JP5179843B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents

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. Therefore, from the viewpoint of an industrial process, it is desired to form a photosensitive resin composition into a dry film. It is rare.

  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 1). Since the photosensitive resin composition has a high Tg of polyimide, it is difficult to press-bond to a substrate or the like.

  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 2). 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 for imparting flame retardancy to a resin composition, a resin composition in which a phosphazene compound is blended with a polyimide resin is disclosed (Patent Document 3). Since the resin composition does not contain a photosensitizer, development cannot be performed. In addition, since the Tg of the resin is high, warping occurs when forming a dry film, and it is difficult to use as a film.

Moreover, the photosensitive resin composition containing the phosphazene compound which has a carbon-carbon double bond is disclosed (patent document 4). Since the photosensitive resin composition is a negative type, there is a problem that the exposed portion is swollen by the developer and it is difficult to perform high resolution fine processing.
Japanese Patent Laid-Open No. 2004-238591 International Publication No. 2003/06010 Pamphlet JP-A-2005-47995 JP 2003-302751 A

  As described above, it has been difficult to satisfy all of photosensitivity, flame retardancy, pressure bonding to a substrate, etc., and warpage during dry film formation.

  The present invention has been made in view of the above points, and is a positive type that is easy to press-bond to a substrate and the like, exhibits good developability, has flame retardancy, and has reduced warpage during dry film formation. It aims at providing the photosensitive resin composition and the photosensitive film which consists of this photosensitive resin composition.

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) a phosphazene represented by the following general formula (1) or general formula (2). at least one compound containing the alkali-soluble resin, wherein the Oh Rukoto in alkali solubility polyimide.
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are organic groups having 3 to 20 carbon atoms, and may be the same or different. M is an integer of 3 to 25, n is an integer of 3 to 10,000, and X and Y are organic groups having 3 to 30 carbon atoms.)

［一般式（２）］

The photosensitive resin composition of the present invention includes (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) a phosphazene represented by the following general formula (1) or general formula (2). at least one compound containing the alkali solubility resin, characterized in that it is a polyamic acid.
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are organic groups having 3 to 20 carbon atoms, and may be the same or different. M is an integer of 3 to 25, n is an integer of 3 to 10,000, and X and Y are organic groups having 3 to 30 carbon atoms.)
[General formula (1)]

[General formula (2)]

  In the photosensitive resin composition of the present invention, the alkali-soluble resin is preferably an alkali-soluble polyimide containing 10% by weight or more of a siloxane structure.

In the photosensitive resin composition of the present invention, it is preferable that R ₁ , R ₂ , R ₃ , and R ₄ in the phosphazene compound have an aromatic ring.

  In the photosensitive resin composition of this invention, it is preferable to contain (D) plasticizer.

  In the photosensitive resin composition of the present invention, the plasticizer is a phosphate ester, an ether compound, a methacryl group-containing compound, an acrylic group-containing compound, a phthalate ester, an aliphatic dibasic acid ester, or an aromatic condensed phosphate ester. It is preferable to contain any one selected from the group consisting of ethylene glycol modified with isocyanuric acid, and ε-caprolactone-modified tris (acryloxyethyl) isocyanurate.

  The photosensitive film of this invention is comprised with 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 made of the photosensitive film or the laminated film. And

According to the photosensitive resin composition of the present invention, it is represented by (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) the above general formula (1) or general formula (2). that at least one phosphazene compound containing the alkali soluble resin is an alkali soluble polyimide or polyamic acid der Runode, warpage during dry filmed is reduced, a flame retardant, a substrate such as The film can be obtained with good developability and good developability.
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are organic groups having 3 to 20 carbon atoms, and may be the same or different. M is an integer of 3 to 25, n is an integer of 3 to 10,000, and X and Y are organic groups having 3 to 30 carbon atoms.)

Hereinafter, embodiments of the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) a phosphazene represented by the above general formula (1) or general formula (2). And at least one of the compounds.

  (A) The alkali-soluble resin is not limited as long as it is a resin that can be dissolved in an alkaline solution. Examples of such a resin include a resin having a functional group that dissolves in a known alkali such as a carboxyl group, an aromatic hydroxyl group, or 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. Alkali-soluble polyimide is particularly preferable.

Here, the alkali-soluble polyimide and the polyamic acid will be described.
In the present invention, the acid dianhydride used for the alkali-soluble polyimide and polyamic acid specifically includes 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 Anhydride, 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) (hereinafter abbreviated as TMEG), p-phenylenebis (trimellitic acid monoester acid anhydride), and the like.

  Among these, ODPA, TMEG, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran) from the viewpoint of the solvent solubility of polyimide and the pressure-bonding property to a substrate and the like. -3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydrides are 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.

  The diamine used in the present invention 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. The aromatic hydroxyl group in the present invention 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 10% by weight or more and 90% by weight or less, more preferably 20% by weight or more and 80% by weight or less, from the viewpoint of warpage and flame retardancy when forming a dry film.

  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 diamine used for producing a polyimide (precursor), or the terminal may be sealed with another acid anhydride, an amine compound or the like.

  In the present invention, the number average molecular weight of the alkali-soluble resin 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 it 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 method for producing an alkali-soluble resin in the present invention will be described by taking a method of synthesizing polyamic acid and then synthesizing an alkali-soluble polyimide as an example.
The polyimide according to the present invention can be obtained by reacting acid dianhydride and diamine to synthesize polyamic acid and then heating (heating imidization). It can also be obtained by reacting an acid dianhydride with 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 then a method for imidizing after adding a catalyst will be described as an example, and the manufacturing conditions for the polyimide according to the present invention 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 and influence on the next reaction.

  The reaction temperature during the production of the polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower. If it is 0 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no influence of a side reaction. Preferably they are 15 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less. 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 for obtaining the alkali-soluble polyimide according to the present invention by adding a catalyst to the polyamic acid to (chemically) imidize will be described.
The imidization catalyst for producing the alkali-soluble polyimide according to the present invention is not particularly limited, but an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ -Lactone compounds such as coumarin and γ-phthalic 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% by weight or less, and more preferably 30% by weight or less, assuming that polyamic acid is 100% by weight.

  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; ketones having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone. Compound: saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compounds; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; carbon numbers such as chloroform, methylene chloride, and 1,2-dichloroethane 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 and influence on the next reaction.

  In the production of the polyimide according to the present invention, the reaction temperature is preferably 15 ° C. or more and 250 ° C. or less. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less. 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 polyimide according to 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.

  Using the polyimide according to the present invention, a resin composition can be obtained with a solvent in which the polyimide can be uniformly dissolved and / or dispersed. The solvent which comprises the resin composition containing the polyimide which concerns on this invention will not be limited if the polyimide which concerns on this invention can be melt | dissolved and / or disperse | distributed uniformly. Examples of such solvents include ether compounds 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; 2 or more carbon atoms such as acetone and methyl ethyl ketone. 6 or less ketone compounds; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; carbon numbers such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compound having 6 to 10 carbon atoms; ester compound 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 and 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 the solubility of the polyimide, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  In the present invention, the concentration of the alkali-soluble resin of the resin composition containing the alkali-soluble resin and the solvent is not particularly limited as long as it is a concentration at which a resin molded body is produced. The polyimide concentration is preferably 1% by weight or more from the viewpoint of the film thickness of the resin molded body to be produced, and the polyimide concentration is preferably 90% by weight or less from the uniformity of the film thickness of the resin molded body. 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.

The photosensitizer having a quinonediazide structure in the present invention is not limited as long as it has 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-sulf 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, compound B-1 or B-2 represented by formula (3) is particularly preferred.

In General formula (3), Q is a structure or a hydrogen atom represented by General formula (4) or (5). As a photosensitive agent in the photosensitive resin composition according to the present invention, compound B-1 has a structure in which an average of 2.34 of the three Qs in the general formula (3) is represented by the general formula (4). It points to what is. Compound B-2 refers to one having an average of 2.3 of the three Qs in the general formula (3) having a structure represented by the general formula (5).

  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 in the present invention is 100% by weight. Preferably, it is 5 to 30% by weight. 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.

R ₁ , R ₂ , R ₃ and R ₄ in the phosphazene compound represented by the general formula (1) and the general formula (2) in the present invention are not limited as long as they are organic groups having 3 to 20 carbon atoms. A carbon number of 3 or more is preferred because it tends to exhibit flame retardancy. A carbon number of 30 or less is preferred because it tends to be compatible with an alkali-soluble resin. Among these, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy. Examples of such functional groups include phenyl groups such as a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group. And functional groups derived from nitrogen-containing heterocyclic compounds such as pyridine, imidazole, triazole, and tetrazole, and the like, and functional groups having a naphthyl group such as 1-naphthyl group and 2-naphthyl group. These compounds may be used alone or in combination of two or more as required. Among these, a compound having a phenyl group, a 4-hydroxyphenyl group, or a 4-cyanophenyl group is preferable because of its availability.

  M in the phosphazene compound represented by the general formula (1) in the present invention is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, m is preferably 3 or more and 10 or less in view of availability.

  N in the phosphazene compound represented by the general formula (2) in the present invention is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

X and Y in the phosphazene compound represented by the general formula (2) in the present invention are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, X is _{-N = P (OC 6 H 5} ) 3, -N = P (OC 6 H 5) 2, (OC 6 H 4 OH) 3, -N = P (OC 6 H 5) ( _{OC 6 H 4 OH) 2,} -N = P (OC 6 H 4 OH) 3, -N = P (O) OC 6 H 5, -N = P (O) (OC 6 H 4 OH) are preferred. Y is _{-P (OC 6 H 5) 4} , -P (OC 6 H 5) 3 (OC 6 H 4 OH), - P (OC 6 H 5) 2 (OC 6 H 4 OH) 2, -P ( _{OC 6 H 5) (OC 6} H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 OH) _2, such as _{-P (O) (OC 6 H} 5) (OC 6 H 4 OH) are preferred.

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

  The photosensitive resin composition of the present invention preferably further contains (D) a plasticizer in (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a phosphazene compound. (D) By containing a plasticizer, since Tg of a composition falls, since it exists in the tendency for the curvature at the time of dry film formation to reduce, it is preferable.

  The plasticizer in the photosensitive resin composition according to the present invention is not particularly limited as long as it imparts plasticity to the resin composition and can lower the Tg of the composition. Examples of such plasticizers include tricresyl phosphate, trixylenyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate (hereinafter abbreviated as TBXP). Phosphate esters; Ether compounds such as polyethylene glycol, polypropylene glycol and crown ether; Methacryl group-containing compounds such as tetraethylene glycol dimethacrylate and polyethylene glycol dimethacrylate; Acrylic group-containing compounds such as tetraethylene glycol diacrylate and polyethylene glycol diacrylate Phthalates such as dimethyl phthalate and diethyl phthalate; tris (2-ethylhexyl) trimellitate Trimellitic acid esters and the like; dimethyl adipate, aliphatic dibasic acid esters such as dibutyl adipate; isocyanuric acid ethylene glycol-modified triacrylate, etc. ε- caprolactone-modified tris (acryloyloxyethyl) isocyanurate. Of these, phosphoric acid esters, methacrylic group-containing compounds, isocyanuric acid ethylene glycol-modified triacrylate, and ε-caprolactone-modified tris (acryloxyethyl) isocyanurate are preferred from the viewpoint of warping after forming into a dry film.

  In the photosensitive resin composition according to the present invention, the amount of the plasticizer added is preferably 30% by weight or less when the amount of the alkali-soluble resin is 100% by weight in view of sufficient plasticity. Moreover, 20 weight% or less is more preferable from a flame-retardant viewpoint of a hardening body.

  In the photosensitive resin composition according to the present invention, (A) an alkali-soluble resin, (B) a photosensitive agent, (C) a phosphazene compound, and / or (D) a plasticizer are uniformly dissolved and / or as required. Alternatively, a solvent that can be dispersed can be included. 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 substrate is coated with the photosensitive resin composition according to the present invention. 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.

  Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After coating, if necessary, heat treatment called pre-baking may be performed with 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.

  Moreover, it is good also as a laminated | multilayer film by providing at least one layer of arbitrary antifouling and protective cover films on a photosensitive film. In the laminated film according to the present invention, the cover film is not limited as long as it is a film that protects a photosensitive film such as low-density polyethylene.

  Next, a printed wiring board can be obtained by pressure-bonding the photosensitive film of the present invention to a substrate having wiring so as to cover the wiring, performing alkali development, and firing.

  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 forming the printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. Examples of such a forming method include a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, etc. in a state where the wiring side of the substrate having the wiring is in contact with the photosensitive film of the present invention. Can be mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is 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 dissolving the light irradiation site by alkali development after the light irradiation. 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 development method include spray development, immersion development, and paddle development.

  Subsequently, the printed wiring board is formed by baking the printed wiring board to which the photosensitive film of the present invention is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. 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 operation panels, etc., insulating layer formation for laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripheral members, semiconductor mounting substrates, heat dissipation It is used for film formation on electronic parts for use in protection, insulation and adhesion of plates, lead pins, semiconductors, etc.

Examples for clarifying the effects of the present invention will be described below.
<Reagent>
In Examples and Comparative Examples, silicone 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 Chemicals) are used reagents. ), TMEG (manufactured by Shin Nippon Chemical Co., Ltd.), compound B-1, compound B-2, TBXP (manufactured by Daihachi Chemical Co., Ltd.), ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, (Aronix M-325) Manufactured by Toagosei Co., Ltd., hereinafter abbreviated as M-325), phosphazene compound (SPB-100, SPH-100, manufactured by Otsuka Chemical Co., Ltd.), toluene (manufactured by Wako Pure Chemical Industries, Ltd., 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, first grade), without any special purification It was used in the reaction.

<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. Using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) as a solvent, 24.8 mmol / L of 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)
Moreover, 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 coating method of the photosensitive resin composition in the present invention was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The said photosensitive resin composition was dripped at the easily peelable PET film (Mitsubishi Chemical Polyester Film company make, DIAFOIL, T100H25), and it coat | coated with clearance 200 micrometers. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) 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 temperature was 110 ° C., the press pressure was 1.23 MPa, and the press time was 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, and 30% at 95 ° C. After coating the photosensitive resin composition on both sides of the Kapton (registered trademark) film by drying for 120 minutes, using a baking oven (manufactured by Koyo Lindberg) for 60 minutes at 120 ° C., then for 60 minutes at 180 ° C. A cured product was obtained by firing. 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>
Evaluation of developability was performed by laminating a copper-clad laminate with a photosensitive dry film (photosensitive layer thickness of about 15 μm) under the above laminating conditions, and using a positive mask to apply an irradiation dose of 1.0 J / Exposure was performed at cm ² , followed by alkaline development with a 1% or 3% aqueous sodium hydroxide solution and rinsing with water, and after drying, the pattern was evaluated with an optical microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. A case where a copper surface appears in the exposed area due to development, and the film thickness of the photosensitive layer in the unexposed area is 13 μm or more, ◎ is a case where it is 10 μm or more and less than 13 μm, and the other resolution is inferior or a film The case where the thickness was less than 10 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.

<Evaluation of press bonding to the substrate>
After laminating using a photosensitive dry film on a copper circuit (copper line width of 50 μm, line spacing is 50 μm, copper wiring thickness of 12 μm) under the above laminating conditions, the resulting laminate is cut to obtain a cross section. Observed with an electron microscope. The case where there was no insufficient embedding and the surface of the coverlay 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, put MBAA (30.0 mmol), silicone diamine (KF-8010, 45.0 mmol) and γ-butyrolactone (120 mL) in a separable flask, and then add ODPA (60.0 mmol) at room temperature. Stir for 2 hours. Subsequently, toluene (60 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dean 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, TMEG (30.0 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. Subsequently, toluene (15 mL) was added, and the mixture was stirred with heating at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that polymer solid content concentration might be 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 (%) of the site derived from the siloxane structure.

  Compound B-2 (20% by weight), SPB-100 (20% by weight) and M-325 (30% by weight) were mixed with 100% by weight of polyimide (1) to prepare a photosensitive resin composition. . The composition is shown in Table 2 below. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the aforementioned 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 spacing was 50 μm, copper wiring thickness was 12 μm) under the above-mentioned laminating conditions. When the obtained laminate was cut and the cross section was observed with an electron microscope, it was embedded without a gap and the surface of the coverlay 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, then coated on the opposite surface, and dried at 95 ° C. for 30 minutes. The cured product is obtained by baking Kapton (registered trademark) coated with the positive photosensitive resin composition obtained by the above in a baking furnace in an air atmosphere at 120 ° C. for 60 minutes and then at 200 ° C. for 60 minutes. It was. The cured product was evaluated for flame retardancy by UL94 VTM test. The results are shown in Table 3 below.

The above photosensitive film was laminated on a copper clad laminate under the above-mentioned laminating 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, and a pattern is formed after drying. Observed with an optical microscope. In each dry film, a copper surface appeared in the exposed area, and the film thickness of the coverlay layer in the unexposed area was 13 μm or more.

(Example 2)
Under a nitrogen atmosphere, silicone diamine (KF-8010, 45.0 mmol) and γ-butyrolactone (120 mL) were added to a separable flask, followed by ODPA (60.0 mmol), and the mixture was stirred at room temperature for 2 hours. Subsequently, toluene (60 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dean 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 (9.0 mmol) and MBAA (30 mmol) were added, and after stirring for 10 minutes, TMEG (25.8 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. Subsequently, toluene (15 mL) was added, and the mixture was stirred with heating at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that polymer solid content concentration might be 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 (%) of the site derived from the siloxane structure.

  Compound B-1 (20% by weight) and SPB-100 (20% by weight) were mixed with 100% by weight of polyimide (2) to prepare a photosensitive resin composition. The composition is shown in Table 2 below. The photosensitive resin composition was warped in the same manner as in Example 1 to evaluate flame retardancy and press-bonding property to a substrate. The alkali developability was evaluated using a 1% aqueous sodium hydroxide solution. The results are shown in Table 3 below.

(Example 3)
Compound B-1 (20% by weight), SPB-100 (20% by weight), TBXP (10% by weight) are mixed with 100% by weight of the polyimide (2) produced in Example 2, and a photosensitive resin composition is mixed. I adjusted things. The composition is shown in Table 2 below. The photosensitive resin composition was warped in the same manner as in Example 2 and evaluated for flame retardancy, press-bonding property to a substrate, and alkali developability. The results are shown in Table 3 below.

Example 4
Compound B-1 (20% by weight), SPH-100 (20% by weight), TBXP (10% by weight) are mixed with 100% by weight of the polyimide (2) produced in Example 2, and a photosensitive resin composition is mixed. I adjusted things. The composition is shown in Table 2 below. The photosensitive resin composition was warped in the same manner as in Example 2 and evaluated for flame retardancy, press-bonding property to a substrate, and alkali developability. The results are shown in Table 3 below.

(Comparative Example 1)
Compound B-1 (20% by weight) was mixed with 100% by weight of the polyimide (2) produced in Example 2 to prepare a photosensitive resin composition. The composition is shown in Table 2 below. The photosensitive resin composition was warped in the same manner as in Example 2 and evaluated for flame retardancy, press-bonding property to a substrate, and alkali developability. The results are shown in Table 3 below.

  From the results in Table 3, it can be seen that in Examples 1 to 4 to which the phosphazene compound of the present invention was added, flame retardancy was improved as compared with Comparative Example 1 in which no phosphazene compound was added. It can also be seen that the developability is also improved. From the above, it can be seen that the flame resistance and developability of the photosensitive film comprising the photosensitive resin composition to which the phosphazene compound of the present invention is added are improved. Moreover, it turns out that it is favorable also about the crimping | bonding property to a board | substrate.

  The photosensitive resin composition according to the present invention is sufficiently suppressed as a photosensitive film, has good developability, and has flame retardancy after curing. Formation of protective layers on flexible wiring boards and circuit boards used, formation of insulating layers on laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting boards, heat sinks, lead pins, semiconductors It is used for film formation on electronic parts for use in protecting itself, insulation and adhesion.

Claims (10)

(A) an alkali-soluble resin, (B) a photosensitizer having a quinonediazide structure, and (C) at least one phosphazene compound represented by the following general formula (1) or general formula (2) : the alkali solubility resin, a photosensitive resin composition characterized Oh Rukoto in alkali solubility polyimide.
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are organic groups having 3 to 20 carbon atoms, and may be the same or different. M is an integer of 3 to 25, n is an integer of 3 to 10,000, and X and Y are organic groups having 3 to 30 carbon atoms.)

(A) an alkali-soluble resin, (B) a photosensitizer having a quinonediazide structure, and (C) at least one phosphazene compound represented by the following general formula (1) or general formula (2): the alkali solubility resin, to that sensation light-sensitive resin composition characterized in that it is a polyamic acid.
(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are organic groups having 3 to 20 carbon atoms, and may be the same or different. M is an integer of 3 to 25, n is an integer of 3 to 10,000, and X and Y are organic groups having 3 to 30 carbon atoms.)
[General formula (1)]

[General formula (2)]

The alkali solubility resin, a photosensitive resin composition according to claim 1 Symbol mounting, characterized in that the siloxane structure is an alkali-soluble polyimide containing more than 10 wt%. The photosensitive resin composition according to claim ₁ , wherein R ₁ , R ₂ , R ₃ and R ₄ in the phosphazene compound have an aromatic ring. (D) The photosensitive resin composition in any one of Claims 1-4 containing a plasticizer. The plasticizer is a phosphate ester, an ether compound, a methacryl group-containing compound, an acrylic group-containing compound, a phthalate ester, an aliphatic dibasic acid ester, an aromatic condensed phosphate ester, an isocyanuric acid ethylene glycol-modified triacrylate, and ε 6. The photosensitive resin composition according to claim 5 , comprising any one selected from the group consisting of caprolactone-modified tris (acryloxyethyl) isocyanurate. A photosensitive film comprising the photosensitive resin composition according to claim 1 . A laminated film comprising: a carrier film; and the photosensitive film according to claim 7 provided on the carrier film. The laminated film according to claim 8 , 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 made of the photosensitive film or laminated film according to any one of claims 7 to 9. A printed wiring board characterized by: