Negative photosensitive resin composition and production method for cured relief pattern

Abstract

Provided is a negative photosensitive resin composition that includes (A) a polyimide precursor or a polyimide, (B) a monofunctional (meth)acrylate compound represented by general formula (3) (in which R6 and R7 are as defined in the description), and (C) an end-capped polyalkylene glycol compound represented by general formula (4) (in which R8–R10 and n2 are as defined in the description).

Description

Negative-type photosensitive resin composition and method for producing cured relief pattern

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

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

[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 the GHz range, 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] Therefore, flip-chip mounting has been proposed, in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, and then the chip is flipped over and directly mounted on a printed circuit board. Because flip-chip mounting allows for precise control of wiring distance, it has been adopted for high-end applications that handle high-speed signals, and for mobile phones and other devices due to its small mounting size, resulting in rapidly expanding demand. More recently, a semiconductor chip mounting technology called fan-out wafer-level packaging (FOWLP) has been proposed, in which a pre-processed wafer is diced to produce individual chips, the individual chips are reassembled on a support, encapsulated with a molding resin, and a rewiring layer is formed after the support is peeled off (see, for example, Patent Document 1). In FOWLP, the rewiring layer is formed with a thin film thickness, which allows for a thinner package, as well as higher-speed transmission and lower costs. Patent Document 1, for example, discloses a photosensitive resin composition used in such a rewiring layer.

[0005] International Publication No. 2019 / 163860

[0006] Patent Document 1 discloses the use of a plasticizer such as epoxidized oil to prevent the occurrence of orange peel when a coating film is formed on a metal surface. However, the composition described in Patent Document 1 often has insufficient adhesion to copper and resolution.

[0007] Therefore, an object of the present invention is to provide a negative photosensitive resin composition having good adhesion to copper and good resolution, and a method for producing a cured relief pattern using the photosensitive resin composition.

[0008] In view of the problems of the above-mentioned conventional techniques, the present inventors have conducted extensive research and experiments, and as a result have found that the above-mentioned problems can be solved by combining a monofunctional (meth)acrylate compound and a specific polyalkylene glycol compound in a negative-type photosensitive resin composition, thereby completing the present invention.

[0009] [Item 1] (A) a polyimide precursor or a polyimide, (B) a compound represented by the following general formula (3): {In the formula, R ６is a hydrogen atom or a methyl group, and R ７ is a monovalent organic group not containing a (meth)acryloyl group.}, and (C) a monofunctional (meth)acrylate compound represented by the following general formula (4): {In the formula, R ８ and R ９ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ８ and R ９ At least one of R is an alkyl group having 1 to 6 carbon atoms, １０ is an alkylene group having 2 to 4 carbon atoms, and n ２ is an integer of 2 to 12.}. [Item 2] A negative-type photosensitive resin composition comprising a terminal-capped polyalkylene glycol-based compound represented by the following general formula (1): [In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a group represented by the following general formula (2): {In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.}, or a saturated aliphatic group having 1 to 4 carbon atoms. Item 3: The negative photosensitive resin composition according to Item 1, wherein in the general formula (4), n ２ Item 4. The negative photosensitive resin composition according to item 1 or 2, wherein R is an integer of 3 to 12. ７ [Item 5] The negative-type photosensitive resin composition according to any one of Items 1 to 4, wherein the molecular weight of the component (B) is 500 or less. [Item 6] In the general formula (3), R ７ [Item 7] The negative photosensitive resin composition according to any one of items 1 to 5, wherein R is an organic group not containing a cyclic skeleton. ６[Item 8] The negative photosensitive resin composition according to any one of items 1 to 6, wherein R is a methyl group. １０ [Item 9] The negative photosensitive resin composition according to any one of items 1 to 7, wherein in the general formula (4), R ８ and R ９ [Item 10] The negative photosensitive resin composition according to any one of items 1 to 8, wherein R in the general formula (3) is independently an alkyl group having 1 to 6 carbon atoms. ７ is an organic group containing a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms. [Item 11] The negative photosensitive resin composition according to any one of Items 1 to 10, comprising 0.1 to 10 parts by mass of the component (B) per 100 parts by mass of the component (A). [Item 12] The negative photosensitive resin composition according to any one of Items 1 to 11, comprising 0.1 to 10 parts by mass of the component (C) per 100 parts by mass of the component (A). [Item 13] The negative photosensitive resin composition according to any one of Items 1 to 12, further comprising (D) a photopolymerization initiator. [Item 14] (D) a group represented by the following general formula (5): (In the formula, R １１ is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms. Item 15. A method for producing a cured relief pattern, comprising: forming a photosensitive resin layer on a substrate by applying the negative photosensitive resin composition according to any one of Items 1 to 14 onto the substrate; exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form a relief pattern; and heat-treating the relief pattern to form a cured relief pattern.

[0010] According to the present invention, it is possible to provide a negative-type photosensitive resin composition that exhibits high adhesion to copper and is capable of obtaining good resolution, and a method for producing a cured relief pattern using the photosensitive resin composition.

[0011] <Negative Photosensitive Resin Composition> The negative photosensitive resin composition according to this embodiment (hereinafter referred to as the photosensitive resin composition of this embodiment) is a negative photosensitive resin composition (hereinafter also referred to as the "photosensitive resin composition") containing: (A) a polyimide precursor or polyimide, (B) a monofunctional (meth)acrylate compound represented by general formula (3), and (C) a terminal-capped polyalkylene glycol-based compound represented by general formula (4). Other components may be included as desired. Each component will be described below in order. Throughout this specification, when a plurality of structures represented by the same symbol in a general formula are present in a molecule, they may be the same or different from each other.

[0012] [Component (A): Polyimide precursor or polyimide] Component (A) is a polyimide precursor or polyimide. In one embodiment, the polyimide precursor may be a polyamic acid or a polyamic acid ester. The polyimide may be obtained by cyclizing a polyimide precursor by heating (for example, at 200°C or higher) to perform a cyclization treatment. The polyimide precursor is represented by the following general formula (1): [In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a group represented by the following general formula (2): {In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.}, or a saturated aliphatic group having 1 to 4 carbon atoms.].

[0013] In the above general formula (1), X １ The tetravalent organic group represented by the formula (I) is preferably an organic group having 6 to 40 carbon atoms, and more preferably, —COOR １ group and -COOR ２A group in which the —CONH— group and the —CONH— group are in the ortho position relative to each other (particularly an aromatic group or an alicyclic aliphatic group). More preferably, the group is represented by the following formula (*): and n is at least one group selected from the group consisting of structures represented by the following formula:

[0014] X １ From the viewpoint of achieving both mechanical properties and photosensitive properties, it is particularly preferable that the tetravalent organic group represented by the formula (X) has a structure selected from at least one of 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA). １ The structure of may be one type or a combination of two or more types, but from the viewpoint of improving resolution, it is preferable to use a combination of two or more types. １ When 4,4'-oxydiphthalic anhydride (ODPA) is selected as the acid anhydride that gives １ is represented by the following general formula (6): The structure is represented by the formula: １ When pyromellitic dianhydride (PMDA) is selected as the acid anhydride that gives １ is represented by the following general formula (7): From the viewpoint of achieving both heat resistance and photosensitive properties, the above X １ is preferably at least one structure selected from the group consisting of the general formulas (6) and (7).

[0015] In the above formula (1), Y １ From the viewpoint of achieving both mechanical properties and photosensitive properties, the divalent organic group represented by the formula (**) below is preferably an aromatic group having 6 to 40 carbon atoms, and is, for example, a divalent organic group represented by the formula (**): However, the present invention is not limited to these. １ The structure may be one type or a combination of two or more types.

[0016] In the above formula (1), Y １ A divalent organic group represented by the formula (i.e., Y１ The diamine giving the formula (Y) is preferably selected from at least one of diaminodiphenyl ether (DADPE), p-phenylenediamine (pPD), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: m-tolidine). It is particularly preferable to select from at least one of diaminodiphenyl ether (DADPE) and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) from the viewpoint of achieving both heat resistance and photosensitive properties. １ When 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB) is selected as the diamine that gives １ is represented by the following general formula (8): Among these, from the viewpoint of achieving both heat resistance and photosensitive properties, the above Y １ is preferably a structure represented by the above general formula (8).

[0017] The component (A) is represented by the above formula (1) and R １ and R ２ It is preferable that at least one of R contains a group represented by the above formula (2). １ and R ２ that is, R in formula (2) ４ and R ５ are preferably both hydrogen atoms.

[0018] [Method for Preparing Polyimide Precursor] The polyimide precursor represented by the general formula (1) in this embodiment can be prepared by, for example, １ and (a) an alcohol formed by bonding a monovalent organic group represented by the general formula (2) and a hydroxyl group to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester or component (a)). １ and diamines containing the same.

[0019] (Preparation of Acid / Ester Form) In this embodiment, a tetravalent organic group X having 6 to 40 carbon atoms １ Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. These may be used alone or in combination of two or more.

[0020] In the present invention, examples of alcohols having a photopolymerizable group that are preferably used to prepare an ester bond type polyimide precursor include 2-hydroxyethyl methacrylate, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the hydroxypropyl acrylate include 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

[0021] As the saturated aliphatic alcohols that can be optionally used together with the alcohols having a photopolymerizable group, saturated aliphatic alcohols having 1 to 4 carbon atoms are preferred, and specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

[0022] The content of the component (a) in the negative photosensitive resin composition is R １ and R ２ It is preferable that the content of the component (a) exceeds 80 mol % relative to the total content of R. When the content of the component (a) exceeds 80 mol %, it is possible to obtain desired photosensitive properties, which is preferable. The content of the component (a) in the negative photosensitive resin composition is １ and R ２It is preferably 85 mol % or more, more preferably 90 mol % or more, and even more preferably 95 mol % or more, based on the total content of the above.

[0023] The above-mentioned tetracarboxylic acid dianhydride and the above-mentioned alcohol are stirred, dissolved, and mixed in a reaction solvent in the presence of a basic catalyst such as pyridine at a reaction temperature of 20 to 50°C for 4 to 10 hours, whereby the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester form can be obtained.

[0024] The reaction solvent is preferably one that dissolves the acid / ester compound and the polyimide precursor that is a polycondensation product of the acid / ester compound and a diamine, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used alone or in combination as needed.

[0025] (Preparation of Polyimide Precursor) A known dehydration condensation agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, or the like, is added to and mixed with the above acid / ester compound (typically a solution in the above reaction solvent) under ice cooling to convert the acid / ester compound into a polyacid anhydride, and then a divalent organic group Y having 6 to 40 carbon atoms in general formula (1) is added to the polyacid anhydride. １A diamine containing the above compound is dissolved or dispersed in a solvent and added dropwise to the resulting mixture, followed by polycondensation, to obtain a polyimide precursor that can be used in the embodiment.

[0026] Divalent organic group Y preferably used in the present invention １Examples of diamines containing the above include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3' -diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(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 compounds 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, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof can be used.

[0027] Among these, it is preferable to use 4,4'-diaminodiphenyl ether, p-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and it is more preferable to use 4,4'-diaminodiphenyl ether, p-phenylenediamine, or 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0028] Furthermore, for the purpose of improving adhesion to various substrates, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized.

[0029] After the reaction is completed, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component, and the polymer is purified by repeating redissolution and reprecipitation procedures, followed by vacuum drying to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion exchange resin and / or a cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

[0030] The molecular weight of the polyimide precursor, 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, and particularly preferably 20,000 to 40,000. A weight average molecular weight of 8,000 or more is preferred because mechanical properties are good, while a weight average molecular weight of 150,000 or less is preferred because dispersibility in a developer and resolution performance of a relief pattern are good.

[0031] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weights of the components used in the examples and comparative examples are determined from calibration curves prepared using standard monodisperse polystyrenes. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample, STANDARD SM-105, manufactured by Showa Denko K.K.

[0032] <Polyimide> The polyimide used in the present embodiment will be described below. The resin component in the photosensitive resin composition is preferably a polyimide resin having a structural unit represented by the following general formula (9). {In the formula, X ２ is a tetravalent organic group, and Y ２ is a divalent organic group, and n is an integer of 2 to 150.} The resin represented by general formula (9) is particularly preferred in that it does not require chemical change in the heat treatment step in order to exhibit sufficient film properties, and is therefore suitable for treatment at lower temperatures.

[0033] In general formula (9), X ２ and / or Y ２ From the viewpoint of heat resistance, the tetravalent organic group preferably contains an aromatic ring structure, more preferably contains 6 to 40 carbon atoms, and further preferably contains a benzene ring structure.

[0034] In general formula (9), X ２ and / or Y ２ The divalent organic group preferably has a structure in which 2 to 6 benzene rings are bonded via a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a fluorinated alkylene group, and an ether group. The alkylene group and the fluorinated alkylene group may be linear or branched.

[0035] Polyimides can be obtained by reacting tetracarboxylic acids, the corresponding tetracarboxylic dianhydrides, tetracarboxylic diester dichlorides, etc. with diamines, the corresponding diisocyanate compounds, trimethylsilylated diamines, etc. Polyimides can be obtained by dehydrating and cyclizing polyamic acids, which are polyimide precursors generally obtained by reacting tetracarboxylic dianhydrides with diamines, by heating or chemical treatment with acids or bases.

[0036] Suitable tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenoxy)-2,2-dicarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-bis(3,4-dicarboxyphenoxy)-2,2-di ... 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride Examples of the aromatic tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, ...

[0037] Among these, it is preferable to use pyromellitic dianhydride (PMDA), diphenylether-3,3',4,4'-tetracarboxylic dianhydride (ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA). These may be used alone or in combination of two or more.

[0038] Suitable diamines include 3,4'-diaminodiphenyl ether (3,4'-ODA), 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), 3,3',5,5'-tetramethylbenzidine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 3,3'dimethylbenzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-bis(p-aminophenyl)hexafluoropropane, and the like. Pan, bis(trifluoromethoxy)benzidine (TFMOB), 2,2'-bis(pentafluoroethoxy)benzidine (TFEOB), 2,2'-trifluoromethyl-4,4'-oxydianiline (OBABTF), 2-phenyl-2-trifluoromethyl-bis(p-aminophenyl)methane, 2-phenyl-2-trifluoromethyl-bis(m-aminophenyl)methane, 2,2'-bis(2-heptafluoroisopropoxy-tetrafluoroethoxy)benzidine (DF POB), 2,2-bis(m-aminophenyl)hexafluoropropane (6-FmDA), 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 3,6-bis(trifluoromethyl)-1,4-diaminobenzene (2TFMPDA), 1-(3,5-diaminophenyl)-2,2-bis(trifluoromethyl)-3,3,4,4,5,5,5-heptafluoropentane, 3,5-diaminobenzotrifluoride (3,5-DABTF), 3,5-diamino- Examples of the compound include 5-(pentafluoroethyl)benzene, 3,5-diamino-5-(heptafluoropropyl)benzene, 2,2'-dimethylbenzidine (DMBZ), 2,2',6,6'-tetramethylbenzidine (TMBZ), 3,6-diamino-9,9-bis(trifluoromethyl)xanthene (6FCAM), 3,6-diamino-9-trifluoromethyl-9-phenylxanthene (3FCAM), and compounds represented by 3,6-diamino-9,9-diphenylxanthene.

[0039] The molar ratio of diamine to acid dianhydride is basically 1:1. However, to obtain a desired terminal structure, one of them may be used in excess. Specifically, by using an excess of diamine, the terminals (both terminals) of the polyimide tend to become amino groups. On the other hand, by using an excess of acid dianhydride, the terminals (both terminals) of the polyimide tend to become acid anhydride groups. As described above, in this embodiment, it is preferable that the polyimide has acid anhydride groups at its terminals. Therefore, in this embodiment, it is preferable to use an excess of acid dianhydride when synthesizing the polyimide.

[0040] The amino group and / or acid anhydride group at the end of the polyimide obtained by condensation polymerization may be reacted with some kind of reagent so that the polyimide end has a desired functional group.

[0041] The molecular weight of the polyimide, as measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight, is preferably 5,000 to 150,000, more preferably 7,000 to 100,000, and particularly preferably 10,000 to 50,000. A weight average molecular weight of 5,000 or more is preferred because mechanical properties are good, while a weight average molecular weight of 150,000 or less is preferred because dispersibility in a developer and resolution performance of a relief pattern are good.

[0042] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weights of the components used in the examples and comparative examples are determined from calibration curves prepared using standard monodisperse polystyrenes. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample, STANDARD SM-105, manufactured by Showa Denko K.K.

[0043] [Component (B): Monofunctional (meth)acrylate compound; Polymerizable compound] The component (B) is a compound represented by the following general formula (3): {In the formula, R ６ is a hydrogen atom or a methyl group, and R ７is a monovalent organic group not containing a (meth)acryloyl group.}. From the viewpoint of resolution, R ６ is preferably a methyl group.

[0044] Although the reason why the use of such component (B) achieves the effects of the present invention is unclear, the present inventors believe as follows. For a cured film obtained by curing a photosensitive resin composition to exhibit excellent adhesion to copper, it is generally required that the cured film contain little material other than the polyimide component. Typically, during the thermal curing process of a photosensitive resin composition, the volatilization of polymerizable compounds such as (meth)acrylate compounds competes with their thermal polymerization reaction, resulting in a significant amount of polymerized material remaining in the cured film. Here, the use of a monofunctional (meth)acrylate compound represented by the above general formula (3), which has few reactive sites, suppresses the increase in molecular weight of the polymerized material. As a result, it is believed that the volatilization of the polymerizable compound during the thermal curing process takes precedence over the thermal polymerization reaction, thereby reducing the amount of polymerized material remaining in the cured film.

[0045] Therefore, from the viewpoint of the volatility of the polymerizable compound, the molecular weight of component (B) is preferably 1,000 or less, more preferably 500 or less, even more preferably 400 or less, and particularly preferably 300 or less.

[0046] The molecular weight of component (B) is measured by gel permeation chromatography as a weight average molecular weight converted into polystyrene.

[0047] Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weights of the components used in the examples and comparative examples are determined from calibration curves prepared using standard monodisperse polystyrenes. It is recommended that the standard monodisperse polystyrene be selected from the organic solvent-based standard sample, STANDARD SM-105, manufactured by Showa Denko K.K.

[0048] R in formula (3) ７is a monovalent organic group that does not contain a (meth)acryloyl group, and preferably does not contain a thermally polymerizable group other than a (meth)acryloyl group, such as a vinyl group or an allyl group. ７ The structure of R is not particularly limited, and may contain a heteroatom, may contain a cyclic structure, may be a linear or branched, saturated or unsaturated hydrocarbon group. For example, an organic group containing an alkyl group or a polyoxyalkylene group may be mentioned. Among these, R ７ is preferably an organic group not containing a cyclic structure, more preferably an organic group containing a linear or branched hydrocarbon group or a polyoxyalkylene group having 1 to 50 carbon atoms, even more preferably an organic group containing a polyoxyalkylene group having 1 to 50 carbon atoms, and particularly preferably an organic group containing a polyoxyethylene group having 1 to 50 carbon atoms. ７ is represented by the following general formula (10): (Ra represents an alkylene group, and n represents an integer of 1 to 30).

[0049] In the general formula (10), Ra is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. Furthermore, n is preferably an integer of 2 to 20, and particularly preferably an integer of 3 to 15.

[0050] Also, R ７ may contain one or more functional groups or substituents other than a (meth)acryloyl group. Examples thereof include a hydroxy group, a carboxy group, a carbonyl group, an alkoxy group, a phenoxy group, a phenyl group, a naphthyl group, a cyano group, an amino group, and groups combining these groups. ７ may contain one or more arbitrary bonds, such as an ether bond, an ester bond, an amide bond, and a urethane bond.

[0051] In one embodiment, R ７is one or a combination of two or more selected from the group consisting of: a linear or branched, saturated or unsaturated chain hydrocarbon group having 1 to 11 carbon atoms; a saturated or unsaturated monocyclic or polycyclic hydrocarbon group (alicyclic hydrocarbon group) having 3 to 21 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, etc.); an aromatic monocyclic hydrocarbon group having 3 to 21 carbon atoms (e.g., a phenyl group, a phenylene group, etc.); a condensed polycyclic aromatic hydrocarbon group having 6 to 30 carbon atoms (e.g., a naphthyl group, etc.); a group having 1 to 5 heteroatoms selected from nitrogen and oxygen (e.g., an ether bond, an ester bond, a carboxy group, etc.); a saturated or unsaturated monocyclic heterocycle having 1 to 10 heteroatoms selected from nitrogen and oxygen; a monocyclic heteroaromatic ring having 1 to 10 heteroatoms selected from nitrogen and oxygen; and a condensed polycyclic aromatic heteroaromatic ring having 1 to 15 heteroatoms selected from nitrogen and oxygen. R ７ is optionally substituted. In one embodiment, R ７ may be an organic group containing a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms, and optionally containing 1 to 5 groups having a heteroatom selected from the group consisting of nitrogen and oxygen. These groups may be substituted. In one embodiment, the cyclic hydrocarbon group may be a saturated or unsaturated alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The chain hydrocarbon group may be saturated or unsaturated, and may be a straight chain or branched chain. In one embodiment, the group having a heteroatom may be a divalent group having an ether bond or an ester bond, or a carboxy group. R ７ Examples of the alkyl group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, a hydroxy group, an alkoxy group, a carboxy group, a phenyl group, a phenoxy group, a naphthyl group, a cyano group, and an amino group.

[0052] From the viewpoint of adhesion (for example, copper adhesion), R ７ The molecular weight of R is preferably 15 to 1000, more preferably 15 to 450, even more preferably 15 to 350, and particularly preferably 15 to 240. ７The molecular weight (for example, weight average molecular weight) of component (B) can be determined by calculation of the chemical formula of component (B).

[0053] The component (B) can be any (meth)acrylate represented by the general formula (3) without any particular limitation. Examples include polyalkylene glycol mono(meth)acrylates (e.g., diethylene glycol mono(meth)acrylate), alkyl mono(meth)acrylates, cycloalkyl mono(meth)acrylates (e.g., cyclohexyl (meth)acrylate), alkoxy polyalkylene glycol mono(meth)acrylates (e.g., methoxy polyethylene glycol mono(meth)acrylate), hydroxyphenyl mono(meth)acrylate, (meth)acryloyloxyalkyl phthalates (e.g., 2-methacryloyloxyethyl phthalate), alkoxylated o-phenylphenol (meth)acrylates (e.g., methoxylated o-phenylphenol (meth)acrylate and ethoxylated o-phenylphenol (meth)acrylate), and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of adhesion to copper, component (B) is preferably at least one selected from the group consisting of polyalkylene glycol mono(meth)acrylate, alkoxypolyalkylene glycol mono(meth)acrylate, and (meth)acryloyloxyalkyl phthalate, and diethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, and 2-methacryloyloxyethyl phthalate are more preferred. From the viewpoint of resolution, component (B) is preferably at least one selected from the group consisting of polyalkylene glycol mono(meth)acrylate, alkoxypolyalkylene glycol mono(meth)acrylate, and (meth)acryloyloxyalkyl phthalate, and polyalkylene glycol mono(meth)acrylate and alkoxypolyalkylene glycol mono(meth)acrylate are more preferred, and diethylene glycol mono(meth)acrylate and methoxypolyethylene glycol mono(meth)acrylate are even more preferred.

[0054] From the viewpoint of adhesion to copper, the content of component (B) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, still more preferably 1 to 9 parts by mass, and particularly preferably 2 to 8 parts by mass, per 100 parts by mass of component (A).

[0055] [Component (C): Terminal-Capped Polyalkylene Glycol-Based Compound] The component (C) is a polyalkylene glycol-based compound represented by the following general formula (4): {In the formula, R ８ and R ９ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ８ and R ９ At least one of R is an alkyl group having 1 to 6 carbon atoms, １０ is an alkylene group having 2 to 4 carbon atoms, and n ２ is an integer of 2 to 12.}. From the viewpoint of compatibility with component (A), R ８ and R ９ are each independently preferably a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. １０ is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an ethylene group. ２ is preferably an integer of 3 to 12, and more preferably an integer of 4 to 10.

[0056] Although the reason why the use of such component (C) achieves the effects of the present invention is unclear, the present inventors believe it to be as follows. When a relief pattern formed using the photosensitive resin composition is heat-cured, component (C) can improve the fluidity of the polyimide film due to its plasticizing effect. This increases the likelihood of association of reactive sites of the polyimide precursor and polymerizable compound, resulting in the development of good resolution. This effect is particularly important for achieving high resolution in this embodiment, in which component (B), which has few reactive sites, is used as the polymerizable compound. Furthermore, at least one end of component (C) is blocked. In the above general formula (4), R８ and R ９ When at least one of the groups is an alkyl group having 1 to 6 carbon atoms, the hydrogen bond with the polyimide precursor or polyimide is weakened, and component (C) is easily volatilized by heating and is less likely to remain in the polyimide film, which is thought to result in good adhesion. From this perspective, component (C) in which both ends are blocked is preferred, that is, in the above general formula (4), R ８ and R ９ are each preferably independently an alkyl group having 1 to 6 carbon atoms.

[0057] From the viewpoint of the difficulty of volatilization in the drying step at 20 to 140°C immediately after applying the photosensitive resin composition to the substrate, n ２ is preferably 3 to 12. From the viewpoint of ease of volatilization in a thermal curing step at 170°C or higher, at least one of the boiling point and the thermal decomposition temperature is preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.

[0058] Examples of component (C) include polyalkylene glycol monoalkyl ethers (e.g., polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether), polyalkylene glycol dialkyl ethers (e.g., polyethylene glycol dimethyl ether (in one embodiment, triethylene glycol dimethyl ether and diethylene glycol dimethyl ether), and polypropylene dimethyl ether (in one embodiment, tripropylene glycol dimethyl ether)). However, the component (C) is not limited to these.

[0059] From the viewpoint of resolution, the amount of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, even more preferably 0.1 to 10 parts by mass, still more preferably 1 to 9 parts by mass, and particularly preferably 2 to 8 parts by mass, relative to 100 parts by mass of the component (A).

[0060] [Component (D): Photopolymerization Initiator] The photosensitive resin composition of the present embodiment may contain a photopolymerization initiator to efficiently cure upon exposure to light. The photopolymerization initiator can be selected from any compound conventionally used as a photopolymerization initiator for UV curing. In one embodiment, the photopolymerization initiator is a photoradical initiator.

[0061] Examples of the photopolymerization initiator (D) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone; thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-di(4'-diazidobenzal)-4-methylcyclohexyl Examples of compounds that can be used include azides such as 2,6'-di(4'-diazidobenzal)cyclohexanone and 2,6'-di(4'-diazidobenzal)cyclohexanone, oximes such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes. Of these, the oximes are preferred from the viewpoint of photosensitivity.

[0062] Among these, from the viewpoint of easily achieving the effects of the present invention, the photopolymerization initiator (D) is preferably a compound represented by the following general formula (5): (In the formula, R １１is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms.

[0063] The content of the (D) photopolymerization initiator is 0.1 to 20 parts by mass per 100 parts by mass of the (A) component, and from the viewpoint of photosensitivity characteristics, it is preferably 2 to 15 parts by mass. When the (D) photopolymerization initiator is contained in an amount of 0.1 part by mass or more per 100 parts by mass of the (A) component, the photosensitive resin composition has excellent photosensitivity, while when the (D) photopolymerization initiator is contained in an amount of 20 parts by mass or less, the photosensitive resin composition has excellent curability.

[0064] <Other Components> The photosensitive resin composition of the present embodiment may further contain a thermal crosslinking agent, a photopolymerization inhibitor, a sensitizer, a thermal polymerization inhibitor, an adhesion aid, a rust inhibitor, a solvent, and the like.

[0065] (Sensitizer) The photosensitive resin composition of the present embodiment may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers 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-dimethylaminocinnamylideneindano. p-dimethylaminobenzylidene indanone, 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-acetyl

[0039] Examples of the methylaminobenzoate include methylaminobenzoate, ... These may be used alone or in combination of two or more. The content of the sensitizer is preferably 0.1 to 25 parts by mass per 100 parts by mass of the component (A).

[0066] (Photopolymerization Inhibitor) The photosensitive resin composition of the present embodiment may optionally contain a photopolymerization inhibitor to appropriately control the photoradical crosslinking reaction. Examples of the photopolymerization inhibitor include a compound containing an aromatic hydroxyl group, a nitroso compound, an N-oxide compound, a quinone compound, an N-oxyl compound, a phenothiazine compound, and a hindered phenol compound.

[0067] Examples of compounds containing an aromatic hydroxyl group include 4-methoxyphenol (p-methoxyphenol), 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6- Diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, catechol, tert-butyl-catechol, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol phenol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, hydroquinone, methylhydroquinone, t-butylhydroquinone, di-t-butyl-p-cresol, pyrogallol, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), phenol resins, and cresol resins.

[0068] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitrosodiphenylamine, 3,5-dibromo-4-nitrosobenzenesulfonic acid, N-nitrosopyrrolidine, N-t-butyl-N-nitrosoaniline, N-nitrosodimethylamine, N-nitrosodiethylamine, 1-nitrosopiperidine, 4-nitrosomorpholine, N-nitroso-N-methylbutylamine, N-nitroso-N-ethylurea, N-nitrosohexamethyleneimine, N-nitrosophenylhydroxyamine cerous salt, N-nitrosophenylhydroxyamine aluminum salt, 2,4,6-Tris-t-butyl-nitrosobenzene, and N-nitrosodiphenylamine.

[0069] Examples of the N-oxide compounds include phenyl-t-butylnitrone, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide, 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picolinic acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide.

[0070] Examples of quinone compounds include p-benzoquinone, p-xyloquinone, p-toluquinone, 2,6-dimethyl-1,4-benzoquinone, tetramethyl-1,4-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-di-tert-butyl-1,4-benzoquinone, 2,6-di-tert-1,4-benzoquinone, thymoquinone, 2,5-di-tert-amylbenzoquinone, and 2-bromo-1,4-benzoquinone. 1,4-benzoquinone, 2,5-dibromo-1,4-benzoquinone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, 2-bromo-5-methyl-1,4-benzoquinone, tetrafluoro-1,4-benzoquinone, tetrabromo-1,4-benzoquinone, 2-chloro-5-methyl-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, methoxy-1,4-benzoquinone, 2,5-dihydroxy- 1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2,6-dimethoxy-1,4-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, 2,5-diphenyl-1,4-benzoquinone, 1,4-naphthoquinone, 1,4-anthraquinone, 2-methyl-1,4-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-hydroxy- Examples of the anthraquinone include 1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 5-hydroxy-2-methyl-1,4-naphthoquinone, 1-nitroanthraquinone, anthraquinone, 1-aminoanthraquinone, 1,2-benzoanthraquinone, 1,4-diaminoanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthraquinone, 2-methylanthraquinone, and 5,12-naphthacenequinone.

[0071] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and piperidine 1-oxyl free radicals. oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, pyrrolidine 1-oxyl free radical compounds, and 3-carboxyproxyl free radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

[0072] Examples of phenothiazine compounds include phenothiazine, 10-methylphenothiazine, 2-methylthiophenothiazine, 2-chlorophenothiazine, 2-ethylthiophenothiazine, 2-(trifluoromethyl)phenothiazine, and 2-methoxyphenothiazine.

[0073] Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), trimethylolpropane, methylisothiazolinone ... 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-2,1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-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, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6 -ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, Examples include azine-2,4,6-(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.

[0074] From the viewpoints of patterning properties and the remaining film rate after development, the photopolymerization inhibitor is particularly preferably 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-methoxyphenol, or 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

[0075] The photopolymerization inhibitor may be used alone or in combination of two or more. The content of the photopolymerization inhibitor is preferably 0.005 to 12 parts by mass per 100 parts by mass of component (A).

[0076] (Rust inhibitor) The photosensitive resin composition of the present embodiment may optionally contain a rust inhibitor to suppress copper migration. The rust inhibitor is not limited as long as it can prevent metals from rusting, and examples thereof include nitrogen-containing heterocyclic compounds. Examples of nitrogen-containing heterocyclic compounds include azole compounds and purine derivatives.

[0077] Examples of the azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 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, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1H-tetrazole-5-acetic acid, and 1-methyl-1H-tetrazole.

[0078] Particularly preferred azole compounds include 5-amino-1H-tetrazole and 1H-tetrazole-5-acetic acid. These azole compounds may be used alone or in combination of two or more.

[0079] Purine derivatives 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, 6-amino-8-phenyl-9H-purine, 2 acetamido-9-acetyl-6-oxopurine, 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, 2-acetamido-6-hydroxypurine, and 8-azahypoxanthine, and derivatives thereof.

[0080] When the photosensitive resin composition contains an azole compound or a purine derivative, the content thereof is preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.1 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the azole compound or the purine derivative relative to 100 parts by mass of the (A) resin is 0.05 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the negative photosensitive resin composition of this embodiment is formed on copper or a copper alloy. On the other hand, when the content of the azole compound or the purine derivative is 5 parts by mass or less, excellent photosensitivity is achieved.

[0081] (Adhesion Aid) The photosensitive resin composition of the present embodiment may optionally contain an adhesion aid in order to improve the adhesion between a film formed using the photosensitive resin composition and a substrate. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, 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, and 3-(triethoxysilyl)propyl succinic anhydride; Examples include silane coupling agents such as N-phenylaminopropyltrimethoxysilane; and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0082] Of these adhesion aids, silane coupling agents are preferred from the viewpoint of adhesion. The content of the adhesion aid is preferably 0.1 to 25 parts by mass per 100 parts by mass of component (A).

[0083] (Solvent) Examples of the solvent include amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, and alcohols, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, and γ-butyrolactone. , propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, morpholine, dichloromethane, 3-methoxy-N,N-dimethylpropanamide, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, benzene, toluene, xylene, mesitylene, and the like can be used. Among these, from the viewpoints of resin solubility, resin composition stability, and adhesion to substrates, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, 3-methoxy-N,N-dimethylpropanamide, benzyl alcohol, phenyl glycol, tetrahydrofurfuryl alcohol, and 1,3-dimethyl-2-imidazolidinone are preferred.

[0084] Among these solvents, those which completely dissolve the produced polymer are particularly preferred, and examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropanamide, tetramethylurea, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. One type of solvent may be used, or two or more types of solvents may be mixed and used.

[0085] In the photosensitive resin composition of this embodiment, the amount of solvent used is preferably 100 to 1,000 parts by mass, more preferably 120 to 700 parts by mass, and even more preferably 125 to 500 parts by mass, per 100 parts by mass of component (A).

[0086] [Method for Producing Cured Relief Pattern] A method for producing a cured relief pattern can be provided, comprising the following steps (1) to (4): (1) a step of applying the negative photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate, (2) a step of exposing the photosensitive resin layer to light, (3) a step of developing the exposed photosensitive resin layer to form a relief pattern, and (4) a step of heat-treating the relief pattern to form a cured relief pattern.

[0087] Each step will be described below.

[0088] (1) Step of applying the negative photosensitive resin composition of the present embodiment onto a substrate to form a photosensitive resin layer on the substrate In this step, the negative photosensitive resin composition of the present embodiment is applied onto a 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 can be used, such as a method of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or a method of spray application using a spray coater.

[0089] If necessary, the coating film made of the negative photosensitive resin composition can be dried. Examples of drying methods include air drying, heat drying using an oven or hot plate, and vacuum drying. It is desirable to dry the coating film under conditions that do not cause imidization of the polyimide precursor in the negative photosensitive resin composition. Specifically, when air drying or heat drying is performed, drying can be performed at 20°C to 140°C for 1 minute to 1 hour. A photosensitive resin layer can be formed on the substrate in this manner.

[0090] (2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in step (1) above is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper, either directly or through a photomask or reticle having a pattern.

[0091] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. As for the baking conditions, the temperature is preferably 40°C to 120°C and the time is preferably 10 seconds to 240 seconds, but is not limited to these ranges as long as the properties of the negative photosensitive resin composition are not impaired.

[0092] (3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. As a development method for developing the exposed (irradiated) photosensitive resin layer, any method can be selected from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment. After development, post-development baking may be performed at any combination of temperature and time, as necessary, for the purpose of adjusting the shape of the relief pattern, etc.

[0093] The developer used for development is preferably, for example, a good solvent for the negative-tone 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-tone photosensitive resin composition. Furthermore, two or more types of each solvent, for example, several types, can be used in combination.

[0094] (4) Step of Heating the Relief Pattern to Form a Hardened Relief Pattern In this step, the relief pattern obtained by the development described above is heated to dissolve the photosensitive component and imidize the polyimide precursor, thereby converting it into a hardened relief pattern made of polyimide. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 200°C to 400°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon.

[0095] <Semiconductor Device> This embodiment also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern. Therefore, a semiconductor device can be provided that has a substrate that is a semiconductor element and a cured relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. The present invention is also applicable to a method for producing a semiconductor device that uses a semiconductor element as the substrate and includes the above-described method for producing a cured relief pattern as part of its process. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-described method for producing a cured relief pattern 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 combining the method with a known method for producing a semiconductor device.

[0096] <Display Device> In this embodiment, a display device is provided that includes a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT liquid crystal display elements and color filter elements, protrusions for MVA-type liquid crystal display devices, and partition walls for cathodes of organic EL elements.

[0097] The negative photosensitive resin composition of the present invention is useful not only for application to the semiconductor devices described above, but also for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

[0098] The present embodiment will be specifically described below using examples. However, the present embodiment is not limited to the examples. In the examples, comparative examples, and production examples, the physical properties of the polymer and the photosensitive resin composition were measured and evaluated according to the following methods.

[0099] Weight-Average Molecular Weight The weight-average molecular weight (Mw) of each polymer and photosensitive resin composition was measured using gel permeation chromatography (standard polystyrene equivalent) under the following conditions.

[0100] Pump: JASCO PU-980 Detector: JASCO RI-930 Column oven: JASCO CO-965 40°C Column: Showa Denko K.K. Shodex KD-806M (two columns in series), or Showa Denko K.K. Shodex 805M / 806M (two columns in series) Standard monodisperse polystyrene: Showa Denko K.K. Shodex STANDARD SM-105 Mobile phase: 0.1 mol / L LiBr / N-methyl-2-pyrrolidone (NMP) Flow rate: 1 mL / min.

[0101] (1) Copper Adhesion Evaluation On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm), a 200 nm thick Ti film and a 400 nm thick Cu film were sputtered in this order using a sputtering apparatus (L-440S-FHL type, manufactured by Canon Anelva Corporation). Subsequently, the photosensitive resin composition was spin-coated on the wafer using a coater developer (D-spin 60A type, manufactured by SOKUDO Co., Ltd.) so that the film thickness after curing was approximately 9 μm. After drying, the entire surface was exposed to light, and the film was heated at 230 ° C. for 2 hours under a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd.) to obtain a cured relief pattern (thermocured polyimide coating film). The heat-treated film was evaluated for adhesion properties between the copper substrate and the cured resin coating film according to the cross-cut method of JIS K 5600-5-6, based on the following criteria. If the evaluation is S, A, or B, the film can be suitably used as a cured relief pattern for semiconductors. S: The lattice number of the cured resin coating film adhered to the substrate is 90 or more and 100 or less. A: The lattice number of the cured resin coating film adhered to the substrate is 80 or more and less than 90. B: The lattice number of the cured resin coating film adhered to the substrate is 40 or more and less than 80. C: The lattice number of the cured resin coating film adhered to the substrate is less than 40.

[0102] (2) Resolution Evaluation A 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625±25 μm) was sputtered with a 200 nm thick Ti film and a 400 nm thick Cu film in that order using a sputtering device (L-440-FHL model, manufactured by Canon Anelva Corporation). Subsequently, a photosensitive resin composition prepared by the method described below was spin-coated onto this wafer using a coater developer (D-spin 60A model, manufactured by SOKUDO Co., Ltd.) to a film thickness of approximately 8 μm, and the wafer was pre-baked on a hot plate at 110° C. for 240 seconds to form a coating film. This coating film was exposed to an exposure dose of 400 mJ / cm using a Prisma GHI (manufactured by Ultratech Co., Ltd.) with an exposure wavelength of i-line (365 nm) through a test patterned reticle. ２ to 1000 mJ / cm ２ up to 50 mJ / cm ２ The film was exposed to i-rays in a stepwise fashion. Next, using a coater developer (D-Spin 60A model, manufactured by SOKUDO Corporation), rotary spray development was performed at 23°C using cyclopentanone as a developer for a time 1.4 times the time required for the unexposed areas to completely dissolve and disappear, followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds, yielding a relief pattern consisting of a resin film. Subsequently, the film was cured in a temperature-programmable curing oven (VF-2000 model, manufactured by Koyo Lindberg) at 230°C for 2 hours under a nitrogen atmosphere, yielding a cured relief pattern.

[0103] The pattern shape and width of the patterned portion of each pattern were observed under an optical microscope to determine the resolution. Regarding the resolution, a pattern having openings of different areas was formed by exposure through a test patterned reticle in the same manner as described above. If the area of ​​the resulting pattern opening was at least half the area of ​​the corresponding pattern mask opening, it was considered resolved, and the length of the mask opening side corresponding to the smallest area among the resolved openings was taken as the resolution. The optimal exposure dose was the exposure dose that provided the best resolution, and the pattern accuracy was evaluated based on the following criteria. A rating of S, A, or B indicates that the pattern can be suitably used as a cured relief pattern for semiconductors. S: The pattern cross section does not have a trailing edge, and no bottom gouging, swelling, or bridging has occurred, and the resolution is less than 5 μm. A: The pattern cross section does not have a trailing edge, and no bottom gouging, swelling, or bridging has occurred, and the resolution is 5 μm or more but less than 6 μm. B: The pattern cross section does not have a trailing edge, and there is no bottom gouging, swelling, or bridging, and the resolution is 6 μm or more and less than 8 μm. C: The pattern cross section has trailing edges, bottom gouging, swelling, or bridging, or the resolution is 8 μm or more.

[0104] <Production Example 1> (Synthesis of (A) Polyimide Precursor A-1) 62 g (0.2 mol) of 4,4'-oxydiphthalic dianhydride ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) were placed in a 2-liter separable flask, and 135 g (0.2 mol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature. 79.1 g of pyridine was added while stirring, and after stirring for 16 hours, a reaction mixture was prepared.

[0105] Next, under ice cooling, a solution of 203 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by the addition of 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: m-tolidine) suspended in 280 ml of γ-butyrolactone over 60 minutes with stirring. After further stirring at room temperature for 4 hours, 40 ml of ethanol was added and stirred for 1 hour, and then 1 liter of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0106] The resulting reaction solution was added to 4 liters of ethanol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 2.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 30 liters of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain a powdered polymer (Polymer A1). The molecular weight of Polymer A1 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0107] <Production Example 2> (Synthesis of (A) Polyimide Precursor A-2) Polymer A2 was obtained by carrying out a reaction in the same manner as in the above-described Production Example 1, except that 155 g (0.5 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was used instead of 62 g (0.2 mol) of 4,4'-oxydiphthalic dianhydride ODPA and 65 g (0.3 mol) of pyromellitic dianhydride (PMDA) in Production Example 1, and 88 g (0.44 mol) of 4,4'-diaminodiphenyl ether (DADPE) was used instead of 94 g (0.44 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB: m-tolidine). The molecular weight of Polymer A2 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was found to be 24,000.

[0108] <Production Example 3> (A) Synthesis of Polyimide Precursor A-3) A reaction was carried out in the same manner as in the above-mentioned Production Example 1, except that 147 g (0.5 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 2, to obtain Polymer A3. The molecular weight of Polymer A3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

[0109] Example 1 Preparation of Negative Photosensitive Resin Composition 100 g of (A) polyimide precursor A-1 (polymer A1), 5 g of diethylene glycol monomethacrylate as component (B1: Blemmer PE90, manufactured by NOF Corporation) as component (B), 5 g of polyethylene glycol dimethyl ether as component (C3: Uniox MM-400, manufactured by NOF Corporation) as component (C), and 10 g of 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime as component (D) were dissolved in 207 g of a mixed solvent of γ-butyrolactone and dimethyl sulfoxide to prepare a negative photosensitive resin composition. The composition was evaluated according to the method described above. The results are shown in Table 1. Unless otherwise specified, the numerical values ​​in the table are in parts by mass.

[0110] Examples 2 to 14, Comparative Examples 1 to 5 Negative photosensitive resin compositions were prepared in the same manner as in Example 1, except that the components (A), (B), and (C) were changed as shown in Table 1, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0111] The components used in the examples and comparative examples are as follows: Component (B) and other (meth)acrylate compounds Component (B1): diethylene glycol monomethacrylate (Blemmer PE90, molecular weight: 90, manufactured by NOF Corporation) Component (B2): 2-methacryloyloxyethyl phthalate (NK Ester CB-1, molecular weight: 278, manufactured by Shin-Nakamura Chemical Co., Ltd.) Component (B3): methoxypolyethylene glycol monomethacrylate (Blemmer PME-400, molecular weight: 400, manufactured by NOF Corporation) Component (B4): methoxypolyethylene glycol monoacrylate (Blemmer AME-400, molecular weight: 400, manufactured by NOF Corporation) Component (B5): methoxypolyethylene glycol monomethacrylate (Blemmer PME-1000, molecular weight: 1000, manufactured by NOF Corporation) Component (B6): cyclohexyl methacrylate (Blemmer CHMA, molecular weight: 168, manufactured by NOF Corporation) Component (B7): Ethoxylated o-phenylphenol acrylate (NK Ester A-LEN-10, molecular weight 268, manufactured by Shin-Nakamura Chemical Co., Ltd.) Component (B8): Tetraethylene glycol dimethacrylate (NK Ester NK-4GT, molecular weight: 330, manufactured by Shin-Nakamura Chemical Co., Ltd.) Component (C) and other plasticizers Component (C1): Triethylene glycol dimethyl ether (n ２ ≒3, molecular weight: 178, manufactured by Tokyo Chemical Industry Co., Ltd.) (C2) Tripropylene glycol dimethyl ether (n ２ ≒3, molecular weight: 220, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (C3) Polyethylene glycol dimethyl ether (n ２ ≒7, Uniox MM-400, molecular weight: 400, manufactured by NOF Corporation) (C4) Polyethylene glycol monomethyl ether (n ２ ≒11, Uniox M-550, molecular weight: 550, manufactured by NOF Corporation) (C5) Diethylene glycol dimethyl ether (n ２ ≒2, molecular weight: 180, manufactured by Tokyo Chemical Industry Co., Ltd.) (C6) Polyethylene glycol monomethyl ether (n ２(C7) Lauryl alcohol ethoxylate (Akator LA-775, manufactured by ADEKA Corporation) (D) Photopolymerization initiator 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime

[0112]

[0113] The negative-tone photosensitive resin composition according to the present invention can provide a negative-tone photosensitive resin composition having good adhesion to copper and good resolution, and a method for producing a cured relief pattern using the photosensitive resin composition. The present invention can be suitably used in the field of photosensitive materials useful for producing electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

Claims

1. (A) a polyimide precursor or polyimide, (B) a compound represented by the following general formula (3): {In the formula, R ６ is a hydrogen atom or a methyl group, and R ７ is a monovalent organic group not containing a (meth)acryloyl group.}, and (C) a monofunctional (meth)acrylate compound represented by the following general formula (4): {In the formula, R ８ and R ９ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ８ and R ９ At least one of R is an alkyl group having 1 to 6 carbon atoms, １０ is an alkylene group having 2 to 4 carbon atoms, and n ２ is an integer of 2 to 12.} A negative-type photosensitive resin composition comprising a terminal-capped polyalkylene glycol compound represented by the following formula:

2. The polyimide precursor is represented by the following general formula (1): [In the formula, X １ is a tetravalent organic group, and Y １ is a divalent organic group, n is an integer from 2 to 150, and R １ and R ２ are each independently a hydrogen atom or a group represented by the following general formula (2): {In the formula, R ３ is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R ４ and R ５ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10.}, or a saturated aliphatic group having 1 to 4 carbon atoms.

3. In the general formula (4), n ２ 3. The negative photosensitive resin composition according to claim 1, wherein is an integer of 3 to 12.

4. In the general formula (3), R ７ The negative photosensitive resin composition according to claim 1 or 2, wherein is an organic group containing a polyoxyalkylene group.

5. The negative photosensitive resin composition according to claim 1 or 2, wherein the molecular weight of component (B) is 500 or less.

6. In the general formula (3), R ７ The negative photosensitive resin composition according to claim 1 or 2, wherein is an organic group not containing a cyclic structure.

7. In the general formula (3), R ６ The negative photosensitive resin composition according to claim 1 or 2, wherein is a methyl group.

8. In the general formula (4), R １０ The negative photosensitive resin composition according to claim 1 or 2, wherein is an ethylene group.

9. In the general formula (4), R ８ and R ９ and each independently represent an alkyl group having 1 to 6 carbon atoms.

10. R in the general formula (3) ７ 3. The negative photosensitive resin composition according to claim 1, wherein is an organic group containing a cyclic hydrocarbon group and a chain hydrocarbon group having 1 to 11 carbon atoms.

11. The negative photosensitive resin composition according to claim 1 or 2, which contains 0.1 to 10 parts by mass of the component (B) per 100 parts by mass of the component (A).

12. The negative photosensitive resin composition according to claim 1 or 2, which contains 0.1 to 10 parts by mass of the component (C) per 100 parts by mass of the component (A).

13. The negative photosensitive resin composition according to claim 1 or 2, further comprising (D) a photopolymerization initiator.

14. (D) The following general formula (5): (In the formula, R １１ wherein R is a hydrogen atom, an alkyl ester, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 1 to 12 carbon atoms.

15. A method for producing a cured relief pattern, comprising the steps of: forming a photosensitive resin layer on a substrate by applying the negative photosensitive resin composition according to claim 1 or 2 onto the substrate; exposing the photosensitive resin layer; developing the exposed photosensitive resin layer to form a relief pattern; and heat-treating the relief pattern to form a cured relief pattern.

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