Negative-type photosensitive resin composition, negative-type photosensitive resin composition film, cured product, method for manufacturing the cured product, hollow structure, and electronic component.

Abstract

The present invention addresses the problem of providing: a negative photosensitive resin composition, from which high aspect ratio pattern processability, good storage stability, and curability are obtained; and a cured product having excellent mechanical properties and heat resistance.　A negative photosensitive resin composition contains (A) a polymer compound, (B) a cation-polymerizable compound, (C) a cation polymerization initiator, and (D) a solvent, wherein the (A) component contains at least one compound selected from the group consisting of polyamide, polyimide, polybenzoxazole, a precursor thereof, and a copolymer thereof, and when all carboxylic acid residues included in the (A) component are A mol, all diamine residues are B mol, and all monoamine residues are C mol, 0.6A≦B+0.5C≦0.98A and 0.05(B+C)≦C≦0.25(B+C) are satisfied.

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition, a negative photosensitive resin composition film, a cured product, a method for producing the cured product, a hollow structure, and an electronic component. More specifically, the present invention relates to a negative photosensitive resin composition suitably used for a surface protective film, an interlayer insulating film of an electronic component, a structure of MEMS (Micro Electro Mechanical Systems), etc.

Background Art

[0002] Conventionally, polyimide-based materials and polybenzoxazole-based materials, which are excellent in heat resistance, electrical insulation, and mechanical properties, have been widely used for surface protective films and interlayer insulating films of electronic components.

[0003] With the recent demand for higher performance of electronic components, fine patterning and high aspect ratio processing are required for surface protective films and interlayer insulating films. In order to meet such requirements, a chemically amplified cation-curable photosensitive resin has been disclosed. (For example, Patent Document 1). In addition, a photo cation-curable photosensitive resin intended to improve mechanical properties and heat resistance by containing an epoxy resin having a specific structure has been disclosed (for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, with the photocationic polymerization materials described above, it was difficult to achieve both sufficient mechanical and thermal properties. Specifically, increasing the crosslinking density to improve the glass transition temperature of the cured film, which is an indicator of thermal properties, resulted in inferior tensile strength and tensile elongation of the cured film, which are indicators of mechanical properties. On the other hand, introducing flexible components to improve tensile strength and tensile elongation lowered the glass transition temperature of the cured film. Furthermore, when conventional polyimide resins or polybenzoxazole resins were added to improve mechanical and thermal properties, the functional groups at the side chains and terminals inhibited or excessively promoted the cationic polymerization reaction, making it difficult to achieve both photocurability and storage stability. [Means for solving the problem]

[0006] The present invention, which solves the above problems, is as follows. A negative-type photosensitive resin composition comprising (A) a polymer compound, (B) a cationic polymerizable compound, and (C) a cationic polymerization initiator, wherein component (A) contains at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof, and satisfying 0.6A ≤ B + 0.5C ≤ 0.98A and 0.05(B + C) ≤ C ≤ 0.25(B + C) when all carboxylic acid residues contained in component (A) are A mol, all diamine residues are B mol, and all monoamine residues are C mol, the negative-type photosensitive resin composition. [Effects of the Invention]

[0007] This invention provides a negative-type photosensitive resin composition that offers high aspect ratio pattern machinability, good storage stability, and photocurability, as well as a cured product with excellent mechanical properties and heat resistance. [Modes for carrying out the invention]

[0008] The negative-type photosensitive resin composition of the present invention is a negative-type photosensitive resin composition comprising (A) a polymer compound, (B) a cationic polymerizable compound, and (C) a cationic polymerization initiator, wherein component (A) contains at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof, and when all carboxylic acid residues contained in component (A) are A mol, all diamine residues are B mol, and all monoamine residues are C mol, the negative-type photosensitive resin composition satisfies 0.6A ≤ B + 0.5C ≤ 0.98A and 0.05(B + C) ≤ C ≤ 0.25(B + C). Hereafter, condition (i) will be defined as the inclusion of at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof in component (A), condition (ii-1) will be defined as 0.6A ≤ B + 0.5C ≤ 0.98A, and condition (ii-2) will be defined as 0.05(B + C) ≤ C ≤ 0.25(B + C), and the satisfaction of conditions (ii-1) and (ii-2) will be referred to as satisfying condition (ii).

[0009] First, let's explain (A) polymer compounds (which may be referred to as component (A) below). In the present invention, the (A) component is a compound comprising at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof. Here, unless otherwise specified, polyamide refers to polyamides other than polyimide precursors and polybenzoxazole precursors. In the present invention, the (A) component preferably contains 80 to 100% by mass of a compound comprising at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and particularly preferably 98 to 100% by mass.

[0010] Examples of polyamides include those obtained by dehydrating and condensing a dicarboxylic acid and a diamine compound using polyphosphate.

[0011] Examples of polyimide precursors include those obtained by reacting tetracarboxylic acids and their derivatives with diamines and their derivatives, such as polyamic acids, polyamic acid esters, polyamic acid amides, or polyisoimides. Examples of polyimides include those obtained by dehydrating and cyclizing the above-mentioned polyamic acids, polyamic acid esters, polyamic acid amides, or polyisoimides by heating or a reaction using an acid or base.

[0012] Examples of polybenzoxazole precursors include poly-(o-hydroxyamides) obtained by reacting dicarboxylic acids and their derivatives with diamines such as o-bisaminophenol. Examples of polybenzoxazoles include those obtained by dehydrating and cyclizing the above-mentioned poly-(o-hydroxyamides) by heating or a reaction using an acid or base.

[0013] Examples of copolymers include copolymers of two polymer compounds, such as a copolymer of polyamide and polyimide or its precursor, a copolymer of polyamide and polybenzoxazole or its precursor, a copolymer of polybenzoxazole or its precursor and polyimide or its precursor, a copolymer of polyimide and its precursor, and a copolymer of polybenzoxazole and its precursor. However, copolymers of three or more polymer compounds are also acceptable.

[0014] (A) The carboxylic acid residues contained in component (A) are residues derived from carboxylic acids or carboxylic acid derivatives that can constitute at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof. For example, this refers to the structure of residues derived from monocarboxylic acids, dicarboxylic acids, tetracarboxylic acids, acid anhydrides, acid dianhydrides, monoacid chlorides, diacid chlorides, etc. Examples of carboxylic acids or carboxylic acid derivatives include, but are not limited to, aromatic dicarboxylic acids, aromatic acid dianhydrides, alicyclic dicarboxylic acids, and alicyclic acid dianhydrides. Furthermore, these may be used alone or in combination of two or more types.

[0015] (A) The diamine residue contained in component (A) refers to a residue derived from a diamine or a derivative thereof that can constitute at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof, and refers to the structure of a residue derived from a diamine, diisocyanate, etc. Examples of diamines or derivatives thereof include, but are not limited to, aromatic diamines, aromatic diisocyanates, alicyclic diamines, and alicyclic diisocyanates. Furthermore, these may be used alone or in combination of two or more types.

[0016] (A) The monoamine residue contained in component (A) refers to a residue derived from a monoamine or a derivative thereof that can constitute at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof, and refers to the structure of a residue derived from, for example, a monoamine, monoisocyanate, etc. Examples of monoamines or derivatives thereof include, but are not limited to, aromatic monoamines, aromatic monoisocyanates, alicyclic monoamines, and alicyclic monoisocyanates. Furthermore, these may be used alone or in combination of two or more types.

[0017] From the viewpoint of heat resistance and chemical resistance of the cured product, it is preferable that the monoamine residue has a crosslinkable functional group. Examples of crosslinkable functional groups include, but are not limited to, hydroxyl groups and ethynyl groups. Among the above crosslinkable functional groups, hydroxyl groups are preferred from the viewpoint of alkali solubility.

[0018] In this invention, as component (A), a compound is used that satisfies the relationship 0.6A ≤ B + 0.5C ≤ 0.98A, where A mol is the total amount of all carboxylic acid residues contained in component (A), B mol is the total amount of all diamine residues, and C mol is the total amount of all monoamine residues. When 0.6A ≤ B + 0.5C, the weight-average molecular weight of the polymer compound (A) tends to be 1,000 or more, and a cured product with good mechanical properties can be obtained. When B + 0.5C ≤ 0.98A, the proportion of molecular chains having diamine residues at the terminals that can deactivate cations can be reduced. This facilitates photocationic polymerization and allows for good photocurability. In terms of obtaining better mechanical properties and photocurability, it is more preferable that the above relationship is 0.8A ≤ B + 0.5C ≤ 0.98A, and even more preferable that it is 0.9A ≤ B + 0.5C ≤ 0.98A.

[0019] Furthermore, in this invention, a compound satisfying 0.05(B+C)≦C≦0.25(B+C) is used as component (A). When 0.05(B+C)≦C, a portion of the molecular chain ends of component (A) are sealed with monoamine residues, which suppresses excessive reaction between the carboxylic acid residues of component (A) and component (B), thereby suppressing the increase in viscosity when the negative-type photosensitive resin composition is stored at room temperature. When C≦0.25(B+C), the weight-average molecular weight of component (A) tends to be 1,000 or more, and a cured product with good mechanical properties can be obtained. In terms of obtaining better storage stability and mechanical properties, it is more preferable that the above relationship is 0.05(B+C)≦C≦0.15(B+C), and even more preferable that it is 0.05(B+C)≦C≦0.10(B+C).

[0020] In the present invention, the content ratio of carboxylic acid residues, diamine residues, and monoamine residues contained in component (A) can be determined by the following methods. For example, by dissolving component (A) in an acidic solution and analyzing it using gas chromatography (GC) or nuclear magnetic resonance (NMR), the carboxylic acid residues, diamine residues, and monoamine residues contained in component (A) can be detected and their ratios can be determined. Alternatively, by directly analyzing the negative-type photosensitive resin composition or component (A) using NMR or the like, the carboxylic acid residues, diamine residues, and monoamine residues contained in component (A) can be detected and their ratios can be determined. When preparing a negative-type photosensitive resin composition using the polymerization solution of component (A) without purification, the ratio of carboxylic acid residues, diamine residues, and monoamine residues contained in component (A) corresponds to the monomer charging ratio during polymerization of component (A), so it can also be calculated from the monomer charging ratio during polymerization of component (A).

[0021] In the present invention, the content of component (A) is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 30% to 70% by mass, based on 100% by mass of the negative-type photosensitive resin composition. Within this range, good processability, mechanical properties, and heat resistance can be obtained.

[0022] In the present invention, component (A) preferably has a weight-average molecular weight of 1,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Within this range, good processability, mechanical properties, and heat resistance can be obtained. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and calculated on a polystyrene basis.

[0023] In the present invention, component (A) is preferably alkali-soluble. Alkali solubility of component (A) is preferable because it allows development with an alkaline aqueous solution without using environmentally harmful organic solvents. Here, alkali solubility refers to dissolving 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C. To exhibit alkali solubility, component (A) is preferably acidic. Specifically, this includes, but is not limited to, phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups. Among the above acidic groups, phenolic hydroxyl groups are preferred from the viewpoint of storage stability of the negative-type photosensitive resin composition and corrosion of copper wiring.

[0024] In the present invention, component (A) preferably has a light transmittance of 90% or more, more preferably 95% or more, and even more preferably 99% or more per 1 μm film thickness at a wavelength of 365 nm. Within this range, when used as a negative-type photosensitive resin composition, it is possible to achieve fine pattern processing even in thick films of 20 μm or more.

[0025] Preferably, at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof contains a structure represented by formula (1) and / or a structure represented by formula (2).

[0026] [ka]

[0027] In formula (1), R 1 R represents a residue derived from a tetravalent carboxylic acid or its derivative having 4 to 40 carbon atoms. 2 * represents a residue derived from a divalent diamine or its derivative having 4 to 40 carbon atoms. * represents a bond site.

[0028] [ka]

[0029] In formula (2), R 3 -(COOR 5 ) m represents a residue derived from a C4-C40 divalent to tetravalent carboxylic acid or its derivative, and R 4 represents a residue derived from a C4-C40 divalent diamine or its derivative. R 5 represents a hydrogen atom or a C1-C30 monovalent hydrocarbon group, and m represents an integer from 0 to 2. * represents a bonding point.

[0030] R in formula (1) 2 and R in formula (2) 4 are residues derived from a C4-C40 divalent diamine or its derivative, and the R 2 and R 4 are preferably diamine residues having a phenolic hydroxyl group. When R 2 in formula (1) and R 4 in formula (2) are diamine residues having a phenolic hydroxyl group, the component (A) can be rendered alkali-soluble.

[0031] Examples of the diamine residue having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, and 2,2'-bis[N- [(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2 ,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-bipheno Examples of such residues include, but are not limited to, aromatic diamine residues such as bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, as well as residues of compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with C1-C10 alkyl groups, fluoroalkyl groups, halogen atoms, etc. Furthermore, component (A) may contain two or more of these diamine residues.

[0032] R in equation (1) 2and R in equation (2) 4 This may include diamine residues having aromatic rings other than the aforementioned diamine residues having phenolic hydroxyl groups. Copolymerizing these is preferable because it can improve heat resistance.

[0033] Examples of diamine residues having the aromatic ring include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, 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-amino Examples include aromatic diamines such as phenoxy)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, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, as well as compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc., having 1 to 10 carbon atoms, but are not limited to these. Furthermore, component (A) may contain two or more of these diamine residues.

[0034] R in equation (1) 1 R is a residue derived from a tetravalent carboxylic acid or its derivative having 4 to 40 carbon atoms, and in formula (2), R 3 -(COOR 5 ) mR is a residue derived from a divalent to tetravalent carboxylic acid or a derivative thereof having 4 to 40 carbon atoms, and 1 and R 3 It is preferable that the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride. It is preferable that the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride because it increases the light transmittance of component (A) at a wavelength of 365 nm, and enables fine pattern processing even in thick films of 20 μm or more. Furthermore, although the reason is not clear, it is preferable that component (A) has a carboxylic acid residue with a structure derived from an alicyclic tetracarboxylic dianhydride because it has higher cationic polymerizability compared to aromatic acid dianhydride residues, improving the heat resistance and chemical resistance of the cured product. Moreover, it is preferable that the R in formula (1) improves the chemical resistance and ion migration resistance of the cured product. 1 and R in equation (2) 3 It is preferable that the carboxylic acid residue has a structure derived from a polycyclic alicyclic tetracarboxylic dianhydride.

[0035] Examples of polycyclic alicyclic tetracarboxylic dianhydride residues include 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride. Examples include residues of norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, and residues of compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with C1-C10 alkyl groups, fluoroalkyl groups, halogen atoms, etc., but are not limited to these. Furthermore, component (A) may contain two or more alicyclic tetracarboxylic dianhydride residues having these polycyclic structures.

[0036] Furthermore, the carboxylic acid residue may include acid dianhydride residues other than the alicyclic tetracarboxylic dianhydride having the polycyclic structure.Specifically, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-di Carboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy Aromatic tetracarboxylic dianhydrides such as phenyl fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Examples include residues of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and residues of compounds in which some of the hydrogen atoms of the aromatic rings or hydrocarbons are substituted with C1-C10 alkyl groups, fluoroalkyl groups, halogen atoms, etc., but are not limited to these. Furthermore, component (A) may contain two or more of these tetracarboxylic dianhydride residues.

[0037] In the present invention, the molecular chain ends of component (A) are sealed with monoamine residues within the range of 0.6A ≤ B + 0.5C ≤ 0.98A and 0.05(B + C) ≤ C ≤ 0.25(B + C), where A mol is the total amount of all carboxylic acid residues contained in component (A), B mol is the total amount of all diamine residues, and C mol is the total amount of all monoamine residues. By sealing the molecular chain ends of component (A) with monoamine residues, excessive reactions between the carboxylic acid residues contained in component (A) and component (B) are suppressed, and the increase in viscosity when the negative-type photosensitive resin composition is stored at room temperature can be suppressed. Specific examples of the aforementioned monoamine residues include, for example, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, Examples of monoamine residues include, but are not limited to, those of 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol, as well as residues of compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are substituted with alkyl groups, fluoroalkyl groups, halogen atoms, etc., having 1 to 10 carbon atoms. Furthermore, component (A) may contain two or more of these monoamine residues.

[0038] In the present invention, the monoamine residue contained in component (A) preferably contains a structure represented by formula (3) from the viewpoint of storage stability and pattern processingability.

[0039] [ka]

[0040] In formula (3), R 6 * represents a monovalent organic group with 1 to 6 carbon atoms. o represents 0 or 1. p represents 0 or 1. * represents a bond site to an amine nitrogen.

[0041] In the present invention, polyamides, polyimides, and polybenzoxazoles, which are examples of polymers included in component (A), are synthesized by, for example, the following methods, but are not limited thereto. Polyimide precursors can be obtained by, for example, reacting tetracarboxylic acid and its derivatives with diamines and their derivatives and monoamines and their derivatives at low temperatures, or by obtaining diesters from tetracarboxylic acid and its derivatives with alcohols, and then reacting them with diamines and their derivatives and monoamines and their derivatives in the presence of a condensing agent. Polyimides can be obtained by, for example, heating the polyimide precursor or by dehydrating and cyclizing it using an acid or base. Polybenzoxazole precursors can be obtained by, for example, reacting dicarboxylic acid and its derivatives with diamines and their derivatives having phenolic hydroxyl groups and monoamines and their derivatives. Polybenzoxazoles can be obtained by, for example, heating the polybenzoxazole precursor or by dehydrating and cyclizing it using an acid or base.

[0042] (A) After synthesis by the method described above, component (A) is preferably added to a large amount of water or alcohol, or a mixture thereof, to precipitate, filter, and dry. The drying temperature is preferably 40 to 100°C, and more preferably 50 to 80°C. This operation is preferable because it removes unreacted monomers, dimers, trimers, and other oligomer components, thereby improving the heat resistance and chemical resistance of the cured product.

[0043] The negative-type photosensitive resin composition contains (B) a cationic polymerizable compound (hereinafter sometimes referred to as component (B)). Component (B) includes, but is not limited to, epoxy compounds, cyclic ether compounds such as oxetane compounds, ethylenically unsaturated compounds such as vinyl ethers and styrene, bicyclo-orthoesters, spiro-orthocarbonates, and spiro-orthoesters. Any epoxy compound can be used, including aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0044] Examples of aromatic epoxy compounds include, but are not limited to, glycidyl ethers of monovalent or polyphenols having at least one aromatic ring, such as phenol, bisphenol A, and phenol novolac.

[0045] Examples of alicyclic epoxy compounds include, but are not limited to, compounds obtained by epoxidizing a compound having at least one unsaturated alicyclic hydrocarbon with an oxidizing agent, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. Examples of aliphatic epoxy compounds include, but are not limited to, polyglycidyl ethers of aliphatic polyhydric alcohols such as 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether, polyglycidyl esters of aliphatic polybasic acids such as diglycidyl tetrahydrophthalate, and epoxidized products of long-chain unsaturated compounds such as epoxidized soybean oil and epoxidized polybutadiene.

[0046] Examples of oxetane compounds include, but are not limited to, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0047] Examples of ethylenically unsaturated compounds that can be used include cationic polymerizable monomers, and include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrenes, and cationic polymerizable nitrogen-containing monomers.

[0048] Examples of aliphatic monovinyl ethers include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0049] Examples of aromatic monovinyl ethers include, but are not limited to, 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0050] Examples of polyfunctional vinyl ethers include, but are not limited to, but buttanediol-1,4-divinyl ether and triethylene glycol divinyl ether. Examples of styrenes include, but are not limited to, styrene, α-methylstyrene, p-methoxystyrene, and p-(tert-butoxy)styrene. Examples of cationic polymerizable nitrogen-containing monomers include, but are not limited to, N-vinylcarbazole and N-vinylpyrrolidone.

[0051] Examples of bicyclo-orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0052] Examples of spiro-oth carbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0053] Examples of spiroolthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane. Among these cationic polymerizable compounds, epoxy compounds, oxetane compounds, and vinyl ethers are preferred, more preferably epoxy compounds and oxetane compounds, and particularly preferably epoxy compounds.

[0054] Component (B) preferably contains a polyfunctional epoxy compound (hereinafter also referred to as component (B-1)) with an epoxy equivalent of 80 g / eq. or more and less than 160 g / eq. The inclusion of component (B-1) is preferable because it improves the heat resistance and chemical resistance of the cured product.

[0055] The octanol / water partition coefficient (logP value) of component (B-1) is preferably between -2 and less than 5. Here, the logP value is an indicator of the lipophilicity or hydrophilicity of a substance, and is defined as the logarithm of the ratio of the concentration of the substance dissolved in the octanol phase to the concentration of the substance dissolved in the aqueous phase in a two-phase octanol / water system. A larger logP value indicates greater lipophilicity, and a smaller logP value indicates greater hydrophilicity. The logP value can be measured by the flask immersion method described in JIS-Z-7260, but it can also be calculated. In this specification, the logP value calculated using ChemDraw from CambridgeSoft is used. The logP value of component (B-1) being within the above range is preferable because it provides excellent pattern processing performance when developed with an alkaline aqueous solution.

[0056] Examples of components with a logP value of -2 or greater and less than 5 (B-1) include TEPIC-VL (product name, manufactured by Nissan Chemical Corporation, logP value -0.01), Showfree PETG (product name, both manufactured by Showa Denko K.K., logP value -1.93), Showfree BATG (product name, manufactured by Showa Denko K.K., logP value 3.44), Denacol EX-810 (product name, manufactured by Nagase ChemteX Co., Ltd.), Denacol EX-211 (product name, manufactured by Nagase ChemteX Co., Ltd., logP value 0.31), Denacol EX-252, Denacol EX-201 (product name, manufactured by Nagase ChemteX Co., Ltd., logP value 0.94), EX-321L (product name, manufactured by Nagase ChemteX Co., Ltd., logP value -0.81), etc., but are not limited to these.

[0057] The content of component (B-1) is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 to 200 parts by mass, and particularly preferably 50 parts by mass or more and 150 parts by mass, per 100 parts by mass of component (A). Setting the content of component (B-1) within the above range is preferable because it exhibits sufficient cationic curability and improves pattern processing in alkaline aqueous solutions.

[0058] The aforementioned component (B) contains component (B-1) and a polyfunctional epoxy compound (hereinafter also referred to as component (B-2)) having an epoxy equivalent of 160 g / eq. to 500 g / eq., preferably containing 40 to 99% by mass of component (B-1) and 1 to 60% by mass of component (B-2), and more preferably containing 50 to 80% by mass of component (B-1) and 20 to 50% by mass of component (B-2). The inclusion of component (B-2) is preferable because it improves the mechanical properties of the cured product. The inclusion of components (B-1) and (B-2) within the above ranges is preferable because it provides excellent heat resistance, chemical resistance, and mechanical properties of the cured product.

[0059] (B-2) Examples of components include, but are not limited to, TECHMORE VG-3101L (product name, manufactured by Air Water Inc.), YX-4000H (product name, manufactured by Mitsubishi Chemical Corporation), YL-983U (product name, manufactured by Mitsubishi Chemical Corporation), and EPICLON EXA-4850 (product name, manufactured by DIC Corporation).

[0060] Furthermore, the epoxy equivalent of component (B) as a whole is preferably 80 g / eq. to 200 g / eq., more preferably 90 g / eq. to 190 g / eq., and more preferably 100 g / eq. to 180 g / eq.. Setting the epoxy equivalent of the cationic polymerizable compound (B) as a whole within the above range is preferable in that the cured product has excellent heat resistance, chemical resistance, and tensile elongation. The epoxy equivalent can be measured by the method standardized in JIS K7236:2001.

[0061] The content of component (B) is not particularly limited, but it is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less, and particularly preferably 100 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of component (A). Setting the content of component (B) within the above range is preferable because it exhibits sufficient cationic curability and improves pattern processing in alkaline aqueous solutions.

[0062] The negative-type photosensitive resin composition contains (C) a cationic polymerization initiator (hereinafter sometimes referred to as component (C)). Component (C) generates acid upon exposure to light or heat, thereby promoting cationic polymerization. From the viewpoint of cationic polymerizability and copper corrosivity, component (C) preferably contains a sulfonium salt.

[0063] Examples of cations that form the sulfonium salt include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxylthio) Santonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chloro) (4-fluorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-Dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthene-2-yl)thiophenyl-9-oxo-9H-thioxanthene-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoyl Triarylsulfoniums such as phenylthio)phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthurenium, 5-phenylthiaanthurenium, 5-tolylthiaanthurenium, 5-(4-ethoxyphenyl)thiaanthurenium, 5-(2,4,6-trimethylphenyl)thiaanthurenium; diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium Diarylsulfoniums such as ruphonium; monoarylsulfoniums such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacylsulfonium, etc., but not limited to these.

[0064] The counter anion forming the sulfonium salt preferably contains at least one selected from the group consisting of borate ions, phosphate ions, and gallate ions, from the viewpoint of cationic polymerizability and copper corrosiveness, and more preferably contains a gallate ion, from the viewpoint of reducing yellowing of the cured film of the photosensitive resin composition. Here, the borate ion is a complex ion having boron as the central atom, the phosphate ion is a complex ion having phosphorus as the central atom, and the gallate ion is a complex ion having gallium as the central atom.

[0065] Examples of borate ions include, but are not limited to, pentafluorophenylborate, trifluorophenylborate, tetrafluorophenylborate, trifluoromethylphenylborate, bis(trifluoromethyl)phenylborate, pentafluoroethylphenylborate, bis(pentafluoroethyl)phenylborate, fluoro-bis(trifluoromethyl)phenylborate, fluoro-pentafluoroethylphenylborate, and fluoro-bis(pentafluoroethyl)phenylborate.

[0066] Examples of phosphate ions include, but are not limited to, hexafluorophosphate and tris(pentafluoroethyl)trifluorophosphate.

[0067] Examples of gallate ions include, but are not limited to, tetrakis(pentafluorophenyl)gallate and tetrakis(3,5-bis(trifluoromethyl)phenyl)gallate.

[0068] The content of component (C) is preferably 0.3 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 8 parts by mass, and particularly preferably 0.7 parts by mass to 5 parts by mass, based on 100 parts by mass of component (B). Setting the content of component (C) within the above range is preferable because it allows component (B) to undergo sufficient cationic polymerization, improving pattern processability and enhancing the storage stability of the negative-type photosensitive resin composition.

[0069] The negative-type photosensitive resin composition may contain solvent (D). The content of solvent (D) is not particularly limited, but is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 5,000 parts by mass or less, and particularly preferably 100 parts by mass or more and 2,000 parts by mass or less, per 100 parts by mass of component (A). Setting the content of component (D) within the above range is preferable because it provides excellent coatability and film flatness, and allows for the formation of a coating film with a thickness of 1 μm or more.

[0070] (D) Examples of solvents include γ-butyrolactone, γ-valerolactone, δ-valerolactone, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate Examples of suitable materials include, but are not limited to, ethyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropylene urea, 1,3-dimethylisobutylamide, methoxy-N,N-dimethylpropionamide, butoxy-N,N-dimethylpropionamide, etc.

[0071] The negative-type photosensitive resin composition may contain (E) a sensitizer in order to absorb ultraviolet light and provide the absorbed light energy to the photoacid generator.

[0072] Component (E) may include, but is not limited to, a 9,10-dialkoxy-anthracene derivative. The alkoxy group may include, but is not limited to, a 1-4 carbon alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group. The 9,10-dialkoxy-anthracene derivative may further have substituents. Substituents may include, but is not limited to, halogen atoms such as fluorine, chlorine, bromine, or iodine atoms, C1-4 alkyl groups such as methyl, ethyl, or propyl groups, or alkyl sulfonate ester groups or alkyl carboxylate ester groups. The alkyl group in the alkyl sulfonate ester group or alkyl carboxylate ester may include, but is not limited to, C1-4 alkyl groups such as methyl, ethyl, or propyl.

[0073] The negative-type photosensitive resin composition may contain a (F) silane compound. The inclusion of component (F) improves the adhesion between the cured product and the substrate.

[0074] Examples of component (F) include, but are not limited to, N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane.

[0075] The negative-type photosensitive resin composition may further contain antioxidants and surfactants.

[0076] The negative-type photosensitive resin composition contains fluoride ions (F - ), chloride ions (Cl - ), bromide ions (Br - ), iodide ion (I - The content of ) is preferably less than 100 ppm by mass, more preferably 50 ppm by mass or less, and particularly preferably 30 ppm by mass or less. Here, content refers to F - Cl - , Br - , I - This represents the sum of the individual contents. - Cl - , Br - , I - The content of each can be analyzed by ion chromatography. - Cl - , Br - , I - The content being within the aforementioned range is preferable because it provides excellent resistance to ion migration under high temperature and high humidity conditions.

[0077] The negative-type photosensitive resin composition is not limited to its form before curing, and examples include a solution (varnish) or a film. When the negative-type photosensitive resin composition is in the form of a film, it is preferable to have a negative-type photosensitive resin composition film formed from the negative-type photosensitive resin composition on a support, and more preferably a negative-type photosensitive resin composition film using a sheet-like support. Examples of applications other than a negative-type photosensitive resin composition film include forms without a support. A negative-type photosensitive resin composition film can be obtained, for example, by coating a negative-type photosensitive resin composition onto a support and then drying it.

[0078] The negative-type photosensitive resin composition film has a melt viscosity of 0.5 × 10⁻⁶ at 40°C. 6 P a·s or more, 1.0×10 7 P It is preferable that the value is less than or equal to a·s. The melt viscosity of the negative-type photosensitive resin composition film at 40°C is 0.5 × 10⁻⁶. 6P A value of a·s or higher is preferable because it reduces the tackiness of the negative-type photosensitive resin composition film surface at room temperature, making the negative-type photosensitive resin composition film easier to handle. The melt viscosity of the negative-type photosensitive resin composition film at 40°C is 1.0 × 10⁻⁶. 7 P A value of a·s or less is preferable because it reduces cracking of the resin composition film at room temperature, reduces defects in the negative-type photosensitive resin composition film, and improves yield. The melt viscosity of the negative-type photosensitive resin composition film at 40°C can be measured by the following method. First, two negative-type photosensitive resin composition films are placed facing each other and heat-pressed together at 60°C to obtain a laminated negative-type photosensitive resin composition film. The above operation is repeated until the thickness of the negative-type photosensitive resin composition film reaches 600 to 700 μm. Next, the laminated negative-type photosensitive resin composition film is heated using a rheometer at a frequency of 0.2 Hz, a strain of 1.0%, and a heating rate of 2°C / min from 30°C to 80°C. The value of the complex melt viscosity at 40°C is read from this measurement.

[0079] The cured product of the present invention is a cured product obtained by curing the negative-type photosensitive resin composition or the negative-type photosensitive resin composition film.

[0080] Any form of cured product is acceptable, as long as the negative-type photosensitive resin composition or the negative-type photosensitive resin composition film is cured with light or heat. Known methods for curing with light or heat include, for example, exposure to 365 nm i-line, 405 nm h-line, and 432 nm g-line of a high-pressure mercury lamp at a rate of 50 mJ to 3000 mJ, and heating treatment at 150°C to 500°C for 5 minutes to 5 hours.

[0081] The present invention describes a method for producing a cured product. The method for producing a cured product includes the steps of: applying the negative-type photosensitive resin composition onto a substrate and drying it to form a negative-type photosensitive resin composition film on the substrate; exposing the negative-type photosensitive resin composition film to light; removing the unexposed portion of the negative-type photosensitive resin composition film with an alkaline aqueous solution to develop it; and heat-treating the developed negative-type photosensitive resin composition film to produce a cured product.

[0082] The step of applying the negative-type photosensitive resin composition onto a substrate and drying it to form a negative-type photosensitive resin composition film on the substrate includes, but is not limited to, a step of applying the negative-type photosensitive resin composition onto a substrate using a spin coater, spray coater, screen coater, blade coater, die coater, calender coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, slit die coater, etc., and drying it at a temperature of 50°C to 150°C for 1 minute to several hours to form a negative-type photosensitive resin composition film.

[0083] The process of exposing the negative-type photosensitive resin composition film includes, but is not limited to, a process of exposing it through a mask having a desired pattern using a high-pressure mercury lamp with i-line at 365 nm, h-line at 405 nm, and g-line at 432 nm at a pressure of 50 mJ or more and 3000 mJ or less. The negative-type photosensitive resin composition film exposed by the above process may be baked after exposure. The post-exposure bake is preferably at 50°C or higher from the viewpoint of curability and adhesion to the substrate, and preferably at 150°C or lower from the viewpoint of resolution.

[0084] The process of developing the negative-type photosensitive resin composition film by removing the unexposed areas with an alkaline aqueous solution includes, but is not limited to, spraying the alkaline aqueous solution onto the film surface of the negative-type photosensitive resin composition film, pouring the developer solution onto the film surface, immersing the entire negative-type photosensitive resin composition film in the alkaline aqueous solution, or immersing it and applying ultrasonic waves. The development conditions, such as development time, development step, and developer solution temperature, should be such that the exposed areas are removed and a pattern can be formed. After development, rinsing with water is preferable. If necessary, rinsing may also be performed by adding alcohols such as ethanol or isopropyl alcohol, ethyl lactate, or propylene glycol monomethyl ether acetate to the water.

[0085] The process of curing the negative-type photosensitive resin composition film after development by heat treatment includes, but is not limited to, a process of curing by heat treatment in a range of 150°C to 500°C for 5 minutes to 5 hours to allow a thermal crosslinking reaction to proceed. The heat treatment can be performed by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature. An example of the former is, but is not limited to, a method of heat treatment at 130°C and 200°C for 30 minutes each. An example of the latter is, but is not limited to, a method of linearly increasing the temperature from room temperature to 400°C over 2 hours.

[0086] The cured product preferably has a ratio of T2 / T1 ≥ 0.98, where T1 is the film thickness after coating and drying, and T2 is the film thickness after curing at 200°C for 1 hour. This ratio is preferable because it reduces stress on the cured film.

[0087] The hollow structure of the present invention comprises a support material containing the cured material.

[0088] The hollow structure is a structure consisting of a recess or protrusion and a roof portion provided on an electronic component, and is formed by heat-pressing a film of the negative-type photosensitive resin composition onto the recess or protrusion to form the roof portion. The photosensitive resin composition can be used as a support material for the recess or protrusion. The thickness of the support material of the hollow structure is preferably 5 μm to 30 μm. The thickness of the roof portion is preferably 10 μm to 30 μm. A support material thickness of 5 μm or more allows for the formation of a hollow structure, and a thickness of 30 μm or less allows for a hollow structure without roof collapse. Furthermore, a roof portion thickness of 10 μm or more improves the film strength of the roof portion when it is formed into a hollow structure, and a thickness of 30 μm or less allows for a thinner hollow structure, which is preferable as it contributes to the miniaturization of electronic components. The hollow structure is preferably sealed with molded resin to enhance its robustness as an electronic component. In other words, it is preferable that the outer periphery of the hollow structure is sealed with molded resin. Methods for sealing the outer periphery of a hollow structure with molding resin include, but are not limited to, transfer molding and compression molding. In these molding methods, the sealing resin, melted at around 180°C, is poured around the electronic component at a pressure of around 6 MPa. In other words, during this sealing process, a high temperature and a pressure of around 6 MPa are applied to the roof portion of the hollow structure. If the film strength of the cured material used for the roof portion of the hollow structure is low, the roof portion of the hollow structure may flex and the structure may collapse. In this respect, hollow structures are preferable because they have sufficient film strength, which improves the yield of electronic components in the molding resin sealing process.

[0089] The electronic component of the present invention comprises the cured material.

[0090] Electronic components refer to all devices that can function by utilizing the properties of semiconductor elements. Electro-optical devices and semiconductor circuit boards with semiconductor elements connected to a substrate, stacks of multiple semiconductor elements, and electronic devices containing these are all included in the definition of electronic components. The cured material is suitably used, for example, as a passivation film for semiconductors, a surface protective film for semiconductor elements, an interlayer insulating film between semiconductor elements and wiring, an interlayer insulating film between multiple semiconductor elements, an interlayer insulating film between wiring layers in high-density mounting multilayer wiring, and an insulating layer for organic electroluminescent devices, but is not limited to these applications and can be used in a variety of other applications. [Examples]

[0091] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples 1, 2, 3, and 12 are for reference only.

[0092] 1. Evaluation In the following evaluations, if the number of measurements (n) was not specified, the evaluation was performed using n=1.

[0093] (1) Evaluation of transmittance A 40% GBL solution of a polymer compound was applied to a glass substrate using a spin coater (1H-360S, Mikasa Corporation), and then pre-baked at 100°C for 3 minutes using a hot plate (SCW-636, Dainippon Screen Co., Ltd.) to produce a coating with a thickness of 1 μm.

[0094] The transmittance (%) at 365 nm of the obtained polymer compound coating film was measured using a UV-Vis spectrophotometer (Hitachi, Ltd. U2900).

[0095] (2) Evaluation of storage stability After preparing the negative-type photosensitive resin composition, the viscosity at 25°C was measured using an E-type viscometer (TVE-25, manufactured by Toki Sangyo Co., Ltd.) 12 to 24 hours later, and this value was defined as V1.

[0096] The negative-type photosensitive resin composition was then sealed and stored at room temperature (23°C) for two weeks. After that, the viscosity was measured, and the value was defined as V2.

[0097] When the viscosity increase rate (%) was defined as (V2-V1) / V1 × 100, the storage stability was evaluated according to the following criteria. Viscosity increase rate of less than 5%: A, Viscosity increase rate of 5% or more but less than 20%: B, Viscosity increase rate of 20% or more: C.

[0098] (3) Evaluation of cation curability A negative-type photosensitive resin composition was applied onto a silicon wafer using a spin coater (1H-360S, manufactured by Mikasa Corporation), and then pre-baked at 100°C for 3 minutes using a hot plate (SCW-636, manufactured by Dainippon Screen Co., Ltd.) to produce a coating with a thickness of 20 μm.

[0099] The resulting coating film was then subjected to a 300 mJ / cm² treatment using a parallel light mask aligner (Canon Inc. PLA-501F) with a high-pressure mercury lamp as the light source, through a mask having a line and space pattern spaced 10 μm apart. 2 500 mJ / cm² 2 , 1000 mJ / cm 2 or 2000 mJ / cm 2 Exposure was performed using [a specific method]. The exposure amount was calculated by measuring the illuminance of the i-line (365 nm).

[0100] Subsequently, the images were exposed to light at 100°C for 3 minutes, then baked. Using an automatic developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), the images were developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for twice the time required for the unexposed areas to completely dissolve, and then rinsed with pure water for 30 seconds. Images that could not be developed with the TMAH aqueous solution were developed with cyclopentanone (CP) and rinsed with isopropyl alcohol.

[0101] Subsequently, the patterned area was observed using an electron microscope. Cationic curability was evaluated based on the minimum exposure level at which a pattern could be formed without dissolution, out of the exposure levels mentioned above. The minimum exposure dose is 300 mJ / cm². 2 The one: A, The minimum exposure dose is 500 mJ / cm². 2 item: B, Minimum exposure dose is 1000 mJ / cm² 2 item: C, Minimum exposure dose is 2000 mJ / cm² 2 item: D, Exposure dose: 2000 mJ / cm 2 But the substance that leached out was: E.

[0102] (4) Evaluation of pattern processability A coating film with a thickness of 20 μm was prepared in the same manner as in "(3) Evaluation of Cationic Curability" above. The obtained coating film was exposed to light using a parallel light mask aligner (PLA-501F, manufactured by Canon Inc.) with a high-pressure mercury lamp as the light source, through a mask having patterns of 20 μm with line widths spaced 40 μm apart, 10 μm with line widths spaced 20 μm apart, and 5 μm with line widths spaced 15 μm apart, at the minimum exposure dose that allowed the 10 μm pattern with line widths spaced 20 μm apart to be formed without dissolution, as in (3) above.

[0103] Afterward, the images were exposed to light at 100°C for 3 minutes, baked, and then developed using an automatic developer with a 2.38% by mass TMAH aqueous solution for twice the time required for the unexposed areas to completely dissolve. Finally, they were rinsed with pure water for 30 seconds. As shown in Example 9 of Table 3, images that could not be developed with the TMAH aqueous solution were developed with cyclopentanone (CP) and rinsed with isopropyl alcohol.

[0104] Subsequently, the patterned areas were observed using an electron microscope, and the pattern processability was evaluated based on the smallest pattern size among the above patterns that showed no abnormalities such as missing sections or dissolution. A, The smallest pattern size without abnormalities is 5 μm. The smallest pattern size without abnormalities is 10 μm: B. The smallest pattern size without abnormalities is 20 μm: C, Items where 20 μm was not removed: D Furthermore, in (3) above, 2000 mJ / cm 2 The substances that eluted were not evaluated and were classified as E.

[0105] (5) Evaluation of heat resistance A negative-type photosensitive resin composition was applied to a silicon wafer using a spin coater and hot plate to achieve a film thickness of 10 μm after pre-baking at 100°C for 3 minutes. Then, 2000 mJ / cm² of light was applied to the entire surface using a parallel light mask aligner. 2 The sample was exposed to light, and then heated to 200°C using an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at a heating rate of 3.5°C / min with an oxygen concentration of 20 ppm by mass or less, followed by heat treatment at 200°C for 1 hour.

[0106] Subsequently, the silicon wafer was immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the cured film of the negative-type photosensitive resin composition from the wafer. The wafer was then cut out to a size of 3.0 cm × 1.5 cm using a single-edged blade, and measurements were taken from 25°C to 400°C under a nitrogen atmosphere at a heating rate of 10°C / min using a thermomechanical analyzer (Seiko Instruments, TMA / SS6100).

[0107] Heat resistance was evaluated based on the glass transition temperature. Glass transition temperature of 200°C or higher: A, Glass transition temperature below 200°C: B.

[0108] (6) Evaluation of mechanical properties The cured film was prepared and peeled off in the same manner as described in "(5) Evaluation of heat resistance" above, cut into strips measuring 1.5 cm x 9 cm, and then pulled at a tensile speed of 50 mm / min (chuck spacing = 2 cm) using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at room temperature of 23.0°C and humidity of 45.0% RH (tensile elongation (%)) and tensile strength (MPa) were measured.

[0109] Measurements were taken on 10 strips of paper per sample, and the average of the top 5 scores was calculated. The mechanical properties were evaluated for tensile elongation and tensile strength based on the following criteria. • Tensile elongation Tensile elongation of 30% or more: A, Tensile elongation of 10% or more but less than 30%: B, Tensile elongation less than 10%: C • Tensile strength Tensile strength of 100 MPa or more: A, Tensile strength of 90 MPa or more but less than 100 MPa: B, Products with a tensile strength of less than 90 MPa: C.

[0110] (7) Evaluation of copper corrosion A negative-type photosensitive resin composition was applied to a copper-plated substrate using a spin coater and hot plate to achieve a film thickness of 10 μm after pre-baking at 100°C for 3 minutes. Then, 2000 mJ / cm² of light was applied to the entire surface using a parallel light mask aligner. 2 The sample was exposed to light, and then heated in an inert oven at an oxygen concentration of 20 ppm by mass or less and a heating rate of 3.5°C / min to 200°C, followed by heat treatment at 200°C for 1 hour.

[0111] The copper-plated substrates with the resulting cured film were stored for 20 hours under conditions of 121°C, 100% humidity, and 2 atmospheres using an advanced accelerated life test apparatus (saturation type pressure cooker test apparatus), and the discoloration of the copper substrates was visually evaluated.

[0112] The degree of discoloration was used to evaluate the corrosion resistance of the copper material. Items showing no discoloration: A, Those that are slightly discolored brown: B, Items that are clearly discolored brown: C.

[0113] (8) Evaluation of yellowing of the cured film After applying and pre-baking the negative-type photosensitive resin composition onto glass using a spin coater and hot plate to a film thickness of 10 μm after pre-baking at 100°C for 3 minutes, the entire surface was treated with 2000 mJ / cm² of light using a parallel light mask aligner. 2 The sample was exposed to light and then heated in air at 200°C for 1 hour using a hot plate.

[0114] Subsequently, the discoloration of the cured film was visually observed, and this was used as a reference to evaluate the yellowing of the cured film. Cases where no yellowing of the cured film is observed: A, Yellowing was observed in: B.

[0115] (9)F - Cl - , Br - , I - Evaluation of content A negative-type photosensitive resin composition was diluted 10-fold with ultrapure water, sonicated for 10 minutes, and then filtered through a membrane filter with a pore size of 0.45 μm to obtain the test solution.

[0116] Next, F is used in the ion chromatograph (Dionex ICS-3000). - Cl - , Br - , I - Standard solutions for each ion were injected to create a calibration curve. Next, 1 mL of the sample solution was injected, and from the resulting peaks and calibration curve, the F in the sample solution was determined. - Cl - , Br - , I - The mass of each ion was determined, and then the total mass of the ions was calculated.

[0117] Based on the ion content determined as the ion mass relative to the mass of the negative-type photosensitive resin composition, F - Cl - , Br - , I - The content was evaluated. Products with an ion content of less than 30 ppm by mass: A, Products with an ion content of 30 ppm by mass or more and less than 50 ppm by mass: B, Products with an ion content of 50 ppm by mass or more and less than 100 ppm by mass: C, Products with an ion content of 100 ppm by mass or more: D.

[0118] (10) Evaluation of ion migration resistance Except for changing the substrate from a silicon wafer to an ion migration evaluation substrate (WALTS-TEG ME0102JY manufactured by Walts), a cured film was fabricated on the ion migration evaluation substrate in the same manner as described in "(5) Evaluation of heat resistance".

[0119] Subsequently, a test specimen for evaluation was prepared by soldering a wire to the terminals of a comb-shaped copper wiring with a line / space of 15 μm / 10 μm on the substrate.

[0120] The test specimens were placed in a HAST apparatus (PM220, manufactured by Kusumoto Kasei Co., Ltd.), and their ion migration resistance was evaluated using an ion migration evaluation apparatus (SIR13, manufactured by Kusumoto Kasei Co., Ltd.) under conditions of 130°C and 85% RH, with an applied voltage of 17.5V and an application time of 96 hours.

[0121] The resistance value when voltage is applied is 1.0 × 10 6 Ion migration resistance was evaluated based on the continuous application time until the value fell below Ω. For applications with a continuous application time of 60 hours or more but less than 96 hours: A, For applications with a continuous application time of 30 hours or more but less than 60 hours: B, C. Those with a continuous application time of less than 30 hours.

[0122] (11) Evaluation of melt viscosity A negative-type photosensitive resin composition was applied to a 50 μm thick PET film using a commarol coater, dried at 120°C for 8 minutes, and then laminated with a 10 μm thick PP film as a protective film to obtain the resin composition film. The film thickness of the resin composition film was adjusted to 25 μm.

[0123] The protective film was peeled off the obtained resin composition film, and the resin composition films of the resin composition film were placed facing each other and heat-pressed at 60°C to obtain a laminated resin composition film (a laminate of the resin composition films).

[0124] Next, the laminate of the resin composition film, from which the PET film of the laminate of the resin composition film has been peeled off, and the resin composition film, from which the protective film of the resin composition film has been peeled off, were placed opposite each other and heat-pressed together as described above, until the thickness of the laminate of the resin composition film reached 600 to 700 μm.

[0125] Next, the complex melt viscosity of the laminate of the resin composition film was measured using a rheometer (MCR302, manufactured by Anton Paar Co., Ltd.) with a 15 mm diameter disposable paraplate, at a frequency of 0.2 Hz, a strain of 1.0%, and a heating rate of 2 °C / min from 30 °C to 80 °C. The value of the complex melt viscosity at 40 °C was then read.

[0126] (12) Evaluation of stress on the cured film A cured film was fabricated on a silicon wafer in the same manner as described in "(5) Evaluation of heat resistance" above, and the stress of the cured film was evaluated using a stress measuring device (FLX2908 manufactured by KLA Tencor Co., Ltd.).

[0127] The substrate had an elastic modulus of 1.805 and a thickness of 775 μm. Using a 670 nm wavelength laser under conditions of 25°C, the change in the radius of curvature of the silicon wafer before and after the fabrication of the cured film was measured, and the stress on the cured film was calculated using Stoney's formula.

[0128] 2. Synthesis of polyimides (A) Synthesis of polymer compounds (P1) to (P18) [Synthesis Example 1: Synthesis of Polyimide (P1)] Under a stream of dry nitrogen, 4,4'-oxydiphthalic anhydride (hereinafter referred to as ODPA) (31.02 g, 0.1 mol) was added to 100 g of γ-butyrolactone (hereinafter referred to as GBL) and dissolved by stirring at 60°C. Subsequently, 2-aminobenzoic acid (1.37 g, 0.01 mol: 10 mol% of all amines and their derivatives) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P1).

[0129] [Synthesis Example 2: Synthesis of Polyimide (P2)] Under a stream of dry nitrogen, ODPA (31.02 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, 3-aminophenol (hereinafter referred to as MAP) (1.09 g, 0.01 mol: 10 mol% of all amines and their derivatives) and BAHF (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P2).

[0130] [Synthesis Example 3: Synthesis of Polyimide (P3)] Under a stream of dry nitrogen, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, MAP (1.09 g, 0.01 mol: 10 mol% of all amines and their derivatives) and BAHF (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P3).

[0131] [Synthesis Example 4: Synthesis of Polyimide (P4)] Under a stream of dry nitrogen, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, MAP (1.74 g, 0.016 mol: 15 mol% of all amines and their derivatives) and BAHF (32.96 g, 0.09 mol: 85 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P4).

[0132] [Synthesis Example 5: Synthesis of Polyimide (P5)] Under a stream of dry nitrogen, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, MAP (1.09 g, 0.01 mol: 14 mol% of all amines and their derivatives) and BAHF (21.98 g, 0.06 mol: 86 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P5).

[0133] [Synthesis Example 6: Synthesis of Polyimide (P6)] Under a stream of dry nitrogen, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, MAP (2.73 g, 0.025 mol: 24 mol% of all amines and their derivatives) and BAHF (29.30 g, 0.08 mol: 76 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P6).

[0134] [Synthesis Example 7: Synthesis of Polyimide (P7)] Under a stream of dry nitrogen, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (hereinafter referred to as TDA-100) (30.03 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, MAP (0.55 g, 0.005 mol: 5 mol% of all amines and their derivatives) and BAHF (32.96 g, 0.09 mol: 95 mol% of all amines and their derivatives) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P7).

[0135] [Synthesis Example 8: Synthesis of Polyamide (P8)] Under a stream of dry nitrogen, BAHF (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) and MAP (1.09 g, 0.01 mol: 10 mol% of all amines and their derivatives) were added to 100 g of GBL and dissolved by stirring at room temperature. Subsequently, while maintaining the temperature of the reaction solution at -10 to 0°C, 4,4'-diphenyl ether dicarboxylic acid dichloride (29.52 g, 0.1 mol) was added in small amounts, and after the addition was complete, the temperature was raised to room temperature and stirred for 3 hours. Next, the reaction solution was added to 3 L of water to precipitate, and this precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours to obtain polyamide (P8).

[0136] [Synthesis Example 9: Synthesis of Polybenzoxazole (P9)] Under a stream of dry nitrogen, BAHF (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) and MAP (1.09 g, 0.01 mol: 10 mol% of all amines and their derivatives) were added to 100 g of GBL and dissolved by stirring at room temperature. Subsequently, 1,2-bis(4-formylphenyl)ethane (hereinafter, BFE) (23.6 g, 0.10 mol) was added in small amounts, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for another 1 hour. The temperature was then raised to 200°C and stirred for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polybenzoxazole (P9).

[0137] [Synthesis Example 10: Synthesis of Polyimide Precursor (P10)] Under a stream of dry nitrogen, ODPA (31.02 g, 0.10 mol) was dissolved in 200 g of GBL. BAHF (32.96 g, 0.09 mol: 90 mol% relative to all amines and their derivatives) was added, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 2 hours. Next, MAP (1.09 g, 0.01 mol: 10 mol% relative to all amines and their derivatives) was added, and the mixture was stirred at 50°C for 2 hours. Subsequently, a solution of N,N-dimethylformamide dimethylacetal (21.5 g, 0.18 mol) diluted in 20 g of GBL was added in small amounts, and the mixture was stirred at 50°C for a further 3 hours. The reaction solution was then added to 3 L of cooled water to precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours to obtain polyimide precursor (P10).

[0138] [Synthesis Example 11: Synthesis of Polybenzoxazole Precursor (P11)] Under a stream of dry nitrogen, BAHF (32.96 g, 0.09 mol: 90 mol% of all amines and their derivatives) and MAP (1.09 g, 0.01 mol: 10 mol% of all amines and their derivatives) were added to 100 g of GBL and dissolved by stirring at room temperature. Subsequently, BFE (23.6 g, 0.10 mol) was added in small increments, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for another 1 hour. The reaction solution was allowed to cool to obtain a GBL solution of polybenzoxazole precursor (P11).

[0139] [Synthesis Example 12: Synthesis of Polyimide (P12)] Under a stream of dry nitrogen, ODPA (31.02 g, 0.1 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (32.96 g, 0.09 mol) was added and stirred at 60°C for 1 hour, then the temperature was raised to 200°C and stirred for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P12).

[0140] [Synthesis Example 13: Synthesis of Polyimide (P13)] Under a stream of dry nitrogen, TDA-100 (30.03 g, 0.10 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (32.96 g, 0.09 mol) was added and stirred at 60°C for 1 hour, then the temperature was raised to 200°C and stirred for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P13).

[0141] [Synthesis Example 14: Synthesis of Polyimide (P14)] Under a stream of dry nitrogen, TDA-100 (30.03 g, 0.10 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (32.96 g, 0.09 mol) and MAP (0.218 g, 0.002 mol) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P14).

[0142] [Synthesis Example 15: Synthesis of Polyimide (P15)] Under a stream of dry nitrogen, TDA-100 (30.03 g, 0.10 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (29.29 g, 0.08 mol) and MAP (3.27 g, 0.03 mol) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P15).

[0143] [Synthesis Example 16: Synthesis of Polyimide (P16)] Under a stream of dry nitrogen, TDA-100 (30.03 g, 0.10 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (32.96 g, 0.09 mol) and MAP (2.18 g, 0.02 mol) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P16). [Synthesis Example 17: Synthesis of Polyimide (P17)] Under a stream of dry nitrogen, TDA-100 (30.03 g, 0.10 mol) was added to 100 g of GBL and dissolved by stirring at 60°C. Subsequently, BAHF (18.31 g, 0.05 mol) and MAP (1.09 g, 0.01 mol) were added, and the mixture was stirred at 60°C for 1 hour, followed by raising the temperature to 200°C and stirring for 4 hours. The reaction solution was allowed to cool to obtain a GBL solution of polyimide (P17).

[0144] Table 1 shows a list of the compositions of the above synthesis examples.

[0145] When carboxylic acid residue A is represented by mol, diamine residue B by mol, and monoamine residue C by mol, those that satisfy the relationships 0.6A ≤ B + 0.5C ≤ 0.98A and 0.05(B + C) ≤ C ≤ 0.25(B + C) are marked as applicable, and those that do not satisfy these relationships are marked as not applicable. [Synthesis Example 18: Synthesis of Polyimide Precursor (P18)] Under a stream of dry nitrogen, ODPA (31.02 g, 0.10 mol) was dissolved in 200 g of GBL. BAHF (32.96 g, 0.09 mol: 90 mol% relative to all amines and their derivatives) was added, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 2 hours. Then, a solution of N,N-dimethylformamide dimethylacetal (21.5 g, 0.18 mol) diluted in 20 g of GBL was added in small amounts, and the mixture was stirred at 50°C for 3 hours. Next, the reaction solution was added to 3 L of cooled water to precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 5 hours to obtain polyimide precursor (P18).

[0146] Table 1 shows the composition of residues (indicated by raw material) contained in P1 to P18, and whether or not the requirements of 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] and 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)] are met, when all carboxylic acid residues contained in component (A) are A mol, all diamine residues are B mol, and all monoamine residues are C mol.

[0147] [Table 1]

[0148] P1 to P11 satisfy both 0.6A≦B+0.5C≦0.98A[condition(ii-1)] and 0.05(B+C)≦C≦0.25(B+C)[condition(ii-2)], whereas P12 to P18 do not satisfy either 0.6A≦B+0.5C≦0.98A[condition(ii-1)] or 0.05(B+C)≦C≦0.25(B+C)[condition(ii-2)].

[0149] 3. (C) Synthesis of a sulfonium salt (M-1) containing a gallate ion as a cationic polymerization initiator. [Synthesis Example 19: Synthesis of a sulfonium salt (M-1) containing a gallate ion] [4-(phenylthio)phenyl]sulfonium triflate (4.16 g, 0.008 mol) was dissolved in 200 g of dichloromethane, and 250 g of an aqueous solution containing equimolar lithium tetrakis(pentafluorophenyl)gallate was mixed at room temperature and stirred for 3 hours. After stirring, the dichloromethane layer was washed twice with water by liquid-liquid extraction, and then the mixture was transferred to a rotary evaporator to remove the solvent by distillation to obtain a sulfonium salt (M-1) containing gallate ions.

[0150] [ka]

[0151] 4. Compounds used in the examples and comparative examples.

[0152] (A) Polymer compound P1~P7: Polyimide polymer compounds obtained in [Synthesis Example 1]~[Synthesis Example 7] that satisfy all of the following conditions: [Condition (i)], 0.6A≦B+0.5C≦0.98A [Condition (ii-1)], and 0.05(B+C)≦C≦0.25(B+C) [Condition (ii-2)]. P8: The polymer compound obtained in [Synthesis Example 8] is a polyamide [Condition (i)], satisfying all of the following conditions: 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] and 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)]. P9: The polymer compound obtained in [Synthesis Example 9] is polybenzoxazole [Condition (i)], satisfying all of the following conditions: 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] and 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)]. P10: The polymer compound obtained in [Synthesis Example 10] is a polyimide precursor [Condition (i)], satisfying all of the following conditions: 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] and 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)]. P11: The polymer compound obtained in [Synthesis Example 11] is a polybenzoxazole precursor [Condition (i)], satisfying all of the following conditions: 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] and 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)]. P12~P17: The polyimide polymer obtained in [Synthesis Example 12]~[Synthesis Example 17] [Condition (i)] does not satisfy either 0.6A≦B+0.5C≦0.98A [Condition (ii-1)] or 0.05(B+C)≦C≦0.25(B+C) [Condition (ii-2)]. P18: The polymer compound obtained in [Synthesis Example 18] is a polyimide precursor [Condition (i)], which satisfies 0.6A ≤ B + 0.5C ≤ 0.98A [Condition (ii-1)] but does not satisfy 0.05(B + C) ≤ C ≤ 0.25(B + C) [Condition (ii-2)]. 1007: (Manufactured by Mitsubishi Chemical Corporation), BisA type phenoxy resin [a polymer compound, but does not satisfy condition (i)].

[0153] (B) Cationic polymerizable compounds (B-1) Component TEPIC-VL: (Manufactured by Nissan Chemical Corporation), epoxy equivalent = 128 g / eq., logP value = -0.01 PETG (manufactured by Showa Denko Corporation), epoxy equivalent = 90 g / eq., logP value = -1.93 BATG: (Manufactured by Showa Denko Corporation), epoxy equivalent = 113 g / eq., logP value = 3.44 Tetramethylbiphenyloxiran: 4,4'-bis(2,3-epoxy)-3,3',5,5'tetramethylbiphenyl, epoxy equivalent = 147, logP value = 5.26 (B-2) Component EXA-4850-150: (Manufactured by DIC Corporation), epoxy equivalent = 450 g / eq. YX-4000H: (Manufactured by Mitsubishi Chemical Corporation), epoxy equivalent = 176 g / eq. YL-983U: (Manufactured by Mitsubishi Chemical Corporation), epoxy equivalent = 175 g / eq. EXA-4816: (Manufactured by DIC Corporation), epoxy equivalent = 403 g / eq.

[0154] (C) Cationic polymerization initiator WPI-116: (Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), iodonium salt WPAG-370: (Manufactured by Fujifilm Wako Pure Chemical Corporation), sulfonium salt M-1: [Synthesis Example 19] Sulfonium salt containing gallate ions CPI-310B: (Manufactured by Sunapro Co., Ltd.), a sulfonium salt containing borate ions.

[0155] [ka]

[0156] CPI-410S: (Manufactured by Sunapro Co., Ltd.), a sulfonium salt containing phosphate ions.

[0157] [ka]

[0158] (D) Solvent γ-butyrolactone (GBL).

[0159] (E) Sensitizer UVS-2171 (manufactured by Kawasaki Chemical Industries, Ltd.).

[0160] (F) Silane compound KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0161] [Example 1] A small amount of the polyimide (P1) GBL solution obtained in Synthesis Example 1 was taken and placed in an aluminum cup of known weight. The total weight was measured, and the weight of the aluminum cup was subtracted to obtain value I. Subsequently, the total weight after removing the solvent by heating at 250°C for 1 hour was measured, and the weight of the aluminum cup was subtracted to obtain value II. Using the solid content concentration calculated as II / I, GBL was added to the polyimide (P1) GBL solution to prepare a solution containing 40% by mass of polyimide (P1), thereby obtaining a 40% by mass GBL solution of polyimide (P1).

[0162] The transmittance of polyimide (P1) was evaluated according to the evaluation method (1) described above. Next, under yellow light, 25 g of a 40% GBL solution of polyimide (P1), 12 g of TEPIC-VL as (B) a cationic polymerizable compound, 0.6 g of WPI-116 as a cationic polymerization initiator, 5 g of GBL as a solvent, 0.4 g of UVS-2171 as a sensitizer, and 0.85 g of KBM303 as a silane compound were mixed and pressure filtered using a filter with a retaining particle size of 1 μm to obtain a negative-type photosensitive resin composition. The storage stability, cationic curability, pattern processability, heat resistance, mechanical properties, and copper corrosion resistance of the negative-type photosensitive resin composition were evaluated according to the evaluation methods (2) to (7) described above.

[0163] [Example 2] to [Example 30] A 40% by mass GBL solution of polymer compound (A) was prepared by adding GBL to a solution of polymer compound (A) in the same manner as in Example 1. The transmittance of polymer compound (A) was evaluated according to the evaluation method (1) described above.

[0164] A negative-type photosensitive resin composition was prepared in the same manner as in Example 1, using components (A) to (D) and other components as shown in Table 2. The storage stability, cationic curability, pattern processability, heat resistance, and mechanical properties of the negative-type photosensitive resin composition were evaluated according to the evaluation methods described in (2) to (7) above.

[0165] [Comparative Example 1]~[Comparative Example 8] Similar to Example 1, GBL was added to the polymer compound (A) or a solution thereof to prepare a solution in which the polymer compound (A) was present at 40% by mass. The transmittance of the polymer compound (A) was evaluated according to the evaluation method (1) described above. The polymer compounds (A) used are as shown in Table 2.

[0166] A negative-type photosensitive resin composition was prepared in the same manner as in Example 1, using components (A) to (D) and other components as shown in Table 2. The storage stability, cationic curability, pattern processability, heat resistance, mechanical properties, and copper corrosion resistance of the negative-type photosensitive resin composition were evaluated according to the evaluation methods described in (2) to (7) above.

[0167] [Table 2-1]

[0168] [Table 2-2]

[0169] [Table 2-3]

[0170] [Table 2-4]

[0171] Table 3 shows the evaluation results for Examples 1-30 and Comparative Examples 1-8.

[0172] [Table 3-1]

[0173] [Table 3-2]

[0174] [Table 3-3]

[0175] [Table 3-4]

[0176] [Example 31]~[Example 34] The components (A) to (D) and other components are as shown in Table 4, and a negative-type photosensitive resin composition is prepared in the same manner as in Example 1. The yellowing of the cured film of the negative-type photosensitive resin composition and F are evaluated according to the evaluation methods (8) to (12) above. - Cl - , Br - , I - The content, ion migration resistance, melt viscosity at 40°C, and stress on the cured film were evaluated.

[0177] [Comparative Example 9]~[Comparative Example 13] The components (A) to (D) and other components are as shown in Table 4, and a negative-type photosensitive resin composition is prepared in the same manner as in Example 1. The yellowing of the cured film of the negative-type photosensitive resin composition and F are evaluated according to the evaluation methods (8) to (12) above. - Cl - , Br - , I - The content, ion migration resistance, melt viscosity at 40°C, and stress on the cured film were evaluated.

[0178] [Table 4]

[0179] The evaluation results for Examples 31-34 and Comparative Examples 9-13 are shown in Table 5.

[0180] [Table 5]

Claims

1. A negative-type photosensitive resin composition comprising (A) a polymer compound, (B) a cationic polymerizable compound, and (C) a cationic polymerization initiator, Component (A) contains at least one compound selected from the group consisting of polyamides, polyimides, polybenzoxazoles, their precursors, and copolymers thereof. The aforementioned component (C) contains a sulfonium salt, When all carboxylic acid residues contained in component (A) are Amol, all diamine residues are Bmol, and all monoamine residues are Cmol, the following conditions are satisfied: 0.6A ≤ B + 0.5C ≤ 0.98A and 0.05(B + C) ≤ C ≤ 0.25(B + C). The light transmittance of component (A) per 1 μm film thickness at a wavelength of 365 nm is 90% or more. A negative-type photosensitive resin composition.

2. The negative-type photosensitive resin composition according to claim 1, wherein the monoamine residue has a structure represented by formula (3). 【Chemistry 1】 (In formula (3), R ６ represents a monovalent organic group with 1 to 6 carbon atoms. o represents 0 or 1. p represents 0 or 1. * represents a bond site to an amine nitrogen.

3. The negative-type photosensitive resin composition according to claim 1 or 2, wherein the (B) component contains a polyfunctional epoxy compound with an epoxy equivalent of (B-1) of 80 g / eq. or more and less than 160 g / eq., and the octanol / water partition coefficient (logP value) of the (B-1) component is -2 or more and less than 5.

4. A negative-type photosensitive resin composition according to any one of claims 1 to 3, comprising 100 parts by mass or more and 150 parts by mass or less of component (B) per 100 parts by mass of component (A).

5. The aforementioned component (B) contains (B-1) a polyfunctional epoxy compound with an epoxy equivalent of 80 g / eq. or more and less than 160 g / eq., and (B-2) a polyfunctional epoxy compound with an epoxy equivalent of 160 g / eq. or more and 500 g / eq. or less. The negative-type photosensitive resin composition according to any one of claims 1 to 4, wherein the component (B) contains 40 to 99% by mass of component (B-1) and 1 to 60% by mass of component (B-2).

6. The negative-type photosensitive resin composition according to any one of claims 1 to 5, wherein the counteranion forming the sulfonium salt contains at least one selected from the group consisting of borate ions, phosphate ions, and gallate ions.

7. The negative-type photosensitive resin composition according to any one of claims 1 to 5, comprising a gallate ion as the counteranion that forms the sulfonium salt.

8. F － , Cl － , Br － , I － A negative-type photosensitive resin composition according to any one of claims 1 to 7, wherein the content of is less than 100 ppm by mass.

9. A negative-type photosensitive resin composition film having a negative-type photosensitive resin composition film formed on a support from a negative-type photosensitive resin composition according to any one of claims 1 to 8, wherein the melt viscosity of the negative-type photosensitive resin composition film at 40°C is 0.5 × 10 ６ The above is a negative-type photosensitive resin composition film with a density of 1.0 × 10⁷ Pa·s or less.

10. A cured product obtained by curing a negative-type photosensitive resin composition according to any one of claims 1 to 8, or a negative-type photosensitive resin composition film according to claim 10.

11. A cured product obtained by curing a negative photosensitive resin composition film according to claim 9, wherein the film thickness of the negative photosensitive resin composition film is T １ , and the film thickness after curing at 200 ° C for 1 hour is T ２ . When it is ２ / T １ ≧0.98, the cured product.

12. A method for producing a cured product, comprising the steps of: applying a negative-type photosensitive resin composition according to any one of claims 1 to 8 onto a substrate and drying it to form a negative-type photosensitive resin composition film on the substrate; exposing the photosensitive resin composition film to light; developing the photosensitive resin composition film by removing the unexposed portion with an alkaline aqueous solution; and heat-treating the developed photosensitive resin film to produce a cured product.

13. A hollow structure comprising a support material containing the cured product described in claim 10.

14. An electronic component comprising the cured product described in claim 10.

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