Resin composition, cured product and method for manufacturing the same, semiconductor device and display device

Abstract

To provide a resin composition which achieves both photosensitivity capable of achieving a high contrast and crack resistance after curing.SOLUTION: A resin composition contains a resin A having an amic acid and / or imide bond repeating structural unit, and a crosslinking agent having two or more crosslinkable groups, wherein the resin A contains 10 mol% or more and 90 mol% or less of the repeating structural unit including a structure represented by formula (3), and satisfies at least one of (requirement 1) the resin composition further contains a photosensitive agent, and (requirement 2) the resin has a photosensitive group. In the formula (3), R6 to R9 are H or organic groups, and R10 and R11 each independently represents an alkylene group having 1 to 6 carbon atoms. n represents an integer of 1 to 10. * represents a chemical bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product thereof, and a method for producing the same, and more particularly to a photosensitive resin composition suitable for use as a surface protective film for semiconductor elements and the like, an interlayer insulating film, an insulating layer for organic electroluminescent elements, and the like, a cured product thereof, and a method for producing the same. [Background technology]

[0002] Polyimide resins and polybenzoxazole resins, which have excellent heat resistance and electrical insulation properties, have traditionally been widely used for surface protection films and interlayer insulating films in semiconductor elements, insulating layers in organic electrolytic elements, and planarizing films for thin-film transistor (TFT) substrates. Furthermore, insulating films with photosensitivity have also been investigated to improve productivity. These photosensitive resin compositions are classified into two types: positive-type materials and negative-type materials, depending on the pattern formation method. The former, positive-type, is a method in which a pattern is obtained by making the exposed area soluble in a developer, while the latter, negative-type, is a method in which a pattern is obtained by making the exposed area insoluble in a developer. Positive-type photosensitive resin compositions containing a naphthoquinone diazide compound in a polyimide precursor or polybenzoxazole precursor as an alkali-soluble resin (Patent Documents 1 and 2), negative-type photosensitive polyimide-based materials such as an "ester type" in which a polyamic acid ester having an ethylenically unsaturated group is used as the base polymer, and an "ionic type" in which a polyamic acid having an ethylenically unsaturated bond via an ionic bond (Patent Documents 3 and 4) have been proposed.

[0003] In positive-tone resin compositions, the solubility in alkaline solution (developer) is reduced in unexposed areas due to the interaction between the phenolic hydroxyl groups in the resin and the naphthoquinone diazide compound, while the solubility in alkaline solution is significantly increased in exposed areas due to the naphthoquinone diazide compound generating an acid upon exposure. This difference in solubility in alkaline solution between the unexposed and exposed areas makes it possible to create positive-tone relief patterns. However, these compositions suffer from significant film loss during development, a small difference in film loss between the exposed and unexposed areas, i.e., low contrast, and are significantly affected by the environment during use, making them difficult to use industrially.

[0004] Furthermore, when the resin composition is used in semiconductors and the like, the film formed after heat curing remains as a permanent film inside the device, and therefore it is necessary that cracks and peeling do not occur during reliability tests such as thermal cycling tests. To address these issues, photosensitive polyimides incorporating a flexible aliphatic skeleton (Patent Document 5) and photosensitive polyimides with a linear thermal expansion coefficient close to that of the substrate (Patent Document 6) have been proposed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-91343 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-116715 [Patent Document 3] Japanese Patent Application Publication No. 51-40922 [Patent Document 4] Japanese Patent Application Publication No. 54-145794 [Patent Document 5] International Publication No. 2017 / 188153 [Patent Document 6] Japanese Patent Application Laid-Open No. 2011-053315 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the above-mentioned patent documents, it is difficult to achieve both crack resistance and contrast during a thermal cycle test in a semiconductor device. Therefore, an object of the present invention is to achieve both photosensitivity that can achieve high contrast and crack resistance after curing. [Means for solving the problem]

[0007] The present invention and its preferred embodiments include the following configurations. [1] A resin composition comprising a resin A having a repeating structural unit represented by formula (1) and / or a repeating structural unit represented by formula (2), and a crosslinking agent having two or more crosslinkable groups, wherein the resin A contains 10 mol % to 90 mol % of repeating structural units including a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A, and further satisfies at least one of the following requirements: (Requirement 1) the resin composition further contains a photosensitizer; and (Requirement 2) the resin A has a photosensitive group.

[0008] [ka]

[0009] In formula (1) and formula (2), X 1 represents a divalent to hexavalent organic group having 4 to 40 carbon atoms, and Y 1 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. 2 represents a tetravalent to hexavalent organic group having 4 to 40 carbon atoms, and Y 2 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. 1 ~R 5 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. p, r, s, and t each independently represent an integer of 0 to 2. p + r represents an integer of 1 to 4. s + t represents an integer of 1 to 4. q represents an integer of 0 to 2. * represents a chemical bond. In formula (3), R 6 ~R 9each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms; R 10 and R 11 each independently represents an alkylene group having 1 to 6 carbon atoms, n represents an integer of 1 to 10, and * represents a chemical bond. [2] The resin composition according to [1], wherein the resin A contains more than 20 mol% and not more than 90 mol% of repeating structural units having a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A. [3] The resin composition according to [1] or [2], wherein the resin A contains 30 mol % or more and 90 mol % or less of repeating structural units having a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A. [4] (Requirement 1) The resin composition according to any one of [1] to [3], which satisfies that the resin composition further contains a photosensitizer, and the photosensitizer is a naphthoquinone diazide compound. [5] (Requirement 2) The resin composition according to any one of [1] to [4], wherein the resin A has a photosensitive group, and the photosensitive group is a naphthoquinone diazide group. [6] R contained in the formula (1) 1 and R 3 and R contained in the formula (2) 4 and R 5 The resin composition according to [5], wherein at least one of the above is a group represented by formula (5).

[0010] [ka]

[0011] In formula (5), * represents a chemical bond. [7] The resin composition according to any one of [1] to [4], which satisfies (requirement 1) that the resin composition further contains a photosensitizer, and does not satisfy (requirement 2) that the resin A has a photosensitive group. [8] The resin composition according to [7], wherein the resin A contains 20 mol % or more and 90 mol % or less of repeating structural units having a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A. [9] The resin composition according to [7] or [8], wherein the resin A contains 30 mol% to 90 mol% of repeating structural units having a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A.

[10] The resin composition according to any one of [7] to [9], wherein the photosensitizer is a naphthoquinone diazide compound.

[11] The resin composition according to any one of [1] to

[10] , wherein the crosslinkable group is an epoxy group.

[12] The resin composition according to any one of [1] to

[11] , wherein the crosslinking agent contains a compound represented by formula (4).

[0012] [ka]

[0013] In formula (4), L 1 each independently represents an alkylene group having 1 to 8 carbon atoms.

[13] The resin composition according to any one of [1] to

[12] , wherein the content of the crosslinking agent relative to 100 parts by mass of the resin A is 10 parts by mass or more and 150 parts by mass or less.

[14] The resin composition according to any one of [1] to

[13] , which is used for forming an insulating layer in hybrid bonding between semiconductor chips, for forming an insulating layer in hybrid bonding between a semiconductor chip and a substrate, or for forming an insulating layer in hybrid bonding between substrates.

[15] A cured product obtained by curing the resin composition according to any one of [1] to

[14] .

[16] A method for producing a cured product, comprising the steps of: forming a resin film from the resin composition according to any one of [1] to

[14] ; irradiating the resin film with actinic radiation; developing a pattern from the resin film irradiated with actinic radiation; and heating the resin film with the developed pattern to form a relief pattern layer.

[17] A semiconductor device comprising the cured product according to

[15] .

[18] A display device comprising the cured product according to

[15] . [Effects of the Invention]

[0014] According to the present invention, it is possible to obtain a resin composition that has both photosensitivity capable of realizing high contrast and crack resistance after curing. Furthermore, the electronic component or semiconductor device of the present invention has high reliability. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a schematic cross-sectional view showing an enlarged cross section of a pad portion of a semiconductor device having bumps; [Figure 2] 1A to 1C are schematic cross-sectional views showing a manufacturing process of a semiconductor device having bumps. [Figure 3] FIG. 1 is a schematic cross-sectional view of a semiconductor device having a fan-out wafer-level package structure. [Figure 4] FIG. 2 is a schematic cross-sectional view of a coil component of the inductor device. [Figure 5] FIG. 1 is a schematic cross-sectional view of a laminate manufactured by a wafer-to-wafer process. [Figure 6] FIG. 1 is a schematic cross-sectional view of a stack manufactured by a chip-to-wafer process. [Figure 7] FIG. 1 is a schematic cross-sectional view of an organic EL display having a planarizing layer and an insulating layer. DETAILED DESCRIPTION OF THE INVENTION

[0016] <Resin composition> The following describes in detail the embodiments of the present invention. The resin composition and the cured product of the resin composition of the present invention are described below. However, the present invention is not limited to the following embodiments, and various modifications are possible as long as the object of the invention can be achieved and the gist of the invention is not deviated from.

[0017] The resin composition of the present invention has the structure described in [1] above. This structure allows the resin composition of the present invention to achieve both photosensitivity capable of achieving high contrast and crack resistance after curing. This is believed to be due to the fact that the inclusion of a resin containing a specific ratio of repeating units including the specific structure represented by formula (3) in the resin composition improves the mechanical properties, such as flexibility and toughness, of the cured product obtained by curing the resin composition. Additionally, the specific structure represented by formula (3) in the resin contributes to improved adhesion to the base substrate and metal wiring, improving conformability to the base substrate and metal wiring, which is believed to contribute to the high crack resistance in thermal cycle tests. Furthermore, the specific structure represented by formula (3) in the resin interacts with photosensitizers, such as naphthoquinone diazide compounds, in the resin composition and photosensitive groups, such as naphthoquinone diazide groups, in the resin, resulting in a significant difference in solubility between exposed and unexposed areas, which is believed to contribute to the high contrast effect.

[0018] <Resin A> The resin composition of the present invention contains a resin A having a repeating structural unit represented by formula (1) and / or a repeating structural unit represented by formula (2).

[0019] [ka]

[0020] In formula (1) and formula (2), X 1 represents a divalent to hexavalent organic group having 4 to 40 carbon atoms, and Y 1 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. 2 represents a tetravalent to hexavalent organic group having 4 to 40 carbon atoms, and Y 2 represents a divalent to tetravalent organic group having 4 to 40 carbon atoms.1 ~R 5 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. p, r, s, and t each independently represent an integer of 0 to 2. p + r represents an integer of 1 to 4. s + t represents an integer of 1 to 4. q represents an integer of 0 to 2. * represents a chemical bond.

[0021] The resin A contains 10 mol % or more and 90 mol % or less of repeating structural units containing a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A.

[0022] [ka]

[0023] In formula (3), R 6 ~R 9 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms; R 10 and R 11 each independently represents an alkylene group having 1 to 6 carbon atoms, n represents an integer of 1 to 10, and * represents a chemical bond.

[0024] In formula (3), R 6 ~R 9 When R is an alkyl group having 1 to 4 carbon atoms, it is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. 6 ~R 9is a phenyl group or an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with an alkyl group having 1 to 4 carbon atoms is more preferred, and an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group is substituted with a methyl group or an ethyl group is even more preferred. In formula (3), n is preferably 7 or less, more preferably 5 or less, even more preferably 3 or less, and particularly preferably 2 or less.

[0025] Resin A can achieve water repellency and high contrast photosensitivity by containing 10 mol % or more, preferably 20 mol % or more, more preferably more than 20 mol %, even more preferably 30 mol % or more, and particularly preferably 40 mol % or more of repeating structural units having the structure represented by formula (3) relative to 100 mol % of all repeating structural units in resin A. Furthermore, solubility in an alkaline aqueous solution can be maintained by having the content of repeating structural units having the structure represented by formula (3) be 90 mol % or less, preferably 70 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less relative to 100 mol % of all repeating structural units in resin A.

[0026] When the resin composition of the present invention satisfies (Requirement 2) that the resin A has a photosensitive group, the resin A preferably contains more than 20 mol % and not more than 90 mol %, and more preferably 30 mol % or more and not more than 90 mol %, of repeating structural units containing a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A.

[0027] When the photosensitive group contained in the resin A is a naphthoquinone diazide group described below, from the viewpoint of improving the photosensitive contrast and improving the crack resistance after curing, the resin A preferably contains more than 20 mol % and not more than 90 mol %, and more preferably 30 mol % or more and not more than 90 mol %, of repeating structural units containing a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A.

[0028] When the resin composition of the present invention satisfies (Requirement 1) that the resin composition further contains a photosensitizer, the resin A preferably contains 20 mol % or more and 90 mol % or less, and more preferably 30 mol % or more and 90 mol % or less, of repeating structural units including a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A.

[0029] When the photosensitizer contained in the resin composition is a naphthoquinone diazide compound described below, from the viewpoint of improving the photosensitive contrast and improving the crack resistance after curing, the resin A preferably contains 20 mol % or more and 90 mol % or less of repeating structural units containing a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A, and more preferably 30 mol % or more and 90 mol % or less.

[0030] Examples of the structure represented by formula (3) include residues of diamines such as LP-7100, KF-8010, KF-8012, and X22-161A (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0031] As the resin A, for example, one or more selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof are preferred in terms of excellent film physical properties, and from the viewpoints of visible light transmittance, exposure sensitivity, and chemical resistance, the resin A is more preferably one or more selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof.

[0032] The resin A is preferably alkali-soluble, meaning that the dissolution rate determined from the reduction in film thickness when a solution of the resin in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with pure water is 50 nm / min or more.

[0033] The resin A can be synthesized by a known method. When the resin A is a polyimide precursor, examples of the production method include a method of reacting a tetracarboxylic dianhydride with a diamine compound at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine compound at low temperature and then partially esterifying the amide acid structure with N,N-dimethylformamide dimethyl acetal or the like, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine compound in the presence of a condensing agent, or a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine compound. When the resin A is a polyimide, it can be obtained, for example, by dehydrating and ring-closing the polyimide precursor obtained by the above-mentioned method in a solvent or by chemical treatment with an acid or base.

[0034] When the resin A is a polybenzoxazole precursor, it can be produced, for example, by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid. For example, a dehydration condensation agent can be reacted with an acid and then the bisaminophenol compound can be added, or a solution of dicarboxylic acid dichloride can be added dropwise to a solution of a bisaminophenol compound to which a tertiary amine has been added. Examples of dehydration condensation agents include dicyclohexylcarbodiimide (DCC). Examples of tertiary amines include pyridine. When the resin A is a polybenzoxazole, it can be produced, for example, by dehydrating and cyclizing the polybenzoxazole precursor obtained by the above-mentioned method by heating it in a solvent or by chemical treatment with an acid or base.

[0035] Examples of the resin A include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof. 1 Or OR in formula (2) 3 In order to obtain a compound having the formula (I), it is preferable to synthesize the compound using a compound having a phenolic hydroxyl group. Examples of the compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and compounds in which at least a portion of the hydrogen atoms in the aromatic ring of these compounds are substituted with alkyl groups or halogen atoms.

[0036] Examples of the tetracarboxylic dianhydride used in the polyimide, the polyimide precursor, and the copolymer thereof include pyromellitic dianhydride, 3,3'-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)propanhydride, and 2,2-bis(2,3-dicarboxyphenyl)propanhydride. Examples of the dianhydride include aromatic tetracarboxylic acid dianhydrides such as 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)ether dianhydride, and 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Two or more of these may be used.

[0037] Examples of dicarboxylic acids used in the polybenzoxazole, the polybenzoxazole precursor, and copolymers thereof include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, and 2,2',3,3'-benzophenone tetracarboxylic acid. ,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and the like. Two or more of these may be used.

[0038] Examples of the diamine component used in the polyimide, the polyimide precursor, and the copolymer thereof include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Examples of suitable aromatic compounds include, but are not limited to, diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings have been substituted with alkyl groups or halogen atoms, as well as aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the structures shown below. Two or more of these compounds may be used.

[0039] Examples of bisaminophenol compounds used in the polybenzoxazole, polybenzoxazole precursor, and copolymers thereof include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and compounds in which at least a portion of the hydrogen atoms in the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms. Two or more of these compounds may be used.

[0040] The ends of these resins can be capped with a terminal capping agent, such as an acid anhydride, an acid chloride, a monocarboxylic acid, or a monoamine.

[0041] The content of the end-capping agent is preferably 2 to 25 mol % relative to 100 mol % of the total of the acid and amine components that constitute the resin.

[0042] <Crosslinking agent> The resin composition of the present invention contains a crosslinking agent having two or more crosslinkable groups. The crosslinking agent refers to a compound having at least two heat-reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. In other words, the crosslinkable group is preferably an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. The crosslinking agent crosslinks the resins themselves and between the resins and other additives, thereby improving the heat resistance, chemical resistance, hardness, and density of the film after thermal curing, and further contributing to improved crack resistance.

[0043] The number of crosslinkable groups possessed by the crosslinking agent is 2 or more, and from the viewpoint of improving the heat resistance, chemical resistance, hardness, density, and crack resistance of the film after thermal curing, the number is preferably 3 or more, and more preferably 4 or more, whereas from the viewpoint of improving the crack resistance after thermal curing, the number of crosslinkable groups possessed by the crosslinking agent is preferably 10 or less.

[0044] Among the crosslinking agents, preferred examples of commercially available products having an alkoxymethyl group or a methylol group as the crosslinkable group include DML-PC, DML-PEP, DML-OC, DML-OEP, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0045] The crosslinking agent preferably has an epoxy group, from the viewpoint of improving the heat resistance of the cured product of the resin composition and being able to react without dehydration. From the same viewpoint, the crosslinking group of the crosslinking agent is preferably an epoxy group.

[0046] Furthermore, it is more preferable that the crosslinking agent contains a compound represented by formula (4), since this can more effectively improve crack resistance in addition to the above-mentioned advantage of having an epoxy group.

[0047] [ka]

[0048] In formula (4), L 1 each independently represents an alkylene group having 1 to 8 carbon atoms.

[0049] Preferred commercially available crosslinking agents containing the compound represented by formula (4) include TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.) and TEPIC-FL (trade name, manufactured by Nissan Chemical Industries, Ltd.).

[0050] The crosslinking agent preferably has two or more types of crosslinkable groups. Preferred embodiments having two or more types of crosslinkable groups are shown below. The crosslinking agent preferably has an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group as the crosslinkable group, and also preferably has another crosslinkable group, more preferably has an alkoxymethyl group, a methylol group, or an epoxy group, and also has an oxetanyl group, and even more preferably has an alkoxymethyl group or a methylol group, and also has an epoxy group.

[0051] The content of the crosslinking agent is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the resin A. On the other hand, the content of the crosslinking agent is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the resin A.

[0052] The content of the crosslinking agent is preferably 10 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the resin A. When the content of the crosslinking agent is 10 parts by mass or more per 100 parts by mass of the resin A, it is possible to effectively improve crack resistance after heat treatment. Furthermore, when the content of the crosslinking agent is 150 parts by mass or less per 100 parts by mass of the resin A, it is possible to suppress fluidity during thermal curing.

[0053] <Photosensitive agent and photosensitive group in resin A> The resin composition of the present invention further satisfies at least one of the following requirements: (Requirement 1) the resin composition further contains a photosensitizer; and (Requirement 2) the resin A has a photosensitive group. By satisfying at least one of these requirements, resolution, sensitivity, and film retention rate are further improved.

[0054] Furthermore, from the viewpoint of achieving high contrast, it is also preferable that the resin composition satisfy (Requirement 1) that the resin composition further contains a photosensitizer, but not (Requirement 2) that the resin A has a photosensitive group. This is because, since the resin composition contains a photosensitizer, it is not necessary to introduce a photosensitive group into the resin A, thereby increasing the design freedom of the resin A. In addition, the chemical structure of the photosensitizer in the resin composition can be selected from the viewpoints of compatibility with the resin A, sensitivity, and the like. This is thought to contribute to improving contrast. In particular, when the resin composition contains a naphthoquinone diazide compound as a photosensitizer and the resin A does not have a naphthoquinone diazide group as a photosensitive group, it is possible to select a chemical structure of the resin A that is suitable for compatibility with the naphthoquinone diazide compound, and therefore the above effect is presumably more pronounced.

[0055] Furthermore, from the viewpoint of improving crack resistance, it is also preferable that the resin composition not satisfy (Requirement 1) that the resin composition further contains a photosensitizer, but satisfy (Requirement 2) that the resin A has a photosensitive group. This is because, since the resin A has a photosensitive group, a photosensitizer is not essential for imparting photosensitivity to the resin composition, and the total amount of additives in the resin composition can be reduced. Therefore, there is less residue of the additive after thermal curing, which is thought to contribute to improving crack resistance. In particular, when the resin A has a naphthoquinone diazide group as the photosensitive group and the resin composition does not contain a naphthoquinone diazide compound as the photosensitizer, the remaining structure derived from the compound having a phenolic hydroxyl group in the naphthoquinone diazide compound is reduced, and the above effect is presumably more pronounced.

[0056] The photosensitizer is a compound that imparts positive or negative photosensitivity to a resin composition by undergoing bond cleavage, reaction, or structural change due to light or radiation to generate another compound. Examples of the photosensitizer include photopolymerization initiators and photoacid generators. Examples of the photopolymerization initiator include compounds that generate radicals, cations, or anions upon exposure to light, and examples of the photoacid generator include naphthoquinone diazide compounds, sulfonium salt compounds, and iodonium salt compounds. Among the photosensitizers, naphthoquinone diazide compounds are particularly preferred.

[0057] The photosensitive group is a group that imparts positive or negative photosensitivity to the resin composition by bond cleavage, reaction, or structural change due to light or radiation. Examples of the photosensitive group include a polymerizable group and a photoacid-generating group. The polymerizable group is a group containing an unsaturated bond such as a double bond or triple bond, typified by a vinyl group, an allyl group, a maleimide group, a (meth)acryloyl group, or a styrene group. The photoacid-generating group is a group that generates acid upon light irradiation, typified by a naphthoquinone diazide group. Among the photosensitive groups, a naphthoquinone diazide group is particularly preferred.

[0058] <Naphthoquinonediazide Compound and Naphthoquinonediazide Group in Resin A> When the resin composition of the present invention satisfies (Requirement 1) that the resin composition further contains a photosensitizer, the photosensitizer is preferably a naphthoquinone diazide compound.

[0059] The resin composition of the present invention preferably satisfies (Requirement 1) that the resin composition further contains a photosensitizer, and does not satisfy (Requirement 2) that the resin A has a photosensitive group. Even when the resin composition of the present invention has this aspect, the photosensitizer is preferably a naphthoquinone diazide compound.

[0060] When the resin composition contains a naphthoquinone diazide compound, the naphthoquinone diazide compound is preferably a sulfonic acid ester of a compound having a phenolic hydroxyl group, which has a naphthoquinone diazide group. The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method.

[0061] As the naphthoquinone diazide group, either a 5-naphthoquinone diazide group or a 4-naphthoquinone diazide group is preferably used. The 5-naphthoquinone diazide group has absorption extending into the g-line region of a mercury lamp, making it suitable for g-line exposure and full-wavelength exposure. The 4-naphthoquinone diazide group has absorption in the i-line region of a mercury lamp, making it suitable for i-line exposure. In the present invention, it is preferable to select either a 4-naphthoquinone diazide group or a 5-naphthoquinone diazide group depending on the exposure wavelength. Furthermore, it is also possible to obtain a naphthoquinone diazide compound containing both a 4-naphthoquinone diazide group and a 5-naphthoquinone diazide group in the same molecule, or to use a 4-naphthoquinone diazide compound and a 5-naphthoquinone diazide compound in combination.

[0062] Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, and DML -MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML -PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP Preferred examples include compounds such as 4-naphthoquinone diazide sulfone groups or 5-naphthoquinone diazide sulfone groups introduced via an ester bond into compounds such as 46DMOC, 46DMOEP, and TM-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), but other compounds can also be used.

[0063] Furthermore, it is preferable that 50 mol% or more of the phenolic hydroxyl groups in the compound having a phenolic hydroxyl group are substituted with naphthoquinone diazide groups. Using a naphthoquinone diazide compound in which 50 mol% or more of the phenolic hydroxyl groups are substituted reduces the affinity of the naphthoquinone diazide compound to an alkaline aqueous solution, significantly reducing the solubility of the unexposed portion of the resin composition in an alkaline aqueous solution. Furthermore, exposure converts the naphthoquinone diazide sulfonyl group to an indene carboxylic acid structure or an indene sulfonic acid structure, resulting in a high dissolution rate of the exposed portion of the resin composition in an alkaline aqueous solution. As a result, the dissolution rate ratio between the exposed and unexposed portions of the composition is increased, resulting in a pattern with high resolution. Using such a naphthoquinone diazide compound, a positive-tone photosensitive resin composition sensitive to the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a typical mercury lamp can be obtained.

[0064] The molecular weight of the naphthoquinone diazide compound is preferably 300 or more, more preferably 350 or more, from the viewpoints of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment. On the other hand, the molecular weight of the naphthoquinone diazide compound is preferably 3,000 or less, more preferably 1,500 or less, from the viewpoints of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment.

[0065] When the resin composition of the present invention satisfies (Requirement 2) that the resin A has a photosensitive group, the photosensitive group is preferably a naphthoquinone diazide group.

[0066] The resin composition of the present invention preferably satisfies (Requirement 2) that the resin A has a photosensitive group, and does not satisfy (Requirement 1) that the resin composition further contains a photosensitizer. Even when the resin composition of the present invention has this embodiment, the photosensitive group is preferably a naphthoquinone diazide group.

[0067] The resin composition of the present invention satisfies (Requirement 2) that the resin A has a photosensitive group, and the photosensitive group is a naphthoquinone diazide group, and R 1 and R 3 and R contained in the formula (2) 4 and R 5 Among these, an embodiment in which at least one is a group represented by formula (5) is preferred in that it leaves fewer residues of additives after thermal curing and contributes to improving crack resistance.

[0068] [ka]

[0069] In formula (5), * represents a chemical bond.

[0070] When the resin A has a naphthoquinone diazide group as a photosensitive group, a preferred example is one in which a hydroxy group or a phenolic hydroxyl group in the resin is modified and a sulfonate ester bond of the naphthoquinone diazide group is introduced.

[0071] As the naphthoquinone diazide group, either a 5-naphthoquinone diazide group or a 4-naphthoquinone diazide group is preferably used. Examples and preferred descriptions of the naphthoquinone diazide group contained in the resin A are the same as the examples and preferred descriptions of the naphthoquinone diazide group in the naphthoquinone diazide compound contained in the resin composition.

[0072] When the resin composition contains a naphthoquinone diazide compound, the content of the naphthoquinone diazide compound is, from the viewpoint of more effectively imparting photosensitivity, preferably 1 part by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the resin A. Furthermore, from the viewpoint of effectively maintaining the crack resistance of the film after heat treatment, the content of the naphthoquinone diazide compound is, from the viewpoint of more effectively maintaining the crack resistance of the film after heat treatment, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, relative to 100 parts by mass of the resin A.

[0073] When the resin A contains naphthoquinone diazide groups, the content of the naphthoquinone diazide groups is preferably 1 mol % or more, and more preferably 10 mol % or more, relative to 100 mol % of the hydroxyl groups contained in the resin A, from the viewpoint of more effectively imparting photosensitivity. Furthermore, the content of the naphthoquinone diazide groups is preferably 100 mol % or less, relative to 100 mol % of the hydroxyl groups contained in the resin A, from the viewpoint of more effectively imparting photosensitivity.

[0074] The naphthoquinone diazide compounds and / or resins having naphthoquinone diazide groups may be used alone or in combination of two or more.

[0075] <Adhesion improver> The photosensitive resin composition of the present invention may contain an adhesion promoter as needed. By incorporating the adhesion promoter, the adhesion between the thermally cured film and metal materials, particularly copper, can be significantly improved, and peeling can be suppressed. Commercially available compounds can be used as the adhesion promoter, and compounds having an O atom, an S atom, or an N atom are preferred. Specific examples include, but are not limited to, silane compounds and silane coupling agents such as the KBM series from Shin-Etsu Silicones Co., Ltd.

[0076] <Surfactant> The resin composition of the present invention may optionally contain a surfactant to improve wettability with the substrate or to improve the thickness uniformity of the coating film. Commercially available surfactants can be used. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Toray Dow Corning Silicones, the BYK series from BYK Japan, the KP series from Shin-Etsu Silicones, the Disform series from NOF Corporation, and the TSF series from Toshiba Silicones. Fluorine-based surfactants include the Megafac® series from Dainippon Ink Mfg. Co., Ltd., the Fluorad series from Sumitomo 3M, the Surflon® series and Asahi Guard® series from Asahi Glass Co., Ltd., the EF series from Shin-Akita Chemical Co., Ltd., and the Polyfox series from Omnova Solutions. Examples of surfactants derived from acrylic and / or methacrylic polymers include, but are not limited to, the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon® series from Kusumoto Chemicals Co., Ltd.

[0077] The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less relative to 100 parts by mass of the resin A. By setting the content within the above range, it is possible to improve the wettability with the substrate and the thickness uniformity of the coating film without causing defects such as bubbles or pinholes.

[0078] <Other alkali-soluble resins> The resin composition of the present invention may contain other alkali-soluble resins in addition to Resin A. Specific examples include alkali-soluble polyimides, polybenzoxazoles, acrylic polymers copolymerized with acrylic acid, novolac resins, resol resins, polymers containing radically polymerizable monomers having alkali-soluble groups, siloxane resins, cyclic olefin resins, and resins having a cardo structure, i.e., a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. Such resins are soluble in alkaline solutions such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. The inclusion of these alkali-soluble resins allows the resin composition to maintain the adhesiveness and excellent sensitivity of the cured product while imparting the properties of each alkali-soluble resin.

[0079] <Solvent> The resin composition of the present invention preferably contains a solvent, such as polar aprotic solvents like N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide; ethers like tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones like acetone, methyl ethyl ketone, and diisobutyl ketone; esters like ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols like ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons like toluene and xylene. Two or more of these may be contained.

[0080] The content of the solvent is preferably 100 parts by mass or more relative to a total of 100 parts by mass of the resin A and the other resins in order to dissolve the composition, and is preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0081] The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa·s. By adjusting the solid content concentration so that the viscosity is 2 mPa·s or higher, it becomes easy to obtain a desired film thickness. On the other hand, if the viscosity is 5,000 mPa·s or lower, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by adjusting the solid content concentration to 5 to 60 mass%.

[0082] <Method of manufacturing resin composition> Next, a method for producing the resin composition of the present invention will be described. Methods for dissolving the components constituting the resin composition include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, typically from room temperature to 80°C. The order in which the components are dissolved is not particularly limited; for example, a method in which the components are dissolved in order starting with the least soluble compound is used. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the resin composition, typically from 200 rpm to 2,000 rpm. Heating may be performed as needed even when stirring, typically at a temperature between room temperature and 80°C. For components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion promoters, adding them last after dissolving the other components can prevent incomplete dissolution of the other components due to the generation of bubbles.

[0083] The obtained resin composition is preferably filtered using a filter to remove dust and particles. The pore size of the filter may be, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, or 0.02 μm, but is not limited to these. The material of the filter may be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE). Among these, polyethylene and nylon are preferred.

[0084] <Cured product> The cured product of the present invention is obtained by curing the resin composition of the present invention. More specifically, the cured product of the present invention can be obtained by thermally curing the resin composition of the present invention.

[0085] Preferred heating conditions for thermal curing are described below. The maximum heating temperature is preferably 140°C or higher and 280°C or lower. By setting the temperature at 140°C or higher, more preferably 160°C or higher, the thermal crosslinking reaction can proceed efficiently. Furthermore, since the resin composition of the present invention is particularly excellent in low-temperature curing properties, from the viewpoint of suppressing malfunctions associated with the thermal history of semiconductor devices described below and improving yield, the temperature is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 220°C or lower. This heat treatment may be carried out for 5 minutes to 5 hours while increasing the temperature stepwise or continuously. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each.

[0086] <Method of manufacturing the cured product> The method for producing a cured product of the present invention includes a step of forming a resin film from the resin composition of the present invention. Examples of methods for forming the resin film include a method of applying the resin composition to a substrate. Examples of substrates that can be used include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and substrates on which circuit components are arranged. Examples of application methods include spin coating, slit coating, dip coating, spray coating, and printing. The thickness of the film formed by application varies depending on the application technique, the solids concentration, and viscosity of the resin composition, but the composition is typically applied so that the film thickness after drying is 0.1 to 150 μm.

[0087] Prior to coating, the substrate may be pretreated with the adhesion promoter. For example, the surface of the substrate may be treated by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment, or the like using a solution prepared by dissolving the adhesion promoter in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass. If necessary, the substrate may be subjected to a reduced pressure drying treatment, followed by a heat treatment at 50°C to 280°C to promote the reaction between the substrate and the adhesion promoter.

[0088] The applied resin composition can then be dried to form a resin film, preferably at 50°C to 140°C for 1 minute to several hours using an oven, a hot plate, infrared rays, or the like.

[0089] The resin film formed on the substrate may be used as the cured product while still on the substrate, or the resin composition may be applied to a releasable substrate (support film), dried, and peeled off to form a resin sheet. The resin sheet may be placed opposite a substrate and bonded by thermocompression to form a cured product. Examples of the releasable substrate include a polyethylene terephthalate film. Thermocompression bonding can be performed by heat pressing, heat lamination, or heat vacuum lamination. The lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. When the resin sheet is photosensitive, the lamination temperature is preferably 140°C or lower to prevent the resin sheet from curing during lamination, which would reduce the resolution of the pattern formed in the exposure and development process.

[0090] The method for producing a cured product of the present invention includes a step of irradiating the resin film with actinic radiation. A mask having a desired pattern is placed on the resin film, and actinic radiation is irradiated through the mask. Examples of actinic radiation include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, ultraviolet light, particularly g-rays (436 nm), h-rays (405 nm), and i-rays (365 nm), which are common exposure wavelengths, are preferably used.

[0091] The method for producing a cured product of the present invention includes a step of developing a pattern from the resin film irradiated with actinic radiation. The developer used for development is preferably an aqueous solution of an alkaline compound such as tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. In some cases, these alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide; alcohols such as methanol, ethanol, or isopropanol; esters such as ethyl lactate or propylene glycol monomethyl ether acetate; or ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone.

[0092] After development, the film is generally rinsed with 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 the water for rinsing.

[0093] The method for producing a cured product of the present invention includes a step of heating a resin film on which a pattern has been developed to form a relief pattern layer. Heating promotes a thermal crosslinking reaction, thereby improving heat resistance and chemical resistance. The heating conditions for heating the resin film can be the same as those preferred for thermal curing described above.

[0094] <Electronic components; semiconductor devices> The electronic component of the present invention comprises the cured product of the present invention. Examples of electronic components include semiconductor devices and multilayer wiring boards. The semiconductor device of the present invention also comprises the cured product of the present invention. The cured product of the present invention can be suitably incorporated into electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the cured product of the present invention is suitable for applications such as semiconductor passivation films, protective films for semiconductor elements, and interlayer insulating films for high-density multilayer wiring. Examples of electronic devices having surface protective films or interlayer insulating films incorporating the cured product of the present invention include MRAMs with low heat resistance. In other words, the cured product of the present invention is suitable for use as a surface protective film for MRAM. In addition to MRAM, polymer memory (Polymer Ferroelectric RAM: PFRAM), phase change memory (Phase Change RAM: PCRAM), and Ovonics Unified Memory (OUM), which are promising next-generation memories, can also use materials with lower heat resistance than conventional memories. Therefore, the cured product of the present invention is also suitable for use as a surface protective film for these devices.

[0095] <Semiconductor device with bumps> A semiconductor device having bumps and including a cured product of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an enlarged cross section of a pad portion of a semiconductor device having bumps. As shown in FIG. 1, a passivation film 3 is formed on a silicon wafer 1 over aluminum (hereinafter, "Al") pads 2 for input / output, and via holes are formed in the passivation film 3. An insulating film 4 formed using the photosensitive resin composition or resin sheet of the present invention as an interlayer insulating film is formed on the passivation film 3. Furthermore, a metal film 5 formed from Cr, Ti, or the like is formed so as to be electrically connected to the Al pads 2. The metal film 5 is insulated from each pad by etching the periphery of solder bumps 10. An insulating film 7 formed using the resin composition or resin sheet of the present invention as an interlayer insulating film is formed on the insulating film 4 and metal wiring 6, and scribe lines 9 are formed in the insulating layer 4 and insulating layer 7. A barrier metal 8 and solder bumps 10 are formed on the insulated pads. When a soft component is added to the resin composition, wafer warpage is reduced, allowing for high-precision exposure and wafer transportation. Furthermore, polyimide and polybenzoxazole have excellent mechanical properties, which can alleviate stress from the encapsulating resin during mounting, preventing damage to the low-k layer and providing a highly reliable semiconductor device.

[0096] Next, a detailed method for manufacturing a semiconductor device having bumps using the cured product of the present invention will be described. FIG. 2 is a schematic cross-sectional view showing the manufacturing process for a semiconductor device having bumps. In step 2a of FIG. 2, a resin composition of the present invention is applied to a silicon wafer 1 on which Al pads 2 and a passivation film 3 have been formed, and a patterned insulating film 4 is formed through a photolithography process. Next, in step 2b of FIG. 2, a metal film 5 is formed by sputtering. Next, as shown in 2c of FIG. 2, metal wiring 6 is formed on the metal film 5 by plating. Next, as shown in 2d' of FIG. 2, a resin composition of the present invention is applied or a resin sheet is attached, and a photolithography process is performed to form an insulating film 7 in the pattern shown in 2d of FIG. 2. In this case, the resin composition of the present invention used to form the insulating film 7 can be processed into a thick film by photolithography in scribe lines 9. Note that additional wiring (so-called rewiring) can be formed on the insulating film 7. To form a multilayer wiring structure with two or more layers, the above process can be repeated to form a multilayer wiring structure in which two or more rewiring layers are separated by an interlayer insulating film obtained from the resin composition of the present invention. During this process, the formed insulating film will come into contact with various chemical solutions multiple times. However, the insulating film obtained from the resin composition of the present invention has excellent adhesion and chemical resistance, allowing for the formation of a satisfactory multilayer wiring structure. While there is no upper limit to the number of layers in a multilayer wiring structure, structures with 10 or fewer layers are often used. Next, as shown in Figures 2e and 2f, barrier metal 8 and solder bumps 10 are formed. The structure is then diced along scribe lines 9 to separate the semiconductor chips. If the insulating film 7 is not patterned along the scribe lines 9 or if residue remains, cracks or other defects may occur during dicing, affecting the reliability of the semiconductor chips.

[0097] Therefore, the ability to perform pattern processing that is excellent in thick film processing, as in the present invention, is very preferable for obtaining high reliability of semiconductor devices. Therefore, the resin composition of the present invention is suitably used for forming an interlayer insulating film for multilayer rewiring in semiconductor devices.

[0098] <Semiconductor device with fan-out wafer-level package structure> A semiconductor device having a fan-out wafer-level package structure and including the cured product of the present invention will be described with reference to the drawings. Fig. 3 is a schematic cross-sectional view of a semiconductor device having a fan-out wafer-level package structure. In detail, it is a schematic cross-sectional view showing an enlarged cross-section of a pad portion of a semiconductor device including the cured product of the present invention as an interlayer insulating film, and has a fan-out wafer-level package (fan-out WLP) structure.

[0099] Similar to the semiconductor device having bumps described above, a silicon wafer 1 on which Al pads 2 and a passivation film 3 are formed is diced and cut into individual semiconductor chips 1a. These are then repositioned on a temporary fixing layer (not shown) formed on a support and sealed with a sealing resin 11. The support and temporary fixing layer are then peeled away, and the sealing resin 11 with the semiconductor chips 1a is used as a pseudo-wafer. An insulating film 4 is formed as a pattern using the photosensitive resin composition of the present invention over the sealing resin 11 (the pseudo-wafer) and the semiconductor chips 1a. Furthermore, a metal film 5 (Cr, Ti, etc.) and metal wiring 6 (rewiring) are formed. Next, an insulating film 7 formed using the resin composition or resin sheet of the present invention as an interlayer insulating film is formed on the insulating film 4 and the metal wiring 6. The openings in the insulating film 7 are formed so as to overlap the sealing resin located outside the semiconductor chips 1a. Then, a barrier metal 8 and solder bumps 10 are formed in the openings in the insulating film 7. The fan-out WLP is an example of a semiconductor package structure in which an extension portion is provided around the semiconductor chip 1a using an encapsulating resin 11 such as epoxy resin, rewiring from the electrodes on the semiconductor chip 1a to the extension portion, and solder bumps are also formed in the extension portion to increase the number of input / output terminals and ensure the required number of terminals. In the fan-out WLP, wiring is formed so as to straddle the boundary between the main surface of the semiconductor chip 1a and the main surface of the encapsulating resin 11, which is flush with the main surface. That is, an interlayer insulating film is formed on a substrate made of two or more materials, namely, the semiconductor chip on which the metal wiring 6 as rewiring is formed and the encapsulating resin, and rewiring is also formed on the interlayer insulating film. In addition, in a semiconductor package structure in which the semiconductor chip 1a is embedded in a recess formed in a printed circuit board such as a glass epoxy resin board, wiring is formed so as to straddle the boundary between the main surface of the semiconductor chip 1a and the main surface of the printed circuit board, which is flush with the main surface of the semiconductor chip 1a. In this embodiment, an interlayer insulating film is formed on a substrate made of two or more materials, and rewiring is also formed on the interlayer insulating film.

[0100] The insulating film obtained from the resin composition of the present invention has high adhesion to a semiconductor chip 1a having metal wiring 6 formed thereon, and also to an encapsulating resin 11 such as an epoxy resin, and is therefore suitable for use as an interlayer insulating film provided on a substrate made of two or more materials. Therefore, the resin composition of the present invention is also suitable for use in forming an interlayer insulating film for multilayer rewiring in a semiconductor device having a fan-out wafer-level package structure.

[0101] <Coil components for inductor devices> A coil component of an inductor device including a cured product of the present invention will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view of the coil component of an inductor device. As shown in FIG. 4, an insulating film 13 is formed on a substrate 12, and a patterned insulating film 14 is formed thereon. Ferrite or the like is used as the substrate 12. The photosensitive resin composition of the present invention may be used to form either or both of the insulating films 13 and 14. A metal film 15 (Cr, Ti, etc.) is formed in the opening of the pattern of the insulating film 14, and metal wiring 16 (Ag, Cu, etc.) is formed on top of this by plating. The metal wiring 16 is formed in a spiral configuration. The process of forming the insulating film 13, insulating film 14, metal film 15, and metal film 16 can be repeated multiple times to form a stack, thereby providing the function of a coil. Finally, the metal wiring 16 (Ag, Cu, etc.) is electrically connected to electrodes 18 via metal wiring 17 (Ag, Cu, etc.) and sealed with sealing resin 19.

[0102] The insulating film obtained from the resin composition of the present invention has high adhesion to metal wiring and also to encapsulating resins, and therefore the resin composition of the present invention is also suitable for use in forming insulating films for coil components of inductor devices.

[0103] <Insulating layer in hybrid bonding> The insulating layer obtained from the resin composition of the present invention exhibits high adhesion to metal electrodes such as copper, maintains resin-to-resin bond strength after surface activation by plasma treatment, and exhibits excellent crack resistance after curing. Therefore, the resin composition of the present invention is also suitable for forming insulating layers in semiconductor devices using hybrid bonding techniques, in which metal electrodes and insulating layers are formed flush with each other without forming bumps, and the metal electrodes and insulating layers are directly bonded to each other. Hybrid bonding techniques include the wafer-to-wafer (W2W) process shown in FIG. 5, which bonds wafers together, the chip-to-wafer (C2W) process shown in FIG. 6, which bonds chips to wafers, and the chip-to-chip (C2C) process, which bonds chips together. The resin composition of the present invention is suitable for forming insulating layers in any of these processes.

[0104] A laminate bonded using the cured product of the present invention as an insulating layer in hybrid bonding will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view of a laminate produced by a W2W process. FIG. 6 is a schematic cross-sectional view of a laminate produced by a C2W process. In detail, FIGS. 5 and 6 are schematic cross-sectional views showing enlarged cross-sections of the bonded portion of a semiconductor device bonded using the cured product of the present invention as an insulating layer in hybrid bonding. The semiconductor device has a direct bonding structure between metal electrodes without using bumps and a direct bonding structure between insulating layers without using an adhesive layer.

[0105] The first substrate 27 is formed on a substrate body 21 (silicon wafer, semiconductor chip, etc.) so that the metal electrodes 22 (Cu, etc.) and the insulating layer 23 are flush with each other. The second substrate 28 is formed on a substrate body 26 (silicon wafer, etc.) so that the metal electrodes 25 (Cu, etc.) and the insulating layer 24 (resin layer or inorganic layer) are flush with each other. The metal electrodes 22 (Cu, etc.) and the metal electrodes 25 (Cu, etc.) are directly bonded together without using bumps, and the insulating layer 23 and the insulating layer 24 (resin layer or inorganic layer) are directly bonded together without using an adhesive layer. The bonding interfaces between the metal electrodes and the bonding interfaces between the insulating layers do not need to be clearly distinguished.

[0106] <Display device: Organic EL display> The display device of the present invention comprises the cured product of the present invention. The cured product of the present invention can also be used as an insulating layer in a display device including a first electrode formed on a substrate and a second electrode disposed opposite the first electrode, specifically, for example, a display device using an LCD (liquid crystal display), an ECD (electrochromic display), an ELD (inorganic electroluminescent display), an organic electroluminescent display, or an LED (light-emitting diode) display. In particular, in recent years, with the further miniaturization of the electrodes and multilayer wiring of semiconductor elements and the wiring of circuit boards, semiconductor devices having copper electrodes, copper wiring, and bumps have become mainstream. These devices are exposed to many chemical solutions, such as flux, during etching of copper or barrier metals and during resist pattern formation. The cured product of the present invention is particularly preferred when used as a protective film for such electrodes and wiring because it has high resistance to these chemical solutions.

[0107] An organic EL display having a planarization layer and an insulating layer and including the cured product of the present invention will be described with reference to the drawings. FIG. 7 is a schematic cross-sectional view of an organic EL display having a planarization layer and an insulating layer. Bottom-gate or top-gate TFTs 31 are arranged in a matrix on a substrate 36, and a TFT insulating film 33 is formed covering the TFTs 31. Metal wiring 32 connected to the TFTs 31 is also provided below the TFT insulating film 33. Contact holes 37 for opening the metal wiring 32 are provided on the TFT insulating film 33, and a planarization layer 34 is provided to fill these contact holes. The planarization layer 34 is patterned using the photosensitive resin composition of the present invention. Openings are provided in the planarization layer 34 so as to reach the contact holes 37 for the metal wiring 32. A transparent electrode made of indium tin oxide (hereinafter, "ITO") 35 is formed on the planarization layer 34 and connected to the metal wiring 32 via the contact holes 37. The ITO 35 is an electrode of a display element (e.g., an organic EL display). An insulating layer 38 is formed as a pattern using the photosensitive resin composition of the present invention so as to cover the periphery of the ITO 35. This organic EL display may be a top-emission type in which emitted light is emitted from the opposite side of the substrate 36, or a bottom-emission type in which light is extracted from the substrate 36 side. Planarizing layers and insulating layers obtained from the resin composition of the present invention have high adhesion to the metal wiring 32 and ITO 35, and excellent heat resistance and therefore low outgassing properties, making them suitable for use as TFT planarizing layers and pixel-dividing insulating layers. Therefore, the resin composition of the present invention is also suitable for use in forming TFT planarizing layers in organic EL displays, or for forming pixel-dividing insulating layers in organic EL displays. [Example]

[0108] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0109] [Compound abbreviation] The abbreviations and names of the compounds used are as follows: BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane SiDA: bis(3-aminopropyl)tetramethyldisiloxane (Shin-Etsu Chemical Co., Ltd., LP-7100) ODPA: 4,4'-oxydiphthalic dianhydride BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane DMFDFA: N,N-dimethylformamide dimethyl acetal PBO: Polybenzoxazole PBO precursor: Polybenzoxazole precursor PBOM: 1,1'-(4,4'-oxybenzoyl)diimidazole NA: 5-norbornene-2,3-dicarboxylic anhydride DCC: dicyclohexylcarbodiimide DAE: 4,4'-diaminodiphenyl ether HEMA: 2-hydroxyethyl methacrylate NK-701: A mixture of glycerin-1,3-dimethacrylate and glycerin-1,2-dimethacrylate (NK Ester 701, manufactured by Shin-Nakamura Chemical Co., Ltd.) NMP: N-methyl-2-pyrrolidone GBL: gamma-butyrolactone PGMEA: Propylene glycol monomethyl ether acetate MeTMS: methyltrimethoxysilane PhTMS: phenyltrimethoxysilane cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane M51: Methyl silicate 51.

[0110] [Measurement and evaluation method] The evaluation methods for each example and comparative example are described below. For the evaluation, a resin composition before curing (hereinafter referred to as varnish) that had been filtered in advance through a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

[0111] (1) Weight average molecular weight The weight-average molecular weight of the synthesized resin was determined in terms of standard polystyrene using gel permeation chromatography (GPC). Specifically, the weight-average molecular weight was measured using the following apparatus and conditions. Measurement equipment: System Waters Alliance e2695 Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Measurement conditions: Column: TOSOH TSK Guard column TOSOH TSK-GEL α-4000 TOSOH TSK-GEL α-2500 Developing solution: NMP (containing 0.05M lithium chloride and 0.05M phosphoric acid) Flow rate: 0.4 ml / min, detector: UV 270 nm In order to enable detection at an analyzable peak intensity, the resin composition may be diluted with a solvent (NMP (containing 0.05 M lithium chloride and 0.05 M phosphoric acid)) before measurement, if necessary.

[0112] (2) Film Thickness Using an optical interference type film thickness measuring device (Dainippon Screen Mfg. Co., Ltd. Lambda Ace (registered trademark) STM-602), the film thickness after pre-baking, development, and curing was measured with a refractive index of 1.629.

[0113] (3) Photosensitivity evaluation The resin compositions obtained in each of the Examples and Comparative Examples were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus (ACT-8 manufactured by Tokyo Electron Limited), and baked on a hot plate at 120°C for 3 minutes to produce a pre-baked film with a thickness of 12 μm. Then, using an i-line stepper (Nikon Corporation NSR-2205i14e2), the wafer was exposed to 1,000 mJ / cm through a mask with a 20 μm line and space pattern. 2The film was exposed at an exposure dose of 1000 ppm. After exposure, the film was developed using the above-mentioned coater / developer with a 2.38% by mass TMAH aqueous solution until the film thickness of the exposed area reached 0 μm, then rinsed with distilled water and spun dry to obtain a pattern. The film thickness of the unexposed area of ​​the developed film was measured to determine the amount of film loss. A film loss of less than 0.5 μm was rated as "5," 0.5 μm or more but less than 2.0 μm as "4," 2.0 μm or more but less than 5.0 μm as "3," 5.0 μm or more but less than 10 μm as "2," and 10 μm or more as "1," with a rating of "2" or higher being considered a pass.

[0114] (4) Crack resistance assessment To evaluate the crack resistance of copper wiring, the following evaluation substrate was prepared. Cylindrical copper wiring, 5 μm thick and 250 μm in diameter, was fabricated on an 8-inch silicon wafer at equal intervals so that the center-to-center distance between the copper wirings was 500 μm. Varnish was applied to the evaluation substrate by spin coating using a coating and developing apparatus (ACT-8 manufactured by Tokyo Electron Limited) so that the film thickness after pre-baking at 120°C for 3 minutes would be 12 μm, and pre-baked to form a pre-baked film. The obtained pre-baked film was exposed to 1,000 mJ / cm using an i-line stepper (NSR-2205i14e2) and a mask capable of forming a 150 μm square opening pattern on the cylindrical copper wiring. 2The film was exposed to an exposure dose of 1000 ppm. After exposure, the film was developed using the above-mentioned developing device with a 2.38% by mass TMAH aqueous solution until a rectangular pattern was formed. The film was then rinsed with distilled water and spun dry to obtain a patterned film. The patterned film was then heated to 230°C at a rate of 3.5°C / min in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, and then heat-treated at 230°C for 1 hour. When the temperature dropped to 50°C or less, the evaluation substrate (hereinafter referred to as the sample) was removed. The sample was then placed in a thermal cycle tester and subjected to 200 cycles of temperature increase and decrease from -65°C to 150°C. The sample was then removed and the presence or absence of cracks in the cured product was observed using an optical microscope. The cylindrical copper wiring at the center of the board and at the four ends of the board was observed from the top at two points on each side, for a total of 10 points, and those with 0 cracks were given a grade of "5", those with 1 to 2 cracks were given a grade of "4", those with 3 to 5 cracks were given a grade of "3", those with 6 to 8 cracks were given a grade of "2", and those with 9 or more cracks were given a grade of "1", with a grade of "2" or higher being considered a pass.

[0115] [Synthesis examples of each resin] [Synthesis Example 1] Polyimide precursor (Resin A-1) Under a dry nitrogen stream, 29.67 g (0.081 mol) of BAHF and 2.24 g (0.009 mol) of SiDA were dissolved in 215 g of NMP. To this solution, 31.02 g (0.100 mol) of ODPA was added along with 15 g of NMP, and the mixture was allowed to react at 40°C for 2 hours. Subsequently, 17.87 g (0.150 mol) of DMFDFA was added along with 10 g of NMP, and the mixture was allowed to react at 40°C for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and 30.01 g (0.500 mol) of acetic acid was added along with 40 g of NMP, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain a powder of an alkali-soluble polyimide precursor (Resin A-1). The weight average molecular weight of Resin A-1 was 13,600.

[0116] [Synthesis Examples 2 to 10] Polyimide Precursors (Resin A-2 to Resin A-10) Powders of alkali-soluble polyimide precursors (Resin A-2 to Resin A-10) were obtained in the same manner as in Synthesis Example 1, except that the ratios of BAHF and SiDA were as shown in Table 1-1.

[0117] [Synthesis Example 11] PBO precursor (resin A-11) Under a dry nitrogen stream, 32.96 g (0.090 mol) of BAHF, 2.49 g (0.010 mol) of SiDA, and 212 g of NMP were dissolved. To this solution, 28.67 g (0.080 mol) of PBOM was added along with 20 g of NMP, and the mixture was allowed to react at 85°C for 3 hours. Subsequently, 6.57 g (0.040 mol) of NA as an end-capping agent was added along with 10 g of NMP, and the mixture was allowed to react at 85°C for 30 minutes. After the reaction was complete, the mixture was cooled to room temperature, and 48.02 g (0.80 mol) of acetic acid was added along with 67 g of NMP, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain a powder of alkali-soluble PBO precursor (Resin A-11). The weight average molecular weight of Resin A-11 was 31,600.

[0118] [Synthesis Examples 12 to 19] PBO Precursors (Resin A-12 to Resin A-19) Powders of alkali-soluble PBO precursors (resins A-12 to A-19) were obtained in the same manner as in Synthesis Example 11, except that the ratios of BAHF and SiDA were as shown in Table 1-2.

[0119] [Synthesis Example 20] Polyimide (Resin A-20) Under a dry nitrogen stream, 29.67 g (0.081 mol) of BAHF and 2.24 g (0.009 mol) of SiDA were dissolved in 215 g of NMP. To this solution, 31.02 g (0.100 mol) of ODPA and 15 g of NMP were added, and the mixture was allowed to react at 180°C for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, and 30.01 g (0.500 mol) of acetic acid and 40 g of NMP were added, followed by stirring at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain a powder of alkali-soluble polyimide (Resin A-20). The weight-average molecular weight of Resin A-20 was 24,600.

[0120] [Synthesis Examples 21 to 28] Polyimides (Resin A-21 to Resin A-28) Powders of alkali-soluble polyimides (Resin A-21 to Resin A-28) were obtained in the same manner as in Synthesis Example 20, except that the ratios of BAHF and SiDA were as shown in Table 1-3.

[0121] [Synthesis Example 29] Polyimide precursor (Resin A-29) Under a dry nitrogen stream, 15.64 g (0.02 mol) of Resin A-1 and 11.82 g (0.044 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 200 g of NMP and the solution was cooled to room temperature. To this solution, 4.86 g (0.048 mol) of triethylamine mixed with 5 g of NMP was added dropwise so that the temperature in the system did not exceed 25°C. After the addition, the mixture was stirred at 25°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer at room temperature for 3 days to obtain an alkali-soluble polyimide precursor (Resin A-29). The weight-average molecular weight of Resin A-29 was 17,600.

[0122] [Synthesis Examples 30 to 32] Polyimides (Resin A-30 to Resin A-32) As shown in Table 1-3, powders of alkali-soluble polyimides (Resins A-30 to A-32) were obtained in the same manner as in Synthesis Example 29, except that Resin A-3, Resin A-6, and Resin A-8 were used instead of Resin A-1, respectively.

[0123] [Synthesis Example 33] PBO precursor (resin A-33) Under a dry nitrogen stream, 27.55 g (0.02 mol) of Resin A-16 and 11.82 g (0.044 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 200 g of NMP and the solution was cooled to room temperature. To this solution, 4.86 g (0.048 mol) of triethylamine mixed with 5 g of NMP was added dropwise so that the temperature in the system did not exceed 25°C. After the addition, the mixture was stirred at 25°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer at room temperature for 3 days to obtain a PBO precursor (Resin A-33). The weight-average molecular weight of Resin A-33 was 35,600.

[0124] [Synthesis Example 34] Polyimide (Resin A-34) Under a dry nitrogen stream, 26.34 g (0.02 mol) of Resin A-25 and 11.82 g (0.044 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 200 g of NMP and the solution was cooled to room temperature. To this solution, 4.86 g (0.048 mol) of triethylamine mixed with 5 g of NMP was added dropwise so that the temperature in the system did not exceed 25°C. After the addition, the mixture was stirred at 25°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer at room temperature for 3 days to obtain an alkali-soluble polyimide (Resin A-34). The weight-average molecular weight of Resin A-34 was 27,000.

[0125] [Synthesis Example 35] Polyimide precursor (Resin A-35) Except for using 11.61 g (0.045 mol) of BAPA instead of BAHF and changing the amount of SiDA to 11.18 g (0.045 mol), the same procedure as in Synthesis Example 1 was repeated to obtain a powder of an alkali-soluble polyimide precursor (Resin A-35). The weight-average molecular weight of Resin A-35 was 14,000.

[0126] [Synthesis Example 36] PBO precursor (resin A-36) A powder of PBO precursor (Resin A-36) was obtained in the same manner as in Synthesis Example 11, except that 12.91 g (0.050 mol) of BAPA was used instead of BAHF and the amount of SiDA was changed to 12.43 g (0.050 mol). The weight-average molecular weight of Resin A-36 was 30,000.

[0127] [Synthesis Example 37] Polyimide (Resin A-37) An alkali-soluble polyimide (Resin A-37) powder was obtained in the same manner as in Synthesis Example 20, except that 11.61 g (0.045 mol) of BAPA was used instead of BAHF and the amount of SiDA was 11.18 g (0.045 mol). The weight-average molecular weight of Resin A-37 was 25,000.

[0128] [Synthesis Example 38] Polyimide precursor (Resin A-38) A powder of an alkali-soluble polyimide precursor (Resin A-38) was obtained in the same manner as in Synthesis Example 29, except that 24.1 g (0.02 mol) of Resin A-35 was used instead of Resin A-1. The weight-average molecular weight of Resin A-38 was 18,000.

[0129] [Synthesis Example 39] PBO precursor (resin A-35) An alkali-soluble PBO precursor powder (Resin A-39) was obtained in the same manner as in Synthesis Example 33, except that 24.39 g (0.02 mol) of Resin A-36 was used instead of Resin A-16. The weight-average molecular weight of Resin A-39 was 36,000.

[0130] [Synthesis Example 40] Polyimide (Resin A-40) An alkali-soluble polyimide (Resin A-40) powder was obtained in the same manner as in Synthesis Example 34, except that 24.1 g (0.02 mol) of Resin A-37 was used instead of Resin A-25. The weight-average molecular weight of Resin A-40 was 29,000.

[0131] [Synthesis Example 41] Polyimide precursor (Resin A-41) 31.02g (0.10mol) of ODPA was placed in a 500ml separable flask, 45.65g (0.20mol) of NK-701 and 87ml of GBL were added, and 16.22g (0.21mol) of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generation by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0132] Next, under ice cooling, a solution of 41.27 g (0.2 mol) of DCC dissolved in 40 mL of GBL was added to the reaction mixture over 20 minutes with stirring, followed by a suspension of 12.01 g (0.0465 mol) of BAPA and 11.56 g (0.0465 mol) of SiDA in 100 mL of γ-butyrolactone, which was added over 20 minutes with stirring. After further stirring at room temperature for 2 hours, 6 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 65 mL of GBL. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0133] The resulting reaction solution was added to 800 ml of ethyl alcohol to produce a crude polymer precipitate. The resulting crude polymer was filtered and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 6 L of water to precipitate the polymer. The precipitate was collected by filtration, washed three times with water, and then vacuum-dried to obtain a powdered polyimide precursor (A-41). The weight-average molecular weight (Mw) of Resin A-41 was 29,000.

[0134] [Synthesis Examples 42 to 45] Polyimide Precursors (Resin A-42 to Resin A-45) Polyimide precursors (resins A-42 to A-45) were obtained in the same manner as in Synthesis Example 41, except that 45.65 g (0.20 mol) of NK-701 was replaced with a mixture of 11.41 g (0.05 mol) of NK-701 and 19.52 g (0.15 mol) of HEMA, and the ratios of BAPA and SiDA were as shown in Table 1-3.

[0135] [Synthesis Example 46] Polysiloxane (Resin E-1) Under a dry nitrogen stream, a 500 ml three-necked flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 12.32 g (0.05 mol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5.88 g of methyl silicate 51 (equivalent to 0.05 moles of silicon), and 155.04 g of PGMEA. A phosphoric acid solution (0.515 g of phosphoric acid (0.30 parts by mass relative to the charged monomer) dissolved in 54.45 g of water was added over 10 minutes while stirring at room temperature. The flask was then immersed in a 40 °C oil bath and stirred for 60 minutes. The oil bath was then heated to 115 °C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was then heated and stirred for 2 hours (internal temperature 100°C) to obtain a solution of polysiloxane (Resin E-1). 1.5 g of the polysiloxane solution was weighed into an aluminum cup and heated at 250°C for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the aluminum cup after heating was weighed to determine the solid content concentration of the polysiloxane solution, which was adjusted to 35% by mass. The weight-average molecular weight (Mw) of Resin E-1 was 6,000.

[0136] The compositions of the obtained resins are shown in Tables 1-1, 1-2, 1-3, 1-4, 1-5, 1-6 and 1-7.

[0137] [Table 1-1]

[0138] [Table 1-2]

[0139] [Table 1-3]

[0140] [Table 1-4]

[0141] [Table 1-5]

[0142] [Table 1-6]

[0143] [Table 1-7]

[0144] [Synthesis Example 47] Naphthoquinone diazide compound (Compound C-1) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer at room temperature for 3 days to obtain the naphthoquinone diazide compound (Compound C-1).

[0145] [Compounds used in Examples and Comparative Examples] The compounds used in the examples and comparative examples are shown below.

[0146] (Crosslinking agent) B-1: TEPIC-FL (trade name, manufactured by Nissan Chemical Industries, Ltd.), a crosslinking agent having three epoxy groups and a structure of formula (4) B-2: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), a crosslinking agent having six alkoxymethyl groups but no epoxy groups B-3: "Techmore (registered trademark)" VG3101L (trade name, manufactured by Printec Co., Ltd.), a crosslinking agent having three epoxy groups but not having the structure of formula (4) (adhesion improver) D-1: KBM-403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), a silane coupling agent having an epoxy group (Photopolymerization initiator) F-1: 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)] ("Irgacure OXE-01 (trade name)" manufactured by BASF).

[0147] [Examples and Comparative Examples] [Example 1] A varnish was prepared by adding 10 g of resin A-1 obtained in Synthesis Example 1 as resin A, 0.5 g of crosslinking agent B-2, 2 g of compound C-1 obtained in Synthesis Example 41 as a naphthoquinone diazide compound, 0.43 g of adhesion improver D-1, and 25 g of GBL as a solvent.

[0148] [Examples 2 to 50, Comparative Examples 1 and 2] Varnishes were prepared in the same manner as in Example 1, except that the types and amounts of compounds used were as shown in Tables 2 to 7.

[0149] Comparative Example 3 A varnish was prepared by adding 9.74 g (solid content: 3.41 g, solvent: 6.33 g) of the solution of resin E-1 obtained in Synthesis Example 39 as the polysiloxane, 3.41 g of crosslinker B-1, 0.68 g of compound C-1 obtained in Synthesis Example 40 as the naphthoquinone diazide compound, 0.15 g of adhesion improver D-1, and 0.90 g of PGMEA as the solvent.

[0150] Although Example 15 was suitable for practical use, increased fluidity was observed during thermal curing. The evaluation results of the Examples and Comparative Examples are shown in Tables 2 to 8. The numerical values ​​for the compositions of compounds other than the solvent in the tables represent parts by mass of the solid content.

[0151] [Table 2]

[0152] [Table 3]

[0153] [Table 4]

[0154] [Table 5]

[0155] [Table 6]

[0156] [Table 7]

[0157] [Table 8] [Explanation of symbols]

[0158] 1: Silicon wafer 1a: Semiconductor chip 2: Pad 3: Passivation film 4,7: insulating film 5: Metal film 6: Metal wiring 8: Barrier metal 9: Scribe line 10: Solder bump 11: Sealing resin 12: Circuit board 13, 14: insulating film 15: Metal film 16,17: Metal wiring 18: Electrode 19: Sealing resin 21, 26: PCB body 22,25: Metal electrode 23: Insulating layer 24: Insulating layer (resin layer or inorganic layer) 27:First board 28:Second board 31:TFT 32: Metal wiring 33: TFT insulating film 34: Flattening layer 35:ITO 36: Circuit board 37: Contact hole 38: Insulating layer

Claims

1. A resin composition comprising a resin A having a repeating structural unit represented by formula (1) and / or a repeating structural unit represented by formula (2), and a crosslinking agent having two or more crosslinkable groups, wherein the resin A contains 10 mol % or more and 90 mol % or less of repeating structural units including a structure represented by formula (3) relative to 100 mol % of all repeating structural units in the resin A, and further satisfies at least one of the following requirements: (Requirement 1) the resin composition further contains a photosensitizer; and (Requirement 2) the resin A has a photosensitive group. 【Chemistry 1】 (In formula (1) and formula (2), X １ represents a divalent to hexavalent organic group having 4 to 40 carbon atoms; Y １ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. ２ represents a tetravalent to hexavalent organic group having 4 to 40 carbon atoms; Y ２ represents a divalent to tetravalent organic group having 4 to 40 carbon atoms. １ ~R ５ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. p, r, s, and t each independently represent an integer of 0 to 2. p + r represents an integer of 1 to 4. s + t represents an integer of 1 to 4. q represents an integer of 0 to 2. * represents a chemical bond. In formula (3), R ６ ~R ９ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group in which at least one hydrogen atom of the phenyl group has been substituted with an alkyl group having 1 to 10 carbon atoms; R １０ and R １１ each independently represents an alkylene group having 1 to 6 carbon atoms; n represents an integer of 1 to 10; * represents a chemical bond.

2. The resin composition according to claim 1, wherein the resin A contains more than 20 mol% and 90 mol% or less of repeating structural units having a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A.

3. The resin composition according to claim 1, wherein the resin A contains 30 mol% or more and 90 mol% or less of repeating structural units including a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A.

4. (Requirement 1) The resin composition according to claim 1, wherein the resin composition further contains a photosensitizer, and the photosensitizer is a naphthoquinone diazide compound.

5. (Requirement 2) The resin composition according to claim 1, wherein the resin A has a photosensitive group, and the photosensitive group is a naphthoquinone diazide group.

6. R contained in the formula (1) １ and R ３ and R contained in the formula (2). ４ and R ５ The resin composition according to claim 5, wherein at least one of the following is a group represented by formula (5): 【Chemistry 2】 (In formula (5), * represents a chemical bond.)

7. The resin composition according to claim 1, which satisfies (Requirement 1) that the resin composition further contains a photosensitizer, and does not satisfy (Requirement 2) that the resin A has a photosensitive group.

8. The resin composition according to claim 7, wherein the resin A contains 20 mol% or more and 90 mol% or less of repeating structural units having a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A.

9. The resin composition according to claim 7, wherein the resin A contains 30 mol% or more and 90 mol% or less of repeating structural units having a structure represented by formula (3) relative to 100 mol% of all repeating structural units in the resin A.

10. The resin composition according to claim 7, wherein the photosensitizer is a naphthoquinone diazide compound.

11. The resin composition according to any one of claims 1 to 10, wherein the crosslinkable group is an epoxy group.

12. The resin composition according to any one of claims 1 to 10, wherein the crosslinking agent comprises a compound represented by formula (4): 【Transformation 3】 (In formula (4), L １ each independently represents an alkylene group having 1 to 8 carbon atoms.

13. The resin composition according to any one of claims 1 to 10, wherein the content of the crosslinking agent relative to 100 parts by mass of the resin A is 10 parts by mass or more and 150 parts by mass or less.

14. The resin composition according to any one of claims 1 to 10, which is used for forming an insulating layer in hybrid bonding between semiconductor chips, for forming an insulating layer in hybrid bonding between a semiconductor chip and a substrate, or for forming an insulating layer in hybrid bonding between substrates.

15. A cured product obtained by curing the resin composition according to any one of claims 1 to 10.

16. 11. A method for producing a cured product, comprising the steps of: forming a resin film from the resin composition according to claim 1; irradiating the resin film with actinic radiation; developing a pattern from the resin film irradiated with the actinic radiation; and heating the resin film with the developed pattern to form a relief pattern layer.

17. A semiconductor device comprising the cured product according to claim 15.

18. A display device comprising the cured product according to claim 15.

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