Photosensitive resin composition and method for producing cured relief pattern

Abstract

The invention relates to a photosensitive resin composition and a method for manufacturing a cured relief pattern. [Problem] The purpose of the present invention is to provide: a photosensitive resin composition which has excellent chemical resistance, exhibits good elongation even when the curing temperature is low, and is capable of producing a cured relief pattern having good adhesion to copper wiring; and a method for producing a cured relief pattern using the photosensitive resin composition. [Solution] The present invention provides a photosensitive resin composition containing (A) a soluble polyimide, (B) a photopolymerization initiator, and (C) an organic solvent, in which N-ethyl-2-pyrrolidone is contained in an amount of 40% by mass or more based on the total mass of the (C) organic solvent, and an organic solvent having a boiling point of less than 140 DEG C is contained in an amount of 20% by mass or less.

Description

Technical Field

[0001] This disclosure relates to photosensitive resin compositions and methods for manufacturing cured embossed patterns, etc. Background Technology

[0002] Previously, insulating materials for electronic components, as well as passivation films, surface protective films, and interlayer insulating films for semiconductor devices, have utilized polyimide resins that possess excellent heat resistance, electrical properties, and mechanical properties. In this particular polyimide resin, a heat-resistant embossed pattern film can be easily formed by coating, exposing, developing, and curing-based thermal imidization of the photosensitive polyimide precursor composition. Compared to conventional non-photosensitive polyimide materials, this photosensitive polyimide precursor composition significantly reduces the number of processing steps.

[0003] However, semiconductor devices (hereinafter also referred to as "components") are mounted on printed circuit boards using various methods depending on their purpose. Traditionally, components were typically fabricated using wire bonding, where fine wires connect the external terminals (pads) of the component to the lead frame. However, with the increasing speed of components, operating at frequencies reaching gigahertz (GHz), the differences in wiring length between the terminals during mounting have become significant enough to affect component operation. Therefore, in the mounting of components for high-end applications, it is necessary to properly control the length of the mounting wiring, and wire bonding has become difficult to meet this requirement.

[0004] Therefore, flip-chip mounting was proposed, in which a redistribution layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed on it, and the chip is flipped over (flip-chip) and directly mounted onto a printed circuit board. This flip-chip mounting allows for precise control of wiring distances, and is therefore used in high-end applications processing high-speed signals. Its small size has led to its widespread use in mobile phones and other applications, resulting in rapidly increasing demand. Furthermore, a semiconductor chip mounting technology called Fan-Out Wafer-Level Packaging (FOWLP) has recently been proposed. This technology involves dicing a pre-processed wafer to create a monolithic chip, reconstructing the monolithic chip on a support and sealing it with molding resin, and forming a redistribution layer after peeling off the support (e.g., Patent Document 1). FOWLP offers advantages such as enabling highly thin packages, high-speed transmission, and low cost.

[0005] When the aforementioned encapsulation is formed, it is usually heated and cured after the photosensitive resin composition is patterned. However, if the shrinkage during heating and curing is large, problems such as impaired film flatness may occur. To solve this problem, a resin composition using solvent-soluble polyimide has been proposed (for example, Patent Document 2).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2005-167191

[0009] Patent Document 2: Japanese Patent Application Publication No. 2021-162834 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] However, to make polyimides solvent-soluble, fluorine atoms are typically introduced into the main chain structure, or high-molecular-weight acid dianhydrides or diamine monomers are used. However, such polyimides tend to exhibit deterioration in chemical resistance. Furthermore, the adhesion between the copper wiring and the polyimide layer is crucial, and photosensitive resin compositions using soluble polyimides suffer from reduced adhesion to copper. Additionally, lowering the curing temperature of the polyimide-containing photosensitive resin composition or the pattern formed using it results in a decrease in elongation.

[0012] Therefore, the purpose of this disclosure is to provide: a photosensitive resin composition with excellent chemical resistance, exhibiting good elongation even at low curing temperatures, and capable of producing a cured embossed pattern with good adhesion to copper wiring; and a method for producing a cured embossed pattern using the photosensitive resin composition.

[0013] Solution for solving the problem

[0014] The inventors have discovered that the above-mentioned problems can be solved by combining soluble polyimide, a photopolymerization initiator, and a specific solvent. Examples of embodiments of this disclosure are given below.

[0015] <1> A photosensitive resin composition comprising (A) a soluble polyimide, (B) a photopolymerization initiator, and (C) an organic solvent.

[0016] Of the organic solvent (C), based on the total mass of the organic solvent (C), the organic solvent containing more than 40% by mass of N-ethyl-2-pyrrolidone and having a boiling point below 140°C is less than 20% by mass.

[0017] <2> According to the photosensitive resin composition of Project 1, wherein the (A) soluble polyimide is free of fluorine atoms.

[0018] <3> The photosensitive resin composition according to item 1 or 2 further comprises (D) a nitrogen-containing heterocyclic compound.

[0019] <4> The photosensitive resin composition according to any one of items 1 to 3 further comprises (E) a photopolymerizable unsaturated monomer.

[0020] <5> According to the photosensitive resin composition of Project 4, wherein the (E) photopolymerizable unsaturated monomer has more than three (meth)acrylate groups in the molecule.

[0021] <6> The photosensitive resin composition according to any one of items 1 to 5 further comprises (F) a thermal crosslinking agent.

[0022] <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-imidazolinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, γ-valerolactone and tetramethylurea.

[0023] <8> 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-imidazolinone and 3-methoxy-N,N-dimethylpropionamide.

[0024] <9> The photosensitive resin composition according to any one of items 1 to 8, wherein the (A) soluble polyimide has photopolymerizable functional groups at the ends of the main chain and / or the side chains of the main chain.

[0025] <10> The photosensitive resin composition according to any one of items 1 to 9, wherein the (A) soluble polyimide is represented by the following formula (1),

[0026]

[0027] {In formula (1), X represents a tetravalent organic group with 4 to 32 carbon atoms, and Y represents a divalent organic group with 4 to 40 carbon atoms}.

[0028] <11> According to the photosensitive resin composition of Project 10, wherein X is at least one selected from the group consisting of the following general formulas (2) to (6),

[0029]

[0030] <12> According to the photosensitive resin composition of item 10 or 11, wherein Y is at least one selected from the group consisting of general formulas (7) to (9) below.

[0031]

[0032]

[0033] <13> The photosensitive resin composition according to any one of items 1 to 12, wherein the photopolymerization initiator (B) is an oxime compound.

[0034] <14> The photosensitive resin composition according to any one of items 1 to 13, wherein the photopolymerization initiator of (B) is represented by the following general formula (19) or general formula (20),

[0035]

[0036] {In the formula, Ra represents a monovalent organic group with 1 to 10 carbon atoms, Rb represents a monovalent organic group with 1 to 20 carbon atoms, Rc represents a monovalent organic group with 1 to 10 carbon atoms, and Rd represents a monovalent organic group with 1 to 10 carbon atoms};

[0037]

[0038] {In the formula, Re represents a monovalent organic group with 1 to 20 carbon atoms, and Rf represents a monovalent organic group with 1 to 10 carbon atoms}.

[0039] <15> According to the photosensitive resin composition of Project 3, wherein the nitrogen-containing heterocyclic compound (D) is a triazole compound, a tetraazole compound, or a purine compound.

[0040] <16> A method for manufacturing a polyimide includes a step of curing a photosensitive resin composition as described in any one of items 1 to 15 to form a polyimide.

[0041] <17> A method for manufacturing a solidified relief pattern includes the following steps:

[0042] (1) The process of coating a photosensitive resin composition as described in any one of items 1 to 15 onto a substrate and forming a photosensitive resin layer on the substrate.

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

[0044] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern; and

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

[0046] The effects of the invention

[0047] According to this disclosure: a photosensitive resin composition exhibiting excellent chemical resistance, good elongation even at low curing temperatures, and capable of producing cured embossed patterns with good adhesion to copper wiring; and a method for producing cured embossed patterns using the photosensitive resin composition. Detailed Implementation

[0048] <Photosensitive Resin Composition>

[0049] The photosensitive resin composition disclosed herein comprises (A) a soluble polyimide, (B) a photopolymerization initiator, and (C) an organic solvent.

[0050] In organic solvent (C), based on the total mass of organic solvent (C), it contains more than 40% by mass of N-ethyl-2-pyrrolidone and less than 20% by mass of organic solvent with a boiling point below 140°C.

[0051] (A) Soluble polyimide

[0052] In this embodiment, (A) the soluble polyimide is not limited as long as it is dissolved in a common organic solvent, but preferably it is dissolved in 5% by mass or more of N-ethyl-2-pyrrolidone used in this embodiment.

[0053] In this embodiment, (A) the soluble polyimide is not limited as long as it is soluble in a common organic solvent, but from the viewpoint of chemical resistance and elongation, it is preferable to be free of fluorine atoms.

[0054] From the viewpoint of chemical resistance, the soluble polyimide of embodiment (A) preferably has photopolymerizable functional groups at the ends of the main chain and / or on the side chains of the main chain. (A) By giving the soluble polyimide these photopolymerizable functional groups, the resolution can be improved.

[0055] Here, the photopolymerizable functional group is not limited to any functional group that can polymerize by light irradiation. Examples of such functional groups include methacryloyl, acryloyl, methacrylamide, acrylamide, and styrene. From the viewpoint of resolution, at least one selected from methacryloyl, acryloyl, and styrene is preferred.

[0056] In this embodiment, the end of the main chain represents the end structure of a soluble polyimide main chain composed of an acid dianhydride and a diamine. Polycondensation can be performed after introducing photopolymerizable functional groups into the acid dianhydride and / or diamine, or photopolymerizable functional groups can be introduced into the end structure after obtaining the soluble polyimide.

[0057] In this embodiment, the side chain of the main chain represents the side chain structure of a soluble polyimide main chain composed of an acid dianhydride and a diamine. Polycondensation can be performed after introducing photopolymerizable functional groups into the acid dianhydride and / or diamine, or photopolymerizable functional groups can be introduced into the side chain structure after obtaining the soluble polyimide.

[0058] The soluble polyimide (A) in this embodiment can be represented by the following general formula (1).

[0059]

[0060] {In formula (1), X represents a tetravalent organic group with 4 to 32 carbon atoms, and Y represents a divalent organic group with 4 to 40 carbon atoms}

[0061] In general formula (1), X is not limited as long as it is a tetravalent organic group with 4 to 32 carbon atoms. From the viewpoint of chemical resistance, it is preferred to have 6 or more carbon atoms, more preferably 8 or more, and particularly preferably 10 or more. From the viewpoint of resolution, it is preferred that X has 30 or fewer carbon atoms, more preferably 28 or fewer, and particularly preferably 26 or fewer.

[0062] In general formula (1), Y is not limited as long as it is a divalent organic group with 4 to 40 carbon atoms. From the viewpoint of chemical resistance, it is preferred to have 6 or more carbon atoms, more preferably 8 or more, and particularly preferably 10 or more. From the viewpoint of resolution, it is preferred that Y has 30 or fewer carbon atoms, more preferably 28 or fewer, and particularly preferably 26 or fewer.

[0063] In this embodiment, X preferably has an aromatic group, and more preferably includes at least one of the groups of structures selected from those represented by the following general formulas (2) to (6).

[0064]

[0065] From the viewpoint of glass transition temperature (Tg) after heat curing, the structures represented by the above formulas (3) and (4) are preferred, and from the viewpoint of elongation after heat curing, the structures shown by formulas (2) and (5) are preferred.

[0066] In this embodiment, Y preferably has an aromatic group, and more preferably includes at least one of the groups of structures selected from those represented by the following general formulas (7) to (9).

[0067]

[0068] In addition to (A) a soluble polyimide, the photosensitive resin composition may also contain (A') a polyimide precursor containing a structural unit represented by the following general formula (1').

[0069]

[0070] {In formula (1'), X1 is a tetravalent organic group with 4 to 40 carbon atoms, Y1 is a divalent organic group with 6 to 40 carbon atoms, and R1 and R2 are independently selected from groups consisting of hydroxyl groups and monovalent organic groups with 1 to 40 carbon atoms.}

[0071] In the above general formula (1'), the organic group can be an organic group containing heteroatoms other than carbon and hydrogen, or an organic group composed 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, when the total amount of (A) soluble polyimide and (A') polyimide precursor is set to 100% by mass, the amount of (A') polyimide precursor can be greater than 0 and less than 100% by mass, preferably greater than 0 and less than 50% by mass, more preferably greater than 0 and less than 20% by mass, and even more preferably greater than 0 and less than 10% by mass.

[0072] In the above general formula (1'), at least one of R1 and R2 is preferably a group that also contains a polymerizable group, which is selected from the group consisting of acid polymerizable groups, base polymerizable groups, and free radical polymerizable groups. Here, the so-called acid polymerizable groups, base polymerizable groups, and free radical polymerizable groups refer to groups that can be polymerized by the action of acids, bases, or free groups.

[0073] (A) Preparation method of soluble polyimide

[0074] A method for preparing (A) soluble polyimide is, for example, obtaining polyamic acid by polycondensation of the aforementioned tetracarboxylic acid dianhydride containing a tetravalent organic group X and the aforementioned diamine containing a divalent organic group Y, followed by heat treatment, thereby obtaining soluble polyimide.

[0075] (Preparation of polyamic acid)

[0076] As a tetracarboxylic acid dianhydride containing a tetravalent organic group X, which is preferred for preparing polyamic acid as a precursor of (A) soluble polyimide, it is preferred to use a compound represented by the following formula (1T).

[0077]

[0078] {In the above formula (1T), X is defined by the above general formula (1).}

[0079] Preferred tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (also known as oxybis(phthalic acid) dianhydride, abbreviated as "ODPA"), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (abbreviated as "BPDA"), diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. More preferably, as tetracarboxylic dianhydrides are pyromellitic dianhydrides, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydrides, benzophenone-3,3',4,4'-tetracarboxylic dianhydrides, biphenyl-3,3',4,4'-tetracarboxylic dianhydrides, and the following general formulas (2T) to (6T), but not limited to these. They can be used alone or in combination of two or more. Among them, dianhydrides represented by the following general formulas (2T) to (6T) are preferred.

[0080]

[0081]

[0082] As diamines containing a divalent organic group Y, compounds represented by the following formula (1D) can be listed.

[0083] H2N-Y-NH2(1D)

[0084] {In the formula, Y is defined by the above general formula (1).}

[0085] More preferably, as a diamine, are p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether (also known as 4,4'-oxodiphenylamine, 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-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, o-toluidine sulfone, 9,9-bis(4-aminophenyl) Compounds containing fluorene, etc., and compounds formed by substituting a portion of the hydrogen atoms on their benzene rings with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dihydroxymethyl-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and the following general formulas (7D) to (9D), etc., but not limited thereto. They can be used alone or in combination of two or more. Among them, the following formulas (7D) to (9D) are preferred.

[0086]

[0087] The above-mentioned tetracarboxylic acid dianhydride and the above-mentioned diamine are preferably dissolved and mixed in the solvent described below, thereby obtaining polyamic acid. As reaction conditions, continuous stirring for 4 to 10 hours is preferred at a temperature of 10–50°C.

[0088] The obtained polyamic acid can be subjected to imidization after separation, or it can be subjected to the subsequent imidization reaction without separation.

[0089] (Preparation of soluble polyimide)

[0090] An imidization catalyst is added as needed to react the obtained polyamic acid at a high temperature, thereby obtaining a soluble polyimide. Preferably, this can be carried out by mixing toluene and / or xylene as an azeotropic solvent with water in a glass container equipped with a Dean-Stark apparatus. The reaction conditions are not limited as long as the desired soluble polyimide can be obtained; a reaction temperature of 150–230°C and continuous stirring for 4–10 hours are preferred.

[0091] After the soluble polyimide reaction is complete and cooled to near room temperature, the resulting polymer component is placed in a poor solvent to precipitate the polymer. Then, through repeated dissolution and reprecipitation operations, the polymer can be purified. Vacuum drying is then performed to separate the target soluble polyimide. To improve purification, the polymer solution can be passed through a column filled with anion exchange resin, cation exchange resin, or both, swollen with a suitable organic solvent to remove ionic impurities.

[0092] When the molecular weight of the soluble polyimide described above (A) is determined by gel permeation chromatography using polystyrene to convert to a weight-average molecular weight, it is preferably 8,000 to 150,000, more preferably 9,000 to 50,000. A weight-average molecular weight of 8,000 or higher provides good mechanical properties, while a weight-average molecular weight of 150,000 or lower provides 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. Furthermore, the weight-average molecular weight is determined from a standard curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent-based standard sample "STANDARD SM-105" manufactured by Showa Denko Corporation.

[0093] The soluble polyimide of this embodiment may be exemplified by having at least one repeating unit having the structure represented by the following formulas (10) to (12).

[0094]

[0095]

[0096] (B) Photopolymerization initiator

[0097] The photosensitive resin composition includes (B) a photopolymerization initiator. Preferably, the photopolymerization initiator is a photoradical polymerization initiator or a photoacid generator.

[0098] Examples of photoradical polymerization initiators include benzophenone, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone compounds; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, and other acetophenone compounds; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, and other thioxanthone compounds; benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal, and other benzoin compounds; benzoin, benzoin methyl ether, and other benzoin compounds; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime; and 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime. Oxime compounds such as 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime; 1,3-diphenyltriketone-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxytriketone-2-(o-benzoyl)oxime, 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyl oxime); N-arylglycine compounds such as N-phenylglycine; peroxides such as benzoyl peroxide, aromatic biimidazole compounds, and titanium ceramsite compounds.

[0099] As a photoacid-generating agent, preferred examples include α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0100] (B) The photopolymerization initiator is not limited to the examples shown above. Among the photopolymerization initiators described above, photoradical polymerization initiators are more preferred, and oxime compounds are particularly preferred from the viewpoint of photosensitivity.

[0101] From the viewpoint of resolution, the oxime compound is preferably at least one selected from the group consisting of the following general formulas (19), (20) and (21).

[0102]

[0103] {In the formula, Ra represents a monovalent organic group with 1 to 10 carbon atoms, Rb represents a monovalent organic group with 1 to 20 carbon atoms, Rc represents a monovalent organic group with 1 to 10 carbon atoms, and Rd represents a monovalent organic group with 1 to 10 carbon atoms.}

[0104]

[0105] {In the formula, Re represents a monovalent organic group with 1 to 20 carbon atoms, and Rf represents a monovalent organic group with 1 to 10 carbon atoms.}

[0106]

[0107] {In the formula, Rg represents a monovalent organic group with 1 to 20 carbon atoms, Rh represents a monovalent organic group with 1 to 10 carbon atoms, and Ri represents a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms.}

[0108] 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 methyl, ethyl, or propyl. 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. From the viewpoint of resolution, it is preferably a monovalent organic group having 3 to 10 carbon atoms containing a saturated alicyclic structure. Rd is not limited as long as it is a monovalent organic group having 1 to 10 carbon atoms. From the viewpoint of resolution, it is preferably an organic group having 1 to 3 carbon atoms, and more preferably methyl, ethyl, or propyl.

[0109] In general formula (20), Re is not limited as long as it is a monovalent organic group with 1 to 20 carbon atoms. From the viewpoint of resolution, it is preferably an organic group with 5 to 20 carbon atoms, and more preferably an organic group with 6 to 15 carbon atoms. Rf is not limited as long as it is a monovalent organic group with 1 to 10 carbon atoms. From the viewpoint of resolution, it is preferably an organic group with 1 to 3 carbon atoms, and more preferably a methyl, ethyl, or propyl group.

[0110] In general formula (21), Rg is not limited as long as it is a monovalent organic group with 1 to 20 carbon atoms. From the viewpoint of heat resistance, it is preferably an alkyl group with 1 to 5 carbon atoms, and more preferably methyl, ethyl, or propyl. Rh is not limited as long as it is a monovalent organic group with 1 to 10 carbon atoms. From the viewpoint of resolution, it is preferably a monovalent organic group with 2 to 9 carbon atoms, and more preferably 2 to 8 carbon atoms. Ri is not limited as long as it is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms. From the viewpoint of resolution, it is preferably a hydrogen atom or a monovalent organic group with 1 to 9 carbon atoms.

[0111] From the perspective of resolution, the structure represented by general formulas (19) to (21) is more preferred.

[0112] Based on 100 parts by weight of (A) soluble polyimide, the amount of (B) photopolymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 8 parts by weight or less. Based on 100 parts by weight of (A) soluble polyimide, the amount of (B) soluble polyimide is 0.1 parts by weight or more from the viewpoint of photosensitivity or patternability, and preferably 20 parts by weight or less from the viewpoint of the physical properties of the cured photosensitive resin layer of the negative photosensitive resin composition.

[0113] (C) Organic solvents

[0114] The photosensitive resin composition of this embodiment contains (C) an organic solvent, and the organic solvent contains at least 40% by mass of N-ethyl-2-pyrrolidone, and at least 20% by mass of an organic solvent with a boiling point below 140°C. By using the organic solvent of this embodiment, a photosensitive resin composition with good chemical resistance, good elongation even at low curing temperatures, and the ability to produce cured embossed patterns with good adhesion to copper wiring can be obtained.

[0115] In this embodiment, based on the total mass of the (C) organic solvent, the organic solvent containing 40% by mass or more of (C-1)N-ethyl-2-pyrrolidone and 20% by mass or less of organic solvent with a boiling point below 140°C results in good chemical resistance, good elongation even at low curing temperatures, and good adhesion to copper wiring. The reasons for this are not yet clear, but the inventors believe that: In order for the soluble polyimide to be solvent-soluble, the concentration of imide groups needs to be reduced. Therefore, the interaction between the imide groups in the polymer is reduced compared to typical polyimides, thus there is a tendency for it to be difficult to exhibit good chemical resistance and elongation. This tendency becomes particularly pronounced as the heat curing temperature decreases. The (C-1)N-ethyl-2-pyrrolidone of this embodiment has a site capable of interacting with imide groups and a boiling point of 218°C. Therefore, when the heat curing temperature is 170°C to 230°C, a portion remains in the film, thereby causing polymer packing and resulting in good chemical resistance and elongation. Furthermore, by leaving a portion of N-ethyl-2-pyrrolidone in the film, the film has a site capable of interacting with both the polymer and copper, thus improving copper adhesion. The effects described above are even more pronounced when the photosensitive resin composition contains the nitrogen-containing heterocyclic compound shown in (D) below.

[0116] By including 40% by mass or more of N-ethyl-2-pyrrolidone in all organic solvents, the residual N-ethyl-2-pyrrolidone in the above-mentioned film can be fully utilized. Based on the total mass of (C) organic solvents, 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.

[0117] From the viewpoint of developability, based on the total mass of (C) organic solvent, 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.

[0118] Furthermore, the effects of the present invention can be fully realized by ensuring that the content of the organic solvent with a boiling point less than 140°C, based on the total mass of the (C) organic solvent, is 20% by mass or less. If the content of the organic solvent with a boiling point less than 140°C, based on the total mass of the (C) organic solvent, exceeds 20% by mass, the residue of N-ethyl-2-pyrrolidone is insufficient, and therefore it is contemplated that the aforementioned effects cannot be achieved. From this viewpoint, the content of the organic solvent with a boiling point less than 140°C, based on the total mass of the (C) organic solvent, is preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0119] Examples of organic solvents with boiling points below 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.

[0120] The solvent in this embodiment may include other solvents (C-2) within a range that does not adversely affect performance. Examples of other solvents include amides, sulfoxides, ureas and their derivatives, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, alcohols, etc. Specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, 1,3-dimethyl-2-imidazolinone, 3-methoxy-N,N-dimethylpropionamide, cyclohexanone, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, benzyl alcohol, phenyl ethylene glycol, tetrahydrofurfuryl alcohol, diethylene glycol dimethyl ether, 1,4-dichlorobutane, o-dichlorobenzene, anisole, xylene, mesitylene, etc.

[0121] From the viewpoint of copper adhesion, when other solvents are included, the other solvents are preferably at least one selected from the group consisting of γ-butyrolactone, 1,3-dimethyl-2-imidazolinone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, γ-valerolactone, and tetramethylurea.

[0122] When other solvents are included, the total solvent amount is set to 100% by mass, and the content of other solvents is preferably 50% by mass or less, more preferably 30% by mass or less, particularly preferably 15% by mass or less, further preferably 10% by mass or less, and most preferably 5% by mass or less.

[0123] (D) Nitrogen-containing heterocyclic compounds

[0124] The photosensitive resin composition of this embodiment may contain (D) a nitrogen-containing heterocyclic compound. By containing this compound, the copper adhesion is improved through its synergistic effect with the aforementioned N-ethyl-2-pyrrolidone.

[0125] In this embodiment, the nitrogen-containing heterocyclic compound is not limited to any heterocyclic compound containing a nitrogen atom. From the viewpoint of synergistic effect with (C) organic solvent or improved copper binding, triazole compound, tetraazole compound, or purine compound is preferred, and purine compound is more preferred.

[0126] Specific examples of triazole compounds include, for instance, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, and 2-(5-methyl-2-hydroxyphenyl)benzotriazole. Triazoles, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, etc.

[0127] Specific examples of tetrazolium compounds include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0128] 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, and 8-aminoadenine. Purines, 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 their derivatives.

[0129] When the photosensitive resin composition contains (D) a nitrogen-containing heterocyclic compound, the mixing amount is preferably 0.01 to 20 parts by mass based on 100 parts by mass of soluble polyimide (A), more preferably 0.03 to 10 parts by mass from the viewpoint of photosensitivity characteristics, and even more preferably 0.05 to 5 parts by mass, for example, 0.01 to 5 parts by mass. When the mixing amount of (D) a nitrogen-containing heterocyclic compound is 0.01 parts by mass or more based on 100 parts by mass of soluble polyimide (A), copper adhesion is further improved when the photosensitive resin composition is formed on copper or copper alloy; on the other hand, when it is 20 parts by mass or less, the resolution is further improved.

[0130] (E) Photopolymerizable unsaturated monomers

[0131] To improve the resolution of the embossed pattern, the photosensitive resin composition may contain (E) photopolymerizable unsaturated monomers. Photopolymerizable unsaturated monomers refer to monomers having photopolymerizable unsaturated bonds, which undergo free radical polymerization via a photoinitiator. Preferably, (meth)acrylate compounds are preferred as such monomers, but there are no particular limitations; examples include monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of ethylene glycol; monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polyethylene glycol; monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of propylene glycol; monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polypropylene glycol; monoacrylates, diacrylates, triacrylates, monomethacrylates, dimethacrylates, and trimethacrylates of glycerol; diacrylates and dimethacrylates of cyclohexanediethanol; and 1,4-butanediol. Diacrylates and dimethacrylates of bisphenol A; diacrylates and dimethacrylates of 1,6-hexanediol; diacrylates and dimethacrylates of neopentyl glycol; monoacrylates, diacrylates, monomethacrylates and dimethacrylates of bisphenol A; trimethylolpropane acrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate; diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates and tetramethacrylates of pentaerythritol; and ethylene oxide adducts or propylene oxide adducts of these compounds.

[0132] From the viewpoint of improving chemical resistance, the (E) photopolymerizable unsaturated monomer preferably has two or more (meth)acrylic groups in the molecule, and more preferably three or more.

[0133] When the photosensitive resin composition contains the aforementioned (E) photopolymerizable unsaturated monomer for improving the resolution of the embossed pattern, the amount of the (E) photopolymerizable unsaturated monomer is preferably 1 to 50 parts by mass, based on 100 parts by mass of (A) soluble polyimide.

[0134] (F) Thermal crosslinking agent

[0135] To improve chemical resistance and increase the glass transition temperature, the photosensitive resin composition may include a (F) thermal crosslinking agent. Examples of thermal crosslinking agents include compounds that can undergo addition or condensation reactions by heat. Substances belonging to the (F) thermal crosslinking agent category can achieve improved chemical resistance and a higher glass transition temperature by reacting with the soluble polyimide (A) of this embodiment. When the photosensitive resin composition includes a (E) photopolymerizable unsaturated monomer, the reaction between component (E) and component (F) can further improve chemical resistance and the glass transition temperature, which is therefore preferable.

[0136] (F) There is no limitation on the reaction start temperature of the thermal crosslinking agent, but it is preferably 130°C or higher, more preferably 140°C or higher, and particularly preferably 150°C or higher.

[0137] Examples of (F) thermal crosslinking agents include alkoxymethyl compounds, epoxy compounds, oxetane compounds, bismaleimide compounds, allyl compounds, and end-capped isocyanate compounds.

[0138] As alkoxymethyl compounds, compounds represented by the following formulas are preferred.

[0139]

[0140]

[0141] Examples of epoxy compounds include those containing bisphenol A groups and hydrogenated bisphenol A diglycidyl ethers (e.g., Epolight 4000 manufactured by Kyoei Chemical Co., Ltd.).

[0142] Examples of oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene, bis[1-ethyl(3-oxetane)]methyl ether, 4,4'-bis[(3-ethyl-3-oxetane)methyl]biphenyl, 4,4'-bis(3-ethyl-3-oxetane)methoxy)biphenyl, ethylene glycol bis(3-ethyl-3-oxetane)methyl ether, diethylene glycol bis(3-ethyl-3-oxetane)methyl ether, and bis(3-ethyl-3-oxetane)butane. Bisphenol A ester, trimethylolpropane tris(3-ethyl-3-oxetanemethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanemethyl) ether, poly[[3-[(3-ethyl-3-oxetane)methoxy]propyl]silsesquioxane] derivatives, oxetane silicates, phenolic varnish-type oxetane, 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene, OXT121 (manufactured by Toa Synthetic, trade name) and OXT221 (manufactured by Toa Synthetic, trade name), etc.

[0143] 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), and 4-methyl-N,N'- -1,3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane.

[0144] Examples of allyl compounds include allyl alcohol, allyl anisole, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3,5-tristylacetate, triallyl trimellitate, triallyl phosphate, triallyl phosphite, and triallyl citrate.

[0145] Examples of end-capped isocyanate compounds include hexamethylene diisocyanate-based end-capped 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 Corporation, and 7960, 7961, 7982, 7991 and 7992 manufactured by Baxenden Corporation), toluene diisocyanate-based end-capped isocyanates (e.g., TAKENATE B-830 manufactured by Mitsui Chemicals Corporation), and 4,4'-diphenylmethane diisocyanate-based end-capped isocyanates (e.g., TAKENATE B-815N manufactured by Mitsui Chemicals Corporation, DAIEI...). SANGYO Corporation manufactures Blonate PMD-OA01 and PMD-MA01, 1,3-bis(isocyanate methyl)cyclohexane-terminated isocyanates (e.g., Mitsui Chemicals Corporation manufactures TAKENATE B-846N, Tosoh Corporation manufactures BI-301, 2507 and 2554, etc.), and isophorone diisocyanate-terminated isocyanates (e.g., Baxenden manufactures 7950, 7951 and 7990, etc.).

[0146] Among these, alkoxymethyl compounds and bismaleimide compounds are preferred in terms of effectively improving chemical resistance and glass transition temperature.

[0147] When the photosensitive resin composition contains a thermal crosslinking agent (F), the amount of the thermal crosslinking agent (F) 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 soluble polyimide (A).

[0148] Hindered phenolic compounds

[0149] To suppress discoloration on copper surfaces, the photosensitive resin composition may optionally contain hindered phenolic compounds.

[0150] Examples of hindered phenolic compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,2-thio-diethylidene bis[3- [3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H) 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-sec-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 Ketones, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3 Examples of 5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, are included, but not limited to these.

[0151] Among them, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0152] Based on 100 parts by weight of soluble polyimide (A), the amount of hindered phenolic compound in the photosensitive resin composition is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight from the viewpoint of photosensitivity characteristics. When the amount of hindered phenolic compound based on 100 parts by weight of soluble polyimide (A) is 0.1 parts by weight or more, for example, if the photosensitive resin composition of this disclosure is formed on copper or copper alloy, discoloration and corrosion of copper or copper alloy can be prevented. On the other hand, when it is 20 parts by weight or less, the photosensitivity is excellent.

[0153] organotitanium compounds

[0154] The photosensitive resin composition may contain organotitanium compounds. By including organotitanium compounds in the photosensitive resin composition, it is possible to form a photosensitive resin layer with excellent chemical resistance even when cured at low temperatures.

[0155] As an example of an organotitanium compound that can be used in this embodiment, one can cite an organic group that is bonded to a titanium atom via a covalent bond or an ionic bond.

[0156] Specific examples of organotitanium compounds are shown in I) to VII) below:

[0157] I) Titanium chelates: Among these, titanium chelates having two or more alkoxy groups are preferred from the perspective of good storage stability of negative photosensitive resin compositions and the ability to obtain good cured patterns. Specific examples are bis(triethanolamine)diisopropoxy titanium, bis(n-butanol)bis(2,4-pentanediol) titanium, diisopropoxybis(2,4-pentanediol) titanium, diisopropoxybis(tetramethylheptanedioic acid) titanium, and diisopropyl bis(ethyl acetoacetate)titanate, etc.

[0158] II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetra(ethoxy)titanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenol titanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc.

[0159] III) Titanium eccentricity compounds: for example, trimethoxypentamyl titanium, 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-pyrrolo-1-yl)phenyl)titanium, etc.

[0160] IV) Monoalkoxy titanium compounds: for example, tris(dioctylphosphoyloxy)isopropanol titanium, tris(dodecylbenzenesulfonyloxy)isopropanol titanium, etc.

[0161] V) Titanium oxide compounds: such as bis(pentanedione) titanium oxide, bis(tetramethylheptadecanoic acid) titanium oxide, phthalocyanine titanium oxide, etc.

[0162] VI) Tetraacetylacetone titanium compounds: such as tetraacetylacetone titanium, etc.

[0163] VII) Titanate coupling agents: such as isopropyltris(dodecylbenzenesulfonyl) titanate, etc.

[0164] Of these, from the viewpoint of exhibiting better chemical resistance, at least one compound selected from the group consisting of I) titanium chelates, II) tetraalkoxy titanium compounds, and III) dicarboxylated titanium compounds is preferred as the organotitanium compound. Particularly preferred are diisopropyl bis(ethyl acetoacetate) titanate, tetra(n-butoxy) titanium, and bis(n-butoxy) titanium. 5 -2,4-Cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium.

[0165] When an organotitanium compound is incorporated into the photosensitive resin composition, based on 100 parts by weight of soluble polyimide (A), the amount of the organotitanium compound incorporated is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight. When the amount incorporated is 0.05 parts by weight or more, the resulting cured pattern exhibits good heat resistance and chemical resistance; on the other hand, when it is 10 parts by weight or less, the photosensitive resin composition exhibits excellent storage stability.

[0166] Adhesive additives

[0167] 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 adhesive aid. As an adhesive aid, aluminum-based adhesive aids, silane coupling agents, etc., may be used.

[0168] Examples of aluminum-based adhesive additives include tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl aluminum acetoacetate diisopropyl ester.

[0169] Examples of silane coupling agents include γ-aminopropyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyl dimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, 3-methacryloyloxypropyl dimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, and N-(3-diethoxymethylsilane). Silylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-(trialkoxysilyl)propylsuccinic anhydride,

[0170] 3-Mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-Mercaptopropyltriethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-Mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SIM6473.0), 3-Mercaptopropyldiethoxymethoxysilane, 3-Mercaptopropylethoxydimethoxysilane, 3-Mercaptopropyltripropoxysilane Alkane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltrimethoxypropoxysilane, 2-mercaptoethyltrimethoxypropoxysilane, 2-mercaptoethyltrimethoxydipropoxysilane, 2-mercaptoethyltrimethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane

[0171] N-(3-Triethoxysilylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxysilylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxysilylpropyl)urea, N-(3-ethoxydimethoxysilylpropyl)urea, N-(3-tripropoxysilylpropyl)urea, N-(3-diethoxypropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-ethoxydipropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea, N-(3-dimethoxypropoxysilylpropyl)urea N-(3-methoxydipropoxysilylpropyl)urea, N-(3-trimethoxysilylethyl)urea, N-(3-ethoxydimethoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-tripropoxysilylethyl)urea, N-(3-ethoxydipropoxysilylethyl)urea, N-(3-dimethoxypropoxysilylethyl)urea, N-(3-methoxydipropoxysilylethyl)urea, N-(3-trimethoxysilylbutyl)urea, N-(3-triethoxysilylbutyl)urea, N-(3-tripropoxysilylbutyl)urea

[0172] 3-(m-aminophenoxy)propyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxysilane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxysilylethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxysilylethyl)pyridine, 2-(dimethoxysilylmethylethyl)pyridine, 2-(diethoxysilylmethylethyl)pyridine, (3-triethoxysilylpropyl)-tert-butylcarbamate, (3-epoxypropoxypropyl) Triethoxysilane; tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetratert-butoxysilane, tetra(methoxyethoxysilane), tetra(methoxy-n-propoxysilane), tetra(ethoxyethoxysilane), tetra(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, ditert-butoxydiacetoxysilane, diisobutoxyaluminoxytriethoxysilane,

[0173] Phenylacetyl silanetriol, methylphenyl silanediol, ethylphenyl silanediol, n-propylphenyl silanediol, isopropylphenyl silanediol, n-butylphenyl silanediol, isobutylphenyl silanediol, tert-butylphenyl silanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenyl silanol, n-propylmethylphenyl silanol, isopropylmethylphenyl silanol, n-butylmethylphenyl silanol, isobutylmethylphenyl silanol, tert-butylmethylphenyl silanol The list includes silane coupling agents represented by the following formulas (S-1), but is not limited to these.

[0174]

[0175] From the viewpoint of adhesive strength, silane coupling agents are more preferred among these adhesive aids. As a silane coupling agent, from the viewpoint of preservation stability, one or more of the following are preferred: selected from the group consisting of phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydip-tolylsilane, triphenylsilanol, and silane coupling agents represented by each of the above formulas (S-1).

[0176] When the photosensitive resin composition contains an adhesive additive, the amount of adhesive additive mixed in is preferably in the range of 0.01 to 25 parts by weight, more preferably in the range of 0.5 to 20 parts by weight, based on 100 parts by weight of soluble polyimide (A). When a silane coupling agent is used as the adhesive additive, the amount mixed in is preferably 0.01 to 20 parts by weight, based on 100 parts by weight of soluble polyimide (A).

[0177] Sensitizer

[0178] To improve photosensitivity, the photosensitive resin composition may optionally contain a sensitizer. Examples of sensitizers include milchone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylamino... Cinnamyl indane, p-dimethylaminophenylmethylene indane, 2-(p-dimethylaminophenylbenzylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminobenzyl)acetone (e.g., 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzylmethoxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, etc.) They can be used individually or in combination, for example, 2 to 5 types.

[0179] When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of sensitizer mixed in is preferably 0.1 to 25 parts by weight, based on 100 parts by weight of soluble polyimide (A).

[0180] Thermal inhibitors

[0181] To improve the stability of viscosity and photosensitivity, especially when stored in a solvent-containing solution, the photosensitive resin composition may optionally contain a heat-inhibiting polymerization agent. Examples of heat-inhibiting polymerization agents 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.

[0182] <Method for manufacturing solidified embossed patterns>

[0183] The method for manufacturing a solidified embossed pattern disclosed herein includes:

[0184] (1) The process of coating the above-disclosed photosensitive resin composition onto a substrate and forming a photosensitive resin layer on the substrate (resin layer formation process).

[0185] (2) The process of exposing the above-mentioned photosensitive resin layer (exposure process);

[0186] (3) The process of developing the exposed photosensitive resin layer to form an embossed pattern (embossed pattern forming process); and

[0187] (4) The process of heating the above relief pattern to form a solidified relief pattern (solidified relief pattern forming process).

[0188] (1) Resin layer formation process

[0189] In this process, a photosensitive resin composition is coated onto the surface of a substrate, and then dried as needed to form a photosensitive resin layer. As a coating method, conventional coating methods for photosensitive resin compositions can be used, such as coating methods using a spin coater, bar coater, doctor blade coater, curtain coater, screen printer, or spray coating method using a spray gun.

[0190] The coating containing the photosensitive resin composition can be dried as needed. Drying methods include air drying, drying using an oven or hot plate, and vacuum drying. Specifically, in the case of air drying or heating drying, drying can be carried out at 20°C to 150°C for 1 minute to 1 hour. As described above, a photosensitive resin layer can be formed on the surface of the substrate.

[0191] (2) Exposure process

[0192] In this process, an exposure device such as a contact aligner, mirror projector, or stepper is used to expose the aforementioned photosensitive resin layer through a patterned photomask or reticle, or directly using an ultraviolet light source. Through this exposure, the polymerizable groups of the soluble polyimide contained in the photosensitive resin composition and / or the polymerizable groups of the photopolymerizable unsaturated monomers (E) are crosslinked by the action of a photopolymerization initiator (B). This crosslinking makes the material insoluble in the developing solution described later, thus enabling the formation of an embossed pattern.

[0193] Then, for purposes such as improving photosensitivity, post-exposure baking (PEB) or pre-development baking, or both, can be performed as needed, based on any combination of temperature and time. The preferred baking conditions are a temperature of 40°C to 120°C and a time of 10 seconds to 240 seconds, but are not limited to this range as long as they do not impair the properties of the photosensitive resin composition.

[0194] (3) Relief pattern formation process

[0195] In this process, the unexposed portions of the exposed photosensitive resin layer are removed through development. The development method for the exposed photosensitive resin layer can be any of the conventional photoresist development methods, such as rotary spraying, paddle spraying, or immersion methods with ultrasonic treatment. After development, post-development baking can be performed as needed, based on any combination of temperature and time, for purposes such as adjusting the shape of the embossed pattern.

[0196] The developer used in developing is preferably a good solvent for the photosensitive resin composition, or a combination of such a good solvent and a poor solvent. Good solvents include, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. Poor solvents include, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When a good solvent and a poor solvent are used in combination, the ratio of the poor solvent to the good solvent is preferably adjusted according to the solubility of the polymer in the negative photosensitive resin composition. Two or more solvents may also be used in combination, for example, multiple solvents.

[0197] (4) Solidification of relief pattern formation process

[0198] In this process, the embossed pattern obtained through the above development is heat-treated to evaporate the photosensitive components and convert them into a cured embossed pattern. Various methods can be used for heat treatment, such as using a hot plate, using an oven, or using a temperature-programmable oven. The heat treatment can be performed at 150°C to 350°C for 30 minutes to 5 hours. The preferred heat treatment temperature is 150°C to 250°C, more preferably 150°C to 230°C, and even more preferably 170°C to 230°C. Air, or inactive gases such as nitrogen or argon, can be used as the atmosphere for heat curing.

[0199] <Manufacturing Method of Polyimide>

[0200] As another aspect of this disclosure, a method for manufacturing polyimide is provided, comprising a step of curing the photosensitive resin composition described above to form polyimide. The curing conditions of the photosensitive resin composition may be, for example, the same as the baking conditions included in the method for manufacturing a cured embossed pattern described above, or the conditions of the (4) cured embossed pattern forming step.

[0201] Semiconductor Devices

[0202] This disclosure also provides a semiconductor device having a cured embossed pattern obtained from the above-described photosensitive resin composition. More specifically, a semiconductor device is provided having a substrate as a semiconductor element and a cured embossed pattern. The cured embossed pattern may be manufactured using the above-described photosensitive resin composition through the above-described method for manufacturing cured embossed patterns.

[0203] This disclosure can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and incorporates the curing relief pattern of the present disclosure as part of a process. In this case, the curing relief pattern formed using the curing relief pattern manufacturing method of the present disclosure can be formed as a surface protective film, interlayer insulating film, redistribution insulating film, flip chip device protective film, or protective film for a semiconductor device with a bump structure, etc., and can be manufactured in combination with known semiconductor device manufacturing methods.

[0204] <Display Device>

[0205] This disclosure provides a display device comprising a display element and a cured film disposed on the upper part of the display element, the cured film being the aforementioned cured relief pattern. Here, the cured relief pattern can be directly contacted and laminated with the display element, or it can be laminated with other layers sandwiched in between. This cured film can be applied, for example, to surface protective films, insulating films, planarization films, etc., of TFT liquid crystal display elements and color filter elements; protrusions for MVA-type liquid crystal display devices; and spacers for cathodes of organic EL elements.

[0206] In addition to its application in semiconductor devices as described above, the photosensitive resin composition disclosed herein can also be used for interlayer insulation of multilayer circuits, cover coatings of flexible copper clad laminates, solder resists, liquid crystal alignment films, and other applications.

[0207] [Example]

[0208] <Measurement and Evaluation Methods>

[0209] (1) Weight-average molecular weight

[0210] The weight-average molecular weight (Mw) of each resin was determined using gel permeation chromatography (converted to standard polystyrene) under the following conditions.

[0211] Pump: JASCO PU-980

[0212] Detector: JASCO RI-930

[0213] Column oven: JASCO CO-965 40℃

[0214] Column: Showa Denko Co., Ltd., Shodex KD-805 / KD-804 / KD-803 in series

[0215] Standard monodisperse polystyrene: Shodex STANDARD SM-105 manufactured by Showa Denko Corporation; mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP).

[0216] Flow rate: 1 mL / min.

[0217] (2) Evaluation of copper tightness

[0218] The photosensitive resin composition prepared by the method described later was coated onto a 6-inch silicon wafer pre-sputtered with Ti and Cu. After pre-baking, it was heated for 2 hours in a temperature-programmed curing oven (VF-2000, Koyo Lindbergh) under a nitrogen atmosphere at the temperatures listed in Table 1, thereby obtaining a resin-cured film approximately 10 μm thick on Cu. Evercel OPP Tape (No. 830NEV, Sekisui Chemicals) was then attached to the sample, and the OPP tape and polyimide coating were cut into 5 mm wide pieces using a cutter. The polyimide coating was then peeled off from the copper substrate using a Tensilon universal testing machine (RTG-1210, A&D).

[0219] In detail, with the peeling direction at 180 degrees relative to the bonding surface with the copper substrate, a 60mm portion of the polyimide coating with OPP tape was peeled off from the copper substrate at a speed of 50mm / min using a Tensilon universal testing machine (RTG-1210, manufactured by A&D). The load at this point was calculated by integral averaging and used as the adhesion strength to evaluate the copper adhesion.

[0220] (3) Elongation determination

[0221] On a 6-inch silicon wafer with an aluminum vapor-deposited layer on its outermost surface, the photosensitive resin compositions obtained in the examples and comparative examples were spin-coated to a cured film thickness of approximately 5 μm. The mixture was then heat-treated for 2 hours at the temperatures listed in Table 1 under a nitrogen atmosphere to obtain a resin-cured film. The cured film was cut into 3 mm wide pieces using a cutting saw and then peeled off from the wafer using a dilute hydrochloric acid aqueous solution. Twenty samples were then left to stand for at least 24 hours at 23°C and 50% humidity, and the elongation (%) was measured using a tensile testing machine (e.g., Tensilon). The tensile testing conditions are as follows.

[0222] Temperature: 23℃

[0223] Humidity: 50%

[0224] Initial sample length: 50 mm

[0225] Test speed: 40 mm / min

[0226] Load sensor rated value: 2 kgf

[0227] (4) Evaluation of the chemical resistance of the cured embossed pattern (polyimide coating)

[0228] The cured relief pattern formed on Cu was immersed in a resist stripping solution {ATMI product ST-44, main components 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 using an optical microscope, and chemical resistance was evaluated based on the presence of cracks or other damage caused by the chemical solution and the rate of change in film thickness after chemical treatment. Chemical resistance was evaluated according to the following criteria.

[0229] "Excellent": No cracks were produced, and the film thickness change rate, based on the film thickness before drug impregnation, was less than 10%.

[0230] "Good": No cracks were produced, and the film thickness change rate, based on the film thickness before drug impregnation, was greater than 10% but less than 15%.

[0231] "Qualified": No cracks were produced, and the film thickness change rate, based on the film thickness before drug impregnation, was between 15% and 20%.

[0232] "Unacceptable": Cracks appear, or the film thickness variation rate exceeds 20%.

[0233] <Manufacturing Example 1>

[0234] In a flask equipped with a stirrer and a condenser, 20.8 g (40.0 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy)phthalic anhydride was dissolved in 100 g of N-methylpyrrolidone within a temperature range of 20°C to 30°C. Next, 15.3 g (37.2 mmol) of 4,4'-isopropylidene bis[(4-aminophenoxy)benzene] was added, and the mixture was stirred for 1 hour. Then, the mixture was heated to 190°C while passing nitrogen gas through it, stirred for 5 hours, and then cooled to below 30°C. The solution was then diluted with 50 g of tetrahydrofuran, precipitated in 2 L of methanol, filtered, recovered, and vacuum dried at 45°C for 1 day to obtain polyimide resin (A-1). The obtained polyimide (A-1) had a weight-average molecular weight of 18,000.

[0235] <Manufacturing Example 2>

[0236] 20.80 g (40 mmol) of 4,4'-(4,4'-isopropylidene diphenoxy) phthalic anhydride was dissolved in 70 g of N-methylpyrrolidone (NMP). Next, 9.08 g (35.2 mmol) of 4,4'-isopropylidene bis(2-aminophenol) was dissolved in 50 g of NMP and added dropwise over 1 hour at a temperature of 10 °C–25 °C. After stirring at 25 °C for 30 minutes, 10 g of toluene was added, and the reaction was carried out at 200 °C for 4 hours under nitrogen gas. The mixture was 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-oxy radical were added. After reacting at 95°C for 15 hours, the mixture was cooled to 25°C and diluted with 120 g of tetrahydrofuran. Then, the reaction mixture was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was re-slurryed with 1 L of water, filtered, and then re-slurryed again with 1 L of methanol and filtered. The resin was then dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 250g of tetrahydrofuran, and 40g of ion exchange resin (MB-1: manufactured by Organo) was added. The mixture was stirred for 4 hours, and after filtering to remove the ion exchange resin, the polyimide resin was precipitated in 2 liters of methanol and stirred for 15 minutes. The polyimide resin was then filtered and dried at 45°C under reduced pressure for 1 day to obtain polyimide (A-2). The weight-average molecular weight of the obtained polyimide (A-2) was 16,000.

[0237] <Manufacturing Example 3>

[0238] The polymerization reaction was carried out in a 1-liter three-necked jacketed round-bottom flask equipped with a mechanical stirrer, thermocouples, and a nitrogen inlet for maintaining positive nitrogen pressure in the reaction mixture. 39.95 g of 4,4'-[1,4-phenylene-bis(1-methylethylene)]bisphenylamine (DAPI) and 600 g of anhydrous N-methyl-2-pyrrolidone were added to the flask. 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-trimethylindanam-5,6-dicarboxylic acid dianhydride (DAPI dianhydride) was added to the stirred diamine solution via a funnel. The funnel was rinsed with 66.0 g of anhydrous N-methylpyrrolidone into the reaction flask. The mixture was heated to 60 °C and stirred for 3 hours.

[0239] 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. The mixture was stirred at 60 °C for 3 hours.

[0240] To carry out the imidization reaction, 10.2 g of acetic anhydride and 2.0 g of pyridine were added to a reaction vessel. The reaction mixture was heated to 100 °C and stirred continuously for 12 hours. A small sample (1 g) was taken out and precipitated in a 50:50 methanol:water solution (10 ml). The solid was separated by filtration and dried. Fourier transform infrared spectroscopy analysis confirmed that the imidization reaction was complete.

[0241] 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 re-slurryed with 1 liter of methanol and filtered. The wet filter cake was dried in air for 12 hours and then vacuum dried at 70°C for 12 hours to obtain polyimide A-3. The weight-average molecular weight of the obtained polyimide (A-3) was 16,000.

[0242] <Example 1>

[0243] A negative photosensitive resin composition was prepared by the following method, and the prepared composition was evaluated. A-1 (100g) as (A) a soluble polyimide, 1,2-propanedione-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) (B-1) (6g) as a photopolymerization initiator, N-ethyl-2-pyrrolidone (200g) as a solvent (C), benzotriazole (0.4g) as a nitrogen-containing heterocyclic compound (D), and polyethylene glycol dimethacrylate (E-1) (30g) as a photopolymerizable unsaturated monomer (E) were added and dissolved to prepare the photosensitive resin composition. The composition was evaluated according to the above method. The results are shown in Table 1. Furthermore, a fan-out type wafer-level chip-scale packaged semiconductor device was fabricated, and it operated without problems.

[0244] <Examples 2 to Examples 24>

[0245] Except for the composition shown in Table 1, the photosensitive resin composition was prepared and evaluated using the same method as in Example 1.

[0246] <Comparative Examples 1 to 4>

[0247] Except for the composition shown in Table 1, the photosensitive resin composition was prepared and evaluated using the same method as in Example 1.

[0248] In addition, a fan-out wafer-level chip-scale packaged semiconductor device was fabricated, but it did not work.

[0249] [Table 1-1]

[0250] Table 1

[0251]

[0252] [Table 1-2]

[0253] Table 1

[0254]

[0255] [Table 1-3]

[0256] Table 1

[0257]

[0258] Explanation of the components in Table 1 (In Table 1, the values ​​for each component are expressed in grams (g)).

[0259] (A) Soluble polyimide

[0260] The above synthetic examples synthesized A-1 to A-3

[0261] (B) Photopolymerization initiator

[0262] B-1: 1,2-Propanedion-3-cyclopentyl-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime)

[0263] B-2: 3-Cyclopentyl-1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyloxime)

[0264] (C) Solvent

[0265] C-1: N-Ethyl-2-pyrrolidone (boiling point: 218℃)

[0266] C-2: Ethyl lactate (boiling point: 154℃)

[0267] C-3: γ-Butyrolactone (boiling point: 204℃)

[0268] C-4: 1,3-Dimethyl-2-imidazolinone (boiling point: 220℃)

[0269] C-5: 3-Methoxy-N,N-Dimethylpropionamide (boiling point: 215℃)

[0270] C-6: 3-Butoxy-N,N-Dimethylpropionamide (boiling point: 252℃)

[0271] C-7: γ-valerolactone (boiling point: 207℃)

[0272] C-8: N-methyl-2-pyrrolidone (boiling point: 204℃)

[0273] C-9: Dimethyl sulfoxide (boiling point: 189℃)

[0274] C-10: Cyclopentanone (boiling point: 131℃)

[0275] (D) Nitrogen-containing heterocyclic compounds

[0276] D-1: Benzotriazole

[0277] D-2: 5-Aminotetrazole

[0278] D-3: N,N-dimethyladenine

[0279] D-4: N-methylguanine

[0280] (E) Photopolymerizable unsaturated monomers

[0281] E-1: Polyethylene glycol dimethacrylate

[0282] E-2: Tris-(2-Acryloyloxyethyl)isocyanurate

[0283] E-3: 1,10-Decanediol diacrylate

[0284] (F) Thermal crosslinking agent

[0285] F-1: 1,3,4,6-Tetra(methoxymethyl)glycourea

[0286] F-2: N,N'-m-phenylenebismaleimide

Claims

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

2. The photosensitive resin composition according to claim 1, wherein The (A) soluble polyimide 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 (E) photopolymerizable unsaturated monomer has 3 or more (meth)acrylic acid groups in a molecule.

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

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

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

10. The photosensitive resin composition according to claim 1, wherein The (A) soluble polyimide is represented by the following formula (1), In formula (1), X represents a 4-valent organic group having a carbon number of 4 to 32, and Y represents a 2-valent organic group having a carbon number of 4 to 40.

11. The photosensitive resin composition according to claim 10, wherein The X is at least one selected from the group consisting of the following general formulae (2) to (6), 12. The photosensitive resin composition according to claim 10, wherein The Y is at least one selected from the group consisting of the following general formulae (7) to (9), 13. The photosensitive resin composition according to claim 1, wherein The (B) photopolymerization initiator is an oxime compound.

14. The photosensitive resin composition according to claim 1, wherein The (B) photopolymerization initiator is represented by the following general formula (19) or general formula (20), In the formula, Ra represents a 1-valent organic group having a carbon number of 1 to 10, Rb represents a 1-valent organic group having a carbon number of 1 to 20, Rc represents a 1-valent organic group having a carbon number of 1 to 10, and Rd represents a 1-valent organic group having a carbon number of 1 to 10; In the formula, Re represents a 1-valent organic group having a carbon number of 1 to 20, and Rf represents a 1-valent organic group having a carbon number of 1 to 10.

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

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

17. A method for producing a cured relief pattern, comprising the following steps: (1) a step of 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) a step of exposing the photosensitive resin layer; (3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern; and (4) a step of performing a heat treatment on the relief pattern to form a cured relief pattern.

Images