized at a lower temperature, and the stability of the composition can be improved. As long as pKa1 is 4 or less, the stability of the hot alkali generator is good, the generation of alkali is suppressed without heating, and the stability of the composition is good. As long as pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of polymer precursors and the like is good. The type of the anion is preferably one selected from the group consisting of a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfuric acid anion. A carboxylic acid anion is more preferable from the viewpoint that both the stability of a salt and the thermal decomposability can be considered. That is, an ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion. The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be set as the hot alkali generator which can further improve the stability, hardenability, and developability of a composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the composition can be further improved. In this embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid whose pKa1 is 4 or less. pKa1 is preferably 3.5 or less, and more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved. Here, pKa1 representation into a first proton polybasic acid dissociation constant (ka) of the logarithm (-Log ₁₀ Ka), and can see the Determination of Organic Structures by Physical Methods (OF: Brown, HC, McDaniel, DH , Hafliger, O., Nachod, FC; codification: Braude, EA, Nachod, FC; Academic Press, New York, 1955), Data for Biochemical Research (OF: Dawson, RMCet al; Oxford, Clarendon Press, 1959 values) described in the . For compounds not described in these documents, software using ACD / pKa (manufactured by ACD / Labs) and values calculated from the structural formulas were used.

The carboxylic acid anion is preferably represented by the following formula (X1). [Chemical Formula 37] In the formula (X1), EWG represents an electron withdrawing group.

The electron-withdrawing group in the present embodiment is one in which the Hammett substituent constant σm represents a positive value. Among them, σm is described in detail by Tono Yufu, Journal of Synthetic Organic Chemistry, Japan Vol. 23 No. 8 (1965) p. 631-642. The electron-withdrawing group in this embodiment is not limited to the substituent described in the above-mentioned document. Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and 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) Wait. In addition, Me represents a methyl group, Ac represents an ethenyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical Formula 38] In the formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom and an alkyl group (carbon numbers of 1 to 12 are preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred. Good), alkenyl (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred), aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 ~ 10 is particularly preferred), hydroxyl or carboxyl. Wherein, R ^X1 of formula (EWG-1) of the formula (EWG-4) R ^X1 is not a carboxyl group. Ar represents an aromatic group (carbon number 6 to 22 is more preferable, 6 to 18 is more preferable, and 6 to 10 is particularly preferable). When R ^x1 to R ^x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and the above-mentioned linking group L or a later-described hetero linking group Lh may be mixed during the formation of the ring. When R ^x1 to R ^x3 are an alkyl group, an alkenyl group, or an aryl group, Ar may have a substituent T as long as the effect of the present invention is not impaired. Among them, Ar particularly preferably has a carboxyl group (preferably 1 to 3). Np is preferably 1 to 6, 1 to 3 is more preferable, and 1 or 2 is particularly preferable.

In this embodiment, a carboxylic acid anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 39] In the formula (XA), L ¹⁰ represents a single bond or is selected from an alkylene group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, and 1 to 3 are particularly preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 to 6 are more preferred, 2 to 3 are particularly preferred), aromatic groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 10 are particularly preferred), -NR ^X -and a divalent linking group of these combinations, R ^X represents a hydrogen atom, an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred), alkenyl ( Carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is particularly preferred) or aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is particularly preferred) .

Specific examples of the carboxylic acid anion include a maleic acid anion, a phthalic acid anion, an N-phenyliminodiacetic acid anion, and an oxalic acid anion. For details of the hot alkali generating agent, refer to the descriptions in paragraphs 0021 to 0007 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification. The following compounds are exemplified as the hot alkali generator. [Chemical Formula 40] [Chemical Formula 41]

[Chemical Formula 42] [Chemical Formula 43]

When a hot alkali generator is used, the content of the hot alkali generator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.25% by mass or more, and more preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, and more preferably 10% by mass or less. As the hot alkali generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range. Moreover, as one Embodiment of this invention, it can also be set as the structure which does not contain a hot alkali generator substantially. The term “substantially not included” means that the total solid content of the composition is less than 0.1% by mass, and can be set to 0.01% by mass or less, and particularly 0.001% by mass or less.

<<< Photobase generator> The photosensitive resin composition used by this invention may contain a photobase generator. The photo-alkali generator is one that generates alkali by exposure and does not show activity under normal temperature and pressure conditions. However, if it is irradiated with electromagnetic waves and heated as an external stimulus, it is not particularly required as long as it generates alkali (alkaline substance). limited. The alkali generated by the exposure functions as a catalyst when the polymer precursor is hardened by heating, and therefore, it can be preferably used when developing processing is performed.

In the present invention, one known as a photobase generator can be used. For example, such as M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev. ., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol 13,153 (2000); M. Winkle, and K. Graziano, J. Photopolym.Sci.Technol., 3,419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol ., 9,13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), examples of migration metal compound complexes, Structures such as ammonium salts, such as those in which the fluorenyl moiety is potentialized by the formation of carboxylic acids and salts, the alkali components are derived from the ionic compounds, carbamate derivatives, and oxime esters that are neutralized by the formation of salts. Non-ionic compounds such as urethane bonds or oxime bonds such as organic compounds, fluorenyl compounds, etc., and alkali components being potentially latent.

The basic substance produced by the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, particularly polyamines such as monoamines and diamines, and fluorene. The produced basic substance is preferably a compound having an amine group having a higher basicity. The reason is that, among these compounds, the catalyst action against the dehydration condensation reaction during the hydrazine imidation of the polymer precursor is strong, and the dehydration condensation reaction at a lower temperature can be exhibited in a lower amount of addition. Catalyst effect. That is, since the catalytic effect of the generated alkaline substance is large, the apparent sensitivity as a photosensitive resin composition is improved. From the viewpoint of the above-mentioned catalyst effect, alkaline substances based on rhenium and aliphatic amines are preferred. As the photobase generator used in the present invention, a compound containing an aromatic ring and a basic substance having an amine group is preferable.

Examples of the photobase generator according to the present invention include a photobase generator having a cinnamate structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. 2009/123122, such as Japanese Patent No. A photobase generator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2006-189591 and Japanese Patent Application Laid-Open No. 2008-247747, as disclosed in Japanese Patent Laid-Open No. 2007-249013 and Japanese Patent Laid-Open No. 2008-003581 A photobase generator having such an oxime structure and a carbamidine oxime structure is disclosed, but it is not limited thereto, and a known photobase generator structure can also be used.

Examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP 2012-93746, and paragraphs 0022 to 0069 of JP 2013-194205. The compounds described in the above, the compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and the compounds described in paragraph 0052 of International Publication WO2010 / 064631.

As commercially available products of photobase generators, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB can also be used. -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.). Examples of the photobase generator include the following compounds. Et represents ethyl and Me represents methyl. [Chemical Formula 44]

When a photobase generator is used, the content of the photobase generator in the composition is preferably 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. As the photobase generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range. Moreover, as one Embodiment of this invention, it can also be set as the structure which does not contain a photobase generator substantially. The term “substantially not included” means that the total solid content of the composition is less than 0.1% by mass, and can be 0.01% by mass or less, and in particular, 0.001% by mass or less.

<Other additives> The photosensitive resin composition of the present invention can be added to various additives such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, and the like, as long as the effects of the present invention are not impaired. Higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are 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 this invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, and promotes the cyclization of the polymer precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include the compounds described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, and more preferably 0.1 parts by mass or more. When the thermal acid generator is contained in an amount of 0.01 parts by mass or more, 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. From the viewpoint of electrical insulation of the cured film, 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. As the thermal acid generator, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.

<<< Sensitizing dye> The photosensitive resin composition of this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal alkali generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, thereby causing electron transfer, energy transfer, and heat generation. As a result, the thermal base generator, thermal radical polymerization initiator, and photoradical polymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, and 0.1 to 15% by mass relative to the total solid content of the photosensitive resin composition of the present invention. More preferably, 0.5 to 10% by mass is more preferable. The sensitizing dye may be used singly or in combination of two or more kinds.

<<< chain transfer agent> The photosensitive resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. The radicals are generated by supplying hydrogen to low-active radicals, or by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol) can be preferably used. Azoles, etc.).

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

<<<Surfactant> From the viewpoint of further improving the coating property, various surfactants can be added to the photosensitive resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred. [Chemical Formula 45]

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

<< Higher Fatty Acid Derivatives> In order to prevent polymerization inhibition by oxygen, the photosensitive resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid or behenyl behenate to the coating. It is locally present on the surface of the composition during the subsequent drying process. When the photosensitive resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one, or may be two or more. When there are two or more higher fatty acid derivatives, the total range is preferably the above range.

<Restrictions on Other Contained Substances> From the viewpoint of coating surface, the moisture content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly less than 0.6% by mass. good.

From the standpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Extraordinary. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably within the above range. In addition, as a method for reducing the metal impurities accidentally contained in the photosensitive resin composition of the present invention, a material having a small metal content can be selected as a raw material constituting the photosensitive resin composition of the present invention, and the photosensitive composition constituting the present invention can be selected. The raw materials of the flexible resin composition are filtered by a filter, and the inside of the device is lined with polytetrafluoroethylene, and distillation is performed under conditions that minimize pollution.

From the viewpoint of wiring corrosiveness, in the photosensitive resin composition of the present invention, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and 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 of a chlorine atom and a bromine atom, or a chloride ion and a bromine ion is the said range, respectively.

As a storage container of 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 or the composition, it is also preferable to use a multi-layer bottle composed of six types of six-layer resin and a six-layer resin bottle having a seven-layer structure. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of composition> The photosensitive resin composition of this invention can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, for the purpose of removing foreign matters such as garbage and particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously cleaned with an organic solvent. In the filtering step of the filter, a plurality of filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurizing is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine a filter and an impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<Curable film, laminated body, semiconductor device, and manufacturing method thereof> Next, a cured film, a laminated body, a semiconductor device, and the manufacturing method thereof 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. The upper limit value can be set to 100 μm or less, and can also be set to 30 μm or less.

Two or more layers of the cured film of the present invention can be used as a laminate. It is preferable that the seed laminated system having two or more hardened films of the present invention has a metal layer between the hardened films. These metal layers are preferably used as metal wiring such as a redistribution layer.

Examples of the fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, and interlayer insulating films for redistribution layers. In particular, since the resolution is good, the interlayer insulating film for a redistribution layer and the like in a three-dimensional mounting device can be preferably used.

In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen printing plates, the use of molded parts, the production of protective lacquers and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Preferred examples include a method for producing a cured film having a step of forming a photosensitive resin composition layer, applying the photosensitive resin composition of the present invention to a substrate to form a layer, and an exposure step for the above-mentioned photosensitive property. The resin composition layer is exposed; and a developing process step, where the exposed photosensitive resin composition layer (resin layer) is subjected to a development process. When development is performed, the photosensitive resin composition of the present invention can be preferably used.

The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the method for manufacturing a laminated body of the present invention, according to the method for manufacturing a cured film of the present invention, after the cured film is formed, the photosensitive resin composition layer forming step, the exposure step, and the developing process step are preferably performed again in this order. In particular, it is preferable that the photosensitive resin composition layer forming step, the exposure step, and the developing treatment step be performed 2 to 5 times (that is, 3 to 6 times in total) in this order. By laminating the cured film in this manner, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on a portion removed by development after a hardened film is provided for development. These details will be described below.

<<< Photosensitive resin composition layer formation step >> The manufacturing method of the preferable embodiment of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies a photosensitive resin composition to a board | substrate, and turns it into a layer. shape. The type of the substrate can be appropriately set depending on the application, but is not particularly limited, and examples thereof include semiconductor manufacturing substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, a semiconductor manufacturing substrate is particularly preferred, and a silicon substrate is more preferred. When the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a substrate. As a method of applying the photosensitive resin composition to a substrate, coating is preferred. Specifically, examples of the applicable method include a dip coating method, an air knife coating method, a curtain coating method, a bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, Slit coating method and inkjet method. 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 preferred. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer having a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, or the like is preferred, and if it is a rectangular substrate, a slit coating method is used. A spray method, an inkjet method, or the like is preferred. In the case of the spin coating method, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<<< Drying Step> The method for producing a laminated body of the present invention may further include a step of drying after removing the solvent after forming the photosensitive resin composition layer. The preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and more preferably 90 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 Step >> The method for producing a laminated body of the present invention may include an exposure step to expose the photosensitive resin composition layer. The exposure amount is not particularly limited as long as the photosensitive resin composition can be hardened. For example, it is preferable to irradiate 100 to 10,000 mJ / cm ² in terms of exposure energy conversion at a wavelength of 365 nm, and more preferably to irradiate 200 to 8000 mJ / cm ² . The exposure wavelength can be appropriately set within a range of 190 to 1000 nm, and 240 to 550 nm is more preferable. Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelengths 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, etc. In the present invention, as for the photosensitive resin composition, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is preferred. Thereby, particularly high exposure sensitivity can be obtained.

<<< Developing process step> The manufacturing method of the laminated body of this invention may include the developing process process which develops the exposed photosensitive resin composition layer. By performing development, an unexposed portion (non-exposed portion) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, a development method such as spin-on immersion, spraying, dipping, or ultrasonic waves can be used. The development is performed using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) can be removed. It is preferred that the developing solution contains an organic solvent. In the present invention, it is preferred that the developer contains an organic solvent having a ClogP of -1 to 5, and more preferably contains an organic solvent having a ClogP of 0 to 3. ClogP can be calculated as a calculated value by inputting a structural formula using ChemBioDraw. As the organic solvent, as the esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate can be suitably cited. Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate, Ethyl alkoxyacetate, butyl ethoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) Etc.)), 3-alkoxypropanoic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (example: 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) , Methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, Ethyl 2-oxobutanoate, etc., and ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and methyl cellosolve acetic acid. Ester, 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, and the like, as well as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like, and as the fluorenes, dimethyl sulfene may be suitably used. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. An organic solvent of 50% by mass or more of the developer is more preferable, an organic solvent of 70% by mass or more is more preferable, and an organic solvent of 90% by mass or more is more preferable. In addition, 100% by mass of the developing solution may be an organic solvent.

The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly limited, and can usually be performed at 20 to 40 ° C. After the treatment with the developer, processing can be performed. Rinse is preferably performed in a solvent different from the developer. For example, it is possible to perform washing using a solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

<<< Heating step> It is preferable that the manufacturing method of the laminated body of this invention includes the process of heating after image development. In the heating step, a cyclization reaction of a polymer precursor is performed. Moreover, although the photosensitive resin composition of this invention contains a radically polymerizable compound other than a polymer precursor, hardening etc. of an unreacted radically polymerizable compound other than a polymer precursor are also performed. The heating temperature (highest heating temperature) is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and still more preferably 160 to 350 ° C. Regarding heating, it is preferred to perform the heating at a temperature increase rate of 1 to 12 ° C./minute from the temperature at the start of heating, to 2 to 10 ° C./minute, and more preferably to 3 to 10 ° C./minute. By setting the temperature increase rate to 2 ° C / min or more, it is possible to ensure productivity and prevent excessive volatilization of the amine. By setting the temperature increase rate to 12 ° C / min or less, the residual stress of the cured film can be reduced. The temperature at the start of heating is preferably 20 to 150 ° C, more preferably 20 to 130 ° C, and even more preferably 25 to 120 ° C. The temperature at the start of heating means the temperature at the step of starting heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to a substrate and dried, the temperature after drying is, for example, a temperature lower than the boiling point of the solvent contained in the photosensitive resin composition by a temperature of 30 to 200 ° C. It is better to gradually increase the temperature. The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes. In particular, in the case of forming a multilayer laminate, it is preferable to heat at a heating temperature of 180 to 320 ° C from the viewpoint of the adhesion between layers of the cured film, and it is more preferable to heat it at 180 to 260 ° C. Although the reason for this is uncertain, the reason is considered to be as follows. That is, by setting the temperature to this temperature, the ethynyl groups of the polymer precursors between the layers undergo a cross-linking reaction.

Heating can be performed in stages. As an example, the temperature can be raised from 25 ° C to 180 ° C at 3 ° C / min, and maintained at 180 ° C for 60 minutes, from 180 ° C to 200 ° C at 2 ° C / minute, and held at 200 ° C for 120 minutes . The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and still more preferably 120 to 185 ° C. In this pre-processing step, it is also preferable to perform processing while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. The characteristics of the film can be improved by these pre-treatment steps. The pre-treatment step can be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pre-treatment may be two or more steps. For example, the pre-treatment step 1 may be performed in a range of 100 to 150 ° C, and then the pre-treatment step 2 may be performed in a range of 150 to 200 ° C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C / minute.

The heating step is preferably performed in an environment with a low temperature concentration by flowing an inert gas such as nitrogen, helium, and 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 step> It is preferable that the method for producing a laminated body of the present invention 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 process. The metal layer is not particularly limited, and conventional types of metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferred, and copper is further preferred. The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations can be considered. More specifically, a patterning method using a combination of sputtering, photolithography, and etching, and a patterning method using a combination of photolithography and electrolytic plating can be cited. The thickness of the metal layer is preferably 0.1 to 50 μm at the thickest wall thickness, and more preferably 1 to 10 μm.

<<< Lamination Step> It is preferable that the manufacturing method of the present invention further includes a lamination step. The lamination step includes a series of steps in which the above-mentioned photosensitive resin composition layer forming step, the above-mentioned exposure step, and the above-mentioned development processing step are sequentially performed again. Of course, the lamination step may further include the above-mentioned drying step or heating step. When a lamination step is performed after the lamination step, a surface activation treatment step may be performed after the above-mentioned exposure step or after the above-mentioned metal layer formation step. As the surface activation treatment, a plasma treatment is exemplified. The lamination step is preferably performed 2 to 5 times, and more preferably 3 to 5 times. For example, a resin layer such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer having a structure of 3 or more and 7 or less is preferable, and 3 or more and 5 or less is more preferable. That is, in the present invention, particularly after the metal layer is provided, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are sequentially performed in order to cover the metal layer. By alternately 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 alternately laminated.

The present invention also discloses a semiconductor device including the cured film or the laminated body of the present invention. As a specific example of a semiconductor device using the photosensitive resin composition of the present invention in the formation of an interlayer insulating film for a redistribution layer, refer to the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and FIG. 1 Records, and incorporate them into this manual. [Example]

Hereinafter, the present invention will be described in more detail with examples. The materials, usage amounts, proportions, processing contents, and processing steps shown in the following examples are within the scope not departing from the spirit of the present invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(Synthesis Example 1) [Polyimide precursor A derived from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and diamine (a) shown below Synthesis of -1] 21.2 g of 4,4'-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diethylene glycol dimethyl ether (di Glyme) was mixed and stirred at 60 ° C for 4 hours to produce a diester of 4,4'-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 38.0 g of the hydroxyl group-containing diamine (a) shown below was dissolved in 100 mL of N-methylpyrrolidone at -10 ° C for 60 minutes. After adding dropwise to the reaction mixture and stirring the mixture for 2 hours, 20 mL of ethanol was added. Next, it was poured into 6 liters of water to precipitate a polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate a polyimide precursor in water, and the solution was filtered and dried at 45 ° C for 3 days under reduced pressure. The polyfluorene imide precursor had a weight average molecular weight of 27,400 and a number average molecular weight of 10,100.

Diamine (a) [Chemical Formula 46]

(Synthesis Example 2) [Polyfluorene derived from pyromellitic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl Synthesis of imine precursor A-2] 14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme were mixed, and It stirred at 60 degreeC for 4 hours, and produced the diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl was dissolved in 100 mL of N-methylpyrrolidone. The solution was added dropwise to the reaction mixture at -10 ° C for 60 minutes, and the mixture was stirred for 2 hours, and then 20 mL of ethanol was added. Next, it was poured into 6 liters of water to precipitate a polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate a polyimide precursor in water, and the solution was filtered and dried at 45 ° C for 3 days under reduced pressure. This polyfluorene imide precursor had a weight average molecular weight of 23,100 and a number average molecular weight of 9,700.

(Synthesis Example 3) [derived from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diamino-2,2'-bis (trifluoro (Methyl) Synthesis of Polyfluorene Imide Precursor A-3 of 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 were mixed and stirred at 60 ° C for 4 hours to produce 4,4'-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate Diester. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl was dissolved in 100 mL of N-methylpyrrolidone. The solution was added dropwise to the reaction mixture at -10 ° C for 60 minutes, and the mixture was stirred for 2 hours, and then 20 mL of ethanol was added. Next, it was poured into 6 liters of water to precipitate a polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate a polyimide precursor in water, and the solution was filtered and dried at 45 ° C for 3 days under reduced pressure. The polyfluorene imide precursor had a weight average molecular weight of 23,500 and a number average molecular weight of 9,400.

(Synthesis Example 4) [Polyimide precursor derived from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate, and 4,4'-diaminodiphenyl ether A-4 Synthesis] 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 They were mixed and stirred at a temperature of 60 ° C. for 4 hours to produce a diester of 4,4′-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 ° C, and 17.0 g of SOCl _{2 was} added over 60 minutes while maintaining the temperature at -10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution prepared by dissolving 25.1 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise at -10 ° C over 60 minutes. After the reaction mixture was stirred for 2 hours, 20 mL of ethanol was added. Next, it was poured into 6 liters of water to precipitate a polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water to precipitate a polyimide precursor in water, and the solution was filtered and dried at 45 ° C for 3 days under reduced pressure. The polyfluorene imide precursor had a weight average molecular weight of 23,200 and a number average molecular weight of 9,600.

(Synthesis Example 5) [Composition of a polybenzoxazole precursor derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxodibenzoxyl chloride Synthesis of compound A-5] 28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, while maintaining the temperature at 0 to 5 ° C, 25.0 g of 4,4'-oxodibenzoic acid chloride was added dropwise over 30 minutes, and the stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C for 2 days. The 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 radical 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, and while maintaining the temperature at 5 ° C or lower, 50.0 g of SOCl _{2 was} added dropwise over 60 minutes, followed by stirring for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. After the obtained organic layer was washed five times with distilled water, the low-boiling-point solvent was removed with an evaporator, thereby obtaining 220.1 g of a radical polymerizable compound B1-1. The obtained compound was the exemplary compound 302 of the radically polymerizable compound having a sulfur atom described above. 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 radical 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, and while maintaining the temperature at 5 ° C or lower, 50.0 g of SOCl _{2 was} added dropwise over 60 minutes, followed by stirring for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. After the obtained organic layer was washed five times with distilled water, the low-boiling-point solvent was removed with an evaporator, and 200.2 g of a radical polymerizable compound B1-2 was obtained. The obtained compound was the exemplary compound 312 of the radically polymerizable compound having a sulfur atom described above.

(Synthesis Example 8) [Synthesis of radical polymerizable compound B1-3 having a sulfur atom] 19.0 g of bis (4-hydroxyphenyl) fluorene, 7.0 g of pyridine, and 100 mL of tetrahydrofuran were mixed. The mixed liquid was cooled to 0 ° C, and 19.0 g of methacrylic acid chloride was added dropwise over 60 minutes while maintaining the temperature at 5 ° C or lower, and then stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. After the obtained organic layer was washed five times with distilled water, the low-boiling-point solvent was removed with an evaporator, thereby obtaining 220.1 g of a radical polymerizable compound B1-3. The obtained compound was exemplified compound 322 of the above radical polymerizable compound having a sulfur atom.

<Molecular weight measurement method> The molecular weight (weight average molecular weight, number average molecular weight) of the polymer precursor is defined by gel permeation chromatography (GPC method) as a polystyrene conversion value. Specifically, HLC-8220 (trade name: manufactured by Tosoh Corporation) was used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (trade name: Tosoh Corporation) were used as the column. System). The eluate was measured using THF (tetrahydrofuran). In addition, a UV ray (ultraviolet) wavelength 254 nm detector was used for detection. In addition, the molecular weight prescribed | regulated in this specification is not specifically limited, It is a value measured according to the said measurement method.

<Example 1 to Example 16, Comparative Example 1 to Comparative Example 3> << Preparation of Photosensitive Resin Composition >> Each component described in the following Table 1 was mixed to prepare a uniform solution. The obtained solution was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration at a pressure of 0.3 MPa to obtain a photosensitive resin composition.

<< Storage stability >> 10 g of the above-mentioned photosensitive resin composition was put in a container (material of the container: light-shielding glass, capacity: 100 mL), sealed, and left to stand at 25 ° C and 65% relative humidity. The stability was evaluated within the time until solids were precipitated from the photosensitive resin composition. The longer the time until precipitation, the higher the stability of the photosensitive resin composition and the better the result. In the precipitation of solids, three samples were stored in a container for a photosensitive resin composition, and one sample container was opened at the time of 30 days, 60 days, and 120 days. The pores were subjected to pressure filtration of the total amount of the photosensitive resin composition as the contents, and the presence or absence of foreign matter on the mesh was observed with the naked eye, and the presence or absence of precipitates was determined as follows. A: No solid precipitation was observed even after more than 120 days. B: More than 60 days, and solids precipitated within 120 days. C: More than 30 days and precipitation of solids within 60 days. D: A solid precipitated within 30 days.

<< Measurement of Exposure Energy >> A photosensitive resin composition is coated on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° 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 a positioner (Karl-Suss MA150 [trade name], manufactured by SUSS MICROTEC AG). The exposure was performed using a high-pressure mercury lamp, and the exposure energy required when the above-mentioned uniform film of 10 μm at a wavelength of 365 nm was cured was measured. The lower the exposure energy, the higher the high sensitivity and the better the result.

[Table 1]

(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 compounds having a sulfur atom produced in Synthesis Examples 6 to 8

(B2) Radical polymerizable compound (both trade names) B2-1: NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd.) B2-2: SR-209 (manufactured by Sartomer Company, Inc.) B2-3: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) B2-4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

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

[Chemical Formula 47]

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

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

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

[Chemical Formula 48] Et represents ethyl.

(H) Solvent H-1: γ-butyrolactone H-2: Dimethyl sulfene H-3: N-methyl-2-pyrrolidone H-4: Ethyl lactate In addition, regarding the solvents in Table 1, For example, when the type column is "H-1 / H-2" and the mass part is "48 + 12", it means that it contains 48 parts by mass of H-1 and 12 parts by mass of H-2.

As is clear from the results in Table 1 above, when a radical polymerizable compound having a sulfur atom is used, storage stability is excellent and sensitivity is high (Examples 1 to 16). In particular, as shown in Example 20, even when a small amount of a radically polymerizable compound having a sulfur atom is blended, the advantages of the present invention are known from the viewpoint of achieving excellent storage stability and high sensitivity. In contrast, when a radical polymerizable compound having a sulfur atom is not blended, the sensitivity is lowered (Comparative Examples 1 to 3).

<Example 100> The photosensitive resin composition of Example 1 was used to apply a photosensitive resin composition to 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. A stepper (Nikon NSR 2005 i9C [trade name]) was used to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500 mJ / cm ² , and the exposed photosensitive resin composition was formed with cyclopentanone The object layer (resin layer) was developed for 60 seconds to form holes having a diameter of 10 μm. Next, the temperature was increased at a temperature increase rate of 10 ° C./minute to 250 ° C. under a nitrogen environment, and then heated 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 by a vapor deposition method so as to cover the hole portion. Furthermore, the same type of photosensitive resin composition was used again on the surface of the metal layer and the photosensitive resin composition layer, and the photosensitive resin composition was filtered and heated to the patterned film for 3 hours in the same manner as described above. In the step, a laminated body composed of a resin layer / metal layer / resin layer was produced. This interlayer insulating film for a redistribution layer has excellent insulation properties. Furthermore, as a result of manufacturing a semiconductor device using this interlayer insulating film for a redistribution layer, it was confirmed that the operation was normal.

Claims (22)

A photosensitive resin composition comprising: a polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor; a radical polymerizable compound having a sulfur atom; a photoradical polymerization initiator ; And solvents. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the polymer precursor includes 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 each 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 each independently represent a hydrogen atom or a monovalent group. Organic In the formula (2), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. The photosensitive resin composition according to item 2 of the patent application range, wherein the polymer precursor includes a repeating unit represented by formula (1). The photosensitive resin composition according to claim 1 or claim 2, wherein the radical 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, 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 1 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 bonded to each other to form a ring. The photosensitive resin composition according to item 4 of the scope of patent application, wherein the formula (3-1) is represented by the following formula (3-2); In formula (3-2), L ¹ represents -S-, -SS-, -S (= O)-or -S (= O) _2- , and X ¹ and X ² each independently represent a single bond, -O -, -C (= O)-, -C (= O) O-, -OC (= O)-, -S-, -S (= O) ₂ -or -NR ³ CO-, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a radical polymerizable group, and La ¹ to La ⁴ each independently represent a single bond, one or two of an alkylene group and a phenylene group. Any one of the group consisting of the above combination and the group consisting of one or two or more of alkylene and phenylene and -O-; R ³ represents a hydrogen atom or an alkyl group; At least one of R ¹ and R ² is a radical polymerizable group. The photosensitive resin composition according to item 5 of the scope of the patent application, wherein the two R ¹ and R ² are each independently a radical polymerizable group. The photosensitive resin composition according to item 5 of the scope of patent application, wherein X ¹ and X ² are -O-. The photosensitive resin composition according to item 5 of the scope of patent application, wherein the L ¹ is -S (= O)-. The photosensitive resin composition according to item 5 of the scope of the patent application, wherein the R ¹ and R ² are each independently a monovalent organic group having an acrylfluorenyl group or a methacrylfluorenyl group. The photosensitive resin composition according to item 4 of the scope of patent application, wherein the formula (3-1) is represented by the following formula (4); In formula (4), R is a hydrogen atom or a methyl group. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, wherein the radical polymerization having a sulfur atom is included in a proportion of 0.001% by mass or more of the solid content contained in the photosensitive resin composition. Sexual compounds. The photosensitive resin composition according to claim 1 or 2, further comprising a radical polymerizable compound other than a radical polymerizable compound having a sulfur atom. The photosensitive resin composition according to claim 1 or claim 2, further comprising an alkali generator. The photosensitive resin composition according to item 1 or item 2 of the scope of patent application, which is used for development. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, which is used for development using a developer containing an organic solvent. The photosensitive resin composition according to item 1 or 2 of the scope of patent application, which is used to form an interlayer insulating film for a redistribution layer. A cured film formed from the photosensitive resin composition described in any one of the first to the sixteenth patent application scope. A laminated body having two or more layers of the hardened film described in item 17 of the scope of patent application. The laminated body according to item 18 of the scope of patent application, wherein a metal layer is provided between the cured films. A method for producing a cured film, comprising the step of using the photosensitive resin composition described in any one of the claims 1 to 16 of the scope of patent application. The method for manufacturing a cured film according to item 20 of the scope of patent application, comprising: a step of forming a photosensitive resin composition layer, applying the photosensitive resin composition to a substrate to form a layer; an exposure step, the photosensitive The photosensitive resin composition layer is exposed; and a developing process step, the exposed photosensitive resin composition layer is subjected to a development process. A semiconductor device having the hardened film described in claim 17 of the scope of patent application.