JP2010204464A - Photosensitive resin composition containing photosensitive agent having phosphazene structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition exhibiting good developability, having a small warpage after baked, and developing flame retardancy, and to provide a photosensitive film made of the photosensitive resin composition. <P>SOLUTION: The photosensitive resin composition contains: (A) an alkali-soluble polyimide and/or polyimide precursor; and (B) a quinone diazide compound prepared by substituting a functional group having a quinonediazide structure for a part of hydrogen atoms in hydroxyl groups of a phosphazene compound having aromatic hydroxyl groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention uses an alkali-soluble polyimide and / or a polyimide precursor and a photosensitive agent having a phosphazene structure, and a photosensitive resin composition suitable for a cover lay of a printed wiring board, and the photosensitive resin composition. The present invention relates to a photosensitive film.

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, conventional screen printing has problems such as a solvent removal process and double-sided processing, so that it is desired to form a photosensitive resin composition into a dry film from the viewpoint of an industrial process. ing.
In general, polyimide has a high elastic modulus because of its rigid main chain structure, and tends to warp when formed into a film. Therefore, an alkali-soluble polyimide into which a flexible structure such as siloxane is introduced is disclosed (Patent Document 1). Although the polyimide has a tendency to improve warpage, the flame retardancy tends to be remarkably lowered.
Moreover, the negative photosensitive resin composition containing a polyimide precursor and a flame retardant is disclosed (patent document 2). The photosensitive resin composition is negative and there is no disclosure regarding positive type. Moreover, in this photosensitive resin composition, since it was necessary to add a flame retardance other than a photosensitive agent, there existed a tendency for developability and a film characteristic to deteriorate.

  Patent Document 3 is disclosed as a photosensitive resin composition using a photosensitive agent having a phosphazene structure. The base polymer of the photosensitive resin composition is a novolak resin and tends to warp when formed into a film. Moreover, the photosensitive agent which has this phosphazene structure aims at light transmittance and heat resistance, and there is no disclosure regarding flame retardancy.

JP 2006-2163 A JP 2008-304569 A US Pat. No. 5,523,191

  The present invention has been made in view of the above points, and has little warping during film formation, has flame retardancy after firing, and has good developability, an alkali-soluble polyimide and / or a polyimide precursor, and a phosphazene structure. It aims at providing the photosensitive resin composition containing the photosensitive agent which has this, and the photosensitive film which consists of this photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive resin composition having an alkali-soluble polyimide and / or a polyimide precursor and a photosensitive agent having a phosphazene structure has good developability. And it discovered that there was little curvature after baking and it had a flame retardance, and came to complete this invention.

That is, the present invention
1. An alkali-soluble polyimide and / or a polyimide precursor, and (B) a quinonediazide compound in which a part of hydrogen atoms of a hydroxyl group of a phosphazene compound having an aromatic hydroxyl group is substituted with a functional group having a quinonediazide structure A photosensitive resin composition.
2. 2. The photosensitive resin composition according to 1 above, wherein the functional group having a quinonediazide structure in the (B) quinonediazide compound is a 1,2-naphthoquinone-2-diazide-5 (or 4) -sulfonyl group. object.
3. 3. The photosensitive resin composition as described in 1 or 2 above, wherein among the (B) quinonediazide compound, the phosphazene compound having an aromatic hydroxyl group has 18 to 100 carbon atoms.
4). The photosensitive resin composition as described in any one of 1 to 3 above, wherein the (B) quinonediazide compound is a quinonediazide compound represented by the following general formula (1).

(In the formula, R _{1 to} R ₁₀ represent a hydrogen atom, an organic group having 1 to 10 carbon atoms, and a hydroxyl group, and may be the same or different. However, among R ₁ to R ₁₀ , (At least one is a hydroxyl group in which a hydrogen atom is substituted with a functional group having a quinonediazide structure. N is an integer of 3 to 10.)

5). The photosensitive resin composition as described in any one of 1 to 4, wherein the alkali-soluble polyimide and / or polyimide precursor has a siloxane structure of 5% by mass or more.
6). The polyimide precursor having the polyimide structure represented by the following general formula (2) and the polyamic acid structure represented by the following general formula (3) as structural units: The photosensitive resin composition in any one of -5.

(In the formula, R ₁₁ and R ₁₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₁₂ is a divalent organic group having 1 to 30 carbon atoms, R ₁₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₁₄ represents a divalent organic group having 1 to 80 carbon atoms, and m represents an integer of 1 to 30.)

7). The photosensitive resin composition as described in any one of 1 to 6 above, which contains a phosphorus compound other than the (B) quinonediazide compound.
8). 8. The photosensitive resin composition as described in 7 above, wherein the phosphorus compound other than the (B) quinonediazide compound has a phosphate structure.
9. The photosensitive resin composition as described in any one of 1 to 8 above, which contains a dissolution inhibitor for the solvent of the (A) alkali-soluble polyimide and / or polyimide precursor.
10. 10. The photosensitive resin composition according to any one of 9 above, wherein the dissolution inhibitor has an amide structure and / or a urea structure.
11. 11. A photosensitive film comprising the photosensitive resin composition according to any one of 1 to 10 above.
12 12. The photosensitive film as described in 11 above, further comprising a carrier film on the entire surface on one side.
13. 13. The photosensitive film as described in 12 above, further comprising a cover film.
14 11. A cover lay comprising the photosensitive resin composition according to any one of 1 to 10 developed and baked.
15. 15. A laminate comprising the coverlay of claim 14 and a copper clad laminate.

  According to the photosensitive resin composition of the present invention, a material having good developability, small warpage after firing, and a film having flame retardancy can be obtained.

The present invention will be specifically described below.
The alkali-soluble polyimide and / or polyimide precursor is not limited as long as it is a polyimide and / or polyimide precursor having an alkali-soluble functional group in the main chain and / or side chain.
The alkali-soluble functional group represents a functional group that dissolves in a known alkali such as a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group.
The alkali-soluble polyimide and / or polyimide precursor will be described.

  A known acid dianhydride can be used for the alkali-soluble polyimide and / or polyimide precursor. Specifically, 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] octo- 7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 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 dianhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, ethylene glycol bis (trimellitic acid monoester anhydride) (hereinafter abbreviated as TMEG), p-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride), and the like.

  Among these, from the viewpoint of controlling the glass transition temperature (Tg) of the obtained polyimide precursor, ODPA, TMEG, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxo) Tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride) are preferred.

  As the diamine used for the alkali-soluble polyimide and / or polyimide precursor, known diamines can be used. Specifically, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 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-amino) Enyl) sulfide, 4,4′-diaminodiphenylsulfone, 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, 4,4′-bis (4-aminophenoxy) biphenyl, 4, 4 '-Bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] s Hong, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethyl Cyclohexane, trimethylene-bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate (hereinafter abbreviated as PMAB), poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) ), N, N′-bis (4-aminophenyl) piperazine, 2- (4-aminophenyl) -6-aminobenzoxazole, 4,4′-diamino-3,3′-diethyl-5,5′- Dimethyldiphenylmethane, 3,4'-diaminodiphenyl ether, 1,3-bis (4-a Nophenoxy) adamantane, 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indene-5-amine, 3,3′-diaminodiphenylsulfone, 2,2-bis {4- (4- Aminophenoxy) phenyl} propane, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, bis {4- (4-aminophenoxy) phenyl} sulfone, bis {4- (3-aminophenoxy) ) Phenyl} sulfone, 4,4′-diamino-2,2′-bis (trifluoromethyl) diphenyl ether, bis {4- (4-aminophenoxy) phenyl} ketone, 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene, 1,4-bis (4-aminophenoxy) -2,5-t-butylbenzene, 1,4- {4-amino-2- (trifluoromethyl) phenoxy} benzene, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 4,4′- Diamino-2- (trifluoromethyl) diphenyl ether, 2,3′-diaminodiphenyl ether, bis (4-aminophenoxy) methane, 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} Hexafluoropropane, 2,5-bis (4-aminophenoxy) -biphenyl, 1,3-bis (4-aminophenoxy) -5- (2-phenylethynyl) benzene, 1,3-bis (3-aminophenoxy) ) -5- (2-phenylethynyl) benzene, 2,4-diamino-4'-phenylethynyldiphenyl ether, 4 , 4′-diamino-2,2′-dimethoxybiphenyl, 4,4′-diamino-2,2 ′, 6,6′-tetrachlorobiphenyl, 4,4′-diamino-2,2′-dichlorobiphenyl, 4,4′-diamino-5,5′-dimethoxy-2,2′-dichlorobiphenyl, 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl, 4,4′-diamino- 3,3′-dichlorodiphenylmethane, N, N′-bis (4-aminophenyl) terephthalamide, 3,5-diaminobenzotrifluoride, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3, 5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 4,6-dihydroxy-1,3-phenylenediamine, 1,3-bis ( - amino-3-hydroxyphenoxy) benzene, 4-aminophenyl-3'-aminobenzoate and 3-amino-6-methyl-4'-amino benzoate.

  Among these, from the viewpoint of Tg control and developability of the polyimide precursor, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB-N), 1,4-bis (3-aminophenoxy) ) Benzene, 1,5-bis (4-aminophenoxy) pentane, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl ether are preferred.

  The alkali-soluble polyimide and / or polyimide precursor preferably has a siloxane structure of 5% by mass to 95% by mass. From the viewpoint of warping after firing and flame retardancy, it is more preferably 10% by mass or more and 90% by mass or less, and particularly preferably 15% by mass or more and 85% by mass or less.

  From the viewpoint of developability, the polyimide precursor may be a polyimide precursor having, as structural units, a polyimide structure represented by the following general formula (2) and a polyamic acid structure represented by the following general formula (3). preferable.

(In the formula, R ₁₁ and R ₁₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₁₂ is a divalent organic group having 1 to 30 carbon atoms, R ₁₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₁₄ represents a divalent organic group having 1 to 80 carbon atoms, and m represents an integer of 1 to 30.)

The end of the main chain of the polyimide precursor is not particularly limited as long as it does not affect the performance. A terminal derived from an acid dianhydride or diamine used for producing a polyimide precursor may be used, or the terminal may be sealed with another acid anhydride, an amine compound, or the like.
The polyimide precursor preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight 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.

About the manufacturing method of a polyimide precursor, the polyimide precursor which has the polyamic acid structure represented by the polyimide structure represented by the said General formula (2) and the said General formula (3) is mentioned as an example, and is demonstrated. .
The polyimide precursor is prepared by reacting acid dianhydride and diamine in an unequal molar amount to synthesize a first stage polyamic acid (step 1), followed by an imidization step (step 2), followed by two steps. It can be synthesized by the step of synthesizing the eye polyamic acid (step 3). Hereinafter, each process will be described.

First, step 1; the step of synthesizing the first stage polyamic acid will be described.
The step of synthesizing the first stage 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 is 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% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass 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 dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether having 2 to 9 carbon atoms. Ether compounds; ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds 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, tetralin; methyl acetate, ethyl acetate, γ-butyrolactone Ester compounds having 3 to 9 carbon atoms such as methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, nitrogen-containing compounds having 2 to 10 carbon atoms such as N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

The reaction temperature during the production of the first stage polyamic acid is preferably 100 ° C. or higher and 250 ° C. or lower from the viewpoint of reactivity. If it is 100 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 120 degreeC or more and 220 degrees C or less, More preferably, they are 120 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, step 2; a method for imidizing polyamic acid will be described.
When manufacturing a polyimide site | part, it can obtain even by adding a well-known imidation catalyst or without a catalyst. The imidization catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid, And tertiary amines such as pyridine, quinoline, N-methylmorpholine and triethylamine. 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 and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, when the polyimide precursor is 100 parts by mass.
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 solvent include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; carbons such as acetone and methyl ethyl ketone. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; such as benzene, toluene, xylene, mesitylene, and tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms; 3 or more carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, methyl benzoate 9 or less ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as 2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

In the production of polyimide, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. 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.

Next, step 3; the step of synthesizing the second stage polyamic acid will be described. The method of synthesizing the second stage polyamic acid can be carried out in the same manner as the first stage polyamic acid.
The polymerization temperature in the second stage is preferably 0 ° C. or higher and 250 ° C. or lower, preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower from the viewpoint of the molecular weight of the resulting polyimide precursor.
Recovery of the polyimide precursor after completion of production can be performed by distilling off the solvent in the reaction solution under reduced pressure.

Examples of the method for purifying the polyimide precursor 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. Further, when a highly pure polyimide precursor is required, an extraction method by a carbon dioxide supercritical method is also possible.
By using a polyimide precursor, a resin composition comprising a solvent in which the polyimide precursor can be uniformly dissolved and / or dispersed can be obtained.

  The solvent which comprises the resin composition containing a polyimide precursor will not be limited if it can melt | dissolve and / or disperse | distribute a polyimide precursor uniformly. Examples of the solvent include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; carbons such as acetone and methyl ethyl ketone. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; such as benzene, toluene, xylene, mesitylene, and tetralin An aromatic hydrocarbon compound having 6 to 10 carbon atoms; 3 or more carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, methyl benzoate 9 or less ester compounds; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as 2-pyrrolidone; sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms. Can be mentioned. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of solubility of the polyimide precursor, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  The concentration of the alkali-soluble polyimide and / or the polyimide precursor in the resin composition comprising the alkali-soluble polyimide and / or the polyimide precursor and a solvent is not particularly limited as long as the resin molded body is produced. The concentration of the alkali-soluble polyimide and / or the polyimide precursor is 1% by mass or more from the viewpoint of the film thickness of the resin molding to be produced, and the concentration of the polyimide precursor is 90% by mass or less from the uniformity of the film thickness of the resin molding. preferable. From the viewpoint of the film thickness of the obtained resin molding, it is more preferably 2% by mass or more and 80% by mass or less.

The quinonediazide compound will be described. The quinonediazide compound is a quinonediazide compound in which a part of hydrogen atoms of a phosphazene compound having an aromatic hydroxyl group is substituted with a functional group having a quinonediazide structure. Among them, the functional group having a quinonediazide structure is not limited as long as it has a quinonediazide structure. Among these, examples of the quinonediazide structure include a 1,2-quinonediazide structure and a 1,4-quinonediazide structure. Among the quinonediazide structures, a 1,2-naphthoquinone-2-diazide-5 (or 4) -sulfonyl group is preferable from the viewpoint of inhibiting dissolution.
Furthermore, the quinonediazide compound is preferably a quinonediazide compound represented by the following general formula (1).

(Wherein R _{1 to} R ₁₀ represent a hydrogen atom, an organic group having 1 to 10 carbon atoms, or a hydroxyl group, and may be the same or different. However, at least one of R1 to R10 One is a hydroxyl group in which a hydrogen atom is substituted with a functional group having a quinonediazide structure, and n is an integer of 3 to 10.

The quinonediazide compound is reacted with a phosphazene compound having an aromatic hydroxyl group and an acid chloride such as 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride. Can be obtained.
The phosphazene compound is not limited as long as it is an phosphazene compound having an aromatic hydroxyl group, and among them, from the viewpoint of developability and flame retardancy, it is preferably 18 to 100 carbon atoms.
Among these, the phosphazene compound is more preferably a compound represented by the following general formula (4).

(In the formula, X is at least one selected from the following general formulas (5) to (8). N is an integer of 3 or more and 10 or less.)

(In the general formula (7), Y represents any one of a divalent organic group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, a sulfonyl group, and a carbonyl group. The general formulas (5) to (8 ), K represents an integer of 1 to 5.
A structure represented by the following general formula (9) is particularly preferable.

  The amount of the quinonediazide compound in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less from the viewpoint of photosensitive contrast when the amount of the alkali-soluble polyimide and / or the polyimide precursor is 100 parts by mass. More preferably, it is 5 parts by mass or more and 30 parts by mass or less. If it is 1 mass part or more, since there exists a tendency for dissolution suppression of an unexposed part to be enough, it is preferable. The amount of 50 parts by mass or less is preferable because the sensitivity tends to be sufficiently high.

  Moreover, it is preferable that the photosensitive resin composition contains phosphorus compounds other than (B) quinonediazide compound for the improvement of developability. (B) The phosphorus compound other than the quinonediazide compound is not limited as long as it is a compound containing a phosphorus atom in the structure. Examples of such compounds include phosphate ester compounds and phosphite ester compounds.

  Examples of the phosphoric acid ester compound include phosphoric acid ester, tris (butoxyethyl) phosphate having a substituent as an aliphatic hydrocarbon group such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, etc. Phosphorus ester, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) and other aromatic organic groups as substituents Examples include acid ester compounds. Among these, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.

  Examples of the phosphite compound include a phosphite compound having an aliphatic hydrocarbon group as a substituent, such as triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, triphenyl phosphite, triphenyl phosphite, Phosphate ester compounds with aromatic organic groups as substituents such as cresyl phosphite, phosphite compounds with organic groups containing oxygen atoms as substituents such as tetraphenyldipropylene glycol diphosphite, etc. Can be mentioned.

(B) Phosphorus compounds other than the quinonediazide compound may be used alone or in combination of two or more.
In the photosensitive resin composition, (B) the addition amount of the phosphorus compound other than the quinonediazide compound is 50 parts by mass from the viewpoint of photosensitive contrast when the amount of the alkali-soluble polyimide and / or polyimide precursor is 100 parts by mass. The following is preferred. 45 parts by mass or less is more preferable, and 40 parts by mass or less is particularly preferable.

  The photosensitive resin composition may contain a dissolution inhibitor (A) in the solvent of the alkali-soluble polyimide and / or polyimide precursor. The dissolution inhibitor is not limited as long as it is a compound that forms a hydrogen bond with a carboxyl group or an aromatic hydroxyl group and lowers the alkali solubility during alkali development. Examples of such a compound include a compound having an amide structure and a compound having a urea structure.

Examples of the compound having an amide structure include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylformamide, N, N-dimethylbutyramide, N, N- Dibutylacetamide, N, N-dipropylacetamide, N, N-dibutylformamide, N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N′-dimethoxy-N, N′-dimethylolamide, N— Examples include methyl-ε-caprolactam, 4-hydroxyphenylbenzamide, acetanilide, 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide, and the like. Among these, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-diisopropylformamide, 4-hydroxyphenylbenzamide, 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide are preferable. Examples of the compound having a urea structure include tetramethylurea, 1,3-dimethylurea, 1,1-dimethylurea, and 3-hydroxyphenylurea. Of these, tetramethylurea and 3-hydroxyphenylurea are preferable.
The amount of the dissolution inhibitor is preferably 1 part by mass or more and 30 parts by mass or less, preferably 2 parts by mass or more and 15 parts by mass or less from the viewpoint of dissolution inhibition when the amount of the alkali-soluble polyimide and / or the polyimide precursor is 100 parts by mass. Less than the mass part is more preferable.

In the photosensitive resin composition, alkali-soluble polyimide and / or polyimide precursor, quinonediazide compound, and / or phosphorus compound other than quinonediazide compound, and / or dissolution inhibitor are uniformly dissolved and / or dispersed as necessary. Possible solvents. As a solvent, the solvent used for the above-mentioned polyimide precursor resin composition can be used.
The photosensitive resin composition can contain other compounds as long as the performance is not adversely affected. Specific examples include heterocyclic compounds for improving adhesion.
The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Here, examples of the hetero atom include oxygen, sulfur, nitrogen, and phosphorus.

  Heterocyclic compounds include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, imidazole such as 2-phenylimidazole, and N-alkyl group-substituted imidazole such as 1,2-dimethylimidazole. Aromatic group-containing imidazole such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-containing imidazole such as cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, imidazole compounds such as silicon-containing imidazole such as imidazolesilane, 5-methylbenzotriazole, 1- (1 ′, 2′- The Carboxymethyl ethyl benzotriazole), triazole compounds such as 1- (2-ethyl-F carboxymethyl aminomethyl benzotriazole), 2-methyl-5-phenyl-benzoxazole such as oxazole compounds.

  The amount of the other compound added is not limited as long as it is 0.01 parts by mass or more and 30 parts by mass or less when the amount of the alkali-soluble polyimide and / or the polyimide precursor is 100 parts by mass. If it is 0.01 mass part or more, there exists a tendency for adhesiveness to fully improve, and if it is 30 mass parts or less, there will be no bad influence on photosensitivity.

  The photosensitive resin composition can be suitably used for a photosensitive film. From the viewpoint of producing a photosensitive film, the concentration of the alkali-soluble polyimide and / or polyimide precursor in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less. 1 mass% or more is preferable from a viewpoint of the film thickness of a photosensitive film, and 90 mass% or less is preferable from a viewpoint of the viscosity of the photosensitive resin composition and the uniformity of a film thickness. From a viewpoint of the film thickness of the obtained photosensitive film, 2 mass% or more and 80 mass% or less are more preferable.

Next, the manufacturing method of a photosensitive film is demonstrated.
First, the substrate is coated with the photosensitive resin composition. 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 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 by the photosensitive resin composition, after apply | coating the solution of the photosensitive resin composition on arbitrary base materials by arbitrary methods, it is made into a dry film, for example, a carrier. It is set as the laminated film which has a film and a photosensitive film.
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 a laminated film, as a cover film, if it is a film which protects photosensitive films, such as low density polyethylene, it will not be limited.
Next, a printed wiring board can be obtained by pressure-bonding the photosensitive film to a substrate having wiring so as to cover the wiring, performing alkali development, and baking.

Examples of the substrate having wiring in the printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper-clad laminate. 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. 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 surface treatment of the substrate having the wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

  The photosensitive film can be subjected to positive photolithography by dissolving the light irradiated portion 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 an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydroxide solution, and an aqueous potassium hydroxide 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.

Next, the printed wiring board is formed by firing the printed wiring board to which the photosensitive film 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.

  The photosensitive resin composition has good developability, small warpage after firing, and exhibits flame retardancy, so printed wiring boards and circuit boards used in operation panels of various electronic devices in the electronics field. Protective layer formation, insulating layer formation of laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors themselves, etc. Used for film formation on electronic parts for use. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

[Example]
<Reagent>
In Examples and Comparative Examples, silicone diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.) TMEG (manufactured by Shin Nippon Rika Co., Ltd.), APB-N (Mitsui) Chemical Company), PMAB (Ihara Chemical Co., Ltd.), Compound A, Tris (butoxyethyl) phosphate (TBXP, Daihachi Chemical Co., Ltd.), aromatic hydroxyl group-containing phosphazene compound (Otsuka Chemical Co., Ltd., SPH-100), toluene ( Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries), triethylene glycol dimethyl ether (Wako Pure Chemical Industries), sodium carbonate (Wako Pure Chemical Industries), acetone ( Wako Pure Chemical Industries, for organic synthesis), triethylamine (Wako Pure Chemical Industries, special grade), 1,2-naphthoquinone-2-diazide-5-sulfur Nyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade), 3′-hydroxyacetanilide (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter abbreviated as 3′-Hy) were subjected to special purification. Used in the reaction.
The structure of Compound A is a structure represented by the following general formula (10).

In the general formula (10), Q is a structure represented by the following general formula (11) or a hydrogen atom.

As a photosensitive agent in the photosensitive resin composition, compound A has a structure in which 2.9 of the three Qs in the general formula (10) are represented by the general formula (11) on average. Point to.

<Weight average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the weight 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).

<Calculation of siloxane content>
About the content rate of the siloxane structure in this invention, it computed with the ratio of the monomer which has a siloxane structure in all the monomers which comprise a polymer.
<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 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 150micrometer. 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 was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 100 ° C., the press pressure was 2.0 MPa, and the press time was 1 minute.
<Developability evaluation>
Evaluation of developability was performed by laminating a copper-clad laminate with a photosensitive dry film (photosensitive layer thickness of about 25 μm) under the above-mentioned laminating conditions, and then using a positive mask to obtain an irradiation dose of 1.1 J / kg. Exposure was performed at cm ² , followed by alkali development with an aqueous sodium carbonate 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. When the copper surface appears in the exposed area by development and the film thickness of the photosensitive layer in the unexposed area is 22 μm or more, ◯, when the film thickness of the photosensitive layer in the unexposed area is 20 μm or more, otherwise The case where the resolution was inferior or the film thickness was less than 20 μm was marked as x.

<Measurement of warpage after firing>
The obtained photosensitive film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 120 ° C. for 1 hour and subsequently at 180 ° C. for 1 hour. The film was cut into 5 cm squares, and those having a floating height of less than 10 mm were evaluated as ◯, and those having a height of 10 mm or more and 15 mm or less as Δ.
<Flame retardance evaluation>
For the evaluation of flame retardancy, a photosensitive film was laminated on both sides of Kapton (registered trademark) under the above-mentioned laminating conditions, and then fired at 120 ° C. for 1 hour and then at 180 ° C. for 1 hour. The film was cut into 20 cm × 5 cm and tested by UL94 VTM test. The case where no scorch was observed after firing and excellent in flame retardancy was indicated as “◯”, and the case where scorch was observed after firing and inferior in flame retardance was indicated as “x”.

<Polyimide precursor (1)>
The polyimide precursor (1) was produced by the following method.
Under a nitrogen atmosphere, in a separable flask, triethylene glycol dimethyl ether (20.97 g), γ-butyrolactone (20.97 g), toluene (20.0 g), silicone diamine (KF-8010, 23.91 mmol), TMEG (40 0.0 mmol), and the mixture was stirred with heating at 120 ° C. for 1 hour. Subsequently, a Dean Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., APB-N (15.7 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours. After stirring, a mixed solvent of triethylene glycol dimethyl ether / γ-butyrolactone was added so that the polymer solid concentration would be 25% by mass to obtain a solution of the polyimide precursor (1). The weight average molecular weight was 30000. The siloxane structure was 49% by mass.

<Polyimide precursor (2)>
The polyimide precursor (2) was produced by the following method.
Under a nitrogen atmosphere, in a separable flask, triethylene glycol dimethyl ether (20.97 g), γ-butyrolactone (20.97 g), silicone diamine (KF-8010, 23.91 mmol), APB-N (15.7 mmol), TMEG (40.0 mmol) was added and stirred at 80 ° C. for 6 hours. After stirring, after cooling to room temperature, a mixed solvent of triethylene glycol dimethyl ether / γ-butyrolactone was added so that the polymer solid content concentration was 25% by mass to obtain a solution of the polyimide precursor (2). The weight average molecular weight was 28000. The siloxane structure was 49% by mass.

<Polyimide precursor (3)>
The polyimide precursor (3) was produced by the following method.
In a separable flask under nitrogen atmosphere, γ-butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), silicone diamine (KF-8010, 19.128 mmol), TMEG (40 0.0000 mmol), a Dean-Stark apparatus and a refluxer were attached, and the mixture was heated and stirred at 180 ° C. for 30 minutes. After removing toluene, which is an azeotropic solvent, the mixture was cooled to 25 ° C., silicone diamine (KF-8010, 4.782 mmol) and APB-N (15.7 mmol) were added, and the mixture was stirred at 25 ° C. for 5 hours. After stirring, a mixed solvent of γ-butyrolactone / triethylene glycol dimethyl ether was added so that the polymer solid concentration would be 30% by weight to obtain a solution of polyimide precursor (3). The weight average molecular weight was 31600. The siloxane structure was 49% by mass.

<Polyimide precursor (4)>
The polyimide precursor (4) was produced by the following method.
Under a nitrogen atmosphere, γ-butyrolactone (25.6 g), APB-N (4.98 mmol), PMAB (4.32 mmol), and ODPA (10.0 mmol) were placed in a separable flask and stirred at room temperature for 6 hours. A solution of the polyimide precursor (4) was obtained. The weight average molecular weight was 35000. The siloxane structure was 0%.

[Example 1]
In a nitrogen atmosphere, SPH-100 (5.0 mmol), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (4.0 mmol) and acetone (40.0 g) were added and dissolved at room temperature, and then triethylamine was dissolved. A solution of (8.6 mmol) in acetone (5.2 g) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then hydrochloric acid (0.202 g) was added thereto. The precipitated white solid was filtered off, and the obtained filtrate was poured into a 0.5 mass% hydrochloric acid aqueous solution (100 g) to be deposited. The target quinonediazide compound (1) was obtained by suction filtration of the solid and drying in a vacuum dryer.

The quinonediazide compound (1) (20 parts by mass) and TBXP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (1) produced above to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive film.
The above photosensitive film was laminated on a copper clad laminate under the above-mentioned laminating conditions. The obtained laminate is exposed using a positive mask at an irradiation amount of 1.1 J / cm ² , followed by alkali development with a 1% by mass aqueous sodium carbonate solution and rinsing with water, and after drying, a pattern is formed. Observed with an optical microscope. The copper surface appeared in the exposed part of each dry film, and the film thickness of the coverlay layer in the unexposed part was 20 μm or more.
The above photosensitive film is laminated to Kapton (registered trademark) under the above laminating conditions, and the obtained film is baked under the above calcining conditions, and the film is cut into 5 cm square, and the floating height of the end portion is increased. This was determined by measuring the thickness.
The above photosensitive film is laminated on both sides of Kapton (registered trademark) under the above laminating conditions, and the resulting film is baked under the above calcining conditions, cut into 20 cm × 5 cm, and subjected to UL94 VTM test. A flame retardancy test was conducted.

[Example 2]
In a nitrogen atmosphere, SPH-100 (5.0 mmol), 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (4.5 mmol) and acetone (40.0 g) were added and dissolved at room temperature, and then triethylamine was dissolved. A solution of (8.6 mmol) in acetone (5.2 g) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then hydrochloric acid (0.202 g) was added thereto. The precipitated white solid was filtered off, and the obtained filtrate was poured into a 0.5 mass% hydrochloric acid aqueous solution (100 g) to be deposited. The target quinonediazide compound (2) was obtained by suction filtration of the solid and drying in a vacuum dryer.
The quinonediazide compound (2) (20 parts by mass) and TBXP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (1) produced above to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive film.
Using the photosensitive film, evaluation of developability, warpage of the film after baking, and flame retardancy were performed in the same manner as in Example 1.

[Example 3]
The quinonediazide compound (1) (20 parts by mass) and 3′-Hy (30 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (2) produced above to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive film.
Using the photosensitive film, evaluation of developability, warpage of the film after baking, and flame retardancy were performed in the same manner as in Example 1.

[Example 4]
The quinonediazide compound (2) (20 parts by mass) and 3′-Hy (30 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (2) produced above to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive film.
Using the photosensitive film, evaluation of developability, warpage of the film after baking, and flame retardancy were performed in the same manner as in Example 1.

[Example 5]
The quinonediazide compound (1) (20 parts by mass) was mixed with 100 parts by mass of the polyimide precursor (3) to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for developability, warpage after firing, and flame retardancy in the same manner as in Example 1, except that a 5 mass% sodium carbonate aqueous solution at 40 ° C was used.

[Example 6]
The quinonediazide compound (2) (20 parts by mass) was mixed with 100 parts by mass of the polyimide precursor (3) to prepare a photosensitive resin composition. Except for using a 5 mass% sodium carbonate aqueous solution at 40 ° C., the developability, warpage after firing, and flame retardancy were evaluated in the same manner as in Example 1.

[Example 7]
The quinonediazide compound (1) (20 parts by mass) and 3′-Hy (15 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (4) to prepare a photosensitive resin composition. The developability, the warp of the film after firing, and the flame retardance were evaluated in the same manner as in Example 1.

[Example 8]
The quinonediazide compound (2) (20 parts by mass) and 3′-Hy (15 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (4) to prepare a photosensitive resin composition. The developability, the warp of the film after firing, and the flame retardance were evaluated in the same manner as in Example 1.

[Comparative Example 1]
SPH-100 (20 parts by mass) and TBXP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (1) produced above to prepare a resin composition. The resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method, and dried at 95 ° C. for 30 minutes to obtain a film.
Using the film, the developability, the warp of the film after baking, and the flame retardance were evaluated in the same manner as in Example 1.

[Comparative Example 2]
Compound A (20 parts by mass) and TBXP (10 parts by mass) were mixed with 100 parts by mass of the polyimide precursor (1) produced above to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive film.
Using the photosensitive film, evaluation of developability, warpage of the film after baking, and flame retardancy were performed in the same manner as in Example 1.

  From the results in Table 1, when a quinonediazide compound (Examples 1 to 8) is used, good developability and flame retardancy and warpage after firing are shown. On the other hand, Comparative Examples 1, 3, 5, and 7 do not contain a compound having a naphthoquinonediazide structure, and thus it is understood that developability is not exhibited. Further, it can be seen that Comparative Examples 2, 4, 6, and 8 do not contain a phosphazene structure and thus do not exhibit flame retardancy.

  A photosensitive resin composition containing a photosensitive agent having a phosphazene structure and an alkali-soluble polyimide and / or a polyimide precursor has good developability as a photosensitive film, and has little warpage after firing and also exhibits flame retardancy. Therefore, in the field of electronics, flexible wiring boards used for operation panels of various electronic devices and circuit board protective layer formation, laminated substrate insulation layer formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor devices It is used to form films on electronic components for use in protection, insulation and adhesion of peripheral members, semiconductor mounting substrates, heat sinks, lead pins, semiconductors, and the like.

Claims (15)

  (A) Alkali-soluble polyimide and / or polyimide precursor, (B) A quinonediazide compound in which a part of the hydroxyl groups of a phosphazene compound having an aromatic hydroxyl group is substituted with a functional group having a quinonediazide structure The photosensitive resin composition characterized by the above-mentioned.   2. The photosensitive resin according to claim 1, wherein the functional group having a quinonediazide structure in the (B) quinonediazide compound is a 1,2-naphthoquinone-2-diazide-5 (or 4) -sulfonyl group. Composition.   The photosensitive resin composition according to claim 1 or 2, wherein the phosphazene compound having an aromatic hydroxyl group in the (B) quinonediazide compound has 18 to 100 carbon atoms. The said (B) quinonediazide compound contains the phosphazene compound which has an aromatic hydroxyl group represented by following General formula (1), The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned. object.

(In the formula, among R _{1 to} R ₁₀ , a hydrogen atom, an organic group having 1 to 10 carbon atoms, and a hydroxyl group may be the same or different. However, among R ₁ to R ₁₀ And at least one is a hydroxyl group in which a hydrogen atom is substituted with a functional group having a quinonediazide structure, and n is an integer of 3 to 10.)   The photosensitive resin composition according to claim 1, wherein the alkali-soluble polyimide and / or polyimide precursor has a siloxane structure of 5% by mass or more. The polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (2) and a polyamic acid structure represented by the following general formula (3) as structural units. The photosensitive resin composition of any one of 1-5.

(In the formula, R ₁₁ and R ₁₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₁₂ is a divalent organic group having 1 to 30 carbon atoms, R ₁₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₁₄ represents a divalent organic group having 1 to 80 carbon atoms, and m represents an integer of 1 to 30.)   The photosensitive resin composition according to claim 1, comprising a phosphorus compound other than the (B) quinonediazide compound.   8. The photosensitive resin composition according to claim 7, wherein the phosphorus compound other than the (B) quinonediazide compound has a phosphate ester structure.   The photosensitive resin composition according to any one of claims 1 to 8, further comprising (A) a dissolution inhibitor of the alkali-soluble polyimide and / or the polyimide precursor in a solvent.   The photosensitive resin composition according to claim 9, wherein the dissolution inhibitor has an amide structure and / or a urea structure.   A photosensitive film comprising the photosensitive resin composition according to claim 1.   Furthermore, the photosensitive film of Claim 11 which has a carrier film in the one side whole surface.   The photosensitive film according to claim 12, further comprising a cover film.   The coverlay which consists of what developed and baked the photosensitive resin composition in any one of Claims 1-10. A laminate comprising the coverlay according to claim 14 and a copper clad laminate.