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

Abstract

The present invention provides a photosensitive resin composition that can form a cured film with excellent imidization rate, chemical resistance, and heat resistance even when cured at low temperatures. [Solution] A photosensitive resin composition comprising component (A): polyimide precursor, component (B): thermal crosslinking agent, component (C): photopolymerization initiator, and component (D): solvent, wherein component (A) is of general formula (A-1): TIFF2026170870000063.tif31167 The compound is represented by the formula (wherein X1, Y1, n1, R1 and R2 are as defined in the specification), and component (B) is a compound having an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, a maleimide group, or an allyl group.

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, those provided in the form of a photosensitive resin composition containing a polyimide precursor are widely used because they allow for easy formation of a heat-resistant relief pattern film on a substrate by coating the composition onto the substrate, exposing the coating film to light, developing it, and performing a 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 in, for example, Patent Document 1.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problem to be Solved by the Invention

[0007] For fan-out type semiconductor devices, from the viewpoint of preventing warpage of wafers during processes and the like, lowering the heat treatment temperature (thermal imidization temperature, also referred to as "cure temperature") is desired. Under low-temperature curing conditions, further improvement in the chemical resistance and heat resistance of the photosensitive resin composition is required.

[0008] An object of the present embodiment is to provide a photosensitive resin composition capable of forming a cured film excellent in imidization rate, chemical resistance and heat resistance even when cured at a low temperature. Another object of the present embodiment is to provide a method for producing a cured relief pattern using the above photosensitive resin composition.

Means for Solving the Problem

[0009] That is, the present disclosure is as follows. [1] Component (A): Polyimide precursor Component (B): Thermal crosslinking agent Component (C): Photopolymerization initiator and Component (D): Solvent A photosensitive resin composition comprising the above components, The component (A) is represented by the general formula (A-1):

Chemical Formula

[10] The photosensitive resin composition according to [9], wherein the boiling point of the compound having a lower boiling point than the component (D) is less than 210°C.

[11] General formula (3):

Chemical Formula

[10] , further comprising the plasticizer (E) represented by the formula.

[12] The photosensitive resin composition according to

[11] , wherein m2 in the general formula (3) is 3 or more.

[13] The photosensitive resin composition according to

[11] or

[12] , which contains 3 to 12 parts by mass of the plasticizer (E) relative to 100 parts by mass of the component (A).

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

[13] , further comprising the (meth)acrylate compound (F).

[15] The photosensitive resin composition according to

[14] , wherein the (meth)acrylate compound (F) comprises a monofunctional (meth)acrylate compound.

[16] The photosensitive resin composition according to

[15] , which contains 0.2 to 40 parts by mass of the monofunctional (meth)acrylate compound relative to 100 parts by mass of the component (A).

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

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

[18] (1) Applying the photosensitive resin composition according to any one of [1] to

[17] onto a substrate to form a photosensitive resin layer on the substrate, (2) Exposing the photosensitive resin layer, (3) Developing the exposed photosensitive resin layer to form a relief pattern, and (4) Heat-treating the relief pattern to form a hardened relief pattern. A method for manufacturing a hardened relief pattern, including [the specified element].

[19] A cured film comprising a cured product of a photosensitive resin composition described in any of [1] to

[17] .

[20] The cured film described in

[19] is an interlayer insulating film. [Effects of the Invention]

[0010] This disclosure provides a photosensitive resin composition that can form a cured film with excellent imidization rate, chemical resistance, and heat resistance even when cured at low temperatures, and a method for producing a cured relief pattern using the above photosensitive resin composition. [Modes for carrying out the invention]

[0011] 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.

[0012] The photosensitive resin composition of this embodiment is Component (A): Polyimide precursor Ingredient (B): Thermal crosslinking agent Component (C): Photopolymerization initiator and Component (D): Solvent A photosensitive resin composition comprising, Component (A) is of general formula (A-1): [ka] (In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is the number of repeating units and is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group having 2 to 40 carbon atoms and having a radical polymerizable group.) This is a compound represented by the formula, Component (B) is a compound having an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, a maleimide group, or an allyl group, and Component (D) is general formula (D1): [ka] Compounds represented by {R1 in formula (D1) is a monovalent organic group having 2 or more carbon atoms.}, and General formula (D2): [ka] A photosensitive resin composition comprising one or more compounds selected from those represented by {Formula (D2) where R2 and R3 are each independently monovalent organic groups having 1 or more carbon atoms}.

[0013] In addition to the components (A) to (D) described above, the photosensitive resin composition of this embodiment may optionally further contain one or more components selected from (E) plasticizers, (F) (meth)acrylate compounds, and other optional components. The components included in the photosensitive resin composition of this embodiment will be described in order below.

[0014] (A) Polyimide precursor or component (A) In this embodiment, (A) the polyimide precursor is the following general formula (A-1): [ka] The structure is represented by {wherein X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is the number of repeating units and is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R1 and R2 is a monovalent organic group having 2 to 40 carbon atoms and having a radical polymerizable group.}.

[0015] The tetravalent organic group represented by X1 in the above general formula (A-1) is preferably a tetravalent 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 -COOR1 group, the -COOR2 group and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group. X1 is more preferably a tetravalent organic group having 6 to 40 carbon atoms and containing an aromatic ring, for example, the following general formulas (X1-1) to (X1-3): [ka] [ka] [ka] The groups represented by {(X1-1) to (X1-3) are defined as follows: {In formulas (X1-1) to (X1-3), R is a group selected from 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; 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.} However, X1 is not limited to the examples given above.

[0016] (A) Since there are n1 structures represented by general formula (A-1) in the polyimide precursor, there are n1 tetravalent organic groups represented by X1 in one molecule of the polyimide precursor (A). 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 general formulas (X1-1) to (X1-3), it is preferable to select from the structures represented by general 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 general formula (X1-1).

[0017] 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, the divalent organic group represented by Y1 is, for example, the following general formulas (Y1-1) to (Y1-3): [ka] [ka] [ka] Examples of groups represented by {(Y1-1) to (Y1-3), where 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, and n is an integer selected from 0 to 4.} are shown. However, Y1 is not limited to the examples given above.

[0018] (A) Since there are n1 structures represented by general formula (A-1) in the polyimide precursor, there are n1 divalent organic groups represented by Y1 in one molecule of the polyimide precursor (A). These n1 organic groups represented by Y1 may all be the same, or they may be a combination of two or more structures.

[0019] From the viewpoint of improving the resolution of the coating film and the crosslinking density of the resulting cured film, at least one of R1 and R2 in the above general formula (A-1) is a monovalent organic group having 2 to 40 carbon atoms that has a radical polymerizable group. At least one of R1 and R2 in general formula (A-1) is given by the following general formula (R-1): [ka] {In formula (R-1), R 25 , R 26 , and R 27 Each of these is independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 1 to 10. It is preferable that the group is represented by}. In the general formula (R-1), m1 is preferably an integer between 1 and 5, and more preferably an integer between 1 and 3.

[0020] The base represented by the above general formula (R-1) is the following general formula (R-2): [ka] {In formula (R-2), R 25 , R 26 , and R 27 These are R in equation (R-1), respectively. 25 , R 26 , and R 27 It has the same meaning. A base represented by} is preferred.

[0021] In general formulas (R-1) and (R-2), R 25 , R 26 , and R 27 Examples of monovalent organic groups having 1 to 3 carbon atoms include the methyl group, ethyl group, n-propyl group, and isopropyl group. R 25 R is preferably a hydrogen atom or a methyl group. 26 and R 27 Preferably, each of these is a hydrogen atom.

[0022] (A) The weight-average molecular weight of the polyimide precursor, measured by gel permeation chromatography in terms of polystyrene, is preferably 8,000 to 150,000, and more preferably 9,000 to 50,000. (A) When the weight-average molecular weight of the polyimide precursor is 8,000 or more, the mechanical properties of the resulting cured film are good. (A) When the weight-average molecular weight of the polyimide precursor 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.

[0023] <(A) Method for preparing polyimide precursors> (A) Polyimide precursors 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.

[0024] (A) The tetracarboxylic dianhydride having a tetravalent organic group X1 used in the preparation of polyimide precursors is given by the following general formula (T-1): [ka] A compound represented by {X1 in formula (T-1) has the same meaning as X1 in the general formula (A-1) above} is preferred. In general formula (T-1), X1 is preferably selected from the groups represented by each of the general formulas (X1-1) to (X1-3), more preferably from the structures represented by general formulas (X1-1) and (X1-2), and even more preferably from the structure represented by general formula (X1-1).

[0025] Specific examples of tetracarboxylic dianhydrides represented by the above general formula (T-1) include pyromellitic anhydride (abbreviated as "PMDA"), 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, and 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) polyimide precursors are not limited to the examples given above.

[0026] (A) Alcohols having radical polymerizable groups used in the preparation of polyimide precursors include, specifically, 2-hydroxyethyl methacrylate (HEMA), 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- 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, and pentaerythritol trimethacrylate, and one or more selected from these can be used. However, the alcohols having radical polymerizable groups used in the preparation of (A) polyimide precursors are not limited to the above examples.

[0027] 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 R1 and R2 in general formula (A-1).

[0028] (A) Other alcohols used in the preparation of polyimide precursors 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, and benzyl alcohol, and one or more selected from these may be used.

[0029] 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.

[0030] Diamines having a divalent organic group Y1 that are used in amide polycondensation with acid / ester compounds include, for example, p-phenylenediamine (abbreviated as "p-PD"), 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 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(3 -aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4 -aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, 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,Examples include 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (abbreviated as "m-TB": m-tolidine), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-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) polyimide precursors are not limited to the examples given above.

[0031] 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, a solution containing an acid / ester compound is treated with a dehydrating condensation agent under ice cooling to convert the acid / ester compound into a polyacid anhydride, and then a diamine having a divalent organic group Y1 is added and the reaction is carried out further to obtain the desired (A) polyimide precursor. Examples of dehydration condensation agents include dicyclohexylcarbodiimide (DCC), 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. Furthermore, the desired (A) polyimide precursor (polyamic acid ester) can also be obtained by acid-chloridizing the acid portion 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.

[0032] 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. For the preparation of the acid / ester compound and the amide polycondensation of the acid / ester compound with the diamine, a solvent that can uniformly dissolve or disperse the tetracarboxylic dianhydride, alcohol, acid / ester compound, and (A) polyimide precursor is preferred in order to carry out the reaction efficiently in a homogeneous system. Specific examples of solvents used in the preparation of acid / ester compounds and in the amide polycondensation of acid / ester compounds with diamines 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, N,N-dimethylacetamide, etc., and one or more selected from these can be used.

[0033] As described above, the desired (A) polyimide precursor is obtained, typically in the form of a solution in which the (A) polyimide precursor is dissolved in the reaction mixture. The obtained (A) polyimide precursor is, if necessary, filtered to remove water-absorbing by-products of the dehydrating condensing agent present in the reaction solution, and then precipitated with a poor solvent to recover as a crude product. 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) polyimide precursor. 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.

[0034] In this embodiment, (A) polyimide precursor may be used alone or as a mixture of two or more types. In addition, a non-photosensitive polyimide precursor that does not have radical polymerizable groups may be used in combination with the (A) polyimide precursor. In this case, from the viewpoint of ensuring the resolution of the coating film, it is preferable that the content of the non-photosensitive polyimide precursor be 200 parts by mass or less per 100 parts by mass of the (A) polyimide precursor.

[0035] (B) Thermal crosslinking agent or component (B) In this embodiment, (B) 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 polyimide precursor and (B) the thermal crosslinking agent, between (B) thermal crosslinking agents themselves, and between (B) the thermal crosslinking agent and other components. The temperature at which the addition reaction or condensation polymerization reaction occurs in (B) the thermal crosslinking agent is preferably 150°C or higher.

[0036] Generally, when a thermal crosslinking agent is added to a negative-type photosensitive resin composition containing a polyimide precursor, thermal crosslinking occurs during the heating process (curing process), improving the chemical resistance, thermal properties, etc., of the resulting cured film. However, on the other hand, when the curing process is carried out at low temperatures, the thermal crosslinking agent tends to inhibit the imidation reaction of the polyimide precursor.

[0037] In this embodiment, the (B) thermal crosslinking agent is a compound having a functional group such as an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, a maleimide group, or an allyl group. In one embodiment, the (B) thermal crosslinking agent in this embodiment may be a compound having at least one selected from the above-mentioned functional groups, and from the viewpoint of improving the glass transition temperature (Tg) of the cured film, an alkoxymethyl group or a methylol group is preferred.

[0038] As a thermal crosslinking agent having an alkoxymethyl group or a methylol group, it is preferable that the alkoxymethyl group or methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Alternatively, (B) the thermal crosslinking agent may be a compound in which multiple alkoxymethyl groups or multiple methylol groups are bonded to a nitrogen atom or a carbon atom forming an aromatic ring. In one embodiment, (B) the thermal crosslinking agent may be any compound in which two or more alkoxymethyl groups or methylol groups are bonded to a nitrogen atom or a carbon atom forming an aromatic ring, from the viewpoint of improving the Tg of the cured film, a compound in which three or more alkoxymethyl groups or methylol groups are bonded is preferred, and a compound in which four or more alkoxymethyl groups or methylol groups are bonded is more preferred. In one embodiment, (B) the thermal crosslinking agent is preferably a compound in which 10 or fewer alkoxymethyl groups or methylol groups are bonded to a nitrogen atom or a carbon atom forming an aromatic ring, more preferably a compound in which 8 or fewer alkoxymethyl groups or methylol groups are bonded, and even more preferably a compound in which 6 or fewer alkoxymethyl groups or methylol groups are bonded. Preferred such compounds include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluryl, methylolated glycoluryl, alkoxymethylated urea, and methylolated urea. For example, the following formula: [ka] [ka] Examples of compounds represented by [formula] include, but are not limited to, those shown.

[0039] Examples of thermal crosslinking agents containing epoxy groups include diethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, orthosecondary butylphenyl glycidyl ether, 1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl]ethyl]phenyl]propane, YDB-340, YDB-412, YDF-2001, YDF-2004 (all trade names, manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000-H, EPPN-501H, EOCN-1020, NC-7000L, EPPN-201L, XD-1000, EOCN-4600 (all product names, manufactured by Nippon Kayaku Co., Ltd.), Epicote® 1001, Epicote® 1007, Epicote® 1009, Epicote® 5050, Epicote® 5051, Epicote® 1031S, Epicote® 180S65, Epicote® 157H70, YX-315-75 (all product names, manufactured by Japan Epoxy Resin Co., Ltd.) EHPE3150, Praxel G402, PUE101, PUE105 (all product names, manufactured by Daicel Chemical Industries, Ltd.) Examples include Epiclon® 830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (all product names, manufactured by DIC Corporation), Denacol® EX-201, EX-251, EX-203, EX-313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-711, EX-731, EX-810, EX-911, EM-150 (all product names, manufactured by Nagase ChemteX Corporation), Epolite® 70P, Epolite 100MF, Epolite 4000 (all product names, manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0040] Examples of thermal crosslinking agents having an oxetanyl group 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)dipheno Examples include, but are not limited to, eth, trimethylolpropanetris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (trade name, manufactured by Toagosei Co., Ltd.), and OXT221 (trade name, manufactured by Toagosei Co., Ltd.).

[0041] Examples of thermal crosslinking agents having a maleimide group 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.

[0042] Examples of thermal crosslinking agents having an allyl group include, but are not limited to, allyl benzoate, allyl cinnamate, N-alyloxyphthalimide, allylphenol, allylphenylsulfone, allylurea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallyl 1,3,5-benzenetricarboxylic acid triallyl, trimellitate triallyl phosphate, triallyl phosphite, triallyl citrate, and 1,3,4,6-tetraallyl glycoluryl.

[0043] Of these thermal crosslinking agents, thermal crosslinking agents containing nitrogen atoms are preferred from the viewpoint of reducing the curing shrinkage of the resulting cured film, and thermal crosslinking agents having methylol groups are preferred from the viewpoint of improving the thermal properties of the resulting cured film. Furthermore, from the viewpoint of improving the Tg of the cured film, the lower limit of the number of functional groups contained in the (B) thermal crosslinking agent of this embodiment is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of functional groups contained in the (B) thermal crosslinking agent of this embodiment is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. The functional groups may be of the same type or a combination of different types. (B) The thermal crosslinking agent may be used alone or in combination of two or more types.

[0044] The (B) thermal crosslinking agent according to this embodiment is based on the general formula (B-1): [ka] (B-2): [ka] (B-3): [ka] (In the formula, R6~R 15 , and R17 ~R 20 The general formula is as follows (Bi): [ka] {where, R 23 R is a divalent organic group having 1 to 3 carbon atoms, 24 is -H, -CH3, or -C2H5.} is a group represented by or -CH3. R 16 This is a divalent group having 1 to 30 carbon atoms, which may have single bonds or branched chains. For example, R 16 The following general formulas (Bii), (Biii) [ka] [ka] {In equations (Bii) and (Biii), R 17 , R 18 , R 21 and R 22 This is the same as the definition in equation (B-3), and R 23 is identical to the definition in equation (Bi), and R 31 It is a tetravalent organic group with 1 to 3 carbon atoms. R 21 and R 22 The compound is preferably represented by the formula (B-3), and is particularly preferred to be represented by the general formula (B-3) from the viewpoint of improving the Tg of the cured film and the in-plane uniformity. R 23 This may be a divalent hydrocarbon group having 1 to 3 carbon atoms. R 31 This may be a tetravalent hydrocarbon group having 1 to 3 carbon atoms.

[0045] In the photosensitive resin composition of this embodiment, the inclusion of a compound represented by general formula (D1) or (D2) is preferable because (B) the thermal crosslinking agent does not inhibit the imidization reaction of (A) the polyimide precursor, thereby further improving the chemical resistance, thermal properties, etc., of the resulting cured film. Furthermore, in the photosensitive resin composition of this embodiment, by combining (B) the thermal crosslinking agent with one or two compounds selected from those represented by general formulas (D1) and (D2), the mobility of (B) the thermal crosslinking agent during the curing process can be maintained, thereby significantly improving the chemical resistance and thermal properties of the resulting cured film.

[0046] In the photosensitive resin composition of this embodiment, the content of (B) the 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) the polyimide precursor. From the viewpoint of ensuring the chemical resistance of the resulting cured film, the content of (B) the thermal crosslinking agent is preferably 0.2 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 5.0 parts by mass or more, particularly preferably 8.0 parts by mass or more, and most preferably 10.0 parts by mass or more per 100 parts by mass of (A) the polyimide precursor. (B) From the viewpoint of ensuring the storage stability of the photosensitive resin composition, the content of the thermal crosslinking agent is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of the polyimide precursor (A).

[0047] (C) Photopolymerization initiator or component (C) In this embodiment, (C) the photopolymerization initiator is preferably a photoradical polymerization initiator. Examples of photoradical polymerization initiators include benzophenone compounds such as benzophenone, o-benzoylmethyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; Acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; Thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; Benzyl compounds such as benzyl, benzyldimethylketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; Oxime compounds such as 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, and 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; Examples include N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl peroxide; aromatic biimidazole compounds; and titanocene compounds, and one or more selected from these can be used.

[0048] The (C) photopolymerization initiator in this embodiment is not limited to the examples given above. From the viewpoint of high photosensitivity, an oxime compound is preferred as the (C) photopolymerization initiator in this embodiment.

[0049] The content of (C) 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) polyimide precursor. From the viewpoint of ensuring the photosensitivity or patternability of the resulting photosensitive resin composition, the content is preferably 0.1 parts by mass or more per 100 parts by mass of (A) polyimide precursor, 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) polyimide precursor. (C) The content of the 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, particularly preferably 2 parts by mass or more and 10 parts by mass or less, and most preferably 3 parts by mass or more and 8 parts by mass or less, per 100 parts by mass of (A) polyimide precursor.

[0050] (D) Solvent or component (D) The solvent (D) contained in the photosensitive resin composition of this embodiment contains one or more compounds selected from the (D1) and (D2) compounds described later, which promotes the imidization reaction of the (A) polyimide precursor even when the heat treatment (curing) temperature during curing is low (for example, 200°C or lower). Although the reason is not clear, the inventors of the present invention surmise that the (D1) and (D2) compounds are due to their high boiling point of 210°C or higher, their hydrogen bonding ability, and their cyclic structure. Furthermore, since compounds (D1) and (D2) have amide or urea bonds that are capable of hydrogen bonding, it is thought that when these compounds are present together, aggregation due to hydrogen bonding between (A) polyimide precursors is suppressed, the mobility of (A) polyimide precursors is maintained, and the imidation reaction of (A) polyimide precursors is promoted. Furthermore, although the mechanism by which compounds (D1) and (D2) have a cyclic structure that promotes the imidation reaction of the (A) polyimide precursor is not yet clear, it is specifically investigated in the examples described later. It is believed that the above factors, combined, promote the imidation reaction of the (A) polyimide precursor. However, this embodiment is not bound by any particular theory.

[0051] In this embodiment, the compound (D1) or compound (D2) contained in component (D) is, respectively, the following general formula (D1) or (D2):

[0052] [ka] It is preferable that the compound is represented by {In formula (D1), R1 is a monovalent organic group having 2 or more carbon atoms, and in formula (D2), R2 and R3 are each independently a monovalent organic group having 1 or more carbon atoms.}.

[0053] From the viewpoint of ensuring that the boiling point of the (D1) compound is 2 or higher, the number of carbon atoms in the organic group R1 in general formula (D1) is preferably 2 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.

[0054] (D1) In order to increase the hydrogen bonding ability of the compound, it is preferable that the number of carbon atoms in the organic group R1 be 5 or less, from the viewpoint of reducing steric hindrance around the amide bond. The number of carbon atoms in the organic group R1 is preferably 2 to 5, and more preferably 2 or 3. Furthermore, it is preferable that R1 is an ethyl group. Therefore, NEP is the most preferred compound for (D1).

[0055] From the viewpoint of ensuring that the boiling point of the (D2) compound is 210°C or higher, it is preferable that the number of carbon atoms in the organic groups R2 and R3 in general formula (D2) be 1 or more. (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.

[0056] (D2) In order to increase the hydrogen bonding ability of the compound, it is preferable that the number of carbon atoms in the organic groups R2 and R3 be 5 or less, from the viewpoint of reducing steric hindrance around the amide bond. The number of carbon atoms in the organic groups R2 and R3 is preferably 1 to 5, and more preferably 1 to 3, independently of each other. Furthermore, it is preferable that both R2 and R3 are methyl groups. Therefore, DMI is the most preferred (D2) compound.

[0057] In this embodiment, the (D) solvent preferably includes a compound represented by general formula (D1) in which R1 is a monovalent organic group having 2 to 5 carbon atoms, or a compound represented by general formula (D2) in which R2 and R3 are each independently monovalent organic groups having 1 to 5 carbon atoms. In this embodiment, solvent (D) preferably contains N-ethyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone.

[0058] By including compound (D1) or compound (D2) in the photosensitive resin composition of this embodiment, the (B) thermal crosslinking agent does not inhibit the imidization reaction of the (A) polyimide precursor, thereby further improving the chemical resistance and thermal properties of the resulting cured film. Furthermore, in the photosensitive resin composition of this embodiment, by combining the (B) thermal crosslinking agent with one or more selected from the (D1) compound and the (D2) compound, the mobility of the (B) thermal crosslinking agent during the curing process can be maintained, thereby significantly improving the chemical resistance, thermal properties, etc. of the resulting cured film.

[0059] In this embodiment, component (D) may contain solvents other than component (D), as long as they do not adversely affect the performance of the resulting photosensitive resin composition. The solvent contained in the photosensitive resin composition in this embodiment (hereinafter also referred to as the total solvent contained in the photosensitive resin composition of this embodiment) preferably contains, in addition to component (D) which contains a compound represented by general formula (D1) and / or general formula (D2) (hereinafter referred to as the (D1) and / or (D2) compound), a compound having a lower boiling point than component (D) (hereinafter referred to as the other solvent). This is preferable because it allows the solvent with the lower boiling point to volatilize even at low temperatures, preventing rapid volatilization of the solvent throughout the cured film, and resulting in excellent in-plane uniformity of the film. The boiling point of the other solvent is preferably 140°C or higher and less than 210°C, more preferably 145°C or higher and 190°C or lower, and even more preferably 150°C or higher and 180°C or lower. The boiling point (°C) of a solvent can be measured using known methods, and catalog values ​​may also be used as a reference.

[0060] Other solvents include, for example, amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols.

[0061] Other solvents include, specifically, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate (EL), methyl lactate, butyl lactate, γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Examples include benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholin, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

[0062] The total content 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 polyimide precursor (A). When compound (D1) and / or compound (D2) are used in combination with other solvents, the content of the other solvent is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of polyimide precursor (A). Furthermore, when other solvents are used in combination as the solvent for the photosensitive resin composition of this embodiment, it is preferable that the total mass of compound (D1) and compound (D2) in relation to the total mass of the solvent be 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.

[0063] In one embodiment, the photosensitive resin composition of this embodiment contains component (D) in a proportion of 50 to 100% by mass relative to the total solvent contained in the photosensitive resin composition of this embodiment. The photosensitive resin composition of this embodiment exhibits its effects significantly when it contains one or more compounds selected from (D1) and (D2) in such proportions.

[0064] (E) Plasticizers The photosensitive resin composition of this embodiment may also contain (E) a plasticizer. (E) Plasticizers are given by the following general formula (3): [ka] (In the formula, m2 is an integer between 2 and 30, and R 28 , R 29 and R 30 Each of these is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The compound is preferably represented by ( ).

[0065] (E) Adding a plasticizer can further accelerate the imidation reaction of the photosensitive resin composition of this embodiment at low temperatures. When a relief pattern formed using the photosensitive resin composition of this embodiment is heat-cured, (E) the plasticizer promotes the heat-fluidity of the (A) polyimide precursor through its plasticizing effect, thereby accelerating heat-cyclization.

[0066] In this embodiment, the photosensitive resin composition containing (B) a thermal crosslinking agent sometimes resulted in a decrease in the cyclization reaction of (A) the polyimide precursor. In this regard, by using (E) a plasticizer, the chemical resistance and thermal properties of the cured film can be further improved without inhibiting the imidization reaction of the polyimide precursor.

[0067] The inventors believe that by having two or more repeating units: m2 in the (E) plasticizer, the effect of improving the fluidity of the (A) polyimide precursor during heating by the (E) plasticizer can be advantageously obtained. From the same viewpoint as above, it is more preferable that the (E) plasticizer in this embodiment has three or more repeating units: m2 of the same structure in succession.

[0068] From the viewpoint of promoting the imidation reaction, the number of repeating structural units: m2 (number of repeating units) is preferably 2 or more and 30 or less, more preferably 3 or more and 29 or less, particularly preferably 5 or more and 28 or less, and most preferably 8 or more and 23 or less.

[0069] From the viewpoint of resolution in the photosensitive resin composition of this embodiment, R 28 , R 29 , R 30 It is preferable that R is a hydrogen atom or a methyl group. 29 and R 30 It is also preferable that neither of them are hydrogen atoms.

[0070] (E) Specific examples of plasticizers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, and polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monopropyl ether, polyoxyethylene monobutyl ether, polyoxyethylene monopentyl ether, polyoxyethylene monohexyl ether, polyoxypropylene monomethyl ether, polyoxypropylene monoethyl ether, polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, polyoxypropylene monopentyl ether, polyoxypropylene monohexyl ether, polyoxytetramethylene monomethyl ether, polyoxytetramethylene monopropyl ether, polyoxytetramethylene monobutyl ether, polyoxytetramethylene monopentyl ether, and polyoxytetramethylene monohexyl ether. Furthermore, examples include polyoxyethylene dimethyl ether, polyoxyethylene diethyl ether, polyoxyethylene dipropyl ether, polyoxyethylene dibutyl ether, polyoxyethylene dipentyl ether, polyoxyethylene dihexyl ether, polyoxypropylene dimethyl ether, polyoxypropylene diethyl ether, polyoxypropylene dipropyl ether, polyoxypropylene dibutyl ether, polyoxypropylene dipentyl ether, polyoxypropylene dihexyl ether, polyoxytetramethylene dimethyl ether, polyoxytetramethylene dipropyl ether, polyoxytetramethylene dibutyl ether, polyoxytetramethylene dipentyl ether, and polyoxytetramethylene dihexyl ether, all of which are modified at both ends with alkyl groups having 1 to 6 carbon atoms.

[0071] (E) Examples of commercially available plasticizers include PEG#300, PEG#400, PEG#600, PEG#1000, Uniox M-400, Uniox M-550, Uniox M-1000, Uniox M-2000, Uniox MM-400, Uniol D-400G, Uniol D-700, Uniol D-1000, and Uniol D-1200, all manufactured by NOF Corporation. Other examples include PTMG650, PTMG850, PTMG1000, PTMG1300, and PTMG1500, all manufactured by Mitsubishi Chemical Corporation. Furthermore, examples include Sanyo Chemical Industries, Ltd.'s Sunnix PP-200, Sunnix PP-400, Sunnix PP-600, Sunnix PP-1000, and Sunnix PP-1200, and Daicel Corporation's Praxel 208, Praxel 210, Praxel 212, and Praxel 210N.

[0072] From the viewpoint of imidization, the content of (E) plasticizer per 100 parts by mass of (A) polyimide precursor is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. From the viewpoint of mechanical properties, the content of (E) plasticizer per 100 parts by mass of (A) polyimide precursor is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 12 parts by mass or less. The content of (E) plasticizer in the photosensitive resin composition of this embodiment is preferably 1 to 40 parts by mass, more preferably 3 to 20 parts by mass, and particularly preferably 3 to 12 parts by mass, per 100 parts by mass of (A) polyimide precursor.

[0073] (F)(meth)acrylate compounds The photosensitive resin composition of this embodiment may also contain (F)(meth)acrylate compounds. (F) Examples of (meth)acrylate compounds include polyfunctional (meth)acrylate compounds and monofunctional (meth)acrylate compounds. In this embodiment, a polyfunctional (meth)acrylate compound means a compound having two or more (meth)acryloyl groups in one molecule, and a monofunctional (meth)acrylate compound means a compound having one (meth)acryloyl group in one molecule.

[0074] Examples of polyfunctional (meth)acrylate compounds 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., as well as ethylene oxide or propylene oxide adducts of these compounds, etc., as well as trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, etc.

[0075] The content of the polyfunctional (meth)acrylate compound in the photosensitive resin composition of this embodiment is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyimide precursor. The content of the polyfunctional (meth)acrylate compound 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) polyimide precursor.

[0076] In this embodiment, the (F)(meth)acrylate compound preferably includes a compound having one (meth)acryloyl group in one molecule. In other words, the (F)(meth)acrylate compound in this embodiment preferably includes a monofunctional (meth)acrylate compound. Generally, it is known that when a negative-type photosensitive resin composition containing a polyimide precursor is infused with a polyfunctional (meth)acrylate compound having two or more photoradical polymerizable groups, the polyfunctional (meth)acrylate compound 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, the crosslinking of the polyfunctional (meth)acrylate compound tends to inhibit the imidation reaction of the polyimide precursor. In this respect, monofunctional (meth)acrylate compounds can further improve the chemical resistance and thermal properties of the cured film without inhibiting the imidation reaction of the polyimide precursor. This is presumed to be due to the fact that the increase in film density due to polymerization involving monofunctional (meth)acrylate compounds is smaller compared to that of polyfunctional (meth)acrylate compounds.

[0077] Examples of (F) monofunctional (meth)acrylate compounds in this embodiment include 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, hydroxypropyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, polyethylene glycol polybutylene glycol mono(meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, behenyl (meth)acrylate Examples include acrylate, cyclohexyl (meth)acrylate, phenoxypolyethylene glycol polybutylene glycol (meth)acrylate, hydroxyphenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, octyl polyethylene glycol polypropylene glycol mono(meth)acrylate, etc., and one or more selected from these may be contained.

[0078] The content of the monofunctional (meth)acrylate compound in the photosensitive resin composition of this embodiment is preferably 0.2 to 40 parts by mass per 100 parts by mass of (A) polyimide precursor. From the viewpoint of ensuring the chemical resistance of the resulting cured film, the content of the monofunctional (meth)acrylate compound 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) polyimide precursor. From the viewpoint of ensuring the storage stability of the photosensitive resin composition, the content of the monofunctional (meth)acrylate compound is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of (A) polyimide precursor.

[0079] Other ingredients The photosensitive resin composition of this embodiment contains (A) a polyimide precursor, (B) a thermal crosslinking agent, (C) a photopolymerization initiator, and (D) a solvent as essential components, and may also contain one or more selected from (E) a plasticizer and (F) a (meth)acrylate compound, 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.

[0080] 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 and purine compounds may be used as rust inhibitors.

[0081] 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. For example, aluminum-based adhesives and silane coupling agents may be used as adhesive aids.

[0082] 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.

[0083] 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.

[0084] To improve the light sensitivity of the photosensitive resin composition of this embodiment, a sensitizer may be added to the photosensitive resin composition.

[0085] In order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition of this embodiment, particularly when stored in a solution containing component (D) as a solvent, a thermal polymerization inhibitor may be added to the photosensitive resin composition.

[0086] 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].

[0087] <(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, it is then dried to form a photosensitive resin layer on the substrate. As for the coating method, methods conventionally used for coating photosensitive resin compositions may be used. Specifically, for example, methods using a spin coater, bar coater, blade coater, curtain coater, and screen printing machine, as well as spray coating methods using a spray coater, can be used.

[0088] 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.

[0089] (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.

[0090] After coating, if necessary, at least one of post-exposure baking (PEB) and pre-development baking may be performed at any temperature and time to improve light sensitivity or for other purposes. For both post-exposure baking and pre-development baking, the preferred baking conditions are a temperature of 40°C to 120°C and a time of 10 to 240 seconds.

[0091] <(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.

[0092] As the developing solution used for development, for example, a good solvent for the negative-type photosensitive resin composition, or a combination of the good solvent and a poor solvent is preferred. 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 and poor solvents may be used individually or in combination 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) polyimide precursor) 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) the polyimide precursor 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.

[0093] <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) polyimide precursor, thereby converting it into a cured relief pattern made of polyimide. Heating may be carried out by means of, for example, a hot plate, an oven, or a rising oven with a temperature program. 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. The heating time may be, 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.

[0094] 《Cured film》 According to yet another aspect of this embodiment, a cured film is provided. The cured film of this embodiment includes a cured product obtained by curing the photosensitive resin composition of this embodiment as described above, and may be a cured relief pattern obtained by curing the photosensitive resin composition of this embodiment, or a cured film without a cured relief pattern. Furthermore, since the photosensitive resin composition of this embodiment can be used to form an interlayer insulating film, the cured film of this embodiment, which is a cured product of the photosensitive resin composition of this embodiment, can be suitably used as an interlayer insulating film.

[0095] The cured film of this embodiment contains polyimide. The polyimide contained in the cured film of this embodiment is of general formula (A-2): [ka] Includes a structure represented by . (In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, and n2 is an integer between 2 and 150.) The preferred groups X1 and Y1 in the above general formula (A-1) are also preferred as the groups X1 and Y1 in general formula (A-2) for the same reasons. A method for producing polyimide that includes a step of converting (A) the polyimide precursor in the photosensitive resin composition of this embodiment to polyimide is also one aspect of this embodiment.

[0096] Semiconductor equipment According to yet another aspect of this embodiment, 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.

[0097] 《Display device》 According to yet another aspect of this embodiment, 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 (in particular, a cured relief pattern formed from the photosensitive resin composition of this embodiment). The cured film (in particular, the cured relief pattern formed from the photosensitive resin composition of this embodiment) 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]

[0098] 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.

[0099] 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.

[0100] (2) Evaluation of the imidization rate A photosensitive resin composition prepared in the examples was rotary coated onto a 6-inch silicon wafer substrate that had been pre-sputtered with Ti and Cu. After that, a pre-bake was performed on a hot plate at 110°C for 240 seconds to form a 10 μm thick photosensitive resin coating on the substrate. 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. 2 After exposure, a cured film with a thickness of approximately 7 μm (hereinafter referred to as the cured film after heating at 200°C for 2 hours under a nitrogen atmosphere was formed using a temperature-boosting curing furnace (VF-2000 model, manufactured by Koyo Thermo Systems Co., Ltd.). Similarly, a cured film (hereinafter referred to as the cured film after heating at 350°C) was formed by performing the same procedure as for the cured film heated at 200°C, except that the heating temperature was changed to 350°C.

[0101] Both cured films obtained were subjected to FT-IR measurements using an ATR-FTIR analyzer (Nicolet Continuum, Thermo Fisher Scientific) with a Si prism. The 1380 cm⁻¹ measurement was performed on the cured films after heating at 200°C and 350°C, respectively. -1 The peak intensity was measured at 1500 cm² in the cured film after heating at 200°C and 350°C, respectively. -1 The values ​​obtained by dividing by the peak intensity were used as the imidization indices for the cured films after heating at 200°C and 350°C, respectively. The imidization rate was defined as the value obtained by dividing the imidization index of the cured film after heating at 200°C by the imidization index of the cured film after heating at 350°C.

[0102] The imidization rate was evaluated based on the following criteria. 5: If the imidation rate is 95% or higher 4. If the imidization rate is 90% or more but less than 95% 3: If the imidization rate is 85% or more but less than 90% 2: If the imidization rate is less than 85%

[0103] (3) Evaluation of chemical resistance (2) A cured film with a thickness of approximately 10 μm was formed after heating at 200°C using the same procedure as that used 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. Chemical resistance was evaluated by applying the formula: (Thickness of the cured film before contact with the resist stripping solution - Thickness of the cured film after contact with the resist stripping solution) ÷ Thickness of the cured film before contact with the resist stripping solution × 100.

[0104] The chemical resistance of the cured film was evaluated according to the following criteria. 5. If no damage is detected and the film thickness change rate is 3% or less. 4. If no damage is detected, and the film thickness change rate is greater than 3% but less than or equal to 5%. 3. If no damage is detected, and the film thickness change rate is greater than 5% but less than or equal to 9%. 2: If no damage is detected, and the film thickness change rate is greater than 9% but less than or equal to 12%. 1: If no damage is detected and the film thickness change rate exceeds 12%, or if damage is detected.

[0105] (4) Measurement of glass transition temperature: Tg Aside from using a 6-inch silicon wafer that had been pre-sputtered with Al and heating the coating film at 200°C for 2 hours, a cured film with a thickness of approximately 10 μm was formed by the same procedure as in (2) Evaluation of Imidification Rate, using the same method as described above. 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.

[0106] 5: If the glass transition temperature is 250°C or higher 4. When the glass transition temperature is between 230°C and 250°C. 3: When the glass transition temperature is 210°C or higher but less than 230°C. 2: When the glass transition temperature is between 190°C and 210°C. 1: If the glass transition temperature is less than 190°C

[0107] (5) Evaluation of the formation of the coated film and the in-plane uniformity of the film thickness A photosensitive resin composition, prepared by the method described below, was applied by rotation using a coater developer (D-Spin 60A, SOKUDO Co., Ltd.) on a 6-inch silicon wafer (Fujimi Electronics Co., Ltd., 625 ± 25 μm thick). A 10 μm thick coating film was then formed by drying. The film thickness at 39 points within the coating film surface was measured using a non-contact film thickness measuring instrument (Nanometrics, NanoSpec / AFT 5100). The average value and the difference between the maximum and minimum film thicknesses were determined. The difference between the maximum and minimum film thicknesses was used as an indicator of in-plane uniformity and evaluated according to the following criteria.

[0108] 5. If the in-plane uniformity of the film thickness is less than 0.05 μm. 4. When the in-plane uniformity of the film thickness is 0.05 μm or more and less than 0.1 μm. 3: When the in-plane uniformity of the film thickness is 0.1 μm or more.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] <Synthesis example A-2> Except for substituting 4,4'-oxydiphthalic acid dianhydride ODPA in Synthesis Example A-1 with 15.5 g (0.05 mol) of ODPA and 10.9 g (0.05 mol) of pyromellitic acid dianhydride (PMDA), and substituting p-phenylenediamine (p-PD) with 19.1 g (0.09 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: m-tolidine), the reaction was carried out in the same manner as described in Synthesis Example A-1 to obtain polyamic acid ester (A-2). The weight-average molecular weight (Mw) of polyamic acid ester (A-2) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 30,000.

[0113] <Synthesis example A-3> Using 31 g (0.1 mol) of 4,4'-oxydiphthalic acid dianhydride ODPA from Synthesis Example A-1, and substituting 17.6 g (0.09 mol) of 4,4'-diaminodiphenyl ether (DADPE) for p-phenylenediamine (p-PD), the reaction was carried out in the same manner as described in Synthesis Example A-1 to obtain polyamic acid ester (A-3). The weight-average molecular weight (Mw) of polyamic acid ester (A-3) was measured by gel permeation chromatography (on a standard polystyrene basis) and found to be 24,000.

[0114] <Synthesis example A-4> The reaction was carried out in the same manner as described in Synthesis Example A-3, except that 29.4 g (0.1 mol) of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 4,4'-oxydiphthalic acid dianhydride ODPA in Synthesis Example A-3, to obtain polyamic acid ester (A-4). The weight-average molecular weight (Mw) of polyamic acid ester (A-4) was measured by gel permeation chromatography (in terms of standard polystyrene) and was found to be 20,000.

[0115] Example 1 A photosensitive resin composition containing the following components was prepared and evaluated. (A) Polyimide precursor: Polyamic acid ester (A-1) 100 parts by mass (B) Thermal crosslinking agent: Nikalac MW-390 (B-1) 5.0 parts by mass (C) Photopolymerization initiator: 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime (C-1) 5.0 parts by mass (D) Solvent: NEP ((D1) compound) 160 parts by mass and other solvent: EL 40 parts by mass

[0116] Examples 2-38 and Comparative Examples 1-4 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 1, and its physical properties were evaluated. In Comparative Example 1 and Comparative Example 3, (B) the thermal crosslinking agent was not used. Furthermore, in the following examples and comparative examples, in addition to components (A) to (D), the following optional components were further added to prepare the photosensitive resin composition. Examples 25-30: (E) Plasticizer added Examples 21-24 and Comparative Example 2: Formulated with (F)(meth)acrylate compound

[0117] [Table 1-1]

[0118] [Table 1-2]

[0119] [Table 1-3]

[0120] Each component (B) to (F) in Table 1 is a compound represented by the following formula, and its abbreviation is as follows: (B) Thermal crosslinking agent B-1:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0121] 〈(D) Solvent〉 ((D1) Compound) NEP: N-ethyl-2-pyrrolidone, boiling point 218°C ((D2) compound DMI: 1,3-dimethyl-2-imidazolidinone, boiling point 220°C (Solvents other than compound (D1) and compound (D2)) EL: Ethyl lactate, boiling point 154℃ GBL: γ-butyllactone, boiling point 204℃ DMSO: Dimethyl sulfoxide, boiling point 189°C NMP: N-methyl-2-pyrrolidone, boiling point 202°C

[0122] (E) Plasticizers E-1: [ka] Number of repetitions: 8 E-2: [ka] Number of repetitions: 7 E-3: [ka] Number of repetitions: 3

[0123] (F)(meth)acrylate compounds F-1: Tetraethylene glycol dimethacrylate (Product name: Bremmer PED-200, Molecular weight: 330) F-2: Diethylene glycol monomethacrylate (Bremmer PE90, molecular weight: 90, manufactured by NOF Corporation) F-3: Methoxypolyethylene glycol monoacrylate (Bremmer AME-400, molecular weight: 400, manufactured by NOF Corporation)

[0124] Table 2 shows the results of the evaluation of the physical properties of the photosensitive resin compositions prepared in the examples.

[0125] [Table 2-1]

[0126] [Table 2-2]

[0127] [Table 2-3]

[0128] As shown in Table 2, it was verified that the photosensitive resin composition of the present embodiment containing one or more selected from the (D1) compound and the (D2) compound as the (D) solvent has excellent in-plane uniformity, a high imidization rate and high glass transition temperature of the obtained cured film, and excellent chemical resistance. [Industrial Applicability]

[0129] The photosensitive resin composition of the present embodiment can be suitably applied to semiconductor devices, interlayer insulating films of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like.

Claims

1. Component (A): Polyimide precursor Ingredient (B): Thermal crosslinking agent Component (C): Photopolymerization initiator and Component (D): Solvent A photosensitive resin composition comprising, The aforementioned component (A) is general formula (A-1): 【Chemistry 1】 (In the formula, X １ Y is a tetravalent organic group, １ is a divalent organic group, n １ is an integer between 2 and 150, and R 1 and R 2 Each is independently a hydrogen atom or a monovalent organic group, R 1 and R 2 At least one of these is a monovalent organic group having 2 to 40 carbon atoms that has a radical polymerizable group.) The aforementioned component (B) is a compound having an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, a maleimide group, or an allyl group, and The aforementioned component (D) is given by the general formula (D1): 【Chemistry 2】 {In formula (D1), R １ is a monovalent organic group having 2 or more carbon atoms. Compounds represented by}, and General formula (D2): 【Transformation 3】 In formula (D2), R ２ and R ３ are each independently a monovalent organic group having 1 or more carbon atoms. A photosensitive resin composition comprising one or more selected from the compounds represented by}.

2. The photosensitive resin composition according to claim 1, wherein component (B) is a compound having a total of four or more at least one selected from alkoxymethyl groups, methylol groups, epoxy groups, oxetanyl groups, maleimide groups, and allyl groups.

3. The photosensitive resin composition according to claim 1 or 2, wherein component (B) is a compound in which a plurality of alkoxymethyl groups or a plurality of methylol groups are bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

4. The aforementioned component (B) is of general formula (B-1): 【Chemistry 4】 (B-2): 【Transformation 5】 or (B-3): 【Transformation 6】 (In the formula, R ６ ~R １５ , and R １７ ~R ２０ Each of these independently corresponds to the following general formula (Bi): 【Transformation 7】 {In the formula, R ２３ R is a divalent organic group having 1 to 3 carbon atoms, ２４ is -H, -CH ３ , or -C ２ H ５ It is a group represented by} or -CH ３ And, R １６ It is a single bond or a divalent group, R ２１ and R ２２ These are, independently, -H and -CH. ３ , -C ２ H ５ The photosensitive resin composition according to claim 1 or 2, which is a compound represented as , or -OH.

5. The photosensitive resin composition according to claim 4, wherein the component (B) is a compound represented by the general formula (B-3).

6. The aforementioned R １ However, the compound represented by the general formula (D1) is a monovalent organic group having 2 to 5 carbon atoms, or the R ２ and R ３ The photosensitive resin composition according to claim 1 or 2, wherein each compound is independently a monovalent organic group having 1 to 5 carbon atoms represented by the general formula (D2).

7. The photosensitive resin composition according to claim 1 or 2, wherein component (D) comprises N-ethyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone.

8. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition contains 50 to 100% by mass of component (D) relative to the total solvent contained in the photosensitive resin composition.

9. The photosensitive resin composition according to claim 1 or 2, comprising a compound having a lower boiling point than component (D) as a solvent.

10. The photosensitive resin composition according to claim 9, wherein the boiling point of the compound with a lower boiling point than component (D) is less than 210°C.

11. General formula (3): 【Transformation 8】 (In the formula, m ２ is an integer between 2 and 30, and R ２８ , R ２９ and R ３０ The photosensitive resin composition according to claim 1 or 2, further comprising (E) a plasticizer represented by (E) (where each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

12. In the general formula (3), m ２ The photosensitive resin composition according to claim 11, wherein the ratio is 3 or more.

13. The photosensitive resin composition according to claim 11, comprising 3 to 12 parts by mass of the plasticizer (E) per 100 parts by mass of component (A).

14. (F) The photosensitive resin composition according to claim 1 or 2, further comprising a (meth)acrylate compound.

15. The photosensitive resin composition according to claim 14, wherein the (F)(meth)acrylate compound comprises a monofunctional (meth)acrylate compound.

16. The photosensitive resin composition according to claim 15, comprising 0.2 to 40 parts by mass of the monofunctional (meth)acrylate compound per 100 parts by mass of component (A).

17. A photosensitive resin composition according to claim 1 or 2, used for forming an interlayer insulating film.

18. (1) Applying the photosensitive resin composition according to claim 1 or 2 onto a substrate to form a photosensitive resin layer on the substrate, (2) Exposing the photosensitive resin layer, (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].

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

20. The cured film according to claim 19, which is an interlayer insulating film.

Images