Photosensitive resin composition

Abstract

To provide a photosensitive resin composition that can produce a resin film having high Tg and thermal weight loss temperature, and excellent chemical resistance, while preventing a decrease in the resolution of a relief pattern.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor, (B) compound having a hydroxyl group and a polymerizable unsaturated bond, (C) a photosensitizer, (D) a solvent, (E) free chlorine, the amount of the free chlorine being 0.0001-2 ppm relative to the total mass of the photosensitive resin composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials of electronic components, and passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor can easily form a heat-resistant relief pattern film by coating, exposure, development, and thermal imidization treatment of the precursor.

[0003] On the other hand, there are various methods for semiconductor package techniques in semiconductor devices. In recent years, a semiconductor package technique called fan-out has become the mainstream as a semiconductor package technique. In a fan-out type semiconductor package, a chip encapsulant larger than the chip size of a semiconductor chip is formed by covering the semiconductor chip with an encapsulant. Further, a redistribution layer extending to the regions of the semiconductor chip and the encapsulant is formed. The redistribution layer is formed with a thin film thickness. Also, since the redistribution layer can be formed up to the region of the encapsulant, the number of external connection terminals can be increased.

[0004] For example, the following Patent Document 1 is known as a fan-out type semiconductor device.

Prior Art Documents

Patent Documents

[0005] ]l

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] On the other hand, in recent years, the mounting methods for semiconductor devices onto printed circuit boards have been changing in order to improve integration density and computing power, as well as to reduce chip size. In structures such as SiP, which allows for higher density mounting, a structure in which the polyimide coating directly contacts the solder bumps is increasingly being used. When forming such a bump structure, the polyimide coating is required to have high heat resistance and chemical resistance. In the case of resin compositions that do not have heat resistance, when mounted on the substrate together with the semiconductor chip through the solder reflow process, a cured film with low heat resistance is produced. A cured film with low heat resistance is prone to degassing and shrinkage due to temperature changes, and is susceptible to cracking and delamination.

[0007] Furthermore, there has been a growing demand for thermosetting materials (low-temperature curing materials) that can be cured at low temperatures. While phenolic resins have been widely developed as low-temperature curing materials for insulating film applications, polyimide resins are preferred from the standpoint of chemical resistance and heat resistance. To cure polyimide resins, which are normally processed at 300-400°C, at low temperatures, it is common to use chemical imidization, which involves adding compounds that promote imidization, or to use soluble polyimide.

[0008] On the other hand, when heat treatment is performed at low temperatures, a large amount of low-molecular-weight compounds remain in the cured film, and the interactions between resins weaken, making it difficult to maintain the film's properties. In particular, in heating processes such as solder reflow in semiconductor device processing, cracks and delamination are likely to occur due to degassing and shrinkage.

[0009] To suppress the delamination of the resin film from the Cu wiring during the reflow process, it is necessary to raise the glass transition temperature (Tg) and weight loss temperature of the resin film. However, in recent low-temperature heat curing processes, the curing process is performed at temperatures below the reflow temperature, resulting in a Tg lower than the reflow temperature and the problem of low-molecular-weight compounds remaining without volatilizing. While lowering the molecular weight between crosslinking points of the cured film tends to increase Tg, increasing the functional group concentration or amount of radical polymerizable compounds, which are commonly used in combination with polyimide precursors in negative-type photosensitive resin compositions, reduces the resolution of the relief pattern. Therefore, it has been difficult to improve the Tg of the resin film while maintaining resolution. Furthermore, to raise the thermogravimetric loss temperature of the resin film, it was necessary to completely volatilize or immobilize the low-molecular-weight compounds in the resin film.

[0010] This invention has been made in view of the above problems, and one of its objectives is to provide a photosensitive resin composition that can produce a resin film with high Tg and thermogravimetric temperature loss temperature and excellent chemical resistance while suppressing a decrease in the resolution of the relief pattern. [Means for solving the problem]

[0011] The present inventors have discovered that the above problems can be solved by a resin composition containing a compound having a hydroxyl group and a polymerizable unsaturated bond, and free chlorine and / or covalent chlorine adjusted to a specific amount, and have completed the present invention. Examples of embodiments of the present invention are listed below. [1] (A) Polyimide precursor and (B) Compounds having a hydroxyl group and a polymerizable unsaturated bond, (C) Photosensitive agent and, (D) Solvent and (E) Free chlorine and A photosensitive resin composition comprising, The amount of free chlorine is 0.0001 to 2 ppm based on the total mass of the photosensitive resin composition, in the photosensitive resin composition. [2] The photosensitive resin composition according to item 1, wherein the above (C) photosensitive agent is a photopolymerization initiator. [3] The photosensitive resin composition according to item 1 or 2, wherein the above (A) polyimide precursor is represented by the following general formula (1). [ka] {In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1 and R2 is given by the following general formula (2): [ka] The group is represented by formula (2), where R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10. [4] A photosensitive resin composition according to any one of items 1 to 3, comprising 100 to 860 parts by mass of the solvent (D) above with respect to 100 parts by mass of the polyimide precursor (A) above. [5] The photosensitive resin composition according to any one of items 1 to 4, wherein the solvent (D) above comprises one or more compounds selected from the group consisting of N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and 2-octanone. [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond has two or more polymerizable unsaturated bonds. [7] The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond in (B) above is a reaction product of an epoxy resin and (meth)acrylic acid. [8] The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond in (B) above is represented by the following general formula (3) or (4). [Chemical formula] {In formula (3), R1 is a monovalent organic group having 1 to 40 carbon atoms.} [Chemical formula] {In formula (4), R2 is a monovalent organic group having 1 to 40 carbon atoms.} [9] The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond in (B) above is represented by the following general formula (5) or (6). [Chemical formula] {In formula (5), R3 is a monovalent organic group having 1 to 40 carbon atoms.} [Chemical formula] {In formula (6), R4 is a monovalent organic group having 1 to 40 carbon atoms.}

[10] The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond in (B) above contains a compound represented by the following general formula (at 7). [Chemical formula] {In formula (7), R2 is a divalent organic group having 1 to 40 carbon atoms.}

[11] The photosensitive resin composition according to any one of Items 1 to 5, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond in (B) above contains a compound represented by the following general formula (8). [ka] {In formula (8), R6 is a divalent organic group having 1 to 40 carbon atoms.}

[12] (A) Polyimide precursor and (B) Compounds having a hydroxyl group and a polymerizable unsaturated bond, (C) Photosensitive agent and, (D) Solvent and (E) Free chlorine and A photosensitive resin composition comprising, A photosensitive resin composition in which, when the above photosensitive resin composition is applied to a substrate by a rotational method so that the film thickness after curing is approximately 10 μm, and then heated on a hot plate at 110°C for 180 seconds to cure, the amount of free chlorine contained in the resulting coating film is 0.0001 to 5 ppm based on the total mass of the coating film.

[13] (G) A photosensitive resin composition according to any one of items 1 to 12, further comprising an epoxy resin.

[14] The photosensitive resin composition according to item 13, wherein the amount of the epoxy resin (G) is 0.1 to 10 parts by mass per 100 parts by mass of the polyimide precursor (A).

[15] A negative-type photosensitive resin composition, as described in any one of items 1 to 14.

[16] (A) Polyimide precursor and (B) Compounds having a hydroxyl group and multiple polymerizable unsaturated bonds, (C) Photosensitive agent and, (D) Solvent and (E) Free chlorine and / or covalently bonded chlorine, A photosensitive resin composition comprising, A photosensitive resin composition in which, after preparation, the total chlorine content in the photosensitive resin composition is 0.0001 to 250 ppm based on the total mass of the photosensitive resin composition when left standing for 3 days at 23°C ± 0.5°C and a relative humidity of 50% ± 10%. [Effects of the Invention]

[0012] The present invention provides a photosensitive resin composition that can produce a resin film with a high glass transition temperature and thermogravimetric loss temperature, and excellent chemical resistance, while maintaining the resolution of the formed relief pattern. In one embodiment, the crosslinking density of the polymer in the resin can be increased after the relief pattern is formed, and the glass transition temperature of the cured film tends to increase while maintaining the resolution. In another embodiment, low-boiling point compounds in the film can be immobilized by reaction, making it possible to improve the thermogravimetric loss temperature. Furthermore, in another embodiment, the high crosslinking density and the specific amount of free chlorine prevent the penetration of chemicals into the cured film, thus improving the chemical resistance of the relief pattern. [Modes for carrying out the invention]

[0013] The embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist. Throughout this specification, structures represented by the same symbols in a general formula, if present in multiple locations within a molecule, are selected independently unless otherwise specified, and may be identical or different from one another. Similarly, structures represented by common symbols in different general formulas are also selected independently unless otherwise specified, and may be identical or different from one another.

[0014] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises (A) a polyimide precursor, (B) a compound having a hydroxyl group and a polymerizable unsaturated bond, (C) a photosensitive agent, (D) a solvent, and (E) a specific amount of free chlorine and / or covalent chlorine. Optionally, the photosensitive resin composition may contain other components. Each component is described below in order.

[0015] The photosensitive resin composition may be either negative or positive type, depending on the desired application, but it is preferable to be negative type from the viewpoint of the physical properties of the (A) polyimide precursor described later.

[0016] (A) Polyimide precursor In this embodiment, (A) the polyimide precursor is a resin component contained in the photosensitive resin composition, and is preferably a polyamide having a structural unit represented by the following general formula (1). [ka] {In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1 and R2 is given by the following general formula (2): [ka] The group is represented by formula (2), where R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.

[0017] (A) The ratio of the monovalent organic group represented by the general formula (2) to all of the R1 and R2 of the precursor represented by the general formula (1) contained in the polyimide precursor is preferably 50 mol% to 100 mol% from the viewpoint of high resolution, and more preferably 75 mol% to 100 mol% from the viewpoint of high chemical resistance and sensitivity.

[0018] In the above general formula (1), n1 is preferably an integer between 3 and 100, and more preferably an integer between 5 and 70, from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition.

[0019] In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, in terms of achieving both heat resistance and photosensitive properties, and more preferably an aromatic group or alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group and the -CONH- group are in the ortho position relative to each other. Specifically, as the tetravalent organic group represented by X1, an organic group having 6 to 40 carbon atoms containing an aromatic ring, for example, the following general formula (20): [ka] {In formula (20), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group; l is an integer selected from 0 to 2; m is an integer selected from 0 to 3; and n is an integer selected from 0 to 4.} Examples of groups having the structure represented by the above formula (20) include, but are not limited to, groups having the structure represented by the above formula. Furthermore, the structure of X1 may be one type or a combination of two or more types. X1 groups having the structure represented by the above formula (20) are particularly preferred in that they achieve both heat resistance and photosensitive properties.

[0020] In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms, in that it can achieve both heat resistance and photosensitive properties, for example, the following formula (21): [ka] {In formula (21), R6 is a monovalent group selected from the group consisting of a hydrogen atom, a fluorine atom, a C1-C10 hydrocarbon group, and a C1-C10 fluorine-containing hydrocarbon group, and n is an integer selected from 0 to 4.} Examples of structures represented by the above formula (21) are, but are not limited to, those shown. Furthermore, the structure of Y1 may be one type or a combination of two or more types. A Y1 group having the structure represented by the above formula (21) is particularly preferred in that it achieves both heat resistance and photosensitive properties.

[0021] As for the Y1 group, among the structures represented by the above formula (21), in particular, the following formula: [ka] The structure represented by is preferred from the viewpoint of imidization rate, degassing properties, copper adhesion, and chemical resistance during low-temperature heating.

[0022] In the above general formula (2), R3 is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitivity. Also, m1 is an integer between 2 and 10, preferably between 2 and 4, from the viewpoint of photosensitivity.

[0023] In one embodiment, (A) the polyimide precursor is given by the following general formula (9): [ka] {In equation (9), R1, R2, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by .

[0024] In general formula (9), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (2).

[0025] In one embodiment, (A) the polyimide precursor is given by the following general formula (10): [ka] {In equation (10), R1, R2, and n1 are as defined above.} It is preferable that the polyimide precursor has a structural unit represented by .

[0026] In general formula (10), it is more preferable that at least one of R1 and R2 is a monovalent organic group represented by general formula (2).

[0027] (A) Method for preparing polyimide precursors The polyimide precursor containing the structure represented by the general formula (1) in this embodiment can be obtained, for example, by reacting a tetracarboxylic dianhydride containing the aforementioned tetravalent organic group X1 having 6 to 40 carbon atoms with (a) alcohols having a structure in which a monovalent organic group and a hydroxyl group are bonded, as represented by the general formula (2), and optionally (b) alcohols having a structure other than the group represented by the general formula (2), to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester); and subsequently polycondensing the obtained acid / ester with diamines containing the aforementioned divalent organic group Y1 having 6 to 40 carbon atoms.

[0028] (Preparation of acid / ester compounds) In this embodiment, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X1 having 6 to 40 carbon atoms include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, 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. These can be used individually or in combination of two or more.

[0029] (b) Examples of alcohols having a structure other than the group represented by the general formula (2) above include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, such as 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.

[0030] The content of the organic group of general formula (2) in the polyimide precursor is preferably 50 mol% or more relative to the total content of R1, R2, R6, and R7. A content of the organic group of general formula (2) exceeding 50 mol% is preferable because it allows for obtaining the desired photosensitive properties. The content of the organic group of general formula (2) in the photosensitive resin composition is preferably 75 mol% or more relative to the total content of R1, R2, R6, and R7.

[0031] By dissolving and mixing the above-mentioned tetracarboxylic dianhydride and the alcohols of (a) in a reaction solvent in the presence of a basic catalyst such as pyridine, the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester product can be obtained. The reaction conditions are preferably stirred for 4 to 10 hours at a reaction temperature of 20 to 50°C.

[0032] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor, which is a polycondensation product of the acid / ester compound and diamines. Examples of reaction solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used individually or in combination of two or more as needed.

[0033] (Preparation of polyimide precursors) A polyimide precursor can be obtained by mixing the above acid / ester compound (typically a solution in the above reaction solvent) with a known dehydrating condensation agent under ice cooling to form a polyacid anhydride, and then adding dropwise a diamine containing a divalent organic group Y1 with 6 to 40 carbon atoms, which has been dissolved or dispersed separately in a solvent, and polycondensing the mixture. Examples of dehydrating condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

[0034] Examples of diamines containing a divalent organic group Y1 with 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3, 4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl Nyl 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-aminophenyl [(((((4-aminophenoxy))phenyl)]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, halogens, etc., for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,Examples include 4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyloxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. However, diamines are not limited to these.

[0035] To improve the adhesion between the photosensitive resin layer formed on the substrate by applying the photosensitive resin composition of this embodiment to the substrate and various substrates, (A) diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can be copolymerized during the preparation of the polyimide precursor.

[0036] After the polycondensation reaction described above is complete, the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution may be filtered off as needed. Then, a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof may be added to the reaction solution to precipitate the polymer components. Furthermore, the polymer may be purified by repeating the above redissolution and reprecipitation operations. The polymer can then be vacuum-dried to isolate the polyimide precursor. To improve the degree of purification, the solution of this polymer may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

[0037] (A) The molecular weight of the polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, and particularly preferably 18,000 to 40,000, when measured by weight-average molecular weight in terms of polystyrene equivalent by gel permeation chromatography. A weight-average molecular weight of 8,000 or more is preferred because it has good mechanical properties, while a weight-average molecular weight of 150,000 or less is preferred because it has good dispersibility in the developer and good resolution of the relief pattern. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended to select the standard monodisperse polystyrene from STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko Corporation.

[0038] (B) Compounds having a hydroxyl group and polymerizable unsaturated bonds The compound having a (B) hydroxyl group and a polymerizable unsaturated bond (hereinafter also simply referred to as "(B) compound") in this embodiment will be described below. The (B) compound has at least one hydroxyl group and at least one polymerizable unsaturated bond in its molecule. The polymerizable unsaturated bond is not limited to any functional group that can be radically polymerized, and examples include acrylic group, methacrylic group, acryloyloxy group, methacryloyloxy group, vinyl group, and allyl group, with acryloyloxy group or methacryloyloxy group (hereinafter referred to as "(meth)acryloyloxy group") being preferred. The (B) compound having a (meth)acryloyloxy group as the polymerizable unsaturated bond may be a reaction product of acrylic acid or methacrylic group (hereinafter referred to as "(meth)acrylic acid") and epoxy resin, or a reaction product of (meth)acrylic acid and a ring-opened epoxy resin. In particular, from the viewpoint of chemical resistance and thermophysical properties, the reaction product of (meth)acrylic acid and epoxy resin represented by the following general formulas (3) to (6), or the reaction product of (meth)acrylic acid and the ring-opened form of epoxy resin is preferred. [ka] {In formulas (3) to (6) above, R1, R2, R3, and R4 are monovalent organic groups having 1 to 40 carbon atoms.}

[0039] (B) Compounds may have one, two or more, or three or more polymerizable unsaturated bonds within the same molecule. When there are two polymerizable unsaturated bonds, the following general formula: [ka] {In the above general formula, R2 and R3 are divalent organic groups having 1 to 40 carbon atoms.} Examples of compounds represented by [the formula shown] are given.

[0040] More specifically, examples of (B) compounds with two polymerizable unsaturated bonds include, but are not limited to, the following group of compounds: [ka] [ka] [ka] [ka]

[0041] Compound (B) having two or more polymerizable unsaturated bonds can be produced by reacting (meth)acrylic acid with a bifunctional or higher epoxy resin. In this case, compounds having one or more oxacycloopropyl groups in the molecule may be produced as reaction impurities. The following general formula is used for reaction impurities: [ka] Examples of compounds represented by the formula {In the above formula, R1, R2, R3, and R4 are each independently divalent organic groups having 1 to 40 carbon atoms.} include the following general formula: [ka] A compound represented by {In the above formula (8), R6 is a divalent organic group having 1 to 40 carbon atoms.} is preferred.

[0042] (B) Examples of compounds with one polymerizable unsaturated bond include, but are not limited to, the following group of compounds: [ka]

[0043] (B) Method for preparing compounds having a hydroxyl group and a polymerizable unsaturated bond. The method for producing compound (B) is not particularly limited as long as a compound having at least one hydroxyl group and at least one polymerizable unsaturated bond in its molecule is obtained. From the viewpoint of adjusting the amount of free chlorine and / or covalent chlorine to a specific amount, compound (B) is preferably a compound derived from epoxy resin. For example, compound (B) can be produced by reacting an epoxy resin or its ring-opened form with a compound having a polymerizable unsaturated bond. Preferably, compound (B) may be produced by obtaining a solution by adding a basic catalyst and a polymerization inhibitor to an epoxy resin or its ring-opened form and mixing it, then adding methacrylic acid or acrylic acid to the solution and reacting it. The reaction may be continued, for example, at 100°C until the acid value falls below a certain value. After synthesis, compound (B) can be obtained by stirring the mixture with an anion exchange resin for one day and filtering it. For example, IRA96SB can be used as the anion exchange resin.

[0044] (B) Examples of epoxy resins used in the synthesis reaction of compounds include, but are not limited to, structures represented by the following general formulas: [ka]

[0045] (B) The ring-opened epoxy resin used in the synthesis reaction of the compound is the following general formula in which the epoxy group is ring-opened: [ka] {In the above formula, R1 and R2 are each independently monovalent organic groups having 1 to 40 carbon atoms.} It is preferable that the compound is converted to the structure represented by .

[0046] The photosensitive resin composition of this embodiment, by containing the above-mentioned compound (B), can provide a resin film that maintains storage stability while having a high glass transition temperature and thermoweight loss temperature, and further exhibiting excellent chemical resistance. Although not bound by theory, the reason for the increase in glass transition temperature is thought to be that the polymerizable unsaturated bonds that remain without polymerization during exposure undergo an addition reaction with hydroxyl groups during high-temperature curing, resulting in a cured film with a higher density of crosslinking than that of ordinary polymerizable unsaturated bond-containing compounds, thereby hindering the movement of the polymer constituting the resin. Note that if the polymerizable unsaturated bond is a (meth)acrylic group, a Michael addition reaction proceeds. The reason for the improved chemical resistance is similarly thought to be that the high crosslinking density reduces solubility in chemicals, and that the amount of free chlorine and / or covalently bonded chlorine is within a specific range, which suppresses the formation of ion pairs with chemicals that promote dissolution, thereby improving chemical resistance. The reason the thermogravimetric temperature rises is thought to be that, particularly during low-temperature curing, the polymerizable unsaturated bonds and hydroxyl groups undergo an addition reaction with the side chains of the polyimide precursor. As a result, even when the temperature rises above the curing temperature, components derived from the side chains of the polyimide precursor do not volatilize and remain, thus preventing weight loss due to heating.

[0047] (B) When a bifunctional or more epoxy resin is used in the synthesis of compound (B), compound (B) may have unreacted epoxy groups. In this case, anionic polymerization proceeds with the hydroxyl group as the initiating species during thermal curing, further increasing the crosslink density.

[0048] (B) The amount of compound to be blended is 1 to 60 parts by mass per 100 parts by mass of (A) polyimide precursor, preferably 1 to 30 parts by mass from the viewpoint of storage stability, and more preferably 4 to 20 parts by mass from the viewpoint of resolution.

[0049] (C) Photosensitive material The photosensitive resin composition of this embodiment contains a photosensitive agent. In one embodiment, the photosensitive agent may be a photopolymerization initiator. Photopolymerization initiators are preferred because they promote the curing of the relief pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, and may include benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives, benzoin, benzoin methyl ether and other benzoin derivatives, 1-phenyl-1,2-butanedione-2-(o-methoxy Preferred photopolymerization initiators include, but are not limited to, oximes such as carbonyl 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, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic biimidazoles, titanocenes, and photoacid generators such as α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Among the above photopolymerization initiators, oximes are particularly preferred in terms of photosensitivity.

[0050] The amount of photopolymerization initiator added is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 1 part by mass to 8 parts by mass, per 100 parts by mass of (A) polyimide precursor. The above amount is preferably 0.1 parts by mass or more from the viewpoint of photosensitivity or patternability, and preferably 20 parts by mass or less from the viewpoint of the physical properties of the photosensitive resin layer after curing of the photosensitive resin composition.

[0051] (D) Solvent The photosensitive resin composition of this embodiment contains a solvent. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specific examples of solvents include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc., which can be used individually or in combination of two or more.

[0052] The above solvent can be used in an amount of, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, and more preferably 100 to 860 parts by mass, per 100 parts by mass of the polyimide precursor (A), depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0053] From the viewpoint of improving the storage stability of the photosensitive resin composition, solvents containing alcohols are preferred. Suitable alcohols are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond. Specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, and propylene glycol-2-(n-propyl) ether; monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether; 2-hydroxyisobutyrate esters; and dialcohols such as ethylene glycol and propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, with ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether being particularly preferred.

[0054] When the solvent contains an alcohol without an olefinic double bond, the content of the alcohol without an olefinic double bond in the total solvent is preferably 5% to 50% by mass, and more preferably 10% to 30% by mass, based on the mass of the total solvent. When the above content of the alcohol without an olefinic double bond is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, while when it is 50% by mass or less, the solubility of the (A) polyimide precursor is improved, which is preferable.

[0055] (E) Free chlorine and / or covalent chlorine The photosensitive resin composition of this embodiment contains chlorine in the form of free chlorine and / or covalent chlorine. Free chlorine refers to anionized chlorine, and covalent chlorine refers to chlorine that exists within the molecule by forming covalent bonds.

[0056] In one embodiment, the amount of free chlorine is 0.0001 to 10 ppm, preferably 0.0001 to 5 ppm, more preferably 0.0001 to 2.0 ppm, and even more preferably 0.0001 to 0.5 ppm, based on the total mass of the photosensitive resin composition. In another embodiment, when the photosensitive resin composition is applied to a substrate by a rotary method so that the thickness of the cured resin film is approximately 10 μm, and cured by heating on a hot plate at 110°C for 180 seconds, the amount of free chlorine contained in the resulting coating film is 0.0001 to 15 ppm, preferably 0.0001 to 10 ppm, more preferably 0.0001 to 5 ppm, and even more preferably 0.0001 to 0.8 ppm, based on the total mass of the coating film. In yet another embodiment, after preparing the photosensitive resin composition, the total amount of chlorine (sum of free chlorine and covalently bonded chlorine) in the photosensitive resin composition after standing for 3 days at 23°C ± 0.5°C and a relative humidity of 50% ± 10% is 0.0001 to 600 ppm, preferably 0.0001 to 420 ppm, more preferably 0.0001 to 250 ppm, and even more preferably 0.0001 to 40 ppm, based on the total mass of the photosensitive resin composition.

[0057] The source of chlorine is not limited; for example, the photosensitive resin composition can contain compounds that can generate free chlorine and / or compounds that have covalently bonded chlorine, thereby adjusting the amount of chlorine within the above range. Generally, epoxy resins contain a large amount of chlorine in the form of free chlorine and / or covalently bonded chlorine, derived from their raw material, epichlorohydrin. Therefore, if compound (B) is a compound derived from epoxy resin, chlorine is contained in compound (B), and as a result, chlorine is also contained in the photosensitive resin composition, making it easier to adjust the amount of chlorine within the above range. However, conventionally, when compound (B) derived from epoxy resin is used in this way, the amount of chlorine is much greater than the above amount. Conventionally, the presence of such chlorine has been tolerated, so those skilled in the art have not paid attention to the amount of chlorine. However, the inventors have found that in a preferred embodiment of the present invention, when compound (B) derived from epoxy resin is used, it is preferable to remove the chlorine present in the compound to appropriately control the amount of chlorine.

[0058] The method for removing chlorine present in compound (B) derived from epoxy resin is not particularly limited. For example, chlorine can be removed by stirring compound (B) in a multiphase with an anion exchange resin. IRA96SB is an example of an anion exchange resin used for chlorine removal, but it is not limited to this.

[0059] Other ingredients The photosensitive resin composition of this embodiment may further contain components other than those listed above (A) to (E). Examples of other components include (A) resin components other than polyimide precursors; sensitizers; (F) monomers other than the (B) compound having photopolymerizable unsaturated bonds; contact aids; (G) epoxy resins; thermal polymerization inhibitors; azole compounds; hindered phenol compounds; and organotitanium compounds.

[0060] The photosensitive resin composition may further contain (G) epoxy resin from the viewpoint of obtaining a cured film with a high degree of crosslinking. The amount of (G) epoxy resin is preferably 0.01 to 25 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass, per 100 parts by mass of (A) polyimide precursor. When using (B) compound derived from epoxy resin, the raw material epoxy resin may be included in the photosensitive resin composition, and it is easier to adjust the amount of epoxy resin within the above range.

[0061] In one embodiment, the photosensitive resin composition may further contain resin components other than the (A) polyimide precursor. Examples of resin components that can be included in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The amount of these resin components blended is preferably in the range of 0.01 parts by mass to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor.

[0062] (A) When preparing a positive-type photosensitive resin composition using a polyoxazole precursor together with a polyimide precursor, a compound having a quinone diazide group, such as a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, may be used in combination as a positive-type photosensitive material.

[0063] In one embodiment, the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of such sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamyridene indigo. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone Examples include ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These can be used individually or in combination (for example, 2 to 5 types).

[0064] The amount of sensitizer added is preferably 0.1 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0065] In one embodiment, in order to improve the resolution of the relief pattern, the photosensitive resin composition may optionally contain monomers other than (B) compounds having (F) photopolymerizable unsaturated bonds. Preferred monomers are (meth)acrylic compounds that undergo radical polymerization reactions with photopolymerization initiators, and are not limited to the following, but include diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, mono or diacrylate and methacrylate of ethylene glycol or polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylate and dimethacrylate, 1,6-hex Examples of compounds include diacrylates and dimethacrylates of sandiol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri- or tetraacrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide adducts of these compounds.

[0066] The amount of photopolymerizable monomer having an unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0067] In one embodiment, the photosensitive resin composition may optionally contain an adhesion aid to improve the adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of adhesion aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl]phthalate. Examples include silane coupling agents such as amidic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane, as well as aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0068] Of these adhesive aids, a silane coupling agent is more preferable in terms of adhesive strength. The amount of adhesive aid added is preferably in the range of 0.5 to 25 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0069] In one embodiment, the photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the viscosity and photosensitivity stability of the photosensitive resin composition, particularly when stored in a solvent-containing solution. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0070] The amount of thermal polymerization inhibitor added is preferably in the range of 0.005 parts by mass to 12 parts by mass per 100 parts by mass of (A) polyimide precursor.

[0071] For example, when using a substrate made of copper or a copper alloy, the photosensitive resin composition may optionally contain an azole compound to suppress discoloration of the substrate. Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, 1-methyl-1H-tetrazol, and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Furthermore, these azole compounds may be used individually or as a mixture of two or more.

[0072] The amount of azole compound blended is preferably 0.1 to 20 parts by mass per 100 parts by mass of (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of azole compound blended per 100 parts by mass of (A) polyimide precursor is 0.1 parts by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while when it is 20 parts by mass or less, it is preferable because it has excellent photosensitivity.

[0073] In this embodiment, to suppress discoloration on copper, the photosensitive resin composition may include a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butyl (Phenolphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butyl) (enol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2, 4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris[4-Triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-Triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-Triazine-2,4,6-(1H,3H,5H)-Trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) Triazine-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-trione Examples include, but are not limited to, riazin-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trione. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0074] The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity characteristics. When the amount of the hindered phenol compound per 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when it is 20 parts by mass or less, it is preferable because it has excellent photosensitivity.

[0075] In one embodiment, the photosensitive resin composition may contain an organotitanium compound. By including an organotitanium compound, a photosensitive resin layer with excellent chemical resistance can be formed even when cured at a low temperature of approximately 250°C.

[0076] Examples of usable organotitanium compounds include those in which an organic chemical substance is bonded to a titanium atom via covalent or ionic bonds.

[0077] Specific examples of organotitanium compounds are shown in I) to VII) below: I) As titanium chelating compounds, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability and a good pattern for the photosensitive resin composition. Specific examples of titanium chelating compounds include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate).

[0078] II) Examples of tetraalkoxy titanium compounds include titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, and titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}].

[0079] III) Examples of titanocene compounds include pentamethylcyclopentadienyltitanium trimethoxide and bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 Examples include (-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium.

[0080] IV) Examples of monoalkoxy titanium compounds include titanium tris(dioctyl phosphate) isopropoxide and titanium tris(dodecylbenzenesulfonate) isopropoxide.

[0081] V) Examples of titanium oxide compounds include titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), and phthalocyanine titanium oxide.

[0082] VI) Examples of titanium tetraacetylacetonate compounds include titanium tetraacetylacetonate.

[0083] VII) Examples of titanate coupling agents include isopropyltridodecylbenzenesulfonyl titanate.

[0084] Among the above I) to VII), it is preferable from the viewpoint of achieving better chemical resistance that the organotitanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethyl acetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium is preferred.

[0085] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of resin (A). When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, excellent storage stability is obtained, which is preferable.

[0086] Compounds with a structure similar to that of an imidation accelerator (a compound exhibiting basicity) may be introduced into the polymer side chains. By doing so, a higher imidation rate can be obtained compared to when an imidation accelerator is used as an additive, and a photosensitive resin composition that achieves both storage stability and chemical resistance can be obtained.

[0087] Preferably, the photosensitive resin composition exhibits a viscosity change of 5% or less compared to its initial state when stored at a temperature of 23°C and a humidity of 50% Rh for 4 weeks. Furthermore, when the photosensitive resin composition is heated at 170°C for 2 hours to obtain a cured coating film, it is preferable that the imidization rate of the cured coating film is 70% or more, and more preferably 85% or more. Thus, in one embodiment, the photosensitive resin composition can provide a polyimide with a high imidization rate and excellent storage stability and chemical resistance.

[0088] [Polyimide] The structure of the polyimide contained in the cured relief pattern formed from the above polyimide precursor composition is preferably represented by the following general formula (11). [ka] {In general formula (11), X 1 and Y 1 These are the same as X1 and Y1 in general formula (1), and m is a positive integer. The preferred X1 and Y1 in general formula (1) are also preferred in the polyimide of general formula (11) for the same reasons. The number of repeating units m in general formula (11) is not particularly limited, but may be an integer from 2 to 150. According to the present invention, a method for producing polyimide can also be provided, which includes a step of converting the photosensitive resin composition described above into polyimide.

[0089] [Hardened relief pattern] According to the present invention, a cured relief pattern using the photosensitive resin composition described above, and a method for producing the same can be provided. In one embodiment, the method for producing the cured relief pattern is as follows: (1) to (4): (1) A step of applying the photosensitive resin composition according to this embodiment onto a substrate to form a photosensitive resin layer on the substrate, (2) A step of exposing the photosensitive resin layer, (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern, (4) A step of heat-treating the relief pattern to form a hardened relief pattern. This method includes [something].

[0090] The following describes each step. (1) A step of applying the photosensitive resin composition of this embodiment onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition according to this embodiment is applied to a substrate, and if necessary, is then dried to form a photosensitive resin layer. Conventional application methods for photosensitive resin compositions can be used, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or spray application using a spray coater.

[0091] If necessary, the coating film made of the photosensitive resin composition can be dried, and drying methods such as air drying, heating with an oven or hot plate, or vacuum drying can be used. Furthermore, it is desirable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor in the photosensitive resin composition. Specifically, when air drying or heating drying is performed, drying can be carried out at a temperature of 20°C to 140°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

[0092] (2) Exposing the photosensitive resin layer In this process, the photosensitive resin layer formed in step (1) above is exposed to ultraviolet light or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either through a patterned photomask or reticle or directly.

[0093] Subsequently, if necessary, post-exposure baking (PEB) and / or pre-development baking may be performed using any combination of temperature and time to improve light sensitivity, etc. The baking conditions are preferably in the range of 40°C to 120°C and 10 seconds to 240 seconds, but are not limited to this range as long as they do not impair the properties of the negative-type photosensitive resin composition.

[0094] (3) A step of developing the photosensitive resin layer after exposure to form a relief pattern. In this process, when the photosensitive resin composition is of the negative type, the unexposed portion of the photosensitive resin layer after exposure is developed and removed. As a development method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected and used from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method with ultrasonic treatment. Furthermore, after development, if necessary, a post-development bake may be performed using any combination of temperature and time for purposes such as adjusting the shape of the relief pattern. As the developer 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. As good solvents, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Suitable poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When using a mixture of good and poor solvents, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the negative-type photosensitive resin composition. Furthermore, two or more solvents, for example, can be used in combination.

[0095] (4) A step of heat-treating the relief pattern to form a hardened relief pattern. In this process, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and the (A) polyimide precursor is imidized, thereby converting it into a cured relief pattern made of polyimide. Various methods can be selected for heat curing, such as using a hot plate, using an oven, or using a heating oven with a temperature programmable. Heating can be carried out, for example, at 170°C to 400°C for 30 minutes to 5 hours. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may be used.

[0096] [Semiconductor device] The photosensitive resin composition of this embodiment can also provide a semiconductor device having a cured relief pattern obtained by the cured relief pattern manufacturing method described above. Therefore, a semiconductor device can be provided having a substrate which is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the cured relief pattern manufacturing method described above. Furthermore, the present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the cured relief pattern manufacturing method described above as part of the process. The semiconductor device of the present invention can be manufactured by forming the cured relief pattern formed by the cured relief pattern manufacturing method above as a surface protective film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining it with a known method for manufacturing a semiconductor device.

[0097] [Display device] The photosensitive resin composition of this embodiment can also provide a display device comprising a display element and a cured film provided on the upper part of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or it may be laminated with another layer in between. For example, the cured film can be a surface protective film, insulating film, and planarization film for TFT liquid crystal display elements and color filter elements, a projection for an MVA type liquid crystal display device, and a partition wall for the cathode of an organic EL element.

[0098] In addition to applications in semiconductor devices as described above, the photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coatings for flexible copper-clad sheets, solder resist films, and liquid crystal alignment films. [Examples]

[0099] 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 manufacturing examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods.

[0100] [Measurement and evaluation methods] (1) Weight average molecular weight The weight-average molecular weight (Mw) of each resin was measured by gel permeation chromatography (on a standard polystyrene basis). The column used for the measurement was the "Shodex 805M / 806M series" manufactured by Showa Denko K.K., the standard monodisperse polystyrene selected was the "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector used was the "Shodex RI-930" manufactured by Showa Denko K.K.

[0101] (2) Measurement of the amount of free chlorine in the resin composition After preparing the photosensitive resin composition, it was left to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for 3 days, and then the amount of free chlorine in the resin composition was measured. Ion concentration was measured at 23.0°C using a ThermoFicher ICS-3000. Based on the measurement results, the chloride ion content in the resin composition was determined under the following measurement conditions. 2 g of the photosensitive resin composition was weighed and added to 4 mL of NMP, then shaken for 10 minutes to dissolve. 30 mL of deionized water was then added and shaken for another 10 minutes. Insoluble components were removed using a centrifuge (himac CF15RN), and the solution was filtered through a disc filter (DISMIC JP050AN). 1 mL of the processed sample solution was automatically inserted into the column using an autosampler. • Guard column for anion analysis: IonPac AS4A-SC (4mm x 250mm) • Guard column pump flow rate: 0.500 mL / min • Separation column for anion analysis: IonPac AS4A-SZ (4mm x 50mm) • Sample introduction line pump flow rate: 0.500 mL / min • Anion chemical suppressor: ACRS-500 (for 4mm)

[0102] (3) Measurement of free chlorine content in cured polyimide coating film A photosensitive resin composition was rotary-coated onto a 6-inch silicon wafer to a cured film thickness of approximately 10 μm, and then heated on a hot plate at 110°C for 180 seconds to obtain a cured polyimide coating. The film thickness was measured using a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The amount of free chlorine in the obtained polyimide coating was measured under the following measurement conditions. 2 g of polyimide coating was weighed and added to 4 mL of NMP, then shaken for 10 minutes to dissolve. 30 mL of deionized water was then added and shaken for another 10 minutes. Insoluble components were removed using a centrifuge (himac CF15RN), and the solution was filtered through a disc filter (DISMIC JP050AN). 1 mL of the processed sample solution was automatically inserted into the column by an autosampler. • Guard column for anion analysis: IonPac AS4A-SC (4mm x 250mm) • Guard column pump flow rate: 0.500 mL / min • Separation column for anion analysis: IonPac AS4A-SZ (4mm x 50mm) • Sample introduction line pump flow rate: 0.500 mL / min • Anion chemical suppressor: ACRS-500 (for 4mm)

[0103] (4) Measurement of glass transition temperature of cured polyimide coating A photosensitive resin composition was rotary coated onto a 6-inch silicon wafer to achieve a cured film thickness of approximately 10 μm. Pre-baking was performed on a hot plate at 110°C for 180 seconds, followed by heating in a temperature-boosting programmable curing furnace (VF-000 model, manufactured by Koyo Lindbergh) under a nitrogen atmosphere at 170°C for 2 hours to obtain a cured polyimide coating. The film thickness was measured using a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating was taken out in strips and subjected to a load of 200 g / mm². 2 The temperature was measured using a thermomechanical test apparatus (TMA-50, Shimadzu Corporation) at a heating rate of 10°C / min in the range of 20 to 500°C. The glass transition temperature (Tg) was defined as the tangent intersection of the thermal yield point of the polyimide film on a measurement chart with temperature on the horizontal axis and displacement on the vertical axis.

[0104] (5) Measurement of the thermogravimetric temperature (5% weight loss temperature) of the cured polyimide coating film A photosensitive resin composition was rotary coated onto a 6-inch silicon wafer to achieve a cured film thickness of approximately 10 μm. After pre-baking on a hot plate at 110°C for 180 seconds, a cured polyimide coating was obtained by heating in a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh) under a nitrogen atmosphere at 170°C for 2 hours. The film thickness was measured using a film thickness measuring device, Lambda Ace (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating was scraped off, and the temperature at which the weight of the film decreased by 5% (5% weight loss temperature) was measured using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50) when the temperature was raised from room temperature at 10°C / min, with the weight of the film at 170°C being 100%.

[0105] (6) Chemical resistance test of hardened relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation) and dried to form a 10μm thick coating film. This coating film was then subjected to a 500mJ / cm² test using a Prisma GHI (manufactured by Ultratech) with a test pattern mask. 2 The coating was irradiated with energy. Next, the coating was spray-developed using cyclopentanone as the developer with a coater developer (D-Spin 60A, manufactured by SOKUDO), and then rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. A wafer on which the relief pattern was formed on Cu was heated in a nitrogen atmosphere at 170°C for 2 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), thereby obtaining a cured relief pattern on Cu consisting of resin with a thickness of approximately 6-7 μm. The fabricated relief patterns were immersed for 5 minutes in a resist stripping film (ATMI, product name ST-44, main components: 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone) heated to 50°C, washed with running water for 30 minutes, and air-dried. The film surface was then visually inspected with an optical microscope to evaluate chemical resistance based on the presence or absence of damage from the chemical solution, such as cracks, and the rate of change in film thickness after chemical treatment. Chemical resistance was evaluated based on the following criteria. Film thickness change rate (%) = (Film thickness after chemical treatment) - (Film thickness before chemical treatment) / (Film thickness before chemical treatment) × 100 "Excellent": Film thickness change rate is less than 5% relative to the film thickness before immersion in the chemical solution. "Good": Film thickness change rate is 5% or more but less than 10% relative to the film thickness before immersion in the chemical solution. "Acceptable": Film thickness change rate is 10% or more but less than 15% based on the film thickness before immersion in the chemical solution. "Not acceptable": The rate of change in film thickness is 15% or more relative to the film thickness before immersion in the chemical solution.

[0106] (7) Resolution of the hardened relief pattern on Cu On a 6-inch silicon wafer (manufactured by Fujimi Electronics Industries, Ltd., thickness 625±25μm), 200nm thick Ti and 400nm thick Cu were sputtered in that order using a sputtering apparatus (L-440S-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described later was rotary coated onto this wafer using a coater developer (D-Spin60A model, manufactured by SOKUDO Corporation) and dried to form a 10μm thick coating film. This coating film was then subjected to a 500mJ / cm² test using a Prisma GHI (manufactured by Ultratech) with a test pattern mask. 2 The coating was irradiated with energy. Next, the coating was spray-developed using cyclopentanone as the developer with a coater developer (D-Spin 60A, manufactured by SOKUDO), and then rinsed with propylene glycol methyl ether acetate to obtain a relief pattern on Cu. A wafer on which the relief pattern was formed on Cu was heated in a nitrogen atmosphere at 170°C for 2 hours using a temperature-boosting programmable curing furnace (VF-2000 model, manufactured by Koyo Lindbergh), thereby obtaining a cured relief pattern on Cu consisting of resin with a thickness of approximately 6-7 μm. The fabricated relief patterns were observed under an optical microscope to determine the size of the minimum aperture pattern. If the area of ​​the aperture in the obtained pattern was at least half the area of ​​the corresponding pattern mask aperture, it was considered resolved. The length of the mask aperture side corresponding to the smallest resolved aperture was defined as the resolution. "Excellent": Minimum aperture pattern size is less than 10 μm "Good": Minimum aperture pattern size is 10 μm or more and less than 14 μm. "Acceptable": Minimum aperture pattern size is 14 μm or more and less than 18 μm. "Not acceptable": Minimum aperture pattern size is 18 μm or larger.

[0107] (8) Measurement of total chlorine content of resin composition After preparing the photosensitive resin composition, it was allowed to stand at room temperature (23.0°C ± 0.5°C, relative humidity 50% ± 10%) for 3 days, and then the total chlorine content (sum of free chlorine and covalently bonded chlorine) of the resin composition was measured. The photosensitive resin composition was burned and decomposed at 800°C, and the decomposition gas was absorbed into ultrapure water, and the total chlorine content in the resin composition was determined by ion chromatography. The ion chromatography consisted of a Dionex IC-1000 and an IonPac AS12A (4mm) column, and the eluent was a 0.3 mM NaHCO3 / 2.7 mM Na2CO3 aqueous solution, measured at a flow rate of 1.5 mL / min.

[0108] [(A) Production of polyimide precursors] <Production Example 1> Synthesis of Polyimide Precursor A-1 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a 2 L separable flask, and 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. The mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain the reaction mixture. After the exothermic reaction was complete, the reaction mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, 93.0 g of 4,4'-oxydianiline (ODA) suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (polymer A-1). The molecular weight of polymer (A-1) was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was found to be 20,000.

[0109] The weight-average molecular weight of the resins obtained in each manufacturing example was measured using gel permeation chromatography (GPC) under the following conditions, and the weight-average molecular weight in terms of standard polystyrene was determined. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Columns: Shodex KD-806M, 2 in series Mobile phase: 0.1mol / L LiBr / NMP Flow rate: 1mL / min.

[0110] <Production Example 2> Synthesis of Polyimide Precursor A-2 Polymer (A-2) was obtained by carrying out the reaction in the same manner as described in Preparation Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in Preparation Example 1. The molecular weight of polymer (A-2) was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was 26,000.

[0111] <Production Example 3> Synthesis of Polyimide Precursor A-3 The reaction was carried out in the same manner as described in Preparation Example 1, except that 48.7 g of p-phenylenediamine was used instead of 93.0 g of 4,4'-oxydianiline (ODA) as in Preparation Example 1, to obtain polymer (A-3). The weight-average molecular weight (Mw) of polymer (A-3) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 24,000.

[0112] <Production Example 4> Synthesis of Polyimide Precursor A-4 The reaction was carried out in the same manner as described in Preparation Example 1, except that 98.6 g of 4,4'-diamino-2,2'-dimethylbiphenyl was used instead of 93.0 g of 4,4'-oxydianiline (ODA) in Preparation Example 1, to obtain polymer (A-4). The weight-average molecular weight (Mw) of polymer (A-4) was measured by gel permeation chromatography (on a standard polystyrene basis) and was found to be 26,000.

[0113] [(B) Manufacturing of compounds] <Manufacturing Example 5> Synthesis of Epoxy (Meth)acrylate Compound B-1 34.0 g of bisphenol A diglycidyl ether was placed in a 1 L separable flask, and 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and 15.5 g of methacrylic acid were added and the mixture was reacted at 100°C. After confirming that the reaction had proceeded by measuring the acid value, 0.5 g of ion exchange resin IRA96SB was added and the mixture was stirred overnight. The process of filtering out the ion exchange resin was repeated three times to obtain B-1, which mainly consists of {[propane-2,2-diylbis(4,1-phenylene)]bis(oxy)}bis(2-hydroxypropane-3,1-diyl)=dimethacrylate.

[0114] <Manufacturing Example 6> Synthesis of Epoxy (Meth)acrylate Compound B-2 Except for using 13.0 g of acrylic acid instead of 15.5 g of methacrylic acid, the reaction was carried out in the same manner as described in Production Example 5 above to obtain B-2, which mainly consists of {[propane-2,2-diylbis(4,1-phenylene)]bis(oxy)}bis(2-hydroxypropane-3,1-diyl)=diacrylate.

[0115] <Manufacturing Example 7> Synthesis of Epoxy (Meth)acrylate Compound B-3 The reaction was carried out in the same manner as described in Production Example 5 above, except that 17.42 g of ethylene glycol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-3, which mainly consists of 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane.

[0116] <Manufacturing Example 8> Synthesis of Epoxy (Meth)acrylate Compound B-4 The reaction was carried out in the same manner as described in Production Example 5 above, except that 17.42 g of ethylene glycol diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, to obtain B-4, which mainly consists of 1,2-bis(3-acryloyloxy-2-hydroxypropoxy)ethane.

[0117] <Manufacturing Example 9> Synthesis of Epoxy (Meth)acrylate Compound B-5 The reaction was carried out in the same manner as described in Production Example 5 above, except that 23.23 g of glycerin diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-5, which mainly consists of glycerol 1,3-diglycerolate dimethacrylate.

[0118] <Manufacturing Example 10> Synthesis of Epoxy (Meth)acrylate Compound B-6 The reaction was carried out in the same manner as described in Production Example 5 above, except that 23.23 g of glycerin diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, to obtain B-6, which mainly consists of glycerol 1,3-diglycerolate diacrylate.

[0119] <Manufacturing Example 11> Synthesis of Epoxy (Meth)acrylate Compound B-7 The reaction was carried out in the same manner as described in Production Example 5 above, except that 31.24 g of bisphenol F type epoxy was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-7, which mainly consists of bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl)]methane.

[0120] <Manufacturing Example 12> Synthesis of Epoxy (Meth)acrylate Compound B-8 The reaction was carried out in the same manner as described in Production Example 5 above, except that 15.02 g of glycidylphenyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-8, which mainly consists of 2-hydroxy-3-phenoxypropyl methacrylate.

[0121] <Manufacturing Example 13> Synthesis of Epoxy (Meth)acrylate Compound B-9 The reaction was carried out in the same manner as described in Production Example 5 above, except that 15.02 g of glycidylphenyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, and 13.0 g of acrylic acid was used instead of 15.5 g of methacrylic acid, to obtain B-9, which mainly consists of 2-hydroxy-3-phenoxypropyl acrylate.

[0122] <Manufacturing Example 14> Synthesis of Epoxy (Meth)acrylate Compound B-10 The reaction was carried out in the same manner as described in Production Example 5 above, except that 35.3 g of hydrogenated bisphenol A diglycidyl ether was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-10, which mainly consists of 2,2-bis[4-(2-hydroxy-3-methacryloxy-1-propoxy)phenyl]propane.

[0123] <Manufacturing Example 15> Synthesis of Epoxy (Meth)acrylate Compound B-11 The reaction was carried out in the same manner as described in Production Example 5 above, except that 46.25 g of 9,9-bis[4-(2-glycidylethoxy)phenyl]fluorene was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-11, which mainly consists of 4,4'-(9-fluorenylidene)bis(2-hydroxy-3-phenoxypropyl methacrylate).

[0124] <Manufacturing Example 16> Synthesis of Epoxy (Meth)acrylate Compound B-12 The reaction was carried out in the same manner as described in Production Example 5 above, except that 24.30 g of 1,6-bis(glycidyloxy)naphthalene was used instead of 34.0 g of bisphenol A diglycidyl ether, to obtain B-12, which mainly consists of 1,6-bis(3-methacryloyloxy-2-hydroxypropyloxy)naphthalene.

[0125] <Manufacturing Example 17> Synthesis of Epoxy (Meth)acrylate Compound B-13 34.0 g of bisphenol A diglycidyl ether was placed in a 1 L separable flask, and 0.4 g of dimethylaniline, 0.04 g of p-methoxyphenol, and 17.4 g of methacrylic acid were added and the reaction was carried out at 100°C. The reaction proceeded as confirmed by measuring the acid value, and without removing free chlorine with an ion exchange resin, B-13 was obtained, mainly composed of {[propane-2,2-diylbis(4,1-phenylene)]bis(oxy)}bis(2-hydroxypropane-3,1-diyl)=dimethacrylate.

[0126] [Manufacturing of photosensitive resin compositions] <Example 1> A negative-type photosensitive resin composition was prepared using polyimide precursor A-1 by the following method, and the prepared composition was evaluated. (A) 100 g of A-1 as the polyimide precursor, (B) 10 g of B-1 as the epoxy (meth)acrylate compound, (C) 5 g of 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime (hereinafter referred to as PDO) as the photopolymerization initiator, (F) 5 g of tetraethylene glycol dimethacrylate (hereinafter referred to as M4G) as the monomer, were dissolved in (D) 100 g of γ-butyrolactone (hereinafter referred to as GBL). The viscosity of the resulting solution was adjusted to approximately 40 poise by adding a small amount of GBL to obtain the negative-type photosensitive resin composition. From the above procedure, (E) the amount of free chlorine and total chlorine in the photosensitive resin composition, as well as the amount of free chlorine contained in the cured film, were adjusted. The composition was evaluated according to the method described above. The results are shown in Table 1.

[0127] <Examples 2-18, Comparative Examples 1-4> A negative-type photosensitive resin composition was prepared in the same manner as in Example 1, except that it was prepared using the mixing ratios shown in Table 1, and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[0128] [Table 1]

[0129] [Table 2]

[0130] As is clear from Tables 1 and 2, the photosensitive resin composition of Example 1 had a glass transition temperature of 210°C, a 5% weight loss temperature of 300°C, resolution of "excellent," and chemical resistance of "excellent." Similarly, the photosensitive resin compositions of Examples 2 to 10 all had a glass transition temperature of 195°C or higher, a 5% weight loss temperature of 290°C or higher, resolution of "acceptable" or better, and chemical resistance of "acceptable" or better.

[0131] In contrast, in Comparative Example 1, the resolution was "excellent," but the glass transition temperature was 170°C and the 5% weight loss temperature was 260°C. As a result of the chemical resistance test, the rate of change in film thickness was 20% compared to the film thickness before immersion, and the evaluation was "unacceptable." In Comparative Example 2, the glass transition temperature was 210°C, the 5% weight loss temperature was 300°C, and the resolution was "good," but the chemical resistance changed by 15%, and the evaluation was "unacceptable." In Comparative Example 3, the glass transition temperature was 200°C and the 5% weight loss temperature was 300°C, but the resolution was "unacceptable." In Comparative Example 4, the chemical resistance was "unacceptable."

[0132] While embodiments of the present invention have been described above, the present invention is not limited thereto and can be modified as appropriate without departing from the spirit of the invention. [Industrial applicability]

[0133] By using the photosensitive resin composition according to the present invention, it is possible to improve the glass transition temperature and 5% weight loss temperature, and enhance chemical resistance, while maintaining high resolution in a cured film treated at low temperatures. Therefore, the photosensitive resin composition according to the present invention can be suitably used in the field of photosensitive materials useful in the manufacture of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) Polyimide precursor and (B) Compounds having a hydroxyl group and a polymerizable unsaturated bond, (C) Photosensitive material, (D) Solvent and (E) Free chlorine, and optionally covalent chlorine, A photosensitive resin composition comprising, The amount of free chlorine is 0.0001 to 2 ppm based on the total mass of the photosensitive resin composition, and the total amount of chlorine in the photosensitive resin composition after being left to stand for 3 days at 23°C ± 0.5°C and 50% ± 10% relative humidity is 0.0001 to 600 ppm based on the total mass of the photosensitive resin composition. The compound (B) has only one or two polymerizable unsaturated bonds within the same molecule. The (A) polyimide precursor is a photosensitive resin composition represented by the following general formula (1). 【Chemistry 1】 {In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1 and R2 is the following general formula (2): 【Chemistry 2】 The group is represented by formula (2), where R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.

2. The photosensitive resin composition according to claim 1, wherein the (C) photosensitive agent is a photopolymerization initiator.

3. The photosensitive resin composition according to claim 1 or 2, comprising 100 to 860 parts by mass of the solvent (D) with respect to 100 parts by mass of the polyimide precursor (A).

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent (D) comprises one or more compounds selected from the group consisting of N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and 2-octanone.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond has two polymerizable unsaturated bonds.

6. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond is a reaction product of an epoxy resin and (meth)atacrylic acid.

7. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (3) or (4). 【Transformation 3】 {In formula (3), R １ This is a monovalent organic group having 1 to 40 carbon atoms. 【Chemistry 4】 {In formula (4), R ２ This is a monovalent organic group having 1 to 40 carbon atoms.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond is represented by the following general formula (5) or (6). 【Transformation 5】 {In formula (5), R ３ This is a monovalent organic group having 1 to 40 carbon atoms. 【Transformation 6】 {In formula (6), R ４ This is a monovalent organic group having 1 to 40 carbon atoms.

9. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond (B) includes a compound represented by the following general formula (7). 【Transformation 7】 {In formula (7), R 2 This is a divalent organic group having 1 to 40 carbon atoms.

10. The photosensitive resin composition according to any one of claims 1 to 4, wherein the compound having a hydroxyl group and a polymerizable unsaturated bond (B) includes a compound represented by the following general formula (8). 【Transformation 8】 {In formula (8), R 6 This is a divalent organic group having 1 to 40 carbon atoms.

11. (A) Polyimide precursor and (B) Compounds having a hydroxyl group and a polymerizable unsaturated bond, (C) Photosensitive material, (D) Solvent and (E) Free chlorine, and optionally covalent chlorine A photosensitive resin composition comprising, When the photosensitive resin composition is applied to a substrate by a rotational method to a cured film thickness of approximately 10 μm, and cured by heating on a hot plate at 110°C for 180 seconds, the amount of free chlorine contained in the resulting coating film is 0.0001 to 5 ppm based on the total mass of the coating film, and when the photosensitive resin composition is left to stand for 3 days at 23°C ± 0.5°C and a relative humidity of 50% ± 10% after preparation, the total amount of chlorine in the photosensitive resin composition is 0.0001 to 600 ppm based on the total mass of the photosensitive resin composition. The (B) compound has only one or two polymerizable unsaturated bonds within the same molecule, and the (A) polyimide precursor is represented by the following general formula (1), in a photosensitive resin composition. 【Chemistry 9】 {In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1 and R2 is the following general formula (2): 【Chemistry 10】 The group is represented by formula (2), where R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.

12. (G) The photosensitive resin composition according to any one of claims 1 to 11, further comprising an epoxy resin.

13. The photosensitive resin composition according to claim 12, wherein the amount of (G) epoxy resin is 0.1 to 10 parts by mass per 100 parts by mass of the (A) polyimide precursor.

14. A photosensitive resin composition according to any one of claims 1 to 13, which is a negative-type photosensitive resin composition.

15. (A) Polyimide precursor and (B) Compounds having a hydroxyl group and multiple polymerizable unsaturated bonds, (C) Photosensitive material, (D) Solvent and (E) Free chlorine and / or covalent chlorine, A photosensitive resin composition comprising, After preparing the photosensitive resin composition, the total chlorine content in the photosensitive resin composition after standing for 3 days at 23°C ± 0.5°C and 50% ± 10% relative humidity is 0.0001 to 250 ppm based on the total mass of the photosensitive resin composition. The (B) compound has only two polymerizable unsaturated bonds within the same molecule, and the (A) polyimide precursor is represented by the following general formula (1), and is a photosensitive resin composition. 【Chemistry 11】 {In formula (1), X1 is a tetravalent organic group having 6 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, n1 is an integer from 2 to 150, and R1 and R2 are each independently a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms. However, at least one of R1 and R2 is the following general formula (2): 【Chemistry 12】 The group is represented by formula (2), where R3, R4, and R5 are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m1 is an integer from 2 to 10.

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