Resin compositions, resin composition films, and semiconductor devices using the like.

Abstract

A resin composition comprising, as component (A), at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide, and polybenzoxazole; as component (B), a cationic polymerizable compound; and as component (C), a photocationic polymerization initiator, wherein component (B) comprises both an epoxy compound as component (B1) and an oxetane compound as component (B2). This invention provides a resin composition having sufficient mechanical and thermal properties, capable of forming thick films with high aspect ratio patterns.

Description

Technical Field

[0001] This invention relates to a resin composition, a resin composition coating, a resin composition film, a hardened film, and a semiconductor device using the like. More specifically, this invention relates to a resin composition suitable for use as a surface protective film, interlayer insulating film, or structure for microelectromechanical systems (MEMS) in semiconductor elements or inductors. Prior Technology

[0002] Previously, surface protective films and interlayer insulating films for semiconductor devices widely used polyimide-based or polybenzoxazole-based materials, which possess excellent heat resistance, electrical insulation, and mechanical properties. However, with the increasing demands for higher density and performance in semiconductor devices in recent years, from a production efficiency perspective, surface protective films and interlayer insulating films require photosensitive materials.

[0003] On the other hand, to adapt to the various packaging structures of semiconductor devices or MEMS in recent years, high aspect ratio processing is required for photosensitive materials. To address this requirement, a chemically amplified photocationic polymeric photosensitive material has been disclosed (e.g., Patent Document 1). Furthermore, a photocationic polymeric material has been disclosed that aims to improve mechanical or thermal properties by containing an epoxy resin with a specific structure in a chemically amplified photocationic polymeric system (e.g., Patent Document 2). Moreover, a photocationic polymeric material with excellent glass transition temperature, tensile strength, and elongation at break of the hardened film has been disclosed by containing polymers such as polyimide in a chemically amplified photocationic polymeric system (e.g., Patent Document 3). [Existing Technical Documents] [Patent Literature]

[0004] [Patent Document 1] International Publication No. 2008 / 007764 [Patent Document 2] Japanese Patent Application Publication No. 2019-38964 [Patent Document 3] Japanese Patent Application Publication No. 2021-055055 Summary of the Invention

[0005] [The problem that the invention aims to solve] However, in such photocationic polymeric materials, sufficient mechanical or thermal properties make it difficult to form thick films with high aspect ratio patterns. In photocationic polymeric materials as described in Patent Document 1 or Patent Document 2, it is difficult to simultaneously achieve sufficient mechanical and thermal properties. In photocationic polymeric materials containing polymers such as polyimide, as described in Patent Document 3, it is difficult to form thick films with high aspect ratio patterns.

[0006] In view of the above situation, the object of the present invention is to provide a resin composition having sufficient mechanical and thermal properties, and capable of forming thick films with high aspect ratio patterns. [Methods for solving problems]

[0007] In view of the above situation, we conducted in-depth research and found that the above problem can be solved by producing photocationically polymerizable materials containing polymers such as polyimide and epoxides and oxetanes, which are cationic polymerizable compounds.

[0008] The present invention for solving the aforementioned problem is as follows.

[0009] A resin composition comprising (A) at least one polymeric compound selected from the group consisting of polyamines, polyimides, polyamine-imides, and polybenzoxazoles; (B) a cationic polymerizable compound; and (C) a photocationic polymerization initiator, wherein the resin composition, The (B) component contains both an epoxy compound as component (B1) and an oxetane compound as component (B2). [The effects of the invention]

[0010] The resin composition of the present invention provides resin compositions having sufficient mechanical and thermal properties and capable of forming thick films with high aspect ratio patterns, resin composition films, resin composition films, hardened films, and semiconductor devices or inductors using the like. Simple Explanation of the Diagram

[0011] Figure 1 is a schematic cross-sectional view showing the distortion of a pattern obtained by developing a resin composition deposited on a substrate. Figure 2 is a schematic cross-sectional view of an inductor. Implementation

[0012] The resin composition of the present invention comprises at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide, and polybenzoxazole as component (A); a cationic polymerizable compound as component (B); and a photocationic polymerization initiator as component (C), wherein component (B) comprises 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 negatively photosensitive resin composition that, when exposed to light, produces an acid in component (C), thereby causing component (B) to undergo a polymerization reaction, resulting in a resin composition that is insoluble in the developing solution.

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

[0015] The weight-average molecular weight of component (A) is not particularly limited, but is preferably 1,000 or more and 200,000 or less. Furthermore, the weight-average molecular weight of the polymer compound in component (A) of the present invention is determined by gel permeation chromatography (GPC) and calculated by conversion to polystyrene.

[0016] Furthermore, it is important that the resin composition of the present invention includes at least one polymeric compound selected from the group consisting of polyamine, polyimide, polyamide-imide, and polybenzoxazole. As long as it includes at least one polymeric compound selected from the group consisting of polyamine, polyimide, polyamide-imide, and polybenzoxazole, it can also include polymeric compounds other than polyamine, polyimide, polyamide-imide, and polybenzoxazole. Moreover, the polyimide precursor and the polybenzoxazole precursor are respectively equivalent to the polyamine.

[0017] Furthermore, component (A) preferably has a molecular chain end structure derived from a carboxylic acid residue. By having the molecular chain end of component (A) derived from a carboxylic acid residue, its molecular chain end can form a molecular structure without an amine terminal structure that can become a suppressor functional group for cationic polymerization, resulting in sufficient cationic polymerizability. Here, the structure at the molecular chain end of component (A) derived from a carboxylic acid residue refers to an organic group derived from a carboxylic acid residue that can constitute polyamide, polyimide, or polyamide-imide.

[0018] The structures (organic groups) derived from carboxylic acid residues at the molecular chain ends of component (A) can be listed as: structures derived from aromatic dicarboxylic acids, aromatic acid dianhydrides, alicyclic dicarboxylic acids, alicyclic acid dianhydrides, aliphatic dicarboxylic acids, aliphatic acid dianhydrides, etc., but are not limited to these. Furthermore, these structures may be used alone or in combination of two or more.

[0019] In this invention, 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] [Chemistry 1]

[0021] In general formulas (1) and (2), X1 and X2 independently represent divalent to octavalent organic groups, Y1 and Y2 independently represent divalent to hexavalent organic groups, R represents hydrogen atoms or organic groups with 1 to 20 carbon atoms, q is an integer from 0 to 2, and r, s, t, and u are independent integers from 0 to 4.

[0022] In general formulas (1) and (2), X1 and X2 independently represent divalent to decavalent organic groups and carboxylic acid residues, respectively. In addition, Y1 and Y2 represent divalent to tetravalent organic groups and diamine residues.

[0023] Furthermore, component (A) preferably has an alicyclic structure. By having an alicyclic structure, component (A) improves the transparency and patterning processability of the resin composition. Additionally, regarding improving the solubility of the resin composition, component (A) more preferably contains carboxylic acid residues with an alicyclic structure. Furthermore, regarding improving chemical resistance and ion migration resistance when forming cured products, component (A) preferably has an organic group derived from an alicyclic tetracarboxylic dianhydride containing a polycyclic structure.

[0024] Specific examples of alicyclic tetracarboxylic dianhydrides with polycyclic structures include: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-4methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-7methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride; norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, etc.

[0025] Additionally, the carboxylic acid residues may also include organic groups derived from dianhydrides other than the alicyclic tetracarboxylic dianhydrides having polycyclic structures. 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'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3- Dicarboxyphenyl)propane 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)guanidine dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis Aromatic tetracarboxylic anhydrides such as (3,4-dicarboxyphenyl)fluorenic dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic 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'-diphenyltetracarboxylic... Examples of dianhydrides include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 1,2,3,4-cyclopentanetetracarboxylic dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydrides, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydrides, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydrides, and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydrides. Furthermore, these dianhydrides may be used alone or in combination of two or more.

[0026] Furthermore, component (A) preferably has phenolic hydroxyl groups, and in component (A), Y1 and Y2 in general formulas (1) and (2) are particularly preferably diamine residues containing phenolic hydroxyl groups. By containing diamine residues containing phenolic hydroxyl groups, moderate solubility of the resin in alkaline developing solution can be obtained, thus achieving high contrast between the exposed and unexposed areas, and forming the desired pattern.

[0027] Specific examples of diamines having phenolic hydroxyl groups include: bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) monazine, 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'-di-trifluoromethyl-5,5'-dihydroxy-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, and other aromatic diamines, or compounds obtained by substituting a portion of the hydrogen atoms of these aromatic rings or hydrocarbons with alkyl, fluoroalkyl, or halogen atoms having 1 to 10 carbon atoms, and diamines having the structures shown below, but are not limited to these. Alternatively, these two or more diamine components can be used in combination.

[0028] [Chemistry 2]

[0029] [Chemistry 3]

[0030] Y1 and Y2 in general formulas (1) and (2) may also contain aromatic diamine residues other than those described above. By copolymerizing these, heat resistance can be improved. Specific examples of diamine residues containing aromatic compounds include: 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, petroleum ether (benzine), m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxyphenyl) sulfide, bis(3-aminophenoxyphenyl) sulfide, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy) Aromatic diamines such as phenyl ethers, 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, or compounds in which a portion of the hydrogen atom of the aromatic ring or hydrocarbon is substituted by an alkyl or fluoroalkyl group having 1 to 10 carbon atoms, or a halogen atom, etc., but not limited to these. Other diamines for copolymerization can be used directly or as corresponding diisocyanate compounds, trimethylsilylated diamines. Alternatively, these two or more diamine components can be used in combination.

[0031] (A) The molar ratios of the structures represented by general formulas (1) and (2) in the composition can be calculated based on the molar ratios of the monomers used during polymerization. Alternatively, if the molar ratios of the structures are determined from the obtained resin, resin composition, or hardened film, they can be confirmed by using nuclear magnetic resonance (NMR) to detect the peak values ​​of the polyamide structure, the amide precursor structure, and the amide structure.

[0032] The component (A), whose molecular chain ends are derived from carboxylic acid residues, such as in the case of polyimides, can be obtained by increasing the content of acid anhydride relative to the diamine used during polymerization. Another method for obtaining the component (A), whose molecular chain ends are derived from carboxylic acid residues, is by adding a specific compound generally used as an end-sealing agent during polymerization; specifically, adding a compound selected from acid anhydrides, monocarboxylic acids, monochlorodimethylamine compounds, and monoreactive ester compounds.

[0033] Furthermore, by using carboxylic acids or anhydrides having hydroxyl, carboxyl, sulfonic acid, thiol, vinyl, ethynyl, or allyl groups as end-sealing agents to seal the molecular chain ends of component (A), the dissolution rate of component (A) in alkaline aqueous solutions or the mechanical properties of the resulting hardened film can be easily adjusted to a better range. Additionally, various end-sealing agents can be reacted to introduce a variety of different end groups.

[0034] Among the preferred end-sealing agents, acid anhydrides, monocarboxylic acids, monochlorodiphenyl compounds, and monoactive ester compounds are phthalic anhydride, maleic anhydride, terephthalic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc.; 3-carboxyphenol, 4-carboxyphenol, 3-carboxybenzylthiophenol, 4-carboxybenzylthiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzyl... Monochloro compounds obtained by chlorohydrinating monocarboxylic acids such as sulfonic acid and 4-carboxybenzenesulfonic acid, and their carboxyl groups; monochloro compounds obtained by chlorohydrinating 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; and active ester compounds obtained by reacting monochloro compounds with N-hydroxybenzotriazole or imidazole, or N-hydroxy-5-norbornene-2,3-dicarboxypropylimide. Two or more of these compounds may also be used.

[0035] The molecular chain ends of component (A) to which the end-sealing agent is incorporated have structures derived from carboxylic acid residues. Furthermore, the end-sealing agent incorporated into component (A) can be easily detected by the following methods. For example, component (A) to which the end-sealing agent is incorporated is dissolved in an acidic solution, decomposing into amine and anhydride components as constituent units. These components are then determined using gas chromatography (GC) or NMR, thereby easily detecting the end-sealing agent used in this invention. Alternatively, the resin components to which the end-sealing agent is incorporated can also be easily detected by directly measuring them using pyrolysis gas chromatograph (PGC) or infrared spectroscopy and 13C-NMR.

[0036] In this invention, component (A) is synthesized, for example, by the following methods, but is not limited thereto. For example, when component (A) is polyimide, the polyimide precursor is obtained by the following methods: a method of reacting tetracarboxylic dianhydride, a diamine compound, and a monoamine at low temperature; a method of reacting tetracarboxylic dianhydride, a dicarboxylic anhydride, and a diamine compound at low temperature; a method of obtaining a diester by reacting tetracarboxylic dianhydride with an alcohol, and then reacting it in the presence of a diamine, a monoamine, and a condensing agent, etc. Then, polyimide can be synthesized using a known amide reaction method. In the case of introducing an end-sealing agent, a portion of the diamine is replaced with a primary monoamine as the end-sealing agent, or a portion of the tetracarboxylic dianhydride is replaced with a dicarboxylic anhydride as the end-sealing agent, to perform the synthesis.

[0037] The (A) component is preferably polymerized using the method described above, then added to a large amount of water or a mixture of methanol and water, allowing it to precipitate, followed by filtration, separation, and drying. The drying temperature is preferably 40°C to 100°C, more preferably 50°C to 80°C. This operation removes unreacted monomers, dimers, trimers, or other oligomers, improving the properties of the thermosetting membrane.

[0038] When component (A) is polyimide, the amide ratio can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (around 1780 cm⁻¹ and 1377 cm⁻¹) caused by the polyimide structure. Second, the polymer is heat-treated at 350°C for 1 hour, and the resulting sample with a amide ratio of 100% is used as a sample. The infrared absorption spectrum is also measured similarly. The peak intensity around 1377 cm⁻¹ of the polymer before and after heat treatment is compared to calculate the amide group content in the polymer before heat treatment, and the amide ratio is determined. In terms of suppressing the change in the ring-closure rate during thermosetting and obtaining a low-stress effect, the amide ratio is preferably 50% or more, and more preferably 80% or more.

[0039] When the total content of the resin composition of the present invention is set to 100% by mass, the total content of component (A) is preferably 15% to 60% by mass, more preferably 25% to 50% by mass. Including 15% or more of component (A) in 100% by mass of the total resin composition improves mechanical and thermal properties, which is therefore preferable. Including 60% or less of component (A) reduces developing residue, which is also preferable. Here, "total resin composition" refers to the total of all components constituting the resin composition except for the solvent.

[0040] <(B) Ingredients> The resin composition of the present invention contains a cationic polymerizable compound as component (B). Importantly, 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 monovalent or polyvalent phenols (phenol, bisphenol A, phenolic varnishes, and compounds of their epoxide adducts) having at least one aromatic ring.

[0043] Examples of alicyclic epoxide compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate).

[0044] Examples of aliphatic epoxides include: polyglycidyl ethers of aliphatic polyols or epoxide adducts (such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether), polyglycidyl ethers of aliphatic polyacids (such as tetrahydrophthalic acid diglycidyl ester), and epoxides of long-chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

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

[0046] [Chemistry 4]

[0047] In general formula (3), R5 is a monovalent organic group. Preferably, the monovalent organic group is selected from groups having oxygen atoms, such as hydrogen atoms, hydrocarbon groups, hydroxyl groups, alkoxy groups, and hydrocarbon groups with ether bonds. Examples of hydrocarbon groups include alkyl groups with 1 or more carbon atoms and 8 or fewer, alkenyl groups with 2 or more carbon atoms and 8 or fewer, and aryl groups with 6 or more carbon atoms and 30 or fewer. Examples of alkoxy groups include alkoxy groups with 1 or more carbon atoms and 8 or fewer, and glycidyl groups. Examples of hydrocarbon groups with ether bonds include groups with ether bonds inserted into the carbon chain of the cyclohydrogen group.

[0048] [Chemistry 5]

[0049] In general formula (4), x, y, and z are independent integers from 1 to 6.

[0050] By including an epoxy compound represented by general formula (3) or general formula (4) in component (B1), the compatibility with component (A) is improved, fine pattern processing is obtained, and the heat resistance and chemical resistance of the hardened film are improved, which is therefore better.

[0051] Examples of epoxy compounds represented by general formula (3) include SHOFREE PETG (trade name, manufactured by Showa Denko). Examples of epoxy compounds represented by general formula (4) include TEPIC-VL (trade name, manufactured by Nissan Chemical).

[0052] As component (B2), a known oxetane compound may be used. For example, 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl(3-ethyl-3-oxetane-butylmethyl) ether, 2-hydroxyethyl(3-ethyl-3-oxetane-butylmethyl) ether, 2-hydroxypropyl(3-ethyl-3-oxetane-butylmethyl) ether, 1,4-bi[(3-ethyl-3-oxetane-butylmethoxy)methyl]benzene, oxetane-butyl sesquioxane, and phenolic varnish oxetane, etc.

[0053] (B2) The preferred component is an oxetane compound having two or more oxetane groups per molecule, more preferably having two or more but six or fewer oxetane groups per molecule. Having two or more oxetane groups improves hardening properties, thus it is preferred. Having six or fewer oxetane groups suppresses cracking during pattern processing, thus it is preferred. Examples of such oxetane compounds include: OXT-121, OXT-221 (both trade names, manufactured by Toa Gosei), ETERNACOLL OXBP, and ETERNACOLL OXIPA (both trade names, manufactured by UBE).

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

[0055] [Chemistry 6]

[0056] In general formula (5), m is an integer from 1 to 6, and R1 and R2 are monovalent organic groups. As a preferred example of a monovalent organic group, an organic group that is the same as the organic group described in R5 can be listed.

[0057] [Chemistry 7]

[0058] In general formula (6), n is an integer from 1 to 6, and R3 and R4 are monovalent organic groups. As a preferred example of a monovalent organic group, an organic group that is the same as the organic group described in R5 can be listed.

[0059] By including an oxetane compound represented by general formula (5) in component (B2), the adhesion to the substrate can be improved and peeling during development can be suppressed, which is better. Examples of such oxetane compounds include OXT-121 (trade name, manufactured by Toa Synthetic Co., Ltd.).

[0060] By including an oxetane compound represented by general formula (6) in component (B2), the adhesion to the substrate can be improved, peeling during development can be suppressed, and the heat resistance of the hardened film can be improved, which is therefore better. Examples of such oxetane compounds include ETERNACOLL OXBP (trade name, manufactured by UBE Corporation).

[0061] Regarding the content of component (B2), when the total amount of component (B1) is set to 100 parts by mass, the total amount of component (B2) is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass. A total amount of component (B2) of 10 parts by mass or more improves cationic polymerization, which can suppress distortion or peeling during pattern processing, and is therefore preferred. A total amount of 200 parts by mass or less improves the resolution during pattern processing, and is therefore preferred.

[0062] Here, FIG1 is used to explain the distortion during pattern processing. FIG1 is a schematic cross-sectional view showing the distortion of pattern 1 of resin composition obtained by laminating resin composition on substrate 2 and developing the resin composition. The distortion during pattern processing refers to the phenomenon that, relative to the pattern that should be formed perpendicularly, the pattern 1 of the resin composition is formed at an angle inclined from the vertical, as shown in FIG1. ​​Here, in particular, the state in which the distortion of the pattern occurs is defined as the state in which the angle α formed by the perpendicular line drawn from the intersection point A of substrate 2 and pattern 1 in FIG1 relative to substrate 2 and the straight line connecting the intersection point A and the upper angle B of pattern 1 is 10° to 90°. That is, in the resin composition of the present invention, by satisfying the condition of the content of component (B2), the angle α in FIG1 can be less than 10°.

[0063] Furthermore, the resin composition of the present invention may contain cationic polymeric compounds other than the (B1) component and the (B2) component. Examples of cationic polymeric compounds other than the (B1) component and the (B2) component include vinyl unsaturated compounds (vinyl ethers and styrene derivatives, etc.), bicyclic orthoesters, spirocyclic orthocarbonates, and spirocyclic orthoesters.

[0064] As an ethylene-unsaturated compound, known cationic polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationic polymerizable nitrogen-containing monomers.

[0065] Examples of aliphatic monovinyl ethers 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 multifunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0068] Examples of styrene-based products include: styrene, α-methylbenzyl ethylene, p-methoxystyrene, and p-tert-butoxystyrene.

[0069] Examples of cationic polymerizable nitrogen-containing monomers include N-vinylcarbazole and N-vinylpyrrolidone.

[0070] Examples of bicyclic 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 spirocyclic 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 spirocyclic 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 set to 100 parts by mass, the total amount of component (B) other than components (B1) and (B2) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. By making the total amount of component (B) other than components (B1) and (B2) 10 parts by mass or less, the cationic polymerization property is improved, which can suppress distortion or peeling during pattern processing, and is therefore preferable.

[0074] Regarding the content of component (B), when the total amount of component (A) is set to 100 parts by mass, the total amount of component (B) is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass. By making the total amount of component (B) 50 parts by mass or more, cationic polymerization is improved, which can suppress distortion or peeling during pattern processing, and therefore is preferred. By making it 200 parts by mass or less, the resolution during pattern processing is improved, and therefore is preferred.

[0075] <(C) Ingredients> The resin composition of the present invention contains a photocationic polymerization initiator as component (C). Component (C) generates an acid by means of light, causing the cationic polymerizable compound to undergo cationic polymerization. As component (C), a compound known as a photocationic polymerization initiator can be used, preferably an onium salt.

[0076] Regarding component (C), examples include aromatic iodonium salts, aromatic strontium salts, aromatic borate salts, and aromatic gallic acid salts. Specific examples of aromatic iodonium salts include diphenyliodonium tetra(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate. These photocationic polymerization initiators can be used alone or in combination of two or more.

[0077] When the total amount of component (A) is set to 100 parts by mass, the content of component (C) 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. This allows the cationic polymeric compound to exhibit sufficient curability, improving pattern processing properties. On the other hand, regarding improving the storage stability of the resin composition before curing, when the total amount of component (A) is set to 100 parts by mass, the content of component (C) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less.

[0078] <Other Ingredients> The resin composition of the present invention may also contain a sensitizer. The sensitizer is a compound that absorbs light and provides the absorbed light energy to component (C), generating an acid and undergoing cationic polymerization. Furthermore, since the sensitizer absorbs light of the irradiation wavelength during patterning, it can reduce the transmittance of the resin composition film formed from the resin composition. Therefore, the transmittance of the resin composition film can be arbitrarily controlled by adjusting the content of the sensitizer in the resin composition.

[0079] The sensitizer is not particularly limited, but anthracene compounds are preferred, and more preferably anthracene compounds having alkoxy groups at positions 9 and 10 (9,10-dialkoxy-anthracene derivatives). Examples of alkoxy groups include C1-C4 alkoxy groups such as methoxy, ethoxy, and propoxy. The 9,10-dialkoxy-anthracene derivative may further have substituents. Examples of substituents in the 9,10-dialkoxy-anthracene derivative include halogen atoms such as fluorine, chlorine, bromine, and iodine, C1-C4 alkyl or sulfonic acid alkyl ester groups such as methyl, ethyl, and propyl, and carboxylic acid alkyl ester groups. Examples of alkyl groups in sulfonic acid alkyl esters or carboxylic acid alkyl esters include C1-C4 alkyl groups such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably at position 2.

[0080] There is no particular limitation on the content of the sensitizer, but when the total mass of the resin composition is set to 100% by mass, it is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. This reduces the transmittance of the resin composition film, suppressing reflected light from the substrate surface even on rough substrates such as ceramics, making the processing of fine patterns easier. On the other hand, regarding suppressing the reduction of the mechanical and thermal properties of the cured film of the resin composition film formed from the resin composition, when the total mass of the resin composition is set to 100% by mass, the content of the sensitizer is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0081] The resin composition of the present invention may contain a thermal crosslinking agent. Preferably, the thermal crosslinking agent is a compound having alkoxymethyl or hydroxymethyl components.

[0082] Examples of compounds having alkoxymethyl or hydroxymethyl groups 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, TM L-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 (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC (registered trademark) MX-280, NIKALAC (registered trademark) MW-100LM, NIKALAC (registered trademark) MX-750LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0083] The resin composition of the present invention may contain more silane compounds. By containing silane compounds, the adhesion of the obtained heat-resistant resin film is improved. Specific examples of silane compounds 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-styrenetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, etc.

[0084] Furthermore, the resin composition of the present invention may also contain surfactants, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane, as needed to improve spreadability with the support. Additionally, to suppress the coefficient of thermal expansion and to achieve high or low dielectric constants, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder, may be included.

[0085] <Resin composition coating, resin composition film> The shape of the resin composition of the present invention before curing is not limited; for example, it can be in the form of varnish or film.

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

[0087] When the resin composition of the present invention is in the form of a film, it is sometimes referred to as a resin composition film in the present invention. The resin composition film of the present invention comprises the resin composition film of the present invention and a support. That is, the resin composition film of the present invention is a film obtained by forming the resin composition film of the present invention on a support.

[0088] In terms of the ease with which a thick film layer can be formed when the resin composition film of the present invention is used to manufacture the semiconductor device having the hardened film of the present invention (described later), a thickness of 40 μm or more is preferred. Furthermore, in terms of suppressing film thickness deviations, a thickness of 70 μm or less is preferred.

[0089] Next, a method for preparing a resin composition film using the varnish-like resin composition of the present invention will be described. The resin composition film of the present invention is obtained by coating a solution of the resin composition of the present invention (hereinafter referred to as resin composition varnish) onto a support, and then drying it as needed. The resin composition varnish is obtained by adding an organic solvent to the resin composition. Any organic solvent used herein can be used to dissolve the resin composition.

[0090] As organic solvents, specific examples include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other ethers; 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, butyl lactate, and other acetate esters; acetone, methyl ethyl ketone, acetone, and so on. Ketones such as methylpropyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, and 2-heptanone; alcohols such as butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene. In addition, examples include: N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and γ-butyrolactone.

[0091] Alternatively, filter paper or a filter can be used to filter the resin-based varnish. There are no particular limitations on the filtration method, but it is preferable to use a filter with a particle size retention of 0.4 μm to 10 μm and to perform filtration by pressure.

[0092] The support used in the resin composition film of the present invention is not particularly limited, and various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. To improve adhesion and peelability, a surface treatment with silicone, silane coupling agent, aluminum chelating agent, polyurea, etc., can be performed at the interface between the support and the resin composition film. Furthermore, the thickness of the support is not particularly limited, but from a workability perspective, a range of 10 μm to 100 μm is preferred.

[0093] Furthermore, to protect the surface, the resin composition film of the present invention may also have a protective film on the resin composition film. This protects the surface of the photosensitive resin composition film from contaminants such as dust or dirt in the atmosphere. Examples of protective films include polyolefin films and polyester films. Preferably, the protective film has low adhesion to the resin composition film.

[0094] Methods for applying resin-based varnishes to a support include: spin coating using a rotary device, spray coating, roller coating, screen printing, doctor blade coating, die coating, burnishing coating, meniscus coating, bar coating, roller coating, corner roller coating, gravure coating, screen coating, and slot die coating. Furthermore, the coating thickness varies depending on the coating method, the concentration of solid components in the composition, and the viscosity, but preferably, the dried film thickness is 0.5 μm or more and 100 μm or less.

[0095] Drying can be performed using ovens, heating plates, infrared radiation, etc. The drying temperature and time should be within a range that allows the organic solvent to evaporate; preferably, they should be appropriately set to a range where the resin film is in an uncured or semi-cured state. Specifically, it is preferable to perform drying within the range of 40°C to 120°C for 1 minute to several tens of minutes. Alternatively, these temperatures can be combined and increased in stages; for example, heat treatment can be performed at 70°C, 80°C, and 90°C for 1 minute each.

[0096] <Curved films, semiconductor devices, inductors> Next, examples will be given to illustrate the resin composition varnish of the present invention, or the method of patterning using the resin composition film thereof.

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

[0098] When using a resin-based varnish, the resin-based varnish is first applied to a substrate. Examples of application methods include spin coating, spray coating, roller coating, and screen printing. The coating thickness varies depending on the application method, the concentration and viscosity of the solid components in the resin, but it is preferable to apply the varnish with a dried film thickness of 0.5 μm to 100 μm. Next, the substrate coated with the resin-based varnish is dried to obtain a substrate with a resin-based film. Drying can be performed using an oven, a heated plate, or infrared radiation. The drying temperature and time should be within a range that allows the organic solvent to evaporate; preferably, they should be set appropriately to allow the resin-based film to reach an uncured or semi-cured state. Specifically, it is preferable to perform the drying at a temperature between 50°C and 150°C for 1 minute to several hours.

[0099] On the other hand, when using a resin composition film with a protective film, the protective film is peeled off, and the resin composition film in the resin composition film is brought face to face with the substrate. This is then bonded by hot pressing, thereby obtaining a substrate with a resin composition film formed on it. Hot pressing can be performed by hot pressing, hot lamination, or hot vacuum lamination. Regarding the adhesion and embedding properties of the substrate, a bonding temperature of 40°C or higher is preferred. Furthermore, to prevent the resin composition film from hardening during bonding and to prevent a decrease in pattern resolution during exposure and development steps, a bonding temperature of 150°C or lower is preferred. After hot pressing, a support can be peeled off from the resin composition film as needed.

[0100] In any case, the substrate used may include, but is not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and materials on which circuits are disposed. Examples of organic circuit boards include: glass-based copper foil laminates such as glass cloth-epoxy copper foil laminates; composite copper foil laminates such as glass nonwoven fabric-epoxy copper foil laminates; heat-resistant / thermoplastic substrates such as polyetherimide resin substrates, polyetherketone resin substrates, and polyurethane resin substrates; and flexible substrates such as polyester copper foil film substrates and polyimide copper foil 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 substrates and iron substrates. Examples of materials used to construct circuits include: conductors containing metals such as silver, gold, and copper; resistive materials containing inorganic oxides; low-dielectric materials containing glass-based materials and / or resins; high-dielectric materials containing resins or inorganic particles with high dielectric constants; and insulators containing glass-based materials.

[0101] Next, the resin composition film formed by the method is exposed to photochemical rays by irradiating it with a mask having a desired pattern. The photochemical rays used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In this invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp are preferred. When the support in the resin composition film is a transparent material relative to these rays, exposure can be performed without peeling the support from the resin composition film.

[0102] To form a pattern, the exposed portions of the resin composition film are removed using a developer after exposure. Preferably, the developer is an aqueous solution of a compound exhibiting alkalinity, 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, or hexamethylenediamine. In addition, depending on the circumstances, 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; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, or a combination of the above.

[0103] Development can be performed by spraying the developing solution onto the surface of the resin composition film, filling the surface of the resin composition film with the developing solution, immersing the resin composition film in the developing solution, or immersing and applying ultrasound. The developing conditions, such as the developing time or developing steps and the temperature of the developing solution, are only required to remove the exposed areas and form a pattern.

[0104] After development, rinsing with water is preferred. Alternatively, alcohols such as ethanol and isopropanol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate, can be added to the water for rinsing.

[0105] Alternatively, the resin composition film can be baked before development, if necessary. This can sometimes improve the resolution of the developed pattern and increase the allowable range of development conditions. The baking temperature is preferably in the range of 50°C to 180°C, and more particularly preferably in the range of 60°C to 120°C. The baking time is preferably from 5 seconds to several hours.

[0106] After patterning, unreacted cationic polymeric compounds and cationic polymerization initiators remain in the resin composition film. Therefore, during hot pressing or curing, these can sometimes thermally decompose and generate gases. To avoid this, it is preferable to irradiate the entire surface of the patterned resin composition film with the exposure light, causing the unreacted photocationic polymerization initiators to generate acid. In this way, during hot pressing or curing, the reaction of the unreacted cationic polymeric compounds proceeds, suppressing the generation of gases originating from thermal decomposition.

[0107] After development, a temperature of 150°C to 500°C is applied to initiate a thermal crosslinking reaction, thereby obtaining a hardened film. This step is referred to as curing. The obtained hardened film, through crosslinking, exhibits improved heat resistance and chemical resistance. The heat treatment method can be selected from two options: a method of gradually increasing the temperature by selecting a specific temperature, or a method of continuously increasing the temperature within a selected temperature range for 5 minutes to 5 hours. An example of the former is a method of heat treatment at 130°C and 200°C for 30 minutes each. An example of the latter is a method of linearly increasing the temperature from room temperature to 400°C over 2 hours.

[0108] The curing film of the present invention is a curing film formed by curing the resin composition of the present invention or the resin composition film of the present invention. The curing film formed by curing the resin composition of the present invention or the resin composition film of the present invention can be used in electronic components such as semiconductor devices.

[0109] When the hardened film of the present invention is used to manufacture a semiconductor device having the hardened film of the present invention, it is preferable that a thicker insulating layer can be formed and the wiring density can be increased. The thickness is preferably 40 μm or more, and more preferably 80 μm or more. In terms of reducing the warpage of the semiconductor device caused by film stress, the thickness is preferably 300 μm or less, and more preferably 200 μm or less.

[0110] The semiconductor device of the present invention is a semiconductor device having the curing film of the present invention. Here, a semiconductor device refers to an entire device that can function by utilizing the characteristics of semiconductor elements. Electro-optical devices or multilayer semiconductor circuit boards formed by connecting semiconductor elements to a substrate, devices formed by multiple semiconductor elements, and electronic devices including these are all included in a semiconductor device. In addition, electronic components such as multilayer wiring boards for connecting semiconductor elements are also included in the semiconductor device. In semiconductors. Specifically, the curing film of the present invention is preferably used as an insulating film for inductors, a semiconductor passivation film, a surface protective film for semiconductor elements, an interlayer insulating film between semiconductor elements and wiring, an interlayer insulating film between multiple semiconductor elements, an interlayer insulating film between wiring layers for high-density mounting multilayer wiring, an insulating layer for organic electroluminescent elements, etc., but is not limited thereto, and can be used for various applications.

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

[0112] An insulating film 4 is provided to maintain the insulation between the inductor 3 and the coil 5 in Figure 2. Preferably, the insulating film 4 is a hardened film formed by curing the resin composition of the present invention. By using a hardened film formed 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, thus increasing the cross-sectional area of ​​the wiring of the coil 5 and thereby improving the inductance.

[0113] Furthermore, regarding the increase in the cross-sectional area of ​​the coil 5, the thickness T of the insulating film 4, which uses a hardened film formed by curing the resin composition of the present invention, is preferably 40 μm or more, and more preferably 80 μm or more. Regarding the reduction in film stress, the thickness T is preferably 300 μm or less, and more preferably 200 μm or less.

[0114] Furthermore, in terms of increasing the wiring density of coil 5, the aspect ratio of the insulating film 4, which uses a hardened film formed by curing the resin composition of the present invention, is preferably 4 or more, and more preferably 8 or more. In order to maintain insulation, the aspect ratio of the insulating film 4 is preferably 30 or less, and more preferably 20 or less. Moreover, the aspect ratio mentioned here is calculated by the following formula (1). Formula (1) (Aspect Ratio) = T (film thickness) / W (pattern width).

[0115] In the inductor 3, an insulating film 4, which is a hardened film formed by curing the resin composition of the present invention, and a coil 5 are formed on the top and bottom of a substrate 7. Preferably, a resin layer 6 is further provided between the insulating film 4 and the substrate 7. By having the resin layer 6, the adhesion of the insulating film 4 to the substrate is improved, which is therefore preferable.

[0116] Furthermore, resin layer 6 preferably comprises at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide, and polybenzoxazole. The content of said polymeric compound in resin layer 6 is preferably 1% to 45% by mass, more preferably 20% to 40% by mass. A content of 1% or more by mass improves heat resistance, which is preferred; a content of 45% or less by mass improves the adhesion of the insulating film 4 to the substrate, which is also preferred.

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

[0118] The present invention will now be described in detail based on specific embodiments, but the present invention is not limited thereto.

[0119] <Evaluation of Pattern Processability> A 5 cm square silicon wafer was used as the substrate. The protective film of the resin composition film prepared in each embodiment and comparative example was peeled off, and the resin composition film was deposited on the substrate in such a way that the resin composition film was in contact with the substrate. The film was then heat-laminated using a vacuum film laminator (manufactured by Meiki Seisakusho, MVLP-500 / 600) under the conditions of a hot plate temperature of 80°C, a vacuum suction time of 20 seconds, a vacuum pressing time of 30 seconds, and a bonding pressure of 0.5 MPa. After the support was peeled off from the resin composition film, a resin composition film with a thickness of 45 μm was formed on the silicon substrate.

[0120] By performing the same steps again on the resin composition film obtained in the manner described, a resin composition film with a total thickness of 90 μm is deposited on a silicon substrate.

[0121] Subsequently, a mask with a linewidth / spacewidth pattern 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 on the exposure apparatus. With an exposure gap of 100 μm between the mask and the photosensitive resin film, exposure was performed using an ultra-high pressure mercury lamp equipped with an I-ray bandpass filter at an exposure dose of 1500 mJ / cm² (I-ray conversion). After exposure, the film was heated at 90°C for 10 minutes. Then, the unexposed areas of the resin film were removed by immersion development using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Finally, the film was rinsed with water. The development time was set to twice the time required for complete dissolution of the unexposed areas.

[0122] The pattern obtained in this manner is observed using an optical microscope, and the minimum linewidth at which no impurities such as residue are present in the pattern is taken as the resolution. Furthermore, the aspect ratio is calculated from the minimum linewidth using the aforementioned formula (1). Additionally, if no pattern is resolved, the resolution is 0 (defective).

[0123] <Evaluation of Glass Transfer Temperature> Except for changing the substrate from a silicon wafer to a copper foil with a planar size of 10 cm × 10 cm (CF-T9DA-SV-1, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), a resin composition film was formed on the copper foil, similar to the method for evaluating pattern processability. Then, exposure was performed using an ultra-high pressure mercury lamp at an exposure dose of 1000 mJ / cm² (i-ray conversion, full wavelength exposure). After exposure, the foil was heated at 120°C for 10 minutes using a heating plate. Then, using an inert oven (manufactured by Thermo Systems Co., Ltd., INL-60), under a N₂ atmosphere (oxygen concentration below 20 ppm), the temperature was increased from room temperature to 200°C over 60 minutes, and then heat-treated at 200°C for 60 minutes to obtain a hardened film with a resin composition film formed on the copper foil. Then, the copper foil was dissolved only with a ferric chloride solution, washed with water, and air-dried to obtain the hardened resin composition film.

[0124] The obtained hardened film was cut into test pieces with dimensions of 5 mm × 40 mm. The dynamic viscoelasticity test device DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) was used to measure the strain at the following conditions: clamp spacing of 20 mm, frequency of 1 Hz, temperature range of room temperature to 350℃, heating rate of 5℃ / min, and strain of 0.1%. The peak temperature of tanδ = storage elastic coefficient / loss elastic coefficient, which is the ratio of storage elastic coefficient to loss elastic coefficient, was taken as the glass transfer temperature.

[0125] Evaluation of Tensile Strength and Elongation The same procedure as for evaluating the glass transition temperature was followed to obtain a hardened film of the resin composition. The obtained hardened film was cut into 10 mm × 80 mm test pieces and subjected to tensile testing using a universal testing machine AG-Xplus (manufactured by Shimadzu Corporation) at room temperature, with a clamping distance of 50 mm and a tensile speed of 50 mm / min. Tensile strength (stress at break) and elongation at break (elongation at break) were measured. Ten test pieces were performed for each specimen, and the average of the first five results was calculated.

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

[0127] Synthesis Example 1: Synthesis of a diamine compound (a) containing a phenolic hydroxyl group 2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) (18.3 g, 0.05 moles) was dissolved in 100 mL of acetone and propylene oxide (17.4 g, 0.3 moles), and the solution was cooled to -15°C. A solution of 3-nitrobenzoyl chloride (20.4 g, 0.11 moles) dissolved in 100 mL of acetone was then added dropwise. After the addition was complete, the reaction was carried out at -15°C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50°C.

[0128] The obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methylceroxex. 2 g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. The reaction was considered complete after approximately 2 hours, when the balloon was confirmed to have stopped shrinking. After the reaction, the palladium compound acting as a catalyst was removed by filtration. The filtrate was concentrated using a rotary evaporator to obtain a hydroxyl-containing diamine compound (a) as shown in the following formula. The obtained solid was used directly in the reaction.

[0129] [Chemistry 8]

[0130] Synthesis Example 2: Synthesis of Polyimide (A-1) Under a dry nitrogen stream, BAHF (29.30 g, 0.08 moles) was added to 80 g of γ-butyrolactone (GBL), and the mixture was stirred and dissolved at 120 °C. Next, 30.03 g (0.1 moles) of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride (TDA-100) was added together with 20 g of GBL, and the mixture was stirred at 120 °C for 1 hour, followed by stirring at 200 °C for 4 hours to obtain a reaction solution. The reaction solution was then added to 3 L of water to collect a white precipitate. The 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 Polyamide Imide (A-2) Under a dry nitrogen stream, a hydroxyl-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 stirred at 120 °C for 1 hour, followed by stirring at 200 °C for 4 hours to obtain a reaction solution. The reaction solution was then added to 3 L of water to collect a white precipitate. The 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 component (A), 5.6 g of PETG (trade name, manufactured by Showa Denko) and 3.7 g of BATG (trade name, manufactured by Showa Denko) as components (B1), 0.7 g of OXT-101 (trade name, manufactured by Toa Gosei) as component (B2), 0.3 g of CPI-310FG (trade name, manufactured by Sanapro) as component (C), 0.2 g of UVS-1331 (trade name, manufactured by Kawasaki Chemical Industry) as a sensitizer, and 0.4 g of KBM-403 (trade name, manufactured by Shin-Etsu Chemical Industry) as a silane compound were dissolved in GBL. Additives other than the solvent were designated as solid components, and the amount of GBL added as the solvent was adjusted to a solid component concentration of 60% by weight. The obtained solution was pressure filtered using a filter that retains a particle size of 1 μm to obtain a resin composition varnish with negative photosensitive properties.

[0133] The obtained resin composition varnish was applied to a 50 μm thick PET film using a corner-cut roller coater and dried at 120°C for 8 minutes to obtain a resin composition film with the resin composition formed on the PET film. The thickness of the resin composition film was adjusted to 45 μm. Then, a 30 μm thick PP film was laminated on the resin composition film as a protective film. Using the obtained resin composition film, pattern processing properties, glass transfer temperature, and tensile strength-elongation were evaluated as described above. The results are shown in Table 2.

[0134] Examples 2 to 15 Except for changing components (A) to (C) and other components to the compounds described below, and changing their mixing as described in Table 1, resin composition films were prepared in the same manner as in Example 1, and the patterning processability, glass transition temperature, and tensile strength-elongation were evaluated as described above. The results are shown in Table 2.

[0135] Comparative Examples 1 to 3 Except for changing components (A) to (C) and other components to the compounds described below, and changing their mixtures as described in Table 1, resin composition films were prepared in the same manner as in Example 1, and the patterning processability was evaluated as described above. The results are shown in Table 2.

[0136] [Table 1-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 (A)Ingredients (parts by weight) A-1 100 - 100 100 100 100 100 100 100 A-2 - 100 - - - - - - - (B) Element (parts by weight) (B1) Element (parts by weight) B1-1 56 56 18 40 40 40 48 30 20 B1-2 37 37 12 26 26 26 32 20 13 B1-3 - - - - - - - - - B1-4 - - - - - - - - - (B2) Element (parts by weight) B2-1 7 7 70 33 - - - - - B2-2 - - - - 33 - - - - B2-3 - - - - - 33 20 50 17 B2-4 - - - - - - - - - (C) Components (parts by weight) C-1 3 3 3 3 3 3 3 3 3 sensitizer (parts by weight) UVS-2171 2 2 2 2 2 2 2 2 2 silane compounds (parts by weight) KBM-403 4 4 4 4 4 4 4 4 4 (B2) Total content of ingredients (parts by weight) 7.6 7.6 233 50 50 50 25 100 50 (B) Total content of components (parts by weight) 100 100 100 99 99 99 100 100 50

[0137] [Table 1-2] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative example 1 Comparative example 2 Comparative example 3 (A)Ingredients (parts by weight) A-1 100 100 100 100 100 100 - 100 100 A-2 - - - - - - - - - (B) Element (parts by weight) (B1) Element (parts by weight) B1-1 48 30 48 - 40 - 30 - 67 B1-2 32 20 32 - 26 - 20 - 33 B1-3 - - - 50 - 50 - - - B1-4 - - - - - - 50 - - (B2) Element (parts by weight) B2-1 - - - - - - 100 - - B2-2 - - - - - - - - - B2-3 80 25 40 50 - - - 100 - B2-4 - - - 33 50 - - - (C) Components (parts by weight) C-1 3 3 3 3 3 3 3 3 3 sensitizer (parts by weight) UVS-2171 2 2 2 2 2 2 2 2 2 silane compounds (parts by weight) KBM-403 4 4 4 4 4 4 4 4 4 (B2) Total content of ingredients (parts by weight) 50 50 50 100 50 100 100 - - (B) Total content of components (parts by weight) 160 75 120 100 100 100 - 100 100

[0138] [Table 2-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 pattern Processability Resolution (μm) 10 10 10 8 7 5 6 6 10 Aspect Ratio 9 9 9 11.3 12.9 18 15 15 9 Thermo / Mechanical characteristic Glass transfer temperature (°C) 260 230 225 250 242 240 245 237 248 Tensile strength (MPa) 85 80 80 85 85 90 85 90 75 Elongation (%) 6 8 6 6 7 8 7 8 7

[0139] [Table 2-2] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Comparative example 1 Comparative example 2 Comparative example 3 pattern Processability Resolution (μm) 8 6 6 7 7 7 10 0 15 Aspect Ratio 11.3 15 15 12.9 12.9 12.9 9 0 6 Thermo / Mechanical characteristic Glass transfer temperature (°C) 238 242 238 220 245 225 160 215 263 Tensile strength (MPa) 75 85 85 80 85 80 60 80 90 Elongation (%) 6 7 8 8 7 8 4 6 6

[0140] The "Total content (parts by mass) of component (B2)" listed in Table 1 represents the total mass of component (B2) when the total of component (B1) is set to 100 parts by mass. Conversely, the "Total content (parts by mass) of component (B)" represents the total mass of component (B) when the total of component (A) is set to 100 parts by mass.

[0141] As clearly shown in Tables 1 and 2, the glass transfer temperature and tensile strength of the hardened film in Comparative Example 1, which does not contain component (A), are worse than those of the Example. In Comparative Example 2, which does not contain component (B1), spots appear in the pattern, making pattern processing impossible. In Comparative Example 3, which does not contain component (B2), if the pattern becomes fine, distortion or peeling occurs, making high aspect ratio pattern processing impossible.

[0142] In contrast, the resin composition of this embodiment exhibits sufficient thermal properties (glass transition temperature) and mechanical properties (tensile strength, elongation at break) to form patterns with a high aspect ratio.

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

[0144] (A) Polymers A-1: Polyimide A-2: Polyamide imide.

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

[0146] (B2) Oxybutane compounds B2-1: OXT-101 (manufactured by Dong-A Synthetic Co., Ltd.), a compound containing an oxocyclic butyl group. B2-2: OXT-221 (manufactured by Dong-A Synthetic Co., Ltd.), a compound containing two oxocyclic butyl groups. B2-3: OXT-121 (manufactured by Dong-A Synthetic Co., Ltd.), a compound having two oxocyclic butyl groups and represented by general formula (5). B2-4: ETERNACOLL OXBP (manufactured by UBE) is a compound having two oxocyclic butyl groups and represented by general formula (6).

[0147] (C) Cationic polymerization initiator C-1: CPI-310FG (Onium salt-based photoacid generator, manufactured by Sanapro (stock)) sensitizer UVS-2171 (Anthracene compound, manufactured by Kawasaki Chemical Industries, Ltd.) silane compounds KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industries, Ltd.)

[0148] 1: Pattern of resin composition 2: Substrate 3: Inductor 4: Insulating film 5: Coil 6: Resin layer 7:Substrate 8: Insulating film 9: Magnetic materials 10: Molding resin A: Intersection α: Angle B: Angle T: Thickness / Film Thickness W: Pattern width

Claims

1. A resin composition comprising: at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide, and polybenzoxazole as component (A); a cationic polymerizable compound as component (B); and a photocationic polymerization initiator as component (C), wherein component (B) comprises both an epoxy compound as component (B1) and an oxobutane compound as component (B2), component (C) is an onium salt-based photoacid generator, and the resin composition is a negative photosensitive resin composition.

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

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

4. The resin composition as claimed in claim 1, wherein the (B2) component contains an oxobutane compound represented by general formula (5) or general formula (6), in general formula (5) m is an integer from 1 to 6, and R1 and R2 are monovalent organic groups, in general formula (6) n is an integer from 1 to 6, and R3 and R4 are monovalent organic groups.

5. The resin composition as claimed in claim 1, wherein the (B1) component contains an epoxy compound represented by general formula (4), in which x, y, and z are each an independent integer from 1 to 6.

6. The resin composition as claimed in claim 1, wherein when the total of component (A) is set to 100 parts by mass, the total of component (B) is 50 to 200 parts by mass.

7. A resin composition comprising: at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide, and polybenzoxazole as component (A); a cationic polymerizable compound as component (B); and a photocationic polymerization initiator as component (C), wherein component (B) comprises both an epoxy compound as component (B1) and an oxobutane compound as component (B2), wherein component (B1) comprises an epoxy compound represented by general formula (3), and the resin composition is a negative photosensitive resin composition, wherein in general formula (3), R5 is a monovalent organic group.

8. A resin composition film having a resin composition coating and a support, wherein the resin composition coating comprises the resin composition as claimed in claim 1.

9. A semiconductor device having a hardened film formed by hardening a resin composition as described in claim 1.

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

11. The semiconductor device of claim 9, wherein the semiconductor device is an inductor having an insulating film and a coil, and a hardened film formed by curing the resin composition is used as the insulating film of the inductor.

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

13. The semiconductor device of claim 12, wherein the resin layer comprises at least one polymeric compound selected from the group consisting of polyamide, polyimide, polyamide-imide and polybenzoxazole, wherein the content of the polymeric compound in the resin layer is 1% to 45% by mass.

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