Photosensitive insulating film-forming composition

Abstract

The present application provides a photosensitive insulating film resin composition capable of giving a cured product with low initial dielectric loss tangent and small change over time, a method for manufacturing a substrate with a cured relief pattern using the photosensitive insulating film resin composition, and a semiconductor device provided with the cured relief pattern. The photosensitive insulating film forming composition contains a polymer having a repeating unit structure represented by the following formula (1), and a solvent. In formula (1), group A 1 represents an aromatic heterocycle represented by (A 1 ), group A 2 represents an aromatic heterocycle represented by (A 2 ), group A 1 , group A 2 may have a crosslinkable substituent, group B 1 represents an organic group having a crosslinkable substituent, and group B 2 represents an organic group having no crosslinkable substituent.

Description

Technical Field

[0001] The present invention relates to a composition for forming a photosensitive insulating film, a photosensitive resin film obtained from the composition, a substrate with a cured embossed pattern using the composition, a method for manufacturing the same, and a semiconductor device having the cured embossed pattern. Background Technology

[0002] Previously, polyimide resins possessing excellent heat resistance, electrical properties, and mechanical properties were used for insulating materials of electronic components, passivation films, surface protective films, and interlayer insulating films of semiconductor devices. Among these polyimide resins, those provided as photosensitive polyimide precursors can easily form heat-resistant embossed pattern coatings through thermal imidization processes involving coating, exposure, development, and curing of the precursor. These photosensitive polyimide precursors significantly shorten the processing steps compared to conventional non-photosensitive polyimide resins.

[0003] On the other hand, in recent years, from the perspective of improving integration and computing power, as well as miniaturizing chip size, the mounting methods of semiconductor devices on printed circuit boards have also been changing. The mounting method, which previously used metal leads and lead-tin eutectic solder, has gradually shifted to structures where polyimide coatings are in direct contact with solder bumps, such as BGAs (Ball Grid Arrays) and CSPs (Chip Scale Packages) that enable higher-density mounting. When forming such bump structures, the coating is required to have high heat resistance and chemical resistance.

[0004] Furthermore, with the miniaturization of semiconductor devices, the problem of wiring delay has become apparent. As a means of improving the wiring resistance of semiconductor devices, a change has been made from the gold or aluminum wiring used so far to copper or copper alloy wiring, which has lower resistance. In addition, methods have been adopted to prevent wiring delay by improving the insulation between wirings. In recent years, low-dielectric-constant materials have often been used as high-insulation materials in semiconductor devices; however, on the other hand, low-dielectric-constant materials are often brittle and fragile. For example, when they are mounted on a substrate with semiconductor chips using a reflow soldering process, there is a problem that the low-dielectric-constant material portions can be destroyed due to shrinkage caused by temperature changes.

[0005] As a means of solving this problem, Patent Document 1 discloses a photosensitive resin composition in which transparency is improved when an aliphatic group with 5 to 30 carbon atoms having an ethylene glycol structure is introduced into a portion of the side chain of the polyimide precursor, and the Young's modulus of the cured film after thermosetting is increased.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Re-evaluation No. 2013-168675 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The photosensitive resin composition containing a polyimide precursor described in Patent Document 1 provides a cured product with high transparency and high Young's modulus after thermosetting. However, when used in the above-mentioned applications, it is necessary to further reduce the dielectric loss tangent and suppress the change of the dielectric loss tangent over time.

[0011] Therefore, the objective of this invention is to provide a photosensitive resin composition, a substrate with a cured embossed pattern using the composition, a method for manufacturing the same, and a semiconductor device having the cured embossed pattern. The photosensitive resin composition provides a cured film that not only reduces the dielectric loss tangent but also suppresses the change in the dielectric loss tangent over time to a small extent after being placed in a normal environment for a period of time.

[0012] Problem-solving methods

[0013] In order to solve the above-mentioned problems, the inventors conducted repeated in-depth research and found that by using a polymer with a repeating unit structure containing specific aromatic heterocycles and crosslinking substituents, a photosensitive resin composition that can provide a low dielectric loss tangent and can maintain the cured film even after long-term storage under normal conditions can be obtained, thus completing the present invention.

[0014] That is, the present invention includes the following.

[0015] [1] A composition for forming a photosensitive insulating film, comprising a polymer having a repeating unit structure represented by the following formula (1), and a solvent,

[0016]

[0017] In formula (1), group A 1 express

[0018]

[0019] The 5- to 8-membered aromatic heterocycles represented may have cross-linking substituents, group A. 2 express

[0020]

[0021] The 5- to 8-membered aromatic heterocycles represented may have cross-linking substituents.

[0022] Group B1 This refers to an organic group with 6 to 40 carbon atoms that has a crosslinking substituent. It may contain at least one heteroatom selected from N, S, and O, and may also contain a halogen atom.

[0023] Group B 2 This refers to an organic group with 6 to 40 carbon atoms that does not have cross-linking substituents. It may contain at least one heteroatom selected from N, S, and O, and may also contain halogen atoms.

[0024] n 1 and n 2 Each number is independently greater than 0 and less than 1.

[0025] m 1 and m 2 Each number is independently greater than 0 and less than 1.

[0026] n is a number greater than or equal to 1, m is a number greater than or equal to 0, and 10 ≤ n + m ≤ 500.

[0027] Wherein, group A 1 Group A 2 When neither has cross-linking substituents, if m≠0, then n 1 and m 1 At least one of them is 1. If m = 0, then n 1 The value is 1.

[0028] The composition for forming a photosensitive insulating film described in [2][1], wherein group A 1 express

[0029]

[0030] The aromatic heterocycle shown may have cross-linking substituents.

[0031] The composition for forming a photosensitive insulating film as described in [3][1] or [2], wherein group A 2 Indicates freedom of choice

[0032]

[0033]

[0034] and

[0035]

[0036] At least one aromatic heterocycle from the group consisting of the aromatic heterocycles shown, any one of which may have crosslinking substituents.

[0037] The composition for forming a photosensitive insulating film according to any one of [4][1] to [3], wherein the group B 1 It is selected from at least one of the following groups,

[0038]

[0039] In the formula, G represents direct bonding, or any one of the following formulas.

[0040] -CH2- -CH(CH3)- -C(CH3)2- -C(CF3)2-

[0041] -C(CH3)(C2H5)- -C(CH3)(C6H5)- -C(C6H5)2-

[0042] -SO2-

[0043]

[0044] L and M each independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group.

[0045] The composition for forming a photosensitive insulating film according to any one of [5][1] to [4], wherein the group B 1 Depend on

[0046]

[0047] express.

[0048] The composition for forming a photosensitive insulating film as described in any one of [6][1] to [5], wherein the group B 2 It is selected from at least one of the following groups,

[0049]

[0050] In the formula, G represents direct bonding, or any one of the following formulas.

[0051] -CH2--CH(CH3)- -C(CH3)2- -C(CF3)2-

[0052] -C(CH3)(C2H5)- -C(CH3)(C6H5)- -C(C6H5)2-

[0053] -SO2-

[0054]

[0055] L and M each independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group.

[0056] The composition for forming a photosensitive insulating film as described in any one of [7][1] to [6], wherein the group B 2 Depend on

[0057]

[0058] express.

[0059] The composition for forming a photosensitive insulating film as described in any one of [8][1] to [7], wherein the crosslinking substituent contains a free radical crosslinking group.

[0060] The composition for forming a photosensitive insulating film according to any one of [9][1] to [8], wherein the crosslinking substituent contains (meth)acrylate, maleimide or allyl.

[0061] The composition for forming a photosensitive insulating film as described in any one of

[10] [1] to [9], wherein m = 0.

[0062]

[11] A photosensitive resin film, characterized in that it is a sintered product of a coating of the photosensitive insulating film forming composition described in any one of [1] to

[10] .

[0063] The photosensitive resin film described in

[12]

[11] has a dielectric loss tangent of 0.01 or less.

[0064]

[13] A method for manufacturing a substrate with a solidified embossed pattern, comprising the following steps:

[0065] (1) The process of coating the photosensitive insulating film forming composition described in any one of [1] to

[10] onto a substrate, and forming a photosensitive resin layer on the substrate.

[0066] (2) The process of exposing the photosensitive resin layer.

[0067] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern, and

[0068] (4) The process of heat-treating the relief pattern to form a solidified relief pattern.

[0069]

[14] A substrate with a solidified embossed pattern manufactured by the method described in

[13] .

[0070]

[15] A semiconductor device comprising a semiconductor element and a cured film disposed on the upper or lower part of the semiconductor element, the cured film being a cured relief pattern as described in

[14] .

[0071] Invention Effects

[0072] According to the present invention, a photosensitive resin composition capable of imparting a low dielectric loss tangent to a cured material can be provided, a photosensitive resin film obtained from the composition, a photosensitive resin film obtained from the composition, a substrate with a cured embossed pattern using the composition, a method for manufacturing the same, and a semiconductor device having the cured embossed pattern can be provided. Detailed Implementation

[0073] [Composition for forming photosensitive insulating films]

[0074] The photosensitive insulating film forming composition of the present invention comprises a polymer having a repeating unit structure represented by the following formula (1), and a solvent.

[0075]

[0076] In formula (1), group A 1 express

[0077]

[0078] The 5- to 8-membered aromatic heterocycles represented may have cross-linking substituents, group A. 2 express

[0079]

[0080] The 5- to 8-membered aromatic heterocycles represented may have cross-linking substituents.

[0081] Group B 1 This refers to an organic group with 6 to 40 carbon atoms that has a crosslinking substituent. It may contain at least one heteroatom selected from N, S, and O, and may also contain a halogen atom.

[0082] Group B 2 This refers to an organic group with 6 to 40 carbon atoms that does not have cross-linking substituents. It may contain at least one heteroatom selected from N, S, and O, and may also contain halogen atoms.

[0083] n 1 and n 2 Each is an independent number greater than 0 and less than 1.

[0084] m 1 and m 2 Each is an independent number greater than 0 and less than 1.

[0085] n is a number greater than or equal to 1, m is a number greater than or equal to 0, and 10 ≤ n + m ≤ 500.

[0086] Wherein, group A 1 Group A 2When neither has cross-linking substituents, if m≠0, then n 1 and m 1 At least one of them is 1. If m = 0, then n 1 The value is 1.

[0087] The following sections will explain each component in turn.

[0088] <Polymer>

[0089] The polymer of the present invention has a repeating unit structure represented by the above formula (1).

[0090] Group A 1 This refers to a 5- to 8-membered aromatic heterocycle that does not contain heteroatoms in the shortest series of covalent bonds between two bond sites. This aromatic heterocycle may have cross-linking substituents.

[0091] Preferred group A 1 express

[0092]

[0093] The aromatic heterocycle shown may have cross-linking substituents.

[0094] Group A 1 It can be one type, or a combination of two or more types.

[0095] In the above formula (1), group A 2 This refers to a 5- to 8-membered aromatic heterocycle containing a nitrogen atom in the series of shortest covalent bonds between two bond sites. This aromatic heterocycle may have cross-linking substituents.

[0096] Preferred group A 2 Indicates freedom of choice

[0097]

[0098] and

[0099]

[0100] At least one aromatic heterocycle from the group consisting of the aromatic heterocycles shown, any one of which may have crosslinking substituents.

[0101] Group A 2 It can be one type, or a combination of two or more types.

[0102] Preferably, the crosslinking substituents include free radical crosslinking groups.

[0103] Preferred crosslinking substituents contain (meth)acrylate, maleimide, or allyl groups.

[0104] As crosslinking substituents containing (meth)acrylate groups, groups represented by the following general formula (2) can be listed.

[0105]

[0106] In the formula, R 3 R 4 and R 5 Each is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, where m is an integer from 1 to 10. * is a group A of general formula (1). 1 Group A 2 or group B 1 The bonding sites.

[0107] For R in the above general formula (2) 3 There are no restrictions as long as it is a monovalent organic group with 1 to 3 hydrogen atoms or carbon atoms. However, when the composition for forming a photosensitive insulating film is negative, hydrogen atoms or methyl groups are preferred from the perspective of photosensitive properties.

[0108] For R in the above general formula (2) 4 and R 5 There are no restrictions as long as each is an independent monovalent organic group consisting of 1 to 3 hydrogen atoms or carbon atoms. However, when the composition for forming a photosensitive insulating film is negative, hydrogen atoms are preferred from the perspective of photosensitive properties.

[0109] In the above general formula (2), M is an integer of 1 or more and less than 10. From the perspective of photosensitive characteristics, it is preferred to be an integer of 1 or more and less than 4.

[0110] Specific examples of monovalent organic groups with 1 to 3 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, and propyl; branched-chain alkyl groups such as isopropyl; alicyclic alkyl groups such as cyclopropyl; alkenyl groups such as vinyl and allyl; alkynyl groups such as ethynyl; alkoxy groups such as methoxy, ethoxy, and propoxy; acyl groups such as acetyl; ester groups such as methoxycarbonyl; formyl; haloformyl; carbamoyl; cyano; heterocyclic groups such as ethylene oxide, aziridinyl, thiocyclic butyl, triazine, oxathiocyclic pentyl, dihydroazirionic butyl, and dihydrothiazolyl.

[0111] In the above formula (1), group B 1 It refers to an organic group with 6 to 40 carbon atoms having a crosslinking substituent, which may contain at least one heteroatom selected from N, S and O, or may contain halogen atoms.

[0112] Preferred group B 1 It is selected from at least one of the following groups,

[0113]

[0114] In the formula, G represents direct bonding or any one of the following formulas.

[0115] -CH2- -CH(CH3)- -C(CH3)2- -C(CF3)2-

[0116] -C(CH3)(C2H5)- -C(CH3)(C6H5)- -C(C6H5)2-

[0117] -SO2-

[0118]

[0119] L and M each independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group.

[0120] Preferred group B 1 Depend on

[0121]

[0122] express.

[0123] In the above formula (1), group B 2 It refers to an organic group with 6 to 40 carbon atoms that does not have cross-linking substituents, and may contain at least one heteroatom selected from N, S and O, or may contain halogen atoms.

[0124] Preferred group B 2 It is selected from at least one of the following groups,

[0125]

[0126] In the formula, G represents direct bonding or any one of the following formulas.

[0127] -CH2- -CH(CH3)- -C(CH3)2- -C(CF3)2-

[0128] -C(CH3)(C2H5)- -C(CH3)(C6H5)- -C(C6H5)2-

[0129] -SO2-

[0130]

[0131] L and M each independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group.

[0132] Preferred group B 2 Depend on

[0133]

[0134] express.

[0135] Group A 1 Group A 2 When neither has cross-linking substituents, if m≠0 then n 1 and m 1 At least one of them is 1, and if m = 0 then n 1 The value is 1. That is, in polymers having a repeating unit structure represented by formula (1), even if group A 1 and group A 2 Neither group has cross-linking substituents, but there is also a group B with cross-linking substituents. 1 .

[0136] In polymers having a repeating unit structure represented by formula (1), group A 2 It is not necessarily required to exist. In this case, m = 0 in equation (1).

[0137] [Preparation method of polymers having repeating unit structures represented by formula (1)]

[0138] Polymers having a repeating unit structure represented by formula (1) can be prepared by known methods. For example, this can be achieved by modifying HO-B... 1 Compounds represented by -OH, HO-B 2 Compounds represented by -OH, XA 1 -X represents compounds and XA 2 -X represents compounds that are appropriately selected and condensed to prepare (where A 1 A 2 B 1 B 2 Synonymous with the above, X is a halogen atom). HO-B 1 Compounds represented by -OH and HO-B 2 Compounds represented by -OH, and XA 1 -X represents compounds and XA 2 The -X designation indicates that one compound may be used individually, or two or more may be used in combination. In this condensation reaction, relative to HO-B... 1 Compounds represented by -OH and HO-B 2 The total amount of compounds represented by -OH, 1 mol, XA 1 -X represents compounds and XA 2 The total amount of compounds represented by -X can usually be set to 0.1 to 10 mol, preferably 0.1 to 2 mol.

[0139] As a catalyst used in condensation reactions, either basic or acidic catalysts can be used, but basic catalysts are preferred.

[0140] Examples of alkaline catalysts include solid alkaline catalysts such as calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate, and potassium carbonate.

[0141] As acidic catalysts, inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and methanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid can be used.

[0142] The amount of catalyst used varies depending on the type of catalyst used, but relative to HO-A 1 Compounds represented by -OH and HO-A 2 The total amount of the compound represented by -OH is 100 parts by mass, typically 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.

[0143] Condensation reactions can also be carried out without a solvent, but are usually carried out using a solvent. There are no particular limitations on the solvent, as long as it can dissolve the reaction matrix and does not hinder the reaction. Examples include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, and dioxane. The condensation reaction temperature is typically from 40°C to 200°C, preferably from 50°C to 180°C. The reaction time varies depending on the reaction temperature, but is typically from 5 minutes to 500 hours, preferably from 5 minutes to 200 hours.

[0144] The weight-average molecular weight of polymers having a repeating unit structure represented by formula (1) is typically 500 to 100,000, preferably 600 to 80,000, 800 to 60,000, or 1,000 to 50,000.

[0145] [solvent]

[0146] As a solvent, organic solvents are preferred in terms of solubility relative to polymers having repeating unit structures represented by formula (1). Specifically, examples include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, methyl lactate, ethyl lactate, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, N-methyl-2-pyrrolidone, etc., which can be used alone or in combination of two or more.

[0147] The solvent described above can be used in a range of 100 parts by mass relative to the desired coating thickness and viscosity of the composition for forming a photosensitive insulating film, for example, 30 parts by mass to 1500 parts by mass, preferably 40 parts by mass to 1000 parts by mass, and more preferably 50 parts by mass to 300 parts by mass, depending on the desired coating thickness and viscosity of the composition for forming a photosensitive insulating film.

[0148] [Other ingredients]

[0149] In embodiments, the composition for forming a photosensitive insulating film may further contain a polymer having a repeating unit structure represented by formula (1) above, and components other than a solvent. Other components may include, for example, resin components other than a polymer having a repeating unit structure represented by formula (1), photopolymerization initiators, adhesive aids, hindered phenolic compounds, carboxylic acid compounds or their anhydrides, crosslinking compounds, sensitizers, thermal polymerization inhibitors, azole compounds, fillers, etc.

[0150] [Resin components other than polymers having repeating unit structures represented by formula (1)]

[0151] In embodiments, the composition for forming a photosensitive insulating film may also contain a resin component other than a polymer having a repeating unit structure represented by formula (1) above. Examples of resin components that may be contained in the composition for forming a photosensitive insulating film include polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc.

[0152] When such a resin is incorporated, the amount of resin component incorporated is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1).

[0153] [Photopolymerization initiator]

[0154] The photosensitive insulating film forming composition of the present invention may contain a photopolymerization initiator. As a photopolymerization initiator, there are no particular limitations as long as it is a compound that absorbs light in the light source used during photocuring. Examples include tert-butyl peroxide, 2,5-dimethyl-2,5-bis(benzoyl peroxide)hexane, 1,4-bis[α-(tert-butyl peroxide)-isopropoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexene hydroperoxide, α-(isopropylphenyl)-isopropyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butyl peroxide)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3 Organic peroxides such as 3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-pentylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxylated benzophenone, tert-butyl peroxybenzoate, and ditert-butyl isophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzoanthraquinone; and benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin. Compounds; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propanoyl)benzyl}-phenyl]-2-methyl-propane-1-one, methyl phenylglyoxylate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl)propane-1-one Alkyl phenyl ketones such as 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one; acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; and oxime esters such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone.

[0155] The aforementioned photopolymerization initiators are available as commercially available products. Examples include: IRGACURE (registered trademark) 651, IRGACURE 184, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, IRGACURE 819, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250, IRGACURE 1173, IRGACURE MBF, IRGACURE TPO, IRGACURE 4265, IRGACURE TPO (all manufactured by BASF), KAYACURE (registered trademark) DETX, KAYACURE MBP, KAYACURE DMBI, and KAYACURE. EPA, KAYACURE OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, VICURE-55 (manufactured by STAUFFER Co., Ltd.), ESACUREKIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB3, Triajin-PMS, Triajin A, Triajin B (manufactured by Sibel Hegner Co., Ltd.), Adeka Optomer N-1717, Adeka Optomer N-1414, Adeka Optomer N-1606 (manufactured by ADEKA Co., Ltd.). These photopolymerization initiators can be used alone or in combination of two or more.

[0156] The amount of photopolymerization initiator is typically 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), and preferably 0.5 to 15 parts by mass from the perspective of photosensitivity. When the amount of photopolymerization initiator is 0.1 parts by mass or more relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), the photosensitivity of the composition for forming a photosensitive insulating film is easily improved. On the other hand, if it is 20 parts by mass or less, the thick film curability of the composition for forming a photosensitive insulating film is easily improved.

[0157] [Cross-linking agent]

[0158] In this embodiment, to improve the resolution of the embossed pattern, a crosslinking agent may be incorporated into the composition for forming the photosensitive insulating film. As such a crosslinking agent, a (meth)acrylic acid compound that undergoes free radical polymerization via a photopolymerization initiator is preferred. Examples, but not particularly limited to, the following crosslinking agents: mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, primarily diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate; mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol; mono-, di-, or triacrylates and methacrylates of glycerol; cyclohexane diacrylate and dimethacrylate; and diacrylates and dimethacrylates of 1,4-butanediol. Compounds including diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, trimethacrylates, isoborneol acrylates and methacrylates, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylates and methacrylates, di- or triacrylates and methacrylates of glycerol, di, tri- or tetraacrylates and methacrylates of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0159] The amount of crosslinking agent is preferably 1 to 100 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), and more preferably 1 to 50 parts by mass.

[0160] Examples of thermal crosslinking agents include hexamethoxymethyl melamine, tetramethoxymethyl ethynylurea, tetramethoxymethyl guanidineamine, 1,3,4,6-tetra(methoxymethyl)ethynylurea, 1,3,4,6-tetra(butoxymethyl)ethynylurea, 1,3,4,6-tetra(hydroxymethyl)ethynylurea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, and 1,1,3,3-tetra(methoxymethyl)urea.

[0161] [filler]

[0162] As fillers, examples include inorganic fillers, specifically sols of silica, aluminum nitride, boron nitride, zirconium oxide, and alumina.

[0163] [Adhesive additives]

[0164] In embodiments, to improve the adhesion between the film formed using the photosensitive insulating film forming composition and the substrate, an adhesive aid may optionally be added to the photosensitive insulating film forming composition. Examples of adhesive aids include, for instance, γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, 3-methacryloyloxypropyl dimethoxymethylsilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, and N-(3-diethoxymethylsilylpropyl) Silane coupling agents such as succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, and N-phenylaminopropyltrimethoxysilane, as well as aluminum adhesives such as tri(ethylacetoacetic acid)aluminum, tri(acetylacetonate)aluminum, and ethyl acetoacetate diisopropoxyaluminum.

[0165] Among these adhesive aids, silane coupling agents are preferred from the perspective of adhesive strength. The amount of adhesive aid is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of a polymer having a repeating unit structure represented by formula (1).

[0166] [Hindered phenolic compounds]

[0167] In an embodiment, in order to suppress discoloration on copper or as an inhibitor of free radical crosslinking sites, a hindered phenolic compound may optionally be incorporated into the composition for forming a photosensitive insulating film. Examples of hindered phenolic compounds include, for example, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. 2,2-Thio-diethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-cinnamoamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-hydroxybenzyl)benzene -Isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl] [3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples of suitable candidates include 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, but these are not limited to these. Of particular preference is 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0168] The amount of hindered phenolic compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), and more preferably 0.5 to 10 parts by mass from the perspective of photosensitivity characteristics. When the amount of hindered phenolic compound is 0.1 parts by mass or more relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), for example, in the case of forming a photosensitive insulating film composition on copper or copper alloy, discoloration and corrosion of copper or copper alloy can be prevented. On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, and therefore it is preferred.

[0169] [Sensitizer]

[0170] In embodiments, to improve photosensitivity, a sensitizer may optionally be incorporated into the composition for forming the photosensitive insulating film. Examples of such sensitizers include, for instance, milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p- Dimethylaminocinnamyl indanone, p-dimethylaminobenzyl indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminophenylmethylene)acetone, 1,3-bis(4'-diethylaminophenylmethylene)acetone, 3,3'-carbonyl-bis(7- Diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These sensitizers can be used alone or in combination.

[0171] The amount of sensitizer is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of polymer having a repeating unit structure represented by formula (1).

[0172] [Thermal polymerization inhibitor]

[0173] In embodiments, particularly to improve the stability of the viscosity and photosensitivity of the composition for forming a photosensitive insulating film when stored in a solvent-containing solution, a thermal polymerization inhibitor may optionally be incorporated. Examples of thermal polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxyamine ammonium salt.

[0174] The amount of the thermopolymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1).

[0175] [azole compounds]

[0176] For example, when using a substrate made of copper or a copper alloy, an azole compound may be optionally incorporated into the composition for forming a photosensitive insulating film to suppress substrate discoloration. Examples of azole compounds include, for instance, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)] [Phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds can be used in one form or in a mixture of two or more.

[0177] The amount of azole compound incorporated is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1), and more preferably 0.5 to 5 parts by mass from the perspective of photosensitivity characteristics. When the amount of azole compound incorporated relative to 100 parts by mass of the polymer having the repeating unit structure represented by formula (1) is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive insulating film forming composition is formed on copper or copper alloy. On the other hand, when it is 20 parts by mass or less, the photosensitivity is excellent, and therefore it is preferred.

[0178] [Manufacturing method for substrates with cured embossed patterns]

[0179] In one embodiment, a method for manufacturing a substrate with a cured embossed pattern is provided, comprising the following steps:

[0180] (1) The process of coating the photosensitive insulating film forming composition of the present invention onto a substrate, and forming a photosensitive resin layer on the substrate.

[0181] (2) The process of exposing the photosensitive resin layer.

[0182] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern, and

[0183] (4) The process of heat-treating the relief pattern to form a solidified relief pattern.

[0184] The following is a description of each process.

[0185] (1) The process of coating the photosensitive insulating film forming composition of the present invention onto a substrate and forming a photosensitive resin layer on the substrate.

[0186] In this process, the photosensitive insulating film forming composition of the present invention is coated onto a substrate, and if necessary, dried thereafter to form a photosensitive resin layer. As the coating method, methods conventionally used for coating the photosensitive insulating film forming composition can be used, such as coating methods using a spin coater, bar coater, doctor blade coater, curtain coater, screen printer, etc., or spray coating methods using a spray gun, etc.

[0187] If necessary, the coating film composed of the photosensitive insulating film forming composition can be dried. Drying methods include, for example, air drying, drying with an oven or heating plate, or vacuum drying. When drying the coating film by air drying or heating, it can be dried at 20°C to 200°C for 1 minute to 1 hour. Alternatively, after coating the photosensitive insulating film forming composition using the specified method, a film can also be formed by pre-baking in a lower temperature region within the above temperature range, baking in a medium temperature region, and then baking in a high temperature region. Through the above operations, a photosensitive resin layer (film) can be formed on the substrate.

[0188] (2) The process of exposing the photosensitive resin layer.

[0189] In this process, exposure devices such as contact aligners, mirror projectors, and steppers are used to expose the photosensitive resin layer formed in the above process (1) through a patterned light mask or a photomask or directly through an ultraviolet light source.

[0190] Examples of light sources used during exposure include g-line, h-line, i-line, ghi-line broadband lasers, and KrF excimer lasers. The preferred exposure dose is 25 mJ / cm². 2 Up to 1000mJ / cm 2 .

[0191] Subsequently, to improve photosensitivity, etc., post-exposure baking (PEB) and / or pre-development baking can be performed by any combination of temperature and time if necessary. The baking conditions are preferably a temperature of 50°C to 200°C and a time of 10 seconds to 600 seconds, but are not limited to this range as long as they do not impair the various properties of the composition forming the photosensitive insulating film.

[0192] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern.

[0193] In this process, the unexposed portions of the exposed photosensitive resin layer are removed by development. As a development method for the exposed (irradiated) photosensitive resin layer, any conventionally known photoresist development method can be selected, such as spin spraying, static methods, or immersion methods accompanied by ultrasonic treatment. Furthermore, after development, to adjust the shape of the embossed pattern, it may be necessary to perform post-development baking using any combination of temperature and time. Preferably, the developing solution used during development includes, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Additionally, two or more solvents can be combined, for example, multiple solvents can be used.

[0194] (4) The process of heat-treating the relief pattern to form a solidified relief pattern.

[0195] In this process, the embossed pattern obtained through the above development is heated to convert it into a cured embossed pattern. Various methods can be selected for heat curing, such as using a heating plate, using an oven, or using a temperature-programmable oven. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. Air, or inert gases such as nitrogen or argon, can be used as the ambient gas during heat curing. Through the above operations, a substrate with a cured embossed pattern can be manufactured.

[0196] The cured relief pattern of the present invention obtained in this way has a dielectric loss tangent of less than 0.01 immediately after formation. After being exposed for 24 hours at 23°C and 50% RH, the dielectric loss tangent increases by less than 0.004 compared to immediately after formation, preferably 0.003 or less.

[0197] The ratio of the dielectric loss tangent of the embossed pattern cured after exposure to 23°C and 50%RH for 24 hours to the dielectric loss tangent of the newly formed cured embossed pattern is typically within ±80%, preferably within ±70%, and more preferably within ±60%.

[0198] [Semiconductor Devices]

[0199] The embodiments also provide a semiconductor device having a cured relief pattern obtained by the above-described method for manufacturing a cured relief pattern. Therefore, a semiconductor device can be provided having a substrate serving as a semiconductor element and a cured relief pattern (cured film) disposed on the upper or lower part of the semiconductor element, the cured relief pattern being formed on the substrate by the above-described method for manufacturing a cured relief pattern. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device, wherein a semiconductor element is used as a substrate and the above-described method for manufacturing a cured relief pattern is included as part of a process. The semiconductor device of the present invention is manufactured by combining a cured relief pattern formed by the above-described method for manufacturing a cured relief pattern with a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, etc., and combining it with known semiconductor device manufacturing methods.

[0200] [Display device]

[0201] In one embodiment, a display device is provided, comprising a display element and a cured film disposed on the upper part of the display element, the cured film being the aforementioned cured relief pattern. Here, the cured relief pattern can be laminated in direct contact with the display element, or other layers can be laminated between them. Examples of such cured films include surface protective films for TFT liquid crystal display elements and color filter elements, insulating films, planarization films, protrusions in MVA-type liquid crystal display devices, and spacers for cathodes of organic EL elements.

[0202] The photosensitive insulating film forming composition of the present invention is applicable not only to semiconductor devices as described above, but also to interlayer insulation of multilayer circuits, cover coatings for flexible copper clad laminates, solder resist films, and liquid crystal alignment films.

[0203] Example

[0204] The following examples illustrate specific examples of the composition for forming a photosensitive insulating film according to the present invention, but the present invention is not limited thereto.

[0205] The weight-average molecular weights shown in the following synthesis examples in this specification are the results of determination by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus (HLC-8320GPC) manufactured by Higashi Sou Corporation, and the determination conditions are as follows.

[0206] GPC column: TSKgel SuperH-RC, TSKgel SuperMultipore HZ-N, TSKgelSuperMultipore HZ-N (manufactured by Higashikata Co., Ltd.)

[0207] Column temperature: 40℃

[0208] Solvent: Tetrahydrofuran (Kanto Chemical Co., Ltd., for high-performance liquid chromatography)

[0209] Standard sample: Polystyrene (Shodex)

[0210] <Synthetic Example 1> (Synthesis of Polymer (1))

[0211] In a 500 mL four-necked flask, 15.00 g (0.101 mol) of 4,6-dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.), 32.07 g (0.099 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.), 32.80 g (0.252 mol) of potassium carbonate (Kanto Chemical Co., Ltd., premium grade), and 155.47 g of N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., dehydrated) were added and the mixture was heated to 70 °C and stirred at 70 °C for 5 hours, followed by stirring at 90 °C for 23 hours. After cooling to below 30 °C, 268.14 g of tetrahydrofuran (Kanto Chemical Co., Ltd., premium grade) was added for dilution. The precipitate formed in the reaction solution was removed by filtration to obtain the reaction mixture. The obtained reaction mixture was added dropwise to 405.10 g of methanol (Kanto Chemical Co., Ltd., premium grade) and 202.55 g of pure water to precipitate the polymer. The precipitate was separated by filtration, washed twice with 202.55 g of methanol, and dried under vacuum to obtain the polymer. The molecular weight of the polymer was determined using GPC (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 33,367, with a yield of 77.84%. The polymer has a repeating unit structure represented by the following formula (2).

[0212]

[0213] <Synthetic Example 2> (Synthesis of Polymer (2))

[0214] Add 25.00 g (0.164 mol) of 4,6-dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.), 26.554 g (0.081 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd.), 18.58 g (0.081 mol) of 2,2-bis(4-hydroxyphenyl)propane (Tokyo Chemical Industry Co., Ltd.), 54.66 g (0.420 mol) of potassium carbonate (Kanto Chemical Co., Ltd., premium grade), and 225.89 g of N-ethyl-2-pyrrolidone (BASF) to a 1000 mL four-necked flask and heat to 100 °C. Stir at 100 °C for 24 hours. After cooling to below 30°C, 171.55 g of tetrahydrofuran (Kanto Chemical Co., Ltd., premium grade) was added for dilution. The precipitate generated in the reaction solution was removed by filtration to obtain the reaction mixture. The obtained reaction mixture was added dropwise to 1418.95 g of methanol (Kanto Chemical Co., Ltd., premium grade) and 283.79 g of pure water to precipitate the polymer. The precipitate was separated by filtration, washed twice with 227.03 g of methanol, and dried under vacuum to obtain the polymer. The molecular weight of the polymer was determined using GPC (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 48,683, with a yield of 74.49%. The polymer has a repeating unit structure represented by the following formula (2).

[0215]

[0216] <Synthetic Example 3> (Synthesis of Polymer (3))

[0217] In a 500 mL four-necked flask, 15.00 g (0.101 mol) of 4,6-dichloropyrimidine (Tokyo Chemical Industry Co., Ltd.), 22.52 g (0.099 mol) of 2,2-bis(4-hydroxyphenyl)propane (Tokyo Chemical Industry Co., Ltd.), 32.79 g (0.252 mol) of potassium carbonate (Kanto Chemical Co., Ltd., premium grade), and 117.31 g of N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., dehydrated) were added, and the mixture was heated to 70 °C and stirred at 70 °C for 51 hours, followed by stirring at 90 °C for 3 hours. After cooling to below 30 °C, 199.33 g of tetrahydrofuran (Kanto Chemical Co., Ltd., premium grade) was added for dilution. The precipitate formed in the reaction solution was removed by filtration to obtain the reaction mixture. The obtained reaction mixture was added dropwise to 309.68 g of methanol (Kanto Chemical Co., Ltd., premium grade) and 154.84 g of pure water to precipitate the polymer. The precipitate was separated by filtration, washed twice with 154.84 g of methanol, and dried under vacuum to obtain the polymer. The molecular weight of the polymer was determined using GPC (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 34,536, with a yield of 50.37%. The polymer has a repeating unit structure represented by the following formula (5).

[0218]

[0219] <Example 1>

[0220] 6.557 g of the polymer obtained in Synthesis Example 1, 0.1311 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 1.3115 g of 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 12.00 g of N-methyl-2-pyrrolidone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0221] <Example 2>

[0222] 10.00 g of the polymer obtained in Synthesis Example 1 was dissolved in 14.99 g of N-methyl-2-pyrrolidone, and then filtered using a PTFE microfilter with a pore size of 5 μm to prepare a resin composition.

[0223] <Example 3>

[0224] 5.6009 g of the polymer obtained in Synthesis Example 1, 0.1311 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 1.1202 g of tris(2-acryloyloxyethyl isocyanate) (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.2496 g of N-methyl-2-pyrrolidone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0225] <Example 4>

[0226] 12.6984 g of the polymer obtained in Synthesis Example 1, 0.7619 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 2.5397 g of trimethylolpropane triacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 24.00 g of N-methyl-2-pyrrolidone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0227] <Example 5>

[0228] 12.6984 g of the polymer obtained in Synthesis Example 1, 0.7619 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 2.5397 g of A-DCP (tricyclodecanedimethylethanol diacrylate) were dissolved in 24.00 g of N-methyl-2-pyrrolidone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0229] <Example 6>

[0230] 6.355 g of the polymer obtained in Synthesis Example 2, 0.3810 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 1.270 g of 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 2.394 g of N-ethyl-2-pyrrolidone and 9.600 g of cyclohexanone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0231] <Comparative Example 1>

[0232] 6.557 g of the polymer obtained in Synthesis Example 3, 0.1311 g of IRGACURE OXE01 (manufactured by BASF, a photopolymerization initiator), and 1.3115 g of 2,2-bis[4-(4-maleimide phenoxy)phenyl]propane (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 12.00 g of N-methyl-2-pyrrolidone to prepare a composition. Subsequently, the composition was filtered using a 5 μm PTFE microfilter to prepare a negative photosensitive resin composition.

[0233] [Photosensitivity Test]

[0234] The prepared resin composition was coated onto a silicon wafer using a spin coater, and pre-baked at 115°C for 270 seconds, followed by a 500 mJ / cm² heat treatment. 2 The film is exposed to cyclohexanone to form a film with a thickness of about 10 μm. Then, the film is immersed in cyclohexanone for 1 minute for development, then rotated to dry, and the film thickness is measured after drying at 115°C for 270 seconds. The film thickness before and after development with cyclohexanone is compared. A film with a residual film rate of 50% or more is considered qualified, and a film with a residual film rate of less than 50% is considered unqualified.

[0235] [Electrical Performance Test]

[0236] The resin compositions prepared in Examples 1-6 were applied to silicon wafers laminated on aluminum using a spin coater, followed by pre-baking at 115°C for 270 seconds and then subjected to a 500 mJ / cm² heat treatment. 2 The film was exposed to nitrogen and baked at 160°C for 1 hour, followed by baking at 230°C for 1 hour to form a film with a thickness of approximately 20 μm. It was then immersed in 6N hydrochloric acid. The film was recovered when the aluminum dissolved and the film floated, and cut into 3 cm long and 9 cm wide sections to obtain a self-supporting film. Using this self-supporting film, the relative permittivity and dielectric loss tangent at 1 GHz were calculated immediately after obtaining the self-supporting film and after storage at 23°C and 50% RH for 24 hours. The detailed measurement method is as follows.

[0237] (Determination Method)

[0238] Perturbation-type cavity resonance method

[0239] (Device Composition)

[0240] Vector Network Analyzer: FieldFox N9926A (manufactured by Keysight Technologies)

[0241] Cavity resonator: Model TMR-1A (manufactured by KEYCOM Co., Ltd.)

[0242] Cavity volume: 1,192,822 mm 3

[0243] Measurement frequency: approximately 1 GHz (depending on the sample's resonant frequency)

[0244] Sample tube: PTFE; Inner diameter: 3mm; Length: approx. 30mm

[0245] The measurement results are shown in Table 1 below.

[0246] Table 1

[0247]

[0248] Industrial availability

[0249] The negative photosensitive insulating film composition of the present invention can provide a cured product with a low initial dielectric loss tangent and a small change over time.

Claims

1. A composition for forming a photosensitive insulating film, comprising a polymer having a repeating unit structure represented by the following formula (1), and a solvent; ###0001### Formula (1) wherein G represents a direct bond, or any one of the following formulas, ###0002### Formula (2) Formula (3) Formula (4) and at least one aromatic heterocycle selected from the group consisting of aromatic heterocycles represented by the following formulas, the aromatic heterocycles having a crosslinkable substituent or not having a crosslinkable substituent, ###0003### Formula (5) Formula (6) Formula (7) Formula (8) Formula (9) Formula (10) Formula (11) Formula (12) Formula (13) Formula (14) Formula (15) Formula (16) Formula (17) Formula (18) Formula (19) Formula (20) Formula (21) Formula (22) Formula (23) Formula (24) Formula (25) Formula (26) Formula (27) Formula (28) Formula (29) Formula (30) Formula (31) Formula (32) Formula (33) Formula (34) Formula (35) Formula (36) Formula (37) Formula (38) Formula (39) Formula (40) Formula (41) Formula (42) Formula (43) Formula (44) Formula (45) Formula (46) Formula (47) Formula (48) Formula (49) Formula (50) Formula (51) Formula (52) Formula (53) Formula (54) Formula (55) Formula (56) Formula (57) Formula (58) Formula (59) Formula (60) Formula (61) Formula (62) Formula (63) Formula (64) Formula (65) Formula (66) Formula (67) Formula (68) Formula (69) Formula (70) Formula (71) Formula (72) Formula (73) Formula (74) Formula (75) Formula (76) Formula (77) Formula (78) Formula (79) Formula (80) Formula (81) Formula (82) Formula (83) Formula (84) Formula (85) Formula (86) Formula (87) Formula (88) Formula (89) Formula (90) Formula (91) Formula (92) Formula (93) Formula (94) Formula (95) Formula (96) Formula (97) Formula (98) Formula (99) Formula (100) Formula (101) Formula (102) Formula (103) Formula (104) Formula (105) Formula (106) Formula (107) Formula (108) Formula (109) Formula (110) Formula (111) Formula (112) Formula (113) Formula (114) Formula (115) Formula (116) Formula (117) Formula (118) Formula (119) Formula (120) Formula (121) Formula (122) Formula (123) Formula (124) Formula (125) Formula (126) Formula (127) Formula (128) Formula (129) Formula (130) Formula (131) Formula (132) Formula (133) Formula (134) Formula (135) Formula (136) Formula (137) Formula (138) Formula (139) Formula (140) Formula (141) Formula (142) Formula (143) Formula (144) Formula (145) Formula (146) Formula (147) Formula (148) Formula (149) Formula (150) Formula (151) Formula (152) Formula (153) Formula (154) Formula (155) Formula (156) Formula (157) Formula (158) Formula (159) Formula (160) Formula (161) Formula (162) Formula (163) Formula (164) Formula (165) Formula (166) Formula (167) Formula (168) Formula (169) Formula (170) Formula (171) Formula (172) Formula (173) Formula (174) Formula (175) Formula (176) Formula (177) Formula (178) Formula (179) Formula (180) Formula (181) Formula (182) Formula (183) Formula (184) Formula (185) Formula (186) Formula (187) Formula (188) Formula (189) Formula (190) Formula (191) Formula (192) Formula (193) Formula (194) Formula (195) Formula (196) Formula (197) Formula (198) Formula (199) Formula (200) Formula (201) Formula (202) Formula (203) Formula (204) Formula (205) Formula (206) Formula (207) Formula (208) Formula (209) Formula (210) Formula (211) Formula (212) Formula (213) Formula (214) Formula (215) Formula (216) Formula (217) Formula (218) Formula (219) Formula (220) Formula (221) Formula (222) Formula (223) Formula (224) Formula (225) Formula (226) Formula (227) Formula (228) Formula (229) Formula (230) Formula (231) Formula (232) Formula (233) Formula (234) Formula (235) Formula (236) Formula (237) Formula (238) Formula (239) Formula (240) Formula (241) Formula (242) Formula (243) Formula (244) Formula (245) Formula (246) Formula (247) Formula (248) Formula (249) Formula (250) Formula (251) Formula (252) Formula (253) Formula (254) Formula (255) Formula (256) Formula (257) Formula (258) Formula (259) Formula (260) Formula (261) Formula (262) Formula (263) Formula (264) Formula (265) Formula (266) Formula (267) Formula (268) Formula (269) Formula (270) Formula (271) Formula (272) Formula (273) Formula (274) Formula (275) Formula (276) Formula (277) Formula (278) Formula (279) Formula (280) Formula (281) Formula (282) Formula (283) Formula (284) Formula (285) Formula (286) Formula (287) Formula (288) Formula (289) Formula (290) Formula (291) Formula (292) Formula (293) Formula (294) Formula (295) Formula (296) Formula (297) Formula (298) Formula (299) Formula (300) Formula (301) Formula (302) Formula (303) Formula (304) Formula (305) Formula (306) Formula (307) Formula (308) Formula (309) Formula (310) Formula (311) Formula (312) Formula (313) Formula (314) Formula (315) Formula (316) Formula (317) Formula (318) Formula (319) Formula (320) Formula (321) Formula (322) Formula (323) Formula (324) Formula (325) Formula (326) Formula (327) Formula (328) Formula (329) Formula (330) Formula (331) Formula (332) Formula (333) Formula (334) Formula (335) Formula (336) Formula (337) Formula (338) Formula (339) Formula (340) Formula (341) Formula (342) Formula (343) Formula (344) Formula (345) Formula (346) Formula (347) Formula (348) Formula (349) Formula (350) Formula (351) Formula (352) Formula (353) Formula (354) Formula (355) Formula (356) Formula (357) Formula (358) Formula (359) Formula (360) Formula (361) Formula (362) Formula (363) Formula (364) Formula (365) Formula (366) Formula (367) Formula (368) Formula (369) Formula (370) Formula (371) Formula (372) Formula (373) Formula (374) Formula (375) Formula (376) Formula (377) Formula (378) Formula (379) Formula (380) Formula (381) Formula (382) Formula (383) Formula (384) Formula (385) Formula (386) Formula (387) Formula (388) Formula (389) Formula (390) Formula (391) Formula (392) Formula (393) Formula (394) Formula (395) Formula (396) Formula (397) Formula (398) Formula (399) Formula (400) Formula (401) Formula (402) Formula (403) Formula (404) Formula (405) Formula (406) Formula (407) Formula (408) Formula (409) Formula (410) Formula (411) Formula (412) Formula (413) Formula (414) Formula (415) Formula (416) Formula (417) Formula (418) Formula (419) Formula (420) Formula (421) Formula (422) Formula (423) Formula (424) Formula (425) Formula (426) Formula (427) Formula (428) Formula (429) Formula (430) Formula (431) Formula (432) Formula (433) Formula (434) Formula (435) Formula (436) Formula (437) Formula (438) Formula (439) Formula (440) Formula (441) Formula (442) Formula (443) Formula (444) Formula (445) Formula (446) Formula (447) Formula (448) Formula (449) Formula (450) Formula (451) Formula (452) Formula (453) Formula (454) Formula (455) Formula (456) Formula (457) Formula (458) Formula (459) Formula (460) Formula (461) Formula (462) Formula (463) Formula (464) Formula (465) Formula (466) Formula (467) Formula (468) Formula (469) Formula (470) Formula (471) Formula (472) Formula (473) Formula (474) Formula (475) Formula (476) Formula (477) Formula (478) Formula (479) Formula (480) Formula (481) Formula (482) Formula (483) Formula (484) Formula (485) Formula ( In formula (1), the group A 1 represents an aromatic heterocycle having a cross-linking substituent or not having a cross-linking substituent, Group A 2 represents a group selected from the group consisting of ​ group B 1 is at least one selected from the group consisting of ​ L, M each independently represent a hydrogen atom, a phenyl group, or a C1-3 alkyl group, and the group B 2 is at least one selected from the group consisting of ​ ​ n 1 is 1, n 2 is a number of 0 or more and 1 or less, m 1 and m 2 each independently is a number of 0 or higher and 1 or lower, ​ 2. The photosensitive insulating film forming composition according to claim 1, wherein the group B 1 by ​ 3. The photosensitive insulating film forming composition according to claim 1 or 2, wherein the group B 2 by ​ ​ ​ ​ 7. A photosensitive resin film characterized by ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ In formula (1), the group A 1 is an aromatic heterocycle having a cross-linking substituent or not having a cross-linking substituent, Group A 2 represents a group selected from the group consisting of ​ group B 1 is at least one selected from the group consisting of ​ ​ group B 2 is at least one selected from the group consisting of ​ ​ n 1 is 1, n 2 is a number of 0 or more and 1 or less, m 1 and m 2 each independently is a number of 0 or more and 1 or less, ​ ​ ​ ​

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