Method for producing a photosensitive resin composition and a cured relief pattern

Abstract

To provide a photosensitive resin composition that can complete the imidation reaction of polyamic acid esters even at low curing temperatures, and can form a cured film with improved chemical resistance. [Solution] A photosensitive resin composition comprising (A) a polyamic acid ester, (B) a photopolymerization initiator, (C) a thermobase generator, and (D) a solvent, wherein the (D) solvent comprises one or two compounds selected from (D1) a compound having an amide bond and a cyclic structure and a boiling point of 210°C or higher, and (D2) a compound having a urea bond and a cyclic structure and a boiling point of 210°C or higher.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition and a method for producing a cured relief pattern. [Background technology]

[0002] Polyimide resins, polybenzoxazole resins, phenolic resins, and the like have been conventionally used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, and interlayer insulating films. These resins are known for possessing excellent heat resistance, electrical properties, and mechanical properties. In particular, photosensitive resin compositions containing polyamic acid esters as precursors to polyimide resins are widely used because they allow for easy formation of heat-resistant relief pattern films on substrates by coating the composition onto the substrate, exposing the coating film to light, developing it, and performing thermal imidization treatment. Such a photosensitive resin composition allows for a significant reduction in processing time compared to conventional non-photosensitive materials.

[0003] Various methods are used for semiconductor packaging in the manufacturing of semiconductor devices. For example, one known packaging method involves covering a semiconductor chip with a encapsulating material (molding resin) to form an element encapsulation material, and then forming a redistribution layer that electrically connects to the semiconductor chip.

[0004] Among semiconductor packaging methods, the Fan-Out type has become the mainstream in recent years. In the fan-out type semiconductor packaging method, first, a chip encapsulation larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Next, a redistribution layer is formed in the area of ​​the semiconductor chip and the encapsulant. In the fan-out type semiconductor packaging method, the redistribution layer is formed as a thin film. In this method, since the redistribution layer can be formed up to the area of ​​the encapsulant, the number of external connection terminals can be increased.

[0005] A fan-out type semiconductor device and a method for manufacturing the same are described, for example, in Patent Document 1. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2011-129767 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] For fan-out type semiconductor devices, lowering the heat treatment temperature (thermal imidization temperature, also called "cure temperature") is desirable from the viewpoint of preventing wafer warping during the manufacturing process. However, when the cure temperature is lowered, the imidization reaction of the polyamic acid ester contained in the photosensitive resin composition is not completed, leading to a problem of reduced chemical resistance.

[0008] This invention was devised in view of the above-mentioned conventional circumstances. The object of the present invention is to provide a photosensitive resin composition that can complete the imidation reaction of polyamic acid esters even at low curing temperatures and form a cured film with improved chemical resistance. Another object of the present invention is to provide a method for producing a cured relief pattern using the above-described photosensitive resin composition. The present invention also relates to cured films, interlayer insulating films, and the like. [Means for solving the problem]

[0009] The inventors have discovered that the above problems can be solved by combining a polyamic acid ester, a photopolymerization initiator, a thermobase generator, and a specific solvent, and have completed the present invention. Examples of embodiments of the present invention are listed below.

[0010] Appearance 1: (A) Polyamic acid ester, (B) Photoinitiator, (C) Thermal base generator, and (D) Solvent A photosensitive resin composition comprising: The (D) solvent is (D1) A compound having an amide bond and a cyclic structure and a boiling point of 210 °C or higher, and (D2) A compound having a urea bond and a cyclic structure and a boiling point of 210 °C or higher Containing one or two selected from Photosensitive resin composition. <<Aspect 2>> The photosensitive resin composition according to Aspect 1, wherein the (B) photoinitiator contains an oxime compound. <<Aspect 3>> The photosensitive resin composition according to Aspect 1, wherein the molecular weight of the (B) photoinitiator is 540 or less. <<Aspect 4>> The photosensitive resin composition according to Aspect 1, wherein the molecular weight of the (B) photoinitiator is 400 or less. <<Aspect 5>> The (B) photoinitiator is 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxyoxime), 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetoxyoxime), and is one or more selected from the above, the photosensitive resin composition according to Aspect 2. "Aspect 6" The photosensitive resin composition according to Aspect 2, wherein the (B) photoinitiator is one or more selected from 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyl oxime). "Aspect 7" The photosensitive resin composition according to any one of Aspects 1 to 6, wherein the (A) polyamic acid ester has a radically polymerizable group. "Aspect 8" The (D1) compound is a compound represented by the following general formula (D1), The (D2) compound is a compound represented by the following general formula (D2), The photosensitive resin composition according to any one of Aspects 1 to 7. [Chemical formula] {In formula (D1), R1 is a monovalent organic group having 2 or more carbon atoms, In formula (D2), R2 and R3 are each independently a monovalent organic group having 1 or more carbon atoms.} "Aspect 9" In the above general formula (D1), R1 is a monovalent organic group having 2 to 5 carbon atoms, In the above general formula (D2), R2 and R3 are each independently a monovalent organic group having 1 to 5 carbon atoms, The photosensitive resin composition according to Aspect 8. "Aspect 10" In the above general formula (D1), R1 is an ethyl group, In the above general formula (D2), both R2 and R3 are methyl groups, The photosensitive resin composition according to Aspect 8. "Aspect 11" The photosensitive resin composition according to any one of Aspects 1 to 10, wherein the proportion of the total mass of the (D1) compound and the (D2) compound in the total mass of the (D) solvent is 50% by mass or more. <Aspect 12> The photosensitive resin composition according to any one of aspects 1 to 11, wherein the (C) thermobase generating agent is a nonionic thermobase generating agent. <Aspect 13> The photosensitive resin composition according to any one of aspects 1 to 12, wherein the (C) thermobase generating agent comprises an amide bond, a urethane bond, or a urea bond. <Aspect 14> The photosensitive resin composition according to any one of aspects 1 to 13, wherein the (C) thermobase generating agent comprises a urethane bond or a urea bond. <Aspect 15> The photosensitive resin composition according to any one of aspects 1 to 13, wherein the (C) thermobase generating agent contains a urea bond. Appearance 16: A photosensitive resin composition according to any one of Appearances 1 to 15, wherein the equivalent amount of imide groups represented by the following formula (1) when the (A) polyamic acid ester is fully imidized is 300 ( / group) or less.

number

[0011] According to the present invention, a photosensitive resin composition is provided that can complete the imidation reaction of polyamic acid esters even at low curing temperatures, and can form a cured film with improved chemical resistance. The present invention also provides a method for producing a cured relief pattern using the above-mentioned photosensitive resin composition. According to the present invention, a cured film, an interlayer insulating film, and the like are also provided. [Modes for carrying out the invention]

[0012] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below, and may be implemented with various modifications within the scope of its essence. Furthermore, throughout this specification, structures represented by the same symbols in a general formula may be identical or different from each other if multiple such structures exist in a molecule.

[0013] The photosensitive resin composition of this embodiment is (A) Polyamic acid ester, (B) Photopolymerization initiator, (C) Thermobase generator, and (D) Solvent A photosensitive resin composition comprising, The solvent (D) is (D1) Compounds having amide bonds and cyclic structures and having a boiling point of 210°C or higher, (D2) Compounds having a urea bond and a cyclic structure, and having a boiling point of 210°C or higher. Includes one or two selected from, It is a photosensitive resin composition. In addition to the above-mentioned components (A) to (D), the photosensitive resin composition of this embodiment may optionally further contain one or more components selected from (E) a thermal crosslinking agent, (F) a monofunctional monomer, and (G) a polyfunctional monomer, as well as other optional components. The components included in the photosensitive resin composition of this embodiment will be described in order below.

[0014] (A) Polyamic acid ester In this embodiment, (A) polyamic acid ester may be a resin component included in a known negative-type photosensitive resin composition, and is not particularly limited as long as it is a resin that can be converted to polyimide by heat cyclization treatment. However, in this embodiment, from the viewpoint of increasing the crosslinking density of the resulting cured film and making the effects of the present invention more easily achieved, it is preferable that (A) the polyamic acid ester has radical polymerizable groups. The (A) polyamic acid ester in this embodiment more preferably has a structure represented by the following general formula (A-1). [ka] {In formula (A-1), X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is the number of repeating units, an integer between 2 and 150, and R3 and R4 are each independently a hydrogen atom or a monovalent organic group, with at least one of R3 and R4 being a monovalent organic group having a radical polymerizable group with 2 to 40 carbon atoms.}

[0015] (A) From the viewpoint of improving the chemical resistance of the resulting cured film, the polyamic acid ester is preferably such that the imide group equivalent when fully imidized is 300 ( / group) or less, more preferably 240 ( / group) or less, and particularly preferably 225 ( / group) or less. This imide group equivalent may be 100 ( / group) or more. The imide group equivalent is the number defined by the following formula (1) when (A) polyamic acid ester is fully imidized, that is, when (A) polyamic acid ester is fully imidized and the structure represented by formula (A-1) above is converted to the structure represented by formula (A-2) below. [ka] {In equation (A-2), X1, Y1, and n1 have the same meanings as X1, Y1, and n1 in the general equation (A-1) above.}

number

[0016] The above indicates that a smaller imide group equivalent leads to a higher concentration of imide groups in the cured film. Cured films with a high concentration of imide groups exhibit superior chemical resistance. This is thought to be due to factors such as the imide bonds being less susceptible to hydrolysis by bases and having low solubility in chemical solutions containing solvents such as resist stripping solutions.

[0017] The tetravalent organic group represented by X1 in the above general formula (A-1) is preferably a divalent organic group having 6 to 40 carbon atoms, from the viewpoint of improving the photosensitivity of the coating film and the heat resistance of the resulting cured film. More preferably, it is a group containing aromatic rings in which the -COOR3 group, the -COOR4 group and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group. More preferably, X1 is a divalent organic group having 6 to 40 carbon atoms and containing an aromatic ring. Examples include the groups represented by the following general formulas (X1-1) to (X1-3). However, X1 is not limited to the examples given below.

[0018] [ka]

[0019] [ka]

[0020] [ka]

[0021] {In equations (X1-1) to (X1-3), R is a group selected from the group consisting of hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups having 1 to 10 carbon atoms, and monovalent fluorine-containing hydrocarbon groups having 1 to 10 carbon atoms; 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.}

[0022] Since there are n1 structures represented by general formula (A-1) in (A) polyamic acid ester, there are n1 tetravalent organic groups represented by X1 in one molecule of (A) polyamic acid ester. These n1 organic groups represented by X1 may all be the same, or they may be a combination of two or more structures. As for the tetravalent organic group represented by X1, from among the groups represented by formulas (X1-1) to (X1-3), it is preferable to select from the structures represented by formulas (X1-1) and (X1-2), respectively, from the viewpoint of being able to reduce the imide group equivalent, and it is more preferable to select from the structure represented by formula (X1-1).

[0023] In the above general formula (A-1), the divalent organic group represented by Y1 is preferably a divalent aromatic group having 6 to 40 carbon atoms, from the viewpoint of improving the photosensitivity of the coating film and the heat resistance of the resulting cured film. Specifically, examples of divalent organic groups represented by Y1 include the groups represented by the following general formulas (Y1-1) to (Y1-3). However, Y1 is not limited to the following examples.

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] {In formulas (Y1-1) to (Y1-3), R is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a monovalent fluorine-containing hydrocarbon group having 1 to 10 carbon atoms.}

[0028] (A) Since there are n1 structures represented by general formula (A-1) in a polyamic acid ester, there are n1 divalent organic groups represented by Y1 in one molecule of polyamic acid ester (A). These n1 organic groups represented by Y1 may all be the same, or they may be a combination of two or more structures. As for the tetravalent organic group represented by Y1, from among the groups represented by formulas (Y1-1) to (Y1-3), it is preferable to select from the structures represented by formulas (Y1-1) and (Y1-2), respectively, from the viewpoint of being able to reduce the imide group equivalent, and it is more preferable to select from the structure represented by formula (Y1-1).

[0029] From the viewpoint of improving the resolution of the coating film and the crosslinking density of the resulting cured film, at least one of R3 and R4 in the above general formula (A-1) is a monovalent organic group having a radical polymerizable group with 2 to 40 carbon atoms. It is preferable that at least one of R3 and R4 in general formula (A-1) is a group represented by the following general formula (R-1). [ka] {In formula (R-1), R5, R6, and R7 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 1 to 10.} In (R-1), m1 is preferably an integer between 1 and 5, and more preferably an integer between 1 and 3.

[0030] The group represented by the above general formula (R-1) is preferably the group represented by the following general formula (R-2). [ka] {In equation (R-2), R5, R6, and R7 have the same meanings as R5, R6, and R7 in equation (R-1), respectively.}

[0031] In formulas (R-1) and (R-2), the monovalent organic groups having 1 to 3 carbon atoms in R5, R6, and R7 specifically include the methyl group, ethyl group, n-propyl group, and isopropyl group. R5 is preferably a hydrogen atom or a methyl group, and R6 and R7 are preferably hydrogen atoms, respectively.

[0032] (A) For polyamic acid esters, the weight-average molecular weight in polystyrene terms, as measured by gel permeation chromatography, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. (A) When the weight-average molecular weight of the polyamic acid ester is 8,000 or more, the mechanical properties of the resulting cured film are good. (A) When the weight-average molecular weight of the polyamic acid ester is 150,000 or less, the dispersibility in the developer is good, and the resolution performance of the relief pattern is good. For gel permeation chromatography, tetrahydrofuran or N-methyl-2-pyrrolidone are recommended as the developing solvent. The weight-average molecular weight mentioned above is determined from a calibration curve created using standard monodisperse polystyrene. For the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample "TSKstandard POLYSTYLENE" manufactured by Tosoh Corporation.

[0033] <(A) Method for preparing polyamic acid esters> (A) Polyamic acid esters can be prepared, for example, by reacting a tetracarboxylic dianhydride having a tetravalent organic group X1 with an alcohol having a radical polymerizable group and optionally another alcohol to prepare a partially esterified tetracarboxylic acid (hereinafter referred to as "acid / ester"), and then by amide polycondensation of this acid / ester with a diamine having a divalent organic group Y1. The reaction to prepare an acid / ester by reacting a tetracarboxylic dianhydride having a tetravalent organic group X1 with an alcohol having a radical polymerizable group, and the amide polycondensation of the obtained acid / ester with a diamine having a divalent organic group Y1, are preferably carried out in a suitable solvent. Typically, the acid / ester mixture is prepared in a suitable solvent, and the resulting reaction mixture is then mixed with a diamine, followed by amide polycondensation.

[0034] (A) As a tetracarboxylic dianhydride having a tetravalent organic group X1 used in the preparation of polyamic acid esters, the compound represented by the following general formula (T-1) is preferred. [ka] {The X1 in equation (T-1) has the same meaning as the X1 in equation (A-1) above.} In formula (T-1), X1 is preferably selected from the groups represented by each of the above formulas (X1-1) to (X1-3), more preferably from the structures represented by formulas (X1-1) and (X1-2), and even more preferably from the structure represented by formula (X1-1).

[0035] Examples of tetracarboxylic dianhydrides represented by the above formula (T-1) include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic acid 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 are pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and one or more selected from these can be used. However, the tetracarboxylic dianhydrides used in the preparation of (A) polyamic acid esters are not limited to the examples given above.

[0036] (A) Alcohols having radical polymerizable groups used in the preparation of polyamic acid esters include, specifically, 2-hydroxyethyl methacrylate, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl Examples include propyl alcohol, 2-methacrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate, glycerol diacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc., and one or more selected from these can be used. However, the alcohols having radical polymerizable groups used in the preparation of (A) polyamic acid esters are not limited to the examples given above.

[0037] From the viewpoint of improving the resolution of the resulting photosensitive resin composition, the proportion of alcohol having a radical polymerizable group used is preferably 30 mol% or more, more preferably 50% or more, particularly preferably 70 mol% or more, and may also be 100 mol%, relative to the total number of moles of R3 and R4 in formula (A-1).

[0038] (A) Other alcohols used in the preparation of polyamic acid esters include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc., and one or more selected from these may be used.

[0039] The above-mentioned tetracarboxylic dianhydride and an alcohol having a radical polymerizable group are reacted in the presence of a suitable basic catalyst (e.g., pyridine) at a temperature of preferably 20 to 50°C for preferably 4 to 10 hours under stirring to obtain an acid / ester compound.

[0040] Diamines having a divalent organic group Y1 that are used in amide polycondensation with acid / ester compounds include, specifically, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "DADPE"), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'- Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) Benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)pro Pan, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, etc., and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., for example, 3,3'-dimethyl-4,Examples include 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., and one or more selected from these can be used. However, the diamines having a divalent organic group Y1 used in the preparation of (A) polyamic acid esters are not limited to the examples given above.

[0041] The amide polycondensation of the above acid / ester compound with a diamine having a divalent organic group Y1 is carried out in the presence of a suitable dehydrating condensation agent, preferably under ice cooling. Typically, the desired (A) polyamic acid ester is obtained by adding a dehydrating condensation agent to a solution containing the acid / ester under ice cooling to convert the acid / ester into a polyacid anhydride, and then further reacting it with a diamine having a divalent organic group Y1. Examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate. Depending on the reactivity of the substrate, 1-hydroxybenzotriazole or the like may be used instead of the dehydrating condensation agent. However, as reported separately, the desired (A) polyamic acid ester can also be obtained by acid-chloridizing the acid moiety of the acid / ester product with thionyl chloride or the like, and then reacting it with a diamine in the presence of a base such as pyridine.

[0042] As described above, the reaction to prepare the acid / ester by reacting a tetracarboxylic dianhydride with an alcohol, and the amide polycondensation of the acid / ester with a diamine, are preferably carried out in a suitable solvent. The solvent used here is preferably one that can uniformly dissolve or disperse tetracarboxylic dianhydride, alcohol, acid / ester compound, and (A) polyamic acid ester in order to carry out the reaction efficiently in a homogeneous system. Examples of solvents include γ-butyrolactone, dimethyl sulfoxide, N,N-dimethylacetacetamide, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N,N-dimethylacetamide. One or more of these can be used.

[0043] As described above, the desired (A) polyamic acid ester is obtained, typically dissolved in the reaction solution. The obtained (A) polyamic acid ester is recovered as a crude product by filtering off any water-absorbing by-products of the dehydrating condensation agent present in the reaction solution, and then precipitating it with a poor solvent, if necessary. Suitable poor solvents include, for example, water, aliphatic lower alcohols, or mixtures thereof. The crude product can be purified by repeated redissolution and reprecipitation operations, and then vacuum-dried to isolate the target (A) polyamic acid ester. To improve the degree of purification, a solution of this polymer may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both of these swollen with a suitable organic solvent, to remove ionic impurities.

[0044] In this embodiment, (A) polyamic acid ester may be used alone or as a mixture of two or more types. In addition, a non-photosensitive polyamic acid ester that does not have radical polymerizable groups may be used in combination with (A) polyamic acid ester. In this case, from the viewpoint of ensuring the resolution of the coating film, it is preferable that the amount of non-photosensitive polyamic acid ester added is 200 parts by mass or less per 100 parts by mass of (A) polyamic acid ester.

[0045] (B) Photopolymerization initiator In this embodiment, (B) the photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of photoradical polymerization initiators include benzophenone compounds, acetophenone compounds, thioxanthone compounds, benzyl compounds, benzoin compounds, oxime compounds, N-arylglycine compounds, peroxides, aromatic biimidazole compounds, titanocene compounds, etc., and one or more selected from these can be used.

[0046] (B) Specific examples of photopolymerization initiators include the following: Examples of benzophenone compounds include benzophenone, o-benzoylmethyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone. Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone. Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone. Examples of benzyl compounds include benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl acetal. Examples of benzoin compounds include benzoin and benzoin methyl ether.

[0047] Examples of oxime compounds include 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), and ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O- Examples include acetyl oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime, ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyloxime), and compounds represented by (B-9) and (B-10) respectively in the examples, as well as trade names such as PBG-326 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.). Examples of arylglycine compounds include N-phenylglycine. Examples of peroxides include benzoyl perchloride.

[0048] The photopolymerization initiator (B) in this embodiment is not limited to the above examples. In this embodiment, (B) the photopolymerization initiator preferably contains an oxime compound, and more preferably is an oxime compound, from the viewpoint of high photosensitivity.

[0049] (B) The molecular weight of the photopolymerization initiator is preferably 540 or less, and more preferably 400 or less. In the photosensitive resin composition of this embodiment, (D) the solvent contains a nitrogen-containing cyclic compound with a boiling point of 210°C or higher. As a result, the amount of residual solvent after pre-baking the coating film of the composition is increased, and the mobility of (B) the photopolymerization initiator is improved in the coating film after pre-baking. This improved mobility of (B) the photopolymerization initiator improves the photosensitivity of the composition and improves the chemical resistance of the cured film by promoting crosslinking. Here, it is thought that by having a molecular weight of (B) photopolymerization initiator of 540 or less or 400 or less, the mobility of (B) photopolymerization initiator is significantly improved, resulting in even greater improvements in sensitivity and chemical resistance.

[0050] Examples of (B) photopolymerization initiators with a molecular weight of 540 or less include 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanoone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), and 1-phenyl-1,2-propanedione-2-(O-benzoyl)-oxime. Examples include ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyloxime). Furthermore, examples of (B) photopolymerization initiators with a molecular weight of 400 or less include 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyloxime).

[0051] (B) The molecular weight of the photopolymerization initiator may be, for example, 100 or more, 150 or more, or 200 or more.

[0052] The amount of (B) photopolymerization initiator in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of (A) polyamic acid ester. From the viewpoint of ensuring the photosensitivity or patternability of the resulting photosensitive resin composition, this amount is preferably 0.1 parts by mass or more per 100 parts by mass of (A) polyamic acid ester, and from the viewpoint of improving the physical properties of the resulting cured film, it is preferably 30 parts by mass or less per 100 parts by mass of (A) polyamic acid ester. The amount of (B) photopolymerization initiator is more preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less, and particularly preferably 3 parts by mass or more and 8 parts by mass or less per 100 parts by mass of (A) polyamic acid ester.

[0053] (C) Thermal base generator In this embodiment, (C) the thermobase generating agent is a compound that generates a base when heated to 40°C or higher. By incorporating (C) a thermobase generating agent into the photosensitive resin composition of this embodiment, it becomes possible to promote the imidation reaction of (A) polyamic acid ester even when the heat treatment temperature during curing film formation is low, which is preferable. In this embodiment, (C) the thermobase generator can be an ammonium salt type thermobase generator, a nonionic thermobase generator, or the like.

[0054] Ammonium salt-type thermobase generators are salts composed of ammonium cations and anions. Examples of ammonium cations in ammonium salt-type thermobase generators include those represented by the following general formulas (CA-1) and (CA-2). [ka] {In formulas (CA-1) and (CA-2), L1 to L6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and L7 is a divalent hydrocarbon group having 1 to 20 carbon atoms.} L1 and L2 in formula (CA-1), and L3 and L4, as well as L5 and L6 in formula (CA-2), may be bonded to each other to form a ring.

[0055] Examples of ammonium anions used in ammonium salt-type thermobase generators include carboxylate anions, phenol anions, phosphate anions, and sulfate anions.

[0056] Nonionic thermobase generators are thermobase generators that do not possess ionic bonds. The ammonium salt-type thermobase generators described above suppress the development of basicity through ionic bonding; therefore, depending on the storage temperature, interactions with other coexisting ionic components, etc., the development of basicity may not be suppressed. Therefore, from the standpoint of storage stability, nonionic thermobase generators are preferable.

[0057] In this embodiment, as a nonionic thermobase generator, a thermobase generator having an amide bond, a urethane bond, or a urea bond is preferred from the viewpoint of obtaining a cured film with high chemical resistance and an appropriate glass transition temperature.

[0058] The inventors of the present invention surmise the following reasons why a thermobase generating agent having an amide bond, a urethane bond, or a urea bond is preferred.

[0059] (C) The thermal base generating agent decomposes during the heat treatment (curing) process when the hardened film is formed, generating a base. However, not all of the added thermal base generating agent decomposes; some of it remains in the film in the same structure as when it was added. The thermobase generators having amide, urethane, and urea bonds have strong hydrogen bonding properties, and it is presumed that they interact with the imide groups of polyimides formed from (A) polyamic acid esters, increasing the density of the film, improving the chemical resistance of the cured film, and raising the glass transition temperature. Furthermore, even if a thermobase generator with strong hydrogen bonding properties is incorporated, as long as compounds (D1) and (D2) in solvent (D) remain in the coating film, aggregation of (A) polyamic acid ester and (C) thermobase generator is suppressed, and therefore, the imidization of (A) polyamic acid ester is not inhibited. In this embodiment, it is thought that after compounds (D1) and (D2) volatilize and dissipate, and the imidization of (A) polyamic acid ester is completed, the interaction between the imidized (A) polyamic acid ester and (C) thermobase generator occurs, resulting in improved chemical resistance and an increase in the glass transition temperature. However, the present invention is not bound by any particular theory.

[0060] Examples of thermobase generators having an amide bond include compounds represented by the following general formula (CA-1). [ka]

[0061] {In formula (CA-1), R8~R 12 Each of these is independently a hydrogen atom, a C1-C10 alkyl group, an alkenyl group, a C6-C10 aryl group, or a C7-C10 arylalkyl group. In formula (CA-1), the base R8~R 12It may have a substituent as long as the effects of the present invention are not inhibited. Examples of the substituent include an amino group, a hydroxyl group, an alkoxyalkyl group, and the like. Further, R8 and R9 may be bonded to each other to form a ring.

[0062] Examples of the thermal base generator having a urethane bond include compounds represented by the following general formulas (CB-1) and (CB-2), respectively.

Chemical formula

[0063] {In formulas (CB-1) and (CB-2), R 13 and R 14 are each independently a hydrogen atom or an organic group which may contain a heteroatom, R 15 and R 16 are each independently an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 17 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.} Examples of the heteroatom in R 17 include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and the like. The number of heteroatoms contained in R 17 is preferably from 0 to 20. R 17 is a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom, and may be an aromatic group or an aliphatic group. Examples of the aromatic group R 17 include groups represented by general formulas (Y1-1), (Y1-2), and (Y1-3) exemplified above as the divalent organic group represented by Y1 in general formula (A-1). Examples of the aliphatic group R 17Examples of such groups include divalent groups having a diamine-derived skeleton. Examples of diamines in this case include 1,4-butanolbis(3-aminopropyl) ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetrodecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, norbonanediamine, ethylenediamine, hexamethylenediamine, 1,4-bis(aminomethyl)cyclohexane, 1,4-cyclohexanediamine, decamethylenediamine, and the like.

[0064] The compounds represented by the above general formulas (CB-1) and (CB-2) are preferably the compounds represented by the following general formulas (CB-1-1) and (CB-2-1). [ka]

[0065] {In formulas (CB-1-1) and (CB-2-1), R 17 R is a divalent organic group having 1 to 20 carbon atoms, which may contain heteroatoms. 18 and R 19 Each of these is independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group, and R 20 This is an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group. R 18 and R 19 A methyl group is preferred, R 20 An aryl group is preferred as the element. The compounds represented by formulas (CB-1-1) and (CB-2-1) are preferably synthesized by, for example, a reaction between an isocyanate compound and an alcohol compound, or a reaction between an amine compound and a dicarbonate compound.

[0066] Specific examples of compounds represented by the above general formulas (CB-1) and (CB-2) include, for example, the following compounds. [ka]

[0067] Examples of thermobase generators containing a urea bond include compounds represented by the following general formulas (CC-1) and (CC-2). [ka]

[0068] {In formulas (CC-1) and (CC-2), R 17 R is a divalent organic group having 1 to 20 carbon atoms, which may contain heteroatoms. 21 and R 22 Each of these is independently a monovalent organic group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom, provided that R 21 and R 22 R cannot become a hydrogen atom at the same time. 23 , R 24 , and R 25 Each of these is independently a monovalent organic group having 1 to 20 carbon atoms, which may contain heteroatoms. The compounds represented by formulas (CC-1) and (CC-2) are preferably synthesized, for example, by the reaction of an isocyanate compound with an amine.

[0069] The compounds represented by formulas (CC-1) and (CC-2) respectively preferably further have one or more functional groups selected from the group consisting of (meth)acrylic groups, hydroxyl groups, and alkoxyl groups, from the viewpoint of improving the chemical resistance of the resulting cured film and raising the glass transition temperature of the imidide of (A) polyamic acid ester. Because thermobase generators having (meth)acrylic groups tend to be present near (A) polyamic acid esters, they can react with the side chain portion of (A) polyamic acid esters, especially when incorporated into negative-type photosensitive resin compositions, to promote polymer crosslinking upon light irradiation. Therefore, it is believed that incorporating thermobase generators having (meth)acrylic groups can dramatically increase the efficiency of imidization conversion of (A) polyamic acid esters, improve the crosslinking density of the imidized product, further enhance chemical resistance, and raise the glass transition temperature. A thermobase generator having one or two of hydroxyl groups and alkoxyl groups is thought to increase the density of the cured film due to hydrogen bonding, thereby further enhancing chemical resistance and raising the glass transition temperature. Furthermore, as mentioned above, even when a thermobase generator with strong hydrogen bonding properties is used, the imidization reaction of (A) polyamic acid ester is not inhibited, and improved chemical resistance and an increase in the glass transition temperature are expected to occur.

[0070] The thermobase generator having a (meth)acrylic group preferably has a (meth)acrylic equivalent of 150 to 400 g / mol. A (meth)acrylic equivalent of 150 g / mol or more tends to result in good chemical resistance of the resulting cured film. A value of 400 g / mol or less tends to result in good developability. The (meth)acrylic equivalent of the (meth)acrylic group-containing thermobase generator may be 200 g / mol or more, 210 g / mol or more, 220 g / mol or more, 230 g / mol or more, 240 g / mol or more, or 250 g / mol or more, and may be 350 g / mol or less, 330 g / mol or less, or 300 g / mol or less. The (meth)acrylic equivalent of the (meth)acrylic group-containing thermobase generator is more preferably 210 to 400 g / mol, and even more preferably 220 to 400 g / mol. The (meth)acrylic equivalent of a thermal base generator is calculated by dividing the molar mass (g / mol) of the thermal base generator by the number of (meth)acrylic groups present in the thermal base generator.

[0071] The compounds represented by formulas (CC-1) and (CC-2) are preferably (meth)acrylic group-containing urea compounds having a structure represented by the following general formula (Ac-1). [ka]

[0072] {In formula (Ac-1), R3 is a hydrogen atom or a methyl group, A is a divalent group selected from the group consisting of -O-, -NH-, and -NL4-, L4 is a monovalent organic group having 1 to 12 carbon atoms, Z1 is an m2-valent organic group having 2 to 24 carbon atoms, Z2 is a divalent organic group having 2 to 8 carbon atoms, m2 is an integer from 1 to 3, and when m2 is 2 or 3, the multiple R3, A, and Z1 in formula (C1) may be the same or different from each other.} In formula (Ac-1), a methyl group is preferred as R5 from the viewpoint of good developability of the coating film. Z1 is not limited to any m2 valent organic group having 2 to 20 carbon atoms. Here, Z1 may contain heteroatoms such as oxygen, sulfur, nitrogen, and phosphorus atoms. If Z1 has 2 or more carbon atoms, the resulting cured film tends to have good chemical resistance, and if it has 20 or fewer carbon atoms, the paint film tends to have good developability. The number of carbon atoms in Z1 is preferably 3 or more, more preferably 4 or more, preferably 18 or less, and most preferably 16 or less. Z2 is a divalent organic group having 2 to 8 carbon atoms. Here, Z2 may contain heteroatoms such as oxygen, sulfur, nitrogen, and phosphorus atoms. If the number of carbon atoms in Z2 is 2 or more, the resulting cured film tends to have good chemical resistance, and if the number of carbon atoms is 8 or less, the cured film tends to have good heat resistance. The number of carbon atoms in Z2 is preferably 6 or less, and more preferably 4 or less.

[0073] Specific examples of compounds represented by the above general formulas (CC-1) and (CC-2) include, for example, the following compounds. [ka]

[0074] Of the above-mentioned thermobase generators, from the viewpoint of the strength of hydrogen bonding, thermobase generators having urea bonds are considered to have the greatest effect in improving chemical resistance and glass transition temperature, followed by thermobase generators having urethane bonds and thermobase generators having amide bonds, in that order, in terms of the degree of improvement in chemical resistance and glass transition temperature. Therefore, in this embodiment, it is preferable to use one or more types of (C) thermobase generating agents selected from thermobase generating agents having urea bonds, thermobase generating agents having urethane bonds, and thermobase generating agents having amide bonds as (C) thermobase generating agents, more preferably to use one or more types selected from thermobase generating agents having urea bonds and thermobase generating agents having urethane bonds, and even more preferably to use thermobase generating agents having urea bonds.

[0075] (D) Solvent In this embodiment, (D) solvent is (D1) Compounds having an amide bond and a cyclic structure, and having a boiling point of 210°C or higher, (D2) Compounds having a urea bond and a cyclic structure, and having a boiling point of 210°C or higher. Includes one or two selected from the following.

[0076] In this embodiment, the solvent (D) contains one or two compounds selected from compound (D1) and compound (D2), which promotes the imidation reaction of the polyamic acid ester (A) even when the heat treatment (curing) temperature during the formation of the cured film is low. The reason for this is not clear, but the inventors surmise that this is due to the fact that compound (D1) and compound (D2) have high boiling points of 210°C or higher, possess hydrogen bonding properties, and have a cyclic structure.

[0077] Compounds (D1) and (D2) have high boiling points of 210°C or higher, so they do not easily volatilize when a photosensitive resin composition is applied to a substrate by, for example, a spin coating method, and the timing of volatilization is slow even during low-temperature curing. Therefore, it is thought that using these solvents maintains the fluidity of the film even during the curing process, and that the mobility of (A) polyamic acid ester and (C) thermal base generator is maintained. If the mobility of (A) polyamic acid ester is maintained, the imidation reaction proceeds more easily. Also, if the mobility of (C) thermal base generator is maintained, the frequency of base generation tends to increase. Furthermore, compounds (D1) and (D2) possess hydrogen bonding properties because they have amide or urea bonds. Therefore, the coexistence of these compounds suppresses aggregation due to hydrogen bonding between (A) polyamic acid esters, thereby maintaining the mobility of the A) polyamic acid esters. Furthermore, the effects of compounds (D1) and (D2) having a cyclic structure are specifically verified in the examples described later.

[0078] Furthermore, the above factors combined are thought to accelerate the imidation reaction of (A) polyamic acid esters. However, the present invention is not bound by any particular theory.

[0079] In this embodiment, the compound (D1) contained in solvent (D) is preferably a compound represented by the following general formula (D1), and the compound (D2) is preferably a compound represented by the following general formula (D2).

[0080] [ka] {In formula (D1), R1 is a monovalent organic group having 2 or more carbon atoms, In formula (D2), R2 and R3 are each independently monovalent organic groups having one or more carbon atoms.

[0081] In formula (D1), the number of carbon atoms in the organic group R1 is preferably 2 or more in order to make the boiling point of the (D1) compound 210°C or higher. (D1)Specific examples of compounds include N-ethyl-2-pyrrolidone (NEP), N-acetyl-2-pyrrolidone, N-butyl-2-pyrrolidone (NBP), N-(3-hydroxypropyl)-2-pyrrolidone, methyl 2-oxo-1-pyrrolidine acetate, N-cyclohexyl-2-pyrrolidone, 2-(2-oxopyrrolidine-1-yl)ethyl methacrylate, and Nn-octyl-2-pyrrolidone.

[0082] The number of carbon atoms in the R1 organic group is preferably 5 or less, from the viewpoint of reducing steric hindrance around the amide bond in order to increase the hydrogen bonding ability of the (D1) compound. The number of carbon atoms in the organic group R1 is preferably 2 to 5, more preferably 2 or 3, and most preferably R1 is an ethyl group. Therefore, NEP is the most preferred compound for (D1).

[0083] The number of carbon atoms in the organic groups R2 and R3 in formula (D2) may be 1 or more in order to ensure that the boiling point of the (D2) compound is 210°C or higher. (D2)Specific examples of compounds include 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, and 1,3-dibutyl-2-imidazolidinone.

[0084] The number of carbon atoms in the organic groups R2 and R3 is preferably 5 or less, from the viewpoint of reducing steric hindrance around the amide bond in order to increase the hydrogen bonding ability of the (D2) compound. The number of carbon atoms in the organic groups R2 and R3 is preferably 1 to 5, more preferably 1 to 5, and most preferably both R2 and R3 are methyl groups. Therefore, DMI is the most preferred (D2) compound.

[0085] The solvent (D) in this embodiment may include other solvents, as long as they do not adversely affect the performance of the resulting photosensitive resin composition. Other solvents include, for example, amides (excluding compounds containing amide bonds included in the above-mentioned (C) thermal base generator), sulfoxides, ureas (excluding compounds containing urea bonds included in the above-mentioned (C) thermal base generator), ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, and the like.

[0086] Other solvents include, specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, and the like.

[0087] The total amount of compound (D1) and compound (D2) in the photosensitive resin composition of this embodiment is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 100 parts by mass or more and 700 parts by mass or less, and even more preferably 125 parts by mass or more and 500 parts by mass or less, per 100 parts by mass of polyamidic acid ester (A). When compound (D1) and compound (D2) are used in combination with other solvents, the amount of other solvents is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of polyamic acid ester (A). Furthermore, when other solvents are used in combination, the total mass of compound (D1) and compound (D2) relative to the total mass of solvent (D) is preferably 50% by mass or more, and more preferably 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. By blending compound (D1) and compound (D2) in such proportions, the effect of including one or two compounds selected from compound (D1) and compound (D2) in the photosensitive resin composition of this embodiment is clearly demonstrated.

[0088] (E) Thermal crosslinking agent The photosensitive resin composition of this embodiment may also contain (E) a thermal crosslinking agent. In this embodiment, (E) the thermal crosslinking agent refers to a compound that undergoes an addition reaction or condensation polymerization reaction upon contact with heat. These reactions can occur, for example, between (A) the polyamic acid ester and (E) the thermal crosslinking agent, between (E) thermal crosslinking agents themselves, and between (E) the thermal crosslinking agent and other components. (E) The temperature at which the addition reaction or condensation polymerization reaction occurs with the thermal crosslinking agent is preferably 150°C or higher.

[0089] Generally, when a thermal crosslinking agent is added to a negative-type photosensitive resin composition containing polyamic acid ester, thermal crosslinking occurs during the heating process (curing process), improving the chemical resistance and thermal properties of the resulting cured film. However, on the other hand, when the curing process is carried out at low temperatures, there is a problem that the thermal crosslinking agent inhibits the imidization reaction of the polyamic acid ester. In this respect, in this embodiment, by (D) the solvent containing one or two selected from compound (D1) and compound (D2), the (E) thermal crosslinking agent does not inhibit the imidization reaction of (A) the polyamic acid ester, and the chemical resistance, thermal properties, etc. of the resulting cured film are improved. Furthermore, in the photosensitive resin composition of this embodiment, by combining the (E) thermal crosslinking agent with one or two selected from the (D1) compound and the (D2) compound, the mobility of the (E) thermal crosslinking agent during the curing process can be maintained, thereby significantly improving the chemical resistance, thermal properties, etc. of the resulting cured film.

[0090] Examples of (E) thermal crosslinking agents in this embodiment include methylol-based thermal crosslinking agents, epoxy-based thermal crosslinking agents, oxetane-based thermal crosslinking agents, bismaleimide-based thermal crosslinking agents, allyl-based thermal crosslinking agents, and blocked isocyanate-based thermal crosslinking agents.

[0091] Examples of methylol-based thermal crosslinking agents include, but are not limited to, the following compounds. [ka] [ka]

[0092] Examples of epoxy-based thermal crosslinking agents include, but are not limited to, 4-hydroxybutyl acrylate glycidyl ether, epoxy compounds containing a bisphenol A type group, and hydrogenated bisphenol A diglycidyl ether (e.g., "Epolite 4000" manufactured by Kyoeisha Chemical Co., Ltd.).

[0093] Examples of oxetane-based thermal crosslinking agents 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)diphenoether. Examples include, but are not limited to, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicates, phenol novolac type oxetanes, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (trade name, manufactured by Toagosei Co., Ltd.), OXT221 (trade name, manufactured by Toagosei Co., Ltd.), etc.

[0094] Examples of bismaleimide-based thermal crosslinking agents 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), and 4-methyl-N,N'-1,3-phenylenebis(maleimide). Examples include, but are not limited to, mbiso(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, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

[0095] Examples of allyl-based thermal crosslinking agents include, but are not limited to, allyl alcohol, allylanisole, allyl benzoate, allyl cinnamate, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0096] Examples of blocked isocyanate-based thermal crosslinking agents include hexamethylene diisocyanate-based blocked isocyanates (e.g., Asahi Kasei Corporation's "Duranate SBN-70D", "SBB-70P", "SBF-70E", "TPA-B80E", "17B-60P", "MF-B60B", "E402-B80B", "MF-K60B", and "WM44-L70G": Mitsui Chemicals, Inc., "Takenate B-882N": Baxenden, "7960", "7961", "7982", "7991", "7992", etc.), and tolylene diisocyanate-based blocked isocyanates (e.g., Mitsui Chemicals, Inc., "Takenate B- Examples include, but are not limited to, 830, 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Mitsui Chemicals, Inc.'s "Takenate B-815N"; Daiei Sangyo Co., Ltd.'s "Bronate PMD-OA01", "PMD-MA01", etc.), 1,3-bis(isocyanatemethyl)cyclohexane-based blocked isocyanates (e.g., Mitsui Chemicals, Inc.'s "Takenate B-846N"; Tosoh Corporation's "Coronate BI-301", "2507", "2554", etc.), and isophorone diisocyanate-based blocked isocyanates (e.g., Baxenden's "7950", "7951", "7990", etc.).

[0097] Of these thermal crosslinking agents, From the viewpoint of high storage stability of the photosensitive resin composition, blocked isocyanate-based thermal crosslinking agents and bismaleimide-based thermal crosslinking agents are preferred. From the viewpoint of having low curing shrinkage of the resulting cured film, a thermal crosslinking agent containing nitrogen atoms is preferred. From the viewpoint of obtaining a cured film with high chemical resistance, methylol-based thermal crosslinking agents are preferred. (E) The thermal crosslinking agent may be used alone or in combination of two or more types.

[0098] In the photosensitive resin composition of this embodiment, the amount of (E) thermal crosslinking agent is preferably 0.2 parts by mass or more and 40 parts by mass or less per 100 parts by mass of (A) polyamic acid ester. From the viewpoint of ensuring the chemical resistance of the resulting cured film, the amount of (E) thermal crosslinking agent is preferably 0.2 parts by mass or more, more preferably 1.0 part by mass or more, and even more preferably 5.0 parts by mass or more per 100 parts by mass of (A) polyamic acid ester. From the viewpoint of ensuring the storage stability of the photosensitive resin composition, the amount of (E) thermal crosslinking agent is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less per 100 parts by mass of (A) polyamic acid ester.

[0099] (F) Monofunctional monomer The photosensitive resin composition of this embodiment may also contain (F) a monofunctional monomer. In this embodiment, (F) monofunctional monomer means a compound having one photoradical polymerizable group. However, those corresponding to (C) thermal base generators described above are excluded from (F) monofunctional monomers in this embodiment. Generally, it is known that when a polyfunctional monomer having two or more photoradical polymerizable groups is blended with a negative-type photosensitive resin composition containing a polyamic acid ester, the polyfunctional monomer polymerizes during the heating process (curing process), improving the film density of the resulting cured film, thereby improving the chemical resistance, thermophysical properties, etc. of the cured film. However, on the other hand, when the curing process is carried out at low temperatures, there is a problem that the imidization reaction of the polyamic acid ester is inhibited by the crosslinking of the polyfunctional monomer. In this respect, monofunctional monomers can improve the chemical resistance, thermophysical properties, etc. of the cured film without inhibiting the imidization reaction of polyamic acid esters. This is presumed to be because the increase in film density due to polymerization involving monofunctional monomers is smaller compared to that of polyfunctional monomers.

[0100] However, in conventional technology, monofunctional monomers have fewer functional groups and lower reactivity compared to polyfunctional monomers, which was thought to cause problems such as unreacted substances remaining in the cured film and lowering the glass transition temperature. In contrast, in the photosensitive resin composition of this embodiment, by combining the (F) monofunctional monomer with one or two compounds selected from the (D1) compound and the (D2) compound, the mobility of the (F) monofunctional monomer during the curing process can be maintained. This is thought to improve the reactivity of the (F) monofunctional monomer, thereby improving the chemical resistance, thermal properties, etc., of the resulting cured film.

[0101] Examples of (F) monofunctional monomers in this embodiment include 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, polyethylene glycol monomethacrylate, hydroxypropyl methacrylate, polypropylene glycol monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polybutylene glycol monomethacrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, glycerin monoacrylate, polyethylene glycol monoacrylate, hydroxypropyl acrylate, polypropylene glycol monoacrylate, polyethylene glycol polypropylene glycol monoacrylate, Examples include polyethylene glycol polybutylene glycol monoacrylate, stearyl methacrylate, lauryl acrylate, cetyl acrylate, behenyl acrylate, cyclohexyl methacrylate, phenoxy polyethylene glycol polybutylene glycol methacrylate, hydroxyphenyl methacrylate, cyclohexyl acrylate, benzyl acrylate, nonylphenoxy polypropylene glycol acrylate, nonylphenoxy polyethylene glycol polypropylene glycol monoacrylate, methoxy polyethylene glycol monomethacrylate, octyl polyethylene glycol polypropylene glycol monomethacrylate, etc., and one or more selected from these may be blended.

[0102] In the photosensitive resin composition of this embodiment, the amount of (F) monofunctional monomer blended is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyamic acid ester. From the viewpoint of ensuring the chemical resistance of the resulting cured film, the amount of (F) monofunctional monomer blended is preferably 0.2 parts by mass or more, more preferably 1.0 part by mass or more, and even more preferably 5.0 parts by mass or more, per 100 parts by mass of (A) polyamic acid ester. From the viewpoint of ensuring the storage stability of the photosensitive resin composition, the amount of (F) monofunctional monomer blended is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of (A) polyamic acid ester.

[0103] (G) Polyfunctional monomers The photosensitive resin composition of this embodiment may contain (G) a polyfunctional monomer, to the extent that it does not impair the performance of the photosensitive resin composition. In this embodiment, (G) polyfunctional monomer means a compound having two or more photoradical polymerizable groups.

[0104] Examples of (G) polyfunctional monomers in this embodiment include (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol diacrylate; cyclohexane di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, isobornyl(meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, etc. In addition, ethylene oxide or propylene oxide adducts of these compounds, Examples include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexaacrylate. The amount of (G) polyfunctional monomer in the photosensitive resin composition of this embodiment is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyamic acid ester. The amount of (G) polyfunctional monomer may be 1.0 part by mass or more, or 5.0 parts by mass or more, or 30 parts by mass or less, or 20 parts by mass or less, per 100 parts by mass of (A) polyamic acid ester.

[0105] Other ingredients The photosensitive resin composition of this embodiment contains (A) a polyamic acid ester, (B) a photopolymerization initiator, (C) a thermal base generator, and (D) a solvent as essential components, and may also contain one or more selected from (E) a thermal crosslinking agent, (F) a monofunctional monomer, and (G) a polyfunctional monomer, but may also optionally contain other components. Examples of such components include rust inhibitors, adhesive aids, hindered phenol compounds, organotitanium compounds, sensitizers, and thermal polymerization inhibitors.

[0106] When forming a cured film on a copper or copper alloy substrate using the photosensitive resin composition of this embodiment, a rust inhibitor may be added to the photosensitive resin composition to improve the adhesion between the substrate and the cured film. For example, azole compounds, purine compounds, etc., may be used as rust inhibitors.

[0107] To improve the adhesion between the cured film formed using the photosensitive resin composition of this embodiment and the substrate, an adhesive aid may be added to the photosensitive resin composition. As adhesive aids, for example, aluminum-based adhesive aids, silane coupling agents, etc., may be used.

[0108] When forming a cured film on a copper or copper alloy substrate using the photosensitive resin composition of this embodiment, a hindered phenol compound may be added to the photosensitive resin composition to prevent discoloration of the substrate surface.

[0109] When using the photosensitive resin composition of this embodiment and performing the curing process at a low temperature to form a cured film, an organotitanium compound may be added to the photosensitive resin composition to improve the chemical resistance of the cured film. Examples of organotitanium compounds that may be used include titanium chelate compounds, monoalkoxytitanium compounds, tetraalkoxytitanium compounds, titanocene compounds, titanium oxide compounds, titanium tetraacetylacetonate compounds, and titanate coupling agents.

[0110] To improve the light sensitivity of the photosensitive resin composition of this embodiment, a sensitizer may be added to the photosensitive resin composition. Furthermore, to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition of this embodiment, especially when stored in a solution containing solvent (D), a thermal polymerization inhibitor may be added to the photosensitive resin composition.

[0111] Method for manufacturing hardened relief patterns According to another aspect of the present invention, a method for manufacturing a cured relief pattern is provided. The method for manufacturing the cured relief pattern of this embodiment is: (1) Applying the photosensitive resin composition of this embodiment onto a substrate to form a photosensitive resin layer on the substrate (photosensitive resin layer formation step), (2) Exposing the photosensitive resin layer (exposure step), (3) Developing the photosensitive resin layer after exposure to form a relief pattern (development step), and (4) Heat treatment of the relief pattern to form a hardened relief pattern (heat treatment step) This method includes [something].

[0112] <(1) Photosensitive resin layer formation process> In the photosensitive resin layer formation process, the photosensitive resin composition of this embodiment is applied to a substrate, and if necessary, then dried to form a photosensitive resin layer on the substrate. As for the coating method, methods that have been conventionally used for coating photosensitive resin compositions may be used. Specifically, for example, methods such as coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., and spray coating with a spray coater can be used.

[0113] The coating obtained as described above may be dried if necessary. Methods for drying the coating film include, for example, heat drying and vacuum drying. Heat drying may be performed, for example, by air drying, oven, or hot plate. When air-drying or heat-drying, it is preferable to dry at a temperature of 20°C to 140°C for 1 minute to 1 hour. As described above, a photosensitive resin layer is formed on the substrate.

[0114] (2) Exposure process In the exposure process, the photosensitive resin layer formed above is exposed to light using an ultraviolet light source or the like. Exposure can be performed using, for example, an exposure device such as a contact aligner, mirror projection, or stepper. Exposure may be performed via a photomask or reticle having a pattern, or it may be performed directly without such a pattern.

[0115] After coating, if necessary, at least one of post-exposure baking (PEB) and pre-development baking may be performed at any temperature and for any duration to improve light sensitivity, etc. For both post-exposure baking and pre-development baking, the preferred baking conditions are a temperature of 40°C to 120°C and a duration of 10 to 240 seconds.

[0116] <(3) Development process> In the development process, the unexposed portions of the photosensitive resin layer after exposure are developed and removed from the substrate, leaving a relief pattern composed of the exposed portions on the substrate. Conventional photoresist development methods can be used for development. Specifically, any method can be selected from, for example, the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment. After development, if necessary, post-development baking may be performed using any combination of temperature and time for purposes such as adjusting the shape of the relief pattern.

[0117] The developer used for development is preferably, for example, a good solvent for the negative-type photosensitive resin composition, or a combination of the good solvent and a poor solvent. Preferred good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Preferred poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. The above good solvents and poor solvents may be used individually or as a mixture of two or more. When using a mixture of a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer (unexposed (A) polyamic acid ester) in the photosensitive resin composition. Furthermore, the photosensitive resin composition of this embodiment may be used for development with an organic solvent. In this case, (A) polyamic acid ester may be alkali-insoluble. Furthermore, the photosensitive resin composition of this embodiment may be used for development with a developer containing 90% or more, preferably 95% or more, of an organic solvent.

[0118] <Heat treatment process> In the heat treatment step, the relief pattern obtained in the development step is heated to dilute the photosensitive components and imidize the (A) polyamic acid ester, thereby converting it into a cured relief pattern made of polyimide. Heating may be carried out, for example, by a hot plate, an oven, or a rising oven with a temperature programmable. The heat treatment may be carried out at a temperature of, for example, 170°C to 400°C, preferably 170°C to 300°C, more preferably 170°C to 250°C, and even more preferably 170°C to 200°C, for a period of time of, for example, 30 minutes to 5 hours. Air may be used as the atmospheric gas during the heat treatment, or an inert gas such as nitrogen or argon may be used.

[0119] 《Cured film》 According to yet another aspect of the present invention, a cured film is provided. The cured film of this embodiment is formed from the photosensitive resin composition of this embodiment described above, and may be a cured film with a cured relief pattern or a cured film without a pattern.

[0120] The cured film of this embodiment contains polyimide. The polyimide contained in the cured film of this embodiment includes the structure represented by formula (A-2) above. The preferred groups X1 and Y1 in formula (A-1) above are also preferred as the groups X1 and Y1 in formula (A-2) for the same reasons. A method for producing polyimide, which includes a step of converting (A) polyamic acid ester in the photosensitive resin composition of this embodiment to polyimide, is also one aspect of the present invention.

[0121] Semiconductor equipment According to yet another aspect of the present invention, a semiconductor device is provided. The semiconductor device of this embodiment has a cured relief pattern formed from the photosensitive resin composition of this embodiment. The semiconductor device of this embodiment may, for example, have a semiconductor or semiconductor substrate, and a cured relief pattern on this substrate. The cured relief pattern in the semiconductor device of this embodiment may be, for example, a surface protective film, an interlayer insulating film, or an insulating film for redistribution. The protective film may be, for example, a protective film for a flip-chip device or a protective film for a semiconductor device having a bump structure.

[0122] 《Display device》 According to yet another aspect of the present invention, a display device is provided. The display device of this embodiment comprises a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured film of this embodiment (particularly the cured relief pattern). The cured film (especially the cured relief pattern) may be laminated in direct contact with the display element, or it may be laminated with another layer in between. The cured film may be, for example, a protective film, an insulating film, a planarizing film, or a protrusion for an MVA type liquid crystal display device, or a partition for the cathode of an organic EL element. The protective film may be, for example, a surface protective film for a TFT liquid crystal display element, or a surface protective film for a color filter element. [Examples]

[0123] The embodiment will be described in detail below with reference to examples, but this embodiment is not limited thereto. In the examples, comparative examples, and synthesis examples, the physical properties of the polyamic acid ester, polyimide, and photosensitive resin composition were measured and evaluated according to the following methods, respectively.

[0124] Measurement and Evaluation Methods (1) Measurement of weight-average molecular weight The weight-average molecular weight (Mw) of each resin was measured by gel permeation chromatography (on a standard polystyrene basis) under the following conditions. Equipment: HLC-8320GPC (manufactured by Tosoh Corporation) Eluent: N-methyl-2-pyrrolidone solution containing lithium bromide monohydrate (30 mmol / L) and phosphoric acid (50 mmol / L). Flow rate: 0.5mL / min Columns: Two TSKgel SUPER HM-H columns and one TSKgel SUPER H-RC column, manufactured by Tosoh Corporation, connected in series. Column temperature: 40℃ Detector: UV-8320 ultraviolet absorption detector manufactured by Tosoh Corporation.

[0125] (2) Evaluation of the imidization rate A photosensitive resin composition was rotary coated onto a 6-inch silicon wafer that had been pre-sputtered with Ti and Cu. A 10 μm thick coating film was formed on the substrate by pre-baking on a hot plate at 110°C for 240 seconds. The rotary coating was performed using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation). The resulting coating film was subjected to a high-pressure mercury lamp treatment of 500 mJ / cm². 2After exposure, a cured film approximately 7 μm thick was formed on the wafer by heating it at 180°C for 2 hours under a nitrogen atmosphere using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Thermo Systems Co., Ltd.). Furthermore, the same coating was used to form a cured film heated to 350°C on the wafer by performing the same procedure, except that the heating temperature was changed to 350°C. Both cured films obtained were subjected to FT-IR measurements using an ATR-FTIR analyzer (Nicolet Continuum, Thermo Fisher Scientific) with a Si prism. (1380 cm²) -1 The peak intensity was 1500cm -1 The value obtained by dividing by the peak intensity was defined as the imidization index. The imidization rate was defined as the value obtained by dividing the imidization index of the cured film heated at 180°C by the imidization index of the cured film heated at 180°C. The imidization rate was evaluated based on the following criteria. Excellent: When the imidation rate is 95% or higher. Good: When the imidation rate is between 90% and 95%. Acceptable: If the imidation rate is 85% or more but less than 90% Not acceptable if the imidation rate is less than 85%

[0126] (3) Evaluation of chemical resistance (2) A cured film with a thickness of approximately 10 μm was formed on the wafer by heating at 180°C using the same procedure as for evaluating the imidization rate. The resulting cured film was immersed for 10 minutes in a resist stripping solution (manufactured by KANTO-PPC Inc., product name "SPR920", main components being tetramethylammonium hydroxide and dimethyl sulfoxide) adjusted to a temperature of 50°C, then washed with running water for 10 minutes and air-dried. Subsequently, the surface of the cured film was examined using an optical microscope to check for damage such as cracks, and the film thickness was measured to investigate the rate of change in film thickness before and after contact with the resist stripping solution. Based on the above, the chemical resistance of the cured film was evaluated according to the following criteria. Excellent: No damage was observed under a microscope, and the rate of change in film thickness was 10% or less. Good: No damage was detected, and the film thickness change rate was between 10% and 15%. Acceptable: If no damage is detected and the film thickness change rate is greater than 15% but less than or equal to 20%. Not permitted if damage is detected or if the film thickness change rate exceeds 20%.

[0127] (4) Evaluation of storage stability The photosensitive resin composition, immediately after preparation, was sealed in a sample bottle and stirred for 3 days under conditions of 23.0±0.5°C and 50%±10% relative humidity. This state was then used as the initial condition, and the mixture was subsequently stored in a constant temperature bath at 40°C for 3 days. The initial and stored photosensitive resin compositions were used, and the imidization rate was measured using the same procedure as in (2) Evaluation of Imidization Rate, except that a 6-inch silicon wafer (manufactured by Valqua FFT Co., Ltd., thickness 625 ± 25 μm) was used as the wafer. The imidization rate of the cured film obtained from the initial photosensitive resin composition was compared with the imidization rate of the cured film obtained from the photosensitive resin composition after storage. The absolute value of the change in imidization rate (percent points (%pt)) before and after storage was investigated, and the storage stability was evaluated according to the following criteria. Percent point (%pt) refers to the difference in imidization rate (%) before and after storage. Excellent: When the absolute value of the change in imidization rate before and after storage is less than 2%pt. Good: The absolute value of the change in imidization rate before and after storage is between 2%pt and 5%pt. Acceptable: If the absolute value of the change in imidization rate before and after storage is between 5%pt and 10%pt. Unacceptable: If the absolute value of the change in imidization rate before and after storage is 10%pt or more.

[0128] (5) Measurement of glass transition temperature Aside from using a 6-inch silicon wafer that had been pre-sputtered with Al as the wafer, a cured film with a thickness of approximately 10 μm was formed on the wafer by heating at 180°C using the same procedure as in (2) evaluation of the imidization rate. The resulting cured film was cut into 3 mm wide strips using a dicing device (DISCO Corporation, "DAD3350"), and treated with 10% by mass hydrochloric acid to obtain polyimide tape. The obtained polyimide tapes were subjected to thermomechanical analysis using a thermomechanical analyzer (Shimadzu Corporation, "TMA-60") under a nitrogen atmosphere, heated from room temperature to 400°C at a heating rate of 10°C / min, to measure the glass transition temperature of the cured film, and evaluated according to the following criteria. Excellent: When the glass transition temperature is 190°C or higher. Good: When the glass transition temperature is between 170°C and 190°C. Possible: If the glass transition temperature is between 150°C and 170°C. Not possible: If the glass transition temperature is below 150°C.

[0129] Synthesis of polyamic acid esters <Synthesis example A-1> Polyamic acid ester (A-1) was synthesized using 4,4'-oxydiphthalic acid dianhydride (ODPA) as the tetracarboxylic dianhydride, 2-hydroxyethyl methacrylate (HEMA) as the alcohol with radical polymerizable groups, and p-phenylenediamine (p-PD) as the diamine. 31.0 g (0.1 mol) of 4,4'-oxydiphthalic anhydride (ODPA) and 37.5 g of γ-butyrolactone were charged into a 1 L separable flask and stirred to form a solution. 26.0 g (0.20 mol) of 2-hydroxyethyl methacrylate (HEMA) was added, and while stirring, 15.8 g (0.20 mol) of pyridine was added. The mixture was then stirred for 5 hours using an oil bath, maintaining the liquid temperature at 40°C, to obtain the reaction mixture. After the reaction mixture cooled to room temperature, it was allowed to stand for 16 hours.

[0130] Next, while stirring the resulting reaction mixture under ice cooling, a solution of 40.7 g of dicyclohexylcarbodiimide (DCC) dissolved in 50.0 g of γ-butyrolactone was added over 40 minutes. Then, a suspension of 9.8 g (0.09 mol) of p-phenylenediamine (p-PD) suspended in 150 g of γ-butyrolactone was added over 60 minutes. After stirring at room temperature for 2 hours, 9.0 g of ethyl alcohol was added and the mixture was stirred for a further 1 hour. After adding 70.0 g of γ-butyrolactone, the reaction mixture was filtered to remove the precipitate formed in the reaction system and obtain the reaction solution.

[0131] The resulting reaction solution was added to 0.6 kg of ethanol to precipitate the crude polymer. The precipitated crude polymer was filtered and dissolved in 300 g of γ-butyrolactone to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3.5 kg of water to reprecipitate the polymer. After filtering the obtained reprecipitate, it was vacuum-dried to obtain a powdered polymer (polyamic acid ester (A-1)). The weight-average molecular weight (Mw) of the obtained polyamic acid ester (A-1), measured by gel permeation chromatography (GPC), was 23,000 in polystyrene equivalent.

[0132] <Synthesis examples A-2 to A-5> Polyamic acid esters (A-2) to (A-5) were obtained in the same manner as in Synthesis Example A-1, except that the types and amounts of tetracarboxylic dianhydride and diamine were changed as shown in Table 1. The weight-average molecular weight (Mw) and imide group equivalents of these polyamic acid esters are shown in Table 1.

[0133] [Table 1]

[0134] The abbreviations for tetracarboxylic dianhydrides in Table 1 have the following meanings: <Tetracarboxylic acid dianhydride> ODPA: 4,4'-Oxydiphthalic acid dianhydride PMDA: Pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride <Diamine> p-PD: p-phenylenediamine m-TB: m-trizine DADPE: 4,4'-diaminodiphenyl ether BAPP: 2,2-Bis[4-(4-aminophenoxy)phenyl]propane

[0135] Example 1 A photosensitive resin composition with the following composition was prepared, and the prepared composition was evaluated. (A) Polyamic acid ester: Polyamic acid ester (A-1) 100 parts by mass (B) Photopolymerization initiator: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (B-1, molecular weight: 267) 5.0 parts by mass (C) Thermal base generator: 8.0 parts by mass of the compound represented by the following formula (C-1) (D) Solvent: NEP

[0136] Examples 2-36 and Comparative Examples 1-8 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1, except that the type and amount of each component were changed as shown in Tables 2 to 4. In Comparative Example 4, (C) the thermal base generator was not used. In addition, in the following examples and comparative examples, the following optional components were further added in addition to components (A) to (D). Examples 24 and 25, and Comparative Example 8: (E) Thermal Crosslinking Agent Example 26 and Comparative Example 7: (F) Monofunctional Monomer Example 27: (G) Polyfunctional monomer

[0137] All of the above evaluation results, along with the solvent formulations, are shown in Tables 5 to 7. [Table 2]

[0138]

Table 3

[0139]

Table 4

[0140]

Table 5

[0141]

Table 6

[0142]

Table 7

[0143] The abbreviations of each component in Tables 2 to 7 have the following meanings respectively. 〈(B) Photoinitiator〉 B-1: 1-Phenyl-1,2-propanedione-2-(O-benzoyl)oxime (B-1 (Molecular weight: 267) B-2: 1-Phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], molecular weight 235 [[ID=5)) B-3: Ethyl 2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime (Molecular weight: 325) B-4: 1,2,3-Propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime] (Molecular weight: 339) B-5: 1,2-Propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetoxyoxime) (Molecular weight: 395) B-6: 1,2-Propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (Molecular weight: 443) B-7: 1,2-Octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (Molecular weight: 445) B-8: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetoxyoxime) (Molecular weight: 412)

[0144] B-9:

Chem.

Chem.

[0145] 〈(C) Thermal base generator〉 C-1:

Chem.

Chem.

Chem.

[0146] C–4:

Chem.

Chem.

Chem.

Chem.

[0147] Note: There seems to be a small error in the original text where "〈(C) Thermal base generator〉" is written as "〈(C)熱塩基発生剤〉" which might be a mix of languages or encoding issue. Also, in the translation, some of the chemical structure references are left as they are in the original as they might be specific notations that are best left unchanged for patent text accuracy. And there is a small typo in the translation where "〈(C) Thermal base generator〉" is written as "〈(C) Thermal base generator〉" which should be just "〈(C) Thermal base generator〉". Also, in the translation of "C–4" and "C–6", the hyphen is kept as it might be a specific format in the original patent text. And in the translation of "

化

Chem.

Chemistry

[0148] C-11: [ka] C-12: [ka] C-13: [ka] C-14: [ka]

[0149] (D) Solvent ((D1) compound) NEP: N-ethyl-2-pyrrolidone, boiling point 218°C NBP: N-butyl-2-pyrrolidone, boiling point 240°C ((D2) compound DMI: 1,3-dimethyl-2-imidazolidinone, boiling point 220°C (Other solvents) EL: Ethyl lactate, boiling point 154℃ GBL: γ-butyllactone, boiling point 204℃ BDMPA: Manufactured by Mitsubishi Chemical Corporation, "KJCBPA(registered trademark)-100", 3-butoxy-N,N-dimethylpropanamide, boiling point 252℃ NMP: N-methyl-2-pyrrolidone, boiling point 202°C DEG: Diethylene glycol, boiling point 245°C

[0150] (E) Thermal crosslinking agent E-1: [ka] E-2: [ka]

[0151] (F) Monofunctional monomer F-1: PE-90, manufactured by NOF Corporation, polyethylene glycol monomethacrylate (G) Polyfunctional monomers G-1: [ka]

[0152] As can be seen from the table above, the photosensitive resin composition of this embodiment, comprising (A) a polyamic acid ester, (B) a photopolymerization initiator, (C) a thermobase generator, and (D) a solvent, wherein (D) the solvent comprises one or two selected from (D1) compound and (D2) compound, has been verified to have excellent storage stability, a high imidization rate and glass transition temperature of the resulting cured film, and excellent chemical resistance. [Industrial applicability]

[0153] The photosensitive resin composition of this embodiment can be suitably applied to semiconductor devices, interlayer insulation of multilayer circuits, cover coats for flexible copper-clad sheets, solder resist films, liquid crystal alignment films, and the like.

Claims

1. (A) Polyamic acid ester, (B) Photopolymerization initiator, (C) Thermal base generator, and (D) Solvent A photosensitive resin composition comprising, The solvent (D) is (D1) Compounds having an amide bond and a cyclic structure and a boiling point of 210°C or higher, (D2) Compounds having a urea bond and a cyclic structure, and having a boiling point of 210°C or higher. Includes one or two selected from, Photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein the (B) photopolymerization initiator comprises an oxime compound.

3. The photosensitive resin composition according to claim 1, wherein the molecular weight of the (B) photopolymerization initiator is 540 or less.

4. The photosensitive resin composition according to claim 1, wherein the molecular weight of the (B) photopolymerization initiator is 400 or less.

5. The (B) photopolymerization initiator is 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, ethyl-2,3-dioxo-3-phenylprop The photosensitive resin composition according to claim 2, comprising one or more selected from onate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyloxime).

6. The photosensitive resin composition according to claim 2, wherein the (B) photopolymerization initiator is one or more selected from 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, ethyl-2,3-dioxo-3-phenylpropionate-2-(O-benzoyl)oxime, 1,2,3-propanetrione, 1,3-diphenyl-2-[O-(ethoxycarbonyl)oxime], and 1,2-propanedione-3-cyclohexyl-1-[4-(phenylthio)phenyl]-2-(O-acetyloxime).

7. The photosensitive resin composition according to claim 1, wherein the (A) polyamic acid ester has a radical polymerizable group.

8. The (D1) compound is a compound represented by the following general formula (D1), The (D2) compound is a compound represented by the following general formula (D2), The photosensitive resin composition according to claim 1. 【Chemistry 1】 {R in equation (D1) １ This is a monovalent organic group having 2 or more carbon atoms, R in equation (D2) ２ and R ３ Each of these is independently a monovalent organic group having one or more carbon atoms.

9. In the above general formula (D1), R １ However, it is a monovalent organic group with 2 to 5 carbon atoms, In the above general formula (D2), R ２ and R ３ However, each is independently a monovalent organic group with 1 to 5 carbon atoms. The photosensitive resin composition according to claim 8.

10. In the above general formula (D1), R １ It is an ethyl group, R in the general formula (D2) above ２ and R ３ are both methyl groups The photosensitive resin composition according to claim 8.

11. The photosensitive resin composition according to claim 1, wherein the total mass of the (D1) compound and the (D2) compound is 50% by mass or more of the total mass of the (D) solvent.

12. The photosensitive resin composition according to claim 1, wherein the (C) thermobase generating agent is a nonionic thermobase generating agent.

13. The photosensitive resin composition according to claim 1, wherein the (C) thermobase generating agent comprises an amide bond, a urethane bond, or a urea bond.

14. The photosensitive resin composition according to claim 1, wherein the (C) thermobase generating agent comprises a urethane bond or a urea bond.

15. The photosensitive resin composition according to claim 1, wherein the (C) thermobase generating agent contains a urea bond.

16. The photosensitive resin composition according to claim 1, wherein the amount of imide group equivalent represented by the following formula (1) when the polyamic acid ester (A) is fully imidized is 300 ( / group) or less. [Math 1]

17. The photosensitive resin composition according to claim 16, wherein the imide group equivalent is 225 ( / group) or less.

18. The photosensitive resin composition according to any one of claims 13 to 15, wherein the (C) thermobase generating agent further comprises a group selected from a (meth)acryloyl group, a hydroxyl group, an alkoxyl group, and an amino group.

19. The photosensitive resin composition according to any one of claims 1 to 12, wherein the (C) thermobase generating agent comprises a urea bond and a (meth)acryloyl group, and the (meth)acrylic equivalent is 150 g / mol or more and 400 g / mol or less.

20. The photosensitive resin composition according to any one of claims 1 to 12, wherein the (C) thermobase generating agent is a compound having a structure represented by the following general formula (Ac-1). 【Chemistry 2】 {In formula (Ac-1), R ３ A is a hydrogen atom or a methyl group, and A is -O-, -NH-, and -NL ４ - is a divalent group selected from the group consisting of L ４ Z is a monovalent organic group having 1 to 12 carbon atoms. １ This is an m2 valent organic group with 2 to 24 carbon atoms, Z ２ C1 is a divalent organic group having 2 to 8 carbon atoms, m2 is an integer from 1 to 3, and when m2 is 2 or 3, multiple R groups exist in formula (C1). ３ , A, and Z １ They may be the same or different from one another.

21. (E) The photosensitive resin composition according to any one of claims 1 to 17, further comprising a thermal crosslinking agent.

22. The photosensitive resin composition according to claim 21, wherein the (E) thermal crosslinking agent is a methylol-based thermal crosslinking agent.

23. (F) The photosensitive resin composition according to any one of claims 1 to 17, further comprising a monofunctional monomer.

24. A photosensitive resin composition according to any one of claims 1 to 17, used for forming an interlayer insulating film.

25. (1) Applying the photosensitive resin composition according to any one of claims 1 to 17 onto a substrate to form a photosensitive resin layer on the substrate, (2) Exposing the photosensitive resin layer, (3) Develop the photosensitive resin layer after exposure to form a relief pattern, and (4) Heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

26. A cured film comprising a cured product of a photosensitive resin composition according to any one of claims 1 to 17.

27. The cured film according to claim 26, which is an interlayer insulating film.

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