JP5319103B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which can be pressure-bonded to a substrate or the like, has flame retardancy and reduces warpage in dry film formation, and a photosensitive film comprising the photosensitive resin composition. <P>SOLUTION: The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a light-sensitive material and (C) a phosphoric ester compound represented by general formula (1), wherein R<SB>1</SB>is a 1-30C aliphatic organic group and three symbols R<SB>1</SB>may be the same or different. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive resin composition suitable for a cover lay of a printed wiring board and a photosensitive film using the same.

  High heat-resistant resins such as polyimide are attracting attention as insulating materials having excellent heat resistance, particularly as insulating layers and protective layers for solid elements in the semiconductor industry. In general, polyimide has a heat resistance of 300 ° C. or higher and excellent mechanical properties, and also has excellent electrical properties such as low dielectric constant and high insulation.

  When a general polyimide material is finely processed, an etching process using a photoresist is performed, which requires a large number of steps. Therefore, a photosensitive polyimide material that can directly form a pattern on the insulating layer polyimide itself has been attracting attention. In particular, there is a strong demand for a photosensitive resin composition that can be developed with an alkaline aqueous solution in consideration of safety during work and influence on the environment. In general, in the case of the negative type, the exposed portion is swollen by the developer, and it is difficult to perform high resolution fine processing. Therefore, fine processing by a positive type photosensitive system is strongly desired.

  In addition, in conventional screen printing, there is a problem that the process of removing the solvent and the double-sided process require two processes, so that it is hoped that the photosensitive resin composition is made into a dry film from the viewpoint of an industrial process. It is rare.

  As a positive photosensitive resin composition, a positive photosensitive resin composition in which a quinonediazide compound is added to a polyimide precursor or a polybenzoxazole precursor is disclosed (Patent Document 1). Although the precursor type is excellent in final film physical properties, since it is a composition in the state of the precursor, some of the precursor types have poor storage stability, which may cause inconvenience in processing.

  As a positive photosensitive resin composition containing a polyimide, a photosensitive resin composition containing a polyimide containing a sulfonic acid group and a naphthoquinonediazide compound is disclosed (Patent Document 2). Although the photosensitive resin composition has improved storage stability, it is difficult to press-bond to a substrate or the like because of the high Tg of polyimide.

  On the other hand, a positive photosensitive resin composition made of polyimide having a siloxane skeleton is disclosed as a positive photosensitive resin composition in which Tg of polyimide is lowered (Patent Document 3). Like the technique in this document, polyimide introduces a siloxane skeleton, but Tg is lowered but flame retardancy tends to be lowered. Moreover, since the said composition is not plastic enough, curvature generate | occur | produces at the time of dry film formation, and it is difficult to use it as a photosensitive film.

  As a method of imparting flame retardancy to a resin composition, a method of adding a phosphorus compound is known (Non-Patent Document 1). However, it is necessary to add a large amount of a phosphorus compound in order to develop flame retardancy with a conventionally known technique. If this technique is used for a photosensitive resin composition, the photosensitive performance tends to be lowered. Patent Document 4 is known as an example of adding a small amount of a phosphorus compound. This document is intended to improve the heat deterioration resistance and does not disclose any flame retardancy.

As described above, it has been difficult to simultaneously satisfy photosensitivity, flame retardancy, pressure bonding to a substrate, and warpage during dry film formation.
Japanese Patent No. 3078175 Japanese Patent Laid-Open No. 2004-238591 International Publication No. 2003/06010 Pamphlet Japanese Patent No. 2955712 Flame retardant technology using non-halogen flame retardant materials (NTS)

  The present invention has been made in view of the above points, and is a positive photosensitive resin composition that is easily crimped to a substrate and the like, has flame retardancy, and has reduced warpage during dry film formation, and the It aims at providing the photosensitive film which consists of photosensitive resin compositions.

（ただし、Ｒ _１ は炭素数１以上３０以下の脂肪族有機基であり、同じであっても異なっていても良い。） As a result of intensive studies to solve the above problems, the present inventors have found that (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a phosphate ester compound represented by the following general formula (1) A photosensitive resin composition containing two or more of the (C) phosphate ester compound or a phosphate ester in which R ₁ in the general formula (1) is a butoxyethyl group is formed into a dry film. The inventors have found that warping at the time is reduced, flame retardancy, and good press-bonding property to a substrate or the like, and the present invention has been completed.
[General formula (1)]

(However, R ₁ is an aliphatic organic group having 1 to 30 carbon atoms and may be the same or different.)

（ただし、Ｒ₁は炭素数１以上３０以下の脂肪族有機基であり、同じであっても異なっていても良い。）
また、本発明の第２の感光性樹脂組成物は、（Ａ）アルカリ溶解性樹脂と、（Ｂ）感光剤と、（Ｃ）前記一般式（１）で表されるリン酸エステル化合物と、を含有し、前記一般式（１）におけるＲ_１が、ブトキシエチル基であるリン酸エステルを含み、前記（Ａ）アルカリ溶解性樹脂が、アルカリ溶解性ポリイミド又はポリアミド酸であることを特徴とする。
また、本発明の第３の感光性樹脂組成物は、（Ａ）アルカリ溶解性樹脂と、（Ｂ）感光剤と、（Ｃ）前記一般式（１）で表されるリン酸エステル化合物と、を含有し、前記一般式（１）におけるＲ _１ が、ブトキシエチル基であるリン酸エステルを含み、前記（Ｂ）感光剤が、キノンジアジド構造を有する化合物であることを特徴とする。
本発明の第１及び第２の感光性樹脂組成物においては、前記（Ｂ）感光剤が、キノンジアジド構造を有する化合物であることが好ましい。 The first photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a phosphate ester compound represented by the following general formula (1). And (C) two or more types of phosphoric ester compounds.

(However, R ₁ is an aliphatic organic group having 1 to 30 carbon atoms and may be the same or different.)
The second photosensitive resin composition of the present invention, the (A) alkali-soluble resin, a phosphoric acid ester compound represented by (B) a photosensitive agent, (C) the general formula (1), Wherein R ₁ in the general formula (1) includes a phosphate ester which is a butoxyethyl group, and the (A) alkali-soluble resin is an alkali-soluble polyimide or polyamic acid. .
The third photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitizer, (C) a phosphate ester compound represented by the general formula (1), And R ₁ in the general formula (1) contains a phosphate ester which is a butoxyethyl group, and the (B) photosensitizer is a compound having a quinonediazide structure.
In the 1st and 2nd photosensitive resin composition of this invention, it is preferable that the said (B) photosensitive agent is a compound which has a quinonediazide structure.

In the first photosensitive resin composition of the present invention, R ₁ in the general formula (1) is selected from the group consisting of a methyl group, an ethyl group, a butyl group, an isobutyl group, a 2-ethylhexyl group, and a butoxyethyl group. Any one of them is preferable.

  In the photosensitive resin composition of this invention, it is preferable that the (C) phosphate ester compound is contained in 50 parts by weight or less with respect to 100 parts by weight of the (A) alkali-soluble resin.

  In the photosensitive resin composition of the present invention, the (A) alkali-soluble resin is preferably an alkali-soluble polyimide.

  In the photosensitive resin composition of the present invention, the (A) alkali-soluble resin is preferably a polyamic acid.

In these cases, containing the alkali soluble polyimide, and Turkey to contain a siloxane structure at least 10% by weight rather preferably, also, the polyamic acid, a siloxane structure 10 wt% to 90 wt% or less it is not preferable to be.

  The photosensitive film of this invention is comprised by the said photosensitive resin composition, It is characterized by the above-mentioned.

  The laminated film of the present invention comprises a carrier film and the photosensitive film provided on the carrier film.

  The laminated film of the present invention preferably includes a cover film formed on the photosensitive film.

  The printed wiring board of the present invention comprises: a base material having wiring; and a cover lay formed on the base material so as to cover the wiring and configured by the photosensitive film or the laminated film. And

  According to the photosensitive resin composition of the present invention, it is possible to obtain a material that can reduce a warp when formed into a dry film, has a flame retardancy, and can provide a film having good pressure-bonding property to a substrate or the like.

Hereinafter, the present invention will be described in detail.
The (A) alkali-soluble resin used in the present invention is not limited as long as it is a resin that can be dissolved in an alkaline solution. Examples of such a resin include resins having a functional group that dissolves in a known alkali such as a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group in the main chain and / or side chain. As such a resin, alkali-soluble polyamides such as alkali-soluble polyimide, polyamic acid, and polybenzoxazole precursor are preferable from the viewpoint of heat resistance, and alkali-soluble polyimide and polyamic acid are more preferable from the viewpoint of dry film formation. Preferably, alkali-soluble polyimide is particularly preferable.

Here, the alkali-soluble polyimide and polyamic acid used in the present invention will be described.
Specific examples of the acid dianhydride used in the alkali-soluble polyimide and polyamic acid according to the present invention include pyromellitic anhydride, oxydiphthalic dianhydride (hereinafter abbreviated as ODPA), biphenyl-3,4,3. ', 4'-tetracarboxylic dianhydride, benzophenone-3,4,3', 4'-tetracarboxylic dianhydride, diphenylsulfone-3,4,3 ', 4'-tetracarboxylic dianhydride 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, 1,2,4 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetra Carboxylic acid , 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2, 3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, ethylene glycol bis ( Trimellitic acid monoester acid anhydride) and p-phenylenebis (trimellitic acid monoester acid anhydride).

  Among these, ODPA, ethylene glycol bis (trimellitic acid monoester acid anhydride), p-phenylene bis (trimellitic acid monoester acid anhydride) from the viewpoint of solvent solubility of polyimide and pressure bonding properties to substrates, etc. ), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride is preferred. Here, the solvent solubility means that polyimide has a property of being dissolved in a known organic solvent at a concentration of 5% by weight or more.

  Next, the diamine used in (A) will be described. Examples of the diamine in the present invention include diamines having an alkali-soluble functional group and other diamines.

  The alkali-soluble functional group is not limited as long as it is a functional group that dissolves in a known alkali such as a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group. Among them, a carboxyl group and an aromatic hydroxyl group are preferable from the viewpoint of inhibiting dissolution of unexposed portions. An aromatic hydroxyl group is a functional group derived from a compound in which a hydroxyl group is directly bonded to an aromatic ring. Specific examples include functional groups derived from compounds in which a hydroxyl group is directly bonded to a benzene ring, such as phenol, catechol, resorcinol, hydroquinone, 1-naphthol, and 2-naphthol.

  Examples of the diamine having an aromatic hydroxyl group include 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4-hydroxybenzene, and 1,4-diamino-6. -Hydroxybenzene, 1,5-diamino-6-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,2-diamino-3,5-dihydroxybenzene, 4- (3,5-diaminophenoxy ) Phenol, 3- (3,5-diaminophenoxy) phenol, 2- (3,5-diaminophenoxy) phenol, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4 , 4′-dihydroxybiphenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis ( -Hydroxy-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone, 2,2-bis (4-hydroxy-3-aminophenyl) sulfide, 2,2-bis (4- Hydroxy-3-aminophenyl) ether, 2,2-bis (4-hydroxy-3-aminophenyl) sulfone, 2,2-bis (4-hydroxy-3-aminophenyl) methane, 4-[(2,4 -Diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, 2,2-bis (4-hydroxy-3-aminophenyl) difluoromethane, 2, 2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoro Propane, bis (4-amino-3-hydroxyphenyl) ketone, 2,2-bis (4-amino-3-hydroxyphenyl) sulfide, 2,2-bis (4-amino-3-hydroxyphenyl) ether, 2 , 2-bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) difluoromethane Etc.

  Examples of the diamine having a carboxyl group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane (hereinafter abbreviated as MBAA), 3,5-diaminobenzoic acid, and the like. Among these, MBAA, 3,5-diaminobenzoic acid, and 1,3-diamino-4,6-dihydroxybenzene are preferable in view of alkali solubility and easy reaction.

  Other diamines include silicone diamine, 1, n-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2 ′ -Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4, 4′-bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1 3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5- Amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2 2- bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, and 1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane. The alkali-soluble resin preferably has a siloxane structure of not less than 10% by weight and not more than 90% by weight, and has a siloxane structure of not less than 20% by weight and not more than 80% by weight, from the viewpoint of warpage and flame retardancy during dry film formation. It is more preferable to have.

  In the present invention, the terminal of the alkali-soluble resin is not particularly limited as long as it has a structure that does not affect the performance. The terminal may be derived from an acid dianhydride or a diamine used for producing a polyimide (precursor), or the terminal may be sealed with another acid anhydride or an amine compound.

  The number average molecular weight of the alkali-soluble resin used in the present invention is preferably 1,000 or more and 1,000,000 or less. Here, the number average molecular weight means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film. Moreover, it is preferable that the said molecular weight is 1000000 or less from a viewpoint of the viscosity of a polyimide containing resin composition and a moldability. The molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000.

  Next, the production method of the alkali-soluble resin used in the present invention will be described by taking as an example a method of synthesizing polyamic acid and then synthesizing alkali-soluble polyimide.

  A polyimide can be obtained by reacting an acid dianhydride and a diamine to synthesize a polyamic acid and then heating (heating imidization). It can also be obtained by reacting an acid dianhydride and a diamine to synthesize a polyamic acid, followed by imidization (chemical imidization) after adding a catalyst. Among these, chemical imidation is preferable in that imidization can be completed at a lower temperature.

  Next, a method for synthesizing a polyamic acid by reacting an acid dianhydride and a diamine will be described, and subsequently, a method for imidizing after adding a catalyst will be described as an example, and manufacturing conditions for polyimide will be described.

  The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, acid dianhydride powder is gradually added thereto, and the mixture is stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours using a mechanical stirrer. In this case, the monomer concentration is 0.5 wt% or more and 95 wt% or less, preferably 1 wt% or more and 90 wt% or less. By performing polymerization in this monomer concentration range, a polyamic acid solution can be obtained.

  Examples of the reaction solvent used in the production of the polyamic acid include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. Ketone compounds having 2 to 6 carbon atoms; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as: ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, methylene chloride, 1, 2 Halogen-containing compounds having 1 to 10 carbon atoms such as dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Compound; Sulfur-containing compounds such as dimethyl sulfoxide are exemplified. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ester compounds having 3 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like.

  The reaction temperature in the production of the polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower in consideration of the reaction start and side reaction effects. The reaction temperature is preferably 15 ° C. or higher and 220 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower.

  The time required for the reaction of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, and particularly preferably 30 minutes to 30 hours.

  Next, a method of obtaining an alkali-soluble polyimide used in the present invention by adding a catalyst to polyamic acid (chemically) to imidize will be described.

  The imidization catalyst for producing the alkali-soluble polyimide is not particularly limited, but an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, γ -Lactone compounds such as phthalide acid; tertiary amines such as pyridine, quinoline, N-methylmorpholine, triethylamine and the like. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine is particularly preferable from the viewpoint of high reactivity.

  The amount of the imidization catalyst added is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the polyamic acid.

  As the reaction solvent, the same solvent as used for the production of polyamic acid can be used. In that case, the polyamic acid solution can be used as it is. Moreover, you may use the solvent different from what was used for manufacture of a polyamic acid.

  Examples of the reaction solvent include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. Ketone compounds having 2 to 6 carbon atoms; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; such as chloroform, methylene chloride, and 1,2-dichloroethane Carbon number A halogen-containing compound having 10 to 10 carbon atoms; a nitrogen-containing compound having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; like dimethyl sulfoxide A sulfur-containing compound is mentioned. If necessary, one kind or a mixture of two or more kinds may be used. Particularly preferable solvents include ester compounds having 3 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like.

  In the production of the polyimide used in the present invention, the reaction temperature is preferably 15 ° C. or more and 250 ° C. or less in consideration of reaction initiation and catalyst activity. The reaction temperature is preferably 20 ° C. or higher and 220 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower.

  The time required for the reaction varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

  After completion of production, the polyimide can be recovered by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying the polyimide used in the present invention include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Furthermore, when a particularly high-purity polyimide is required, an extraction method using a carbon dioxide supercritical method is also possible.

  By using this polyimide, a resin composition containing a solvent in which the polyimide can be uniformly dissolved and / or dispersed can be obtained.

  The solvent which comprises the resin composition containing the polyimide which concerns on this invention will not be limited if the said polyimide can be melt | dissolved and / or disperse | distributed uniformly. Examples of such solvents include those having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and propylene glycol monomethyl acetate. Compound; ketone compound having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; benzene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as toluene, xylene, mesitylene and tetralin; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate and γ-butyrolactone; chloroform, methylene chloride Chlorine-containing compounds having 1 to 10 carbon atoms such as 1,2-dichloroethane; 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Examples thereof include the following nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of polyimide solubility, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  The concentration of the alkali-soluble resin in the resin composition containing the alkali-soluble resin and the solvent according to the present invention is not particularly limited as long as the resin-molded body is produced. Further, from the viewpoint of the film thickness of the resin molded body to be produced, the polyimide concentration is preferably 1% by weight or more, and from the uniformity of the film thickness of the resin molded body, the polyimide concentration is preferably 90% by weight or less. From the viewpoint of the film thickness of the resin molding to be obtained, it is more preferably 2% by weight or more and 80% by weight or less.

  Examples of the photosensitive agent used in the present invention include those whose structure changes due to light irradiation and whose solubility in a solvent changes. Examples of such a compound include compounds containing a quinonediazide structure.

Examples of the compound containing a quinonediazide structure include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2-naphthoquinonediazidesulfone. And acid amides. Specifically, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone Acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones; 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinonedia Dido-5-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,3′-tetrahydroxybenzophenone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-te Lahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as acid esters; 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as 1,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; , 3 ′, 4 ′, 5′-hexahydroxybenzophenone-1 2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ', 4', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as -5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis ( 2,4-Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1, 1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid Ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane- , 2-Naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3- Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) ) -3-Phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl]- 1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2- Naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3 '-Tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3, 3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfur Acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 4′-trihydroxyflavan-1,2-naphthoquinone diazide-5-sulfonic acid ester. From the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinone diazide sulfonic acid esters are preferable, 1,2-naphthoquinone diazide-4-sulfonic acid esters, and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Of these, the compound represented by the general formula (2) is particularly preferable.

In General formula (2), Q is a structure or a hydrogen atom represented by General formula (3) or (4). As a photosensitive agent in the photosensitive resin composition according to the present invention, an average of 2.3 of the three Qs in the general formula (2) has a structure represented by the general formula (3) (compound Among the three Qs in B-1) and general formula (2), an average of 2.34 has a structure represented by general formula (4) (compound B-2) is particularly preferable.

  The amount of the photosensitive agent in the photosensitive resin composition according to the present invention is 1% by weight or more and 50% by weight or less from the viewpoint of photosensitive contrast when the amount of the alkali-soluble resin according to the present invention is 100 parts by weight. Is more preferable, and more preferably 5 wt% or more and 30 wt% or less. If it is 1% by weight or more, it is preferable because dissolution inhibition before exposure tends to be sufficient. Less than 50% by weight is preferable because the sensitivity tends to be sufficiently high.

  The (C) phosphate ester compound represented by the general formula (1) used in the present invention is not limited as long as it is a phosphate ester compound having an aliphatic organic group having 1 to 30 carbon atoms. A carbon number of 1 or more is preferred because warpage during dry film formation tends to be improved. A carbon number of 30 or less is preferred because it tends to exhibit flame retardancy. Such compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate (hereinafter abbreviated as TBP), tris (2-ethylhexyl) phosphate (hereinafter abbreviated as TOP). Oxygen such as phosphate ester substituted with aliphatic hydrocarbon group such as triisobutyl phosphate (hereinafter abbreviated as TIBP), tris (butoxyethyl) phosphate (hereinafter abbreviated as TBXP) And phosphoric acid ester having an aliphatic organic group containing an atom as a substituent. From the non-volatile viewpoint at the time of baking, TBP, TOP, TIBP, and TBXP are preferable. Further, TBXP is particularly preferable from the viewpoint of the solubility of the exposed area during development.

  (C) The phosphate ester compound may be used alone or in combination of two or more. Among these, it is preferable to use a combination of two or more types because both flame retardancy and warpage during dry film formation tend to be compatible. Examples of the two types of combinations include a combination of TBP and TBXP, a combination of TOP and TBXP, a combination of TIBP and TBXP, a combination of TBP and TOP, and the like.

  In the photosensitive resin composition according to the present invention, the addition amount of the phosphoric ester compound is 50 parts by weight or less from the viewpoint of photosensitivity when the amount of (A) the alkali-soluble resin is 100 parts by weight. preferable. From the viewpoint of heat resistance of the cured body, it is preferably 45 parts by weight or less, and more preferably 40 parts by weight or less.

  The photosensitive resin composition according to the present invention includes a solvent in which (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a phosphate ester compound can be uniformly dissolved and / or dispersed as necessary. be able to. As a solvent, the solvent used for the above-mentioned polyimide resin composition can be used.

  The photosensitive resin composition of this invention can be used suitably for a photosensitive film. From the viewpoint of producing a photosensitive film, the concentration of polyimide in the photosensitive resin composition is preferably 1% by weight or more and 90% by weight or less. The concentration of polyimide is preferably 1% by weight or more from the viewpoint of the film thickness of the photosensitive film, and preferably 90% by weight or less from the viewpoint of the viscosity and film thickness uniformity of the photosensitive resin composition. From the viewpoint of the film thickness of the resulting photosensitive film, it is more preferably 2% by weight or more and 80% by weight or less.

Next, the manufacturing method of the photosensitive film which concerns on this invention is demonstrated.
First, the photosensitive resin composition according to the present invention is coated on a substrate. The substrate is not limited as long as it is a substrate that is not damaged during the formation of the photosensitive dry film. Examples of such a substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film. Examples of the carrier film in the present invention include a polyethylene terephthalate film and a metal film. A heat-resistant resin and a carrier film are preferable from the viewpoint of easy handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.

  The coating methods include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, and flow coating. , Spin coating, slit coating, brush coating, and the like. After the coating, if necessary, a heat treatment called a pre-bake may be performed by a hot plate or the like.

  Thus, when using the photosensitive film comprised with the photosensitive resin composition of this invention, after apply | coating the solution of the photosensitive resin composition on arbitrary base materials by arbitrary methods, it makes a dry film. For example, a laminated film having a carrier film and a photosensitive film is used.

  Further, at least one cover film for antifouling or protection may be provided on the photosensitive film to form a laminated film. Examples of the cover film in the laminated film include a photosensitive film made of low-density polyethylene or the like.

  The photosensitive film comprised with the resin composition of this invention can be used for the printed wiring board obtained by crimping | bonding to the base material which has wiring so that the said wiring may be covered, performing alkali development, and baking. .

  Examples of the substrate having wiring in the printed wiring board according to the present invention include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a polyimide film. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  The method for producing the printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. As such a production method, in a state where the wiring side of the substrate having the wiring and the photosensitive film of the present invention are in contact, a hot press, a thermal lamination, a thermal vacuum press, a thermal vacuum lamination, etc. The method of performing etc. is mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a thermal vacuum press and a thermal vacuum lamination are preferable.

  The heating temperature when laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can be in close contact with the substrate. From the viewpoint of adhesion to the substrate, and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  The photosensitive film according to the present invention can be subjected to positive photolithography by irradiating light and then dissolving the light-irradiated portion by alkali development. In this case, examples of the light source used for light irradiation include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

  The aqueous alkali solution used for development is not limited as long as it is a solution capable of dissolving the light irradiation site. Examples of such a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the developing method include spray development, immersion development, and paddle development.

  Firing when the photosensitive film of the present invention is pressure-bonded and fired is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoint of solvent removal, side reaction, decomposition, or the like. More preferably, it is 100 degreeC or more and 300 degrees C or less.

  The reaction atmosphere in the firing can be carried out in an air atmosphere or an inert gas atmosphere. In the production of the printed wiring board, the time required for the firing varies depending on the reaction conditions, but is usually within 24 hours, particularly preferably in the range of 1 to 8 hours.

  Since the photosensitive resin composition according to the present invention is sufficiently suppressed in warp as a photosensitive film, has good developability, and exhibits chemical resistance when used as a cured product, various electronic devices in the electronics field Protective layer formation for printed wiring boards and circuit boards used for control panels, insulation layer formation for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat dissipation It is used for film formation on electronic components for use in protection, insulation and adhesion of plates, lead pins, semiconductors, etc.

Next, examples performed for clarifying the effects of the present invention will be described.
<Reagent>
In Examples and Comparative Examples, silicon diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), MBAA (manufactured by Wakayama Seika Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.), APB (Mitsui) Chemical B), Compound B-1, Compound B-2, TBP (Daihachi Chemical), TOP (Daihachi Chemical), TBXP (Daihachi Chemical), TIBP (Ajinomoto Fine Techno) , Resorcinol bis (diphenyl phosphate) (manufactured by Ajinomoto Fine Techno Co., Ltd., hereinafter abbreviated as RDP), acetyl tributyl citrate (manufactured by Pfizer Chemical Co., Ltd., hereinafter abbreviated as ATC), toluene (Wako Pure Chemical Industries, Ltd.) Industrial company, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries, special grade), pyridine (Wako Pure Chemical Industries, for organic synthesis), γ-valerolactone (Wako Pure Chemical Industries, 1 Grade) was used in the reaction without any special purification.

<Number average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the number average molecular weight, was measured under the following conditions. N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used as a solvent, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement). 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)

  The calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Film thickness measurement>
The film thickness of the cured body was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo).

<Dry film manufacturing method>
The photosensitive resin composition was coated by a doctor blade method using FILMCATOR (manufactured by TESTER SANGYO, PI1210). That is, the photosensitive resin composition was dropped onto an easy-peeling PET film (Mitsubishi Chemical Polyester Film Co., Ltd., DIAFOIL, T100H25) and coated with a clearance of 200 μm. The coated film was dried at 95 ° C. for 30 minutes using a drier (manufactured by ESPEC, SPHH-10 l) to obtain a photosensitive dry film.

<Lamination conditions>
Lamination in the present invention was performed using a vacuum press (manufactured by Meiki Seisakusho). The press was performed at a press temperature of 110 ° C., a press pressure of 1.23 MPa, and a press time of 5 minutes.

<Flame retardance test>
The flame retardancy test was performed according to the following procedure. The photosensitive resin composition is coated on one side of a Kapton (registered trademark) film by the above-mentioned coating method, dried at 95 ° C. for 30 minutes, and then coated on the opposite side with the photosensitive resin composition. After coating the photosensitive resin composition on both sides of the Kapton (registered trademark) film by drying at 95 ° C. for 30 minutes, using a baking furnace (manufactured by Koyo Lindberg) at 120 ° C. The photosensitive resin composition was cured by baking for 60 minutes at 200 ° C. for 60 minutes to obtain a cured body. This cured product was cut into 20 cm × 5 cm, and flame retardancy was evaluated by UL94 VTM test. Samples whose afterflame time of each sample was 10 seconds or less and did not burn to the 12.5 cm mark were set to VTM-0, and each sample was burnt to the mark of 10 seconds or 12.5 cm. The obtained sample was regarded as flame retardant x.

<Developability evaluation>
The evaluation of developability was carried out using a photosensitive dry film (photosensitive layer thickness of about 20 μm) on a copper-clad laminate and laminating under the above-mentioned lamination conditions, and then using a positive mask. Exposure was performed at 1.0 J / cm ² , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water. After drying, the pattern was evaluated with an optical microscope. A circular pattern with a 100 μm diameter (interval of 100 μm pitch) was used for the mask. By development, when the copper surface appears in the exposed part and the film thickness of the photosensitive layer in the unexposed part is 18 μm or more, ◎, and in the case of 15 μm or more and less than 18 μm, ◯, other resolution is inferior The case where the film thickness was less than 15 μm was evaluated as x.

<Evaluation of warpage>
In the evaluation of the warpage, when an A4 size photosensitive dry film was produced, the case where there was no part that lifted more than 5 mm in the edge part was marked with ◯, and the case where a part exceeding it was marked with x.

<Vacuum embedding evaluation>
After laminating using a photosensitive dry film on a copper circuit (copper line width of 50 μm, line spacing of 50 μm, copper wiring thickness of 12 μm) under the above-mentioned lamination conditions, the resulting laminate is cut. The cross section was observed with an electron microscope. The case where there was no insufficient embedding and the surface of the cover layer had good flatness was rated as “◯”. The case where embedding was insufficient and voids were observed was marked as x.

[Example 1]
Under a nitrogen atmosphere, MBAA (30.0 mmol), silicone diamine (KF-8010, 30.0 mmol), APB (15.0 mmol), γ-butyrolactone (100 mL) were placed in a separable flask, followed by ODPA (60 mL). 0.0 mmol) was added and stirred at room temperature for 2 hours. Subsequently, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dein-Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 120 ° C., APB (15.0 mmol) was added, and after stirring for 10 minutes, ODPA (30.0 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. Subsequently, toluene (10 mL) was added, and the mixture was heated and stirred at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that it might become polymer solid content concentration 30 weight%, and the γ-butyrolactone solution of polyimide (1) was obtained by cooling to room temperature. Table 1 below shows the number average molecular weight and the weight (content) (%) of the site derived from the siloxane structure. Moreover, it shows in following Table 2 about the compounding quantity of a polyimide, a photosensitive agent, and phosphate ester. Moreover, the compounding quantities of the following Examples and Comparative Examples are also shown in Table 2 below.

  Compound B-2 (20% by weight), TBP (15% by weight) and TBXP (15% by weight) were mixed with 100% by weight of polyimide (1) to prepare a positive photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-mentioned coating method, and dried at 95 ° C. for 30 minutes to obtain a photosensitive dry film. The warpage was a dry film, and was ◯.

  The photosensitive dry film was laminated on a copper circuit (copper line width of 50 μm, line interval was 50 μm, copper wiring thickness was 12 μm) under the above-mentioned lamination conditions. The obtained laminate was cut and the cross section was observed with an electron microscope. As a result, it was embedded without voids and the surface of the cover layer was flat.

  The positive photosensitive resin composition is coated on Kapton (registered trademark) by the above-described coating method, dried at 95 ° C. for 30 minutes, and then coated on the opposite side, Kapton (registered trademark) coated with the positive photosensitive resin composition obtained by drying for 30 minutes at 120 ° C. in an air atmosphere at 120 ° C. for 60 minutes and then at 200 ° C. for 60 minutes. By doing, the hardening body was obtained. The cured product was evaluated for flame retardancy by UL94 VTM test. The results are shown in Table 3 below.

The photosensitive dry film was laminated on a copper clad laminate under the above-mentioned lamination conditions. The resulting laminate is exposed using a positive mask at an irradiation dose of 1.0 J / cm ² , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water. Were observed with an optical microscope. In each dry film, a copper surface appeared in the exposed area, and the film thickness of the cover layer in the unexposed area was 15 μm or more (20 μm).

[Example 2]
Compound B-2 (20 parts by weight), TOP (15 parts by weight) and TBXP (15 parts by weight) are mixed with 100 parts by weight of the polyimide (1) produced in Example 1, and a photosensitive resin composition is prepared. It was adjusted. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Example 3]
Compound B-2 (20 parts by weight), TIBP (15 parts by weight) and TBXP (15 parts by weight) are mixed with 100 parts by weight of the polyimide (1) produced in Example 1, and a photosensitive resin composition is prepared. It was adjusted. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Example 4]
Under a nitrogen atmosphere, put MBAA (30.0 mmol), silicone diamine (KF-8010, 45.0 mmol), and γ-butyrolactone (100 mL) in a separable flask, and then add ODPA (60.0 mmol) at room temperature. For 2 hours. Subsequently, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dein-Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 120 ° C., APB (15.0 mmol) was added, and after stirring for 10 minutes, ODPA (30.0 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. Subsequently, toluene (10 mL) was added, and the mixture was heated and stirred at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that it might become polymer solid content concentration 30 weight%, and the γ-butyrolactone solution of polyimide (2) was obtained by cooling to room temperature. Table 1 below shows the number average molecular weight and the weight (content) (%) of the site derived from the siloxane structure.

  Compound B-1 (20 parts by weight) and TBXP (15 parts by weight) were mixed with 100 parts by weight of polyimide (2) to prepare a photosensitive resin composition. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 1]
Compound B-2 (20 parts by weight) was mixed with 100 parts by weight of the polyimide (1) produced in Example 1 to prepare a photosensitive resin composition. In the same manner as in Example 1, the warpage, flame retardancy, embedding property, and alkali developability of the film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 2]
To 100 parts by weight of the polyimide (1) produced in Example 1, Compound B-2 (20 parts by weight) and RDP (30 parts by weight), which is a phosphoric ester having an aromatic group, were mixed to obtain a photosensitive resin. The composition was adjusted. In the same manner as in Example 1, the warpage, flame retardancy, embedding property, and alkali developability of the film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 3]
Compound B-2 (20 parts by weight) and ATC (30 parts by weight), which is a general plasticizer, are mixed with 100 parts by weight of the polyimide (1) produced in Example 3, and a photosensitive resin composition is prepared. It was adjusted. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 4]
Compound B-1 (20 parts by weight) was mixed with 100 parts by weight of the polyimide (2) produced in Example 1 to prepare a photosensitive resin composition. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 5]
Compound B-1 (20 parts by weight) and RDP (30 parts by weight), which is a phosphate ester having an aromatic group, are mixed with 100 parts by weight of the polyimide (2) produced in Example 1, and a photosensitive resin is mixed. The composition was adjusted. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

[Comparative Example 6]
Compound B-1 (20% by weight) and ATC (30 parts by weight), which is a general plasticizer, are mixed with 100 parts by weight of the polyimide (2) produced in Example 3 to obtain a photosensitive resin composition. Adjusted. In the same manner as in Example 1, the warp, flame retardancy, embedding property, and alkali developability of the photosensitive film prepared from the photosensitive resin composition were evaluated. The results are shown in Table 3 below.

As can be seen from Table 3, the photosensitive films (Examples 1 to 4) composed of the photosensitive resin composition to which the specific phosphate compound was added were composed of the photosensitive resin composition not added. Compared to photosensitive films (Comparative Example 2 and Comparative Example 5) comprising a photosensitive film (Comparative Example 1 and Comparative Example 4) and a photosensitive resin composition to which an aromatic phosphate compound is added, flame retardancy Warpage and embeddability are improved while maintaining the properties. Moreover, in the photosensitive film (Comparative Example 3 and Comparative Example 6) comprised with the photosensitive resin composition which added the general plasticizer, although a curvature and embedding property are improved, a flame retardance falls. From the above, the photosensitive film composed of a photosensitive resin composition to which a specific phosphoric acid compound has been added has improved warpage and embedding properties when formed into a dry film while maintaining flame retardancy. Moreover, the developability was also good.

  The photosensitive resin composition of the present invention is sufficiently suppressed as a photosensitive film, has good developability, and has flame retardancy after curing, so that it can be used as an operation panel for various electronic devices in the electronics field. Protective layer formation for flexible wiring boards and circuit boards used, insulating layer formation for laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripheral members, semiconductor mounting substrates, heat sinks, lead pins It is used for film formation on electronic parts for use in protection, insulation and adhesion of the semiconductor itself.

Claims (14)

(A) An alkali-soluble resin, (B) a photosensitizer, and (C) a phosphoric acid ester compound represented by the following general formula (1), and two types of the (C) phosphoric acid ester compound The photosensitive resin composition characterized by including above.

(However, R ₁ is an aliphatic organic group having 1 to 30 carbon atoms and may be the same or different.) (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a phosphate ester compound represented by the following general formula (1), wherein R ₁ in the general formula (1) is A photosensitive resin composition comprising a phosphate ester which is a butoxyethyl group , wherein the (A) alkali-soluble resin is an alkali-soluble polyimide or polyamic acid .
[General formula (1)]

(However, R ₁ is an aliphatic organic group having 1 to 30 carbon atoms and may be the same or different.) (A) an alkali-soluble resin, (B) a photosensitizer, and (C) a phosphate ester compound represented by the following general formula (1), wherein R ₁ in the general formula (1) is A photosensitive resin composition comprising a phosphoric ester which is a butoxyethyl group, wherein the photosensitive agent (B) is a compound having a quinonediazide structure.
[General formula (1)]

(However, R ₁ is an aliphatic organic group having 1 to 30 carbon atoms and may be the same or different.) 3. The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) is a compound having a quinonediazide structure. R ₁ in the general formula (1) is any one selected from the group consisting of a methyl group, an ethyl group, a butyl group, an isobutyl group, a 2-ethylhexyl group, and a butoxyethyl group. Item 2. A photosensitive resin composition according to Item 1. 6. The phosphoric acid ester compound (C) is contained in 50 parts by weight or less with respect to 100 parts by weight of the (A) alkali-soluble resin, according to any one of claims 1 to 5 . Photosensitive resin composition. (A) the alkali-soluble resin, a photosensitive resin composition according to claim 1, characterized in that the alkaline soluble polyimide to claim 6. (A) the alkali-soluble resin, a photosensitive resin composition according to claim 1, characterized in that the polyamic acid to claim 6. The alkali solubility polyimide, photosensitive resin composition according to claim 7 Symbol mounting features and Turkey to siloxane structures 10 wt% or more. 9. The photosensitive resin composition according to claim 8, wherein the polyamic acid contains a siloxane structure in an amount of 10% by weight to 90% by weight. Photosensitive film, characterized in that it is constituted by a photosensitive resin composition as claimed in any one of claims 10. A laminated film comprising: a carrier film; and the photosensitive film according to claim 11 provided on the carrier film. The laminated film according to claim 12 , further comprising a cover film formed on the photosensitive film. A substrate having wiring, and a cover lay formed on the substrate so as to cover the wiring and configured by the photosensitive film or laminated film according to any one of claims 11 to 13. A printed wiring board characterized by: