JP6903916B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition and a method for producing a resin film. More specifically, a surface protective film for a semiconductor element, an insulating film for rewiring, an interlayer insulating film for a thin film transistor, an insulating film for an organic electroluminescence (hereinafter referred to as EL) element, and a display device drive using an organic EL element. Suitable for applications such as thin film transistor (hereinafter referred to as TFT) substrate flattening film, circuit board wiring protection insulating film, on-chip microlenses of solid-state imaging devices, and flattening films for various displays and solid-state imaging devices. The present invention relates to a photosensitive resin composition and a method for producing a photosensitive resin film.

Resins typified by polyimide and polybenzoxazole are used for surface protective films such as semiconductor devices, interlayer insulating films for thin film transistors, and organic EL devices because of their excellent mechanical properties, heat resistance, electrical insulation, and chemical resistance. It is used as an insulating layer and a flattening film for TFT substrates.

In recent years, electronic components called thin film inductors have attracted attention. This thin film inductor has a spiral thin film coil structure formed on a substrate by repeating processes such as photolithography and plating, and is a common mode mainly for mobile devices such as wearable devices, smartphones, tablet terminals, and digital cameras. It is used for filter applications.

In particular, as electronic devices such as smartphones become more sophisticated and multifunctional, the number of parts increases, the space for each part becomes smaller, and there is a demand for smaller parts and thinner parts. Such products require a thin film inductor that can save space.

Conventionally, a semi-additive method has been adopted for forming a coil pattern of such a thin film inductor, and a polyimide-based heat-resistant resin composition is formed as an interlayer insulating film after the coil pattern is completed through photolithography and plating steps. Further, in the case of a laminated coil structure, the above steps are repeated.

Japanese Unexamined Patent Publication No. 2012-256023 Japanese Unexamined Patent Publication No. 2012-208360

However, in recent years, an increase in warpage due to the internal stress of the interlayer insulating film has become a problem with the multi-layered lamination of thin film intercuda. As the number of layers increases, the amount of warpage of the wafer increases, causing wafer cracking and transfer errors, and there is a problem that chemical stress cracks occur in the interlayer insulating film during the chemical treatment during coil pattern formation. Therefore, there is a demand for a resin composition that has low warpage during lamination and can withstand chemical treatment associated with coil pattern formation.

Examples of the resin composition capable of reducing warpage include a resin composition using a novolak resin, a photosensitive compound, and a thermal cross-linking agent containing a methylol group (Patent Document 1), an alkali-soluble polyimide, and a compound having two or more epoxy groups. , A resin composition using a photoacid generator (Patent Document 2) has been mentioned, but all of them have a problem in achieving both low warpage and chemical resistance.

An object of the present invention is to provide a resin composition capable of obtaining a cured film having low stress and high chemical resistance, which has low warpage during lamination and can withstand chemical treatment associated with coil pattern formation. ..

In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution. That is, it contains (a) an alkali-soluble resin, (b) an aromatic ring to which a methylol group is bonded, and a compound having a linear aliphatic structure (hereinafter, may be abbreviated as (b) compound). It is a resin composition characterized by.

Further, the present invention is a resin composition in which the linear aliphatic structure of the compound (b) has one or more structures selected from the group consisting of an alkylene group and an alkyl ether group.

Further, the compound (b) is a resin composition containing a compound having one or more structures selected from the group consisting of the structures represented by the following general formulas (1) to (3).

(In the general formulas (1) to (3), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, respectively, and represent a hydrogen atom or a methyl group. _{(CH 2-} OR ₁ ) _p and (CH _2- OR ₁ ) _q in the formula (2) may be the same or different, respectively. Further, (CH _2- OR ₁ ) _r , (CH 2-OR 1) r in the general formula (3). CH _2- OR ₁ ) _s and (CH _2- OR ₁ ) _t may be the same or different, respectively. Also, m> 1, n> 1, o> 1, p + q> 1, r + s + t> 1, p. ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A, B, and D may be the same or different, respectively, and may be the same or different, single bond, ether bond, hydroxyl group, isopropylidene group, ketone. Represents an organic group having one or more selected from the group consisting of a group, a carbonyl group, an amide group, and a sulfonyl group.)
Further, the compound (b) is a resin composition containing a compound having a structure represented by the following general formula (4).

(In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, respectively, and represent a hydrogen atom or a methyl group. Also, m> 1, n> 1 , O> 1, p + q> 1, r + s + t> 1, p ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A and B may be the same or different, respectively. Represents an organic group having one or more selected from the group consisting of a bond, an ether bond, a hydroxyl group, an isopropylidene group, a ketone group, a carbonyl group, an amide group, and a sulfonyl group.)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a resin composition capable of obtaining a cured film having low stress and high chemical resistance, which has low warpage during lamination and can withstand chemical treatment associated with coil pattern formation.

FIG. 5 is an enlarged cross-sectional view of a multilayer structure portion of an electronic component in which insulating layers and coil conductor layers are alternately laminated.

The resin composition of the present invention contains (a) an alkali-soluble resin, (b) an aromatic ring to which a methylol group is bonded, and a compound having a linear aliphatic structure.

The resin composition of the present invention is (a) one or more resins selected from the group consisting of a polyimide precursor, a polyamide-imide, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, and a phenol resin as an alkali-soluble resin. Contains. These resins can be heated or catalyzed to become polymers with an imide ring, an oxazole ring, or other cyclic structure. Preferred examples include a polyimide having a closed ring, a polyamic acid or polyamic acid ester as a polyimide precursor, and a polyhydroxyamide as a polybenzoxazole precursor. The annular structure dramatically improves heat resistance and chemical resistance.

Polyimide can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic dianester dichloride, etc. with a diamine, a corresponding diisocyanate compound, a trimethylsilylated diamine, etc., and a tetracarboxylic acid residue. And has a diamine residue. For example, it can be obtained by dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting tetracarboxylic dianhydride with diamine, by heat treatment. During this heat treatment, a solvent that azeotropes with water, such as m-xylene, can also be added. Alternatively, it can also be obtained by adding a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring-closing catalyst, and dehydrating and ring-closing by chemical heat treatment. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and dehydrating and ring-closing by heat treatment at a low temperature of 100 ° C. or lower. The polyimide precursor will be described later.

Polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, or the like, and has a dicarboxylic acid residue and a bisaminophenol residue. For example, it can be obtained by dehydrating and ring-closing polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bis-aminophenol compound with a dicarboxylic acid, by heat treatment. Alternatively, it can be obtained by adding anhydrous phosphoric acid, a base, a carbodiimide compound, or the like and dehydrating and closing the ring by chemical treatment. The polybenzoxazole precursor will be described later.

^{In the present invention, the polyimide has OR 6} , SO ₃ R ⁶ , CONR ⁶ R ⁷ , COOR ⁶ , SO ₂ NR ⁶ R ^{7 in} tetracarboxylic acid residue and / or diamine residue from the viewpoint of solubility in alkaline aqueous solution. It is preferable to have an acidic group or an acidic group derivative represented by the above, and it is more preferable to have a hydroxyl group. Here, R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The acidic group ^{indicates a case where all of R 6} and R ⁷ are hydrogen atoms, and the acidic group derivative indicates a case where R ⁶ or R ⁷ contains a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

In addition, polybenzoxazole is an acidic group or acidic group represented ^{by OR 6} , SO ₃ R ⁶ , CONR ⁶ R ⁷ , COOR ⁶ , SO ₂ NR ⁶ R ^7, etc. at dicarboxylic acid residues and / or bisaminophenol residues. It preferably has a group derivative, and more preferably has a hydroxyl group. Here, R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The acidic group ^{indicates a case where all of R 6} and R ⁷ are hydrogen atoms, and the acidic group derivative indicates a case where R ⁶ or R ⁷ contains a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

In the present invention, preferred structures of the tetracarboxylic acid residue of polyimide and the dicarboxylic acid residue of polybenzoxazole (hereinafter, these are collectively referred to as an acid residue) are the structures shown below and the hydrogen atom in these structures. Examples thereof include a structure in which 1 to 4 are substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

Wherein, J is a direct _{bond, -COO -, - CONH -,} - CH 2 -, - C 2 H 4 -, - O -, - C 3 H 6 -, - C 3 F 6 -, - SO 2 - _{, -S -, - Si (CH} 3) 2 -, - OSi (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 H _{4 -C 3 H 6 -C 6 H} 4 -, or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - represents any.

In the present invention, preferred structures of the diamine residue of polyimide and the bisaminophenol residue of polybenzoxazole (hereinafter, these are collectively referred to as diamine residue) are the structures shown below and one of the hydrogen atoms in these structures. Examples thereof include a structure in which 1 to 4 parts are substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

Wherein, J is each a direct _{bond, -COO -, - CONH -,} - CH 2 -, - C 2 H 4 -, - O -, - C 3 H 6 -, - C 3 F 6 -, - SO 2 _{-, - S -, - Si} (CH 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - _{C 6 H 4 -C 3 H 6} -C 6 H 4 -, or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - indicating either. R ⁸ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, respectively.

In the present invention, the polyimide precursor and the polybenzoxazole precursor are resins having an amide bond in the main chain, and are dehydrated and ring-closed by heat treatment or chemical treatment to obtain the above-mentioned polyimide or polybenzoxazole. The number of repetitions of the structural unit is preferably 100 to 100,000. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide and the like, and polyamic acid and polyamic acid ester are preferable. Examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, polyamideimide and the like, and polyhydroxyamide is preferable.

From the viewpoint of solubility in alkaline aqueous solution, polyimide precursor and polybenzoxazole precursor have OR ⁹ , SO ₃ R ⁹ , CONR ⁹ R ¹⁰ , COOR ⁹ , SO ₂ NR ⁹ R ^{10 in acid residue or diamine residue.} It is preferable to have an acidic group or an acidic group derivative represented by such as, and it is more preferable to have a hydroxyl group. Here, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Here, the acidic group ^{indicates a case where R 9} and R ¹⁰ are all hydrogen atoms, and the acidic group derivative indicates a case where R ⁹ or R ¹⁰ contains a monovalent organic group having 1 to 20 carbon atoms. .. Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

Examples of the acid component constituting the acid residue of the polyimide precursor and the polybenzoxazole precursor include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, and benzophenone. Examples of tricarboxylic acids such as dicarboxylic acid and triphenyldicarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid and the like. Examples of tetracarboxylic acids include pyromellitic acid, 3,3', 4,4'. -Biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid , 2,2', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoro Propane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2, 3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6 , 7-Naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid Acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1. ] Heptanetetracarboxylic acid, bicyclo [3.3.1. ] Tetracarboxylic acid, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic acid, bicyclo [2.2.2. ] Aliphatic tetracarboxylic acids such as octanetetracarboxylic acid and adamatanetetracarboxylic acid can be mentioned. Further, some of the hydrogen atoms of the dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid exemplified above are acidic represented by OR ⁹ , SO ₃ R ⁹ , CONR ⁹ R ¹⁰ , COOR ⁹ , SO ₂ NR ⁹ R ^{10, and the} like. It is preferably substituted with a group or an acidic group derivative, and more preferably 1 to 4 with a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group or the like. Here, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

These acids can be used as is, or as acid anhydrides or active esters. Moreover, you may use 2 or more kinds of these.

Further, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane, adhesion to a substrate, oxygen plasma used for cleaning, UV ozone, etc. The resistance to treatment can be increased. It is preferable to use 1 to 30 mol% of these silicon atom-containing tetracarboxylic dians as the total acid component, and 1 mol% or more is preferable in terms of substrate adhesion and effect on plasma treatment. When it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an alkaline aqueous solution.

Examples of the diamine components constituting the diamine residues of the polyimide precursor and the polybenzoxazole precursor are 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-amino-4-). Hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino- Hydroxyl group-containing diamines such as 4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl group-containing diamines such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether. , 3-sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamines, dithiohydroxyphenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-Aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) Sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2, 2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) ) -4,4'-diaminobiphenyl, compounds in which some of the hydrogen atoms of these aromatic rings are replaced with alkyl groups or halogen atoms such as F, Cl, Br, I, cyclohexyldiamine, methylenebiscyclohexylamine, etc. Biphenyl And so on. Further, in these diamines, a part of the hydrogen atom is an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, F, Cl, Br, It may be replaced with a halogen atom such as I. Further, the diamine exemplified above preferably has an acidic group or an acidic group derivative ^{represented by OR 9} , SO ₃ R ⁹ , CONR ⁹ R ¹⁰ , COOR ⁹ , and SO ₂ NR ⁹ R ^{10, and has a hydroxyl group.} Is more preferable. Here, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

These diamines can be used as is or as the corresponding diisocyanate compound, trimethylsilylated diamine. Moreover, you may use 2 or more kinds of these. For applications where heat resistance is required, it is preferable to use 50 mol% or more of the total amount of aromatic diamine.

Further, by using a silicon atom-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component, adhesion to the substrate is performed. It is possible to improve the properties and resistance to oxygen plasma and UV ozone treatment used for cleaning and the like. These silicon atom-containing diamines are preferably used in an amount of 1 to 30 mol% of the total diamine component, and more than 1 mol% is preferable in that the adhesiveness can be improved and the resistance to plasma treatment can be enhanced. When it is 30 mol% or less, it is preferable in terms of the solubility of the obtained resin in an alkaline aqueous solution.

Further, it is preferable to seal the ends of polyimide, polybenzoxazole, and their precursors with a monoamine having a hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group, an acid anhydride, a monocarboxylic acid, and an acid chloride. Two or more of these may be used. By having the above-mentioned group at the resin terminal, the dissolution rate of the resin in an alkaline aqueous solution can be easily adjusted within a preferable range.

Preferred examples of monoamines are 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino. Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy -6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3- Aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino- 4,6-Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino-4-tert-butylphenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Can be mentioned.

Preferred examples of acid anhydrides, monocarboxylic acids and acid chlorides include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, acid anhydrides such as 3-hydroxyphthalic acid anhydride, 3-. Carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto Monocarboxylic acids such as -7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzene sulfonic acid, 4-carboxybenzene sulfonic acid and their carboxyl groups are acid chlorides. Monoic acid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxylene Reaction of monoacid chloride compounds and monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as naphthalene is acid chloride with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide The active ester compound obtained by the above can be mentioned.

The content of monoamine, acid anhydride, monocarboxylic acid, and acid chloride used as the above-mentioned terminal encapsulant is preferably in the range of 0.1 to 60 mol% of the number of moles of the acid component monomer or diamine component monomer charged. , 5-50 mol% is more preferred. Within such a range, it is possible to obtain a resin composition having an appropriate viscosity of the solution when the resin composition is applied and having excellent film physical characteristics.

(A) The terminal sealant introduced into the alkali-soluble resin can be easily detected by the following method. For example, a resin into which an end-capping agent has been introduced is dissolved in an acidic solution, decomposed into a diamine component and an acid component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR to obtain a terminal. The encapsulant can be easily detected. Apart from this, it is also possible to detect the resin in which the terminal encapsulant has been introduced by directly ^{measuring the pyrolysis gas chromatograph (PGC), the infrared spectrum and the 13} C-NMR spectrum.

Further, (a) a polymerizable functional group may be provided at the end of the alkali-soluble resin. Examples of the polymerizable functional group include an ethylenically unsaturated group, an acetylene group, a methylol group, an alkoxymethyl group and the like.

In the present invention, (a) the alkali-soluble resin is preferably polyimide, a polyimide precursor or a polybenzoxazole precursor, and more preferably polyimide.

Further, the photosensitive resin composition of the present invention may contain another alkali-soluble resin in addition to (a) the alkali-soluble resin. The alkali-soluble resin refers to a resin having an acidic group that is soluble in alkali, and specific examples thereof include a radically polymerizable resin having an acrylic acid, a phenol-novolac resin, polyhydroxystyrene, and polysiloxane. Further, the alkali solubility may be adjusted by protecting the acidic groups of these resins. In addition to tetramethylammonium hydroxide, such a resin is dissolved in an alkaline aqueous solution such as choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. Although two or more of these resins may be contained, it is preferable that the proportion of the resin (a) in the entire resin is 70% by mass or less from the viewpoint of obtaining a resin film having excellent film physical characteristics after thermosetting.

The resin composition of the present invention contains (b) an aromatic ring to which a methylol group is bonded and a compound having a linear aliphatic structure. The linear aliphatic structure of the compound (b) preferably has one or more structures selected from the group consisting of an alkylene group and an alkyl ether group.

The resin composition of the present invention contains an aromatic ring to which a methylol group is bonded and a compound having a linear aliphatic structure as a thermal cross-linking agent to obtain a cured film having low stress and high chemical resistance. Can be done. The reason why such an effect is obtained is presumed as follows.

The compound (b) has an aromatic ring to which a methylol group is bonded, and the reaction mechanism in which the methylol group is directly added to the aromatic ring of the polymer (a) forms a crosslinked structure between the polymers, so that the compound is thermoset. Later film properties and chemical resistance can be improved. Further, since the compound (b) has an aromatic ring, the compound itself exhibits heat resistance, and it is possible to suppress thermal decomposition during thermosetting and reduce the shrinkage rate.

Further, since the compound (b) has a linear aliphatic structure and a highly flexible alkylene group and an alkyl ether group, an increase in elastic modulus is suppressed even if a crosslinked structure is formed between the polymers during thermosetting. , The elastic modulus of the cured film can be lowered to reduce the stress. Further, since it has high flexibility, a cured film having excellent elongation can be obtained.

By adding an appropriate amount of the compound (b) to the alkali-soluble resin (a), a cured film having low stress and excellent chemical resistance can be formed.

In the present invention, the content of the compound (b) is preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. When it is 10 parts by mass or more, it is preferable in terms of chemical resistance and low stress, and more preferably 15 parts by mass or more. When it is 50 parts by mass or less, it is preferable in that (a) excellent film characteristics such as mechanical properties and electrical insulation properties inherent in the alkali-soluble resin can be obtained, and more preferably 45 parts by mass or less.

The compound (b) is not particularly limited, but for example, a compound having one or more structures selected from the group consisting of the structures represented by the following general formulas (1) to (3). It is preferable to include it. Here, the compound (b) may have any one of the structures represented by the general formulas (1) to (3), or may have a structure of any one of the general formulas (1) to the general formula (1). -It may have two or more structures selected from the group consisting of the structures represented by the general formula (3).

When it has two or more structures selected from the group consisting of the structures represented by the general formulas (1) to (3), it is represented by the general formula (2) with respect to 100 mol% of the compound (b). The total content ratio of the structures represented by the general formulas (1) and (3) is 0 mol% or more and 50 mol% or less, and the total is 100 mol. % Is preferable in terms of chemical resistance and heat resistance.

(In the general formulas (1) to (3), the structural units including the aromatic ring may be the same or different. Further, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are respectively. It may be the same or different and represents a hydrogen atom or a methyl group. Further, (CH _2- OR ₁ ) _p and (CH _2- OR ₁ ) _q in the general formula (2) may be the same or different, respectively. _{Also, (CH 2-} OR ₁ ) _r , (CH _2- OR ₁ ) _s , and (CH _2- OR ₁ ) _t in the general formula (3) may be the same or different, respectively. > 1, n> 1, o> 1, p + q> 1, r + s + t> 1, p ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A, B, and D are the same, respectively. However, it may be different, and represents an organic group having one or more selected from the group consisting of a single bond, an ether bond, a hydroxyl group, an isopropylidene group, a ketone group, a carbonyl group, an amide group, and a sulfonyl group.)
Further, it is more preferable that the compound (b) contains a compound having a structure represented by the following general formula (4) in terms of chemical resistance and heat resistance. Here, the compound (b) may have only a compound having a structure represented by the general formula (4) instead of the structures represented by the general formulas (1) to (3). A compound having a structure represented by the general formula (4) in addition to one or more structures selected from the group consisting of the structures represented by the general formulas (1) to (3). May be good. The content ratio of the compound having the structure represented by the following general formula (4) is 50 mol% or more and 100 mol% or less with respect to 100 mol% of the compound (b) for chemical resistance and heat resistance. It is preferable in that respect.

(In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, respectively, and represent a hydrogen atom or a methyl group. Also, m> 1, n> 1 , O> 1, p + q> 1, r + s + t> 1, p ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A and B may be the same or different, respectively. Represents an organic group having one or more selected from the group consisting of a bond, an ether bond, a hydroxyl group, an isopropylidene group, a ketone group, a carbonyl group, an amide group, and a sulfonyl group.)
(B) The compound can be used alone or in combination of two or more.

Further, the weight average molecular weight of the compound (b) is preferably 3,000 or more and 20,000 or less. When it is 3,000 or more, it is preferable from the viewpoint of suppressing shrinkage at the time of thermosetting, and more preferably 5,000 or more. When it is 20,000 or less, it is preferable from the viewpoint of improving the solubility in an organic solvent, and more preferably 15,000 or less.

(B) The weight average molecular weight of the compound can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), a light scattering method, a small-angle X-ray scattering method, or the like. The weight average molecular weight in the present invention refers to a value calculated by using the simplest polystyrene-equivalent GPC measurement.

The resin composition of the present invention may contain (c) a photosensitizer. Examples of the photosensitizer include a combination of (c-1) a photoacid generator, (c-2) a photopolymerization initiator, and (c-3) a compound having two or more ethylenically unsaturated bonds. (C-1) By containing the photoacid generator, acid is generated in the light-irradiated part, the solubility of the light-irradiated part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light-irradiated part is dissolved is obtained. be able to. Further, by containing (c-2) a photopolymerization initiator and (c-3) a compound having two or more ethylenically unsaturated bonds, the active radicals generated in the light-irradiated portion are radicals having ethylenically unsaturated bonds. It is possible to obtain a negative-type relief pattern in which the light-irradiated portion is insolubilized by advancing the polymerization.

Examples of the (c-1) photoacid generator include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. The quinone diazide compound includes a polyhydroxy compound ester-bonded with quinone diazide sulfonic acid, a polyamino compound with quinone diazide sulfonic acid conjugated with a sulfonamide, and a polyhydroxypolyamino compound with quinone diazide sulfonic acid ester-bonded and / or sulfonamide. Examples include those combined. It is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. Further, it is preferable to contain two or more kinds of (c-1) photoacid generators, whereby a heat-resistant resin composition imparted with high-sensitivity photosensitivity can be obtained.

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

(C-1) Of the photoacid generators, a sulfonium salt, a phosphonium salt, and a diazonium salt are preferable because they appropriately stabilize the acid component generated by exposure. Of these, the sulfonium salt is preferable. Further, a sensitizer or the like can be contained as needed.

(C-2) Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, and 1- (4-isopropylphenyl) -2-hydroxy-. 2-Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2 -(O-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl -4'-methyl-diphenylsulfide, alkylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- ( 1-oxo-2-propenyloxy) ethyl] benzenemethanamineium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1- Propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo) -9H-thioxanthene-2-iroxy) -N, N, N-trimethyl-1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 1,2-octanedione-1- [4-] (Phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) , 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacrydone, 2-ethylanthraquinone, ben Jill, 9,10-phenanthrene quinone, phenylquinone, methylphenylglycoester, η5-cyclopentadienyl-η6-cumenyl-iron (1+)-hexafluorophosphofate (1-), diphenyl sulfide derivative, bis (Η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2- Dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β -Chloranthraquinone, anthron, benzanthron, dibenzsveron, methyleneanthron, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylene) cyclohexane, 2,6-bis (p-azidobenzylene) -4-methylcyclohexanone , 2-Phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanthrion-2- (o-ethoxycarbonyl) oxime, naphthalensulfonyl chloride, quinoline sulfonyl chloride, N-phenyl Photoreducing dyes such as eosin, methylene blue and ascorbin, such as thioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide, etc. Examples thereof include a combination with a reducing agent such as acid and triethanolamine. Two or more of these may be contained.

(C-3) Examples of the compound having two or more ethylenically unsaturated bonds include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethyl propantriacrylate, ethoxylated bisphenol A dimethacrylate, glycerin dimethacrylate, and tri. Acrylic monomers such as propylene glycol dimethacrylate, butanediol dimethacrylate, glycerin triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated isocyanuric acid triacrylate. be able to. Two or more of these may be contained.

The content of (c) the photosensitizer is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of (a) alkali-soluble resin.

The content of the (c-1) photoacid generator is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin from the viewpoint of increasing sensitivity. Of these, the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, the phosphonium salt and the diazonium salt is preferably 0.5 to 20 parts by mass. Within this content range, it is preferable in that the addition amount does not become excessive and the residue of the developing pattern is not generated, sufficient acid is generated by light irradiation, and the sensitivity is improved.

The content of the (c-2) photopolymerization initiator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. If it is 0.1 part by mass or more, sufficient radicals are generated by light irradiation, and the sensitivity is improved. Further, when the amount is 20 parts by mass or less, the light-unirradiated portion is not cured due to the generation of excessive radicals, and the alkali developability is improved.

The content of the compound (c-3) having two or more ethylenically unsaturated bonds is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. When it is 5 parts by mass or more, the radical polymerization of the ethylenically unsaturated bond by the active radical proceeds sufficiently and the sensitivity is improved, which is preferable. When it is 50 parts by mass or less, it is preferable in that the alkali developability is improved without curing the light-unirradiated part due to the progress of excessive radical polymerization.

The photosensitive resin composition of the present invention may contain (d) other thermal cross-linking agents other than (b) the compound.

(D) Other heat-crossing agents include, for example, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (above, ML-TBC) as having one heat-crossing group. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above), such as product name, manufactured by Honshu Kagaku Kogyo Co., Ltd., and PA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.). , Product name, Asahi Organic Materials Industry Co., Ltd., DMLMBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML- OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML- Bis25X-PCHP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), "Nikalac (registered trademark)" MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, B- m-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl -P-cresol, etc. as having three, TriML-P, TriML-35XL, TriML-TrisCR-HAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. TM-BIP-A as having four (Product name, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (Product name, manufactured by Honshu Chemical Industry Co., Ltd.), HML-TPPHBA, HML-TPHAP, etc., which have six such as "Nicarac" (registered trademark) MX-280 and "Nicarak" (registered trademark) MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), "Nicarac" (registered trademark) MW-390, "Nicarac" (registered trademark) MW-100LM (above, product name, Sanwa Chemical Co., Ltd.).

The structures of typical (d) other thermal cross-linking agents that are particularly preferably used in the photosensitive resin composition of the present invention are shown below.

These (d) other thermal cross-linking agents are used alone or in combination of two or more.

The content of (d) other thermal cross-linking agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass with respect to 100 parts by mass of the total amount of (a) alkali-soluble resin. It is 5 parts or more, particularly preferably 5 parts by mass or more, preferably 150 parts by mass or less, and particularly preferably 130 parts by mass or less. (A) Heat resistance of the heat-resistant fat composition coating obtained by heat treatment of the photosensitive resin composition coating by reducing the content of (d) other thermal cross-linking agent to 150 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. Does not reduce sex. On the other hand, when the amount is 0.5 parts by mass or more, the heat resistance of the heat-resistant resin composition coating is improved due to the effect of increasing the molecular weight by sufficient cross-linking.

In addition, a compound having a phenolic hydroxyl group can be contained for the purpose of adjusting the alkali developability of the photosensitive resin composition of the present invention.

Examples of the compound having a phenolic hydroxyl group that can be used in the present invention include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, and BisOCR-CP. , BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236TP , Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, Examples thereof include BIP-BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.).

Among these, compounds having a preferable phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-. BIPC-F. By containing this compound having a phenolic hydroxyl group, the obtained resin composition is easily dissolved in an alkaline developer before exposure, becomes sparingly soluble in an alkaline developer when exposed, and has less film loss due to development. , Development becomes easy in a short time.

The content of the compound having a phenolic hydroxyl group is preferably 1 to 60 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of the (a) alkali-soluble resin.

The heat-resistant resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include an alkoxysilane-containing compound and the like. Two or more of these may be contained. By containing these compounds, the adhesiveness between the film and the substrate after firing or curing can be improved.

Specific examples of the alkoxysilane-containing compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenylamino. Butyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane , 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxy Examples thereof include silane, 3-aminopropyltriethoxysilane, vinyltricrolsilane, and vinyltris (β-methoxyethoxy) silane.

The total content of the adhesion improver is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of (a) alkali-soluble resin. The amount of 0.01 parts by mass or more is preferable in that the adhesiveness between the film and the substrate after firing or curing can be improved. The amount of 15 parts by mass or less is preferable in that the adhesiveness is improved without lowering the alkali developability due to excessive adhesion.

The heat-resistant resin composition of the present invention may contain a surfactant, which can improve the wettability with the substrate.

Surfactants include "FLOORAD" (registered trademark) (3M Japan Co., Ltd.), "Megafuck" (registered trademark) (DIC Co., Ltd.), "Surflon" (registered trademark) (Asahi Glass Co., Ltd.) Fluorine-based surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), " Organic siloxane surfactants such as "BYK" (registered trademark) (manufactured by BIC Chemie Co., Ltd.), acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), etc. are mentioned. Available from.

In the present invention, each component (a) to (d), a compound having a phenolic hydroxyl group, an adhesion improver and a surfactant are used in a state of being dissolved or dispersed in an organic solvent. As the organic solvent, a solvent having a boiling point under atmospheric pressure of 80 ° C. to 250 ° C. is preferably used.

Specific examples of the organic solvent preferably used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Ethers such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, lactic acid. Acetates such as butyl, acetylacetone, methylpropyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone and other ketones, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, Alcohols such as 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2- Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylpropyleneurea, 3-methoxy-N, N -Dimethylpropionamide, deltavalerolactone and the like. These may be used alone or in combination of two or more.

Of these, those in which (a) an alkali-soluble resin is dissolved and the boiling point under atmospheric pressure is 100 ° C. to 210 ° C. are particularly preferable. When the boiling point is within this range, the organic solvent does not volatilize too much at the time of coating the composition, and the coating does not become impossible, and the heat treatment temperature of the composition does not have to be raised, so that the material of the underlying substrate is restricted. There is no. Further, by using (a) an organic solvent that dissolves the alkali-soluble resin, a coating film having good uniformity can be formed on the base substrate.

Specific preferred organic solvents having such a boiling point include cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, and 3-methyl. Examples thereof include -3-methoxybutanol, gamma butyrolactone and N-methyl-2-pyrrolidone.

The organic solvent used in the resin composition of the present invention is preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of (a) alkali-soluble resin. It is 800 parts by mass or less, particularly preferably 500 parts by mass or less.

Next, a method for producing the resin composition of the present invention will be described. For example, a resin composition can be obtained by dissolving the alkali-soluble resin (a) and the compound (b), and if necessary, the components (c) and (d). Examples of the melting method include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C. Further, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.

The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. The filter pore diameter includes, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.03 μm, 0.02 μm, 0.01 μm, 0.005 μm, and the like, but is not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but PE and NY are preferable.

Next, a method for producing a resin film using the resin composition of the present invention will be described with reference to an example.

First, the photosensitive resin composition is applied onto the substrate. Silicon wafers, ceramics, gallium arsenide, etc. are used as the substrate, but the substrate is not limited thereto. The substrate may be pretreated with a chemical solution such as a silane coupling agent or a titanium chelating agent. For example, a solution prepared by dissolving the above-mentioned coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate in an amount of 0.5 to 20% by mass. Surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, the reaction between the substrate and the coupling agent can be allowed to proceed by subsequently applying a temperature of 50 ° C to 300 ° C.

As a method for applying the resin composition, there are methods such as rotary coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 1 to 50 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive coating film. This process is also called prebaking. Drying is preferably carried out in the range of 70 to 140 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like. When a hot plate is used, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. As the material of the proxy pin, there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or "Teflon (registered trademark)", and any material of the proxy pin may be used as long as it has heat resistance. .. The height of the proxy pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, and the like, but is preferably 0.1 to 10 mm.

Next, the photosensitive coating film is irradiated with chemical rays through a mask having a desired pattern and exposed. The chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps. .. If it has positive photosensitivity, the exposed area dissolves in the developer. When it has a negative photosensitive property, the exposed portion is cured and insolubilized in a developing solution.

Next, if necessary, a post-exposure baking process is performed. The temperature is preferably in the range of 50 to 180 ° C, and more preferably in the range of 60 to 150 ° C. The time is not particularly limited, but 10 seconds to several hours is preferable from the viewpoint of subsequent developability.

After the exposure, in order to form a pattern of the resin film, the exposed part is removed using a developing solution. The developing solution is tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl. An aqueous solution of an alkaline compound such as methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable. In some cases, these alkaline aqueous solutions are mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol and isopropanol. Alcohols such as, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added in an amount of one or more. After development, it is common to rinse with water. For the rinsing treatment, one or more kinds of alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate, propylene glycol monomethyl ether acetate and 3-methoxymethylpropanate may be added to water.

After development, the obtained coating film pattern is heated in a temperature range of 150 to 500 ° C. to convert the resin film into a cured relief pattern. It is preferable that this heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. Examples include a method of heat-treating at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, and a method of linearly raising the temperature from room temperature to 320 ° C. over 2 hours.

The cured relief pattern formed by the resin composition of the present invention is suitably used for applications such as surface protective films for semiconductor parts, interlayer insulating films for thin film inductors and multilayer wiring for high-density mounting, and insulating layers for organic electroluminescent devices. ..

Next, an example of application to an electronic component having a coil conductor using the resin composition of the present invention will be described with reference to FIG. FIG. 1 is an enlarged cross-sectional view of a multilayer structure portion formed by alternately stacking insulating layers and coil conductor layers in an electronic component having a coil conductor of the present invention.

An insulating film 2a made of the resin composition of the present invention is formed on the substrate 1, and a coil conductor layer 3a is formed on the insulating film 2a. Similarly, the coil conductor layers 3b to 3d corresponding to the insulating films 2b to 2d are formed, and the insulating films 2e and 2f are formed.

The inner peripheral ends of the coil conductor layers 3a and 3b are connected to each other via a through-hole portion 4a penetrating the insulating layer 2b. Therefore, the coil conductor layers 3a and 3b form a single inductor composed of a series circuit of two coils. Similarly, the coil conductor layers 3c and 3d are connected to each other via a through-hole portion 4b penetrating the insulating layer 2d between the inner peripheral ends, so that the coil conductor layers 3c and 3d consist of a series circuit of two coils. It constitutes a single inductor.

The properties required for the insulating film in the above structure are low warpage when laminated and withstand chemical treatment associated with coil pattern formation, and the resin composition of the present invention can be suitably used for this application. it can.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The evaluation of the resin composition in the examples was carried out by the following method.

<Evaluation of low stress (warping stress)>
The warping stress of a 6-inch silicon wafer was measured using a stress device FLX3300-T (manufactured by Toho Technology Co., Ltd.). Next, the varnish was applied and prebaked by a spin coating method using a coating / developing device Mark-7 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 12 μm, and then the inert oven CLH-21CD-S (Koyo Thermo). Using a system (manufactured by System Co., Ltd.), the temperature was raised to 220 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 220 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the silicon wafer was taken out, the film thickness of the cured film on the silicon wafer was measured, and then the warping stress of the cured film was measured using the above stress device. Here, the warpage stress is preferably less than 25 MPa, more preferably less than 15 MPa. The warping stress was evaluated as 3 when it was less than 15 MPa, 2 when it was 15 MPa or more and less than 25 MPa, and 1 when it was 25 MPa or more.

<Evaluation of chemical resistance>
For the varnishes described in each Example and Comparative Example, the cure film prepared on the silicon wafer by the above method was immersed in dimethyl sulfoxide (DMSO) at room temperature for 30 minutes, and the film thickness before and after the treatment was measured. Then, the film thickness fluctuation rate was calculated. Furthermore, the presence or absence of cracks and peeling was confirmed with an optical microscope. Here, the film thickness volatility is preferably less than 3%, more preferably less than 1%. The chemical resistance evaluation was evaluated with a film thickness variation rate of 0% or more and less than 1% as 3, a case of 1% or more and less than 3% as 2, and a case of 3% or more as 1. The case where no crack or peeling was observed was evaluated as 3, the case where peeling was not observed from the substrate due to only cracks was evaluated as 2, and the case where peeling was observed from the substrate was evaluated as 1.

<Synthesis Example 1 Polyimide Synthesis>
Under a dry nitrogen stream, 32.9 g (0.09 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF, manufactured by Central Glass Co., Ltd.) was dissolved in 500 g of NMP. To this, 31.0 g (0.1 mol) of ODPA was added together with 50 g of NMP, and the mixture was stirred at 30 ° C. for 2 hours. Then, 2.18 g (0.02 mol) of 3-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Further, 5 g of pyridine (manufactured by Tokyo Kasei Co., Ltd.) is diluted with toluene (30 g manufactured by Tokyo Kasei Co., Ltd.) and added to the solution. The reaction was carried out at a temperature of 120 ° C. for 2 hours and further at 180 ° C. for 2 hours. The temperature of this solution was lowered to room temperature, and the solution was poured into 3 L of water to obtain a white powder. The powder was collected by filtration and washed with water three times. After washing, the white powder was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain polyimide.

<Synthesis Example 2 Synthesis of Hydroxy Group-Containing Diamine Compound (HFHA)>
2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g (0.05 mol), 100 mL of acetone, propylene oxide (manufactured by Tokyo Kasei Co., Ltd.) ) Was dissolved in 17.4 g (0.3 mol) and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the obtained white solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of methyl cell solve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into this with a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HFHA) represented by the following formula.

<Synthesis Example 3 Synthesis of Polyimide Precursor>
51.3 g (0.085 mol) of HFHA obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.24 g under a dry nitrogen stream. (0.005 mol), 3-aminophenol (manufactured by Tokyo Kasei Co., Ltd.) 2.18 g (0.02 mol) was dissolved in 200 g of N-methyl-2-pyrrolidone (NMP). To this, 31.0 g (0.1 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA, manufactured by Manac Inc.) was added, and the mixture was stirred at 40 ° C. for 2 hours. Then, a solution of 7.14 g (0.06 mol) of dimethylformamide dimethylacetal (DFA manufactured by Mitsubishi Rayon Co., Ltd.) diluted with 5 g of NMP was added dropwise over 10 minutes. After the dropping, stirring was continued at 40 ° C. for 2 hours. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the mixture was washed 3 times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide precursor.

<Synthesis Example 4 Synthesis of Polybenzoxazole Precursor>
Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. Here, 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) are added to 25 g of γ-butyrolactone. The dissolved solution was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropping, stirring was continued at −15 ° C. for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10% by mass of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polybenzoxazole precursor.

<Synthesis Example 5 Synthesis of quinonediazide compound>
TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazide sulfonic acid chloride (manufactured by Toyo Synthetic Co., Ltd., NAC-5) under a dry nitrogen stream. 26.8 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35 ° C. After the dropping, the mixture was stirred at 40 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration and further washed with 1 L of 1% hydrochloric acid water. Then, it was washed twice with 2 L of water. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

<Synthesis Example 6 Synthesis of Linear Bifunctional Epoxy Compound>
Hexaethylene glycol (manufactured by Tokyo Kasei Co., Ltd.) 35. for a mixture of epichlorohydrin (manufactured by Tokyo Kasei Co., Ltd.) 69.4 g (0.750 mol), sodium hydroxide 30 g (0.750 mol) and 3 mL of water. 3 g (0.125 mol) was added dropwise and the mixture was stirred at 65 ° C. for 2 hours. It was cooled, filtered and washed with dichloromethane. Further, it was dried and distilled under reduced pressure to obtain a linear bifunctional epoxy compound.

<Synthesis Example 7 Thermal cross-linking agent having an aromatic ring to which a methylol group is bonded and a linear aliphatic structure>
20.6 g (0.09 mol) of bisphenol A (manufactured by Tokyo Kasei Co., Ltd.) and 39.4 g (0.10 mol) of the linear bifunctional epoxy compound obtained in Synthesis Example 6 were charged, and 150 It was melt-mixed at ° C. Then, 0.016 g of triphenylphosphine was added, and the mixture was stirred at 150 ° C. for 4 hours. Then, 100 g of methyl isobutyl ketone was added, 100 g of a 5% aqueous sodium hydroxide solution was added, and the mixture was stirred at 90 ° C. for 30 minutes, then allowed to stand and separated, and the organic solvent layer was neutralized with phosphoric acid and washed with water.

The organic solvent layer after washing with water was added dropwise over 5 minutes with 25.0 g of a 20% aqueous sodium hydroxide solution while stirring at 40 ° C. Then, while stirring at 50 ° C., 25.0 g of a 35% formaldehyde aqueous solution was added dropwise over 30 minutes, and the mixture was reacted at the same temperature for 5 hours. After completion of the reaction, 70 g of a 10% aqueous acetic acid solution was added dropwise over 10 minutes to neutralize the reaction mixture. Then, a liquid separation operation was performed to remove the aqueous layer, the mixture was cooled to room temperature, stirred overnight, and then distilled under reduced pressure to distill off methyl isobutyl ketone to obtain the desired product. To this was added γ-butyrolactone to prepare a 50% by mass γ-butyrolactone solution of the target product. The weight average molecular weight was 5360.

[Example 1]
(A) As an alkali-soluble resin, 3.50 g of the polyimide of Synthesis Example 1, (b) As a compound, 2.10 g of a thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7, and (c) Synthesized as a photosensitizer. 0.70 g of the quinone diazide compound of Example 5, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.55 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 2]
(A) As an alkali-soluble resin, 3.50 g of polyimide of Synthesis Example 1, (b) As a compound, 1.40 g of a thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7, and (c) Synthesized as a photosensitizer. 0.70 g of the quinone diazide compound of Example 5, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.60 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 3]
(A) As an alkali-soluble resin, 3.50 g of the polyimide of Synthesis Example 1, (b) As a compound, 2.80 g of the thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7, and (c) Synthesized as a photosensitizer. 0.70 g of the quinone diazide compound of Example 5, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.50 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 4]
(A) 3.50 g of the polyimide precursor of Synthesis Example 3 as an alkali-soluble resin, 2.10 g of the thermal cross-linking agent (50% by mass γ-butyrolactone solution) of Synthesis Example 7 as a compound (b), (c) Photosensitizer 0.70 g of the quinone diazide compound of Synthesis Example 5, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.55 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 5]
(A) 3.50 g of the polybenzoxazole precursor of Synthesis Example 4 as an alkali-soluble resin, 2.10 g of a thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7 as a compound (b), (c) 0.70 g of the quinone diazide compound of Synthesis Example 5 as a photosensitizer, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyflow No. 1 as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.55 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 6]
(A) 3.50 g of the polybenzoxazole precursor of Synthesis Example 4 as an alkali-soluble resin, 2.10 g of the thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7 as a compound (b), (c). 0.70 g of the quinone diazide compound of Synthesis Example 5 as a photosensitizer, 0.70 g of TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) as another thermal cross-linking agent, and KBM-1003 (KBM-1003) as an adhesion improver. Product name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.15 g, Polyflow No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 4.20 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Example 7]
(A) As an alkali-soluble resin, 3.50 g of polyimide of Synthesis Example 1, (b) As a compound, 4.20 g of a thermal cross-linking agent (50 mass% γ-butyrolactone solution) of Synthesis Example 7, and (c) Synthesized as a photosensitizer. 0.70 g of the quinone diazide compound of Example 5, 0.15 g of KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver, and Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.40 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Comparative Example 1]
(A) 3.50 g of polyimide of Synthesis Example 1 as an alkali-soluble resin, 0.70 g of a quinonediazide compound of Synthesis Example 5 as a photosensitizer, and KBM-1003 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as an adhesion improver. 0.15 g, Polyimide No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.71 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

[Comparative Example 2]
(A) 3.50 g of the polybenzoxazole precursor of Synthesis Example 4 as an alkali-soluble resin, 0.70 g of the quinonediazide compound of Synthesis Example 5 as a photosensitizer, and (d) TM-BIP- as another thermal cross-linking agent. A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) 0.70 g, KBM-1003 (trade name, manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.15 g as an adhesive improver, Polyflow No. as a surfactant. 0.001 g of 77 (trade name, manufactured by Kyoei Kagaku Co., Ltd.) was added to 3.55 g of γ-butyrolactone and stirred to obtain a varnish of a photosensitive resin composition. Using the obtained varnish, the warp stress and chemical resistance were evaluated by the method described above.

Table 1 shows Examples 1 to 7 and Comparative Examples 1 and 2 with respect to the above composition and evaluation results.

The names shown in Table 1 have the following meanings.
TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.)
KBM-1003: Silane coupling agent KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
PF77: Polyflow No. 77 (Product name, manufactured by Kyoei Kagaku Co., Ltd.)
GBL: γ-Butyrolactone

1 Substrates 2a, 2b, 2c, 2d, 2e, 2f Insulating film 3a, 3b, 3c, 3d Coil conductor layers 4a, 4b Through-holes

Claims (9)

It contains (a) an alkali-soluble resin, (b) an aromatic ring to which a methylol group is bonded, and a compound having a linear aliphatic structure.
The (a) alkali-soluble resin contains one or more selected from the group consisting of a polyimide precursor, a polyamide-imide, a polyimide, a polybenzoxazole precursor, a polybenzoxazole, and a phenol resin.
(B) A compound having an aromatic ring to which a methylol group is bonded and a linear aliphatic structure is selected from the group consisting of the structures represented by the following general formulas (1) to (3). A resin composition comprising a compound having the above structure.

(In the general formulas (1) to (3), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, respectively, and represent a hydrogen atom or a methyl group. _{(CH 2-} OR ₁ ) _p and (CH _2- OR ₁ ) _q in the formula (2) may be the same or different, respectively. Further, (CH _2- OR ₁ ) _r , (CH 2-OR 1) r in the general formula (3). CH _2- OR ₁ ) _s and (CH _2- OR ₁ ) _t may be the same or different, respectively. Also, m> 1, n> 1, o> 1, p + q> 1, r + s + t> 1, p. ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A, B, and D may be the same or different, respectively, and may be the same or different, single bond, ether bond, hydroxyl group, isopropylidene group, ketone. Represents an organic group having one or more selected from the group consisting of a group, a carbonyl group, an amide group, and a sulfonyl group.) The resin composition according to claim 1, wherein the aromatic ring to which the (b) methylol group is bonded and the compound having a linear aliphatic structure include a compound having a structure represented by the following general formula (4). Stuff.

(In the general formula (4), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, respectively, and represent a hydrogen atom or a methyl group. Also, m> 1, n> 1 , O> 1, p + q> 1, r + s + t> 1, p ≧ 0, q ≧ 0, r ≧ 0, s ≧ 0, t ≧ 0. A and B may be the same or different, respectively. Represents an organic group having one or more selected from the group consisting of a bond, an ether bond, a hydroxyl group, an isopropylidene group, a ketone group, a carbonyl group, an amide group, and a sulfonyl group.) (B) The resin composition according to claim 1 or 2, wherein the aromatic ring to which the methylol group is bonded and the compound having a linear aliphatic structure have a weight average molecular weight of 3000 or more and 20000 or less. The aromatic ring to which the methylol group is bonded and the compound having a linear aliphatic structure are contained in an amount of 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a). The resin composition according to any one of claims 1 to 3. A resin sheet formed from the resin composition according to any one of claims 1 to 4. A cured film obtained by curing the resin composition according to any one of claims 1 to 4 or the resin sheet according to claim 5. An electronic component or a semiconductor component in which the cured film according to claim 6 is arranged as an interlayer insulating film or a surface protective film. An electronic component having a coil structure in which the cured film according to claim 6 is repeatedly arranged in 2 to 10 layers as an interlayer insulating film. A semiconductor component in which the cured film according to claim 6 is repeatedly arranged in 2 to 10 layers as an interlayer insulating film.

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