Photosensitive resin composition, and method for producing cured relief pattern, cured film and interlayer insulation film which use the photosensitive resin composition

Abstract

To provide a photosensitive resin composition which can enhance heat resistance of a cured film even in low temperature curing at 250°C or lower, is excellent in mechanical elongation of a cured film, and has high adhesion to copper and high chemical resistance; and to provide a method for producing a cured relief pattern, a cured film and an interlayer insulation film, which use the photosensitive resin composition.SOLUTION: A photosensitive resin composition of the present invention contains the following components (A) to (C): (A) polyamic acid ester; (B) an acid anhydride compound; and (C) a photopolymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a method for producing a cured relief pattern using the same, a cured film, and an interlayer insulating film. [Background technology]

[0002] Polyimide resins, polybenzoxazole resins, phenolic resins, and the like, which have excellent heat resistance and electrical and mechanical properties, have conventionally been used as insulating materials for electronic components, and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these resins, those provided in the form of a photosensitive resin composition can easily form a heat-resistant relief pattern film by coating, exposing, developing, and curing the composition to a ring-closing treatment (imidization, benzoxazole formation) or thermal crosslinking. This allows for a significant reduction in the process time compared to conventional non-photosensitive materials, and they are therefore used in the fabrication of semiconductor devices.

[0003] Semiconductor devices (hereinafter also referred to as "elements") are mounted on printed circuit boards by various methods depending on the purpose. Conventional elements have generally been fabricated using wire bonding, which connects the external terminals (pads) of the element to the lead frame with thin wires. However, as elements have become faster and their operating frequencies have reached GHz, differences in the wiring length of each terminal during mounting have come to affect the operation of the element. As a result, when mounting elements for high-end applications, it has become necessary to accurately control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] To address this issue, flip-chip packaging has been proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the redistribution layer, and the chip is then flipped over and directly mounted on a printed circuit board. Because flip-chip packaging allows for precise control of wiring distance, it has been adopted for high-end applications that handle high-speed signals, and for mobile phones and other devices due to its small packaging size, resulting in rapidly expanding demand. More recently, a semiconductor chip packaging technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which individual chips are manufactured by dicing a pre-processed wafer, the individual chips are reassembled on a support, encapsulated with a molding resin, and a redistribution layer is formed after the support is peeled off (see, for example, Patent Document 1). In FOWLP, the redistribution layer is formed with a thin film thickness, which allows for a thinner package, as well as higher-speed transmission and lower costs. Patent Documents 1 and 2, for example, disclose photosensitive resin compositions for use in such redistribution layers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2023-025070 [Patent Document 2] Patent Publication No. 2021-162834 Summary of the Invention [Problem to be solved by the invention]

[0006] In FOWLP, it is desirable to have a curing temperature (thermal imidization temperature) lower than conventional methods, from the viewpoint of preventing wafer warpage during the process. However, lowering the curing temperature poses a problem of deterioration in heat resistance, such as glass transition temperature, and mechanical strength, such as elongation. Patent Document 2 describes that adding a polyfunctional (meth)acrylate compound is expected to improve heat resistance and mechanical properties. However, there is a concern that adding a polyfunctional (meth)acrylate compound may deteriorate adhesion to copper.

[0007] The present invention has been devised in view of the above circumstances, and aims to provide a photosensitive resin composition that can enhance the heat resistance of a cured film even when cured at a low temperature of 250°C or less, and that produces a cured film with excellent mechanical elongation, high adhesion to copper, and high chemical resistance; a method for producing a cured relief pattern using the same; and a cured film and an interlayer insulating film. [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by combining a polyamic acid ester with an acid anhydride compound, and have thus completed the present invention. That is, the present invention is as follows.

[0009] [1] The following components (A) to (C): (A) polyamic acid ester, (B) an acid anhydride compound, and (C) Photopolymerization initiator A photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], wherein the component (B) is an acid anhydride containing no alkoxysilyl group and having a molecular weight of 100 or more. [3] The photosensitive resin composition according to [1] or [2], wherein the proportion of the component (B) relative to 100 parts by mass of the component (A) is 1.5 parts by mass or more. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the component (A) has a structure represented by the following general formula (1): [ka] (In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of which represents a monovalent organic group having a radically polymerizable group having 1 to 40 carbon atoms, and n is an integer of 2 to 100.) [5] The photosensitive resin composition according to any one of [1] to [4], wherein the proportion of the component (B) relative to 100 parts by mass of the component (A) is 2.0 parts by mass or more. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the proportion of the component (B) relative to the total mass of the photosensitive resin composition is 0.5 mass % or more. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the repeating unit of the component (A) has a side chain equivalent weight represented by the following formula of 400 or less: Side chain equivalent weight = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A) [8] The photosensitive resin composition according to any one of [1] to [6], wherein the side chain equivalent weight per repeating unit of the component (A), represented by the following formula, is 350 or less. Side chain equivalent weight = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A) [9] In addition, the following ingredients: (E) UV absorber The photosensitive resin composition according to any one of [1] to [8], comprising:

[10] The photosensitive resin composition according to [9], wherein the component (E) contains a compound having a quinone diazide group.

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

[10] , wherein the molecular weight of the component (B) is 1,000 or less.

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

[11] , wherein the component (B) is an aromatic carboxylic acid anhydride.

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

[11] , wherein the component (B) has a cyclic acid anhydride structure.

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

[11] , wherein the component (B) has a five-membered ring acid anhydride structure.

[15] The photosensitive resin composition according to any one of [1] to

[14] , wherein the component (B) has a structure represented by the following general formula (2): [ka] (In the formula, R3 to R6 each independently represent a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and these may be bonded to form a ring.)

[16] The photosensitive resin composition according to any one of [1] to

[15] , which is used for an interlayer insulating film.

[17] The following steps: (1) A step of applying the photosensitive resin composition according to any one of [1] to

[16] onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

[18] A cured film comprising a cured product of the photosensitive resin composition according to any one of [1] to

[16] .

[19] An interlayer insulating film obtained by using the photosensitive resin composition according to any one of [1] to

[16] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a photosensitive resin composition that can enhance the heat resistance of a cured film even when cured at a low temperature of 250°C or less, and that can produce a cured film with excellent elongation, high adhesion to copper, and high chemical resistance, as well as a method for producing a cured relief pattern using the same, a cured film, and an interlayer insulating film. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the gist. Throughout this specification, structures represented by the same symbol in a general formula may be the same or different when multiple structures are present in a molecule. In addition, numerical ranges expressed using "to" in the specification are intended to include the upper and lower limit values.

[0012] <Photosensitive resin composition> The photosensitive resin composition of the present invention comprises the following components (A) to (C): (A) polyamic acid ester, (B) an acid anhydride compound, and (C) Photopolymerization initiator Includes. In one embodiment, the photosensitive resin composition of the present invention comprises the following components (A) to (C): (A) polyamic acid ester, (B) an acid anhydride compound containing no alkoxysilyl group, and (C) a photopolymerization initiator, The proportion of component (B) is 1.5 parts by mass or more per 100 parts by mass of component (A). The photosensitive resin composition of the present invention may be a so-called negative photosensitive resin composition in which exposed areas become insoluble in a developer.

[0013] Without being limited by theory, the inventors believe that the reason why the photosensitive resin composition of the present invention exhibits the above-mentioned effects is as follows. When (A) a polyamic acid ester and (B) an acid anhydride compound are used in combination, when the polyamic acid ester is converted into a polyimide by heat treatment, the hydroxyl groups on the side chains that are eliminated react with the acid anhydride compound to generate carboxyl groups, which then interact with the copper substrate, resulting in high adhesion to copper. In addition, when the side chains contain polymerizable functional groups, the side chains are less likely to volatilize, increasing the amount of polymerizable functional groups remaining in the film. This improves the crosslink density in the system, contributing to improved mechanical properties, heat resistance, and chemical resistance.

[0014] (A) Polyamic acid ester The (A) polyamic acid ester (hereinafter also referred to as component (A)) is a resin component contained in the photosensitive resin composition. There are no particular restrictions on the resin that can be used as long as it forms a polyimide upon thermal cyclization treatment. However, from the viewpoint of increasing the crosslink density in the system and making it easier to achieve the effects of the present invention, it is preferable that component (A) has a polyamic acid ester structure represented by the following general formula (1): [ka] (In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, R1 and R2 are each independently a hydrogen atom or a monovalent organic group, at least one of which represents a monovalent organic group having a radically polymerizable group having 1 to 40 carbon atoms, and n is an integer of 2 to 100.)

[0015] The structure of the polyamic acid ester (A) preferably has a side chain equivalent per repeating unit of 400 or less, preferably 360 or less, and more preferably 350 or less. The side chain equivalent is expressed as the molecular weight of the repeating unit divided by the number of side chains. In other words, the smaller the side chain equivalent, the greater the amount of side chains in the polymer. The side chain here refers to an organic group that is eliminated when the polyamic acid ester is imidized by heating, and preferably refers to an organic group having one or more carbon atoms. The side chain equivalent can be calculated using the following formula: Side chain equivalent weight = molecular weight per repeating unit of component (A) / number of side chains per repeating unit of component (A)

[0016] Without being limited by theory, it is believed that the smaller the side chain equivalent weight, the more side chain components react with the acid anhydride, and the more pronounced the effect.

[0017] When two or more polymers are used or when two or more skeletons are copolymerized, the side chain equivalent weight is calculated for each skeleton, and the weighted average of the blend ratio is expressed.

[0018] In general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably an aromatic group or an alicyclic aliphatic group in which the -COOR1 and -COOR2 groups and the -CONH- group are located at the ortho positions relative to each other. Examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms and containing an aromatic ring, and specific examples include groups having the structures represented by the following general formulas (X1-1) to (X1-3), but are not limited to these. [ka] [ka] [ka]

[0019] In formulas (X1-1) to (X1-3), R is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C10 hydrocarbon group, and a C1 to C10 fluorinated hydrocarbon group, l is an integer selected from 0 to 2, m is an integer selected from 0 to 3, and n is an integer selected from 0 to 4. The structure of X1 may be one type or a combination of two or more types. Of the X1 groups having structures represented by each of the above formulas (X1-1) to (X1-3), (X1-2) is particularly preferred in that it has a small side chain equivalent weight, and structures represented by each of the above formulas (X1-1) are more preferred.

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in order to achieve both heat resistance and photosensitive properties, and examples thereof include, but are not limited to, structures represented by the following formulas (Y1-1) to (Y1-3).

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] In formulas (Y1-1) to (Y1-3), R represents a hydrogen atom, a fluorine atom, or a C1 to C 10 and hydrocarbon groups of C1 to C 10 and n is an integer selected from 0 to 4. The structure of Y1 may be one type or a combination of two or more types. Of the Y1 groups having structures represented by the above formulae (Y1-1) to (Y1-3), (Y1-2) is particularly preferred in that it has a small side chain equivalent weight, and structures represented by the above formulae (Y1-1) are even more preferred.

[0025] At least one of R1 and R2 in the general formula (1) is preferably a group containing a radically polymerizable group, where the radically polymerizable group refers to a group that can be polymerized by the action of a radical.

[0026] From the viewpoint of crosslink density, at least one of R1 and R2 is preferably a group containing a radical polymerizable group, more preferably a monovalent organic group having 1 to 40 carbon atoms, and even more preferably a group represented by the following general formula (3): [ka] In formula (3), R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer of 1 to 10, preferably an integer of 1 to 5, or an integer of 1 to 3. For example, the group represented by general formula (3) is preferably a group represented by the following formula (4). [ka] In formula (4), R7, R8, and R9 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. More specific examples of the monovalent organic group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R7 is preferably a hydrogen atom or a methyl group, and R8 and R9 are preferably hydrogen atoms.

[0027] (A) Method for preparing polyamic acid ester The polyamic acid ester (A) can be prepared, for example, by reacting a tetracarboxylic acid dianhydride containing the aforementioned tetravalent organic group X1 with an alcohol having a radically polymerizable group and, optionally, other alcohols to prepare a partially esterified tetracarboxylic acid (hereinafter referred to as an acid / ester), followed by amide polycondensation of the partially esterified tetracarboxylic acid (acid / ester) with a diamine containing the aforementioned divalent organic group Y1 to obtain the polyamic acid ester (A).

[0028] As the tetracarboxylic acid dianhydride containing a tetravalent organic group X1, which is suitably used for preparing the (A) polyamic acid ester, a compound represented by the following general formula (5) is preferred. [ka] In formula (5), X1 is as defined in general formula (1) above. This X1 is preferably selected from the structures represented by the general formulae (X1-1) to (X1-3) above, more preferably the structures represented by the general formulae (X1-1) to (X1-2), and even more preferably the structure represented by (X1-1).

[0029] Particularly preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. Particularly preferred examples include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0030] (A) Examples of alcohols having a radical polymerizable group that are suitably used for preparing the polyamic acid ester include 2-hydroxyethyl methacrylate, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxypropyl acrylate, 2-hydroxy-3-methyl-2-propanol ... Examples of the copolymer include acryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, glycerol diacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate.

[0031] The above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol are dissolved and mixed in the presence of a suitable basic catalyst such as pyridine, preferably in a solvent as described below, preferably at a temperature of 20 to 50°C, preferably for 4 to 10 hours with stirring, whereby an esterification reaction of the acid anhydride group of the tetracarboxylic dianhydride proceeds, and the desired acid / ester form can be obtained.

[0032] (Preparation of Polyamic Acid Ester) The acid / ester compound (typically in the form of a solution dissolved in a solvent, as described below) is mixed with an appropriate dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, or N,N'-disuccinimidyl carbonate, under ice cooling to convert the acid / ester compound into a polyanhydride. A diamine containing a divalent organic group Y1, as preferred in this embodiment, dissolved or dispersed in a separate solvent is then added dropwise to the resulting mixture to carry out amide polycondensation, thereby obtaining the desired polyimide precursor. Depending on the reactivity of the substrate, 1-hydroxybenzotriazole or the like may also be used. Alternatively, the acid moiety of the acid / ester compound can be converted into an acid chloride using thionyl chloride or the like, followed by reaction with a diamine in the presence of a base such as pyridine to obtain the desired polyamic acid ester.

[0033] The diamine containing the divalent organic group Y1 preferably used in this embodiment is a diamine represented by the formula: H2N-Y1-NH2 A compound represented by the following formula is preferred: {wherein Y1 is as defined in the above general formula (1).} It is more preferred that Y1 is a structure represented by each of the above general formulae (Y1-1) to (Y1-3).

[0034] More preferred diamines include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "DADPE"), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4' -diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3 -aminophenoxy)phenyl] sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,Examples of the diaminodiphenylmethane include, but are not limited to, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl. These may be used alone or in combination of two or more.

[0035] In the production of the polyimide precursor (A), a reaction solvent may be used to efficiently carry out the reaction in a homogeneous system. The reaction solvent is not particularly limited as long as it can uniformly dissolve or suspend the tetracarboxylic dianhydride, diamine, and compound having a polymerizable group at its end. Examples of the reaction solvent include γ-butyrolactone, dimethyl sulfoxide, N,N-dimethylacetoacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0036] After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as needed, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both, swollen with an appropriate organic solvent to remove ionic impurities.

[0037] The molecular weight of the polyamic acid ester (A), as measured by gel permeation chromatography (GPC) in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for GPC. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrenes. It is recommended that standard monodisperse polystyrenes be selected from the organic solvent standard sample "TSKstandard POLYSTYLENE" manufactured by TOSOH.

[0038] As the (A) polyamic acid ester, a non-photosensitive polyamic acid ester prepared using only the above-mentioned alcohol having no polymerizable group may be used in combination with the photosensitive polyamic acid ester of the present invention. In this case, from the viewpoints of resolution, mechanical properties, heat resistance, and chemical resistance, the amount of the non-photosensitive polyamic acid ester blended is preferably 200 parts by mass or less per 100 parts by mass of the photosensitive polyamic acid ester.

[0039] (B) Acid anhydride compound The acid anhydride compound (B) used in this embodiment will be described. In this embodiment, it is believed that adding an acid anhydride compound to the photosensitive resin composition reacts with the side chains released from the polymer during imidization to improve the heat resistance of the cured film, and to impart high elongation and high adhesion to copper to the cured film.

[0040] In particular, the acid anhydride compound (B) (hereinafter also referred to as component (B)) in this embodiment contains an alkoxysilyl group: —Si(OR 10 )3(R 10 In the present embodiment, the acid anhydride compound (B) does not preferably contain an alkoxysilyl group, and therefore ... 10 )3 by hydrolysis of liberated R10 The reaction between OH and the acid anhydride structure is suppressed, and the inhibition of the reaction between the leaving side chain and the acid anhydride is suppressed, which contributes to improving the heat resistance and elongation of the cured film, as well as high adhesion to copper.

[0041] The (B) acid anhydride compound preferably has a molecular weight of 100 or more. A molecular weight of 100 or more is less likely to volatilize during the drying and curing processes after coating, and is therefore more likely to react with the eliminated side chains, thereby demonstrating its effectiveness. The lower limit of the molecular weight of the (B) acid anhydride compound is more preferably 110 or more, even more preferably 120 or more, particularly preferably 130 or more, and most preferably 140 or more. Furthermore, from the standpoint of the acid anhydride equivalent, the upper limit of the molecular weight of the (B) acid anhydride compound is preferably 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. The molecular weight (e.g., weight average molecular weight) of the (B) component can be determined by calculating the chemical formula of the (B) component. In one embodiment, the (B) component is an acid anhydride having a molecular weight of 100 or more and not containing an alkoxysilyl group. Furthermore, the structure of the acid anhydride compound is not particularly limited, but from the viewpoint of reactivity, component (B) is preferably an aromatic carboxylic acid anhydride, preferably has a cyclic acid anhydride structure, more preferably has a five-membered ring acid anhydride structure, and more preferably has a structure represented by the following general formula (2): [ka] (In the formula, R3 to R6 each independently represent a hydrogen atom or an organic group having 1 to 40 carbon atoms, and these may be bonded to form a ring.)

[0042] (B) The acid anhydride compound may be an aliphatic carboxylic acid anhydride or an aromatic carboxylic acid anhydride.

[0043] Examples of aliphatic acid anhydride compounds include acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, 2-methylbutyric anhydride, pivalic anhydride, isovaleric anhydride, valeric anhydride, 2-methylvaleric anhydride, 3-methylvaleric anhydride, 4-methylvaleric anhydride, hexanoic anhydride, 2-methylhexanoic anhydride, 3-methylhexanoic anhydride, 4-methylhexanoic anhydride, 5-methylhexanoic anhydride, heptanoic anhydride, 2-methylheptanoic anhydride, 3-methylheptanoic anhydride, and 4-methylheptanoic anhydride. , 5-methylheptanoic anhydride, 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride (glutaric anhydride), decanoic anhydride, 1,2-cyclohexanedicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, and the like.

[0044] Examples of aromatic carboxylic acid anhydrides include benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, 4-methylphthalic anhydride, 4-ethynylphthalic anhydride, 4-(methylethynyl)phthalic anhydride, and homophthalic anhydride.

[0045] The content of the (B) acid anhydride compound is preferably 1.5 parts by mass or more and 10 parts by mass or less, more preferably 2.0 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the (A) polyamic acid ester. From the viewpoints of elongation, glass transition temperature (hereinafter also referred to as Tg), and copper adhesion, the content is preferably 1.5 parts by mass or more, and from the viewpoint of storage stability, the content is preferably 10 parts by mass or less. Furthermore, from the viewpoints of elongation, glass transition temperature, and copper adhesion, the content of the acid anhydride compound is preferably 0.5% by mass or more, preferably 0.6% by mass or more, relative to the total mass of the photosensitive resin composition, from the viewpoints of elongation, glass transition temperature, and copper adhesion, and is preferably 5% by mass or less, preferably 4% by mass or less, from the viewpoint of storage stability.

[0046] (C) Photopolymerization initiator The photopolymerization initiator (C) (hereinafter also referred to as component (C)) used in this embodiment will be described below. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0047] Examples of the photoradical polymerization initiator include benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl compounds such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl) Examples of suitable oxime compounds include oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, and ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (trade name: KZ-129); N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazole compounds; and titanocene compounds.

[0048] The photopolymerization initiator (C) used in this embodiment is not limited to the above examples, but is more preferably an oxime compound, particularly in terms of photosensitivity.

[0049] The content of the (C) photopolymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the (A) polyamic acid. The content is preferably 0.1 part by mass or more from the viewpoint of photosensitivity or patterning ability, and is preferably 30 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0050] (D) Solvent The photosensitive resin composition of this embodiment may optionally contain a (D) solvent (hereinafter also referred to as component (D)). The (D) solvent is not limited as long as it can uniformly dissolve or suspend the (A) polyamic acid ester, the (B) acid anhydride compound, and the (C) photopolymerization initiator. Examples of such solvents include γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, N,N-dimethylacetoacetamide, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. These solvents may be used alone or in combination.

[0051] The (D) solvent can be used in an amount of, for example, 30 to 1,000 parts by mass, preferably 100 to 1,000 parts by mass, per 100 parts by mass of the (A) polyamic acid ester, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0052] When the (D) solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50 mass %. The lower limit is more preferably 10 mass % or more from the viewpoint of the storage stability of the photosensitive resin composition. The upper limit is more preferably 30 mass % or less from the viewpoint of the solubility of the (A) polyamic acid ester.

[0053] (E) UV absorber The photosensitive resin composition of this embodiment may optionally contain (E) an ultraviolet absorber (hereinafter also referred to as component (E)). It is believed that the use of (E) an ultraviolet absorber can control the photopolymerization reaction and adjust the crosslink density to an appropriate level.

[0054] The (E) ultraviolet absorber is preferably at least one compound selected from the group consisting of 2-(2'-hydroxyphenyl)benzotriazole compounds, hydroxyphenyltriazine compounds, 2-hydroxybenzophenone compounds, cyanoacrylate compounds, azobenzene compounds, polyphenol compounds, and compounds having a quinone diazide group.

[0055] Specific examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 6-(2-benzotriazolyl)-4-tert-octyl-6'- tert-Butyl-4'-methyl-2,2'-methylenebisphenol, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl) Benzotriazole and other 2-(2'-hydroxyphenyl)benzotriazole compounds; 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl Hydroxyphenyltriazine compounds such as 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, bemotrizinol, and 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine; 2-hydroxybenzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate;Examples include cyanoacrylate compounds, azobenzene compounds, polyphenol compounds such as catechin, rutin, cyanidin, and curcumin, and compounds having a quinone azide group (hereinafter also referred to as "quinone diazide compounds" or "compounds having a quinone diazide group"). Other examples include a compound synthesized from 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (trade name Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride, a compound synthesized from Tris-PA and 1,2-naphthoquinone diazide-4-sulfonic acid chloride, a compound synthesized from p-cumylphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride, a compound synthesized from p-cumylphenol and 1,2-naphthoquinone diazide-4-sulfonic acid chloride, and Tekoc-4HBPA (trade name Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) as described in WO2022 / 154020. Examples of such compounds include a compound synthesized from (product name) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride, a compound synthesized from 2,2-bis(4-hydroxyphenyl)propane and 1,2-naphthoquinone diazide-5-sulfonic acid chloride, and a compound synthesized from p-cresol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride;

[0056] The ultraviolet absorber (E) preferably contains a compound having a quinone diazide group. A compound having a quinone diazide group generates a carboxylic acid when exposed to light. The carboxylic acid interacts with the carboxyl group generated by the reaction of the acid anhydride with the side chain, increasing the crosslink density and further improving the glass transition temperature and elongation of the cured film. Furthermore, the resulting carboxyl group interacts with the copper substrate, resulting in improved copper adhesion.

[0057] The content of the (E) ultraviolet absorber is preferably 1 part by mass or more and 30 parts by mass or more, and more preferably 2 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the (A) polyamic acid ester. The content is preferably 1 part by mass or more from the viewpoints of the elongation, glass transition temperature, and copper adhesion of the cured film, and 30 parts by mass or less from the viewpoints of photosensitivity or patterning ability.

[0058] The photosensitive resin composition may further contain components other than the above components (A) to (E). Examples of the components other than components (A) to (E) include, but are not limited to, rust inhibitors, adhesion promoters, hindered phenol compounds, organic titanium compounds, thermal crosslinking agents, sensitizers, and thermal polymerization inhibitors.

[0059] (rust inhibitor) The rust inhibitor used in this embodiment will be described. When a photosensitive resin composition is used to form a cured film on a substrate made of copper or a copper alloy, the photosensitive resin composition may optionally contain a rust inhibitor in order to improve adhesion between the copper and the polyimide film. Examples of the rust inhibitor include nitrogen-containing heterocyclic compounds, and specific examples include azole compounds and purine compounds.

[0060] Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-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, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-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, and the like.

[0061] Particularly preferred are 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0062] Specific examples of purine compounds include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9 aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0063] When the photosensitive resin composition contains a rust inhibitor, the content thereof is preferably 0.01 to 20 parts by mass per 100 parts by mass of the (A) polyamic acid ester. The lower limit is more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, because adhesion to copper is improved when the photosensitive resin composition is formed on copper or a copper alloy. The upper limit is more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, from the viewpoint of photosensitivity.

[0064] (adhesion aid) In order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the photosensitive resin composition may optionally contain an adhesion promoter, such as an aluminum-based adhesion promoter or a silane coupling agent.

[0065] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0066] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, and N-(3-diethoxymethylsilylpropyl) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.: trade name) KBM803, manufactured by Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxy Dimethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane,

[0067] N-(3-triethoxysilylpropyl)urea (Shin-Etsu Chemical Co., Ltd.: trade name LS3610, Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl) Urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea, 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2),

[0068] 2-(Trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetra tetrakis(methoxy-n-propoxysilane), tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide,

[0069] Di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane, phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyl phenyl silanediol, isobutyl phenyl silanediol, tert-butyl phenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol , n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, etc. Further examples include silane coupling agents having structures represented by the following formula (S-1), but are not limited to these. [ka]

[0070] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength.As the silane coupling agent, among the above-mentioned silane coupling agents, it is preferable to use one or more selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents having the structure represented by each of the above formula (S-1).

[0071] When the photosensitive resin composition contains an adhesion promoter, the amount of the adhesion promoter is preferably 0.01 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the (A) polyamic acid ester. When a silane coupling agent is used, the amount is preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the (A) polyamic acid ester. From the viewpoint of copper adhesion, the lower limit of the amount is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. From the viewpoint of preventing the generation of foreign matter due to precipitation, the upper limit is more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less.

[0072] (hindered phenol compounds) To suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,

[0073] 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-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-t-butyl-3-hydro 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,Examples include, but are not limited to, 5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0074] When the photosensitive resin composition contains a hindered phenol compound, the content thereof is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyamic acid ester. The lower limit thereof is more preferably 0.5 parts by mass or more, since discoloration and corrosion of copper or a copper alloy are prevented when the photosensitive resin composition is formed on copper or a copper alloy. The upper limit thereof is more preferably 10 parts by mass or less, from the viewpoint of photosensitivity.

[0075] (organotitanium compounds) The photosensitive resin composition may contain an organotitanium compound. By containing the organotitanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0076] Usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Specific examples include titanium(IV) oxide acetylacetonate, titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like. II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

[0077] III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0078] Among these, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred as the organic titanium compound from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and titanium(IV) oxide acetylacetonate are preferred.

[0079] When the photosensitive resin composition contains an organotitanium compound, the content thereof is preferably 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the (A) polyamic acid ester. The lower limit thereof is more preferably 0.2 parts by mass or more from the viewpoint of the heat resistance and chemical resistance of the resulting cured film. The upper limit thereof is more preferably 4 parts by mass or less from the viewpoint of the storage stability of the photosensitive resin composition.

[0080] (thermal crosslinking agent) In order to suppress the cure shrinkage of the cured film, the photosensitive resin composition may optionally contain a thermal crosslinking agent.

[0081] The thermal crosslinking agent refers to a compound that undergoes an addition reaction or a condensation polymerization reaction when heated. These reactions occur between (A) the polyamic acid ester and the thermal crosslinking agent, between other thermal crosslinking agents, or between a thermal crosslinking agent and other components, and the reaction temperature is preferably 150°C or higher.

[0082] Examples of the thermal crosslinking agent include an alkoxymethyl compound, an epoxy compound, an oxetane compound, a bismaleimide compound, an allyl compound, and a blocked isocyanate compound. From the viewpoint of suppressing cure shrinkage, the thermal crosslinking agent preferably contains a nitrogen atom.

[0083] Examples of the alkoxymethyl compound include, but are not limited to, the following compounds: [ka] [ka]

[0084] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing bisphenol A groups, and hydrogenated bisphenol A diglycidyl ether (e.g., Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.). Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, and bis(3-ethyl-3-oxetanylmethyl) Examples of suitable oxetane derivatives include diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, trade name: OXT121 (manufactured by Toagosei Co., Ltd.), and trade name: OXT221 (manufactured by Toagosei Co., Ltd.).

[0085] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3-furan

[0033] Examples of suitable phenylene bis(maleimide) include N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0086] Examples of the allyl compound include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0087] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), and 4-methyl-4-isocyanate. Examples of the blocked isocyanate include 4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Coronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden). Among these, blocked isocyanates and bismaleimide compounds are preferred from the viewpoint of storage stability. The thermal crosslinking agents may be used alone or in combination of two or more.

[0088] The content of the thermal crosslinking agent in the photosensitive resin composition is preferably 0.2 to 40 parts by mass relative to 100 parts by mass of the (A) polyamic acid ester. From the viewpoint of chemical resistance, the lower limit is more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more. From the viewpoint of storage stability of the photosensitive resin composition, the upper limit is more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0089] (sensitizer) The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0090] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of the (A) polyamic acid ester.

[0091] (thermal polymerization inhibitor) The photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the stability of viscosity and photosensitivity, particularly when stored in the form of a solution containing a solvent.

[0092] Examples of the thermal polymerization inhibitor that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, 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-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0093] <Method for producing cured relief pattern> The method for producing a cured relief pattern of the present invention comprises the steps of: (1) a step of applying the above-described photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate (a resin layer forming step); (2) a step of exposing the photosensitive resin layer to light (exposure step); (3) a step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern formation step); (4) a step of heat-treating the relief pattern to form a cured relief pattern (a cured relief pattern forming step); Includes:

[0094] (1) Resin layer formation process In this step, the photosensitive resin composition is applied to a substrate and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0095] If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, in the case of air drying or heat drying, drying can be carried out under conditions of 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on a substrate.

[0096] (2) Exposure process In this process, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a patterned photomask or reticle. If the polyamic acid ester (A) has a polymerizable functional group, this exposure causes the polymerizable functional group to crosslink due to the action of the photopolymerization initiator (C). This crosslinking renders the exposed portion insoluble in the developer solution described below, enabling the formation of a relief pattern. If the polyamic acid ester does not have a polymerizable functional group, a monomer having a polymerizable functional group can be added to the composition, causing crosslinking upon exposure to form a relief pattern.

[0097] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) or post-development baking, or both, may be performed at any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40°C to 200°C and a time of 10 to 600 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition of the present invention.

[0098] (3) Relief pattern formation process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0099] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Two or more solvents, for example, a combination of several solvents, can also be used.

[0100] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to dissolve the photosensitive component and, if a polyamic acid ester (A) is used, to imidize it and convert it into a cured relief pattern composed of polyimide. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 160°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 300°C or lower, more preferably 250°C or lower. Air or an inert gas such as nitrogen or argon can be used as the atmospheric gas during heat curing. Use of the photosensitive resin composition of the present invention can enhance the heat resistance of the cured film, even when cured at a low temperature of 250°C or lower.

[0101] <Cured polyimide film> The present invention also provides a cured film containing a cured product formed from the photosensitive resin composition of the present invention. The cured film formed from the photosensitive resin composition is believed to contain a polyimide having a structure represented by the following formula. Such a cured film has a high glass transition temperature, excellent elongation, high copper adhesion, and chemical resistance. [ka] (In the formula, X1, Y1, and n are defined as above.)

[0102] <Semiconductor device> The present invention also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, the present invention provides a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern. The cured relief pattern may be produced by the above-described method for producing a cured relief pattern using the above-described photosensitive resin composition. Such a semiconductor device has excellent reliability because it has a cured relief pattern with a cured film having excellent glass transition temperature and elongation, high adhesion to copper, and chemical resistance.

[0103] The present invention also provides a method for manufacturing a semiconductor device, using a semiconductor element as a substrate and including the method for manufacturing a cured relief pattern of the present embodiment as part of the process. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure can be formed as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for redistribution wiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and the resulting film can be combined with a known method for manufacturing a semiconductor device. In particular, the photosensitive resin composition of the present invention can be suitably used as an interlayer insulating film.

[0104] <Display device> The present disclosure also provides a display device including a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. The cured film can be used, for example, as a surface protection film, insulating film, or planarizing film for a TFT liquid crystal display element or a color filter element; a protrusion for an MVA-type liquid crystal display device; or a partition wall for a cathode of an organic EL element. [Example]

[0105] The present embodiment will be described in detail below with reference to examples, but the present embodiment is not limited thereto. In the examples, comparative examples, reference examples, and synthesis examples, the physical properties of the polyamic acid ester, polyimide, or photosensitive resin composition were measured and evaluated according to the following methods.

[0106] <Measurement and evaluation methods> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene equivalent) under the following conditions. Device: HLC-8320GPC (Tosoh Corporation) Eluent: N-methyl-2-pyrrolidone Lithium bromide monohydrate 30mmol / L Phosphate 50mmol / L Flow rate: 0.5mL / min Column: 2 TSK-GEL SUPER HM-H columns / 1 TSK-GEL SUPER H-RC column Column temperature: 40℃ Detector: UV-8320

[0107] (2) Preparation of cured film for measuring glass transition temperature and elongation A photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer that had been previously sputtered with Al using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) so that the film thickness after drying would be 10 μm. The resulting photosensitive resin film was then pre-baked on a hot plate at 110°C for 240 seconds to form a coating film with a thickness of 10 μm. A high-pressure mercury lamp was used to irradiate the resulting photosensitive resin film with 500 mJ / cm2. 2 After that, the film was heated in a temperature-programmed curing oven (VF-2000 model, manufactured by Koyo Lindberg) at 230°C for 2 hours in a nitrogen atmosphere to obtain a cured film for elongation measurement.

[0108] (3) Measurement of elongation The cured film on the Al wafer obtained in (2) above was cut into 3 mm wide strips using a dicing machine (DISCO, DAD3350) and treated with 10% hydrochloric acid to obtain 3 mm wide polyimide tape. The obtained polyimide tape was left to stand for 24 hours or more in an atmosphere at a temperature of 23°C and a humidity of 50%. The elongation of the left polyimide tape was measured using a tensile tester (UTM-II-20 model, manufactured by Orientec Co., Ltd.) at a test speed of 40 mm / min and an initial load of 0.5 fs, and the elongation and average elongation were calculated as defined below. In this application, the test was performed 10 times. Elongation (%) = 100 × {(specimen length at break - specimen length before test) / specimen length before test} Average elongation (%) = total elongation for all tests / number of tests

[0109] The average elongation determined above was evaluated based on the following criteria. Excellent: Average elongation of 35% or more Good: Average elongation is 20% or more but less than 35% Acceptable: Average elongation is 8% or more but less than 20% Unacceptable: Average elongation less than 8%

[0110] (4) Measurement of glass transition temperature (Tg) The cured film on the Al wafer obtained in (2) above was cut into 3 mm wide strips using a dicing machine (DISCO, DAD3350) and treated with 10% hydrochloric acid to obtain 3 mm wide polyimide tape. The resulting polyimide tape was heated from room temperature to 400°C at a heating rate of 10°C / min in a nitrogen atmosphere using a thermomechanical analyzer (TMA) (TMA-60, Shimadzu Corporation), and the glass transition temperature (°C) was measured.

[0111] (5) Copper adhesion evaluation The photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer that had been previously sputtered with Ti and Cu using a coater developer (D-Spin 60A, manufactured by SOKUDO Co., Ltd.) so that the film thickness after drying would be 10 μm. The wafer was then pre-baked on a hot plate at 110°C for 240 seconds to form a coating film with a thickness of 10 μm. The resulting photosensitive resin film was then irradiated with 500 mJ / cm2 of a high-pressure mercury lamp. 2 The film was then exposed to light and heated for 2 hours at 230°C in a nitrogen atmosphere using a temperature-programmable curing furnace (VF-2000 model, manufactured by Koyo Lindberg Co., Ltd.), to obtain a cured film of resin approximately 7 μm thick on the Cu.

[0112] The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6 standard, based on the following criteria. "Excellent": The lattice number of the cured resin coating adhered to the substrate is 99 or more "Good": The lattice number of the cured resin coating adhered to the substrate is 80 or more but less than 99 "Acceptable": The lattice number of the cured resin coating adhered to the substrate is 60 or more but less than 80 "Not acceptable": The lattice number of the cured resin coating adhered to the substrate is less than 60.

[0113] (6) Chemical resistance evaluation The cured relief pattern formed on Cu was immersed for 10 minutes in a resist stripper (KANTO-PPC, product name SPR920, main components tetramethylammonium hydroxide, dimethyl sulfoxide) heated to 50°C, rinsed with running water for 10 minutes, and air-dried. The film surface was then visually observed with an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and the rate of change in film thickness after chemical treatment. The evaluation criteria were as follows: no cracks or other defects occurred, and the film thickness change rate was 10% or less based on the film thickness before immersion in chemicals, as "excellent"; more than 10% to 15% or less, as "good"; more than 15% to 20% or less, as "passable"; and films with cracks or a film thickness change rate of more than 20% were rated "unacceptable."

[0114] (7) Storage stability evaluation After preparation of the photosensitive resin composition, the mixture was stirred at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for three days, which constituted the initial state, and then allowed to stand at room temperature for four weeks. The initial PI precursor resin composition was spin-coated onto a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a spin coater (D-SPIN60A, SOKUDO Co., Ltd.) and dried on a hot plate at 100°C for 180 seconds to produce a pre-baked film (spin-coated film) with a thickness of 10.0 μm ± 0.2 μm (D'). This spin-coated film was then exposed to 400 mJ / cm irradiation using a Prisma GHI S / N5503 projection exposure system (Ultratech Co., Ltd.) equipped with a gh-ray cut filter and a test pattern reticle with a circular recessed 10 μm diameter pattern. 2 It was exposed with.

[0115] The coating film formed on the wafer was then spray-developed using cyclopentanone in a developer (D-SPIN636, manufactured by Dainippon Screen Co., Ltd.) and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. The development time for spray development was defined as 1.4 times the minimum time required for the resin composition in the unexposed areas to develop in the 10.0 μm spin-coated film. The film thickness of the resulting relief pattern was measured, and the residual film rate after development was calculated using the following calculation method. Residual film rate after development (%) = (film thickness after exposure and development / film thickness before exposure) x 100 (%)

[0116] The PI precursor resin composition was then left to stand at room temperature for 4 weeks, and spin-coated, exposed, and developed under the same conditions as for the initial PI precursor resin composition to produce a relief pattern film, and the residual film ratio after development was calculated in the same manner. Storage stability was evaluated according to the following criteria based on the change in the residual film ratio over time obtained from the evaluation of the initial PI precursor resin. Excellent: The change in the developed residual film rate over time is 0 to less than ±2%. Good: The change in relative film thickness over time is between ±2% and ±5%. Acceptable: The change in relative film thickness over time is between ±5% and ±10%. Unacceptable: The relative film thickness changes by more than ±10% over time.

[0117] <Synthesis Example 1> (Synthesis of Polymer A-1: ​​Polyamic Acid Ester A-1) 31.0g (0.1mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 1L separable flask and 37.5g of γ-butyrolactone was added. Next, 26.0g (0.20mol) of 2-hydroxyethyl methacrylate (HEMA) was added, and 15.8g (0.20mol) of pyridine was added while stirring. After stirring for 5 hours at 40°C using an oil bath, a reaction mixture was obtained. After the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

[0118] Next, while stirring the resulting reaction mixture under ice cooling, a solution of 40.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 50.0 g of γ-butyrolactone was added over 40 minutes, followed by the addition of a suspension of 9.8 g (0.09 mol) of p-phenylenediamine (p-PD) in 150 g of γ-butyrolactone over 60 minutes. After stirring at room temperature for 2 hours, 9.0 g of ethyl alcohol was added and the mixture was stirred for an additional hour. Next, 70.0 g of γ-butyrolactone was added. The reaction mixture was filtered to remove any precipitate that had formed in the reaction system, yielding a reaction solution.

[0119] The resulting reaction solution was added to 0.6 kg of ethyl alcohol to precipitate a crude polymer. The precipitated crude polymer was collected by filtration and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 3.5 kg of water to reprecipitate the polymer. The resulting reprecipitate was collected by filtration and then vacuum dried to obtain a powdered polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 23,000.

[0120] <Synthesis Example 2> (Synthesis of Polymer A-2: Polyamic Acid Ester A-2) Polymer A-2 was obtained by carrying out the reaction in the same manner as in Synthesis Example 1, except that 31.0 g (0.1 mol) of ODPA in Synthesis Example 1 was replaced with 12.4 g (0.04 mol) of ODPA and 13.1 g (0.06 mol) of pyromellitic dianhydride (PMDA), and 9.8 g of p-PD was replaced with 19.1 g (0.09 mol) of m-tolidine (m-TB). The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 30,000.

[0121] <Synthesis Example 3> (Synthesis of Polymer A-3: Polyamic Acid Ester A-3) Polymer A-3 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that 18.0 g (0.09 mol) of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 9.8 g of p-PD in Synthesis Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0122] <Synthesis Example 4> (Synthesis of Polymer A-4: Polyamic Acid Ester A-4) Polymer A-4 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 31.0 g of ODPA in Synthesis Example 3. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0123] <Synthesis Example 5> (Synthesis of Polymer A-5: Polyamic Acid Ester A-5) Polymer A-5 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that 9.8 g of p-PD in Synthesis Example 1 was changed to 19.1 g (0.09 mol) of m-TB. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 30,000.

[0124] <Synthesis Example 6> (Synthesis of Polymer A-6: Polyamic Acid Ester A-6) Polymer A-6 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that 36.9 g (0.09 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) was used instead of 9.8 g of p-PD in Synthesis Example 1. The molecular weight of Polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0125] <Synthesis Example 7> (Synthesis of Polymer A-7: Polyamic Acid Ester A-7) Polymer A-7 was obtained by carrying out a reaction in the same manner as in Synthesis Example 1, except that 52.0 g (0.1 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA) was used instead of 31.0 g (0.1 mol) of ODPA in Synthesis Example 6. The molecular weight of Polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000.

[0126] The side chain equivalent weights for each polymer are shown in the table below. [Table 1]

[0127] <Synthesis Example 8> (Synthesis of UV absorber E-1) Into a 1 L separable flask equipped with a stirrer, a dropping funnel, and a thermometer, 30.0 g (0.707 mol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (trade name Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) was placed as a hydroxy compound.

[0128] 53.56 g (0.198 mol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride, an amount equivalent to 93.3 mol% of the OH groups of the hydroxy compound, was dissolved in 300 g of acetone with stirring and then placed in a flask. The flask was then adjusted to 30°C in a thermostatic bath. Next, 20.0 g of triethylamine was dissolved in 18 g of acetone and placed in a dropping funnel. This was then added dropwise to the flask over 30 minutes. After the dropwise addition, stirring was continued for another 30 minutes, after which hydrochloric acid was added dropwise and stirred for another 30 minutes to terminate the reaction. The reaction mixture was then filtered to remove triethylamine hydrochloride. 1640 g of purified water and 30 g of hydrochloric acid were mixed and stirred in a 3 L beaker, and the filtrate was added dropwise to the mixture with stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 40°C under reduced pressure for 48 hours to obtain photosensitive diazonaphthoquinone (E-1).

[0129] Example 1 A photosensitive resin composition was prepared using the following method, and the resulting composition was evaluated. (A) 100 g of polymer A-1, (B) 1.5 g of 4-methylphthalic anhydride (B-1: molecular weight: 162) as an acid anhydride compound, and (C) 3 g of ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (C-1) as a photopolymerization initiator were dissolved in 160 g of γ-butyrolactone (hereinafter referred to as GBL, D-1) and 35 g of dimethyl sulfoxide (hereinafter referred to as DMSO, D-2) to prepare the photosensitive resin composition of Example 1. The composition was evaluated according to the aforementioned methods. The results are shown in Table 2.

[0130] <Examples 2 to 30 and Reference Examples 1 to 8> A photosensitive resin composition similar to that in Example 1 was prepared and evaluated in the same manner as in Example 1, except that the blending amounts of each component were changed as shown in Table 2. The results are shown in Table 2. The additives used in the examples are as follows. (B-2) Homophthalic anhydride (molecular weight: 162) (B-3) Benzoic anhydride (molecular weight: 226) (B-4) Glutaric anhydride (molecular weight: 114) (B-5) Succinic anhydride (molecular weight: 100) (B-6) Acetic anhydride (molecular weight: 102) (B-7) Maleic anhydride (molecular weight: 98) (B-8) 3-Trimethoxysilylpropylsuccinic anhydride (molecular weight: 262) (B'-1) 4-Methylphthalic acid (molecular weight: 180) (C-1) Ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (D-1) γ-butyrolactone (GBL) (D-2) Dimethyl sulfoxide (DMSO) (E-1) Ultraviolet absorber obtained in Synthesis Example 8 (E-2) ADK STAB LA-29 (ADEKA)

[0131] [Table 2-1]

[0132] [Table 2-2]

[0133] [Table 2-3]

[0134] As shown in Table 2, the photosensitive resin compositions of Examples 1 to 30 were rated "fair" or better in all of the elongation of the cured film, the improvement in glass transition temperature (heat resistance), the copper adhesion, and the chemical resistance. Compared with Reference Examples 1 to 8, Examples 1 to 30 showed even greater improvements in all of the elongation of the cured film, the improvement in glass transition temperature (heat resistance), the copper adhesion, and the chemical resistance. Furthermore, it was revealed that the glass transition temperature of the cured film was improved more significantly with a polymer having a smaller side chain equivalent weight, as shown in Tables 1 and 2. For example, Example 12 had a higher glass transition temperature (Tg: 185°C for Example 12, Tg: 180°C for Reference Example 7) than Reference Example 7, which used the same polymer, and therefore the heat resistance of the cured film was improved. Furthermore, it was found that acid anhydride compounds with a molecular weight of 100 or more and a structure without an alkoxysilyl group significantly improved the glass transition temperature and copper adhesion of the cured film. [Industrial Applicability]

[0135] In addition to being applied to the semiconductor devices described above, the photosensitive resin composition of the present disclosure is also useful for applications such as an interlayer insulating film in a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film.

Claims

1. The following components (A) to (C): (A) a polyamic acid ester, (B) an acid anhydride compound, and (C) A photosensitive resin composition containing a photopolymerization initiator.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (B) is an acid anhydride containing no alkoxysilyl group and having a molecular weight of 100 or more.

3. 3. The photosensitive resin composition according to claim 1, wherein the ratio of the component (B) to 100 parts by mass of the component (A) is 1.5 parts by mass or more.

4. 3. The photosensitive resin composition according to claim 1, wherein the component (A) has a structure represented by the following general formula (1): 【Chemical 1】 (In the formula, X １ is a tetravalent organic group, Y １ is a divalent organic group, R １ and R ２ are each independently a hydrogen atom or a monovalent organic group, at least one of which represents a monovalent organic group having a radically polymerizable group having 1 to 40 carbon atoms, and n is an integer of 2 to 100.

5. 3. The photosensitive resin composition according to claim 1, wherein the ratio of the component (B) to 100 parts by mass of the component (A) is 2.0 parts by mass or more.

6. 3. The photosensitive resin composition according to claim 1, wherein the proportion of the component (B) relative to the total mass of the photosensitive resin composition is 0.5 mass% or more.

7. 3. The photosensitive resin composition according to claim 1, wherein the repeating unit of the component (A) has a side chain equivalent weight represented by the following formula of 400 or less: Side chain equivalent weight = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A)

8. 3. The photosensitive resin composition according to claim 1, wherein the component (A) has a side chain equivalent weight per repeating unit represented by the following formula of 350 or less: Side chain equivalent weight = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A)

9. In addition, the following ingredients: (E) ultraviolet absorber The photosensitive resin composition according to claim 1 or 2, comprising:

10. The photosensitive resin composition according to claim 9 , wherein the component (E) comprises a compound having a quinone diazide group.

11. 3. The photosensitive resin composition according to claim 1, wherein the molecular weight of the component (B) is 1,000 or less.

12. 3. The photosensitive resin composition according to claim 1, wherein the component (B) is an aromatic carboxylic acid anhydride.

13. The photosensitive resin composition according to claim 1 or 2, wherein the component (B) has a cyclic acid anhydride structure.

14. The photosensitive resin composition according to claim 1 or 2, wherein the component (B) has a five-membered ring acid anhydride structure.

15. The photosensitive resin composition according to claim 1 or 2, wherein the component (B) has a structure represented by the following general formula (2): 【Chemistry 2】 (In the formula, R ３ ~R ６ are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and may be bonded to form a ring.

16. The photosensitive resin composition according to claim 1 or 2, which is used for an interlayer insulating film.

17. The following steps: (1) applying the photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

18. A cured film comprising a cured product of the photosensitive resin composition according to claim 1 or 2.

19. An interlayer insulating film formed using the photosensitive resin composition according to claim 1 or 2.

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