Photosensitive resin composition and method for producing cured relief pattern

Abstract

The present disclosure aims to provide a photosensitive resin composition that has excellent chemical resistance, exhibits good elongation even at low curing temperatures, and is capable of producing a cured relief pattern that has good adhesion to copper wiring, and a method for producing a cured relief pattern using the photosensitive resin composition. (A) a soluble polyimide; (B) a photopolymerization initiator; and (C) an organic solvent. The photosensitive resin composition comprises the above-mentioned (C) organic solvent, wherein the (C) organic solvent contains 40 mass % or more of N-ethyl-2-pyrrolidone and 20 mass % or less of an organic solvent having a boiling point of less than 140°C, based on the total mass of the (C) organic solvent.

Description

[Technical Field]

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

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have traditionally been used as insulating materials for electronic components, and as passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursor compositions can easily form heat-resistant relief pattern films by applying the composition, exposing it to light, developing it, and subjecting it to a thermal imidization treatment involving curing. Such photosensitive polyimide precursor compositions have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimide materials.

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

[0004] To address this issue, flip-chip packaging has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on the rewiring layer, and then the chip is flipped over and directly mounted on a printed circuit board. Flip-chip packaging, which allows for precise control of wiring distance, is being adopted for high-end devices that handle high-speed signals, and for mobile phones and other devices due to its small packaging size. Demand for this technology is rapidly expanding. Furthermore, a semiconductor chip packaging technology called fan-out wafer-level packaging (FOWLP) has recently been proposed, in which individual chips are manufactured by dicing a pre-processed wafer, reassembled on a support, encapsulated with a molded resin, and then a rewiring layer is formed after the support is peeled off (see, for example, Patent Document 1). FOWLP offers the advantages of reducing the height of the package while also achieving high-speed transmission and low cost.

[0005] When forming the package, the photosensitive resin composition is generally patterned and then heat-cured, but if the shrinkage during heat-curing is large, problems such as loss of film flatness may occur. To solve this problem, a resin composition using a solvent-soluble polyimide has been proposed (for example, Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-167191 [Patent Document 2] Patent Publication No. 2021-162834 Summary of the Invention [Problem to be solved by the invention]

[0007] However, to make polyimides solvent-soluble, fluorine atoms or the like are generally introduced into the main chain structure, or acid dianhydrides or diamine monomers with large molecular weights are used, but such polyimides tend to have poor chemical resistance. Furthermore, while adhesion between copper wiring and polyimide layers is important, photosensitive resin compositions using soluble polyimides have the problem of poor adhesion to copper. Furthermore, lowering the curing temperature of polyimide-containing photosensitive resin compositions or patterns formed using them has the problem of reduced elongation.

[0008] Therefore, an object of the present disclosure is to provide a photosensitive resin composition that has excellent chemical resistance, exhibits good elongation even at low curing temperatures, and is capable of producing a cured relief pattern that has good adhesion to copper wiring, and a method for producing a cured relief pattern using the photosensitive resin composition. [Means for solving the problem]

[0009] The present inventors have found that the above-mentioned problems can be solved by combining a soluble polyimide, a photopolymerization initiator, and a specific solvent. Examples of embodiments of the present disclosure are listed below. <1> (A) a soluble polyimide; (B) a photopolymerization initiator; (C) an organic solvent; A photosensitive resin composition comprising: The photosensitive resin composition contains 40% by mass or more of N-ethyl-2-pyrrolidone in the (C) organic solvent, and 20% by mass or less of an organic solvent having a boiling point of less than 140°C, based on the total mass of the (C) organic solvent. <2> 2. The photosensitive resin composition according to item 1, wherein the (A) soluble polyimide does not contain a fluorine atom. <3> 3. The photosensitive resin composition according to item 1 or 2, further comprising (D) a nitrogen-containing heterocyclic compound. <4> 4. The photosensitive resin composition according to any one of items 1 to 3, further comprising (E) a photopolymerizable unsaturated monomer. <5> 5. The photosensitive resin composition according to item 4, wherein the (E) photopolymerizable unsaturated monomer has three or more (meth)acrylic groups in the molecule. <6> 6. The photosensitive resin composition according to any one of items 1 to 5, further comprising (F) a thermal crosslinking agent. <7> 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the (C) organic solvent further comprises (C-2) at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-valerolactone, and tetramethylurea. <8> 7. The photosensitive resin composition according to any one of items 1 to 6, wherein the (C) organic solvent further contains (C-2) at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N,N-dimethylpropanamide. <9> 9. The photosensitive resin composition according to any one of items 1 to 8, wherein the (A) soluble polyimide has a photopolymerizable functional group at a main chain terminal and / or a main chain side chain. <10> The (A) soluble polyimide is represented by the following general formula (1): [ka] {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, and Y represents a divalent organic group having 4 to 40 carbon atoms.} 10. The photosensitive resin composition according to any one of items 1 to 9, represented by the following formula: <11> The X is represented by the following general formulas (2) to (6): [ka] [ka] [ka] [ka] [ka] Item 11. The photosensitive resin composition according to item 10, wherein the photosensitive resin composition is at least one selected from the group consisting of: <12> The Y is represented by the following general formulas (7) to (9): [ka] [ka] [ka] Item 12. The photosensitive resin composition according to item 10 or 11, wherein the photosensitive resin composition is at least one selected from the group consisting of: <13> 13. The photosensitive resin composition according to any one of items 1 to 12, wherein the (B) photopolymerization initiator is an oxime compound. <14> The (B) photopolymerization initiator is represented by the following general formula (19) or (20): [ka] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group having 1 to 20 carbon atoms, Rc represents a monovalent organic group having 1 to 10 carbon atoms, and Rd represents a monovalent organic group having 1 to 10 carbon atoms} [ka] {wherein Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms} 14. The photosensitive resin composition according to any one of items 1 to 13, represented by the following formula: <15> 4. The photosensitive resin composition according to item 3, wherein the (D) nitrogen-containing heterocyclic compound is a triazole compound, a tetrazole compound, or a purine compound. <16> 16. A method for producing a polyimide, comprising a step of curing the photosensitive resin composition according to any one of items 1 to 15 to form a polyimide. <17> The following steps: (1) A step of applying the photosensitive resin composition according to any one of items 1 to 15 to a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising: [Effects of the Invention]

[0010] According to the present disclosure, there are provided a photosensitive resin composition that has excellent chemical resistance, exhibits good elongation even at low curing temperatures, and is capable of producing a cured relief pattern that has good adhesion to copper wiring, and a method for producing a cured relief pattern using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] <Photosensitive resin composition> The photosensitive resin composition of the present disclosure comprises: (A) a soluble polyimide; (B) a photopolymerization initiator; and (C) an organic solvent, wherein the (C) organic solvent contains 40 mass % or more of N-ethyl-2-pyrrolidone and 20 mass % or less of an organic solvent having a boiling point of less than 140°C, based on the total mass of the (C) organic solvent.

[0012] (A) Soluble polyimide The soluble polyimide (A) according to this embodiment is not limited as long as it dissolves in a common organic solvent, but it is preferable that it dissolves in an amount of 5 mass % or more in N-ethyl-2-pyrrolidone used in this embodiment.

[0013] The soluble polyimide (A) according to the present embodiment is not limited as long as it dissolves in a common organic solvent, but it is preferable that it does not contain fluorine atoms from the viewpoint of chemical resistance and elongation.

[0014] From the viewpoint of chemical resistance, the soluble polyimide (A) according to the present embodiment preferably has a photopolymerizable functional group at the end of the main chain and / or at a side chain of the main chain. When the soluble polyimide (A) has the photopolymerizable functional group, resolution can be improved.

[0015] Here, the photopolymerizable functional group is not limited as long as it is a functional group that can be polymerized by light irradiation. Examples of such functional groups include a methacryloyl group, an acryloyl group, a methacrylamide group, an acrylamide group, and a styryl group. From the viewpoint of resolution, at least one selected from a methacryloyl group, an acryloyl group, and a styryl group is preferred.

[0016] The term "main chain terminal" in this embodiment refers to the terminal structure of the soluble polyimide main chain composed of an acid dianhydride and a diamine. Polycondensation can be carried out after introducing a photopolymerizable functional group into the acid dianhydride and / or the diamine, or the photopolymerizable functional group can be introduced into the terminal structure after obtaining the soluble polyimide.

[0017] The "main chain side chain" in this embodiment refers to a side chain structure of a soluble polyimide main chain composed of an acid dianhydride and a diamine. Polycondensation can be carried out after introducing a photopolymerizable functional group into the acid dianhydride and / or the diamine, or the photopolymerizable functional group can be introduced into the side chain structure after obtaining a soluble polyimide.

[0018] The soluble polyimide (A) according to the present embodiment is represented by the following general formula (1): [ka] {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, and Y represents a divalent organic group having 4 to 40 carbon atoms.} It can be expressed as:

[0019] In general formula (1), X is not limited as long as it is a tetravalent organic group having 4 to 32 carbon atoms, but from the viewpoint of chemical resistance, it preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and particularly preferably 10 or more carbon atoms. From the viewpoint of resolution, the number of carbon atoms in X is preferably 30 or less, more preferably 28 or less, and particularly preferably 26 or less.

[0020] In general formula (1), Y is not limited as long as it is a divalent organic group having 4 to 40 carbon atoms, but from the viewpoint of chemical resistance, it preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and particularly preferably 10 or more carbon atoms. From the viewpoint of resolution, the number of carbon atoms in Y is preferably 30 or less, more preferably 28 or less, and particularly preferably 26 or less.

[0021] X according to the present embodiment preferably has an aromatic group, and more preferably contains at least one selected from the group consisting of structures represented by the following general formulas (2) to (6). [ka] [ka] [ka] [ka] [ka] From the viewpoint of the glass transition temperature (Tg) after heat curing, the structures represented by the above formulas (3) and (4) are preferred, and from the viewpoint of the elongation after heat curing, the structures represented by the formulas (2) and (5) are preferred.

[0022] Y according to this embodiment preferably has an aromatic group, and more preferably contains at least one selected from the group consisting of structures represented by the following general formulas (7) to (9). [ka] [ka] [ka]

[0023] The photosensitive resin composition may further contain, in addition to (A) the soluble polyimide, (A') a polyimide precursor containing a structural unit represented by the following general formula (1'). [ka] {In formula (1'), X1 is a tetravalent organic group having 4 to 40 carbon atoms, Y1 is a divalent organic group having 6 to 40 carbon atoms, and R1 and R2 are each independently selected from the group consisting of a hydroxyl group and a monovalent organic group having 1 to 40 carbon atoms.}

[0024] In the general formula (1'), the organic group may be an organic group containing a heteroatom other than carbon and hydrogen, or may be an organic group consisting of carbon and hydrogen atoms. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. When the photosensitive resin composition further contains (A') a polyimide precursor, the amount of the polyimide precursor may be more than 0 but less than 100% by mass, preferably more than 0 but less than 50% by mass, more preferably more than 0 but less than 20% by mass, and even more preferably more than 0 but less than 10% by mass, based on the total amount of the soluble polyimide (A) and the polyimide precursor (A').

[0025] At least one of R1 and R2 in the general formula (1') is preferably a group further containing a polymerizable group selected from the group consisting of an acid-polymerizable group, a base-polymerizable group, and a radical-polymerizable group, where the acid-polymerizable group, the base-polymerizable group, and the radical-polymerizable group refer to groups that can be polymerized by the action of an acid, a base, or a radical, respectively.

[0026] (A) Method for preparing soluble polyimides (A) A method for preparing a soluble polyimide is, for example: a tetracarboxylic acid dianhydride containing the tetravalent organic group X; A soluble polyimide can be obtained by polycondensing the diamine containing the divalent organic group Y to obtain a polyamic acid, followed by heat treatment.

[0027] (Preparation of Polyamic Acid) (A) The tetracarboxylic acid dianhydride containing a tetravalent organic group X, which is suitably used for preparing the polyamic acid that is the precursor of the soluble polyimide, is represented by the following formula (1T): [ka] {In the above formula (1T), X is defined as in the above general formula (1).} A compound represented by the following formula is preferred.

[0028] Preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxydiphthalic dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. More preferred examples of the tetracarboxylic dianhydride include pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, and the compounds represented by the following general formulae (2T) to (6T), but are not limited to these. These may be used alone or in combination of two or more. Among these, the acid dianhydrides represented by the following general formulae (2T) to (6T) are preferred. [ka] [ka] [ka] [ka] [ka]

[0029] The diamine containing a divalent organic group Y includes a diamine represented by the following formula (1D): H2N-Y-NH2(1D) {wherein Y is as defined in general formula (1) above.} A compound represented by the following formula is preferred.

[0030] More preferred diamines include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxydianiline, abbreviated as "ODA"), 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- 4,4-bis(4-aminophenoxy)phenyl] sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and those in which some of the hydrogen atoms on the benzene ring are substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, or the like, such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,Examples include, but are not limited to, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the following general formulae (7D) to (9D). These can be used alone, or two or more of them can be mixed and used. Among these, the following formulae (7D) to (9D) are preferred. [ka] [ka] [ka]

[0031] The polyamic acid can be obtained by dissolving and mixing the tetracarboxylic dianhydride and the diamine, preferably in a solvent as described below, at a temperature of 10 to 50°C and preferably with stirring for 4 to 10 hours. The resulting polyamic acid can be isolated before the imidization reaction, or can be subjected to the next imidization reaction without isolation.

[0032] (Preparation of Soluble Polyimides) The polyamic acid obtained above can be reacted at high temperature, optionally with an imidization catalyst, to obtain a soluble polyimide. Preferably, the reaction is carried out in a glass vessel equipped with a Dean-Stark apparatus, by mixing with toluene or xylene, an azeotropic solvent with water. The reaction conditions are not limited as long as the desired soluble polyimide is obtained, but the reaction temperature is preferably 150 to 230°C, and stirring is preferably continued for 4 to 10 hours.

[0033] After the soluble polyimide reaction is complete, the resulting polymer component can be cooled to about room temperature and then poured into a poor solvent to precipitate the polymer component. The polymer can then be purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired soluble polyimide. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion exchange resin, a cation exchange resin, or both, swollen with an appropriate organic solvent to remove ionic impurities.

[0034] The molecular weight of the soluble polyimide (A), as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight average molecular weight of 8,000 or more provides good mechanical properties, while a weight average molecular weight of 150,000 or less provides good dispersibility in a developer and good relief pattern resolution. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent standard sample "STANDARD SM-105" manufactured by Showa Denko K.K.

[0035] Examples of the soluble polyimide according to this embodiment include those having at least one of the structures represented by the following formulas (10) to (12) as a repeating unit. [ka] [ka] [ka]

[0036] (B) Photopolymerization initiator The photosensitive resin composition contains (B) a photopolymerization initiator, which is preferably a photoradical polymerization initiator or a photoacid generator.

[0037] Examples of the photoradical polymerization initiator include benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone compounds such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl compounds such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin compounds such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, and 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime; Examples of suitable oxime compounds include oxime compounds such as 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), and 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(o-acetyloxime); N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazole compounds; and titanocene compounds.

[0038] A preferred example of the photoacid generator is α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0039] The (B) photopolymerization initiator is not limited to the above examples. Among the above photopolymerization initiators, photoradical polymerization initiators are more preferred, and oxime compounds are even more preferred, particularly from the viewpoint of photosensitivity.

[0040] From the viewpoint of resolution, the oxime compound is preferably at least one selected from the group consisting of the following general formulae (19), (20) and (21). [ka] {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group having 1 to 20 carbon atoms, Rc represents a monovalent organic group having 1 to 10 carbon atoms, and Rd represents a monovalent organic group having 1 to 10 carbon atoms.} [ka] {In the formula, Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms.} [ka] {In the formula, Rg represents a monovalent organic group having 1 to 20 carbon atoms, Rh represents a monovalent organic group having 1 to 10 carbon atoms, and Ri represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.}

[0041] In general formula (19), Ra is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms; from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group. Rb is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms; from the viewpoint of resolution, it is preferably an aromatic group having 6 to 20 carbon atoms or a monovalent organic group derived from a heterocyclic compound having 5 to 20 carbon atoms. Rc is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms; among these, from the viewpoint of resolution, a monovalent organic group containing a saturated alicyclic structure having 3 to 10 carbon atoms is preferred. Rd is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms; among these, from the viewpoint of resolution, an organic group having 1 to 3 carbon atoms is preferred, and more preferably a methyl group, an ethyl group, or a propyl group.

[0042] In general formula (20), Re is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms, and from the viewpoint of resolution, it is preferably an organic group having 5 to 20 carbon atoms, and more preferably an organic group having 6 to 15 carbon atoms. Rf is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, and from the viewpoint of resolution, it is preferably an organic group having 1 to 3 carbon atoms, and more preferably a methyl group, ethyl group, or propyl group.

[0043] In general formula (21), Rg is not limited as long as it is a monovalent organic group having 1 to 20 carbon atoms, but from the viewpoint of heat resistance, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group. Rh is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a group having 2 to 9 carbon atoms, and more preferably a group having 2 to 8 carbon atoms. Ri is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, but from the viewpoint of resolution, it is preferably a hydrogen atom or a monovalent organic group having 1 to 9 carbon atoms.

[0044] Among the general formulae (19) to (21), the structure represented by the general formula (19) or (20) is more preferable in terms of resolution.

[0045] The blending amount of the (B) photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of the (A) soluble polyimide. The blending amount is preferably 0.1 part by mass or more, based on 100 parts by mass of the (A) soluble polyimide, from the viewpoint of photosensitivity or patterning ability, and is preferably 20 parts by mass or less, from the viewpoint of the physical properties of the photosensitive resin layer after curing of the negative photosensitive resin composition.

[0046] (C) Organic solvent The photosensitive resin composition according to this embodiment contains (C) an organic solvent, and contains 40 mass % or more of N-ethyl-2-pyrrolidone and 20 mass % or less of organic solvents having a boiling point of less than 140° C. The use of the organic solvent according to this embodiment makes it possible to obtain a photosensitive resin composition that has good chemical resistance, exhibits good elongation even at low curing temperatures, and is capable of producing a cured relief pattern that has good adhesion to copper wiring.

[0047] In this embodiment, the content of (C-1) N-ethyl-2-pyrrolidone is 40% by mass or more, based on the total mass of the organic solvent (C), and the content of an organic solvent having a boiling point of less than 140°C is 20% by mass or less. It is unclear whether this contributes to good chemical resistance, good elongation even at low curing temperatures, and good adhesion to copper wiring. However, the present inventors believe as follows. Specifically, to make a soluble polyimide solvent-soluble, the imide group concentration must be reduced. Therefore, the interaction between imide groups in the polymer is reduced compared to general polyimides, making it difficult to achieve chemical resistance and elongation. This tendency becomes particularly pronounced as the heat curing temperature decreases. Since (C-1) N-ethyl-2-pyrrolidone according to this embodiment has a moiety capable of interacting with imide groups and a boiling point of 218°C, some of it remains in the film when the heat curing temperature is 170°C to 230°C, causing packing between the polymers and resulting in good chemical resistance and elongation. Furthermore, since some N-ethyl-2-pyrrolidone remains in the film, the film has sites that can interact with both the polymer and copper, thereby improving copper adhesion. The above-described effects are more pronounced when the photosensitive resin composition contains the nitrogen-containing heterocyclic compound (D) shown below.

[0048] The N-ethyl-2-pyrrolidone remains sufficiently in the film when the total organic solvent contains 40% by mass or more of N-ethyl-2-pyrrolidone, and the content of N-ethyl-2-pyrrolidone is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 75% by mass or more, based on the total mass of the organic solvent (C).

[0049] From the viewpoint of developability, the content of N-ethyl-2-pyrrolidone is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less, based on the total mass of the (C) organic solvent.

[0050] Furthermore, the effects of the present invention are fully exhibited when the content of the organic solvent having a boiling point of less than 140°C is 20% by mass or less, based on the total mass of the organic solvent (C). If the content of the organic solvent having a boiling point of less than 140°C exceeds 20% by mass, based on the total mass of the organic solvent (C), it is expected that the above-mentioned effects will not be achieved because the amount of N-ethyl-2-pyrrolidone remaining will be insufficient. From this perspective, the content of the organic solvent having a boiling point of less than 140°C is preferably 15% by mass or less, and particularly preferably 10% by mass or less, based on the total mass of the organic solvent (C).

[0051] Examples of organic solvents having a boiling point of less than 140°C include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, methyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, dichloroethane, chlorobenzene, hexane, heptane, benzene, and toluene.

[0052] The solvent according to the present embodiment may contain other solvents (C-2) to the extent that they do not adversely affect performance. Examples of other solvents include amides, sulfoxides, urea and its derivatives, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols. Specific examples of other solvents that may be used include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, cyclohexanone, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, 1,4-dichlorobutane, o-dichlorobenzene, anisole, xylene, and mesitylene.

[0053] When other solvents are contained, the other solvents are preferably at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-valerolactone, and tetramethylurea, from the viewpoint of copper adhesion.

[0054] When other solvents are contained, the content of the other solvents is preferably 50% by mass or less, more preferably 30% by mass or less, particularly preferably 15% by mass or less, even more preferably 10% by mass or less, and most preferably 5% by mass or less, with the total amount of solvents being 100% by mass.

[0055] (D) Nitrogen-containing heterocyclic compound The photosensitive resin composition according to the present embodiment may contain (D) a nitrogen-containing heterocyclic compound, which, due to the synergistic effect with the N-ethyl-2-pyrrolidone, further improves copper adhesion.

[0056] The nitrogen-containing heterocyclic compound according to the present embodiment is not limited as long as it is a heterocyclic compound containing a nitrogen atom. From the viewpoint of a synergistic effect with the (C) organic solvent or improvement in copper adhesion, however, a triazole compound, a tetrazole compound, or a purine compound is preferable, and a purine compound is more preferable.

[0057] Specific examples of the triazole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, and 2-(5-methyl-2-hydroxyphenyl)benzotriazole. benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, and 5-carboxy-1H-benzotriazole.

[0058] Specific examples of the tetrazole compound include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0059] Specific examples of purine compounds include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 2-hydroxy ... 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, 8-aminoadenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9-methyladenine, 9 aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and the like, and derivatives thereof.

[0060] When the photosensitive resin composition contains (D) a nitrogen-containing heterocyclic compound, the blending amount is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, for example, 0.01 to 5 parts by mass, based on 100 parts by mass of (A) soluble polyimide. When the blending amount of (D) a nitrogen-containing heterocyclic compound is 0.01 part by mass or more based on 100 parts by mass of (A) soluble polyimide, copper adhesion is further improved when the photosensitive resin composition is formed on copper or a copper alloy, while when the blending amount is 20 parts by mass or less, resolution is further improved.

[0061] (E) Photopolymerizable unsaturated monomer The photosensitive resin composition may contain (E) a photopolymerizable unsaturated monomer to improve the resolution of the relief pattern. The photopolymerizable unsaturated monomer refers to a monomer having a photopolymerizable unsaturated bond, which undergoes a radical polymerization reaction in the presence of a photopolymerization initiator. Such a monomer is preferably a (meth)acrylic compound, and examples thereof include, but are not limited to, monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of ethylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polyethylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of propylene glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of polypropylene glycol; monoacrylate, diacrylate, triacrylate, monomethacrylate, dimethacrylate, and trimethacrylate of glycerol; diacrylate and dimethacrylate of cyclohexanedimethanol; and diacrylate of 1,4-butanediol. acrylates and dimethacrylates; diacrylates and dimethacrylates of 1,6-hexanediol; diacrylates and dimethacrylates of neopentyl glycol; monoacrylate, diacrylate, monomethacrylate, and dimethacrylate of bisphenol A; benzene trimethacrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate, and tetramethacrylate of pentaerythritol; and ethylene oxide adducts or propylene oxide adducts of these compounds.

[0062] Among these, (E) the photopolymerizable unsaturated monomer preferably has two or more (meth)acrylic groups in the molecule, and more preferably has three or more (meth)acrylic groups, from the viewpoint of improving chemical resistance.

[0063] When the photosensitive resin composition contains the above-mentioned (E) photopolymerizable unsaturated monomer for improving the resolution of the relief pattern, the blending amount of the (E) photopolymerizable unsaturated monomer is preferably 1 to 50 parts by mass based on 100 parts by mass of the (A) soluble polyimide.

[0064] (F) Thermal crosslinking agent The photosensitive resin composition may contain a thermal crosslinking agent (F) to improve chemical resistance and increase the glass transition temperature. Examples of thermal crosslinking agents include compounds that undergo an addition reaction or a condensation polymerization reaction when heated. The reaction of a substance corresponding to the thermal crosslinking agent (F) with the soluble polyimide (A) according to this embodiment improves chemical resistance and increases the glass transition temperature. It is preferable that the photosensitive resin composition contains a photopolymerizable unsaturated monomer (E), because the reaction between the component (E) and the component (F) can further improve chemical resistance and the glass transition temperature.

[0065] The reaction initiation temperature of the (F) thermal crosslinking agent is not limited, but is preferably 130°C or higher, more preferably 140°C or higher, and particularly preferably 150°C or higher.

[0066] Examples of the (F) thermal crosslinking agent include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and blocked isocyanate compounds.

[0067] The alkoxymethyl compound includes compounds of the following formula: [ka] [ka] Examples of the compound include compounds represented by the following formula:

[0068] Examples of epoxy compounds include epoxy compounds containing a bisphenol A group and hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.).

[0069] Examples of the oxetane compound include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, bis(3-ethyl-3-oxetanylmethyl) ) diphenoate, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, poly[[3-[(3-ethyl-3-oxetanyl)methoxy]propyl]silasesquioxane] derivatives, oxetanyl silicate, phenol novolac-type oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, OXT121 (manufactured by Toagosei, trade name), and OXT221 (manufactured by Toagosei, trade name).

[0070] Examples of bismaleimide compounds include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3- phenylene bis(maleimide), N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0071] Examples of allyl compounds include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allylphenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0072] Examples of the blocked isocyanate compound include hexamethylene diisocyanate-based blocked isocyanates (e.g., Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882N manufactured by Mitsui Chemicals, Inc., and 7960, 7961, 7982, 7991, and 7992 manufactured by Baxenden), tolylene diisocyanate-based blocked isocyanates (e.g., Takenate B-830 manufactured by Mitsui Chemicals, Inc.), ), 4,4'-diphenylmethane diisocyanate-based blocked isocyanates (e.g., Takenate B-815N manufactured by Mitsui Chemicals, Inc., and Coronate PMD-OA01 and PMD-MA01 manufactured by Daiei Sangyo Co., Ltd.), 1,3-bis(isocyanatomethyl)cyclohexane-based blocked isocyanates (e.g., Takenate B-846N manufactured by Mitsui Chemicals, Inc., and Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation), and isophorone diisocyanate-based blocked isocyanates (e.g., 7950, 7951, and 7990 manufactured by Baxenden).

[0073] Among these, alkoxymethyl compounds and bismaleimide compounds are preferred in terms of effectively improving chemical resistance and glass transition temperature.

[0074] When the photosensitive resin composition contains a (F) thermal crosslinking agent, the amount of the (F) thermal crosslinking agent blended is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, based on 100 parts by mass of the (A) soluble polyimide.

[0075] Hindered phenol compounds To inhibit discoloration on copper surfaces, the photosensitive resin composition may optionally contain a hindered phenol compound.

[0076] Examples of the hindered phenol compound 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'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylenediamine, 2,5 ...4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, 2,5-di-t-butyl-4-methylphenol, 2 ethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4- Ethyl-6-t-butylphenol), Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 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)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione )-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-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6- Examples of the hydroxybenzoates include, but are not limited to, (1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0077] Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like are particularly preferred.

[0078] The amount of the hindered phenol compound in the photosensitive resin composition is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the (A) soluble polyimide, from the viewpoint of photosensitivity. When the amount of the hindered phenol compound is 0.1 part by mass or more based on 100 parts by mass of the (A) soluble polyimide, for example, when the photosensitive resin composition of the present disclosure is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, excellent photosensitivity is achieved.

[0079] Organotitanium Compounds The photosensitive resin composition may contain an organotitanium compound. By containing the organotitanium compound in the photosensitive resin composition, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

[0080] The organic titanium compound that can be used in this embodiment includes a compound in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.

[0081] Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and produce good cured patterns. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0082] Among them, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

[0083] When an organotitanium compound is blended into the photosensitive resin composition, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the (A) soluble polyimide. When the blending amount is 0.05 part by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance, while when the blending amount is 10 parts by mass or less, the storage stability of the photosensitive resin composition is excellent.

[0084] Adhesion aid In order to improve the adhesion between the film formed using the photosensitive resin composition and the substrate, the negative photosensitive resin composition may optionally contain an adhesion promoter, such as an aluminum-based adhesion promoter or a silane coupling agent.

[0085] Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0086] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilyl) propyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride,

[0087] 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.: trade name KBM803, Chisso Corporation: trade name Sila-Ace S810), 3-mercaptopropyltriethoxysilane (Azmax Corporation: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd.: trade name LS1375, Azmax Corporation: trade name SIM6474.0), mercaptomethyltrimethoxysilane (Azmax Corporation: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (Azmax Corporation: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyl Diethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane,

[0088] N-(3-triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Corporation: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea , N-(3-ethoxydimethoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-trippropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-trippropoxysilylbutyl)urea,

[0089] 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Corporation: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-t-butylcarbamate, (3-glycidoxypropyl)triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis(methoxyethoxysilane), tetrakis(methoxy-n-propoxysilane) , tetrakis(ethoxyethoxysilane), tetrakis(methoxyethoxyethoxysilane), bis(trimethoxysilyl)ethane, bis(trimethoxysilyl)hexane, bis(triethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)ethylene, bis(triethoxysilyl)octane, bis(triethoxysilyl)octadiene, bis[3-(triethoxysilyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane,

[0090] Phenyl silanetriol, methyl phenyl silanediol, ethyl phenyl silanediol, n-propyl phenyl silanediol, isopropyl phenyl silanediol, n-butyl phenyl silanediol, isobutyl phenyl silanediol, tert-butyl phenyl silanediol, diphenyl silanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethyl methyl phenyl silanol, n-propyl methyl phenyl silanol, isopropyl methyl phenyl silanol, n-butyl methyl phenyl silanol, isobutyl methylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, and the like, as well as those represented by the following formula (S-1): [ka] Examples of silane coupling agents include, but are not limited to, those represented by the following formula:

[0091] Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength.As the silane coupling agent, among the above-mentioned silane coupling agents, it is preferable to use one or more selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol, and the silane coupling agents represented by the above formula (S-1), from the viewpoint of storage stability.

[0092] When the photosensitive resin composition contains an adhesion promoter, the amount of the adhesion promoter is preferably in the range of 0.01 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the soluble polyimide (A).When a silane coupling agent is used as the adhesion promoter, the amount is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the soluble polyimide (A).

[0093] sensitizer The photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene indole. Non, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination of, for example, 2 to 5 types.

[0094] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer added is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the (A) soluble polyimide.

[0095] Thermal polymerization inhibitor The photosensitive resin composition may optionally contain a thermal polymerization inhibitor to improve the stability of viscosity and photosensitivity, particularly when stored in a solvent-containing solution. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0096] <Method for producing cured relief pattern> The method of producing a cured relief pattern of the present disclosure includes: (1) a step of applying the above-described photosensitive resin composition of the present disclosure to a substrate to form a photosensitive resin layer on the substrate (a resin layer forming step); (2) a step of exposing the photosensitive resin layer to light (exposure step); (3) a step of developing the exposed photosensitive resin layer to form a relief pattern (relief pattern formation step); (4) a step of heat-treating the relief pattern to form a cured relief pattern (a cured relief pattern forming step); Includes:

[0097] (1) Resin layer formation process In this step, the photosensitive resin composition is applied to the surface of the substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., or spray application using a spray coater, etc., can be used.

[0098] If necessary, the coating film containing the photosensitive resin composition can be dried. Drying methods include air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, in the case of air drying or heat drying, drying can be carried out at 20°C to 150°C for 1 minute to 1 hour. In this manner, a photosensitive resin layer can be formed on the surface of the substrate.

[0099] (2) Exposure process In this step, the photosensitive resin layer formed above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a patterned photomask or reticle. This exposure causes the polymerizable groups of the soluble polyimide contained in the photosensitive resin composition and / or the polymerizable groups of the photopolymerizable unsaturated monomer (E) to crosslink due to the action of the photopolymerization initiator (B). This crosslinking makes the exposed areas insoluble in the developer described below, enabling the formation of a relief pattern.

[0100] Thereafter, for the purpose of improving photosensitivity, etc., post-exposure baking (PEB) or pre-development baking, or both, may be performed at any combination of temperature and time, as necessary. The baking conditions are preferably a temperature of 40°C to 120°C and a time of 10 to 240 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

[0101] (3) Relief pattern formation process In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The developing method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist developing methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as needed, for the purpose of adjusting the shape of the relief pattern, etc.

[0102] The developer used for development is preferably, for example, a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. Examples of good solvents include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the negative photosensitive resin composition. Two or more solvents, for example, a combination of several solvents, can also be used.

[0103] (4) Hardened relief pattern formation process In this step, the relief pattern obtained by the development is heat-treated to volatilize the photosensitive component and convert it into a cured relief pattern. Heat treatment can be performed using a variety of methods, including a hot plate, an oven, or a temperature-programmable heating oven. Heat treatment can be performed, for example, at 150°C to 350°C for 30 minutes to 5 hours. The heat treatment temperature is preferably 150°C to 250°C, more preferably 150°C to 230°C, and even more preferably 170°C to 230°C. Air may be used as the atmospheric gas during heat curing, or an inert gas such as nitrogen or argon may also be used.

[0104] <Polyimide manufacturing method> In another aspect of the present disclosure, there is provided a method for producing a polyimide, comprising the step of curing the photosensitive resin composition described above to form a polyimide. The curing conditions for the photosensitive resin composition may be the same as the baking conditions included in the method for producing a cured relief pattern described above, or the conditions for the step (4) of forming a cured relief pattern.

[0105] <Semiconductor device> The present disclosure also provides a semiconductor device having a cured relief pattern obtained from the above-described photosensitive resin composition. More specifically, the present disclosure provides a semiconductor device having a substrate that is a semiconductor element and a cured relief pattern. The cured relief pattern may be produced by the above-described method for producing a cured relief pattern using the above-described photosensitive resin composition.

[0106] The present disclosure can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-described method for manufacturing a cured relief pattern of the present disclosure as part of the process. In this case, the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure can be formed as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining the cured relief pattern formed by the method for manufacturing a cured relief pattern of the present disclosure with a known method for manufacturing a semiconductor device.

[0107] <Display device> The present disclosure provides a display device including a display element and a cured film disposed on the display element, the cured film having the above-described cured relief pattern. The cured relief pattern may be laminated in direct contact with the display element, or may be laminated via another layer. The cured film can be used, for example, as a surface protection film, insulating film, or planarizing film for a TFT liquid crystal display element or a color filter element; a protrusion for an MVA-type liquid crystal display device; or a partition wall for a cathode of an organic EL element.

[0108] In addition to being applicable to the semiconductor devices described above, the photosensitive resin composition of the present disclosure is also useful for applications such as interlayer insulation in multilayer circuits, cover coatings for flexible copper-clad boards, solder resist films, and liquid crystal alignment films. [Example]

[0109] <Measurement and evaluation methods> (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions. Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40℃ Column: Showa Denko Shodex KD-805 / KD-804 / KD-803 in series Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko K.K. Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1mL / min.

[0110] (2) Copper adhesion evaluation The photosensitive resin composition prepared by the method described below was applied to a 6-inch silicon wafer previously sputtered with Ti and Cu, prebaked, and then heat-treated for 2 hours in a temperature-programmable curing oven (VF-2000, manufactured by Koyo Lindberg) at the temperatures listed in Table 1 under a nitrogen atmosphere to obtain a cured resin film approximately 10 μm thick on the Cu. This sample was then affixed with Evercel OPP tape (No. 830NEV, manufactured by Sekisui Chemical Co., Ltd.), and the OPP tape and polyimide coating were cut to a 5 mm width with a cutter. The polyimide coating was then peeled off using a Tensilon universal testing machine (RTG-1210, manufactured by A&D Co., Ltd.) so that the copper substrate and polyimide were separated. Specifically, the polyimide coating film with OPP tape attached was peeled off from the copper substrate by 60 mm at a speed of 50 mm / min using a Tensilon universal material testing machine (RTG-1210, manufactured by A&D Co., Ltd.) so that the peeling direction was 180 degrees to the adhesive surface with the copper substrate. The load applied during this process was calculated as an integrated average, and this value was used as the adhesion strength to evaluate the copper adhesion.

[0111] (3) Elongation measurement The photosensitive resin compositions obtained in the Examples and Comparative Examples were spin-coated onto a 6-inch silicon wafer having an aluminum vapor-deposited layer on the outermost surface to a film thickness of approximately 5 μm after curing, and then heat-treated for 2 hours in a nitrogen atmosphere at the temperature listed in Table 1 to obtain a cured resin film. The resulting cured film was cut into 3 mm widths using a dicing saw and then peeled off from the wafer using a dilute hydrochloric acid solution. 20 of the resulting samples were left to stand in an atmosphere of 23°C and 50% humidity for 24 hours or more, after which the elongation (%) was measured using a tensile tester (e.g., Tensilon). The measurement conditions for the tensile tester were as follows: Temperature: 23℃ Humidity: 50% Initial sample length: 50 mm Test speed: 40mm / min Load cell rating: 2kgf

[0112] (4) Chemical resistance evaluation of cured relief pattern (polyimide coating) The cured relief pattern formed on Cu was immersed in a resist stripper (product name ST-44, manufactured by ATMI, mainly consisting of 2-(2-aminoethoxy)ethanol and 1-cyclohexyl-2-pyrrolidone) heated to 50°C for 5 minutes, rinsed with running water for 1 minute, and air-dried. The film surface was then visually observed under an optical microscope to evaluate chemical resistance based on the presence or absence of damage caused by the chemical solution, such as cracks, and the rate of change in film thickness after chemical treatment. Chemical resistance was evaluated according to the following criteria. "Excellent": No cracks occur, and the rate of change in film thickness is 10% or less based on the film thickness before immersion in chemicals "Good": No cracks occur, and the rate of change in film thickness is more than 10% and less than 15% based on the film thickness before chemical immersion. "Acceptable": No cracks occur, and the film thickness change rate is more than 15% and less than 20% based on the film thickness before chemical immersion. "Unacceptable": Cracks have occurred or the change in film thickness exceeds 20%

[0113] <Production Example 1> In a flask equipped with a stirrer and condenser, 20.8 g (40.0 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 100 g of N-methylpyrrolidone at 20 to 30°C. Subsequently, 15.3 g (37.2 mmol) of 4,4'-isopropylidenebis[(4-aminophenoxy)benzene] was added and stirred for 1 hour. The mixture was then heated to 190°C under a nitrogen flow, stirred for 5 hours, and cooled to below 30°C. The mixture was then diluted with 50 g of tetrahydrofuran, precipitated in 2 L of methanol, filtered, and vacuum dried at 45°C for 1 day to obtain polyimide resin (A-1). The weight-average molecular weight of the resulting polyimide (A-1) was 18,000.

[0114] <Production Example 2> 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Next, 9.08 g (35.2 mmol) of 4,4'-isopropylidenebis(2-aminophenol) was dissolved in 50 g of NMP and added dropwise over 1 hour at a temperature of 10 to 25°C. After stirring at 25°C for 30 minutes, 10 g of toluene was added. The mixture was reacted at 200°C for 4 hours under nitrogen flow and then cooled to 25°C. Next, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added and reacted at 95 °C for 15 hours, then cooled to 25 °C and diluted with 120 g of tetrahydrofuran. The reaction solution was then added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the resulting polyimide resin was filtered. The resin was then reslurried in 1 L of water and filtered, then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40 °C for 8 hours. Next, the dried resin was dissolved in 250 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1, manufactured by Organo Corporation) was added. The mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide (A-2). The weight-average molecular weight of the resulting polyimide (A-2) was 16,000.

[0115] <Production Example 3> The polymerization reaction was carried out in a 1-L, three-neck, jacketed, round-bottom flask equipped with a mechanical stirrer, thermocouple, and nitrogen inlet to maintain a positive nitrogen pressure throughout the reaction. The flask was charged with 39.95 g of 4,4'-[1,4-phenylene-bis(1-methylethylidene)]bisaniline (DAPI) and 600 g of anhydrous N-methyl-2-pyrrolidone. The contents were stirred at 18-20 °C until a homogeneous solution was obtained. Next, 51.75 g of 1-(3',4'-dicarboxyphenyl)-1,3,3-trimethylindane-5,6-dicarboxylic dianhydride (DAPI dianhydride) was added to the stirred diamine solution via a funnel. The addition funnel was rinsed into the reaction flask with 66.0 g of anhydrous N-methylpyrrolidone. The mixture was heated to 60 °C and stirred for 3 hours.

[0116] To carry out the end-capping reaction, 4.2 g of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (oxonadic anhydride) and 2.0 g of pyridine were added to a flask and stirred at 60° C. for 3 hours.

[0117] To carry out the imidization reaction, 10.2 g of acetic anhydride and 2.0 g of pyridine were charged to a reaction vessel. The reaction mixture was heated to 100°C and stirred for 12 hours. A small sample (1 g) was removed and precipitated in 50:50 methanol:water (10 ml). The solid was isolated by filtration and dried. Fourier transform infrared spectroscopy indicated that the imidization reaction was complete.

[0118] The resulting solution was cooled to room temperature and added dropwise to 4 liters of vigorously stirred deionized water to precipitate the polymer. The polymer was collected by filtration and washed with 1 liter of deionized water. The filter cake was reslurried in 1 liter of methanol and filtered. The wet filter cake was dried in air for 12 hours, and then the polymer was dried under vacuum at 70°C for 12 hours to obtain polyimide A-3. The weight-average molecular weight of the resulting polyimide (A-3) was 16,000.

[0119] Example 1 A negative-tone photosensitive resin composition was prepared using the following method and evaluated. (A) 100 g of soluble polyimide A-1, (B) 6 g of 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (B-1) as a photopolymerization initiator, (C) 200 g of N-ethyl-2-pyrrolidone as a solvent, (D) 0.4 g of benzotriazole as a nitrogen-containing heterocyclic compound, and (E) 30 g of polyethylene glycol dimethacrylate (E-1) as a photopolymerizable unsaturated monomer were dissolved to prepare a photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1. A fanout-type wafer-level chip size package semiconductor device was also fabricated and operated without any problems.

[0120] <Examples 2 to 24> Photosensitive resin compositions were prepared in the same manner as in Example 1, except that the compositions shown in Table 1 were used, and then evaluated.

[0121] <Comparative Examples 1 to 4> Photosensitive resin compositions were prepared in the same manner as in Example 1, except that the compositions shown in Table 1 were used, and then evaluated. Furthermore, when a fan-out type wafer level chip size package type semiconductor device was fabricated, it did not function.

[0122] [Table 1-1]

[0123] [Table 1-2]

[0124] [Table 1-3]

[0125] Explanation of ingredients in Table 1 (In Table 1, the numerical values ​​of each ingredient are in grams (g)) (A) Soluble polyimide A-1 to A-3 synthesized in the above synthesis example

[0126] (B) Photopolymerization initiator B-1: 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) B-2: 3-Cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]propanone-1-(O-acetyloxime)

[0127] (C) Solvent C-1: N-ethyl-2-pyrrolidone (boiling point: 218°C) C-2: Ethyl lactate (boiling point: 154°C) C-3: γ-butyrolactone (boiling point: 204°C) C-4: 1,3-dimethyl-2-imidazolidinone (boiling point: 220°C) C-5: 3-Methoxy-N,N-dimethylpropanamide (boiling point: 215°C) C-6: 3-butoxy-N,N-dimethylpropanamide (boiling point: 252°C) C-7: γ-valerolactone (boiling point: 207°C) C-8: N-methyl-2-pyrrolidone (boiling point: 204°C) C-9: Dimethyl sulfoxide (boiling point: 189°C) C-10: Cyclopentanone (boiling point: 131°C)

[0128] (D) Nitrogen-containing heterocyclic compound D-1: Benzotriazole D-2: 5-aminotetrazole D-3: N,N-dimethyladenine D-4: N-methylguanine

[0129] (E) Photopolymerizable unsaturated monomer E-1: Polyethylene glycol dimethacrylate E-2: Tris-(2-acryloxyethyl) isocyanurate E-3: 1,10-decanediol diacrylate (F) Thermal crosslinking agent F-1: 1,3,4,6-tetrakis(methoxymethyl)glycoluril F-2: N,N'-m-phenylenebismaleimide

Claims

1. (A) a soluble polyimide; (B) a photopolymerization initiator; (C) an organic solvent; A photosensitive resin composition comprising: The photosensitive resin composition contains 40 mass% or more of N-ethyl-2-pyrrolidone in the organic solvent (C), and 20 mass% or less of an organic solvent having a boiling point of lower than 140°C, based on the total mass of the organic solvent (C).

2. 2. The photosensitive resin composition according to claim 1, wherein the soluble polyimide (A) does not contain a fluorine atom.

3. The photosensitive resin composition according to claim 1 , further comprising (D) a nitrogen-containing heterocyclic compound.

4. The photosensitive resin composition according to claim 1 , further comprising (E) a photopolymerizable unsaturated monomer.

5. The photosensitive resin composition according to claim 4, wherein the photopolymerizable unsaturated monomer (E) has three or more (meth)acrylic groups in the molecule.

6. The photosensitive resin composition according to claim 1 , further comprising (F) a thermal crosslinking agent.

7. 2. The photosensitive resin composition according to claim 1, wherein the organic solvent (C) further comprises at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-valerolactone, and tetramethylurea.

8. 2. The photosensitive resin composition according to claim 1, wherein the organic solvent (C) further comprises at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N,N-dimethylpropanamide.

9. 2. The photosensitive resin composition according to claim 1, wherein the soluble polyimide (A) has a photopolymerizable functional group at a main chain terminal and / or a main chain side chain.

10. The soluble polyimide (A) is represented by the following general formula (1): 【Chemistry 1】 {In formula (1), X represents a tetravalent organic group having 4 to 32 carbon atoms, and Y represents a divalent organic group having 4 to 40 carbon atoms.} The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is represented by the formula:

11. The X is represented by the following general formulas (2) to (6): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 The photosensitive resin composition according to claim 10, wherein the photosensitive resin composition is at least one selected from the group consisting of:

12. The Y is represented by the following general formulas (7) to (9): 【Transformation 7】 【Transformation 8】 【Chemistry 9】 The photosensitive resin composition according to claim 10, wherein the photosensitive resin composition is at least one selected from the group consisting of:

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

14. The photopolymerization initiator (B) is represented by the following general formula (19) or (20): 【Chemistry 10】 {In the formula, Ra represents a monovalent organic group having 1 to 10 carbon atoms, Rb represents a monovalent organic group having 1 to 20 carbon atoms, Rc represents a monovalent organic group having 1 to 10 carbon atoms, and Rd represents a monovalent organic group having 1 to 10 carbon atoms} 【Chemistry 11】 {wherein Re represents a monovalent organic group having 1 to 20 carbon atoms, and Rf represents a monovalent organic group having 1 to 10 carbon atoms} The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is represented by the formula:

15. The photosensitive resin composition according to claim 3 , wherein the nitrogen-containing heterocyclic compound (D) is a triazole compound, a tetrazole compound, or a purine compound.

16. A method for producing a polyimide, comprising the step of curing the photosensitive resin composition according to any one of claims 1 to 15 to form a polyimide.

17. The following steps: (1) applying the photosensitive resin composition according to any one of claims 1 to 15 to a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; 1. A method for producing a cured relief pattern, comprising:

Images