Resin composition, resin composition coating film, resin composition film, cured film, and semiconductor device using these products

Abstract

Provided is a resin composition comprising a component (A) comprising at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamideimide and polybenzoxazole, a component (B) comprising a cationically polymerizable compound, and a component (C) comprising a photo-cationic polymerization initiator, in which the component (B) comprises both of a component (B1) comprising an epoxy compound and a component (B2) comprising an oxetane compound. A resin composition is provided, which has satisfactory mechanical properties and thermal properties and is capable of forming a pattern having a large thickness and a high aspect ratio.

Description

Resin composition, resin composition coating, resin composition film, cured film, and semiconductor device using the same

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

[0002] Conventionally, polyimide-based materials and polybenzoxazole-based materials, which have excellent heat resistance, electrical insulation, and mechanical properties, have been widely used for surface protection films and interlayer insulating films of semiconductor elements. However, 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 intended to improve mechanical and thermal properties by incorporating an epoxy resin with a specific structure into a chemically amplified photocationic polymerization system have been disclosed (e.g., Patent Document 2). Furthermore, photocationic polymerization materials have been disclosed that, by incorporating a polymer compound such as polyimide into a chemically amplified photocationic polymerization system, exhibit excellent glass transition temperatures, tensile strength, tensile elongation, and the like of the cured film (e.g., Patent Document 3).

[0004] International Publication No. 2008 / 007764 Japanese Patent Application Laid-Open No. 2019-38964 Japanese Patent Application Laid-Open No. 2021-055055

[0005] However, with the above-mentioned cationic photopolymerizable materials, it is difficult to have sufficient mechanical and thermal properties and further to form a pattern with a high aspect ratio in a thick film. With the cationic photopolymerizable materials such as those disclosed in Patent Documents 1 and 2, it is difficult to achieve both sufficient mechanical and thermal properties. With the cationic photopolymerizable materials containing a polymer compound such as polyimide, such as those disclosed in Patent Document 3, it is difficult to form a pattern with a high aspect ratio in a thick film.

[0006] In view of the above circumstances, an object of the present invention is to provide a resin composition that has sufficient mechanical and thermal properties and is capable of forming a thick film pattern with a high aspect ratio.

[0007] In view of this situation, the authors have conducted extensive research and have found that the above-mentioned problems can be solved by using a photocationically polymerizable material containing a polymer compound such as polyimide and both an epoxy compound and an oxetane compound as cationically polymerizable compounds.

[0008] The present invention for solving the above problems is as follows.

[0009] A resin composition comprising, as component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole; as component (B), a cationically polymerizable compound; and as component (C), a photocationic polymerization initiator, wherein the component (B) contains both an epoxy compound as component (B1) and an oxetane compound as component (B2).

[0010] The resin composition of the present invention provides a resin composition, a resin composition coating, a resin composition film, a cured film, and a semiconductor device or an inductor using these, which have sufficient mechanical properties and thermal properties and are capable of forming a thick film pattern with a high aspect ratio.

[0011] 1 is a cross-sectional view showing a pattern distortion obtained by developing a resin composition laminated on a substrate.

[0012] The resin composition of the present invention is a resin composition containing, as component (A), at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, as component (B), a cationically polymerizable compound as component (B), and a photocationic polymerization initiator as component (C), wherein component (B) contains both an epoxy compound as component (B1) and an oxetane compound as component (B2).

[0013] The resin composition of the present invention is preferably a resin composition that exhibits negative photosensitivity in that, upon irradiation with light, component (C) generates an acid, which causes component (B) to undergo a polymerization reaction, resulting in the resin composition becoming insoluble in a developer, i.e., a negative photosensitive resin composition.

[0014] <Component (A)> The resin composition of the present invention contains, as component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole. By containing component (A), the resin composition of the present invention has excellent film-forming properties when forming a film-like resin composition coating, etc. Furthermore, the polymer compound in component (A) may be used alone or in combination of two or more.

[0015] The weight average molecular weight of the component (A) is not particularly limited, but is preferably from 1,000 to 200,000. The weight average molecular weight of the polymer compound in the component (A) in the present invention is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.

[0016] It is also important that the resin composition of the present invention contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole. As long as it contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, it may also contain polymer compounds other than polyamide, polyimide, polyamideimide, and polybenzoxazole. The polyimide precursor and polybenzoxazole precursor correspond to the above-mentioned polyamide, respectively.

[0017] Furthermore, the component (A) preferably has a structure at its molecular chain terminal derived from a carboxylic acid residue. By having a structure at the molecular chain terminal of the component (A) derived from a carboxylic acid residue, the molecular chain terminal can have a molecular structure that does not have an amine terminal structure that can serve as a functional group inhibiting cationic polymerization, and as a result, sufficient cationic polymerizability can be exhibited. Here, the structure derived from a carboxylic acid residue at the molecular chain terminal of the component (A) refers to an organic group derived from a carboxylic acid residue that can constitute a polyamide, polyimide, or polyamideimide.

[0018] Examples of the structure (organic group) derived from a carboxylic acid residue at the molecular chain terminal of component (A) include, but are not limited to, structures derived from 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.

[0019] 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).

[0020]

[0021] In the general formulas (1) and (2), X １ and X ２ each independently represents a divalent to octavalent organic group; Y １ and Y ２each independently represents a divalent to hexavalent organic group, R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, q represents an integer of 0 to 2, and r, s, t, and u each independently represent an integer of 0 to 4.

[0022] X in general formulas (1) and (2) １ and X ２ each independently represents a divalent to decavalent organic group, and represents a carboxylic acid residue. １ and Y ２ represents a divalent to tetravalent organic group, and represents a diamine residue.

[0023] Furthermore, the component (A) preferably has an alicyclic structure. When the component (A) has an alicyclic structure, the transparency of the resin composition is improved and pattern processability is improved. Furthermore, the component (A) more preferably contains a carboxylic acid residue having an alicyclic structure, from the viewpoint of improving the solubility of the resin composition. Furthermore, the component (A) particularly preferably has an organic group derived from an alicyclic tetracarboxylic dianhydride having a polycyclic structure, from the viewpoint of improving the chemical resistance and ion migration resistance when formed into a cured product.

[0024] Specific examples of the 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, norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, and the like.

[0025] The carboxylic acid residue may also contain an organic group derived from an acid dianhydride other than the alicyclic tetracarboxylic dianhydride having a polycyclic structure. Specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride. Dianhydride, 1,1-bis(3,4-dicarboxyphenyl)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 dianhydride, 9,9-bis(3,4-dicarboxyphenyl) Aromatic tetracarboxylic dianhydrides such as fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1 Examples of suitable dianhydrides include, but are not limited to, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0026] Furthermore, the component (A) preferably has a phenolic hydroxyl group, and in the component (A), Y in the general formulas (1) and (2) １ and Y ２ It is particularly preferred that the resin contains a diamine residue having a phenolic hydroxyl group. By containing a diamine residue having a phenolic hydroxyl group, 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.

[0027] 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 are substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like; and diamines having the structure shown below. Furthermore, two or more of these diamine components may be used in combination.

[0028]

[0029]

[0030] 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.

[0031] The molar ratio of the structures represented by general formulas (1) and (2) in component (A) can be calculated from the molar ratio of the monomers used in polymerization. When determining the molar ratio of the structures from the obtained resin, resin composition, or cured film, it can be confirmed by a method of detecting peaks of the polyamide structure, imide precursor structure, or imide structure using a nuclear magnetic resonance (NMR) spectrometer.

[0032] The component (A) having a structure derived from a carboxylic acid residue at the molecular chain terminal can be obtained, for example, in the case of a polyimide having a structure derived from a carboxylic acid residue at the molecular chain terminal, by increasing the content of acid anhydride relative to the diamine used during polymerization. Another method for obtaining the component (A) having a structure derived from a carboxylic acid residue at the molecular chain terminal can be by adding, during polymerization, a specific compound generally used as an end-capping agent, specifically a compound selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds.

[0033] Furthermore, by capping the molecular chain ends of the component (A) with a terminal capping agent containing 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 the 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.

[0034] 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; Preferred are monocarboxylic acids such as cyclohexanedicarboxylic acid and 4-carboxybenzenesulfonic acid, and 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 active 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.

[0035] The component (A) into which these terminal blocking agents have been introduced has a structure in which the molecular chain terminals are derived from carboxylic acid residues. The terminal blocking agent introduced into the component (A) can be easily detected by the following method. For example, the component (A) into which the terminal blocking agent has been introduced is dissolved in an acidic solution, decomposed into the structural units, amine components and acid anhydride components, and these components are measured using gas chromatography (GC) or NMR, whereby the terminal blocking agent used in the present invention can be easily detected. Separately, the resin component into which the terminal blocking agent has been introduced can be directly analyzed using pyrolysis gas chromatography (PGC), infrared spectroscopy, and １３ It can also be easily detected by measurement using C-NMR.

[0036] In the present invention, the component (A) can be synthesized, for example, by the following method, but is not limited thereto. For example, when the component (A) is a polyimide, a polyimide precursor can be 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 preparing a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine with a monoamine in the presence of a condensing agent. A polyimide can then be synthesized using a known imidization reaction method. When a terminal-capping agent is used, the polyimide can be synthesized by replacing part of the diamine with a primary monoamine, or by replacing part of the tetracarboxylic dianhydride with a dicarboxylic anhydride, which is the terminal-capping agent.

[0037] After polymerizing the component (A) using the above method, it is preferable to add it to a large amount of water or a mixture of methanol and water, precipitate it, and then filter, dry, and isolate it. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This operation removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties after thermal curing.

[0038] When the component (A) is a polyimide, the imidization rate 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 due to the polyimide (1780 cm －１ Near 1377 cm －１ Next, the polymer is heat-treated at 350°C for 1 hour, and the sample is used as a sample with an imidization rate of 100%, and the infrared absorption spectrum is measured in the same manner. －１ The imidization ratio is determined by calculating the content of imide groups in the polymer before heat treatment by comparing the peak intensities around the peak. From the viewpoints of suppressing changes in the ring closure ratio during heat curing and achieving a stress reduction effect, the imidization ratio is preferably 50% or more, and more preferably 80% or more.

[0039] When the entire resin composition of the present invention is taken as 100% by mass, the total content of component (A) is preferably 15 to 60% by mass, and more preferably 25 to 50% by mass. Containing 15% by mass or more of component (A) relative to 100% by mass of the entire resin composition is preferable in terms of improving mechanical properties and thermal properties. Containing 60% by mass or less of component (A) is preferable in terms of reducing development residues. Here, the entire resin composition refers to the sum of all components constituting the resin composition, excluding the solvent.

[0040] <Component (B)> The resin composition of the present invention contains a cationically polymerizable compound as component (B). It is important that component (B) contains both an epoxy compound as component (B1) and an oxetane compound as component (B2).

[0041] As the component (B1), known epoxy compounds can be used, such as aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0042] 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).

[0043] 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).

[0044] 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 products of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0045] Furthermore, the component (B1) preferably contains an epoxy compound represented by general formula (3) or general formula (4).

[0046]

[0047] In general formula (3), R ５ is a monovalent organic group. The monovalent organic group is preferably a group selected from a hydrogen atom, a hydrocarbon group, and a functional group having an oxygen atom, such as a hydroxy group, an alkoxy group, or a hydrocarbon group having an ether bond. Examples of the hydrocarbon group include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 30 carbon atoms. Examples of the alkoxy group include an alkyloxy group and a glycidyl group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having an ether bond include a group in which an ether bond is inserted into the carbon chain of the above-mentioned cyclized hydrogen group.

[0048]

[0049] In the general formula (4), x, y, and z each independently represent an integer of 1 to 6.

[0050] The component (B1) preferably contains an epoxy compound represented by general formula (3) or general formula (4) because this improves compatibility with the component (A), enables fine pattern processability, and improves the heat resistance and chemical resistance of the cured film.

[0051] Examples of epoxy compounds represented by general formula (3) include Showfree PETG (trade name, manufactured by Showa Denko K.K.) and the like. Examples of epoxy compounds represented by general formula (4) include TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.).

[0052] Known oxetane compounds can be used as the component (B2), such as 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.

[0053] The component (B2) is preferably an oxetane compound having two or more oxetanyl groups per molecule, and more preferably two to six oxetanyl groups per molecule. Having two or more oxetanyl groups in the oxetane compound is preferred in terms of improved curability. Having six or fewer oxetanyl groups in the oxetane compound is preferred in terms of suppressing cracks that occur during pattern processing. Examples of such oxetane compounds include OXT-121 and OXT-221 (all trade names, manufactured by Toagosei Co., Ltd.), ETERNACOLL OXBP, and ETERNACOLL OXIPA (all trade names, manufactured by UBE Corporation).

[0054] Furthermore, the component (B2) preferably contains an oxetane compound represented by general formula (5) or general formula (6).

[0055]

[0056] In the general formula (5), m is an integer of 1 to 6, and R １ , R ２ is a monovalent organic group. Preferred examples of the monovalent organic group include the above-mentioned R ５ The same as those described in the above can be mentioned.

[0057]

[0058] In general formula (6), n is an integer of 1 to 6, and R ３ , R ４ is a monovalent organic group. Preferred examples of the monovalent organic group include the above-mentioned R ５The same as those described in the above can be mentioned.

[0059] The component (B2) preferably contains an oxetane compound represented by general formula (5), which improves adhesion to the substrate and suppresses peeling during development. Examples of such oxetane compounds include OXT-121 (trade name, manufactured by Toagosei Co., Ltd.).

[0060] The component (B2) preferably contains an oxetane compound represented by general formula (6), which improves adhesion to the substrate, inhibits peeling during development, and improves the heat resistance of the cured film. Examples of such oxetane compounds include ETERNACOLL OXBP (trade name, manufactured by UBE Co., Ltd.).

[0061] The content of the component (B2) is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the total of the component (B1). A total of 10 parts by mass or more of the component (B2) is preferred in that cationic polymerizability is improved and distortion and peeling during pattern processing can be suppressed, while a total of 200 parts by mass or less is preferred in that resolution during pattern processing is improved.

[0062] Here, wrinkling during pattern processing will be explained using FIG. 1 . FIG. 1 is a cross-sectional view schematically illustrating wrinkling of a resin composition pattern 1 obtained by laminating a resin composition on a substrate 2 and developing the resin composition. Wrinkling during pattern processing refers to a phenomenon in which a pattern 1 of the resin composition is formed at an angle inclined from the vertical, as shown in FIG. 1 , while a perpendicular pattern should be formed. Here, in particular, a state in which the angle α formed by the perpendicular line drawn from intersection A between substrate 2 and pattern 1 to substrate 2 in FIG. 1 and the line connecting intersection A and corner B at the top of pattern 1 is 10 to 90° is defined as a state in which pattern wrinkling has occurred. That is, in the resin composition of the present invention, by satisfying the above-mentioned content of component (B2), the angle α in FIG. 1 can be made less than 10°.

[0063] The resin composition of the present invention may further contain a cationically polymerizable compound other than the components (B1) and (B2). Examples of the cationically polymerizable compound other than the components (B1) and (B2) include ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters.

[0064] 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.

[0065] Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0066] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0067] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0068] Examples of styrenes include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0069] Examples of the cationically polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] When the total amount of component (B) is 100 parts by mass, the total amount of components (B) other than components (B1) and (B2) is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. Having the total amount of components (B) other than components (B1) and (B2) 10 parts by mass or less is preferable in that cationic polymerization is improved and distortion and peeling during pattern processing can be suppressed.

[0074] The content of component (B) is preferably 50 to 200 parts by mass, and more preferably 70 to 150 parts by mass, per 100 parts by mass of component (A). A total content of component (B) of 50 parts by mass or more is preferred in that cationic polymerizability is improved and distortion and peeling during pattern processing can be suppressed, while a content of 200 parts by mass or less is preferred in that resolution during pattern processing is improved.

[0075] <Component (C)> The resin composition of the present invention contains a cationic photopolymerization initiator as component (C). The component (C) generates an acid when exposed to light, causing cationic polymerization of a cationic polymerizable compound. As component (C), any compound known as a cationic photopolymerization initiator can be used, but an onium salt is preferred.

[0076] Specific examples of the component (C) include aromatic iodonium complex salts, aromatic sulfonium complex salts, aromatic borate complex salts, and aromatic gallate 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 photocationic polymerization initiators may be used alone, or two or more types may be used in combination.

[0077] The content of the (C) component is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.7 parts by mass or more, relative to 100 parts by mass of the total of the (A) components. This allows the cationically polymerizable compound to exhibit sufficient curability and improve pattern processability. On the other hand, in order to improve the storage stability of the resin composition before curing, the content of the (C) component is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, relative to 100 parts by mass of the total of the (A) components.

[0078] <Other Components> The resin composition of the present invention may contain a sensitizer. The sensitizer is a compound that absorbs light, provides the absorbed light energy to the component (C), and generates an acid to cause cationic polymerization. Furthermore, the sensitizer absorbs light of the irradiation wavelength during pattern processing, and can therefore reduce the transmittance of a resin composition film formed from the resin composition. Therefore, it is possible to arbitrarily control the transmittance of the resin composition film by adjusting the content of the sensitizer in the resin composition.

[0079] Although the sensitizer is not particularly limited, an anthracene compound is preferred, and for example, an anthracene compound having alkoxy groups at the 9th and 10th positions (9,10-dialkoxy-anthracene derivative) is more preferred. 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 alkyls such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position.

[0080] The content of the sensitizer is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, when the mass of the entire resin composition is 100% by mass. This reduces the transmittance of the resin composition film, suppresses reflected light from the substrate surface even on substrates with rough surfaces such as ceramics, and facilitates the processing of fine patterns. On the other hand, from the viewpoint of suppressing deterioration in the mechanical properties and thermal properties of the cured film of the resin composition film formed from the resin composition, when the mass of the entire resin composition is 100% by mass, the content of the sensitizer is preferably 10% by mass or less, more preferably 5% by mass or less.

[0081] The resin composition of the present invention may contain a thermal crosslinking agent, preferably a compound having an alkoxymethyl group or a methylol group.

[0082] 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 (registered trademark) MX-280, NIKALAC (registered trademark) MW-100LM, and NIKALAC (registered trademark) MX-750LM (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0083] The resin composition of the present invention may further contain a silane compound. By containing a silane compound, the adhesion of the resulting heat-resistant resin coating is improved. Specific examples of the silane compound 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.

[0084] Furthermore, the resin composition of the present invention may contain, as necessary, surfactants for the purpose of improving wettability with the support, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Furthermore, for the purpose of suppressing the thermal expansion coefficient or increasing or decreasing the dielectric constant, the resin composition may contain inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder.

[0085] <Resin Composition Coating, Resin Composition Film> The form of the resin composition of the present invention before curing is not limited, and examples thereof include a varnish form and a film form.

[0086] When the resin composition of the present invention is used in the form of a varnish, a solution prepared by dissolving the above components (A) to (C) and any other components that may be added as required in an organic solvent can be used.

[0087] When the resin composition of the present invention is in the form of a film, it may be referred to as a resin composition film in the present invention. The resin composition film of the present invention has the resin composition film of the present invention and a support. That is, the resin composition film of the present invention is a film in which the resin composition film of the present invention is formed on a support.

[0088] The resin composition coating of the present invention preferably has a thickness of 40 μm or more, since a thick film can be easily formed when fabricating a semiconductor device having the cured film of the present invention, as described below. Furthermore, the thickness is preferably 70 μm or less, since variations in film thickness can be suppressed.

[0089] Next, a method for producing a resin composition film using the resin composition of the present invention in varnish form will be described. The resin composition film of the present invention can be obtained by applying a solution of the resin composition of the present invention (hereinafter referred to as resin composition varnish) 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 dissolves the resin composition.

[0090] 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.

[0091] 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.

[0092] The support used in the resin composition film of the present invention is not particularly limited, but various commercially available films such as polyethylene terephthalate (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.

[0093] Furthermore, the resin composition film of the present invention may further have a protective film on the resin composition coating to protect the surface. This makes it possible to protect the surface of the photosensitive 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.

[0094] Examples of methods for applying the resin composition varnish to a support include spin coating using a spinner, spray coating, roll coating, screen printing, a blade coater, a die coater, a calendar coater, a meniscus coater, a bar coater, a roll coater, a comma roll coater, a gravure coater, a screen coater, and a slit die coater. The coating thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, and the like, but the film thickness after drying is preferably 0.5 μm or more and 100 μm or less.

[0095] 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.

[0096] <Cured Film, Semiconductor Device, Inductor> Next, examples of a method for patterning the resin composition varnish of the present invention or a resin composition film using the same will be described.

[0097] First, a method for forming a resin composition coating on a substrate using the resin composition varnish or resin composition film of the present invention will be described.

[0098] When using a resin composition varnish, the resin composition varnish is first applied to a 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 preferable to apply the resin composition varnish so that the film thickness after drying is 0.5 μm or more and 100 μm or less. Next, the substrate coated with the resin composition varnish is dried to obtain a substrate with a resin composition coating formed thereon. 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 within a range that leaves the resin composition coating 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.

[0099] On the other hand, when a resin composition film is used, if a protective film is present, it is peeled off, and the resin composition coating in the resin composition film is placed face to face with a substrate and bonded by thermocompression to obtain a substrate on which a resin composition coating is formed. Thermocompression bonding can be performed by heat pressing, heat lamination, thermal vacuum lamination, etc. The lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, in order to prevent the resin composition film from curing during lamination and thereby deteriorating the resolution of pattern formation in the exposure and development steps, the lamination temperature is preferably 150°C or lower. After thermocompression bonding, the support may be peeled off from the resin composition film as needed.

[0100] 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.

[0101] Next, the resin composition film formed by the above method is irradiated with actinic radiation through a mask having a desired pattern, thereby exposing the resin composition film. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, X-rays, etc., but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) 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.

[0102] To form a pattern, after exposure, the exposed portions of the resin composition coating are removed using a developer. Examples of the developer include aqueous solutions of 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, and other alkaline compounds. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 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, either singly or in combination.

[0103] The development can be carried out by a method such as spraying the developer onto the surface of the resin composition film, puddling the developer onto the surface of the resin composition film, immersing the resin composition film in the developer, or immersing the resin composition film in the developer and applying ultrasonic waves, etc. The development conditions, such as the development time, development steps, and developer temperature, may be any conditions that allow the exposed area to be removed and a pattern to be formed.

[0104] After development, it is preferable to carry out a rinsing treatment using water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

[0105] Furthermore, if necessary, the resin composition film may be baked before development. This may improve the resolution of the pattern after development 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 5 seconds to several hours.

[0106] After pattern formation, unreacted cationically polymerizable compounds and photocationic polymerization initiators remain in the resin composition film. 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 film after pattern formation with the above-mentioned exposure light to generate acid from the unreacted photocationic polymerization initiator. This can prevent the reaction of the unreacted cationically polymerizable compounds from progressing during thermocompression bonding or curing, thereby preventing the generation of gas due to thermal decomposition.

[0107] After development, a temperature of 150°C to 500°C is applied to promote a thermal crosslinking reaction, yielding a cured film. This process is called curing. The resulting cured film can have improved heat resistance and chemical resistance due to crosslinking. This heat treatment method can be selected by either 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.

[0108] The cured film of the present invention is a cured film obtained by curing the resin composition of the present invention or the resin composition coating in the resin composition film of the present invention. The cured film obtained by curing the resin composition of the present invention or the resin composition coating in the resin composition film of the present invention can be used for electronic parts such as semiconductor devices.

[0109] The cured film of the present invention preferably has a thickness of 40 μm or more, more preferably 80 μm or more, from the viewpoints of forming a thicker insulating layer and improving wiring density when producing a semiconductor device having the cured film of the present invention described above, and the thickness is preferably 300 μm or less, more preferably 200 μm or less, from the viewpoint of reducing warpage of the semiconductor device due to film stress.

[0110] The semiconductor device of the present invention is a semiconductor device having the cured film of the present invention. Here, the term "semiconductor device" 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 containing these. Semiconductor devices also include electronic components such as multilayer wiring boards for connecting semiconductor elements. In semiconductor devices, the cured film of the present invention is particularly suitable for applications such as insulating films for inductors, passivation films for semiconductors, 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 elements. However, the cured film can be used for a variety of applications, including but not limited to these.

[0111] The resin composition of the present invention is characterized by its ability to be patterned to a high aspect ratio, and is therefore preferably used in semiconductor devices having a cured film with a high aspect ratio, such as inductors. Figure 2 shows a cross-sectional view of a schematic representation of an inductor. However, the inductor according to the present invention is not limited to the embodiments described below.

[0112] 2, an insulating film 4 is provided to maintain insulation between the inductor 3 and the coil 5. It is preferable to use a cured film obtained by curing the resin composition of the present invention as the insulating film 4. By using a cured film obtained by curing the resin composition of the present invention as the insulating film 4, sufficient insulation can be exhibited even if the width W of the insulating film 4 is small, so that the cross-sectional area of ​​the wiring of the coil 5 can be increased and the inductance can be increased.

[0113] Furthermore, the thickness T of the insulating film 4 formed using the cured film obtained by curing the resin composition of the present invention is preferably 40 μm or more, and more preferably 80 μm or more, in order to increase the cross-sectional area of ​​the coil 5. The thickness T is preferably 300 μm or less, and more preferably 200 μm or less, in order to reduce the film stress.

[0114] Furthermore, the aspect ratio of the insulating film 4 formed using a cured film obtained by curing the resin composition of the present invention is preferably 4 or more, and more preferably 8 or more, in order to improve the wiring density of the coil 5. In order to maintain insulation properties, the aspect ratio of the insulating film 4 is preferably 30 or less, and more preferably 20 or less. The aspect ratio referred to here is calculated using the following formula (1): Formula (1) (aspect ratio) = T (film thickness) / W (pattern width).

[0115] In the inductor 3, the insulating film 4 and the coil 5, which are made of a cured film obtained by curing the resin composition of the present invention, are formed above and below the substrate 7. It is preferable that a resin layer 6 is further provided between the insulating film 4 and the substrate 7. The presence of the resin layer 6 is preferable in that it improves the adhesion of the insulating film 4 to the substrate.

[0116] Furthermore, the resin layer 6 preferably contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole. The content of the polymer compound in the resin layer 6 is preferably 1 to 45 mass %, more preferably 20 to 40 mass %. A content of 1 mass % or more is preferred in terms of improving heat resistance, and a content of 45 mass % or less is preferred in terms of improving adhesion of the insulating film 4 to the substrate.

[0117] Furthermore, the inductor 3 in FIG. 2 has an insulating film 8, a magnetic material 9, and a molding resin 10.

[0118] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0119] <Evaluation of Pattern Processability> A 5 ​​cm square silicon wafer was used as a substrate. The protective film of the resin composition film produced in each Example and Comparative Example was peeled off, and the resin composition film was laminated on a substrate so that the resin composition coating was in contact with the substrate. The film was then subjected to thermal lamination using a vacuum diaphragm laminator (MVLP-500 / 600, manufactured by Meiki Seisakusho Co., Ltd.) under conditions of an upper and lower heating platen temperature of 80°C, a vacuuming time of 20 seconds, a vacuum pressing time of 30 seconds, and an application pressure of 0.5 MPa. The support was then peeled off from the resin composition film to form a resin composition coating having a thickness of 45 μm on the silicon substrate.

[0120] The resin composition coating thus obtained was subjected to the same process as above once again to laminate a resin composition coating having a total thickness of 90 μm on the silicon substrate.

[0121] Next, a mask having a pattern with a line width / space width of 5 μm / 50 μm, 6 μm / 50 μm, 7 μm / 50 μm, 8 μm / 50 μm, 9 μm / 50 μm, 10 μm / 50 μm, and 15 μm / 50 μm was set in the exposure device, and an exposure dose of 1500 mJ / cm was applied using an ultra-high pressure mercury lamp equipped with an i-line bandpass filter under the condition of an exposure gap of 100 μm between the mask and the photosensitive resin composition film. ２ (i-line equivalent). After exposure, post-exposure baking was performed on a hot plate at 90°C for 10 minutes. Thereafter, the unexposed portions of the resin composition coating were removed by dip development using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), followed by rinsing treatment with water. The development time was set to twice the time required for the unexposed portions to completely dissolve.

[0122] The patterns thus obtained were observed under an optical microscope, and the minimum line width when there were no abnormalities such as residues in the pattern was taken as the resolution. The aspect ratio was calculated from the minimum line width using the above formula (1). If no patterns were resolved, the resolution was taken as 0 (poor).

[0123] <Evaluation of Glass Transition Temperature> A resin composition coating was formed on copper foil (CF-T9DA-SV-1, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) having a planar size of 10 cm × 10 cm in place of a silicon wafer, in the same manner as in the evaluation method for pattern processability described above, except that the substrate was changed from a silicon wafer to a copper foil having a planar size of 10 cm × 10 cm. Then, an ultra-high pressure mercury lamp was used to form a resin composition coating on the copper foil, and the resin composition coating was subjected to an exposure of 1000 mJ / cm. ２ After the exposure, the film was baked on a hot plate at 120°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 in 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 coating formed on the copper foil. Thereafter, only the copper foil was dissolved using a ferric chloride solution, washed with water, and air-dried to obtain a cured film of the resin composition.

[0124] The obtained cured film was cut into test pieces of 5 mm x 40 mm size, and measurements were carried out using a dynamic viscoelasticity measuring device DVA-200 (manufactured by IT Measurement Control Co., Ltd.) under the conditions of a chuck distance of 20 mm, a frequency of 1 Hz, a temperature range of room temperature to 350°C, a heating rate of 5°C / min, and a measurement strain of 0.1%, and the glass transition temperature was determined as the peak top temperature of tan δ = storage modulus / loss modulus, which is the ratio of storage modulus to loss modulus.

[0125] <Evaluation of Tensile Strength and Tensile Elongation> A cured film of the resin composition was obtained in the same manner as in the evaluation method for glass transition temperature. The obtained cured film was cut into test pieces of 10 mm x 80 mm size, and a tensile test was performed using a universal testing machine AG-Xplus (manufactured by Shimadzu Corporation) at room temperature, with a chuck distance of 50 mm and a tensile speed of 50 mm / min, to measure the tensile strength (stress at break) and tensile elongation (elongation at break). Measurements were performed on 10 test pieces per specimen, and the average of the top five points was calculated from the results.

[0126] The compounds used in the examples and comparative examples were synthesized by the following methods.

[0127] Synthesis Example 1 Synthesis of Phenolic 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 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 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 and dried in vacuo at 50°C.

[0128] 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 after confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the filtrate 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 as is in the reaction.

[0129]

[0130] Synthesis Example 2 Synthesis of Polyimide (A-1) 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 dissolved with stirring at 120°C. Next, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (hereinafter referred to as 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.

[0131] Synthesis Example 3 Synthesis of Polyamideimide (A-2) Under a dry nitrogen stream, hydroxyl group-containing diamine compound (a) (15.72 g, 0.04 mol) and BAHF (14.65 g, 0.04 mol) were added to 100 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.

[0132] Example 1 10 g of polyimide (A-1) as the component (A), 5.6 g of PETG (trade name, manufactured by Showa Denko K.K.) and 3.7 g of BATG (trade name, manufactured by Showa Denko K.K.) as the component (B1), 0.7 g of OXT-101 (trade name, manufactured by Toa Gosei Co., Ltd.) as the component (B2), 0.3 g of CPI-310FG (trade name, manufactured by San-Apro Co., Ltd.) as the component (C), 0.2 g of UVS-1331 (trade name, manufactured by Kawasaki Kasei Kasei K.K.) as a sensitizer, and 0.4 g of KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane compound were dissolved in GBL. The amount of GBL added as a solvent was adjusted so that the solids concentration was 60 wt %, with additives other than the solvent being the solids content. The resulting solution was filtered under pressure using a filter with a retention particle size of 1 μm to obtain a resin composition varnish having negative photosensitivity.

[0133] The resulting resin composition varnish was applied to a 50 μm-thick PET film using a comma roll coater and dried at 120°C for 8 minutes to obtain a resin composition film in which the resin composition was formed on the PET film. The film thickness of the resin composition coating was adjusted to 45 μm. A 30 μm-thick PP film was then laminated onto the resin composition coating as a protective film. The resulting resin composition film was used to evaluate the pattern processability, glass transition temperature, tensile strength, and tensile elongation as described above. The results are shown in Table 2.

[0134] Examples 2 to 15 Resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to the compounds listed below and their mixing ratios were changed as shown in Table 1. The pattern processability, glass transition temperature, tensile strength, and tensile elongation were evaluated as described above. The results are shown in Table 2.

[0135] Comparative Examples 1 to 3 Resin composition films were prepared in the same manner as in Example 1, except that components (A) to (C) and other components were changed to the compounds below and their mixing ratios were changed as shown in Table 1. The pattern processability was evaluated as described above. The results are shown in Table 2.

[0136]

[0137]

[0138]

[0139]

[0140] In Table 1, the "total content (parts by mass) of component (B2)" represents the total parts by mass of component (B2) when the total of component (B1) is 100 parts by mass. Also, the "total content (parts by mass) of component (B)" represents the total parts by mass of component (B) when the total of component (A) is 100 parts by mass.

[0141] As is clear from Tables 1 and 2, Comparative Example 1, which did not contain component (A), produced a cured film inferior in glass transition temperature and tensile strength to the Examples. Comparative Example 2, which did not contain component (B1), produced a pattern that was clogged, making pattern processing impossible. Comparative Example 3, which did not contain component (B2), produced a fine pattern that was distorted or peeled, making it impossible to process a pattern with a high aspect ratio.

[0142] In contrast, the resin composition of this example had sufficient thermal properties (glass transition temperature) and mechanical properties (tensile strength, tensile elongation), and it was shown that a pattern with a high aspect ratio could be formed.

[0143] The compounds used in each synthesis example, example and comparative example are shown below.

[0144] (A) Polymer Compounds A-1: ​​Polyimide A-2: Polyamideimide.

[0145] (B1) Epoxy Compounds B1-1: PETG (manufactured by Showa Denko K.K.), an epoxy compound represented by general formula (3) B1-2: BATG (manufactured by Showa Denko K.K.) B1-3: TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.), an epoxy compound represented by general formula (4) B1-4: 1007 (manufactured by Mitsubishi Chemical Corporation), a bisphenol A-type epoxy resin.

[0146] (B2) Oxetane Compounds B2-1: OXT-101 (manufactured by Toagosei Co., Ltd.), a compound having one oxetanyl group B2-2: OXT-221 (manufactured by Toagosei Co., Ltd.), a compound having two oxetanyl groups B2-3: OXT-121 (manufactured by Toagosei Co., Ltd.), a compound having two oxetanyl groups and represented by general formula (5) B2-4: ETERNACOLL OXBP (manufactured by UBE Co., Ltd.), a compound having two oxetanyl groups and represented by general formula (6).

[0147] (C) Cationic polymerization initiator C-1: CPI-310FG (onium salt-based photoacid generator, manufactured by San-Apro Co., Ltd.) Sensitizer UVS-2171 (anthracene compound, manufactured by Kawasaki Chemical Industries, Ltd.) Silane compound KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0148] REFERENCE SIGNS LIST 1 Resin composition pattern 2 Base material 3 Inductor 4 Insulating film 5 Coil 6 Resin layer 7 Substrate 8 Insulating film 9 Magnetic material 10 Molding resin

Claims

1. A resin composition comprising, as a component (A), at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, as a component (B), a cationically polymerizable compound as a component (C), and a photocationic polymerization initiator as a component (C), the component (B) contains both an epoxy compound as the component (B1) and an oxetane compound as the component (B2), the total amount of the (B) component is 50 to 200 parts by mass when the total amount of the (A) component is 100 parts by mass, The resin composition is a negative photosensitive resin composition.

2. The resin composition according to claim 1, wherein the total amount of the (B2) component is 10 to 200 parts by mass when the total amount of the (B1) component is 100 parts by mass.

3. The resin composition according to claim 1, wherein the component (B2) contains an oxetane compound having two or more oxetanyl groups in one molecule.

4. 2. The resin composition according to claim 1, wherein the component (B2) contains at least one oxetane compound selected from the group consisting of oxetane compounds represented by general formula (5) or general formula (6): 【Chemistry 1】 In the general formula (5), m is an integer of 1 to 6, and R １ , R ２ is a monovalent organic group. 【Chemistry 2】 In general formula (6), n is an integer of 1 to 6, and R ３ , R ４ is a monovalent organic group.

5. The resin composition according to claim 1, wherein the component (B1) contains an epoxy compound represented by general formula (3): 【Transformation 3】 In general formula (3), R ５ is a monovalent organic group.

6. The resin composition described in claim 1, wherein the component (B1) contains an epoxy compound represented by general formula (4). 【Chemistry 4】 In the general formula (4), x, y, and z each independently represent an integer of 1 to 6.

7. A resin composition described in claim 1, wherein the (C) component is an onium salt-based photoacid generator.

8. A resin composition film having a resin composition coating and a support, wherein the resin composition coating is made of the resin composition according to claim 1.

9. A semiconductor device having a cured film formed by curing the resin composition according to claim 1.

10. 10. The semiconductor device according to claim 9, wherein the thickness of the cured film is 40 to 300 μm and the aspect ratio of the cured film is 4 to 20.

11. 10. The semiconductor device according to claim 9, wherein the semiconductor device is an inductor having an insulating film and a coil, and the cured film obtained by curing the resin composition is used as the insulating film of the inductor.

12. 12. The semiconductor device according to claim 11, wherein the semiconductor device is an inductor having an insulating film and a coil formed on a substrate, and further comprising a resin layer between the insulating film and the substrate.

13. 13. The semiconductor device according to claim 12, wherein the resin layer contains at least one polymer compound selected from the group consisting of polyamide, polyimide, polyamideimide, and polybenzoxazole, and the content of the polymer compound in the resin layer is 1 to 45 mass %.

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