Photosensitive resin composition, method for producing cured relief pattern using same, cured film, and interlayer insulating film

Abstract

Provided are: a photosensitive resin composition which is capable of improving the heat resistance of a cured film even when cured at a low temperature of 250 DEG C or less, has excellent mechanical elongation of the cured film, and is capable of providing a cured relief pattern, a cured film, and an interlayer insulating film, said cured relief pattern being produced using the photosensitive resin composition; and the copper alloy has high adaptation to copper and high chemical resistance. This photosensitive resin composition contains the following components (A) to (C): (A) a polyamic acid ester, (B) an acid anhydride compound, and (C) a photopolymerization initiator.

Description

Technical Field

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

[0002] Traditionally, polyimide resins, polybenzoxazole resins, and phenolic resins, which possess excellent heat resistance, electrical properties, and mechanical properties, have been used in insulating materials for electronic components and passivation films, surface protective films, and interlayer insulating films for semiconductor devices. Among these resins, those provided in the form of photosensitive resin compositions can easily form heat-resistant relief pattern coatings through coating, exposure, development, curing, and ring closure (imidization, benzoxazoleization), followed by thermal crosslinking. Therefore, these resins have the advantage of significantly shortening the process compared to conventional non-photosensitive materials and are therefore used in the manufacture of semiconductor devices.

[0003] Semiconductor devices (hereinafter referred to as "components") are mounted on printed circuit boards using various methods depending on their intended purpose. Conventional components are typically manufactured using wire bonding, where thin wires are connected from the component's external terminals (pads) to the leadframe. However, with the increasing speed of components and operating frequencies reaching gigahertz, variations in the wiring lengths between terminals during mounting have reached levels that can affect component operation. Therefore, precise control of mounting wiring lengths is essential for mounting components for high-end applications, a requirement that is difficult to achieve with wire bonding.

[0004] Therefore, a flip chip installation is proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, and after a bump (electrode) is formed thereon, the chip is flipped (flipped) and directly mounted on a printed circuit board. The flip chip installation is used in components for high-end applications that process high-speed signals because the wiring distance can be accurately controlled, or is used in portable phones and the like because the installation size is small, and its demand is rapidly expanding. Furthermore, a semiconductor chip installation technology called fan-out wafer level packaging (FOWLP) has recently been proposed, in which a wafer that has completed the previous process is cut to manufacture a single chip, a single chip is rebuilt on a support, and a molded resin is used for sealing. After peeling off the support, a redistribution layer is formed (e.g., patent document 1). In FOWLP, since the redistribution layer is formed with a thin film thickness, it has the following advantages: the height of the package can be made thinner, and high-speed transmission and low cost can be achieved. As documents disclosing the photosensitive resin composition used in such a redistribution layer, there are, for example, patent documents 1 and 2.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2023-025070

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2021-162834 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] In FOWLP, from the perspective of preventing wafer warpage during the process, it is desirable to lower the curing temperature (thermal imidization treatment temperature) than before. However, if the curing temperature is lowered, problems such as deterioration in heat resistance, such as the glass transition temperature, and mechanical strength, such as elongation, can be listed. According to Patent Document 2, there is a description that by adding a multifunctional (meth)acrylate compound, it is expected that heat resistance and mechanical properties will be improved. However, there is concern that the addition of a multifunctional (meth)acrylate compound will deteriorate the adhesion to copper.

[0011] The present invention has been made in view of such circumstances, and its object is to provide a photosensitive resin composition that can improve the heat resistance of a cured film even when cured at a low temperature of 250°C or less, and that has excellent mechanical elongation, high adhesion to copper, and high chemical resistance, as well as a method for producing a cured relief pattern, a cured film, and an interlayer insulating film using the same.

[0012] Solutions for solving problems

[0013] The present inventors have found that the above-mentioned problems can be solved by combining polyamic acid ester and an acid anhydride compound, thereby completing the present invention.

[0014] That is, the present invention is as follows.

[0015] [1] A photosensitive resin composition comprising the following components (A) to (C):

[0016] (A) polyamic acid ester,

[0017] (B) an acid anhydride compound, and

[0018] (C) Photopolymerization initiator.

[0019] [2] The photosensitive resin composition according to [1], wherein the component (B) is an acid anhydride having a molecular weight of 100 or more and containing no alkoxysilyl group.

[0020] [3] The photosensitive resin composition according to [1] or [2], wherein the ratio of the component (B) to 100 parts by mass of the component (A) is 1.5 parts by mass or more.

[0021] [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).

[0022]

[0023] (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 is a monovalent organic group having 1 to 40 carbon atoms and a free radical polymerizable group, and n is an integer from 2 to 100.)

[0024] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the ratio of the component (B) to 100 parts by mass of the component (A) is 2.0 parts by mass or more.

[0025] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the ratio of the component (B) to the total mass of the photosensitive resin composition is 0.5% by mass or more.

[0026] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the side chain equivalent represented by the following formula per repeating unit of the component (A) is 400 or less.

[0027] Side chain equivalent = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A)

[0028] [8] The photosensitive resin composition according to any one of [1] to [6], wherein the side chain equivalent represented by the following formula per repeating unit of the component (A) is 350 or less.

[0029] Side chain equivalent = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A)

[0030] [9] The photosensitive resin composition according to any one of [1] to [8], further comprising the following components:

[0031] (E) Ultraviolet light absorber.

[0032]

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

[0033]

[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.

[0034]

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

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

[0035]

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

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

[0036]

[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.

[0037]

[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).

[0038]

[0039] (In the formula, R3 to R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and they are optionally bonded to form a ring.)

[0040]

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

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

[0041]

[17] A method for manufacturing a solidified relief pattern, comprising the following steps:

[0042] (1) a step of applying the photosensitive resin composition according to any one of [1] to

[16] on a substrate to form a photosensitive resin layer on the substrate;

[0043] (2) exposing the photosensitive resin layer;

[0044] (3) developing the exposed photosensitive resin layer to form a relief pattern; and

[0045] (4) A step of heating the relief pattern to form a solidified relief pattern.

[0046]

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

[16] .

[0047]

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

[16] .

[0048] Effects of the Invention

[0049] According to the present invention, there are provided a photosensitive resin composition that can improve the heat resistance of a cured film even at a low temperature of 250°C or less, has excellent elongation of the cured film, has high adhesion to copper, and has high chemical resistance, as well as a method for producing a cured relief pattern, a cured film, and an interlayer insulating film using the same. DETAILED DESCRIPTION

[0050] Hereinafter, embodiments of the present application will be described in detail. The present application is not limited to the following embodiments and can be implemented by various modifications within the scope of its main purpose. Throughout this specification, when multiple structures represented by the same symbol in the general formula exist in a molecule, they may be the same or different from each other.

[0051] In addition, the numerical range shown using "to" in the specification includes the numerical values ​​of the upper limit and the lower limit.

[0052] <Photosensitive resin composition>

[0053] The photosensitive resin composition of the present invention comprises the following components (A) to (C):

[0054] (A) polyamic acid ester,

[0055] (B) an acid anhydride compound, and

[0056] (C) Photopolymerization initiator.

[0057] In one embodiment, the photosensitive resin composition of the present invention comprises the following components (A) to (C):

[0058] (A) polyamic acid ester,

[0059] (B) an acid anhydride compound not containing an alkoxysilyl group, and

[0060] (C) a photopolymerization initiator,

[0061] The ratio of the component (B) to 100 parts by mass of the component (A) is 1.5 parts by mass or more.

[0062] The photosensitive resin composition of the present invention may be a so-called negative-type photosensitive resin composition in which an exposed portion is insoluble in a developer.

[0063] Although not limited by theory, the present inventors believe that the reasons why the photosensitive resin composition of the present invention exerts the above-mentioned effects are as follows. It can be considered that by using (A) polyamic acid ester and (B) anhydride compound in combination, when the polyamic acid ester is converted into polyimide by heat treatment, the hydroxyl group of the side chain that has been detached reacts with the anhydride compound to generate a carboxyl group, which acts on the copper substrate, thereby showing high adhesion to copper. It can also be considered that when the side chain has a polymerizable functional group, the amount of polymerizable functional groups remaining in the film increases because the side chain is not easily volatile, thereby increasing the crosslinking density in the system, which helps to improve mechanical properties, heat resistance and chemical resistance.

[0064] (A) Polyamic acid ester

[0065] (A) Polyamic acid ester (hereinafter also referred to as component (A)) is a resin component contained in the photosensitive resin composition. Any resin that forms a polyimide by heat cyclization treatment can be used without particular limitation. From the viewpoint of increasing the crosslinking density within the system and facilitating further exertion of the effects of the present invention, component (A) preferably has a polyamic acid ester structure represented by the following general formula (1).

[0066]

[0067] (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 is a monovalent organic group having 1 to 40 carbon atoms and a free radical polymerizable group, and n is an integer from 2 to 100.)

[0068] As the structure of the aforementioned (A) polyamic acid ester, the side chain equivalent of each repeating unit is preferably 400 or less, preferably 360 or less, more preferably 350 or less. The side chain equivalent represents the molecular weight of the repeating unit divided by the number of side chains and the numerical value obtained. That is, the smaller the side chain equivalent, the more side chains in the polymer are represented. It should be noted that the side chain mentioned herein represents the organic group that the aforementioned polyamic acid ester is detached from when imidized during heating, preferably an organic group having more than 1 carbon atom. The side chain equivalent can be calculated using the following formula.

[0069] Side chain equivalent = molecular weight per repeating unit of component (A) / number of side chains per repeating unit of component (A)

[0070] While not intending to be bound by theory, it is believed that as the side chain equivalent weight decreases, more side chain components react with the acid anhydride, and the effect is more significantly exhibited.

[0071] In addition, when two or more polymers are used or two or more backbones are copolymerized, the side chain equivalent is calculated for each backbone, and the weighted average of the compounding ratio is shown.

[0072] In the general formula (1), from the viewpoint of achieving both heat resistance and photosensitivity, 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 alicyclic aliphatic group in which the -COOR1 group and the -COOR2 group are ortho to the -CONH- group. Examples of the tetravalent organic group represented by X1 include organic groups having 6 to 40 carbon atoms containing an aromatic ring, and specifically, groups having the structures represented by the following general formulae (X1-1) to (X1-3) are exemplified, but are not limited thereto.

[0073]

[0074]

[0075] 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-C10 hydrocarbon group, and a C1-C10 fluorine-containing 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. From the viewpoint of a small side chain equivalent, the X1 group having the structure represented by each of the above formulas (X1-1) to (X1-3) is particularly preferably (X1-2), and more preferably the structure represented by each of the above formulas (X1-1).

[0076] In the above general formula (1), from the viewpoint of achieving both heat resistance and photosensitivity, the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, and examples thereof include, but are not limited to, the structures represented by the following formulae (Y1-1) to (Y1-3).

[0077]

[0078]

[0079] In formulas (Y1-1) to (Y1-3), R is a member selected from the group consisting of a hydrogen atom, a fluorine atom, a C1 to C 10 Hydrocarbon and C1~C 10 wherein n is an integer selected from the group consisting of fluorinated hydrocarbon groups, and n is an integer selected from 0 to 4. The structure of Y1 may be one or a combination of two or more. From the viewpoint of small side chain equivalent, the Y1 group having the structure represented by each of the above formulas (Y1-1) to (Y1-3) is particularly preferably (Y1-2), and more preferably the structure represented by each of the above formulas (Y1-1).

[0080] At least one of R1 and R2 in the general formula (1) is preferably a group containing a radical polymerizable group. Here, the radical polymerizable group refers to a group that can be polymerized by the action of a radical.

[0081] From the viewpoint of crosslinking 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).

[0082]

[0083] 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).

[0084]

[0085] 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 specifically, monovalent organic groups having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl. R7 is preferably a hydrogen atom or a methyl group, and R8 and R9 are preferably a hydrogen atom.

[0086] (A) Preparation method of polyamic acid ester

[0087] Examples of methods for preparing the polyamic acid ester (A) include a method in which a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 is reacted with an alcohol having a radically polymerizable group and optionally another alcohol to prepare a partially esterified tetracarboxylic acid (hereinafter referred to as an acid / ester). Subsequently, the partially esterified tetracarboxylic acid (acid / ester) is subjected to amide polycondensation with a diamine containing the aforementioned divalent organic group Y1 to obtain the polyamic acid ester (A).

[0088] As the tetracarboxylic dianhydride containing the tetravalent organic group X1 suitable for use in preparing the (A) polyamic acid ester, a compound represented by the following general formula (5) is preferred.

[0089]

[0090] In formula (5), X1 is a group defined in general formula (1). X1 is preferably selected from the structures represented by the general formulas (X1-1) to (X1-3), more preferably the structures represented by the general formulas (X1-1) to (X1-2), and even more preferably the structure represented by (X1-1).

[0091] Particularly preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenyl ether-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"), diphenyl sulfone-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 pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and biphenyl-3,3',4,4'-tetracarboxylic dianhydride, but are not limited thereto.

[0092] Examples of the alcohol having a radical polymerizable group suitable for use in preparing the polyamic acid ester (A) include 2-hydroxyethyl methacrylate, 2-acryloyloxyethanol, 1-acryloyloxy-3-propanol, 2-acrylamidoethanol, 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-tert-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethanol, 1-methacryloyloxypropyl acrylate, Oxy-3-propanol, 2-methacrylamidoethanol, 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-tert-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, glycerol diacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like.

[0093] The desired acid / ester can be obtained by dissolving and mixing the above-mentioned suitable tetracarboxylic dianhydride and the above-mentioned alcohol, preferably in a solvent as described below, preferably at a temperature of 20 to 50° C., preferably by stirring for 4 to 10 hours. This allows the anhydride group of the tetracarboxylic dianhydride to undergo an esterification reaction, thereby performing an esterification reaction.

[0094] (Preparation of polyamic acid ester)

[0095] By putting into mixing suitable dehydration condensation agent, such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-two-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate etc. in the above-mentioned acid / ester body (typically, being dissolved in the solution in the solvent mentioned later) under ice-cold, after acid / ester body is made into polyanhydride, dropwise putting into and making the diamine containing divalent organic group Y1 suitable for use in the present embodiment be dissolved separately or dispersed in the obtained material of solvent, it is carried out amide polycondensation, so that the polyimide precursor as the target can be obtained. In addition, according to the reactivity of substrate, 1-hydroxybenzotriazole etc. can be used. As an alternative, after the acid part of the above-mentioned acid / ester body is made into acyl chloride using thionyl chloride etc., it is reacted with diamine in the presence of a base such as pyridine, so that the polyamic acid ester as the target can be obtained.

[0096] As the diamine containing the divalent organic group Y1 preferably used in the present embodiment, a compound represented by the following formula is preferable.

[0097] H2N-Y1-NH2

[0098] {wherein, Y1 is a group defined in the above general formula (1).}

[0099] More preferably, Y1 has the structure represented by each of the above-mentioned general formulae (Y1-1) to (Y1-3).

[0100] More preferably, as the diamine, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydiphenylamine, 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'-diaminodiphenyl sulfone, Biphenyl, 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)benzene Bis(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-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-tolidine Sulfone, 9,9-bis(4-aminophenyl)fluorene, etc.; and substances in which some of the hydrogen atoms on the benzene rings are replaced by methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc., but are not limited thereto. These may be used alone or in combination of two or more thereof.

[0101] 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 terminal polymerizable group compound. Examples thereof include γ-butyrolactone, dimethyl sulfoxide, N,N-dimethylacetoacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide.

[0102] After the amide polycondensation reaction is completed, the water absorption byproducts of the dehydration condensation agent present in the reaction solution can be filtered out as needed. A poor solvent such as water, aliphatic lower alcohol, or a mixture thereof can then be added to the resulting polymer component to precipitate the polymer component. The polymer can then be purified by repeating redissolution and reprecipitation procedures, and vacuum drying can be performed to isolate the target polyimide precursor. To increase the degree of purification, the polymer solution can be passed through a column filled with an anion exchange resin, a cation exchange resin, or both swollen with a suitable organic solvent to remove ionic impurities.

[0103] When measured in the form of a polystyrene-converted weight average molecular weight based on gel permeation chromatography, the molecular weight of the above-mentioned (A) polyamic acid ester is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when the weight average molecular weight is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. As developing solvents for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample "TSKstandadPOLYSTYLENE" manufactured by TOSOH.

[0104] As (A) polyamic acid ester, a non-photosensitive polyamic acid ester prepared using only an alcohol having no polymerizable group can be mixed with the photosensitive polyamic acid ester specified in the present invention. In this case, from the viewpoint of resolution / mechanical properties / heat resistance / chemical resistance, the amount of the non-photosensitive polyamic acid ester is preferably 200 parts by mass or less based on 100 parts by mass of the photosensitive polyamic acid ester.

[0105] (B) Acid anhydride compound

[0106] The acid anhydride compound (B) used in this embodiment will be described. It is believed that in this embodiment, by adding the acid anhydride compound to the photosensitive resin composition, it reacts with the side chains released from the polymer during imidization, thereby improving the heat resistance of the cured film and exhibiting high elongation and high adhesion to copper.

[0107] In particular, the (B) acid anhydride compound (hereinafter also referred to as (B) component) in the present embodiment preferably does not have an alkoxysilyl group: -Si(OR 10 )3(R 10 is an alkyl group). By making the acid anhydride compound (B) in this embodiment not contain an alkoxysilyl group, the formation of -Si(OR 10 )3 hydrolysis and free R 10 The reaction of OH with the acid anhydride structure can suppress the reaction of the detached side chain with the acid anhydride, thereby contributing to improved heat resistance and elongation of the cured film and high adhesion to copper.

[0108] (B) anhydride compound preferably has a molecular weight of 100 or more. It can be considered that: by making the molecular weight more than 100, it is not easy to volatilize in the drying process and the curing process after the coating, and therefore, the ratio of the reaction with the detached side chain is high, and it is easy to exert the effect. The lower limit of the molecular weight of the (B) anhydride compound is more preferably more than 110, more preferably more than 120, particularly preferably more than 130, and most preferably more than 140. In addition, as the upper limit of the molecular weight of the (B) anhydride compound, from the viewpoint of anhydride equivalent, it is preferably less than 1000, less than 900, less than 800, less than 700, less than 600 or less than 500. It should be noted that the molecular weight (such as weight average molecular weight) of (B) component can be obtained by calculating the chemical formula of (B) component. In one embodiment, (B) component is an anhydride having a molecular weight of more than 100 that does not contain an alkoxysilyl group.

[0109] Furthermore, the structure of the acid anhydride compound is not particularly limited. From the viewpoint of reactivity, the 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 further preferably has a structure represented by the following general formula (2).

[0110]

[0111] (In the formula, R3 to R6 are each independently a hydrogen atom or an organic group having 1 to 40 carbon atoms, and they are optionally bonded to form a ring.)

[0112] (B) The acid anhydride compound may be an aliphatic carboxylic acid anhydride or an aromatic carboxylic acid anhydride.

[0113] Examples of the aliphatic acid anhydride compound 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, 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, decanoic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride.

[0114] Examples of the aromatic carboxylic anhydride include benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, 4-methylphthalic anhydride, 4-ethynylphthalic anhydride, 4-(methylethynyl)phthalic anhydride, and homopolymeric phthalic anhydride.

[0115] The content of (B) acid anhydride compound is preferably 1.5 mass parts or more and 10 mass parts or less relative to 100 mass parts of (A) polyamic acid ester, more preferably 2.0 mass parts or more and 5 mass parts or less. From the viewpoint of elongation, glass transition temperature (hereinafter also referred to as Tg), and copper adhesion, the above-mentioned content is preferably 1.5 mass parts or more, and from the viewpoint of storage stability, it is preferably 10 mass parts or less. In addition, from the viewpoint of elongation, glass transition temperature, and copper adhesion, the content of acid anhydride compound is preferably 0.5 mass % or more, preferably 0.6 mass % or more relative to the gross mass of the photosensitive resin composition, and from the viewpoint of storage stability, it is preferably 5 mass % or less, preferably 4 mass % or less.

[0116] (C) Photopolymerization initiator

[0117] The (C) photopolymerization initiator (hereinafter also referred to as the (C) component) used in the present embodiment will be described. As the photopolymerization initiator, a photoradical polymerization initiator is preferred.

[0118] Examples of the photoradical polymerization initiator include benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl compounds such as benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime. , oxime compounds such as 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, titanocene compounds, etc.

[0119] The (C) photopolymerization initiator used in the present embodiment is not limited to the above examples, but is more preferably an oxime compound from the viewpoint of photosensitivity.

[0120] The content of the photopolymerization initiator (C) 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 polyamic acid (A). From the viewpoint of photosensitivity and patterning properties, the content is 0.1 parts by mass or more, and from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition, it is preferably 30 parts by mass or less.

[0121] (D) Solvent

[0122] The photosensitive resin composition of the present embodiment may optionally contain a (D) solvent (hereinafter also referred to as the (D) component). The (D) solvent is not limited as long as it is a solvent that 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-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, etc. These solvents can be used alone or in combination of two or more.

[0123] 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 relative to 100 parts by mass of the (A) polyamic acid ester, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0124] When the (D) solvent contains an alcohol having no ethylenic double bond, the content of the alcohol having no ethylenic double bond in the total solvent is preferably 5 to 50% by mass. From the perspective of storage stability of the photosensitive resin composition, the lower limit is more preferably 10% by mass or more. From the perspective of solubility of the (A) polyamic acid ester, the upper limit is more preferably 30% by mass or less.

[0125] (E) Ultraviolet light absorber

[0126] The photosensitive resin composition of this embodiment may optionally contain (E) an ultraviolet light absorber (hereinafter also referred to as (E) component). It is believed that the use of the (E) ultraviolet light absorber can control the photopolymerization reaction and adjust the crosslinking density to an appropriate level.

[0127] The (E) ultraviolet light 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 quinonediazide group.

[0128] Specific examples of the ultraviolet light 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, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole. 2-(2'-hydroxyphenyl)benzotriazole compounds such as 2-(2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, and 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole; 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1-benzotriazole; ,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-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, bis-ethylhexyloxyphenol methoxyphenyltriazine (Bemotrizinol), 2,4,6-tris(2, Hydroxyphenyltriazine compounds such as 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate; polyphenol compounds such as cyanoacrylate compounds, azobenzene compounds, catechin, rutin, cyanidin, and curcumin; compounds having a quinone azide group (hereinafter also referred to as "quinone diazide compounds" or "compounds having a quinone diazide group"), etc.In addition, the compounds described in WO2022 / 154020 include a compound synthesized from 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylene)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris-PA) and 1,2-naphthoquinonediazide-5-sulfonyl chloride, a compound synthesized from Tris-PA and 1,2-naphthoquinonediazide-4-sulfonyl chloride, a compound synthesized from p-cumylphenol and 1,2-naphthoquinonediazide-5- Compounds synthesized from 1,2-naphthoquinonediazide-5-sulfonyl chloride, compounds synthesized from p-cumylphenol and 1,2-naphthoquinonediazide-4-sulfonyl chloride, compounds synthesized from Tekoc-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 1,2-naphthoquinonediazide-5-sulfonyl chloride, compounds synthesized from (2,2-bis(4-hydroxyphenyl)propane) and 1,2-naphthoquinonediazide-5-sulfonyl chloride, compounds synthesized from p-cresol and 1,2-naphthoquinonediazide-5-sulfonyl chloride, etc.

[0129] (E) The ultraviolet light absorber preferably comprises a compound having a quinonediazide group. Compounds having quinonediazide groups generate carboxylic acids in response to light. The carboxyl groups generated by the reaction of the acid anhydride with the side chain interact with the carboxylic acid, thereby increasing the crosslink density and further improving the glass transition temperature and elongation of the cured film. Furthermore, the generated carboxyl groups interact with the copper substrate, thereby improving copper adhesion.

[0130] The content of the ultraviolet light absorber (E) is preferably 1 part by mass or more and 30 parts by mass, more preferably 2 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the polyamic acid ester (A). From the viewpoints of the elongation, glass transition temperature, and copper adhesion of the cured film, the content is 1 part by mass or more, and from the viewpoints of photosensitivity and patterning properties, it is preferably 30 parts by mass or less.

[0131] The photosensitive resin composition may further contain components other than the above-mentioned components (A) to (E). Components other than components (A) to (E) are not limited, and examples thereof include rust inhibitors, adhesion promoters, hindered phenol compounds, organic titanium compounds, thermal crosslinking agents, sensitizers, and thermal polymerization inhibitors.

[0132] (Rust Inhibitor)

[0133] 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 to improve the adhesion between the copper and the polyimide film. Examples of rust inhibitors include nitrogen-containing heterocyclic compounds, specifically azole compounds and purine compounds.

[0134] 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-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)] phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole, 5-carboxyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0135] Particularly preferred examples include 5-amino-1H-tetrazole, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or as a mixture of two or more.

[0136] 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-aminopurine, 1-Benzyl adenine, 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 the like, and derivatives thereof.

[0137] When the photosensitive resin composition contains a rust inhibitor, its content is preferably 0.01 mass parts or more and 20 mass parts or less relative to 100 mass parts of (A) polyamic acid ester. When the photosensitive resin composition is formed on copper or a copper alloy, the adhesion to copper is improved, so its lower limit is more preferably 0.03 mass parts or more, and more preferably 0.05 mass parts or more. From the viewpoint of photosensitivity, its upper limit is more preferably 10 mass parts or less, and more preferably 5 mass parts or less.

[0138] (Adhesion aid)

[0139] 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. As the adhesion promoter, aluminum-based adhesion promoters, silane coupling agents, etc. can be used.

[0140] Examples of the aluminum-based adhesion promoter include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate diisopropoxide aluminum.

[0141] Examples of the silane coupling agent include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3- [Triethoxysilyl]propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM803, manufactured by Chisso Co., Ltd., trade name: Sila-Ace S810), 3-mercaptopropyltriethoxysilane (manufactured by AZMAX, trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: LS1375, manufactured by AZMAX, trade name: SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by AZMAX, trade name: SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AZMAX, trade name: SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-Mercaptopropyldiethoxypropoxysilane, 3-Mercaptopropylethoxydipropoxysilane, 3-Mercaptopropyldimethoxypropoxysilane, 3-Mercaptopropylmethoxydipropoxysilane, 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyldiethoxymethoxysilane, 2-Mercaptoethylethoxydimethoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethyltripropoxysilane, 2-Mercaptoethylethoxydipropoxysilane, 2-Mercaptoethyldimethoxypropoxysilane, 2-Mercaptoethylmethoxydipropoxysilane, 4-Mercaptobutyltrimethoxysilane, 4-Mercaptobutyltriethoxysilane, 4-Mercaptobutyltripropoxysilane,

[0142] N-(3-Triethoxysilylpropyl)urea (Shin-Etsu Chemical Co., Ltd., trade name: LS3610, AZMAX Co., Ltd., trade name: SIU9055.0), N-(3-Trimethoxysilylpropyl)urea (AZMAX Co., Ltd., 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-tripropoxysilylpropyl)urea 99.0), p-aminophenyltrimethoxysilane (manufactured by AZMAX Corporation, trade name: SLA0599.1), aminophenyltrimethoxysilane (manufactured by AZMAX Corporation, trade name: SLA0599.2),

[0143] 2-(Trimethoxysilylethyl)pyridine (manufactured by AZMAX, trade name: SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-tert-butoxysilane, Tetrakis(methoxyethoxysilane), 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,

[0144] Di-tert-butoxydiacetoxysilane, diisobutoxyaluminumoxytriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethyl Phenylsilanol, 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. In addition, silane coupling agents having structures represented by the following formula (S-1) can be listed, but are not limited to them.

[0145]

[0146] Among these adhesion promoters, silane coupling agents are more preferably used from the viewpoint of adhesion. As the silane coupling agent, among the above-mentioned silane coupling agents, from the viewpoint of storage stability, it is preferred 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 silane coupling agents having the structures represented by the above formula (S-1).

[0147] When the photosensitive resin composition contains an adhesive auxiliary agent, the amount of the adhesive auxiliary agent is preferably 0.01 mass parts or more and 25 mass parts or less relative to 100 mass parts of (A) polyamic acid ester, or more preferably 0.5 mass parts or more and 20 mass parts or less. The amount of the silane coupling agent is preferably 0.2 mass parts or more and 10 mass parts or less relative to 100 mass parts of (A) polyamic acid ester, and from the viewpoint of copper adhesion, the lower limit of the amount of the adhesive agent is more preferably 0.5 mass parts or more, and more preferably 1 mass part or more. From the viewpoint of producing foreign matter due to precipitation, its upper limit is more preferably 8 mass parts or less, and more preferably 6 mass parts or less.

[0148] (Hindered phenol compound)

[0149] In order to suppress discoloration on the copper surface, the photosensitive resin composition may optionally contain a hindered phenol compound. Examples of the hindered phenol compound include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4 -hydroxyphenyl) propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,

[0150] 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-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris( 4-tert-Butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-Butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-Butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc., but are not limited to these. Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are particularly preferred.

[0151] When the photosensitive resin composition contains a hindered phenol compound, its content is preferably 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polyamic acid ester (A). When the photosensitive resin composition is formed on copper or a copper alloy, from the perspective of preventing discoloration and corrosion of the copper or copper alloy, the lower limit is more preferably 0.5 parts by mass or more. From the perspective of photosensitivity, the upper limit is more preferably 10 parts by mass or less.

[0152] (Organotitanium compound)

[0153] The photosensitive resin composition may contain an organic titanium compound. By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when the photosensitive resin composition is cured at a low temperature.

[0154] Examples of usable organic titanium compounds include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in the following I) to VII):

[0155] I) Titanium chelate compounds: Specific examples include titanium (IV) acetylacetonate, bis(triethanolamine)titanium diisopropoxide, di(n-butoxy)bis(2,4-pentanedione)titanium, diisopropoxybis(2,4-pentanedione)titanium, diisopropoxybis(tetramethylheptanedione)titanium, and diisopropoxybis(ethyl acetoacetate)titanium.

[0156] II) Tetraalkoxytitanium compounds: for example, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetra(2-ethylhexyl)oxide, titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearylate, and titanium tetra[bis{2,2-(allyloxymethyl)butoxide}]oxide.

[0157] III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

[0158] IV) Monoalkoxytitanium compounds: for example, tris(dioctylphosphino)titanium isopropoxide, tris(dodecylbenzenesulfonyl)titanium isopropoxide, and the like.

[0159] V) Titanium oxide compounds: for example, bis(pentanedione)titanium oxide, bis(tetramethylheptanedione)titanium oxide, and titanium phthalocyanine oxide.

[0160] VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate.

[0161] VII) Titanate coupling agent: for example, isopropyl tri(dodecylbenzenesulfonyl) titanate, etc.

[0162] Among them, as the organic titanium compound, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred. Particularly preferred are diisopropoxybis(ethyl acetoacetate)titanium, titanium tetra-n-butoxide, bis(η-butyl)titanium, and the like. 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and titanium(IV) acetylacetonate.

[0163] When the photosensitive resin composition contains an organic titanium compound, its content is preferably 0.05 mass parts or more and 10 mass parts or less relative to 100 mass parts of (A) polyamic acid ester. From the viewpoint of heat resistance and chemical resistance of the obtained cured film, its lower limit is more preferably 0.2 mass parts or more. From the viewpoint of storage stability of the photosensitive resin composition, its upper limit is more preferably 4 mass parts or less.

[0164] (Thermal crosslinking agent)

[0165] The photosensitive resin composition may optionally contain a thermal crosslinking agent in order to suppress the curing shrinkage of the film after curing.

[0166] A thermal crosslinking agent is a compound that undergoes an addition reaction or a condensation polymerization reaction by heat. These reactions occur in combinations of (A) polyamic acid ester and the thermal crosslinking agent, thermal crosslinking agents with each other, and thermal crosslinking agents with other components, and the reaction temperature is preferably 150° C. or higher.

[0167] Examples of the thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds. From the viewpoint of suppressing cure shrinkage, the thermal crosslinking agent preferably contains a nitrogen atom.

[0168] Examples of the alkoxymethyl compound include the following compounds, but are not limited thereto.

[0169]

[0170]

[0171] Examples of epoxy compounds include 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing bisphenol A type groups, and hydrogenated bisphenol A diglycidyl ether (e.g., EPOLIGHT 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) ) diphenol salt, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silsesquioxane] derivative, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, trade name: OXT121 (manufactured by Toagosei Co., Ltd.), trade name: OXT221 (manufactured by Toagosei Co., Ltd.), etc.

[0172] Examples of the bismaleimide compound 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'-bis(maleimide) -1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0173] Examples of the allyl compound include allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allylphenyl 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.

[0174] 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; and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden Corporation); toluene diisocyanate-based blocked isocyanates (e.g., TAKENATE B-830 manufactured by Mitsui Chemicals); and 4,4′-diphenylmethane diisocyanate-based blocked isocyanates (e.g., TAKENATE B-815N manufactured by Mitsui Chemicals; and Blonate manufactured by Daiei Sangyo Co., Ltd.). PMD-OA01 and PMD-MA01, etc.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., TAKENATE B-846N manufactured by Mitsui Chemicals; 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 agent may be used alone or in combination of two or more.

[0175] 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 polyamic acid ester (A). From the viewpoint of chemical resistance, the lower limit is more preferably 1 part by mass or more, and further 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 further preferably 20 parts by mass or less.

[0176] (Sensitizer)

[0177] In order to improve photosensitivity, the photosensitive resin composition may optionally contain a sensitizer.

[0178] Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-bis(dimethylamino)chalcone. Methylaminocinnamylene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-dimethylaminobenzylidene)acetone ethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isopentyl dimethylaminobenzoate, isopentyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of 2 to 5 types.

[0179] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount thereof added is preferably 0.1 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the (A) polyamic acid ester.

[0180] (Thermal polymerization inhibitor)

[0181] In particular, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the stability of viscosity and photosensitivity when stored in a solution state containing a solvent.

[0182] As the thermal polymerization inhibitor, for example, 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, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. can be used.

[0183] <Method for Manufacturing Cured Relief Pattern>

[0184] The method for producing a solidified relief pattern of the present invention comprises:

[0185] (1) a step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate (resin layer forming step);

[0186] (2) exposing the photosensitive resin layer to light (exposure step);

[0187] (3) a step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern forming step); and

[0188] (4) A step of heating the relief pattern to form a cured relief pattern (cured relief pattern forming step).

[0189] (1) Resin layer forming process

[0190] In this step, a photosensitive resin composition is applied to a substrate and then dried, if necessary, to form a photosensitive resin layer. Conventional methods for applying photosensitive resin compositions can be used, such as methods using a spin coater, bar coater, blade coater, curtain coater, screen printer, or the like, and spray coating using a spray coater.

[0191] The coating film comprising the photosensitive resin composition can be dried as needed. Drying methods include air drying, heat drying in an oven or hot plate, and vacuum drying. Specifically, air drying or heat drying can be performed at 20°C to 150°C for 1 minute to 1 hour. This will form a photosensitive resin layer on the substrate.

[0192] (2) Exposure process

[0193] In this process, an exposure device such as a contact aligner, a mirror projector, a stepper is used, and the photosensitive resin layer formed above is exposed through a photomask or a photomask with a pattern or directly using an ultraviolet light source. By this exposure, when (A) polyamic acid ester has a polymerizable functional group, the polymerizable functional group is cross-linked by the action of (C) a photopolymerization initiator. By this cross-linking, the exposed portion becomes insoluble in the developer described later, and therefore, a relief pattern can be formed. When polyamic acid ester does not have a polymerizable functional group, a monomer with a polymerizable functional group is added to the composition, and it is cross-linked by exposure, thereby forming a relief pattern.

[0194] Subsequently, a post-exposure bake (PEB), a post-development bake, or both may be performed as needed, using any combination of temperature and time, for the purpose of improving photosensitivity, etc. The baking conditions are preferably 40°C to 200°C and 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.

[0195] (3) Relief pattern forming process

[0196] In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be selected from any of the conventional photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. After development, a post-development bake can be performed, optionally at any temperature and time combination, to adjust the shape of the relief pattern.

[0197] As the developer used in the development, it is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. As the good solvent, it is preferably, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. As the poor solvent, it is preferably, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate and water. When a good solvent and a poor solvent are mixed for use, it is preferably adjusted according to the solubility of the polymer in the photosensitive resin composition to the ratio of the poor solvent to the good solvent. Solvents can also be used in combination of two or more, for example, multiple.

[0198] (4) Curing relief pattern forming process

[0199] In this process, the relief pattern obtained by the above-mentioned development is heat-treated to volatilize the photosensitive component, and in the case of using (A) polyamic acid ester, it is imidized to convert it into a cured relief pattern formed by polyimide. As a heat treatment method, various methods such as a method based on a hot plate, a method using an oven, and a method using a heating oven capable of setting a temperature program can be selected. The heat treatment can be carried out under conditions of, for example, 160°C to 350°C and 30 minutes to 5 hours. The temperature of the heat treatment is preferably 300°C or less, more preferably 250°C or less. As the atmosphere gas during heat curing, air can be used, or inert gases such as nitrogen and argon can be used. By using the photosensitive resin composition of the present invention, the heat resistance of the cured film can be improved even if it is cured at a low temperature of 250°C or less.

[0200] <Polyimide Cured Film>

[0201] The present invention also provides a cured film comprising a cured product formed from the photosensitive resin composition of the present invention. It is believed that the cured film formed from the photosensitive resin composition comprises a polyimide having a structure represented by the following formula. This cured film has a high glass transition temperature, excellent elongation, high copper adhesion, and chemical resistance.

[0202]

[0203] (In the formula, the definitions of X1, Y1 and n are the same as above.)

[0204] <Semiconductor Device>

[0205] The present invention also provides a semiconductor device having a cured relief pattern obtained from the above-mentioned photosensitive resin composition. Specifically, the present invention provides a semiconductor device having a substrate serving as a semiconductor element and a cured relief pattern. The cured relief pattern can be produced using the above-mentioned photosensitive resin composition and the above-mentioned method for producing a cured relief pattern.

[0206] Such a semiconductor device has excellent reliability because the cured film has excellent glass transition temperature and elongation and includes a cured relief pattern having high adhesion to copper and high chemical resistance.

[0207] 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 according to the present embodiment as part of the process. In this case, the cured relief pattern formed using the method for manufacturing a cured relief pattern of the present application can be used as a surface protective film, interlayer insulating film, rewiring insulating film, flip-chip device protective film, or protective film for a semiconductor device having a bump structure, and can be combined with known semiconductor device manufacturing methods to produce a semiconductor device. In particular, the photosensitive resin composition of the present invention is suitable for use as an interlayer insulating film.

[0208] <Display Device>

[0209] The present application also provides a display device comprising a display element and a cured film disposed on top of the display element, the cured film being the aforementioned cured relief pattern. The cured relief pattern may be laminated directly in contact with the display element or sandwiched between other layers. This cured film can be used, for example, as surface protective films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements; as protrusions for MVA-type liquid crystal displays; and as partition walls for cathodes in organic EL elements.

[0210] Example

[0211] Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited thereto. In Examples, Comparative Examples, Reference Examples, and Synthesis Examples, the physical properties of polyamic acid esters, polyimides, or photosensitive resin compositions were measured and evaluated by the following methods.

[0212] <Measurement and Evaluation Methods>

[0213] (1) Weight average molecular weight

[0214] The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (in terms of standard polystyrene) under the following conditions.

[0215] Device: HLC-8320GPC (manufactured by Tosoh Corporation)

[0216] Eluent: N-methyl-2-pyrrolidone

[0217] Lithium bromide monohydrate 30mmol / L

[0218] Phosphoric acid 50mmol / L

[0219] Flow rate: 0.5 mL / min

[0220] Column: TSK-GEL SUPER HM-H 2 pieces / TSK-GEL SUPER H-RC 1 piece

[0221] Column temperature: 40°C

[0222] Detector: UV-8320

[0223] (2) Preparation of Cured Film for Measurement of Glass Transition Temperature and Elongation

[0224] Using a Coater Developer (D-Spin60A, manufactured by SOKUDO), a photosensitive resin composition prepared by the method described below was spin-coated onto a 6-inch silicon wafer previously sputtered with Al, to a film thickness of 10 μm after drying. This was then pre-baked at 110°C for 240 seconds on a hot plate to form a 10 μm thick coating. The resulting photosensitive resin film was subjected to a high-pressure mercury lamp at a concentration of 500 mJ / cm 2 The film was then exposed to light and then heat-treated at 230° C. for 2 hours in a nitrogen atmosphere using a temperature program curing oven (VF-2000, manufactured by KOYO LINDBERG) to obtain a cured film for elongation measurement.

[0225] (3) Determination of elongation

[0226] The cured film on the Al wafer obtained in (2) was cut into 3 mm wide strips using a cutting device (DISCO, DAD3350) and treated with 10% hydrochloric acid to obtain a 3 mm wide polyimide tape. The obtained polyimide tape was allowed to stand for more than 24 hours in an atmosphere of 23°C and 50% humidity. A tensile testing machine (UTM-II-20, manufactured by ORIENTEC) was used to measure the elongation of the polyimide tape after standing at a test speed of 40 mm / min and an initial load of 0.5 fs. The elongation and average elongation were calculated according to the following definitions. It should be noted that in this application, the number of tests was set to 10 for testing.

[0227] Elongation (%) = 100 × {(sample length at break - sample length before test) / sample length before test}

[0228] Average elongation (%) = total elongation of each test / number of tests

[0229] The average elongation obtained above was evaluated according to the following criteria.

[0230] Excellent: average elongation above 35%

[0231] Good: Average elongation is 20% or more and less than 35%

[0232] Qualified: average elongation is more than 8% and less than 20%

[0233] Unqualified: average elongation less than 8%

[0234] (4) Determination of glass transition temperature (Tg)

[0235] The cured film on the Al wafer obtained in step (2) was cut into 3 mm wide strips using a dicing device (DISCO, DAD3350) and treated with 10% hydrochloric acid to obtain a 3 mm wide polyimide tape. The obtained 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, manufactured by Shimadzu Corporation) to measure the glass transition temperature (°C).

[0236] (5) Copper adhesion evaluation

[0237] A photosensitive resin composition prepared by the method described below was spin-coated on a 6-inch silicon wafer previously sputtered with Ti and Cu using a Coater Developer (D-Spin60A, manufactured by SOKUDO Corporation) to a film thickness of 10 μm after drying. The composition was then pre-baked at 110°C for 240 seconds on a hot plate to form a 10 μm thick coating. The resulting photosensitive resin film was subjected to a high-pressure mercury lamp at a concentration of 500 mJ / cm 2 The Cu was exposed to light and heated at 230° C. for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000, manufactured by KOYO LINDBERG). As a result, a cured film of about 7 μm thick made of resin was obtained on the Cu.

[0238] 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 based on the following criteria.

[0239] "Excellent": The number of grids of the cured resin coating film adhered to the substrate is 99 or more

[0240] "Good": The number of grids of the cured resin coating film adhered to the substrate is 80 or more and less than 99

[0241] "Pass": The number of grids of the cured resin coating film adhered to the substrate is 60 or more and less than 80

[0242] "Unqualified": The number of grids of the cured resin coating film bonded to the substrate is less than 60

[0243] (6) Chemical resistance evaluation

[0244] The cured relief pattern formed on the Cu was immersed in a resist stripping solution (manufactured by KANTO-PPC, product name: SPR920, main components: tetramethylammonium hydroxide and dimethyl sulfoxide) heated to 50°C for 10 minutes, rinsed with running water for 10 minutes, and air-dried. The film surface was then visually observed using an optical microscope, and chemical resistance was evaluated based on the presence of damage caused by the chemical solution, such as cracks, and the rate of change in film thickness after chemical solution treatment.

[0245] As the evaluation criteria, the case where no cracks occur and the film thickness change rate is 10% or less based on the film thickness before chemical immersion is regarded as "excellent", the case where it exceeds 10% and is 15% or less is regarded as "good", the case where it exceeds 15% and is 20% or less is regarded as "acceptable", and the case where cracks occur or the film thickness change rate exceeds 20% is regarded as "unacceptable".

[0246] (7) Storage stability evaluation

[0247] After preparing the photosensitive resin composition, the state of stirring at room temperature (23.0°C ± 0.5°C, relative humidity of 50% ± 10%) for 3 days was set as the initial state, and then it was allowed to stand at room temperature for 4 weeks. Using a spin coater (D-SPIN60A model, manufactured by SOKUDO), the initial state of the PI precursor resin composition was spin-coated on a 6-inch silicon wafer (manufactured by Fujimi Electronics Industry Co., Ltd., thickness of 625 ± 25 μm), and dried on a hot plate at 100°C for 180 seconds to prepare a pre-baked film (spin-coated film) with a thickness of 10.0 μm ± 0.2 μm (D'). Using a mask with a test pattern having a hollow circular concave pattern with a diameter of 10 μm, an equal magnification projection exposure device PrismaGHI S / N5503 (manufactured by UltraTech) was used, and a gh line cutoff filter was installed, and the exposure was carried out at 400 mJ / cm 2 The spin-coated film is exposed to light.

[0248] Next, the coating formed on the wafer was spray-developed using cyclopentanone using a developer (D-SPIN636, manufactured by Dainippon Screen Mfg. Co., Ltd.), and rinsed with propylene glycol methyl ether acetate to obtain a polyamic acid ester pattern. It should be noted that the development time for spray development is defined as 1.4 times the minimum time for development of the resin composition in the unexposed portion of the 10.0 μm spin-coated film. The film thickness of the resulting relief pattern was measured, and the development residual film rate was calculated using the following calculation method.

[0249] Residual film rate after development (%) = (film thickness after exposure and development / film thickness before exposure) × 100 (%)

[0250] Next, the PI precursor resin composition, which had been left at room temperature for four weeks, was spin-coated, exposed, and developed using the same conditions as the initial PI precursor resin composition to produce a relief pattern film. The residual film development rate was also calculated in the same manner. Storage stability was evaluated based on the change in the residual film development rate over time, as determined by evaluating the initial PI precursor resin, according to the following criteria.

[0251] Excellent: The change in the development residual film ratio over time is 0 to less than ±2%.

[0252] Good: The change in relative film thickness over time is ±2% or more and less than ±5%.

[0253] Acceptable: The change in relative film thickness over time is ±5% or more and less than ±10%.

[0254] Unacceptable: The change in relative film thickness over time is ±10% or more.

[0255] <Synthesis Example 1> (Synthesis of Polymer A-1: ​​Polyamic Acid Ester A-1)

[0256] 31.0 g (0.1 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 1 L separable flask, followed by 37.5 g of γ-butyrolactone. Next, 26.0 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA) was added, and 15.8 g (0.20 mol) of pyridine was added while stirring. The mixture was stirred at 40°C for 5 hours in an oil bath to obtain a reaction mixture. After the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

[0257] Next, while stirring the resulting reaction mixture, a solution of 40.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 50.0 g of γ-butyrolactone was added over 40 minutes under ice-cooling. Subsequently, a suspension of 9.8 g (0.09 mol) of p-phenylenediamine (p-PD) in 150 g of γ-butyrolactone was added over 60 minutes. After stirring at room temperature for 2 hours, 9.0 g of ethanol was added, followed by further stirring for 1 hour, and then 70.0 g of γ-butyrolactone was added. The reaction mixture was filtered to remove the precipitate formed in the reaction system, yielding a reaction solution.

[0258] The resulting reaction solution was added to 0.6 kg of ethanol to precipitate a crude polymer. The precipitated crude polymer was filtered 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 reprecipitate was filtered and 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 conversion), and the weight average molecular weight (Mw) was 23,000.

[0259] <Synthesis Example 2> (Synthesis of Polymer A-2: Polyamic Acid Ester A-2)

[0260] The reaction was carried out 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). Polymer A-2 was obtained by measuring the molecular weight of polymer A-2 by gel permeation chromatography (based on standard polystyrene). The weight average molecular weight (Mw) was 30,000.

[0261] <Synthesis Example 3> (Synthesis of Polymer A-3: Polyamic Acid Ester A-3)

[0262] Polymer A-3 was obtained by reacting in the same manner as in Synthesis Example 1, except that 9.8 g of p-PD in Synthesis Example 1 was replaced with 18.0 g (0.09 mol) of 4,4'-diaminodiphenyl ether (DADPE). The molecular weight of Polymer A-3 was measured by gel permeation chromatography (based on standard polystyrene) to reveal a weight average molecular weight (Mw) of 30,000.

[0263] <Synthesis Example 4> (Synthesis of Polymer A-4: Polyamic Acid Ester A-4)

[0264] Polymer A-4 was obtained by reacting in the same manner as in Synthesis Example 1, except that 31.0 g of ODPA in Synthesis Example 3 was replaced with 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). The molecular weight of Polymer A-4 was measured by gel permeation chromatography (based on standard polystyrene) to reveal a weight average molecular weight (Mw) of 30,000.

[0265] <Synthesis Example 5> (Synthesis of Polymer A-5: Polyamic Acid Ester A-5)

[0266] Polymer A-5 was obtained by reacting in the same manner as in Synthesis Example 1, except that 9.8 g of p-PD in Synthesis Example 1 was replaced with 19.1 g (0.09 mol) of m-TB. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (based on standard polystyrene) and the weight average molecular weight (Mw) was 30,000.

[0267] <Synthesis Example 6> (Synthesis of Polymer A-6: Polyamic Acid Ester A-6)

[0268] A reaction was carried out in the same manner as in Synthesis Example 1, except that 9.8 g of p-PD in Synthesis Example 1 was replaced with 36.9 g (0.09 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP). Polymer A-6 was obtained by measuring the molecular weight of Polymer A-6 by gel permeation chromatography (based on standard polystyrene). The weight average molecular weight (Mw) was 25,000.

[0269] <Synthesis Example 7> (Synthesis of Polymer A-7: Polyamic Acid Ester A-7)

[0270] A reaction was carried out in the same manner as in Synthesis Example 1, except that 31.0 g (0.1 mol) of ODPA in Synthesis Example 6 was replaced with 52.0 g (0.1 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA). Polymer A-7 was obtained by measuring the molecular weight of Polymer A-7 by gel permeation chromatography (based on standard polystyrene). The weight average molecular weight (Mw) was 25,000.

[0271] The side chain equivalent weight of each polymer is shown in the table below.

[0272] [Table 1]

[0273]

[0274] <Synthesis Example 8> (Synthesis of Ultraviolet Absorber E-1)

[0275] 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)ethylene)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris-PA) as a hydroxy compound was added.

[0276] 53.56 g (0.198 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride, equivalent to 93.3 mol% of the OH groups of the hydroxyl compound, was dissolved in 300 g of acetone with stirring and then placed in a flask, which was maintained at 30°C in a thermostat. Next, 20.0 g of triethylamine was dissolved in 18 g of acetone, placed in a dropping funnel, and added dropwise to the flask over 30 minutes. After the addition was complete, stirring was continued for a further 30 minutes, followed by the addition of hydrochloric acid, which was then stirred for a further 30 minutes to complete the reaction. The reaction product was then filtered to remove the triethylamine hydrochloride. In a 3 L beaker, 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred, and the filtrate was added dropwise to the mixture while stirring to obtain a precipitate. The precipitate was washed with water, filtered, and then dried under reduced pressure at 40°C for 48 hours to obtain photosensitive naphthoquinone diazide (E-1).

[0277] <Example 1>

[0278] A photosensitive resin composition was prepared and evaluated using the following method. The photosensitive resin composition of Example 1 was prepared by dissolving 100 g of (A) polymer A-1, 1.5 g of 4-methylphthalic anhydride (B-1: molecular weight: 162) as the (B) acid anhydride compound, and 3 g of ethyl 2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (C-1) as the (C) photopolymerization initiator in 160 g of γ-butyrolactone (GBL, D-1) and 35 g of dimethyl sulfoxide (DMSO, D-2). This composition was evaluated using the aforementioned method. The results are shown in Table 2.

[0279] <Examples 2 to 30, Reference Examples 1 to 8>

[0280] A photosensitive resin composition was prepared in the same manner as in Example 1 except that the amount of each component was changed as shown in Table 2, and the same evaluation as in Example 1 was performed. The results are shown in Table 2. Additives used in the examples are shown below.

[0281] (B-2) High phthalic anhydride (molecular weight: 162)

[0282] (B-3) Benzoic anhydride (molecular weight: 226)

[0283] (B-4) Glutaric anhydride (molecular weight: 114)

[0284] (B-5) Succinic anhydride (molecular weight: 100)

[0285] (B-6) Acetic anhydride (molecular weight: 102)

[0286] (B-7) Maleic anhydride (molecular weight: 98)

[0287] (B-8) 3-Trimethoxysilylpropylsuccinic anhydride (molecular weight: 262)

[0288] (B'-1) 4-Methylphthalic acid (molecular weight: 180)

[0289] (C-1) 2,3-Dioxo-3-phenylpropionic acid ethyl ester-2-(O-benzoyl)oxime

[0290] (D-1)γ-Butyrolactone (GBL)

[0291] (D-2) dimethyl sulfoxide (DMSO)

[0292] (E-1) Ultraviolet light absorber obtained in Synthesis Example 8

[0293] (E-2) ADEKASTAB LA-29 (manufactured by ADEKA Corporation) [Table 2-1]

[0294]

[0295] [Table 2-2]

[0296]

[0297] [Table 2-3]

[0298]

[0299] As shown in Table 2, the photosensitive resin compositions of Examples 1 to 30 all achieved "acceptable" or better results in terms of cured film elongation, improvement in glass transition temperature (heat resistance), copper adhesion, and chemical resistance. Compared to Reference Examples 1 to 8, Examples 1 to 30 achieved further improvements in terms of cured film elongation, improvement in glass transition temperature (heat resistance), copper adhesion, and chemical resistance.

[0300] Furthermore, as shown in Tables 1 and 2, the glass transition temperature of the cured film increases significantly with polymers having smaller side chain equivalent weights. For example, Example 12 exhibits a higher glass transition temperature (Tg: 185°C for Example 12 and Tg: 180°C for Reference Example 7) than Reference Example 7, which uses the same polymer. This improves the heat resistance of the cured film.

[0301] Furthermore, it was found that when the acid anhydride compound has a molecular weight of 100 or more and does not have an alkoxysilyl group structure, the glass transition temperature and copper adhesion of the cured film are significantly improved.

[0302] Industrial applicability

[0303] The photosensitive resin composition of the present application is useful not only in the semiconductor devices described above, but also in applications such as interlayer insulation films for multilayer circuits, top coats for flexible copper-clad laminates, solder resists, and liquid crystal alignment films.

Claims

1. A photosensitive resin composition comprising the following components (A) to (C): (A) polyamic acid ester, (B) an acid anhydride compound, and (C) Photopolymerization initiator.

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

3. The photosensitive resin composition according to claim 1 or 2, wherein The ratio of the (B) component to 100 parts by mass of the (A) component is 1.5 parts by mass or more.

4. The photosensitive resin composition according to claim 1 or 2, wherein The component (A) has the structure of the following general formula (1), In formula (1), 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 1 to 40 carbon atoms and a free radical polymerizable group, and n is an integer from 2 to 100.

5. The photosensitive resin composition according to claim 1 or 2, wherein The ratio of the (B) component to 100 parts by mass of the (A) component is 2.0 parts by mass or more.

6. The photosensitive resin composition according to claim 1 or 2, wherein The ratio of the (B) component to the total mass of the photosensitive resin composition is 0.5% by mass or more.

7. The photosensitive resin composition according to claim 1 or 2, wherein The side chain equivalent of the following formula per repeating unit of the component (A) is 400 or less, Side chain equivalent = 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 claim 1 or 2, wherein The side chain equivalent of the following formula per repeating unit of the component (A) is 350 or less, Side chain equivalent = molecular weight per repeating unit of the component (A) / number of side chains per repeating unit of the component (A).

9. The photosensitive resin composition according to claim 1 or 2, further comprising the following components: (E) Ultraviolet light absorber.

10. The photosensitive resin composition according to claim 9, wherein The component (E) contains a compound having a quinonediazide group.

11. The photosensitive resin composition according to claim 1 or 2, wherein The molecular weight of the component (B) is 1,000 or less.

12. The photosensitive resin composition according to claim 1 or 2, 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): In formula (2), R3 to R6 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms, and they may be bonded to form a ring. The photosensitive resin composition according to claim 1 or 2, which is used for an interlayer insulating film.

17. A method for producing a solidified relief pattern, comprising the following steps: (1) a step of coating the photosensitive resin composition according to claim 1 or 2 on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; and (4) A step of heating the relief pattern to form a solidified relief pattern. 18 . A cured film comprising a cured product of the photosensitive resin composition according to claim 1 . 19 . An interlayer insulating film formed using the photosensitive resin composition according to claim 1 .

Images