Resin composition, resin composition film, cured film, and semiconductor device

Abstract

Provided are: a resin composition having excellent sensitivity during pattern processing and having excellent adhesion to inorganic materials; a resin composition film; and a semiconductor device employing the same. The resin composition contains a polymer compound as component (A), a cationic polymerizable compound as component (B), a cationic polymerization initiator as component (C), and a silane coupling agent as component (D), the resin composition being characterized in that component (D) has a carboxyl group and / or an acid anhydride group.

Description

Resin composition, resin composition film, cured film, and semiconductor device

[0001] The present invention relates to a resin composition, a resin composition film, a cured film, and a semiconductor device. More specifically, the present invention relates to a resin composition suitable for use in surface protection films for semiconductor elements and inductor devices, interlayer insulating films, and MEMS (microelectromechanical systems) structures.

[0002] Conventionally, polyimide-based materials and polybenzoxazole-based materials, which have excellent heat resistance, electrical insulation properties, and mechanical properties, have been widely used for surface protection films and interlayer insulating films of semiconductor elements. With the recent demand for higher density and performance of semiconductor elements, photosensitive materials are required for surface protection films and interlayer insulating films from the viewpoint of production efficiency.

[0003] Meanwhile, photosensitive materials are being required to be processed to high aspect ratios for various packaging structures of recent semiconductor elements and MEMS. To meet such demands, chemically amplified photocationic polymerization photosensitive materials have been disclosed (e.g., Patent Document 1). Furthermore, photocationic polymerization materials have been disclosed that incorporate epoxy resins with specific structures into chemically amplified photocationic polymerization systems, thereby improving mechanical and thermal properties (e.g., Patent Document 2). Furthermore, photocationic polymerization materials that incorporate polymeric compounds such as polyimides and epoxy compounds with specific structures have been disclosed (e.g., Patent Document 3), which exhibit excellent heat resistance and tensile elongation.

[0004] International Publication No. 2008 / 007764 Japanese Patent Application Laid-Open No. 2019-38964 Japanese Patent Application Laid-Open No. 2021-55055

[0005] However, with the above-mentioned cationic photopolymerizable materials, it has been difficult to achieve both sufficient adhesion to inorganic substrates and sensitivity during pattern processing. It is generally known that the inclusion of a silane coupling agent having a functional group suitable for a resin composition improves the adhesion of the resin composition to inorganic substrates. Silane coupling agents having an amino group are known to be particularly effective for resin compositions containing epoxy compounds. However, when a silane coupling agent having an amino group is included in a cationic photopolymerizable material, the cationic species generated from the cationic polymerization initiator are trapped by the amino group, resulting in a significant decrease in sensitivity during pattern processing. Therefore, it is difficult to use a silane coupling agent having an amino group in a cationic photopolymerizable material, and the methods described in Patent Documents 2 and 3 have not been able to obtain a cationic photopolymerizable material that achieves both sufficient adhesion and sensitivity during pattern processing.

[0006] In view of this situation, the authors have conducted extensive research and have found that a photocationic polymerization material using a silane coupling agent having a carboxyl group and / or an acid anhydride group exhibits sufficient adhesion to inorganic substrates and sensitivity during pattern processing.

[0007] The present invention for solving the above problems is as follows.

[0008] A resin composition comprising a polymer compound as component (A), a cationically polymerizable compound as component (B), a cationic polymerization initiator as component (C), and a silane coupling agent as component (D), wherein component (D) has a carboxyl group and / or an acid anhydride group.

[0009] The resin composition of the present invention provides a resin composition, a resin composition film, a cured film, and a semiconductor device that exhibit sufficient adhesion to inorganic substrates and sensitivity during pattern processing.

[0010] The present invention relates to a resin composition containing a polymer compound as component (A), a cationically polymerizable compound as component (B), a cationic polymerization initiator as component (C), and a silane coupling agent as component (D), wherein component (D) has a carboxyl group and / or an acid anhydride group.

[0011] Component (A) The resin composition of the present invention contains a polymer compound as component (A), which provides excellent film-forming properties when formed into a film. As long as component (A) is a polymer compound, its weight-average molecular weight is not particularly limited, but it is preferable that the weight-average molecular weight be 1,000 or more and 200,000 or less. Component (A) may be used alone or in combination of two or more. The weight-average molecular weight of component (A) in the present invention is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0012] In the resin composition of the present invention, the component (A) is preferably at least one compound selected from the group consisting of polyamide, polyimide, and polyamideimide. When the component (A) contains at least one compound selected from the group consisting of polyamide, polyimide, and polyamideimide, the component (A) can also contain a polymer compound other than polyamide, polyimide, and polyamideimide. The polyimide precursor and polybenzoxazole precursor correspond to the above-mentioned polyamide, respectively.

[0013] It is preferable that the molecular chain terminal of component (A) be a carboxylic acid residue. By having a carboxylic acid residue at the molecular chain terminal of component (A), the molecular chain terminal can be made to have a molecular structure that does not have an amine terminal structure, which can serve as a functional group that inhibits cationic polymerization, and as a result, sufficient cationic polymerizability can be exhibited. Here, "the molecular chain terminal of component (A) is a carboxylic acid residue" means that the molecular chain terminal of component (A) is an organic group derived from a carboxylic acid that can constitute a polyamide, polyimide, or polyamideimide. Therefore, "the molecular chain terminal of component (A) is a carboxylic acid residue" specifically means that the molecular chain terminal of component (A) is an organic group derived from a monocarboxylic acid, dicarboxylic acid, monoacid chloride compound, diacid chloride compound, tetracarboxylic acid, acid anhydride, acid dianhydride, or the like.

[0014] Suitable carboxylic acids used to convert the molecular chain terminals of component (A) to carboxylic acid residues include, but are not limited to, aromatic dicarboxylic acids, aromatic acid dianhydrides, alicyclic dicarboxylic acids, alicyclic acid dianhydrides, aliphatic dicarboxylic acids, aliphatic acid dianhydrides, etc. These may be used alone or in combination of two or more.

[0015] In the present invention, the component (A) is preferably a compound having at least one structure selected from the structures represented by general formula (1) and general formula (2).

[0016]

[0017] (In the general formulas (1) and (2), X １ and X ２ are independently, X １ represents a divalent to decavalent organic group, and X ２ represents a tetravalent to decavalent organic group; Y １ and Y ２ each independently represents a divalent to tetravalent organic group, and R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. q is an integer of 0 to 2, and r, s, t, and u are each independently an integer of 0 to 4.) Y in general formulas (1) and (2) １ and Y ２represents a divalent to tetravalent organic group, and represents an organic group derived from a diamine.

[0018] Y in the general formulas (1) and (2) of the component (A) １ and Y ２ Preferably, the component (A) contains a diamine residue having a phenolic hydroxyl group. By including a diamine residue having a phenolic hydroxyl group in the component (A), the resin can be made to have appropriate solubility in an alkaline developer, thereby achieving high contrast between exposed and unexposed areas and enabling the formation of a desired pattern.

[0019] Specific examples of diamines having a phenolic hydroxyl group include, but are not limited to, aromatic diamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine; compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like; and diamines having the structures shown below. The other diamine to be copolymerized may be used as it is, or in the form of a corresponding diisocyanate compound or trimethylsilylated diamine. Two or more of these diamine components may also be used in combination.

[0020]

[0021]

[0022] Y in general formulas (1) and (2) １ and Y ２may contain a diamine residue having an aromatic group other than those mentioned above. By copolymerizing these, heat resistance can be improved. Specific examples of the diamine residue having an aromatic group 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-aminophenoxy)biphenyl}, bis(4-aminophenoxy)biphenyl ... Examples of aromatic diamines include, but are not limited to, aromatic diamines such as {4-(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 in these aromatic rings or hydrocarbons have been substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. The other diamine to be copolymerized can be used as is or as the corresponding diisocyanate compound or trimethylsilylated diamine. Two or more of these diamine components may also be used in combination.

[0023] In the present invention, in the general formula (1) and the general formula (2), X １ and X ２ are independently, X １ and X ２ is preferably a carboxylic acid residue, and X １ is preferably a divalent to decavalent organic group, and X ２is preferably a tetravalent to decavalent organic group.

[0024] The carboxylic acid residue preferably has a structure derived from an alicyclic tetracarboxylic dianhydride. That is, the (A) polymer compound is at least one compound selected from the group consisting of polyamide, polyimide, and polyamideimide, and preferably further has a structure derived from an alicyclic tetracarboxylic dianhydride. When the carboxylic acid residue has a structure derived from an alicyclic tetracarboxylic dianhydride, the resin composition has a high light transmittance at the exposure wavelength, making it easy to process a thick film of 20 μm or more. Furthermore, although the reason is unclear, the (A) polymer compound has a structure derived from an alicyclic tetracarboxylic dianhydride, which is preferable in that it has a higher cationic polymerization reactivity than aromatic acid dianhydrides and improves the chemical resistance of the cured film.

[0025] Furthermore, among the alicyclic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides having a polycyclic structure are preferred because they improve the chemical resistance and ion migration resistance of the cured product.

[0026] Specific examples of the organic group derived from an alicyclic tetracarboxylic dianhydride having a polycyclic structure include 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, furan-3-yl)-7-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride, norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, and norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride.

[0027] The molar ratio of the structures represented by general formulas (1) and (2) in the present invention can be confirmed by a method of calculation from the molar ratio of the monomers used in polymerization, or by a method of detecting peaks of the polyamide structure, imide precursor structure, and imide structure in the obtained resin, resin composition, and cured film using a nuclear magnetic resonance (NMR) spectrometer.

[0028] Component (A) having a carboxylic acid residue at the molecular chain terminal can be obtained by increasing the content of acid anhydride relative to the diamine used during polymerization, for example, in the case of a polyimide having a carboxylic acid residue at the molecular chain terminal. However, as an alternative method for obtaining component (A) having a carboxylic acid residue at the molecular chain terminal, it can also be obtained by using a specific compound from among the compounds generally used as an end-capping agent, specifically, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.

[0029] By capping the molecular chain ends of component (A) with a terminal capping agent of a carboxylic acid or acid anhydride having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of component (A) in an alkaline aqueous solution and the mechanical properties of the resulting cured film can be easily adjusted within preferred ranges. Furthermore, multiple terminal capping agents may be reacted to introduce multiple different terminal groups.

[0030] Examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds suitable as end-capping agents include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, and 3-carboxyphenol. Preferred are monocarboxylic acids such as cyclohexanedicarboxylic acid and 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which the carboxyl group of these is converted to an acid chloride, monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is converted to an acid chloride, and activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole, imidazole, or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.

[0031] Polymers incorporating these end-capping agents become component (A) in which the molecular chain terminals are derived from carboxylic acid residues. The end-capping agents that can be used to obtain component (A) in which the molecular chain terminals are derived from carboxylic acid residues can be easily detected by the following method. For example, component (A) into which the end-capping agent has been incorporated is dissolved in an acidic solution and decomposed into the structural units, amine components and acid anhydride components, and the end-capping agents used in the present invention can be easily detected by gas chromatography (GC) or NMR. Alternatively, the end-capping agents can also be easily detected by directly measuring the resin component into which the end-capping agent has been incorporated using pyrolysis gas chromatography (PGC), infrared spectroscopy, and C-NMR spectroscopy.

[0032] In the present invention, component (A) is synthesized, for example, by the following method, but is not limited thereto. The polyimide structure is synthesized by a known method by replacing a portion of the diamine with a primary monoamine, which is an end-capping agent, or by replacing the tetracarboxylic dianhydride with a dicarboxylic anhydride, which is an end-capping agent. For example, a polyimide precursor is obtained by reacting a tetracarboxylic dianhydride with a diamine compound and a monoamine at low temperature, by reacting a tetracarboxylic dianhydride with a dicarboxylic anhydride and a diamine compound at low temperature, or by obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting the diamine with a monoamine in the presence of a condensing agent. Then, a polyimide can be synthesized by a known imidization reaction method.

[0033] In the present invention, after component (A) has been polymerized by the above method, it is preferably poured into a large amount of water or a mixture of methanol and water, precipitated, filtered, dried, and isolated. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This procedure removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties after thermal curing.

[0034] The imidization rate of the polyimide preferably used as the component (A) can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured, and the absorption peak of the imide structure attributable to the polyimide (1780 cm －１ Near 1377 cm －１ Next, the polymer was heat-treated at 350°C for 1 hour, and the imidization rate was set to 100%. The infrared absorption spectrum was measured to confirm the presence of the peak at 1377cm of the resin before and after the heat treatment. －１ The imidization rate is calculated by comparing the peak intensities around the peaks. The imidization rate is preferably 50% or more, and more preferably 80% or more, because this suppresses changes in the ring closure rate during thermal curing and provides the effect of reducing stress.

[0035] Component (B) The resin composition of the present invention contains a cationically polymerizable compound as component (B). Component (B) is preferably an epoxy compound or an oxetane compound. Preferred examples of the component (B) include cyclic ether compounds such as epoxy compounds or oxetane compounds, ethylenically unsaturated compounds such as vinyl ethers and styrenes, bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.

[0036] As the epoxy compound, known compounds can be used, including aromatic epoxy compounds, alicyclic epoxy compounds and aliphatic epoxy compounds.

[0037] Examples of aromatic epoxy compounds include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0038] Examples of alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0039] Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0040] As the oxetane compound, known compounds can be used, and examples thereof include 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.

[0041] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationically polymerizable nitrogen-containing monomers.

[0042] Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0043] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0044] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0045] Examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0046] Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0047] 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.

[0048] Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0049] Examples of spiro orthoesters 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.

[0050] Of these cationically polymerizable compounds, epoxy compounds, oxetane compounds and vinyl ethers are preferred, epoxy compounds and oxetane compounds are more preferred, and epoxy compounds are particularly preferred.

[0051] The component (B) may be used alone or in combination of two or more types.

[0052] The content of component (B), relative to 100 parts by mass of the total amount of component (A), is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, from the viewpoint of exhibiting sufficient cationic curability and improving pattern processability, while the content is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, from the viewpoint of improving resolution.

[0053] Component (C) The resin composition of the present invention contains a cationic polymerization initiator as component (C). Here, a cationic polymerization initiator is a compound that generates an acid directly or indirectly upon exposure to light or heat, thereby inducing cationic polymerization. Known compounds can be used as such cationic polymerization initiators without any particular limitation. Specific examples of the cationic polymerization initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts. Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate. These components (C) may be used alone or in combination of two or more.

[0054] The resin composition of the present invention is preferably a negative-type photosensitive resin composition. In the present invention, the component (C) is preferably a photocationic polymerization initiator. By selecting a photocationic polymerization initiator as the component (C), a contrast in the progress of cationic polymerization can be created between the irradiated and unirradiated areas of the resin composition, and by dissolving the resin composition in any developer, a negative-type pattern can be formed, which is preferable as a negative-type photosensitive resin composition.

[0055] Component (D) The resin composition of the present invention contains a silane coupling agent as component (D). It is important that component (D) contains a carboxyl group and / or an acid anhydride group. Here, the term "silane coupling agent" refers to a silane compound having two or more functional groups. By containing a carboxyl group and / or an acid anhydride group, component (D) can improve adhesion to inorganic substrates. Furthermore, by trapping compounds that inhibit cationic polymerization, such as amines, which may be present in very small amounts in the resin composition, the carboxyl group or acid anhydride group can improve the reactivity of cationic polymerization, thereby providing a resin composition with excellent sensitivity during pattern processing. Specific examples of silane coupling agents containing a carboxyl group include X-12-1135 (manufactured by Shin-Etsu Chemical Co., Ltd.). Specific examples of silane coupling agents containing an acid anhydride group include KBM-967TR-1 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0056] In the present invention, the component (D) preferably has a structure represented by general formula (3).

[0057]

[0058] In formula (3), n is an integer of 1 or more, and X is an organic group.

[0059] In formula (3), n is an integer of 1 or more, and more preferably an integer of 1 to 6. Furthermore, X is not particularly limited as long as it is an organic group, and more preferably an organic group having 1 to 6 carbon atoms.

[0060] Specific examples of X satisfying formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, and a phenyl group, and are preferably a methyl group or an ethyl group.

[0061] When component (D) has the structure of general formula (3), sensitivity during pattern processing is further improved. Specific examples of silane coupling agents having the structure of general formula (3) include KBM-967TR-1 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0062] The resin composition of the present invention may contain a silane coupling agent having a functional group other than a carboxyl group or an acid anhydride group, provided that it contains a silane coupling agent having a carboxyl group and / or an acid anhydride group as component (D). Specific examples of silane coupling agents having a functional group other than a carboxyl group or an acid anhydride group include 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.

[0063] When the resin composition of the present invention is taken as 100% by mass, the total amount of component (D) is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass. If the total amount of component (D) is less than the preferred range, adhesion decreases, and if it exceeds the preferred range, development residues are likely to occur.

[0064] The resin composition of the present invention may contain a sensitizer to absorb ultraviolet light and transfer the absorbed light energy to the photoacid generator. A preferred example of the sensitizer is an anthracene compound having alkoxy groups at the 9th and 10th positions (9,10-dialkoxy-anthracene derivative). Examples of the alkoxy group include C1 to C4 alkoxy groups such as methoxy, ethoxy, and propoxy. The 9,10-dialkoxy-anthracene derivative may further have a substituent. Examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; C1 to C4 alkyl groups such as methyl, ethyl, and propyl; sulfonate alkyl ester groups; and carboxylate alkyl ester groups. Examples of the alkyl in the sulfonate alkyl ester group and carboxylate alkyl ester group include C1 to C4 alkyl groups such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

[0065] The resin composition of the present invention may contain a thermal crosslinking agent. In this case, the thermal crosslinking agent is not particularly limited, but is preferably a compound having an alkoxymethyl group or a methylol group.

[0066] Examples of compounds having an alkoxymethyl group or a methylol group include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM -MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.)

[0067] The resin composition of the present invention may contain, as necessary, a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate, an alcohol such as ethanol, a ketone such as cyclohexanone or methyl isobutyl ketone, or an ether such as tetrahydrofuran or dioxane, in order to improve wettability with the substrate. Furthermore, the resin composition may contain inorganic particles such as silicon dioxide or titanium dioxide, or polyimide powder, in order to suppress the thermal expansion coefficient or increase or decrease the dielectric constant.

[0068] The shape of the resin composition of the present invention before curing is not limited, and examples thereof include a varnish, a film, etc. Hereinafter, the resin composition of the present invention in the form of a varnish will be referred to as a resin composition varnish, and the resin composition of the present invention in the form of a film will be referred to as a resin composition film of the present invention.

[0069] The resin composition film of the present invention may be in the form of a film formed on a support, or may be in the form of a supportless film. When the resin composition of the present invention is used in the form of a varnish, a solution of components (A) to (D) and any other components added as needed in an organic solvent can be used. The resin composition film of the present invention can be obtained, for example, by applying the resin composition of the present invention to a support and then drying it as necessary.

[0070] Next, a method for producing the resin composition film of the present invention will be described.

[0071] The resin composition film of the present invention can be obtained by applying a solution (varnish) of the resin composition of the present invention to a support and then drying it as necessary. The resin composition varnish can be obtained by adding an organic solvent to the resin composition. The organic solvent used here may be any solvent that can dissolve the resin composition.

[0072] Specific examples of organic solvents include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; and others such as N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone.

[0073] The resin composition varnish may be filtered using filter paper or a filter. Although the filtration method is not particularly limited, a method of filtering by pressure filtration using a filter with a retention particle size of 0.4 μm to 10 μm is preferred.

[0074] The resin composition film of the present invention is preferably formed on a support and used. The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (sometimes referred to as PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the resin composition film may be subjected to a surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

[0075] The resin composition film of the present invention may have a protective film on the film to protect the surface. This can protect the surface of the resin composition film from pollutants such as dust and dirt in the atmosphere. Examples of the protective film include polyolefin films and polyester films. It is preferable that the protective film has low adhesive strength to the resin composition film.

[0076] Examples of methods for applying the resin composition varnish to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 μm or more and 100 μm or less.

[0077] Drying can be performed using an oven, a hot plate, infrared rays, or the like. The drying temperature and drying time may be within a range that allows the organic solvent to volatilize, and are preferably set appropriately within a range that leaves the resin composition film in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 120°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 70°C, 80°C, and 90°C for 1 minute each.

[0078] Next, examples of a method for patterning the varnish of the resin composition of the present invention or a resin composition film using the same, and a method for thermocompression bonding to other members will be described.

[0079] First, a method for forming a resin composition film on a substrate using the resin composition of the present invention or a resin composition film using the same will be described. When using a resin composition varnish, the varnish is first applied to the substrate. Examples of application methods include spin coating using a spinner, spray coating, roll coating, and screen printing. The coating thickness varies depending on the application technique, the solids concentration, and viscosity of the resin composition, but it is generally preferable to apply the coating so that the film thickness after drying is 0.5 μm to 100 μm. Next, the substrate coated with the resin composition varnish is dried to obtain a resin composition coating. Drying can be performed using an oven, a hot plate, infrared rays, or the like. The drying temperature and drying time should be within a range that allows the organic solvent to volatilize, and are preferably set appropriately so that the resin composition coating is in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 50 to 150°C for 1 minute to several hours.

[0080] On the other hand, when a resin composition film is used, if a protective film is present, the protective film is peeled off, and the resin composition film and substrate are placed opposite each other and bonded together by thermocompression to obtain a resin composition coating. Thermocompression bonding can be performed by a heat press treatment, a heat lamination treatment, a thermal vacuum lamination treatment, or the like. The bonding temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, to prevent the resin composition film from curing during bonding, which would deteriorate the resolution of pattern formation in the exposure and development steps, the bonding temperature is preferably 150°C or lower.

[0081] In either case, the substrates used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and circuit components arranged on these substrates. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven cloth / epoxy copper-clad laminates, heat-resistant thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit components include conductors containing metals such as silver, gold, and copper; resistors containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins or high-dielectric-constant inorganic particles; and insulators containing glass-based materials.

[0082] Next, the resin composition film formed by the above method is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. In the resin composition film, if the support is made of a material transparent to these rays, exposure may be performed without peeling the support from the resin composition film.

[0083] To form a pattern, the exposed area is removed with a developer after exposure. Examples of the developer include an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, these alkaline aqueous solutions may contain, alone or in combination, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone.

[0084] Development can be carried out by spraying the developer onto the coating surface, puddling the developer onto the coating surface, immersing the coating in the developer, or immersing the coating in the developer and applying ultrasonic waves, etc. The development conditions, such as the development time and the temperature of the developer in the development step, may be any conditions that allow the exposed area to be removed and a pattern to be formed.

[0085] After development, it is preferable to carry out a rinsing treatment with water. Here, too, the rinsing treatment may be carried out by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0086] If necessary, a baking treatment may be carried out before development. This may improve the resolution of the developed pattern and increase the tolerance for development conditions. The baking temperature is preferably in the range of 50 to 180°C, more preferably in the range of 60 to 120°C. The baking time is preferably from 5 seconds to several hours.

[0087] After pattern formation, unreacted cationically polymerizable compounds and cationic polymerization initiators remain in the resin composition coating. Therefore, these may thermally decompose and generate gas during thermocompression bonding or curing. To avoid this, it is preferable to irradiate the entire surface of the resin composition coating after pattern formation with the above-mentioned exposure light to generate acid from the cationic polymerization initiator. By doing so, the reaction of the unreacted cationically polymerizable compounds proceeds during thermocompression bonding or curing, and the generation of gas resulting from thermal decomposition can be suppressed.

[0088] After development, a temperature of 150°C to 500°C is applied to promote a thermal crosslinking reaction. Crosslinking can improve heat resistance and chemical resistance. This heat treatment method can be selected by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. An example of the former is a method in which heat treatment is performed at 130°C and 200°C for 30 minutes each. An example of the latter is a method in which the temperature is linearly increased from room temperature to 400°C over 2 hours.

[0089] The resin composition of the present invention and the cured film of the present invention obtained by curing the resin composition film of the present invention can be used in electronic components such as semiconductor devices. In other words, the semiconductor device of the present invention includes the cured film of the present invention. The term "semiconductor device" as used herein refers to any device that can function by utilizing the characteristics of a semiconductor element. Semiconductor devices include electro-optical devices in which semiconductor elements are connected to a substrate, semiconductor circuit boards, stacks of multiple semiconductor elements, and electronic devices that include these. Semiconductor devices also include electronic components such as multilayer wiring boards for connecting semiconductor elements. Specifically, the present invention is suitable for applications such as semiconductor passivation films, surface protection films for semiconductor elements, interlayer insulating films between semiconductor elements and wiring, interlayer insulating films between multiple semiconductor elements, interlayer insulating films between wiring layers in multilayer wiring for high-density packaging, and insulating layers in organic electroluminescent devices. However, the present invention is not limited to these applications and can be used for a variety of other purposes.

[0090] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0091] <Evaluation of Sensitivity During Pattern Processing> When a protective film was present on the resin composition film produced in each Example and Comparative Example, it was peeled off, and the peeled surface was laminated onto a 4-inch silicon wafer using a vacuum diaphragm laminator (MVLP-500 / 600, manufactured by Meiki Seisakusho Co., Ltd.) under conditions of upper and lower heating platen temperature of 80°C, vacuuming time of 20 seconds, vacuum pressing time of 30 seconds, and application pressure of 0.3 MPa, thereby forming a resin composition film on the silicon wafer. Then, when a support film was present, it was peeled off, and then a mask having a pattern with a via size of 20 μmφ was set in an exposure device, and an exposure dose of 100 to 1000 mJ / cm was measured using an ultra-high pressure mercury lamp under conditions of an exposure gap of 100 μm between the mask and the resin composition film. ２ (i-line equivalent, full wavelength exposure). After exposure, post-exposure baking was performed on a hot plate at 80°C for 10 minutes. Thereafter, the unexposed areas were removed by dip development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and the film was rinsed with water. The development time was twice the time required for the unexposed areas to completely dissolve. The pattern obtained in this manner was observed under an optical microscope to check for abnormalities such as clogging. Furthermore, the residual film ratio was calculated from the film thickness of the obtained pattern before and after development. The obtained residual film ratio was rounded to one decimal place. The minimum exposure dose at which the pattern was not clogged and the residual film ratio was 90% or more was determined, and the sensitivity during pattern processing was evaluated on a five-level scale from A++ to C as follows: A++: 300 mJ / cm ２ Less than A+: 300 mJ / cm ２ More than 500mJ / cm ２ Less than A: 500 mJ / cm ２ More than 800mJ / cm ２ Less than B: 800 mJ / cm ２ More than 1000mJ / cm ２ Below C: (1000mJ / cm ２ (The following exposures) Pattern processing is not possible.

[0092] <Evaluation of Adhesion> A resin composition film was formed on a silicon wafer in the same manner as in the evaluation method for pattern processability. If a support film was present, it was peeled off, and then the resin composition film was exposed to light at an exposure dose of 500 mJ / cm using an ultra-high pressure mercury lamp. ２ After the exposure, the film was baked on a hot plate at 80°C for 10 minutes. Then, the film was heated in an inert oven (manufactured by Koyo Thermo Systems Co., Ltd., INL-60) under N ２ The temperature was raised from room temperature to 200°C over 60 minutes under an atmosphere (oxygen concentration 20 ppm or less), and then heat-treated at 200°C for 60 minutes to obtain a cured film of the resin composition film formed on a silicon wafer. The obtained cured film was subjected to an unsaturated pressure cooker test (130°C, humidity 85%) for 96 hours. After the test, a cross-cut test was performed on the sample and the sample was evaluated using the following four-point scale. A+: No peeling was observed in any of the grids. A: Slight peeling was observed near the intersections of the grids. B: Partial peeling was observed along the grid lines. C: Peeling occurred completely.

[0093] The compounds used in the examples and comparative examples were synthesized by the following methods.

[0094] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (a) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (18.3 g, 0.05 mol) was dissolved in 100 mL of acetone and propylene oxide (17.4 g, 0.3 mol), and the solution was cooled to −15°C. A solution of 3-nitrobenzoyl chloride (20.4 g, 0.11 mol) dissolved in 100 mL of acetone was added dropwise to the solution. After the dropwise addition was completed, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuo at 50°C.

[0095] 30 g of the resulting white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by the addition of 2 g of 5% palladium-carbon. Hydrogen was then introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated by confirming that the balloon was no longer deflating. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (a) represented by the following formula. The resulting solid was used directly in the reaction.

[0096]

[0097] Synthesis Example 2 Synthesis of Polyimide (A-2) Under a dry nitrogen stream, BAHF (36.63 g, 0.10 mol) was added to 80 g of γ-butyrolactone (hereinafter referred to as GBL) and dissolved by stirring at 120°C. Next, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (hereinafter referred to as TDA-100) (24.02 g, 0.08 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and a white precipitate was collected. 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 a polyimide having a structure in which molecular chain terminals are derived from amino residues.

[0098] Synthesis Example 2: Synthesis of Polyamide (A-3) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 mol) was added to 100 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and dissolved by stirring at room temperature. Then, 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 portions. After the addition was completed, the temperature was raised to room temperature and stirring was continued for 3 hours. Next, the reaction solution was poured into 3 L of water, and a white precipitate was collected. This precipitate was collected by filtration, washed three times with water, and then dried for 5 hours in a vacuum dryer at 80°C to obtain a polyamide having a structure in which the molecular chain terminals are derived from carboxylic acid residues.

[0099] Synthesis Example 3 Synthesis of Polyimide (A-4) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 mol) was added to 80 g of γ-butyrolactone (hereinafter referred to as GBL), and the mixture was stirred and dissolved at 120°C. Next, TDA-100 (30.03 g, 0.1 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and a white precipitate was collected. 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 a polyimide having a structure in which molecular chain terminals are derived from carboxylic acid residues.

[0100] Synthesis Example 4 Synthesis of Polyamideimide (A-5) Under a dry nitrogen stream, hydroxyl group-containing diamine compound (a) (31.43 g, 0.08 mol) was added to 80 g of GBL and stirred at 120°C. Next, TDA-100 (30.03 g, 0.1 mol) was added together with 20 g of GBL, and the mixture was stirred at 120°C for 1 hour, and then at 200°C for 4 hours to obtain a reaction solution. Next, the reaction solution was poured into 3 L of water, and a white precipitate was collected. 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 a polyamideimide having a structure in which the molecular chain terminals are derived from carboxylic acid residues.

[0101] Example 1 10 g of GPH-103 (trade name, manufactured by Nippon Kayaku Co., Ltd.) as component (A), 12.5 g of TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) as component (B), 1 g of CPI-310FG (trade name, manufactured by San-Apro Co., Ltd.) as component (C), and 1 g of X-12-1135 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as component (D) were dissolved in GBL. The amount of solvent added was adjusted so that the solids concentration was 60 mass%, with additives other than the solvent considered to be the solids content. Thereafter, the mixture was pressure-filtered using a filter with a retention particle size of 1 μm to obtain a resin composition varnish.

[0102] Examples 2 to 7, Comparative Examples 1 to 5 Resin composition varnishes were obtained in the same manner as in Example 1, except that the components (A) to (D) and other components were changed to compounds having the structures shown below and the mixing ratios thereof were changed as shown in Table 1.

[0103]

[0104] The compounds used in each synthesis example, example and comparative example are shown below.

[0105] (A) Polymeric compounds A-1: ​​GPH-103 (alkali-soluble biphenylaralkyl phenol compound, manufactured by Nippon Kayaku Co., Ltd.) A-2: Polyimide having amine residues at the molecular chain terminals A-3: Polyamide having carboxylic acid residues at the molecular chain terminals A-4: Polyimide having carboxylic acid residues at the molecular chain terminals A-5: Polyamideimide having carboxylic acid residues at the molecular chain terminals.

[0106] (B) Cationic polymerizable compounds B-1: TEPIC-VL (epoxy compound, manufactured by Nissan Chemical Industries, Ltd.) B-2: OXT-221 (oxetane compound, manufactured by Toagosei Co., Ltd.).

[0107] (C) Cationic Polymerization Initiator C-1: CPI-310FG (a sulfonium salt-based photoacid generator, manufactured by San-Apro Co., Ltd.).

[0108] (D) Silane Coupling Agents D-1: X-12-1135 (a silane coupling agent having a carboxyl group, manufactured by Nissan Chemical Industries, Ltd.) D-2: KBM-967TR-1 (a silane coupling agent having an acid anhydride group, manufactured by Nissan Chemical Industries, Ltd.) D-3: KBM-303 (a silane coupling agent having an epoxy group, manufactured by Shin-Etsu Chemical Co., Ltd.) D-4: KBM-903 (a silane coupling agent having an amino group, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0109] The above resin composition varnish was applied to a 50 μm thick PET film using a comma roll coater, dried at 120 ° C for 8 minutes, and then laminated with a 10 μm thick polypropylene film as a protective film to obtain a resin composition film. The film thickness of the resin composition film was adjusted to 20 μm. The obtained resin composition film was used to evaluate the sensitivity and adhesion during pattern processing as described above. The results are shown in Table 2.

[0110]

[0111] The results in Table 2 show that the resin compositions of Examples 1 to 7 are superior to those of Comparative Examples 1 to 5 in sensitivity and adhesion during pattern processing.

[0112] That is, according to the present invention, it is possible to provide a resin composition, a resin composition film, a cured film, and a semiconductor device using these, which exhibit sufficient adhesion to inorganic substrates and sensitivity during pattern processing.

Claims

1. A resin composition comprising a polymer compound as component (A), a cationic polymerizable compound as component (B), a cationic polymerization initiator as component (C), and a silane coupling agent as component (D), The resin composition, wherein the component (D) has a carboxyl group and / or an acid anhydride group.

2. The resin composition according to claim 1, wherein the component (A) is at least one compound selected from the group consisting of polyamides, polyimides, and polyamideimides.

3. The resin composition according to claim 1 or 2, wherein the component (A) has a carboxylic acid residue at a molecular chain terminal.

4. The resin composition according to claim 1 or 2, wherein the component (D) has a structure represented by general formula (3). 【Chemistry 1】 In formula (3), n is an integer of 1 or more, and X is an organic group.

5. The resin composition according to claim 1 or 2, wherein the component (B) is an epoxy compound or an oxetane compound.

6. The resin composition according to claim 1 or 2, which is a negative-type photosensitive resin composition.

7. A resin composition film comprising the resin composition according to claim 1.

8. A cured film obtained by curing the resin composition according to claim 1 or the resin composition film according to claim 7.

9. A semiconductor device comprising the cured film according to claim 8.

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