JP5390964B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for forming a protective layer on a flexible wiring board and a circuit board used for operation panels of various electronic devices in the field of electronics, and a photosensitive film using the same.

  In recent years, portable electronic devices such as mobile phones and digital cameras have been reduced in size and weight. In order to efficiently mount these devices in a limited space, it has been required to increase the definition of flexible printed wiring boards (hereinafter referred to as FPC). The FPC is usually provided with a protective material (coverlay) for protecting the wiring.

  There are two types of coverlays: “non-photosensitive” and “photosensitive”. With the recent miniaturization of electronic equipment, finer processing has been required, and non-photosensitive coverlays have been required. It became impossible to respond. Therefore, “photosensitive coverlay” that can be finely processed by photolithography is attracting attention.

  In addition, from the viewpoint of improving the reliability of electronic materials, high performance is required for performance such as “low resilience”, “flame retardant”, “solder heat resistance”, and “insulation reliability” as performance required for the coverlay. Therefore, a polyimide having excellent flexibility and flexibility is used as the material for the coverlay.

  In general, the photosensitive coverlay is classified into a negative type and a positive type. 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, a polyimide resin that can be finely processed by a positive photosensitive system has been proposed (for example, see Patent Document 1). Moreover, the photosensitive resin composition which consists of a specific alkali-soluble resin and the photosensitive agent which has a quinonediazide structure is proposed (for example, refer patent document 2).

  However, in the conventional photosensitive coverlay, there is a case where a part of the development remains in the development part in the development process, and such a development residue may appear red on the copper surface (hereinafter referred to as a blush). Such a blush is a problem that must be improved because it leads to defective plating or peeling of plating in a later process.

  In order to improve such a blush, various methods have been proposed (see, for example, Patent Document 3), but pattern fineness and warping after firing are not satisfactory.

  Moreover, although there exists disclosure of the combination of an alkali-soluble polymer, an o-quinonediazide compound, and an organic acid (for example, refer patent document 4), it has at least 1 or more hydroxyl group in a structure, and 2 or more There was no illustration of the organic acid which has a carboxyl group, and there was also no blush improvement effect.

Japanese Patent No. 2906737 WO99 / 19771 pamphlet JP-A-5-11439 JP 2004-29712 A

  The present invention has been made in view of such points, and a photosensitive resin composition capable of forming a coverlay having no red surface on a copper surface after development, a photosensitive film using the photosensitive resin composition, and the photosensitive resin composition An object of the present invention is to provide a printed wiring board using the above.

  As a result of diligent studies to solve the above problems, the present inventor has found that an alkali-soluble resin, a quinonediazide structure, and a photosensitive acid containing an organic acid having at least one hydroxyl group in the structure and having at least two carboxyl groups. The present invention has been completed by finding that the conductive resin composition has no blush on the developed copper surface. That is, the present invention provides a photosensitive resin composition described below, a photosensitive film using the photosensitive resin composition, and a printed wiring board using the photosensitive resin composition and the photosensitive film. To do.

  The photosensitive resin composition of the present invention comprises (A) 100 parts by mass of an alkali-soluble resin, (B) 1 part by mass to 50 parts by mass of a photosensitive agent having a quinonediazide structure, (C) at least one hydroxyl group, and And 0.01 to 20 parts by mass of an organic acid having at least two carboxyl groups.

  In the photosensitive resin composition of the present invention, the alkali-soluble resin is preferably an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor.

  In the photosensitive resin composition of this invention, it is preferable that the said alkali-soluble polyimide and / or alkali-soluble polyimide precursor contain 5 mass% or more of diamine containing a siloxane structure in all polymers.

  In the photosensitive resin composition of the present invention, the alkali-soluble polyimide precursor has a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as structural units. It is preferable that it is the polyimide precursor which has.

（式中、Ｒ_１及びＲ_５は炭素数が１〜３０の４価の有機基でそれぞれ同じであっても異なっていてもよい。Ｒ_２は炭素数が１〜３０の２価の有機基、Ｒ_３は炭素数が１〜３０の１価の有機基、Ｒ_４は炭素数が１〜８０の２価の有機基、ｎは１以上３０以下の整数を表す。）

(In the formula, R ₁ and R ₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₂ is a divalent organic group having 1 to 30 carbon atoms. R ₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₄ represents a divalent organic group having 1 to 80 carbon atoms, and n represents an integer of 1 to 30.)

  In the photosensitive resin composition of this invention, it is preferable to contain 1-50 mass parts of (D) phosphate ester compounds.

  In the photosensitive resin composition of this invention, it is preferable to contain (E) phosphazene compound 1 mass part-50 mass parts.

  The photosensitive film of this invention is obtained by apply | coating the said photosensitive resin composition to a base material, 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 is characterized in that a cover lay made of the photosensitive film has a structure formed so as to cover a substrate having wiring.

  In the printed wiring board of this invention, it is preferable to comprise the structure formed so that the coverlay comprised from the said laminated | multilayer film might cover the base material which has wiring.

  The photosensitive resin composition of the present invention comprises (A) 100 parts by mass of an alkali-soluble resin, (B) 1 part by mass to 50 parts by mass of a photosensitive agent having a quinonediazide structure, (C) at least one hydroxyl group, and A photosensitive resin composition capable of forming a coverlay having no blush on the copper surface after development, because it contains 0.01 to 20 parts by mass of an organic acid having at least two carboxyl groups, and the photosensitive resin composition A photosensitive film using a product and a printed wiring board using the same can be provided.

The present invention will be specifically described below.
The photosensitive resin composition of the present invention comprises (B) a photosensitive agent having a quinonediazide structure in an amount of 1 part by mass to 50 parts by mass and (C) at least one hydroxyl group with respect to 100 parts by mass of the (A) alkali-soluble resin. And a photosensitive resin composition containing 0.01 to 20 parts by mass of an organic acid having at least two carboxyl groups.

(A) Alkali-soluble resin Alkali-soluble resin means what has the property to melt | dissolve 0.1 mass% or more in 0.1 mass%-10 mass% alkaline aqueous solution, such as sodium hydroxide and sodium carbonate. Among these, the alkali-soluble resin is preferably an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor. The alkali-soluble polyimide and / or the alkali-soluble polyimide precursor can be obtained by reacting an acid dianhydride described below with a diamine. Specifically, pyromellitic anhydride, oxydiphthalic dianhydride (hereinafter abbreviated as “ODPA”), biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzophenone-3,3 ′ , 4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid Dianhydride, meta-terphenyl-3,3 ′, 4,4′-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-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclo Pentatricarboxylic acid-2,6: 3 5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-di Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as “TMEG”), p-phenylenebis ( Trimellitic acid monoester anhydride), ethylene bis (trimellitate) dianhydride, and the like.

  Among these, ODPA, TMEG, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran-3-) from the viewpoint of solvent solubility and low Tg of polyimide. Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid An anhydride, ethylene bis (trimellitate) dianhydride is preferred. Here, the solvent solubility means that the polyimide has a property of being dissolved in a known organic solvent at a concentration of 5% by mass or more.

  Next, the diamine used for the alkali-soluble polyimide and / or the alkali-soluble polyimide precursor will be described. Examples of the diamine include diamines having an alkali-soluble functional group and / or other diamines.

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

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

  Examples of the diamine having an aromatic hydroxyl group include polytetramethylene oxide-di-p-aminobenzoate (hereinafter abbreviated as PMAB), 1,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxy. Benzene, 1,3-diamino-4-hydroxybenzene, 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 Phenyl, 2,2-bis (4-hydroxy-3-aminophenyl) propane, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, bis (4-hydroxy-3-aminophenyl) ketone Bis (4-hydroxy-3-aminophenyl) sulfide, bis (4-hydroxy-3-aminophenyl) ether, bis (4-hydroxy-3-aminophenyl) sulfone, bis (4-hydroxy-3-aminophenyl) ) Methane, 4-[(2,4-diamino-5-pyrimidinyl) methyl] phenol, p- (3,6-diamino-s-triazin-2-yl) phenol, bis (4-hydroxy-3-aminophenyl) ) Difluoromethane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (4- Mino-3-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) ketone, bis (4-amino-3-hydroxyphenyl) sulfide, bis (4-amino-3-hydroxyphenyl) ether, Bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) difluoromethane and the like can be mentioned.

  Other diamines include 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-amino) Phenoxy) -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-N), 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- ( -Aminophenoxy) phenyl] hexafluoropropane, 1,5-bis (4-aminophenoxy) pentane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3'-diaminodiphenylsulfone, etc. Is mentioned.

  Among these, APB-N, 1,4-bis (4-aminophenoxy) benzene, 3,3′-diaminodiphenylsulfone, 3,4′- from the viewpoints of Tg control and developability of the alkali-soluble resin. Diaminodiphenyl ether is preferred.

  The alkali-soluble polyimide and / or the alkali-soluble polyimide precursor contains a diamine containing a siloxane structure (hereinafter also referred to as “site derived from the siloxane structure”) in the entire polymer from the viewpoints of warpage during dry film formation and lithography properties. It is preferably 5% by weight or more, more preferably 20% by weight or more, and most preferably 40% by weight or more and 55% by weight or less.

  Among them, the alkali-soluble resin is composed of a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) from the viewpoints of warpage and developability during dry film formation. It is preferable that it is a polyimide precursor which has as a unit. Specifically, silicone diamine (KF-8010) is mentioned.

（式中、Ｒ_１及びＲ_５は炭素数が１〜３０の４価の有機基でそれぞれ同じであっても異なっていてもよい。Ｒ_２は炭素数が１〜３０の２価の有機基、Ｒ_３は炭素数が１〜３０の１価の有機基、Ｒ_４は炭素数が１〜８０の２価の有機基、ｎは１以上３０以下の整数を表す。）

(In the formula, R ₁ and R ₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₂ is a divalent organic group having 1 to 30 carbon atoms. R ₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₄ represents a divalent organic group having 1 to 80 carbon atoms, and n represents an integer of 1 to 30.)

  The terminal of the alkali-soluble resin is not particularly limited as long as it does not affect the performance, and may be an acid dianhydride used when producing a polyimide (precursor) or a terminal derived from a diamine. The terminal can also be sealed with an acid anhydride, an amine compound, or the like. An example is maleic anhydride.

  The number average molecular weight of the alkali-soluble resin is preferably from 1,000 to 1,000,000. Here, the number average molecular weight means a number average molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The number average 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 number average molecular weight is more preferably from 5,000 to 500,000, and most preferably from 10,000 to 300,000.

  In the following, regarding the method for producing an alkali-soluble resin, a polyimide precursor having the polyimide structure represented by the general formula (1) and the polyamic acid structure represented by the general formula (2) as constituent units is taken as an example. explain.

  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.

  Step 1: 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 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% 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 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 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; benzene, toluene, An aromatic hydrocarbon compound having 6 to 10 carbon atoms such as xylene, mesitylene and tetralin; an ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate and γ-butyrolactone; Halogen-containing compounds having 1 to 10 carbon atoms, such as acetonitrile, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Such nitrogen-containing compounds having 2 to 10 carbon atoms; 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 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 from the viewpoint of solubility. Is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The reaction temperature for producing 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, particularly preferably in the range of 30 minutes to 30 hours.

  Process 2: 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.

  The addition amount of the imidization catalyst is preferably 50% by mass or less, and more preferably 30% by mass or less from the viewpoint of controlling the polymerization rate when the polyamic acid is 100% 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 reaction solvent include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; 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; such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate and γ-butyrolactone; chloroform, methylene chloride, 1, 2 Halogen-containing compounds having 1 to 10 carbon atoms such as dichloroethane; 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone The following nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide are 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 from the viewpoint of solubility. 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.

  Process 3: About the synthesis method of the polyamic acid of a 2nd step, it can implement by the method similar to the polyamic acid of a 1st step.

  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, particularly preferably 0 ° C. or higher and 80 ° C. or lower from the viewpoint of the molecular weight of the resulting polyimide precursor.

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

  Examples of the method for purifying the polyimide 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 in a poor solvent can be carried out. Furthermore, when a highly pure polyimide is required, an extraction method using supercritical carbon dioxide is also possible.

  By using the obtained polyimide precursor, it is possible to obtain a solution and / or dispersion of a resin composition comprising a solvent in which the polyimide precursor can be uniformly dissolved and / or dispersed.

  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 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 An aromatic hydrocarbon compound having 6 to 10 carbon atoms; an ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, Chlorine-containing compounds having 1 to 10 carbon atoms such as methylene chloride and 1,2-dichloroethane; such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms; 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.

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

(B) Photosensitizer having a quinonediazide structure As photosensitizers having a quinonediazide structure, 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid ester And 1,2-naphthoquinonediazide sulfonic 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 ′, 3′4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3 ′, 4-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, 2,2′3,4, -tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′3,4, -tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-teto Hydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as esters; 2,2 ′, 3,4,6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid esters, 2, 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as 2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,3', 4 , 4 ′, 5′6, -hexahydroxybenzophenone-1, -Naphthoquinonediazide-4-sulfonic acid ester, 2,3 ', 4,4', 5'6, -hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3 ', 4,4 ', 5,5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3', 4,4 ', 5,5'-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-1, 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-5,5 ', 6,6', 7,7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'- Tetramethyl-1,1′-spirobiindene-5,5 ′, 6,6 ′, 7,7′-hexanol-1,2-naphthoquinonediazide-5-sulfone Acid ester, 2,2,4-trimethyl-2 ′, 4′7, -trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-2 ′, 4 ′, And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as 7-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, and from the viewpoint of photosensitivity, 1,2-naphthoquinone diazide-5-sulfonic acid esters are more preferable. Especially, the compound A shown by following formula (3) is especially preferable.

上記式（３）において、Ｑは下記式（４）で表される構造又は水素原子である。

In the above formula (3), Q is a structure represented by the following formula (4) or a hydrogen atom.

  The amount of the photosensitive agent having a quinonediazide structure is preferably 1 part by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 30 parts by weight or less from the viewpoint of the photosensitive contrast with respect to 100 parts by weight of the alkali-soluble resin. It is as follows. The amount of 1 part by mass or more is preferable because dissolution suppression before exposure tends to be sufficient. If it is 50 mass parts or less, since it exists in the tendency for a sensitivity to be high enough, it is preferable.

(C) Organic acid The organic acid is not limited as long as it is an organic acid having at least one hydroxyl group and at least two carboxyl groups in the structure. It is preferable because it is obtained, and it is preferable that the number of carboxyl groups is 5 or less because a high blush improvement effect can be obtained. Specific compounds include tartronic acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, 2-hydroxy-2-methylmalonic acid, desoxolic acid, benzyltartronic acid, sodium isomalate, 2-hydroxy -2- (2β, 3α, 5β-trihydroxy-5α-carboxycyclohexane-1α-yl) malonic acid, α-hydroxy-α- (3-indolylmethyl) malonic acid, 2-[(3-nitro-6 -Chloroimidazo [1,2-b] pyridazin-2-yl) methyl] -2-hydroxymalonic acid, 2-[(3-nitroimidazo [1,2-a] pyridin-2-yl) methyl] -2 -Hydroxymalonic acid, 2-[(3-nitro-6-chloroimidazo [1,2-a] pyridin-2-yl) methyl] -2-hydroxymalonic acid, 2-[( -Nitro-6-bromoimidazo [1,2-a] pyridin-2-yl) methyl] -2-hydroxymalonic acid, 2-[(5-nitroimidazo [2,1-b] thiazol-6-yl) Methyl] -2-hydroxymalonic acid, dihydroxytartaric acid, desoxosaric acid, facelic acid, fucic acid, eucomic acid, picidic acid, capellatic acid, 2-hydroxy-2- (2-ethylhexyloxycarbonylmethyl) succinic acid, 2-hydroxy -2- (butoxycarbonylmethyl) succinic acid, 2-hydroxy-2- (2-hydroxyethylaminocarbonylmethyl) succinic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid dihydrogen 1-isopropyl, 2- Hydroxy-1,2,3-propanetricarboxylate dihydrogen 2-isopropyl, oxalomalic acid, α-ben Luric acid, 2-hydroxy-3-methylbutanedioic acid, meso-tartaric acid, D-threo-β-hydroxyaspartic acid, L-threo-β-hydroxyaspartic acid, 2- (1,2-dicarboxyethoxy)- 3-hydroxybutanedioic acid, (2R) -2-amino-3-hydroxybutanedioic acid, 3-hydroxy-L-aspartic acid, 2-hydroxy-2-isopropylsuccinic acid, 2-methylcitric acid, L-itatartal Acid, 1-isopropyl (R) -citric acid, 1-isopropyl (S) -citric acid, phthalic acid, chicory acid, 4-hydroxy-5-methoxyisophthalic acid, 3,6-dihydroxyphthalic acid, β-coccinic acid 4-hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 3- (2-furyl) -5-hydroxyphthalic acid, 3- (2 Thienyl) -5-hydroxyphthalic acid, 3,4,6-trifluoro-5-hydroxyphthalic acid, 5-hydroxy-1,2,4-benzenetricarboxylic acid, 4,8-dimethoxy-7-hydroxy-2- Oxo-2H-1-benzopyran-5,6-dicarboxylic acid, 6-hydroxy-1,2,3,4,5-benzenepentacarboxylic acid, 3-methyl-5- (2,3-dihydroxy-5-methyl Phenoxy) 2-methyl phthalate, 3-methyl-5- (2,3-dihydroxy-5-methylphenoxy) phthalic acid, 3,3′-oxybis (4,5-dihydroxy-1,2-benzenedicarboxylic acid) 3,5-dihydroxy-1,2-benzenedicarboxylic acid, and the like. The carboxyl group contained in these organic acids can be in the form of a carboxylic acid or a carboxylic acid metal salt. There. The molecular weight of the organic acid is preferably 1000 or less, more preferably 500 or less, from the viewpoint of developability. In addition, citric acid, malic acid, and tartaric acid are preferable from the viewpoints of availability and ease of handling. The addition amount of the organic acid may be 0.01 parts by mass or more and 20 parts by mass or less, preferably 0.01 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin from the viewpoint of developability. Hereinafter, it is more preferably 0.05 parts by mass or more and 5 parts by mass or less. When the amount is 0.01 parts by mass or more, the blush improvement effect is sufficiently obtained, and when the amount is 10 parts by mass or less, the fine wire adhesion is excellent.

(D) Phosphate ester compound The phosphate ester compound is not limited as long as it is a phosphate ester compound having an aliphatic organic group having 1 to 30 carbon atoms. A carbon number of 1 or more is preferable because low warpage, pattern definition, and flexibility are improved when a coverlay is provided on the flexible printed wiring board. Furthermore, when manufacturing a dry film, it is preferable because warpage during the formation of a dry film and embedding in a wiring pattern are improved. A carbon number of 30 or less is preferred because it tends to exhibit flame retardancy. Among these, a compound represented by the following general formula (5) is preferable.

（Ｒ_６は炭素数が１〜２０の１価の有機基である。）

(R ₆ is a monovalent organic group having 1 to 20 carbon atoms.)

Furthermore, R ₆ is preferably an organic group selected from a methyl group, an ethyl group, a butyl group, an isobutyl group, a 2-ethylhexyl group, a butoxyethyl group, a phenyl group, a cresyl group, a xylenyl group, and an aminophenyl group.

  Examples of such compounds include phosphate ester compounds having an aliphatic hydrocarbon group as a substituent such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, and tris (2-ethylhexyl) phosphate. From the non-volatile viewpoint at the time of baking, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, and tris (butoxyethyl) phosphate are preferable.

  The phosphate ester compound having an aliphatic organic group having 1 to 30 carbon atoms may be used alone or in combination of two or more. Among them, it is preferable to use a combination of two or more types because both flame retardancy and warpage during dry film formation tend to be compatible. The two types of combinations include tributyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, tributyl phosphate, tristris (2-ethylhexyl) phosphate, Examples thereof include a combination of isobutyl phosphate and tris (butoxyethyl) phosphate.

  In the phosphoric ester compound having an aliphatic organic group having 1 to 30 carbon atoms, when the aliphatic organic group has an ether structure, there is an effect of shortening the development time at the time of development. Is preferably a phosphate ester compound having an ether structure. Specific examples include tris (butoxyethyl) phosphate. The addition amount of the phosphate ester compound in which the aliphatic organic group has an ether structure is preferably 50 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin, from the viewpoint of lithographic properties for obtaining a fine pattern, 45 mass parts is more preferable, and 40 mass parts or less is especially preferable. Moreover, 2 mass parts or more are preferable from a viewpoint of the flame retardance and development time of a coverlay, 5 mass parts or more are more preferable, and 10 mass parts or more are especially preferable.

(E) Flame retardant A flame retardant is a phosphazene compound represented by the following general formula (6) or the following general formula (7).

（Ｒ_７、Ｒ_８は、炭素数が３以上３０以下の有機基である。ｍは３以上２５以下の整数である。）

(R ₇ and R ₈ are organic groups having 3 to 30 carbon atoms. M is an integer of 3 to 25.)

（Ｒ_９、Ｒ_１０は、炭素数が３以上３０以下の有機基である。ｏは３以上１００００以下の整数である。Ａ及びＢは炭素数が３以上３０以下の有機基である。）

(R ₉ and R ₁₀ are organic groups having 3 to 30 carbon atoms. O is an integer of 3 to 10,000. A and B are organic groups having 3 to 30 carbon atoms.)

Here, if R ₇ , R ₈ , R ₉ , R ₁₀ have 3 or more carbon atoms, flame retardancy is exhibited, and if they have 30 or less carbon atoms, an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor and It is preferable because it is compatible. Among these, from the viewpoint of flame retardancy, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable.

  Examples of such functional groups include phenyl groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, and 4-hydroxyphenyl group. And functional groups derived from nitrogen-containing heterocyclic compounds such as pyridine, imidazole, triazole, and tetrazole. Among these, a compound having a phenyl group, a 4-methylphenyl group, a 4-hydroxyphenyl group, or a cyanophenyl group is preferable because of its availability.

If m in the phosphazene compound represented by the general formula (6) is 3 or more, flame retardancy is exhibited, and if it is 25 or less, solubility in an organic solvent is high. Among these, m is preferably 3 or more and 10 or less from the viewpoint of availability. Specific examples of the compound include FP-100 in which R ₇ and R ₈ in the general formula (6) are phenyl groups, R ₇ in the general formula (6) is a 4-methylphenyl group, and R ₈ is a phenyl group. There is a certain FP-390.

  In the phosphazene compound represented by the general formula (7), o 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, it is preferable that p is 3 or more and 100 or less because of availability.

In A and B in the phosphazene compound represented by the general formula (7), A represents —N═P (OC ₆ H ₅ ) ₃ , —N═P (OC ₆ H ₅ ) ₃ , —N═P (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), - it is preferable N = a _{P (O) (OC 6 H} 4 OH). B is _{-P (OC 6 H 5) 4} , -P (OC 6 H5) 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 and _{-P (O) (OC 6 H} 5) (OC 6 H 4 OH) are preferred.

  The amount of the phosphazene compound added to 100 parts by mass of the alkali-soluble resin is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and more preferably 40 parts by mass or less from the viewpoint of lithographic properties for obtaining a fine pattern. Is particularly preferred. Moreover, 2 mass parts or more are preferable from a flame-retardant viewpoint of a coverlay, 5 mass parts or more are more preferable, and 7 mass parts or more are especially preferable.

(F) Other additives Additives that are already known can be added within a quantitative and qualitative range that does not depart from the effects of the present invention. Specific additives include surfactants, antioxidants, UV inhibitors, light stabilizers, waxes, fillers, pigments, dyes, foaming agents, antifoaming agents, dehydrating agents, antistatic agents, antibacterial agents , Antifungal agents, leveling agents, dispersants, ethylenically unsaturated compounds, and the like.

(G) Solvent Although the alkali-soluble resin can be dissolved in a solvent, the solvent is not limited as long as it can uniformly dissolve and / or disperse the alkali-soluble resin. Examples of such a solvent include ether compounds having 2 to 8 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, triethylene glycol dimethyl ether, ethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate; acetone, A ketone compound having 2 to 6 carbon atoms such as methyl ethyl ketone; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate, γ-butyrolacto An ester compound having 3 to 6 carbon atoms such as: a chlorine-containing compound having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone; 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.

(H) Manufacturing method of photosensitive film The manufacturing method of a photosensitive film is demonstrated.
First, the substrate is coated with the photosensitive resin composition. As a base material, if it is a base material which is not damaged in the below-mentioned photosensitive dry film formation, it will not be limited. 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 in view of the peelability after the substrate is bonded.

  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. The above is the manufacturing method of the photosensitive film.

  There is a method in which a solution of the photosensitive resin composition is applied on an arbitrary substrate by an arbitrary method and then dried to form a dry film, for example, a laminated film having a carrier 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. As a cover film, if it is a film which protects photosensitive films, such as low density polyethylene, it will not be limited.

  By the way, a hard substrate such as a glass epoxy substrate or a glass maleimide substrate or a flexible substrate such as a polyimide film is used as a substrate having wiring such as a printed wiring board. Among these, a flexible substrate is preferable from the viewpoint of bendability. A flexible copper-clad laminate is obtained by bonding a copper foil to a polyimide film or the like that is a flexible substrate.

  In the method for forming a printed wiring board, the photosensitive film is formed on a 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.

  After the light irradiation, the photosensitive film can be subjected to positive photolithography by dissolving the light irradiation site by alkali development (hereinafter also referred to as “development”). In this case, examples of the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

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

  The photosensitive film can be used as a protective material (coverlay) for protecting the wiring.

  The present invention will be described in detail based on examples made to clarify the effects of the present invention, but the present invention is not limited to the following examples.

<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 Chemical Co., Ltd.), APB-N (manufactured by Mitsui Chemicals), PMAB (manufactured by Ihara Chemical Co., Ltd.), citric acid (manufactured by Wako Pure Chemical Industries, Ltd.), malic acid (manufactured by Wako Pure Chemical Industries, Ltd.), tartaric acid (manufactured by Wako Pure Chemical Industries, Ltd.), lactic acid (manufactured by Wako Pure Chemical Industries, Ltd.), Phthalic acid (manufactured by Wako Pure Chemical Industries, Ltd.), succinic acid (manufactured by Wako Pure Chemical Industries, Ltd.), tris (butoxyethyl) phosphate (manufactured by Wako Pure Chemical Industries, Ltd.), FP-100 (manufactured by Fushimi Pharmaceutical Co., Ltd.), FP-390 (Fushimi Pharmaceutical), toluene (Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries), triethylene glycol dimethyl ether (Wako Pure Chemical Industries), sodium carbonate (Japanese) Made by Kojun Pharmaceutical Co., Ltd. (Manufactured by Daitokemikkusu Co.) PA-6 was used in the reaction without performing any special purification. PA-6 has a structure represented by the following general formula (3).

上記一般式（３）において、Ｑは下記一般式（４）で表される構造又は水素原子である。

In the general formula (3), Q is a structure represented by the following general formula (4) or a hydrogen atom.

<Weight average molecular weight>
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 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. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
Column: Shodex KD-806M (manufactured by Showa Denko)
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)

<Calculation of siloxane content>
About the content rate of the siloxane structure in this invention, it computed by 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 of 100 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. The film thickness after drying was adjusted to 15 μm.

<Lamination conditions>
Lamination was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 100 ° C., the press pressure was 0.5 MPa, and the press time was 1 minute.

<Flexible copper clad laminate and copper foil pretreatment method>
As a pretreatment method of the flexible copper clad laminate and the copper foil, a sodium persulfate treatment (immersion in 150 g / L for 1 minute), followed by immersion in purified water for 1 minute and drying at room temperature was used.

<Development conditions>
Development is performed by laminating on a flexible copper-clad laminate using a photosensitive film (photosensitive layer thickness of about 15 μm) under the above laminating conditions, and then using a positive mask to give an irradiation dose of 1.1 J / cm ^2. The film was exposed to light, and subsequently subjected to alkali development with a 1% aqueous sodium carbonate solution, followed by washing with water.

<Blush evaluation>
After developing on the said conditions, it was set as (circle) that the blush on copper was seen by visual observation, and the blush on copper was not seen.

<Pattern definition>
After developing under the above conditions, microscopic observation was performed, and a circle pattern of less than 60 μm was evaluated as ◯, and a circle pattern of 60 μm to 130 μm was evaluated as Δ.

<Fine wire adhesion>
After developing under the above conditions, the fine line pattern on copper is observed with a microscope. If the line width remains less than 60 μm, ◎, if the line width remains 60 μm to 100 μm, ○, the line width 100 μm to If it remained at 150 μm, it was evaluated as Δ.

<Measurement of warpage after firing>
The evaluation of the warpage was performed by laminating a photosensitive film (photosensitive layer thickness of about 15 μm) on Kapton 100EN (manufactured by Toray DuPont), cutting out to 50 mm × 50 mm, and then 120 ° C. for 1 hour and 180 ° C. for 1 hour. Heat treatment was performed. The film was placed on a table and the edge lift was observed. The table surface was set to 0 mm, and the lift from the table surface was measured using a ruler. The case of 0 mm to 8 mm was evaluated as ◯, and the case of 9 mm to 13 mm was evaluated as Δ.

<Flame retardance>
The flame retardant evaluation was carried out by laminating a photosensitive film on both surfaces of Kapton (registered trademark) under the above-mentioned laminating conditions, followed by heat treatment at 120 ° C. for 1 hour and then at 180 ° C. for 1 hour to make the film 20 cm × 5 cm. It cut out and performed the UL94VTM test. VTM-0 was evaluated as ◯ and the others were evaluated as ×.

<Polyimide precursor (1)>
Under a nitrogen atmosphere, triethylene glycol dimethyl ether (12 g), γ-butyrolactone (28 g), toluene (20.0 g), silicone diamine (KF-8010, 23.1 mmol), TMEG (38.02 mmol) were placed in a separable flask. The mixture was stirred 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 which is an azeotropic solvent, the mixture was cooled to 25 ° C., then maleic anhydride (0.53 mmol) and APB-N (15.6 mmol) were 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, and the siloxane structure was 49% by mass.

<Polyimide precursor (2)>
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 (2) was obtained. The weight average molecular weight was 35000, and the siloxane structure was 0%.

[Examples 1 to 7]
A solution of the polyimide precursor (1) was mixed with the composition shown in Table 1 to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the method described above to obtain a photosensitive film. This photosensitive film was laminated on a flexible copper-clad laminate (which had been pretreated by the method described above) by the method described above. The blush, pattern fineness, and fine wire adhesion of the obtained laminated film were evaluated. Further, the photosensitive film was laminated on Kapton (registered trademark), and the warpage after firing was evaluated by the above method. Furthermore, the said photosensitive film was laminated on both surfaces of Kapton (trademark), and the flame retardance was evaluated by the said method. The results are shown in Table 1.

[Examples 8 to 9]
The solution of the polyimide precursor (2) produced above was mixed with the composition shown in Table 1 to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the method described above to obtain a photosensitive film. This photosensitive film was laminated on a flexible copper-clad laminate (which had been pretreated by the above-described method) by the method described above. The blush, pattern fineness, and fine wire adhesion of the obtained laminated film were evaluated. Further, the photosensitive film was laminated on Kapton (registered trademark), and the warpage after firing was evaluated by the above method. Furthermore, the said photosensitive film was laminated on both surfaces of Kapton (trademark), and the flame retardance was evaluated by the said method. The results are shown in Table 1.

[Comparative Examples 1 to 4]
The solution of the polyimide precursor (1) produced above was mixed with the composition shown in Table 1 to prepare a photosensitive resin composition. The obtained photosensitive resin composition was formed into a dry film by the above-described method to obtain a photosensitive film. This photosensitive film was laminated with a flexible copper-clad laminate (pretreated by the above method) by the above-described method. The blush, pattern fineness, and fine wire adhesion of the obtained laminated film were evaluated. Further, the photosensitive film was laminated on Kapton (registered trademark), and the warpage after firing was evaluated by the above method. Furthermore, the said photosensitive film was laminated on both surfaces of Kapton (trademark), and the flame retardance was evaluated by the said method. The results are shown in Table 1.

  From the results of Table 1, (A) 1 part by weight to 50 parts by weight of a photosensitive agent having a quinonediazide structure, (C) at least one hydroxyl group, and at least 2 parts per 100 parts by weight of the alkali-soluble resin. It turns out that it is effective for blush improvement by containing 0.01 mass part-20 mass parts of organic acids which have one carboxyl group. On the other hand, when no organic acid is added (Comparative Example 1), when an organic acid having one carboxyl group is used (Comparative Example 2), in an organic acid having no hydroxyl group (Comparative Example 3 and Comparative Example 4), You can see that the blush does not improve.

  The photosensitive resin composition according to the present invention eliminates the blush of the copper surface as a photosensitive film, so that a flexible wiring board used for operation panels of various electronic devices in the electronics field and a protective layer formation for circuit boards, Electrons for use in protection, insulation, and adhesion of laminated substrate formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors, etc. Used for film formation on parts.

Claims (11)

  (A) 100 parts by mass of an alkali-soluble resin, (B) 1 part by mass to 50 parts by mass of a photosensitizer having a quinonediazide structure, (C) an organic acid having at least one hydroxyl group and at least two carboxyl groups The photosensitive resin composition characterized by containing 0.01 mass part-20 mass parts.   The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is an alkali-soluble polyimide and / or an alkali-soluble polyimide precursor.   The photosensitive resin composition according to claim 2, wherein the alkali-soluble polyimide and / or the alkali-soluble polyimide precursor contains a diamine having a siloxane structure in an amount of 5% by mass or more based on the total polymer. The alkali-soluble polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as structural units. The photosensitive resin composition of Claim 2 or Claim 3.

(In the formula, R ₁ and R ₅ are tetravalent organic groups having 1 to 30 carbon atoms, which may be the same or different. R ₂ is a divalent organic group having 1 to 30 carbon atoms. R ₃ represents a monovalent organic group having 1 to 30 carbon atoms, R ₄ represents a divalent organic group having 1 to 80 carbon atoms, and n represents an integer of 1 to 30.)   (D) 1 to 50 mass parts of phosphate ester compounds are contained, The photosensitive resin composition in any one of Claims 1-4 characterized by the above-mentioned.   (E) 1 to 50 mass parts of phosphazene compounds are contained, The photosensitive resin composition in any one of Claims 1-5 characterized by the above-mentioned.   A photosensitive film obtained by applying the photosensitive resin composition according to claim 1 to a substrate.   A laminated film comprising: a carrier film; and the photosensitive film according to claim 7 provided on the carrier film.   A laminated film comprising a cover film formed on the photosensitive film according to claim 7.   A printed wiring board, wherein a cover lay composed of the photosensitive film according to claim 7 is formed so as to cover a substrate having wiring.   A printed wiring board, wherein a cover lay composed of the laminated film according to claim 8 or 9 is formed so as to cover a substrate having wiring.