Photosensitive resin composition, dry film, cured product, and electronic component

Abstract

To provide a photosensitive resin composition with large dissolution contrast and excellent resolution.SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor with at least one of structures represented by general formulas (1) and (2), (B) a photoacid generator, and (C) a compound having two or more vinyl ether groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition containing a polyimide precursor having a specific structure, a dry film provided with a resin layer formed from the photosensitive resin composition, a cured product formed from the photosensitive resin composition, and an electronic component such as a printed wiring board or a semiconductor element having the cured product as a forming material.

Background Art

[0002] Photosensitive resin compositions containing polyimide precursors are widely used in various fields because they exhibit excellent properties such as insulation, heat resistance, and mechanical strength. For example, their application to buffer coat films of flexible printed wiring boards and semiconductor elements and to insulating films for redistribution layers of wafer-level packages (WLPs) is being promoted.

[0003] Specifically, an alkali-developable photosensitive resin composition is coated and dried on a substrate to form a coating film, then exposed through a pattern mask, and then alkali development is performed using the difference in solubility of the exposed and unexposed portions in an alkali developer to form a film having a desired pattern. By heating this pattern film, the polyimide precursor contained in the photosensitive resin composition can be subjected to a ring-closing reaction to obtain a cured film that has been imidized.

[0004] In recent semiconductor devices, with the demands for higher functionality and miniaturization, it is required to form a cured film with a finer pattern on the buffer coat film and the insulating film for the rewiring layer of the wafer-level package. The photosensitive resin composition is required to have excellent resolution. In response to such demands, attempts have been made to improve the resolution by increasing the difference in the dissolution rate of the exposed and unexposed portions in the alkali developer solution, i.e., the so-called dissolution contrast, in the coating film composed of the photosensitive resin composition. For example, in Patent Document 1, a technique for obtaining a high-sensitivity and high-contrast pattern with a photosensitive polyimide resin composition containing a polyimide precursor formed from a carboxylic dianhydride and a diamine having a siloxane structure and a diazonaphthoquinone-based compound has been proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the composition of Patent Document 1 does not sufficiently satisfy the dissolution contrast required to achieve the resolution required for recent semiconductor devices, and the resolution is not sufficient.

[0007] The present invention has been made in view of the above problems, and its main object is to provide a photosensitive resin composition having a large dissolution contrast and excellent resolution.

[0008] Another object of the present invention is to provide dry films, printed wiring boards, and electronic components such as semiconductor devices using the photosensitive resin composition.

Means for Solving the Problems

[0009] The inventors of the present invention have found that by combining a polyimide precursor having a specific structure with a compound having two or more vinyl ether groups, the dissolution contrast can be increased and excellent resolution can be obtained, and thus the present invention has been completed.

[0010] That is, the photosensitive resin composition of the present invention is characterized by containing (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), (B) a photoacid generator, and (C) a compound having two or more vinyl ether groups. The coating film obtained by applying and drying the photosensitive resin composition of the present invention has improved dissolution resistance to an alkaline developer by the reaction of the carboxyl group of the polyimide precursor of (A) and the vinyl group of the compound having two or more vinyl ether groups of (C) to form an ester bond in the drying step. Then, when the coating film is exposed, an acid is generated from the (B) photoacid generator, and the decomposition of the ester bond is promoted. As a result, it is presumed that a large difference occurs in the dissolution rate of the unexposed portion and the exposed portion in the alkaline developer.

Effects of the Invention

[0011] According to the present invention, there is provided a photosensitive resin composition having a large dissolution contrast and excellent resolution.

[0012] The gist of the present invention is as follows. [1] A photosensitive resin composition, characterized by containing (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), (B) a photoacid generator, (C) a compound having two or more vinyl ether groups.

Chemical formula

[0013] [2] The photosensitive resin composition according to [1], wherein X is selected from the groups represented below. [Chemical formula] (In the formula, a is an integer from 0 to 2, b is an integer from 0 to 2.)

[0014] [3] The photosensitive resin composition according to [1] or [2], wherein the number of carbon atoms of B is 1 to 10 and the number of fluorine atoms is 1 to 10.

[0015] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the carboxyl group concentration in the polyimide precursor is 300 to 800 mol / g.

[0016] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the fluorine concentration in the polyimide precursor is 20 to 200 mol / g.

[0017] [6] The photosensitive resin composition according to any one of [1] to [5], further comprising an adhesive.

[0018] [7] The photosensitive resin composition according to any one of [1] to [6], further comprising a base compound.

[0019] [8] The photosensitive resin composition according to any one of [1] to [7], further comprising a surfactant.

[0020] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the photoacid generator contains an N-sulfonyloxyimide type photoacid generator.

[0021]

[10] The photosensitive resin composition according to [9], wherein the photoacid generator further contains a naphthoquinonediazide compound.

[0022]

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

[10] , wherein the compound having two or more vinyl ether groups is at least one selected from diethylene glycol divinyl ether and cyclohexanedimethanol divinyl ether.

[0023]

[12] A dry film characterized by comprising a resin layer formed of the photosensitive resin composition according to any one of [1] to

[10] on a film.

[0024]

[13] A cured product characterized by being formed of the resin layer of the photosensitive resin composition according to any one of [1] to

[11] or the dry film according to

[12] .

[0025]

[14] An electronic component characterized by having the cured product according to

[13] as a forming material.

Embodiments for Carrying Out the Invention

[0026] <Photosensitive Resin Composition> The photosensitive resin composition of the present invention contains (A) a polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2), (B) a photoacid generator, and (C) a compound having two or more vinyl ether groups. The photosensitive resin composition of the present invention is useful as a positive-type photosensitive resin composition.

[0027] The photosensitive resin composition of the present invention has a large solubility contrast. For the coating film formed from the composition, the ratio of the dissolution rate of the exposed portion in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) at 25°C to the dissolution rate of the unexposed portion in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) at 25°C can be, for example, 500 or more, and this brings about excellent resolution. The dissolution rate of the exposed portion can be 50 to 3000 nm / s, preferably 100 to 2000 nm / s. On the other hand, the dissolution rate of the unexposed portion can be 0 to 20 nm / s, preferably 0 to 5 nm / s. The dissolution rate in this specification can be measured by the method described in the examples.

[0028] [(A) Polyimide precursor] (A) The polyimide precursor is a polyamic acid having at least one of the structures represented by the following general formulas (1) and (2), and may have only one of the structures of general formula (1) or general formula (2), or both structures. [Chemical formula]

[0029] In general formulas (1) and (2), X is a tetravalent organic group. Examples of the tetravalent organic group include, but are not limited to, groups having the following structures. In the structure, a and b are each independently an integer of 0 to 2, and from the viewpoint of being easily soluble in various solvents (i.e., having good solvent solubility) and the light transmittance of the dry coating film, it is preferably 0 to 1, and particularly preferably 0. [Chemical formula]

[0030] Among the above tetravalent organic groups, the following structures are preferred from the viewpoint of obtaining good solvent solubility. [Chemical formula]

[0031] Specific examples of the above-mentioned preferred tetravalent organic group include, but are not limited to, the following structures.

Chemical formula

[0032] From the viewpoint of improving the dissolution rate in the exposed area and obtaining a large dissolution contrast, the following structures are particularly preferred.

Chemical formula

[0033] In general formulas (1) and (2), A is a single bond, O, or a divalent organic group. The divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Examples of the divalent organic group include an alkylene group, a cycloalkylene group, an arylene group, an alkyl ether group, a ketone group, an ester group, and the like.

[0034] In general formulas (1) and (2), B is a fluoroalcohol group, and can be a hydroxyalkyl group in which one or more hydrogen atoms in the alkyl moiety are substituted with fluorine atoms. When general formula (1) or (2) has a plurality of Bs, they may be the same or different. The fluoroalcohol group preferably has 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. The fluoroalcohol group preferably has 1 to 10 fluorine atoms, more preferably 4 to 8 fluorine atoms. Thereby, the solvent solubility and the light transmittance of the cured product can be improved.

[0035] A fluoroalcohol group having one or more trifluoromethyl groups is preferred, and a fluoroalkyl group having one or two trifluoromethyl groups is more preferred. Examples of the fluoroalcohol group include, but are not limited to, the following groups.

Chemical formula

[0036] In general formulas (1) and (2), R is a hydrogen atom, or an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylamino group, or an aryl group, and these groups may be unsubstituted or may have substituents. R is preferably a hydrogen atom or the like. In the structure, when a plurality of Rs are present, they may be the same or different.

[0037] The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. The preferred number of carbon atoms of the alkyl moiety of the alkoxy group and the alkylamino group is the same. The number of carbon atoms of the cycloalkyl group is preferably 4 to 12, more preferably 5 to 10. The preferred number of carbon atoms of the cycloalkyl moiety of the cycloalkoxy group is the same. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 18. Examples of the substituent include a halogen atom, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group, and the like.

[0038] Examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, an n-hexyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a chloroethyl group, a dichloroethyl group, a trichloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxylpropyl group, etc.; a cyclohexyl group; a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, a trifluoromethoxy group, etc.; a cyclohexyloxy group, etc.; a methylamino group, a dimethylamino group, a trimethylamino group, an ethylamino group, a propylamino group, etc.; a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, a biphenyl group, etc.

[0039] In General Formulas (1) and (2), n1 is, independently of each other, an integer of 1 or more, preferably an integer of 1 to 20. When n1 is an integer of 2 or more, each structure may be the same or different, preferably the same. In General Formula (1), n2 and n3 are, independently of each other, integers of 0 to 4, provided that n2 + n3 is 1 or more. n2 + n3 is preferably an integer of 1 to 2, and it is more preferable that n2 is 1 and n3 is 1. In General Formula (2), n4 is an integer of 1 to 4, preferably an integer of 1 to 2.

[0040] Examples of the structure satisfying General Formula (1) or (2) include, but are not limited to, the following structures.

[0041]

Chemical Formula

[0042]

Chem.

[0043]

Chem.

[0044]

Chem.

[0045]

Chem.

[0046]

Chem.

[0047]

Chem.

[0048]

Chem.

[0049]

Chem.

[0050]

Chem.

[0051]

Chem.

[0052] [Chemistry]

[0053] [Chemistry]

[0054] [Chemistry]

[0055] [Chemistry]

[0056] [Chemistry]

[0057] (A) The weight average molecular weight (Mw) of the polyimide precursor is preferably from 4,000 to 80,000, more preferably from 6,000 to 60,000. Thereby, the occurrence of cracks in the cured product can be further reduced. (A) The number average molecular weight (Mn) of the polyimide precursor is preferably from 2,000 to 30,000, more preferably from 2,500 to 20,000. Thereby, the solubility of the exposed portion in the photosensitive resin composition in the alkaline developer and the alkali resistance solubility of the unexposed portion in the alkaline developer are obtained in good balance. Mw / Mn is preferably from 2.0 to 4.0, more preferably from 2.3 to 3.0. Thereby, residues and swelling generated during development are reduced. In the present specification, the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography (GPC) and converted with standard polystyrene.

[0058] (A) The glass transition temperature (Tg) of the polyimide obtained by subjecting the polyimide precursor to a ring-closing reaction is preferably 180 °C or higher, more preferably 200 °C or higher. Thereby, excellent heat resistance can be obtained as the cured product.

[0059] (A) The carboxyl group concentration in the polyimide precursor is preferably 300 to 800 mol / g, more preferably 300 to 600 mol / g. Thereby, the dissolution rate and dissolution contrast of the exposed portion can be further improved.

[0060] (A) The fluorine concentration in the polyimide precursor is preferably 20 to 200 mol / g, more preferably 40 to 100 mol / g. Thereby, the solvent solubility and light transmittance can be further improved.

[0061] Within the range that does not impair the effects of the present invention, a part of the (A) polyimide precursor may have a structure in which the structures represented by general formulas (1) and (2) are ring-closed. For example, the following structures can be mentioned.

Chemical formula

[0062] (A) The content of the structure in which the structures represented by general formulas (1) and (2) are ring-closed (that is, the imidization rate) in the polyimide precursor is preferably 50% or less, more preferably 40% or less, and even more preferably 20% or less from the viewpoint of improving the alkali developability resistance of the unexposed portion. The imidization rate may be 0%.

[0063] (A) The polyimide precursor can be obtained by reacting an acid dianhydride represented by the general formula (i) with a diamine represented by the general formula (ii) and / or the general formula (iii) in the structures of the general formulas (1) and (2). The reaction can be carried out under known conditions. For example, the diamine can be dissolved in a reaction solvent, and the acid dianhydride can be added as a solid to the solution. After the acid dianhydride is dissolved in the solution, the target product can be obtained by introducing end groups. The end groups can be those known as the end groups of the polyimide precursor. [Chemical formula] (In the formula, X, A, B, R, n2, n3, n4 have the same meanings as in the general formulas (1) and (2).)

[0064] [(B) Photoacid generator] The photosensitive resin composition of the present invention contains (B) a photoacid generator, and thereby, the solubility of the photosensitive resin composition in an alkaline developer can be adjusted. (B) The photoacid generator may be used alone or in any combination of two or more in an arbitrary ratio.

[0065] The blending amount of (B) the photoacid generator can be appropriately selected. For example, it can be 0.1 to 35 parts by mass, preferably 1 to 23 parts by mass, based on 100 parts by mass of (A) the polyimide precursor.

[0066] A photoacid generator is a compound that generates an acid upon irradiation with light such as ultraviolet light or visible light. Examples include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone-based compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, cyano group-containing oxime sulfonate compounds, and the like.

[0067] Among them, a photoacid generator that generates sulfonic acids is preferred. The blending amount of the photoacid generator that generates sulfonic acids can be 0.10 to 5 parts by mass, preferably 0.15 to 4 parts by mass, based on 100 parts by mass of (A) the polyimide precursor.

[0068] Examples of sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, dodecylbenzenesulfonic acid, pentafluorobenzenesulfonic acid, trifluoromethanesulfonic acid, 2,2,2-trifluoroethanesulfonic acid, nonafluorobutanesulfonic acid, heptadecafluorooctanesulfonic acid, camphorsulfonic acid, 4-trifluoromethylbenzenesulfonic acid, 4-fluorobenzenesulfonic acid, and the like.

[0069] Examples of photoacid generators that generate sulfonic acids include N-sulfonyloxyimide type photoacid generators.

[0070] Examples of N-sulfonyloxyimide type photoacid generators include compounds in which a hydrogen atom bonded to the nitrogen atom of imides such as naphthalenedicarboximide, succinimide, phthalimide, cyclohexyl dicarboximide, 5-norbornene-2,3-dicarboximide, 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboximide is substituted with a sulfonyloxy group such as methanesulfonyloxy group, ethanesulfonyloxy group, propanesulfonyloxy group, butanesulfonyloxy group, octanesulfonyloxy group, benzenesulfonyloxy group, toluenesulfonyloxy group, naphthalenesulfonyloxy group, dodecylbenzenesulfonyloxy group, pentafluorobenzenesulfonyloxy group, trifluoromethanesulfonyloxy group, 2,2,2-trifluoroethanesulfonyloxy group, nonafluorobutanesulfonyloxy group, heptadecafluorooctanesulfonyloxy group, camphorsulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, 4-fluorobenzenesulfonyloxy group. Among them, compounds in which a hydrogen atom bonded to the nitrogen atom of naphthalenedicarboximide is substituted with a sulfonyloxy group are preferred.

[0071] As the N-sulfonyloxyimide type photoacid generator, a photoacid generator having a naphthalenedicarboximide structure is preferable, and the sulfonic acid derivative compound described in International Publication No. 2014 / 084269 can be used.

[0072] For example, the formula:

Chemical formula

[0073]

Chemical formula

[0074] Combining a naphthoquinonediazide compound with a photoacid generator that generates sulfonic acids is preferable from the viewpoint of obtaining a high residual film ratio. In this case, the blending amount of the naphthoquinonediazide compound can be 1 to 30 parts by mass, preferably 3 to 20 parts by mass, based on 100 parts by mass of the (A) polyimide precursor.

[0075] Examples of the naphthoquinonediazide compound include, specifically, naphthoquinonediazide adducts of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (e.g., TS533, TS567, TS583, TS593 manufactured by Sanpo Chemical Laboratory), naphthoquinonediazide adducts of tetrahydroxybenzophenone (e.g., BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory), naphthoquinonediazide adducts of 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl}phenol (e.g., TKF-428, TKF-528 manufactured by Sanpo Chemical Laboratory), naphthoquinonediazide adducts of bis{3-(4-hydroxybenzyl)-4-hydroxy-2,5-dimethylphenyl}methane (e.g., CBN-250 manufactured by Toyo Gosei Co., Ltd.), tris(4-hydroxyphenyl)ethane (e.g., HP-190DF manufactured by Toyo Gosei Co., Ltd.), and the like.

[0076] [(C) Compound having two or more vinyl ether groups] The photosensitive resin composition of the present invention contains a compound having two or more vinyl ether groups (CH2=CH-O-), and a large dissolution contrast can be obtained by the interaction between this compound and the (A) polyimide precursor. From the viewpoint of the dissolution suppression effect of the unexposed portion, the number of vinyl ether groups is preferably 2 to 6, and more preferably 2 to 4. The compound having two or more vinyl ether groups may be used alone or in any combination of two or more in any ratio. Combining two compounds having two or more vinyl ether groups in a mass ratio of 3:7 to 7:3 is preferable from the viewpoints of dissolution contrast and resolution. The ratio is more preferably 4:6 to 6:4.

[0077] The compound having two or more vinyl ether groups is not particularly limited, and examples thereof include bis(4-(vinyloxymethyl)cyclohexylmethyl)glutarate, tri(ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, tris(4-vinyloxy)butyl trimellitate, bis(4-(vinyloxy)butyl) terephthalate, bis(4-(vinyloxy)butyl) isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, cyclohexanedimethanol divinyl ether, 2,2-bis{4-[2-(vinyloxy)ethoxy]phenyl}propane, 1,1,1-tris{4-[2-(vinyloxy)ethoxy]phenyl}ethane, 1,3,5-tris[2-(vinyloxy)ethoxy]benzene, 1,2,3-tris[2-(vinyloxy)ethoxy]benzene, 2,2-bis{4-[2-(vinyloxy)ethoxy]cyclohexyl}propane, 1,4-bis{4-[2-(vinyloxy)ethoxy]phenyl}cyclohexane, and the like.

[0078] From the viewpoint of dissolution contrast, it is preferably to contain diethylene glycol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether, and it is more preferable to combine them in a ratio of 3:7 to 7:3 by mass ratio, and the ratio is more preferably 4:6 to 6:4.

[0079] The blending amount of the compound having two or more vinyl ether groups can be 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 15 to 40 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0080] [Adhesive agent] From the viewpoint of obtaining good adhesiveness to a substrate or the like, the photosensitive resin composition of the present invention preferably contains an adhesive agent. The adhesive agent is not particularly limited, and examples thereof include silane coupling agents, titanate coupling agents, and aluminum coupling agents. The adhesive agent may be used alone or in any combination of two or more. Examples of the silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, phenyltrimethoxysilane, and the like. Examples of the titanate coupling agent include isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltris(dioctylpyrophosphate) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, and the like. Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate and the like.

[0081] Among them, N-phenyl-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane are preferable because they improve the adhesiveness to the substrate and do not have an adverse effect on the development rate.

[0082] The blending amount of the adhesive agent can be 10 parts by mass or less, preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the (A) polyimide precursor.

[0083] [Base compound] From the viewpoints of improving dissolution contrast and resolution, and improving the stability of the coating film during the standing time from when the photosensitive resin composition is applied until exposure, the photosensitive resin composition of the present invention preferably contains a base compound. The base compound may be used alone or in any combination of two or more. Examples of the base compound include amine compounds such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N’,N’-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4’-diaminodiphenylmethane, 4,4’-diaminodiphenylether, 4,4’-diaminobenzophenone, 4,4’-diaminodiphenylamine; amide compounds such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide; lactams such as pyrrolidone, N-methylpyrrolidone; urea compounds such as methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3,-tetramethylurea, 1,3-diphenylurea; nitrogen-containing heterocyclic compounds such as imidazole, benzimidazole, 4-methylimidazole, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine; morpholine compounds such as morpholine, 4-methylmorpholine. Among them, amine compounds are preferred, and alkanolamines such as triethanolamine are more preferred.

[0084] The compounding amount of the base compound can be 5 parts by mass or less, preferably 0.01 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the (A) polyimide precursor.

[0085] [Surfactant] The photosensitive resin composition of the present invention preferably contains a surfactant in order to improve the adhesion and resolution with the substrate. The surfactant is not particularly limited, and examples thereof include fluorosurfactants and silicone surfactants.

[0086] Examples of the fluorosurfactant include the "Megafac" series manufactured by DIC Corporation (for example, Megafac F-281, F-477, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-569, etc.). Examples of the silicone surfactant include the surface conditioner series of BYK-Chemie (for example, BYK-302, BYK-307, BYK-322, BYK-323, BYK-326, BYK-331, BYK-332, BYK-333, BYK-348, BYK-349, BYK-377, BYK-378, BY-3455, BYK-3760, etc.). These may be used alone or in combination of two or more.

[0087] The blending amount of the surfactant can be 1 part by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and is preferably 0.01 part by mass or more and 0.5 part by mass or less.

[0088] [Crosslinking agent] The photosensitive resin composition of the present invention can contain a crosslinking agent as long as the effects of the present invention are not impaired. By containing a crosslinking agent, it can be expected to lower the curing temperature of the photosensitive resin composition. The crosslinking agent is not particularly limited, and examples thereof include crosslinking agents having a cyclic ether group such as an epoxy group or a cyclic thioether group such as an episulfide group, crosslinking agents having an alcoholic hydroxyl group in which a hydroxyl group is bonded to an alkylene group having 1 to 12 carbon atoms such as a methylol group, compounds having an ether bond such as an alkoxymethyl group, crosslinking agents having a triazine ring structure, urea-based crosslinking agents, etc. Among them, crosslinking agents having an epoxy group and crosslinking agents having a methylol group are preferred. The crosslinking agent may be used alone or in any combination of two or more kinds in any ratio. When the crosslinking agent is contained, it can be 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polyimide precursor (A).

[0089] [Plasticizer] Within the range not impairing the effects of the present invention, the photosensitive resin composition of the present invention can contain a plasticizer. By containing a plasticizer, promotion of low-temperature curability can be expected. The plasticizer is not particularly limited, and examples thereof include bifunctional (meth)acrylic compounds, sulfonamide compounds, phthalic acid ester compounds, maleic acid ester compounds, aliphatic dibasic acid esters, phosphate esters, ether compounds such as crown ethers, etc. Among them, a bifunctional (meth)acrylic compound is preferable. The plasticizer may be used alone or in any combination of two or more kinds in any ratio. When the plasticizer is contained, it can be 3 to 40 parts by mass based on 100 parts by mass of the polyimide precursor (A).

[0090] [Other components] Within the range not impairing the effects of the present invention, the photosensitive resin composition of the present invention can also contain various organic or inorganic low-molecular or high-molecular compounds for promoting the cyclization reaction of the polyimide precursor, known photosensitizers for improving photosensitivity, etc., for imparting processing characteristics and various functions. For example, surfactants, leveling agents, colorants, fibers, fine particles, etc. can be mentioned. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon, and layered silicates.

[0091] [Solvent] The photosensitive resin composition of the present invention can contain a solvent. The solvent is not particularly limited, but a solvent having a boiling point of 200 ° C or lower is preferable from the viewpoint that the residual amount of the solvent can be easily reduced even when the heating temperature of the pattern film is lowered. For example, 2-methoxy-1-methylethyl acetate (PGMEA), 4-methyl-2-pentanone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and the like. The solvent may be used alone or in combination of two or more in any ratio.

[0092] The blending amount of the solvent is not particularly limited and can be 200 to 2000 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

[0093] [Preparation of Photosensitive Resin Composition] The photosensitive resin composition of the present invention can be obtained by mixing (A) a polyimide precursor, (B) a photoacid generator, (C) a compound having two or more vinyl ether groups, and an optional component such as a solvent. The mixing may be carried out under heating.

[0094] <Dry film> The dry film of the present invention comprises a film (for example, a support (carrier) film) and a resin layer formed on this film using the photosensitive resin composition of the present invention. The dry film may further include a film (protective film) for further protecting (covering) the resin layer formed on the film.

[0095] [Support (carrier) film] The support (carrier) film is not particularly limited, and examples thereof include films made of thermoplastic resins such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, and polystyrene films. Among them, from the viewpoints of heat resistance, mechanical strength, and handleability, a film made of polyethylene terephthalate is preferable. A laminate of these films can also be used as the support (carrier) film.

[0096] The support (carrier) film is preferably a film stretched in a uniaxial direction or a biaxial direction from the viewpoint of improving mechanical strength.

[0097] The thickness of the support (carrier) film is not particularly limited, and for example, it can be 10 to 150 μm.

[0098] [Protective film] For the purpose of preventing dust from adhering to the surface of the resin layer, it is preferable to laminate a peelable protective film on the surface of the resin layer.

[0099] The peelable protective film is not particularly limited as long as the adhesive force between the resin layer and the protective film is smaller than the adhesive force between the resin layer and the support (carrier) film during peeling. Examples thereof include polyethylene films, polytetrafluoroethylene films, polypropylene films, and surface-treated papers.

[0100] The thickness of the protective film is not particularly limited and can be, for example, 10 to 150 μm.

[0101] [Resin layer] The resin layer is formed using the photosensitive resin composition of the present invention. The thickness of the resin layer is not particularly limited and can be appropriately selected according to the application and the like, and can be, for example, 1 to 150 μm.

[0102] The method for forming the resin layer is not particularly limited. For example, it can be formed by applying a photosensitive resin composition on a support (carrier) film and drying it. The coating method is not particularly limited, and comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. can be used. It is preferable to apply and dry the resin layer so as to have a uniform thickness. The resin layer may be formed by applying and drying a photosensitive resin composition on the protective film.

[0103] [Cured product] The cured product of the present invention is formed using the photosensitive resin composition of the present invention. A pattern may be formed on the cured product. Examples of the method for producing the cured product include the following.

[0104] [First step] The first step is a step of forming a dry coating film of the photosensitive resin composition of the present invention. For example, a dry coating film can be formed by applying the photosensitive composition of the present invention on a substrate to form a coating film and drying it, or by transferring a resin layer from the dry film of the present invention onto the substrate.

[0105] The method for applying the photosensitive resin composition onto the substrate is not particularly limited, and examples include methods of applying using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., a method of spray coating with a spray coater, an inkjet method, etc.

[0106] The drying method of the coating film is not particularly limited, and examples thereof include air drying, heat drying using an oven or a hot plate, vacuum drying, and the like. It is desirable to dry the coating film under conditions such that the ring closure of the polyimide precursor in the photosensitive resin composition does not occur. Examples thereof include natural drying, blow drying, and heat drying under conditions of 70 to 140 °C for 1 to 30 minutes. From the viewpoint of simplicity of the operation method, it is preferable to perform drying for 1 to 20 minutes using a hot plate. Vacuum drying is also possible, and in this case, it can be performed under conditions of room temperature for 20 minutes to 1 hour.

[0107] The transfer of the resin layer of the dry film onto the substrate is preferably performed under pressure and heating using a vacuum laminator or the like. By using a vacuum laminator, in the case of a substrate on which a circuit is formed, even if there are irregularities on the surface of the circuit board, the resin layer of the dry film is filled into the irregularities under vacuum conditions, so that the mixing of air bubbles can be avoided, and the hole filling property of the recesses on the surface of the circuit board can also be improved.

[0108] The substrate is not particularly limited, and examples thereof include a printed wiring board in which a circuit is formed in advance with copper or the like, and a flexible printed wiring board. Materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminate for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. are used, and copper-clad laminates of all grades (such as FR-4), other metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc. can also be used. Quality, and all grades (such as FR-4) of copper-clad laminates, as well as other metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc. can also be used.

[0109] [Second Step] The second step is a step of irradiating the dried coating film formed in the first step with active energy rays for exposure. The exposure may be performed selectively through a photomask having a pattern or non-selectively without passing through the photomask.

[0110] As the active energy rays, those having a wavelength capable of activating a photoacid generator such as a photoacid generator are used, and those having a maximum wavelength in the range of 350 to 410 nm are preferred. The exposure amount can be appropriately adjusted according to the film thickness and the like, and generally it is 10 to 1000 mJ / cm 2 and can be preferably 20 to 800 mJ / cm 2 . As the exposure machine, a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and capable of irradiating ultraviolet rays in the range of 350 to 450 nm can be used. A direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) may be used.

[0111] [Step 3] The third step is a step of closing a part of the polyimide precursor in the unexposed portion by heating the coated film after exposure for a short time, and is an optional step that is carried out as necessary. When this step is carried out, it is preferable to make the ring closure rate about 30%. The heating time and the heating temperature can be appropriately changed according to the type of the polyimide precursor, the coating film thickness, and the type of the photoacid generator.

[0112] [Step 4] The fourth step is a step of treating the coated film after exposure, and in some cases, the coated film that has been heated for a short time, with a developer to remove the exposed portion in the coated film to obtain a pattern film. The developing method is not particularly limited, and examples thereof include a rotary spray method, a paddle method, and an immersion method accompanied by ultrasonic treatment.

[0113] The developer is not particularly limited, and examples thereof include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, ethylamine, diethylamine, triethyl Examples of the aqueous solution include organic amines such as monoethanolamine and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added.

[0114] After the treatment with the developer, if necessary, the coating film can be washed with a rinse solution to obtain a pattern film. The rinse solution is not particularly limited, and examples thereof include distilled water, methanol, ethanol, and isopropyl alcohol. The rinse solution may be used alone or in any combination of two or more.

[0115] [Step 5] The fifth step is a step of heating the pattern film to obtain a cured coating film (cured product). By heating, the polyimide precursor contained in the photosensitive resin composition undergoes a cyclization reaction to become polyimide.

[0116] From the viewpoint of preventing warping of the cured product, the heating temperature is preferably 150 to 250°C, more preferably 170 to 220°C. For heating, for example, a hot plate, an oven, and a temperature-programmable heating oven can be used. The heating may be carried out in the air or in an inert gas atmosphere such as nitrogen or argon.

[0117] [Use] The use of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include paints, printing inks, and adhesives. The photosensitive resin composition of the present invention can be suitably used as a forming material for display devices, semiconductor elements, electronic components, optical components, building materials, and the like.

[0118] Examples of the forming material for display devices include layer-forming materials and image-forming materials in color filters, films for flexible displays, resist materials, alignment films, and the like. Examples of the material for forming a semiconductor element include layer forming materials such as a resist material, a buffer coat film, and an insulating film for a redistribution layer of a wafer level package (WLP). Examples of the material for forming an electronic component include a sealing material and a layer forming material such as a printed wiring board, an interlayer insulating film, and a wiring coating film. Examples of the material for forming an optical component include an optical material and a layer forming material such as a hologram, an optical waveguide, an optical circuit, an optical circuit component, and an antireflection film. As a building material, it can be used for paints, coating agents, etc.

[0119] The photosensitive resin composition of the present invention is preferably used as a pattern forming material, and particularly as a surface protective film, a buffer coat film, an interlayer insulating film, a redistribution insulating film, a protective film for a flip chip device, a protective film for a device having a bump structure, an interlayer insulating film for a multilayer circuit, an insulating material for passive components, a solder resist, and a protective film for a printed wiring board such as a coverlay film, a liquid crystal alignment film, etc.

Examples

[0120] The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

[0121] The measurements and evaluations in the examples were carried out as follows. <Number average molecular weight, weight average molecular weight> The number average molecular weight and the weight average molecular weight are values measured by gel permeation chromatography (GPC) and converted with standard polystyrene. [Measurement conditions] GPC measurement: GL7700 (GL Science) Columns used: Tosoh TSKgel(R) α-2500 (φ7.8 mm × 30 cm), α-4000 (φ7.8 mm × 30 cm) Column temperature: 40 °C Eluent conditions: 100 mmol / L H3PO4, 10 mmol / L LiBr, in NMP Eluent flow rate: 0.5 mL / min Calibration standard reagent: Polystyrene standard (Showdex) Sample concentration: 0.1% eluent Detector: UV (wavelengths 260 nm and 300 nm), room temperature

[0122] <Dissolution rate, dissolution contrast> The varnishes prepared in the examples and comparative examples were applied onto a silicon wafer using a spin coater and dried under the conditions of 110°C for 3 minutes to obtain a dry film with a film thickness of approximately 1 μm. The obtained silicon wafer with the dry film was cut into strip-shaped test pieces, and two types of test pieces were prepared: one irradiated with light of wavelength 365 nm at the exposure amount shown in Table 1 using a high-pressure mercury lamp, and the other without light irradiation. Each test piece was subjected to post-exposure baking (PEB) under the conditions shown in Table 1, and then developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH). The dissolution rate of the test piece irradiated with light was defined as the dissolution rate of the exposed part, and the dissolution rate of the test piece without light irradiation was defined as the dissolution rate of the unexposed part. The dissolution rate of the exposed part was determined by the following formula, where the development time was the time from when the test piece was immersed in the developer until the dry film on the test piece was completely dissolved in the developer. The dissolution of the dry film in the developer was visually observed. The dissolution rate of the unexposed part was determined by the following formula, where the film thickness of the dry film on the test piece at the stage 1 hour after immersion in the developer was defined as the film thickness after development. The development time was 1 hour (3600 s). The dissolution contrast was (dissolution rate of the exposed part / dissolution rate of the unexposed part).

Equation

[0123] <Resolution> The silicon wafer with a dry film prepared in the above dissolution rate test was irradiated with light having a wavelength of 365 nm from a high-pressure mercury lamp at the exposure amount shown in Table 1 through a mask with a pattern engraved thereon. After exposure, post-exposure bake (PEB) was performed under the conditions shown in Table 1, and after developing in a 2.38% TMAH aqueous solution for 60 seconds, it was rinsed with water to obtain a pattern of a positive-type cured film. The L / S (line / space) of the pattern engraved on the mask was changed from 1 μm / 1 μm to 30 μm / 30 μm in 1-μm increments for both the line and the space, and the pattern of the obtained positive-type cured film was observed using an electron microscope (SEM, JSM-6010 manufactured by JEOL Ltd.). The minimum L / S at which the exposed portion could be patterned without scum (development residue) was defined as the resolution.

[0124] <Residual film ratio> Regarding the positive-type cured film pattern after development in the above resolution test, the film thickness of the unexposed portion was measured, and the residual film ratio was calculated using the following formula.

Equation

[0125] Each component used in the examples and comparative examples is as follows.

[0126] <Synthesis Example 1: Polyimide Precursor (A-1)> 53 g of propylene glycol monomethyl ether acetate (PGMEA) and 6.91 g (13.02 mmol) of 3,3'-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-methylenedianiline (HFA-MDA) were charged into a flask and stirred until dissolved. After confirming that the monomers were completely dissolved, 5.20 g (10.00 mmol) of 5,5'-[1-methyl-1,1-ethanediylbis(1,4-phenylene)bisoxy]bis(isobenzofuran-1,3-dione) (BPADA) was added as a solid over 5 minutes, and stirring was continued at room temperature for 1 hour. Then, 0.26 g (1.59 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a solid to the stirred solution, and stirring was carried out at room temperature for 16 hours to obtain a polyimide precursor (A-1) (HFA-containing polyamic acid) varnish. The number average molecular weight (Mn) of the polyimide precursor (A-1) was 3,200, the weight average molecular weight (Mw) was 7,950, the carboxyl group equivalent was 525 g / mol, and the fluorine group equivalent was 87 g / mol.

[0127] Polyimide precursor A-1 [Chemical formula]

[0128] <Synthesis Example 2: Polyimide Precursor (A-2)>[ 15 g of PGMEA and 1.33 g (3.00 mmol) of HFA-MDA were charged into a flask and stirred until dissolved. After confirming that the monomers were completely dissolved, 1.59 g (3.00 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 0.023 g (0.14 mmol) of 5-norbornene-2,3-dicarboxylic anhydride were added as solids, and stirring was carried out at room temperature for 16 hours to obtain a polyimide precursor (A-2) (HFA-containing polyamic acid) varnish. The number average molecular weight (Mn) of the polyimide precursor (A-2) was 16,900, the weight average molecular weight (Mw) was 41,700, the carboxyl group equivalent was 487 g / mol, and the fluorine group equivalent was 54 g / mol.

[0129] Polyimide precursor (A-2)

Chemical formula

[0130] <Synthesis Example 3: Polyimide precursor (A-3)> 27 g of PGMEA and 1.59 g (3.00 mmol) of HFA-MDA were charged into a flask and stirred until dissolved. After confirming that the monomers were completely dissolved, 0.97 g (3.00 mmol) of 3,3’,4,4’-benzophenonetetracarboxylic dianhydride and 0.14 g (0.023 mmol) of 5-norbornene-2,3-dicarboxylic dianhydride were added as solids, and the mixture was stirred at room temperature for 16 hours to obtain a polyimide precursor (A-3) (HFA-containing polyamic acid) varnish. The number average molecular weight (Mn) of the polyimide precursor (A-3) was 15,400, the weight average molecular weight (Mw) was 36,500, the carboxyl group equivalent was 426 g / mol, and the fluorine group equivalent was 71 g / mol.

[0131] Polyimide precursor (A-3)

Chemical formula

[0132] <Synthesis Example 4: Polyimide precursor (A’-1)> 81 g of PGMEA and 6.96 g (21.74 mmol) of 2,2’-bis(trifluoromethyl)benzidine (TFMB) were charged into a flask and stirred until dissolved. After confirming that the monomers were completely dissolved, 8.11 g (18.26 mmol) of 6FDA was added as a solid over 5 minutes, and stirring was continued at room temperature for 1 hour. Then, 1.15 g (6.98 mmol) of 5-norbornene-2,3-dicarboxylic dianhydride was added as a solid to the stirred solution, and the mixture was stirred at room temperature for 16 hours to obtain a polyimide precursor (A’-1) (polyamic acid) varnish. The number average molecular weight of the polyimide precursor (A’-1) was 5,200, the weight average molecular weight (Mw) was 13,000, the carboxyl group equivalent was 382 g / mol, and the fluorine group equivalent was 63 g / mol.

[0133] Polyimide precursor (A’-1)

Chem.

[0134] <Photoacid generator (B-1)>

Chem.

[0135] <Photoacid generator (B-2)>

Chem.

[0136] <Photoacid generator (B-3)>

Chem.

[0137] <Vinyl ether compound (C-1)>

Chem.

[0138] <Vinyl ether compound (C-2)>

Chem.

[0139] <Vinyl ether compound (3-functional vinyl ether compound) (C-3)> 1.23 g (9.79 mmol) of fluoroglycinol, 1.67 g (41.9 mmol) of NaOH, and 15 mL of dimethylformamide (DMF) were added to a flask equipped with a cooling tube and a thermometer, and the mixture was stirred at 60 °C for 1 hour. Then, 4.46 g (41.9 mmol) of 2-chloroethyl vinyl ether was added, and the mixture was stirred at 70 °C for 15 hours. After quenching the reaction mixture with water, extraction was performed with toluene, and the organic layer was washed with an aqueous NaCl solution. After drying the organic layer over magnesium sulfate, the solvent was removed by an evaporator to obtain a trifunctional vinyl ether compound (C-3) having the following structure.

[0140] Vinyl ether compound (C-3)

Chemical formula

[0141] <Adhesive D-1>

Chemical formula

[0142] <Basic compound E-1> Triethanolamine

Chemical formula

[0143] <Surfactant F-1> Megafac F-477 manufactured by DIC (fluorine-containing group, hydrophilic resin, and lipophilic group-containing oligomer) <Surfactant F-2> Megafac F-554 manufactured by DIC (fluorine-containing group and lipophilic group-containing oligomer) <Surfactant F-3> Megafac F-563 manufactured by DIC (fluorine-containing group and lipophilic group-containing oligomer) <Surfactant F-4> BYK-322 manufactured by BYK-Chemie GmbH (silicone-based surface conditioner for solvent-based paints) <Surfactant F-5> BYK-331 manufactured by BYK Chemie (silicone-based surface conditioner for solvent-free and solvent-based general industrial and automotive paints, and printing inks) <Surfactant F-6> BYK-333 manufactured by BYK Chemie (silicone-based surface conditioner for solvent-free, solvent-based, and water-based paints and printing inks) <Surfactant F-7> BYK-3760 manufactured by BYK Chemie (silicone-based surface conditioner for solvent-based, water-based, and UV-curable paints, and printing inks)

[0144] <Example 1> A varnish of Synthesis Example 1 containing 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 0.3 parts by mass of photoacid generator (B-1), and 56 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 1.

[0145] <Example 2> A varnish of Synthesis Example 1 containing 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 0.3 parts by mass of photoacid generator (B-1), and 72 parts by mass of vinyl ether compound (C-2) were blended to obtain the photosensitive resin composition of Example 2.

[0146] <Example 3> A varnish of Synthesis Example 1 containing 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 0.3 parts by mass of photoacid generator (B-1), and 62 parts by mass of vinyl ether compound (C-3) were blended to obtain the photosensitive resin composition of Example 3.

[0147] <Example 4> A varnish of Synthesis Example 1 containing 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 0.3 parts by mass of photoacid generator (B-1), 44 parts by mass of vinyl ether compound (C-1), and 0.5 parts by mass of adhesion promoter (D-1) were blended to obtain the photosensitive resin composition of Example 4.

[0148] <Example 5> A varnish of Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 0.5 part by mass of photoacid generator (B-1), 20 parts by mass of photoacid generator (B-2), and 29 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 5.

[0149] <Example 6> A varnish of Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 1 part by mass of photoacid generator (B-1), 10 parts by mass of photoacid generator (B-2), and 29 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 6.

[0150] <Example 7> A varnish of Synthesis Example 1 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-1), 1 part by mass of photoacid generator (B-1), 20 parts by mass of photoacid generator (B-2), 29 parts by mass of vinyl ether compound (C-1), and 0.5 part by mass of adhesion promoter (D-1) were blended to obtain the photosensitive resin composition of Example 7.

[0151] <Example 8> A varnish of Synthesis Example 2 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-2), 1 part by mass of photoacid generator (B-11), 10 parts by mass of photoacid generator (B-2), and 32 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 8.

[0152] <Example 9> A varnish of Synthesis Example 3 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A-3), 1 part by mass of photoacid generator (B-1), 10 parts by mass of photoacid generator (B-2), and 32 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Example 9.

[0153] <Comparative Example 1> A varnish of Synthesis Example 4 of 100 parts by mass (equivalent to solid content) of polyimide precursor (A’-1), 0.3 part by mass of photoacid generator (B-1), and 76 parts by mass of vinyl ether compound (C-1) were blended to obtain the photosensitive resin composition of Comparative Example 1.

[0154] The photosensitive compositions of Examples 10 to 28 were prepared by blending the amounts of the respective components shown in Table 1. In the table, the amounts of the resin, photoacid generator, vinyl ether compound, adhesion promoter, and base compound are shown in parts by mass. For the polyimide precursor (A-1), the varnish of Synthesis Example 1 was used in an amount such that the solid content equivalent was the amount shown in the table.

[0155] For the photosensitive resin compositions of the examples and comparative examples, each measurement and evaluation were carried out under the conditions shown in Table 1. The results are shown in Table 1.

[0156]

Table 1

[0157] The photosensitive resin compositions of Examples 1 to 28 had a large dissolution contrast and exhibited excellent resolution. Among them, Examples 5 to 8 in which a photoacid generator and a naphthoquinone diazide compound were used in combination as the photoacid generator showed a high residual film ratio. Also, Example 11 in which two types of vinyl ether compounds were combined and Example 12 in which a base compound was blended showed excellent resolution with a large dissolution contrast. Furthermore, Examples 13 to 28 are examples in which a surfactant was blended, and all showed a high residual film ratio. Examples 20 to 28 in which two types of vinyl ether compounds were combined and a base compound was further blended showed a large dissolution contrast and extremely excellent resolution.

Claims

1. (A) A polyimide precursor having at least one of the structures represented by the following general formulas (1) and (2); (B) A photoacid generator; (C) A compound having two or more vinyl ether groups; An adhesive and / or a surfactant; A photosensitive resin composition containing the same. 【Chemical Formula 1】 (In the formula, X is a tetravalent organic group; A is a single bond, O or a divalent organic group; B is a fluoroalcohol group; R is a hydrogen atom, or a substituted or unsubstituted alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylamino group or aryl group; n1 is an integer of 1 or more; n2 is an integer of 0 to 4, n3 is an integer of 0 to 4, but n2 + n3 is 1 or more; n4 is an integer of 1 to 4.)

2. The photosensitive resin composition according to claim 1, wherein X is selected from the groups represented by the following. 【Chemical Formula 2】 【Chemical Formula】 【Chemical Formula】 (In the formula, a is an integer of 0 to 2; b is an integer of 0 to 2.)

3. The photosensitive resin composition according to claim 1 or 2, wherein the carbon atom number of B is 1 to 10 and the fluorine atom number is 1 to 10.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the carboxyl group concentration in the polyimide precursor is 300 to 800 mol / g.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the fluorine concentration in the polyimide precursor is 20 to 200 mol / g.

6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising a base compound.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photoacid generator includes an N-sulfonyloxyimide type photoacid generator.

8. The photosensitive resin composition according to claim 7, wherein the photoacid generator further includes a naphthoquinone diazide compound.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the compound having two or more vinyl ether groups is at least one selected from diethylene glycol divinyl ether and cyclohexane dimethanol divinyl ether.

10. A dry film comprising a resin layer formed by the photosensitive resin composition according to any one of claims 1 to 9 on a film.

11. A cured product formed by the photosensitive resin composition according to any one of claims 1 to 9 or the resin layer of the dry film according to claim 10.

12. An electronic component having the cured product according to claim 11 as a forming material.

Images