JP2008309970A - Photosensitive resin composition and photosensitive film using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition which has plating durability and excellent image developing characteristics and also provide a photosensitive film comprising this photosensitive composition. <P>SOLUTION: This photosensitive resin composition contains (A) an alkali soluble resin, (B) a photosensitive agent of a quinonediazide structure, and (C) a compound having a carboxyl group in its molecular structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition suitable for a printed circuit board coverlay, comprising an alkali-soluble resin, a photosensitizer having a quinonediazide structure, and a nitrogen-containing heterocyclic compound having a hydrophobic site in the molecular structure. The present invention relates to a photosensitive film using the same.

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

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

  In addition, 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.

  Moreover, plating tolerance is mentioned as a function of the coverlay for printed wiring boards generally. Conventional coverlays have problems such as short-circuiting of wiring due to the plating solution submerged under the coverlay layer after plating.

A photosensitive resin composition containing a salt of a carboxylic acid to be photodecarboxylated and an amine as a polyimide precursor has been proposed (Patent Document 1). The purpose of the resin composition is to improve solubility contrast, and there is no disclosure regarding plating resistance.
Japanese Patent Laid-Open No. 2007-10185

  This invention is made | formed in view of this point, and it aims at providing the photosensitive film which consists of a positive photosensitive composition with favorable plating tolerance, and this photosensitive resin composition.

  The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) a compound having a carboxyl group in the molecular structure. And

  In the photosensitive resin composition of the present invention, the compound is preferably a compound having two or more carboxyl groups in one molecular structure.

  In the photosensitive resin composition of the present invention, the compound preferably has an amino group.

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

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

（式中、Ｒ_１，Ｒ_２，Ｒ_４は４価の有機基を表し、同じであっても異なっていても良い。Ｒ_３は炭素数１以上２０以下の炭化水素基を表す。Ｒ_５はアルカリ溶解性官能基を少なくとも一つ以上有する２価の有機基を表す。ａは３以上２０以下の整数を表す。ｂは１以上１０以下の整数を表す。ｃは１以上２０以下の整数を表す。ｘ＋ｙ＋ｚ＝１００かつ０．００１≦ｘ／（ｘ＋ｙ＋ｚ）≦０．９、０＜ｙ＜９９．９９９、０＜ｚ＜９９．９９９である。） In the photosensitive resin composition of the present invention, the alkali-soluble resin preferably has a structure represented by the following general formula (1).

(In the formula, R ₁ , R ₂ and R ₄ represent a tetravalent organic group and may be the same or different. R ₃ represents a hydrocarbon group having 1 to 20 carbon atoms. R ₅ Represents a divalent organic group having at least one alkali-soluble functional group, a represents an integer of 3 to 20, b represents an integer of 1 to 10, and c represents an integer of 1 to 20. X + y + z = 100 and 0.001 ≦ x / (x + y + z) ≦ 0.9, 0 <y <99.999, 0 <z <99.999.)

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

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

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

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

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

  According to the photosensitive resin composition of the present invention, it contains (A) an alkali-soluble resin, (B) a photosensitive agent having a quinonediazide structure, and (C) a compound having a carboxyl group in the molecular structure. In addition, a film material having good developability and good plating resistance can be obtained.

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

  Here, the alkali-soluble polyimide and the polyamic acid in the present invention will be described. Specific examples of the acid dianhydride used for the alkali-soluble polyimide and polyamic acid in the present invention include pyromellitic anhydride, oxydiphthalic dianhydride (hereinafter abbreviated as ODPA), biphenyl-3,4,3 ′. , 4′-tetracarboxylic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetra Rubonic acid 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 anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Examples include ethylene glycol bis (trimellitic acid monoester acid anhydride), p-phenylene bis (trimellitic acid monoester acid anhydride), and the like.

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

  The diamine used in the present invention will be described. In the present invention, examples of the diamine include diamines having an alkali-soluble functional group and / or other diamines.

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

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

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

  Other diamines include 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 (tri Fluoromethyl) -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-amido) 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-aminophenoxybenzene) ), 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] Examples include hexafluoropropane and 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane. The alkali-soluble resin preferably has a siloxane structure of 10% by weight or more, and more preferably 20% by weight or more from the viewpoint of warpage during dry film formation.

（式中、Ｒ_１，Ｒ_２，Ｒ_４は４価の有機基を表し、同じであっても異なっていても良い。Ｒ_３は炭素数１以上２０以下の炭化水素基を表す。Ｒ_５はアルカリ溶解性官能基を少なくとも一つ以上有する２価の有機基を表す。ａは３以上２０以下の整数を表す。ｂは１以上１０以下の整数を表す。ｃは１以上２０以下の整数を表す。ｘ＋ｙ＋ｚ＝１００かつ０．００１≦ｘ／（ｘ＋ｙ＋ｚ）≦０．９、０＜ｙ＜９９．９９９、０＜ｚ＜９９．９９９である。） As the alkali-soluble resin according to the present invention, a polyimide represented by the following general formula (1) is particularly preferable from the viewpoints of warpage during dry film formation and flame retardancy of the film.

(In the formula, R ₁ , R ₂ and R ₄ represent a tetravalent organic group and may be the same or different. R ₃ represents a hydrocarbon group having 1 to 20 carbon atoms. R ₅ Represents a divalent organic group having at least one alkali-soluble functional group, a represents an integer of 3 to 20, b represents an integer of 1 to 10, and c represents an integer of 1 to 20. X + y + z = 100 and 0.001 ≦ x / (x + y + z) ≦ 0.9, 0 <y <99.999, 0 <z <99.999.)

The diamine used for the polyimide represented by the general formula (1) will be described.
The diamine used for the polyimide represented by the general formula (1) is a 1, n-bis (4-aminophenoxy) alkane represented by the general formula (2), a silicone diamine represented by the general formula (3), A diamine having an alkali-soluble functional group and / or other diamine.

  “A” in the general formula (2) is 3 or more and 20 or less in consideration of the low Tg and flame retardancy of the polyimide that can reduce the warp when forming a dry film. Among them, from the viewpoint of the balance between low Tg and flame retardancy, 3 to 10 is preferable, and 3 to 5 is particularly preferable.

In the general formula (3), R ₃ represents a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. b is an integer of 1 to 10, and c represents an integer of 1 to 20.

Examples of the hydrocarbon group having 1 to 20 carbon atoms (R ₃ ) include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, a functional group containing a cyclic structure, and a group obtained by combining them.

  Examples of the aliphatic saturated hydrocarbon group include primary hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group, secondary hydrocarbon groups such as isobutyl group and isopentyl group, and tertiary hydrocarbon groups such as t-butyl group.

  Examples of the aliphatic unsaturated hydrocarbon group include a hydrocarbon group containing a double bond such as a vinyl group and an allyl group, and a hydrocarbon group containing a triple bond such as an ethynyl group.

  Examples of the functional group containing a cyclic structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and a cyclooctyl group, a polycyclic functional group such as a norbornyl group and an adamantyl group, pyrrole, furan, Examples include thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, a heterocyclic functional group having a dioxane structure, an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring structure.

The hydrocarbon group having 1 to 20 carbon atoms (R ₃ ) may include a halogen atom, a hetero atom, and a metal atom. Examples of the halogen atom in the present invention include fluorine, chlorine, bromine and iodine. Moreover, oxygen, sulfur, nitrogen, and phosphorus are mentioned in the hetero atom in this invention. The metal atom in the present invention includes silicon and titanium.

In addition, the hydrocarbon group (R ₃ ) having 1 to 20 carbon atoms is bonded via a hetero atom and / or a metal atom, even though it is directly bonded to a hetero atom and / or a metal atom to which R ₃ is bonded. May be.

The carbon number of R _{3 in} the general formula (3) is preferably 1 or more and 20 or less in consideration of flame retardancy. From the viewpoint of solvent solubility, 1 or more and 10 or less are particularly preferable.

  In the general formula (3), b is 1 or more and 10 or less in consideration of flame retardancy. From the viewpoint of solvent solubility of the polyimide to be formed, b is preferably 2 or more and 8 or less, and more preferably 3 or more and 6 or less.

  C in the general formula (3) is 1 or more and 20 or less in consideration of flame retardancy. From the viewpoint of solvent solubility of the polyimide to be produced, c is preferably 1 or more and 15 or less, and more preferably 1 or more and 12 or less.

  Next, the acid dianhydride used for the polyimide represented by the general formula (1) will be described. Acid dianhydride used in the polyimide represented by the general formula (1) reacts with 1, n-bis (4-aminophenoxy) alkane, diamine having an alkali-soluble functional group, silicone diamine and / or other diamine. The acid dianhydride that can be used is not particularly limited.

R ₁ , R ₃ and R ₅ in the general formula (1) are tetravalent organic groups which may be the same or different. R ₁ , R ₂ and R ₄ are tetravalent organic groups derived from an acid dianhydride represented by the following general formulas (4), (5) and (6).

As R ₁ , R ₃ and R ₅ in the general formula (1), specifically, the acid dianhydrides described above can be used.

  X, y and z constituting the copolymerization component in the general formula (1) are x + y + z = 100 and 0.001 ≦ x / (x + y + z) ≦ 0.9, 0 <y <99.999, 0 <z <99. .999 is not particularly limited. The content of the site derived from silicone diamine is preferably 10% by weight or more from the viewpoint of Tg of the obtained dry film.

  In the present invention, the terminal of the alkali-soluble resin is not particularly limited as long as it has a structure that does not affect the performance. A terminal derived from an acid dianhydride or a 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.

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

  Hereinafter, a method for synthesizing polyamic acid and then synthesizing an alkali-soluble polyimide will be described as an example of a method for producing an alkali-soluble resin.

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

  In the following, a method for synthesizing a polyamic acid by reacting an acid dianhydride and a diamine will be described. Subsequently, a method for imidization after adding a catalyst will be described as an example, and manufacturing conditions for the polyimide according to the present invention will be described. .

  The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved 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 weight or more and 95% by weight or less, preferably 1% by weight or more and 90% by weight or less. By performing polymerization in this monomer concentration range, a polyamic acid solution can be obtained.

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

  The reaction temperature during the production of the polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower. If it is 0 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no influence of a side reaction. Preferably they are 15 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

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

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

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

  The amount of the imidization catalyst added is preferably 50% by weight or less, and more preferably 30% by weight or less, assuming that polyamic acid is 100% by weight.

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

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

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

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

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

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

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

  In the present invention, the solvent constituting the polyimide-containing resin composition is not limited as long as it can uniformly dissolve and / or disperse the polyimide according to the present invention. Examples of such solvents include ether compounds having 2 to 6 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and propylene glycol monomethyl acetate; 2 or more carbon atoms such as acetone and methyl ethyl ketone. 6 or less ketone compounds; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin; carbon numbers such as benzene, toluene, xylene, mesitylene and tetralin Aromatic hydrocarbon compound having 6 to 10 carbon atoms; ester compound having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, methylene chloride Chlorine-containing compounds having 1 to 10 carbon atoms such as 1,2-dichloroethane; 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Examples thereof include the following nitrogen-containing compounds; sulfur-containing compounds such as dimethyl sulfoxide. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of the solubility of the polyimide, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

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

  The photosensitive agent having a quinonediazide structure in the present invention is not limited as long as it has a quinonediazide structure in the molecular structure.

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

In the general formula (7), Q is a structure represented by the general formula (8) or a hydrogen atom. As a photosensitizer in the photosensitive resin composition according to the present invention, compound B-1 has a structure in which, on average, 2.3 of the three Qs in the general formula (7) are represented by the general formula (8). It points to what is.

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

  In the present invention, the compound having a carboxyl group in the molecular structure is not limited as long as it has a carboxyl group. The compound preferably has a molecular weight of 1000 or less from the viewpoint of compatibility with the alkali-soluble resin. Examples of such compounds include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid, carboxylic acids having unsaturated bonds such as oleic acid, linoleic acid, and linolenic acid, benzoic acid, toluic acid, and hydroxybenzoic acid. Acids, aromatic carboxylic acids such as nitrobenzoic acid, carboxylic acids having two carboxyl groups in one molecular structure such as phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, maleic acid, fumaric acid and adipic acid, ethylenediamine Examples thereof include carboxylic acids having 4 carboxyl groups in one molecular structure such as acetic acid (hereinafter abbreviated as EDTA), carboxylic acids having amino groups such as aminobenzoic acid, alanine, arginine, asparagine and phenylalanine. Among these, a carboxylic acid having two or more carboxyl groups is preferable from the viewpoint of alkali developability, and a carboxylic acid having an amino group is particularly preferable from the viewpoint of compatibility with an alkali-soluble resin.

  In the present invention, the compound having a carboxyl group in the molecular structure may be one kind or a mixture of two or more kinds as necessary.

  The addition amount of the compound having a carboxyl group in the molecular structure in the photosensitive resin composition according to the present invention is 30% by weight from the viewpoint of developability when the amount of (A) the alkali-soluble resin is 100% by weight. The following is preferred. From the viewpoint of flame retardancy of the cured product, it is preferably 20% by weight or less, and more preferably 10% by weight or less.

  In the present invention, although the effect on the plating resistance of a compound having a carboxyl group in the molecular structure is not clear, the present inventors presume as follows. That is, it is presumed that the carboxyl group of the compound having a carboxyl group is coordinated to the metal atom, thereby preventing the plating from penetrating the metal atom and the coverlay interface.

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

The plasticizer in the photosensitive resin composition according to the present invention is not limited as long as it imparts plasticity to the resin composition and can lower the Tg of the composition. As such plasticizers, ether compounds such as polyethylene glycol, polypropylene glycol and crown ether; methacrylic group-containing compounds such as tetraethylene glycol dimethacrylate and polyethylene glycol dimethacrylate; acrylics such as tetraethylene glycol diacrylate and polyethylene glycol diacrylate Group-containing compounds; phthalic acid esters such as dimethyl phthalate and diethyl phthalate; trimellitic acid esters such as tris (2-ethylhexyl) trimellitate; aliphatic dibasic acid esters such as dimethyl adipate and dibutyl adipate; trimethyl phosphate and tris (butoxyethyl) ) Phosphate esters such as phosphate; (C ₆ H ₅ O) ₂ P (O) OC ₆ H ₄ C (CH ₃ ) ₂ Aromatic condensed phosphate ester represented by C ₆ H ₄ OP (O) (OC ₆ H ₅ ) ₂ ; isocyanuric acid ethylene glycol-modified diacrylate, isocyanuric acid ethylene glycol-modified diacrylate, and the like. Among these, a methacryl group-containing compound, an isocyanuric acid ethylene glycol-modified diacrylate, and an isocyanuric acid ethylene glycol-modified diacrylate are preferable from the viewpoint of warping after formation of a dry film.

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

  In the photosensitive resin composition according to the present invention, (A) an alkali-soluble resin, (B) a photosensitive agent, and (C) a compound having a carboxyl group in the molecular structure and / or a plasticizer are uniformly included as necessary. Solvents that can be dissolved and / or dispersed can be included. As a solvent, the solvent used for the above-mentioned polyimide resin composition can be used.

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

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

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

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

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

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

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

  The method for forming the printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. Examples of such a forming method include a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating, etc. in a state where the wiring side of the substrate having the wiring is in contact with the photosensitive film of the present invention. Can be mentioned. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a heat vacuum press or a heat vacuum laminate is preferable.

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

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

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

  Subsequently, the printed wiring board is formed by baking the printed wiring board to which the photosensitive film of the present invention is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. More preferably, it is 100 degreeC or more and 300 degrees C or less.

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

  Since the photosensitive resin composition according to the present invention is sufficiently suppressed in warpage as a photosensitive film, has good developability, and exhibits good plating resistance when used as a cured product, Protective layer formation for printed wiring boards and circuit boards used for operation panels of equipment, insulation layer formation for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, semiconductor device peripheral members, semiconductor mounting substrates, It is used for film formation on electronic parts for use in protection, insulation and adhesion of heat sinks, lead pins, semiconductors, etc.

Examples carried out to clarify the effects of the present invention will be described below.
<Reagent>
In Examples and Comparative Examples, 1,5-bis (4-aminophenoxy) alkane (manufactured by Wakayama Seika Co., Ltd.) (hereinafter abbreviated as DA5MG), silicone diamine (KF-8010) (Shin-Etsu Chemical) ), MBAA (manufactured by Wakayama Seika Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.), compound B-1, tetraethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 4G), EDTA (Wako Pure Chemical Industries, Ltd.) Manufactured by Kogyo Co., Ltd.), Kirest MZ-2 (produced by Kirest Co., Ltd.), Kirest MZ-8 (produced by Kirest Co., Ltd.), toluene (manufactured by Wako Pure Chemical Industries, Ltd., for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.) Special grade), pyridine (manufactured by Wako Pure Chemical Industries, Ltd., for organic synthesis), and γ-valerolactone (manufactured by Wako Pure Chemical Industries, Ltd., first grade) were used for the reaction without carrying out any special purification.

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

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

<Dry film manufacturing method>
The coating method of the photosensitive resin composition in the present invention was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The said photosensitive resin composition was dripped at the easily peelable PET film (Mitsubishi Chemical Polyester Film company make, DIAFOIL, T100H25), and it coat | coated with clearance 200 micrometers. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.

<Lamination conditions>
Lamination in the present invention was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 100 ° C., the press pressure was 1.23 MPa, and the press time was 5 minutes.

<Pretreatment method of copper clad laminate>
As a pretreatment method for the copper-clad laminate in the present invention, a hydrochloric acid treatment (immersion in 3% hydrochloric acid for 1 minute), followed by immersion in purified water for 1 minute and drying at room temperature was used.

<Curing body manufacturing method>
A method for producing a cured body is a copper-clad laminate (manufactured by Nippon Steel Chemical Co., MB12-25) obtained by treating the photosensitive dry film produced by the above-described coating method by the above-described laminating method and the above-described pretreatment method. -00CEM) and firing using a firing furnace (manufactured by Koyo Lindberg). By baking at 120 ° C. for 60 minutes and then at 180 ° C. for 60 minutes in an air atmosphere, a cured body was obtained.

<Developability evaluation>
Evaluation of developability was performed by laminating a copper-clad laminate using a photosensitive dry film (photosensitive layer thickness of about 20 μm) under the above-mentioned laminating conditions, and then using a positive mask to apply a dose of 1.3 J / Exposure was performed at cm ² , followed by alkaline development with a 3% aqueous sodium hydroxide solution and rinsing with water, and after drying, the pattern was evaluated with an optical microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. The case where the copper surface appears in the exposed area due to development and the film thickness of the photosensitive layer in the unexposed area is 15 μm or more is marked as ◯, and the case where the resolution is inferior or the film thickness is 15 μm or smaller is marked as x. did.

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

<Tin plating resistance evaluation>
As the plating resistance, tin plating resistance was evaluated. The photosensitive dry film produced by the above method is laminated on the copper clad laminate subjected to the pretreatment method under the lamination condition, and then a 400 μm diameter circular pattern is formed under the development condition and baked. It was. Using the developed and fired samples, tin plating resistance was evaluated under the following conditions. After the test, the case in which the plating solution did not soak, swell, or peel from the circular hole was evaluated as ◯, and the case in which the plating solution soaked, swelled, or peeled off was observed as x.
Degreasing: The coverlay is immersed in an acidic degreasing solution (FR cleaner) at 30 ° C. for 5 minutes.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Soft etch: The coverlay was immersed in a 10% by weight aqueous sodium persulfate solution at room temperature for 30 seconds.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Acid treatment: Coverlay was immersed in 10 vol% sulfuric acid aqueous solution at room temperature for 30 seconds.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Tin plating: The coverlay is immersed in a tin plating solution (Rohm and Haas Electronic Materials, LT-34) at 70 ° C. for 5 minutes.
Water washing: The coverlay is immersed in purified water at 50 ° C. for 1 minute.

Example 1
Under a nitrogen atmosphere, MBAA (29.97 mmol), ODPA (59.96 mmol), and γ-butyrolactone (120 mL) were placed in a separable flask and stirred at room temperature for 2 hours. Subsequently, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dean Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 120 ° C., silicone diamine (KF-8010, 45.0 mmol) and DA5MG (14.98 mmol) were added, and after stirring for 10 minutes, ODPA (29.98 mmol) was added, and the mixture was heated and stirred at 120 ° C. for 2 hours. did. Subsequently, toluene (10 mL) was added, and the mixture was heated and stirred at 180 ° C. for 2 hours. It cooled to 140 degreeC, (gamma) -butyrolactone was added so that polymer solid content concentration might be 30 weight%, and the γ-butyrolactone solution of polyimide (1) was obtained by cooling to room temperature. The number average molecular weight was 69000, and the weight (%) of the site derived from the siloxane structure was 47.8% by weight.

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

The above photosensitive dry 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 dose of 1.3 J / cm ² , followed by alkali development with a 3% aqueous sodium hydroxide solution and rinsing with water, and after drying, a pattern is formed. Observed with an optical microscope. A copper surface appeared in the exposed part of each dry film, and the film thickness of the coverlay layer in the unexposed part was 15 μm or more.

The above-mentioned photosensitive dry film is laminated on the copper-clad laminate subjected to the above-mentioned pretreatment under the above-mentioned laminating conditions, and exposed at a dose of 1.3 J / cm ² using a positive mask, Subsequently, alkaline development treatment with a 3% aqueous sodium hydroxide solution and rinsing with water were performed to form a circular pattern with a diameter of 400 μm, followed by firing. The coverlay was evaluated for tin plating resistance as described above. The plating solution was not soaked, peeled off, or swollen from the circular holes, and was good.

(Example 2)
Compound B-1 (20% by weight), Kirest MZ-2 (1% by weight) and tetraethylene glycol dimethacrylate (15% by weight) were mixed with 100% by weight of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was warped in the same manner as in Example 1 and evaluated for alkali developability and tin plating resistance. The results are shown in Table 2 below.

(Example 3)
Compound B-1 (20 wt%), Kirest MZ-8 (1 wt%) and tetraethylene glycol dimethacrylate (15 wt%) were mixed with 100 wt% of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was warped in the same manner as in Example 1 and evaluated for alkali developability and tin plating resistance. The results are shown in Table 2 below.

(Comparative Example 1)
Compound B-1 (20% by weight) and tetraethylene glycol dimethacrylate (15% by weight) were mixed with 100% by weight of polyimide (1) produced in Example 1 to prepare a photosensitive resin composition. . The photosensitive resin composition was warped in the same manner as in Example 1 and evaluated for alkali developability and tin plating resistance. The results are shown in Table 2 below.

From the results of Table 2, it can be seen that in Examples 1 to 3 in which a compound having a carboxyl group in the molecular structure was added, tin plating resistance was improved as compared with Comparative Example 1 in which the compound was not added. From the above, it can be seen that a photosensitive film made of a photosensitive resin composition in which a compound having a carboxyl group in the molecular structure is added has tin plating resistance. It can also be seen that the warpage and developability are good.

  The photosensitive resin composition in the present invention is used as an operation panel for various electronic devices in the electronics field because warpage is sufficiently suppressed as a photosensitive film, developability is good, and it has plating resistance. Formation of protective layers on flexible wiring boards and circuit boards, insulation layers on laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting boards, heat sinks, lead pins, semiconductors themselves, etc. Used for film formation on electronic parts for protection, insulation and adhesion.

Claims (11)

  A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photosensitizer having a quinonediazide structure, and (C) a compound having a carboxyl group in the molecular structure.   2. The photosensitive resin composition according to claim 1, wherein the compound is a compound having two or more carboxyl groups in one molecular structure.   The photosensitive resin composition according to claim 1, wherein the compound has an amino group.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin is a polyamic acid.   The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is an alkali-soluble polyimide containing a siloxane structure in an amount of 10% by weight or more. The photosensitive resin composition according to any one of claims 1 to 3, or 5, wherein the alkali-soluble resin has a structure represented by the following general formula (1).

(In the formula, R ₁ , R ₂ and R ₄ represent a tetravalent organic group and may be the same or different. R ₃ represents a hydrocarbon group having 1 to 20 carbon atoms. R ₅ Represents a divalent organic group having at least one alkali-soluble functional group, a represents an integer of 3 to 20, b represents an integer of 1 to 10, and c represents an integer of 1 to 20. X + y + z = 100 and 0.001 ≦ x / (x + y + z) ≦ 0.9, 0 <y <99.999, 0 <z <99.999.)   (D) The photosensitive resin composition in any one of the Claims 1-6 containing a plasticizer.   A photosensitive film comprising the photosensitive resin composition according to claim 1.   A laminated film comprising: a carrier film; and the photosensitive film according to claim 8 provided on the carrier film.   The laminated film according to claim 9, further comprising a cover film formed on the photosensitive film.   A substrate having wiring, and a cover lay formed on the substrate so as to cover the wiring and made of the photosensitive film or laminated film according to any one of claims 8 to 10. A printed wiring board characterized by: