JP2011209426A - Photosensitive resin composition and photosensitive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having good developability and good plating resistance and a photosensitive film comprising the photosensitive resin composition.SOLUTION: The photosensitive resin composition contains an alkali-soluble resin, a compound having a quinonediazido structure, and a nitrogen-containing heterocyclic compound having at least one structure selected from the group consisting of a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure.

Description

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

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

  In general, when a polyimide material is finely processed, an etching process using a photoresist is performed, and thus a large number of processes are required. 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. As the photosensitive resin composition, a negative photosensitive resin composition in which an exposed portion is a pattern and a positive photosensitive resin composition in which an unexposed portion is a pattern are known. In general, in the case of a negative photosensitive resin composition, the exposed portion is swollen by the developer, and it is difficult to perform fine processing with high resolution. Therefore, fine processing by a photosensitive system using a positive photosensitive resin composition is strongly desired.

  In addition, in conventional screen printing in which a photosensitive resin composition is applied to a substrate, there are problems such as a solvent removal process and two processes when performing double-sided processing. It is desired to make the composition into a dry film.

  Moreover, plating resistance is mentioned as a function generally required for the coverlay for printed wiring boards. However, the conventional coverlay has a problem such as a short circuit of the wiring because the plating solution sinks under the coverlay layer after the plating process.

  Conventionally, as a resin composition having a nitrogen-containing heterocyclic compound, a non-photosensitive resin composition containing a nitrogen-containing heterocyclic compound in a polyimide resin composition has been proposed (Patent Document 1). Further, a positive photosensitive resin composition in which an oxazole compound is contained in a polyimide precursor composition has been proposed (Patent Document 2). Furthermore, a positive photosensitive resin composition has been proposed in which a polyimide resin composition contains a heterocyclic compound containing two or more nitrogen atoms (Patent Document 3).

JP 2004-115815 A International Publication No. 2009/136557 Pamphlet JP 2006-184660 A

  However, as disclosed in the resin composition described in Patent Document 3, the conventional resin composition has good developability when the film thickness is thin or when the developer concentration is high, but the film thickness is small. When it is thick or when the developer concentration is low, a residue is generated during development, which tends to cause development failure. Therefore, there has been a demand for a photosensitive resin composition having both developability and plating resistance when the film thickness is large or the developer concentration is low.

  This invention is made | formed in view of this point, and provides the photosensitive film which consists of a positive photosensitive resin composition which has favorable developability and favorable plating resistance, and a photosensitive resin composition. Objective.

  As a result of diligent study by the present inventors, a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, in accordance with an alkali-soluble resin and a compound having a quinonediazide structure as a photosensitive resin composition. , A nitrogen-containing heterocyclic compound having any structure selected from the group consisting of a quinoline structure and an isoquinoline structure, has been found to exhibit good developability and good plating resistance. . The present invention is as follows.

  The photosensitive resin composition of the present invention comprises an alkali-soluble resin, a compound having a quinonediazide structure, a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure. And a nitrogen-containing heterocyclic compound having at least one structure selected from the group consisting of:

  In the photosensitive resin composition of the present invention, the nitrogen-containing heterocyclic compound preferably has a pyrrole structure and / or a pyridine structure.

  In the photosensitive resin composition of the present invention, the nitrogen-containing heterocyclic compound has a pyridine structure, and at least one functional group selected from the group consisting of a carboxyl group and a functional group derived from a carboxyl group in the molecular structure. It is preferable to have.

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

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

（式（１）、（２）中、Ｒ_１、Ｒ_６は炭素数１〜炭素数５０の４価の有機基、Ｒ_２は炭素数１〜炭素数３０の２価の有機基、Ｒ_５は炭素数１〜炭素数８０の２価の有機基、Ｒ_３は炭素数１〜炭素数３０の１価の有機基、ｎは１以上３０以下の整数を表す。）

(In formulas (1) and (2), R ₁ and R ₆ are tetravalent organic groups having 1 to 50 carbon atoms, R ₂ is a divalent organic group having 1 to 30 carbon atoms, and R _5. Is a divalent organic group having 1 to 80 carbon atoms, R ₃ is a monovalent organic group having 1 to 30 carbon atoms, and n is an integer of 1 to 30.)

  In the photosensitive resin composition of this invention, it is preferable to contain a phosphorus compound.

  In the photosensitive resin composition of the present invention, the phosphorus compound is preferably a compound having a phosphate ester structure and / or a phosphazene structure.

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

  The photosensitive film of the present invention is obtained by heat-treating the photosensitive resin composition.

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

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

  The printed wiring board of the present invention comprises a base material having wiring, and a cover lay formed on the base material so as to cover the wiring and configured from the photosensitive film or the laminated film. Features.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive film which consists of positive photosensitive resin composition and photosensitive resin composition which has favorable developability and favorable plating tolerance can be provided.

  The photosensitive resin composition according to the present invention includes (A) an alkali-soluble resin, (B) a compound having a quinonediazide structure, (C) a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, And a nitrogen-containing heterocyclic compound having at least one structure selected from the group consisting of an indole structure, a quinoline structure, and an isoquinoline structure. Each component requirement will be specifically described below.

(A) Alkali-soluble resin 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 resins having a known alkali-soluble functional group such as a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group in the main chain and / or side chain. Among these, alkali-soluble polyamides such as alkali-soluble polyimides, polyimide precursors, and polybenzoxazole precursors are preferable from the viewpoint of heat resistance, and polyimide precursors are particularly preferable from the viewpoints of dry film formation and developability.

  From the viewpoint of developability, the polyimide precursor preferably has a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units.

（式（１）、（２）中、Ｒ_１、Ｒ_６は炭素数１〜炭素数５０の４価の有機基、Ｒ_２は炭素数１〜炭素数３０の２価の有機基、Ｒ_５は炭素数１〜炭素数８０の２価の有機基、Ｒ_３は炭素数１〜炭素数３０の１価の有機基、ｎは１以上３０以下の整数を表す。）

(In formulas (1) and (2), R ₁ and R ₆ are tetravalent organic groups having 1 to 50 carbon atoms, R ₂ is a divalent organic group having 1 to 30 carbon atoms, and R _5. Is a divalent organic group having 1 to 80 carbon atoms, R ₃ is a monovalent organic group having 1 to 30 carbon atoms, and n is an integer of 1 to 30.)

Among the general formulas (1) and (2), R ₁ and R ₆ are tetravalent organic groups having 1 to 30 carbon atoms, and R ₅ is a divalent organic group having 1 to 30 carbon atoms. An organic group is preferred.

  Moreover, as a polyimide precursor, from the viewpoint of developability, among the structures represented by the general formula (1) and the general formula (2), the following general formula (3) and / or the general formula (4) It is more preferable that the structure is represented.

（式（３）、（４）中、Ｒ_１、Ｒ_４、Ｒ_６は炭素数１〜炭素数５０の４価の有機基、Ｒ_２は炭素数１〜炭素数３０の２価の有機基、Ｒ_５は炭素数１〜炭素数８０の２価の有機基、Ｒ_３は炭素数１〜炭素数３０の１価の有機基、ｎは１以上３０以下の整数を表す。ｘ、ｙ、ｚは各単位のｍｏｌ％を表し、０＜ｘ＜１００、０＜ｙ＜１００、０＜ｚ＜１００、０．０５≦ｚ／（ｘ＋ｙ＋ｚ）≦０．９５を満たす。ａ、ｂ、ｃ、ｄは各単位のｍｏｌ％を表し、０＜ａ＜１００、０＜ｂ＜１００、０＜ｃ＜１００、０＜ｄ＜１００、０．０５≦（ｃ＋ｄ）／（ａ＋ｂ＋ｃ＋ｄ）≦０．９５を満たす。）

(In formulas (3) and (4), R ₁ , R ₄ and R ₆ are tetravalent organic groups having 1 to 50 carbon atoms, and R ₂ is a divalent organic group having 1 to 30 carbon atoms. , R ₅ is a divalent organic group having 1 to 80 carbon atoms, R ₃ is a monovalent organic group having 1 to 30 carbon atoms, and n is an integer of 1 to 30. x, y, z represents mol% of each unit, and satisfies 0 <x <100, 0 <y <100, 0 <z <100, 0.05 ≦ z / (x + y + z) ≦ 0.95, a, b, c, d represents mol% of each unit, and 0 <a <100, 0 <b <100, 0 <c <100, 0 <d <100, 0.05 ≦ (c + d) / (a + b + c + d) ≦ 0.95 Fulfill.)

Among the above general formulas (3) and (4), R ₁ , R ₄ and R ₆ are tetravalent organic groups having 1 to 30 carbon atoms, and R ₅ is 1 to 30 carbon atoms. The divalent organic group R ₃ is preferably a monovalent organic group having 1 to 30 carbon atoms.

  From the viewpoint of developability and storage stability, in the above general formula (3) and the above general formula (4), 0.1 ≦ z / (x + y + z) ≦ 0.9, 0.1 ≦ (c + d) / ( a + b + c + d) ≦ 0.9, 0 ≦ c / (c + d) ≦ 0.4, preferably 0.2 ≦ x / (x + y + z) ≦ 0.8, 0.2 ≦ (c + d) / (a + b + c + d) ≦ It is more preferable that 0.8 and 0.1 ≦ c / (c + d) ≦ 0.3.

Specifically, R ₁ , R ₄ , and R ₆ in the general formula (1) to the general formula (4) are respectively acid dianhydrides represented by the following general formula (5) to the following general formula (7). It is a tetravalent organic group derived from a product, and may be the same or different.

  Specific examples of the acid dianhydride represented by the general formula (5) to the general formula (7) include pyromellitic anhydride, oxydiphthalic dianhydride, 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 dianhydride, meta-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid 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 -Cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid Acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, ethylene glycol bis (trimellitic acid monoester acid anhydride) ( (Hereinafter abbreviated as TMEG), p-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid anhydride) Etc.

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

Further, from the viewpoint of developability, it is preferable that any one of R ₁ , R ₄ , and R _{6 in} the general formula (5) to the general formula (7) has an ester structure. As such acid dianhydrides, TMEG, p-phenylenebis (trimellitic acid monoester acid anhydride), pentanediol bis (trimellitic acid monoester acid anhydride), decanediol bis (trimellitic acid monoester acid) Anhydride).

R ₂ and R ₃ in the general formulas (1), (3), and (4) are organic groups derived from silicone diamine represented by the following general formula (8).

In the general formula (8), R ₃ represents an organic group having 1 to 30 carbon atoms, which may be the same or different. Examples of the organic group (R ₃ ) having 1 to 30 carbon atoms include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, a functional group including 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 the cyclic structure include monocyclic functional groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group; polycyclic functional groups such as norbornyl group and adamantyl group; benzene ring, naphthalene An aromatic hydrocarbon group containing an aromatic ring structure such as a ring, an anthracene ring, or a phenanthrene ring is exemplified.

The organic group (R ₃ ) having 1 to 30 carbon atoms may include a halogen atom, a hetero atom, and a metal atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Moreover, oxygen, sulfur, nitrogen, and phosphorus are mentioned as a hetero atom. Examples of the metal atom include silicon and titanium.

In the case where the organic group (R ₃ ) having 1 to 30 carbon atoms contains a hetero atom and / or a metal atom, R ₃ may be bonded directly to the hetero atom and / or the metal atom, It may be bonded via a metal atom.

  As a compound represented by the said General formula (8), silicone diamine (The Shin-Etsu Chemical Co., Ltd. make, PAM-E, KF-8010, X-22-161A, X-22-1660B-3) is mentioned, for example. .

In the general formula (8), the carbon number of R ₃ is preferably 1 or more and 20 or less from the viewpoint of flame retardancy. Furthermore, from the viewpoint of solvent solubility of the polyimide precursor to be produced, the number of carbon atoms of R ₃ is particularly preferably 1 or more and 10 or less.

  In the polyimide precursor according to the present invention, the solvent solubility means that the polyimide precursor is at least one selected from γ-butyrolactone, 1-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide. It means the property of dissolving in a solvent at a concentration of 5% by mass or more in a kind of organic solvent.

In the general formula (8), R ₂ is not limited as long as it is a divalent organic group having 1 to 30 carbon atoms. Among these, from the viewpoint of flame retardancy, divalents derived from aliphatic saturated hydrocarbons having 10 or less carbon atoms represented by CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , and the like. The organic group is preferred.

  N in the general formula (8) is not limited as long as it is an integer satisfying 1 or more and 30 or less. In this, 1 or more and 25 or less are preferable from a flame-retardant viewpoint, and 1 or more and 20 or less are especially preferable.

R ₅ in the general formula (2) and the general formula (3) is a divalent organic group derived from a diamine represented by the following general formula (9). It may be.

  Examples of such diamines include 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, and 1,4-diamino. Benzene, 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′-bi (4-aminophenyl) sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4′- Bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino -3-aminomethyl-3,5,5-trimethylcyclohexane, trimethylene-bis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis ( 4-aminobenzoate), N, N′-bis (4-aminophenyl) piperazine, 2- (4-aminophenyl) -6-aminobenzoxazole, 4,4′-diamino-3,3′-diethyl-5 , 5'-dimethyldiphenylmethane, 1,3-bis (4-aminophenoxy) adaman 1- (4-aminophenyl) -1,3,3-trimethyl-1H-indene-5-amine, 3,3′-diaminodiphenylsulfone, 2,2-bis {4- (4-aminophenoxy) Phenyl} propane, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, bis {4- (4-aminophenoxy) phenyl} sulfone, bis {4- (3-aminophenoxy) phenyl} Sulfone, 4,4′-diamino-2,2′-bis (trifluoromethyl) diphenyl ether, bis {4- (4-aminophenoxy) phenyl} ketone, 1,4-bis (4-aminophenoxy) -2, 3,5-trimethylbenzene, 1,4-bis (4-aminophenoxy) -2,5-t-butylbenzene, 1,4-bis {4-amino-2- ( Trifluoromethyl) phenoxy} benzene, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 4,4′-diamino-2- (trifluoromethyl) Diphenyl ether, 2,3′-diaminodiphenyl ether, bis (4-aminophenoxy) methane, 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexafluoropropane, 2,5-bis (4-aminophenoxy) -biphenyl, 1,3-bis (4-aminophenoxy) -5- (2-phenylethynyl) benzene, 1,3-bis (3-aminophenoxy) -5- (2-phenylethynyl) ) Benzene, 2,4-diamino-4′-phenylethynyldiphenyl ether, 4,4′-diamino-2,2 '-Dimethoxybiphenyl, 4,4'-diamino-2,2', 6,6'-tetrachlorobiphenyl, 4,4'-diamino-2,2'-dichlorobiphenyl, 4,4'-diamino-5, 5′-dimethoxy-2,2′-dichlorobiphenyl, 4,4′-bis (4-aminobenzamide) -3,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dichlorodiphenylmethane, N , N′-bis (4-aminophenyl) terephthalamide, 3,5-diaminobenzotrifluoride, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3 '-Dihydroxy-4,4'-diaminobiphenyl, 4,6-dihydroxy-1,3-phenylenediamine, 1,3-bis (4-amino-3-hydroxy) Phenoxy) benzene, 4-aminophenyl-3'-aminobenzoate and 3-amino-6-methyl-4'-amino benzoate. Among these, APB, 1,4-bis (3-aminophenoxy) benzene, 1,5-bis (4-aminophenoxy) pentane, 3,3 ′ from the viewpoint of Tg control and developability of the polyimide precursor -Diaminodiphenyl sulfone and 3,4'-diaminodiphenyl ether are preferred.

  In the present invention, the end of the main chain of the polyimide precursor is not particularly limited as long as it does not affect the performance. The terminal end of the main chain of the polyimide precursor may be an acid dianhydride or a terminal derived from a diamine used for producing the polyimide precursor, or the terminal of the main chain is sealed with another acid anhydride or an amine compound. May be.

  In the present invention, the polyimide precursor preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight of the polyimide precursor is preferably 1000 or more from the viewpoint of the strength of the polyimide film, and is preferably 1000000 or less from the viewpoint of the viscosity and moldability of the polyimide-containing resin composition. The weight average molecular weight of the polyimide precursor is more preferably from 5,000 to 500,000, further preferably from 10,000 to 300,000, and particularly preferably from 20,000 to 70,000 from the viewpoint of improving developability.

  The polyimide precursor according to the present invention is obtained by polymerizing and cyclizing the acid dianhydride represented by the general formula (5) and the silicone diamine represented by the general formula (8) in a non-equal molar amount. The diamine represented by the general formula (9) and / or the silicone diamine represented by the general formula (8) and the acid dianhydride represented by the general formulas (6) and (7) are polymerized. Can be obtained.

  The polyimide precursor having the polyimide structure represented by the general formula (1) and the polyamic acid structure represented by the general formula (2) as repeating units is a step of synthesizing the first stage polyamic acid (step 1), Subsequently, the first stage polyamic acid can be imidized (step 2), and then the second stage polyamic acid can be synthesized (step 3). Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first stage polyamic acid will be described. In this step, acid dianhydride and diamine are reacted in non-equal molar amounts to synthesize a first-stage polyamic acid. The method for synthesizing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, the first stage polyamic acid is obtained by the following method. First, diamine is dissolved and / or dispersed in a reaction solvent, acid dianhydride powder is added thereto, and the mixture is stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours using a mechanical stirrer. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less. By performing polymerization in this monomer concentration range, a polyamic acid solution can be obtained.

  The reaction solvent used in the synthesis of the polyamic acid includes dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and 2 or more and 9 or less carbon atoms. Ether compounds of: ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin Hydrocarbon compounds; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate an ester compound having 3 to 9 carbon atoms such as γ-butyrolactone and methyl benzoate; a halogen-containing compound having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, Nitrogen-containing compounds having 2 to 10 carbon atoms such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The reaction temperature in the synthesis of the first stage polyamic acid is preferably 100 ° C. or higher and 250 ° C. or lower from the viewpoint of the reactivity of the silicone diamine. If it is 100 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no influence of a side reaction. Preferably they are 120 degreeC or more and 220 degrees C or less, More preferably, they are 120 degreeC or more and 200 degrees C or less. The time required for the reaction of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, and particularly preferably in the range of 30 minutes to 30 hours.

(Process 2)
Next, the process for imidizing the first stage polyamic acid will be described. In this step, a known imidation catalyst is added to the first stage polyamic acid to perform imidization. In addition, the imidation catalyst is not necessarily required, and imidization can be performed even without a catalyst. The imidation catalyst is not particularly limited, but an acid anhydride such as acetic anhydride, a lactone compound such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid, And tertiary amines such as pyridine, quinoline, N-methylmorpholine and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

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

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

  Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. 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, decalin; benzene, toluene, xylene Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, benzoic acid Ester compounds having 3 to 9 carbon atoms such as chill; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other 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 ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The imidation 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)
Next, the process of synthesizing the second stage polyamic acid will be described. The method of synthesizing the second stage polyamic acid can be carried out in the same manner as the first stage polyamic acid.

  The reaction temperature during the synthesis of the polyamic acid in the second stage is preferably 0 ° C. or higher and 250 ° C. or lower, preferably 0 ° C. or higher and 100 ° C. or lower, and 0 ° C. or higher and 80 ° C. or lower from the viewpoint of the molecular weight of the resulting polyimide precursor. Particularly preferred. Recovery of the polyimide precursor after completion of production can be performed by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying a polyimide precursor according to the present invention include a method of removing insoluble acid dianhydride and diamine in a reaction solution by vacuum filtration, pressure filtration, or the like. Moreover, the purification method by what is called reprecipitation which adds a reaction solution to a poor solvent and precipitates can be implemented. Further, when a particularly high-purity polyimide precursor is required, purification by an extraction method using supercritical carbon dioxide is also possible.

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

  The solvent used for the resin composition containing the polyimide precursor according to the present invention is not particularly 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; carbons such as acetone and methyl ethyl ketone. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene, mesitylene Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as tetralin; esterification having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate and γ-butyrolactone Products; chlorine-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as 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.

  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. The concentration of the alkali-soluble resin is 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the alkali-soluble resin is 90% by mass or less from the uniformity of the film thickness of the resin molded body. preferable. Moreover, from the viewpoint of the film thickness of the resin molded body to be obtained, the concentration of the alkali-soluble resin is more preferably 2% by mass or more and 80% by mass or less.

(B) Compound having a quinonediazide structure The compound having a quinonediazide structure according to the present invention is not particularly limited as long as it has a quinonediazide structure in the molecular structure.

  Examples of the compound containing the 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-naphthoquino Diazide-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-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2 3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2 -1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as naphthoquinone diazide-5-sulfonic acid ester; 2,2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide- 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as 4-sulfonic acid ester, 2,2 ′, 3,4,6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester Class: 2, 3 ', 4, 4', 5 ', 6-hex Sahydroxybenzophenone-1,2-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-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as 1,2-naphthoquinone diazide-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-sulfone 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-sulfonic acid ester, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfone 1,2-naphtho of (polyhydroxyphenyl) alkanes such as acid esters, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate And quinonediazide sulfonic acid esters. From the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinone diazide sulfonic acid esters are preferable, 1,2-naphthoquinone diazide-4-sulfonic acid esters, and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Among these, a compound represented by the following general formula (10) (Q is a structure or a hydrogen atom represented by the following general formula (11)) is particularly preferable.

  In addition, in the Example mentioned later, the compound B as a compound which has a quinonediazide structure is a structure where 2.9 on average among three Q in the said General formula (10) is represented by the said General formula (11). It points to what is.

  The amount of the compound having a quinonediazide structure is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 30 parts by mass or less from the viewpoint of photosensitive contrast with respect to 100 parts by mass of the alkali-soluble resin. It is. If it is 1 mass part or more, since there exists a tendency for dissolution suppression of an unexposed part to be enough, it is preferable. If it is 50 mass parts or less, since the sensitivity at the time of exposure tends to be sufficiently high, it is preferable.

(C) Nitrogen-containing heterocyclic compound The nitrogen-containing heterocyclic compound in the present invention is at least selected from the group consisting of a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure. It is a nitrogen-containing heterocyclic compound having any one structure.

  Examples of the nitrogen-containing heterocyclic compound having a pyrrole structure include pyrrole, 2-pyrrolecarboxylic acid, 1-methyl-2-pyrrolecarboxylic acid, methyl 3-pyrrolecarboxylate, 3,4-dihydroxypyrrole-2,5-dicarboxylic acid. Examples include dimethyl. Examples of the nitrogen-containing heterocyclic compound having an isoxazole structure include isoxazole, 3,5-dimethylisoxazole, and 5-methylisoxazole-3-carboxylic acid. Examples of the nitrogen-containing heterocyclic compound having a thiazole structure include thiazole, 4,5-dimethylthiazole, 4-thiazolecarboxylic acid, 4-methyl-5-thiazolecarboxylic acid, ethyl 2,4-dimethylthiazole-5-carboxylate, and the like. Is mentioned. Examples of the nitrogen-containing heterocyclic compound having an isothiazole structure include isothiazole, 5-isothiazole carboxylic acid, and 3-hydroxyisothiazole-5-carboxylic acid. Examples of the nitrogen-containing heterocyclic compound having a pyridine structure include pyridine, 2,6-pyridinedimethanol, 2,3-dihydroxypyridine, picoline, picolinic acid, methyl picolinate, ethyl picolinate, nicotinic acid, methyl nicotinate, and nicotine. Examples include ethyl acid, 2,3-pyridinedicarboxylic acid, diethyl 2,3-pyridinedicarboxylate and the like. Examples of the nitrogen-containing heterocyclic compound having an indole structure include indole and 2-indolecarboxylic acid. Examples of the nitrogen-containing heterocyclic compound having a quinoline structure include quinoline, 2-quinolinecarbonitrile, 2-quinolinecarbaldehyde, 3-quinolinecarboxylic acid, 4-quinolinecarboxylic acid, 8-quinolinecarboxylic acid, and 2,4-quinolinediol. , 2-quinolinethiol, 4-quinolinol, 5-quinolinol and the like. Examples of the nitrogen-containing heterocyclic compound having an isoquinoline structure include isoquinoline, 1-isoquinolinecarbonitrile, isoquinoline-1-carboxylic acid, and 5-isoquinoline sulfonic acid.

  Among these, from the viewpoint of developability, a nitrogen-containing heterocyclic compound having a pyrrole structure and a nitrogen-containing heterocyclic compound having a pyridine structure are more preferable, and among the nitrogen-containing heterocyclic compounds having a pyridine structure, the molecular structure is also preferred. It preferably has at least one functional group selected from the group consisting of a carboxyl group and a functional group derived from a carboxyl group. Examples of the functional group derived from a carboxyl group in the present invention include an ester group, an amide group, a thioester group, and a functional group derived from an acid halide. Among these, from the viewpoint of developability, an ester group and an amide group are more preferable, and an ester group having 1 to 20 carbon atoms is particularly preferable.

  Of these, ethyl picolinate, ethyl nicotinate, and diethyl 3,4-pyridinedicarboxylate are particularly preferred from the viewpoints of developability and plating resistance. The nitrogen-containing heterocyclic compound may be one kind or a mixture of two or more kinds as necessary.

  In the present invention, a nitrogen-containing heterocyclic compound having at least one structure selected from the group consisting of a pyrrole structure, an isoxazole structure, a thiazole structure, an isothiazole structure, a pyridine structure, an indole structure, a quinoline structure, and an isoquinoline structure is favorable. Although it is not clear as to whether the plating resistance is developed while maintaining a good developability, the present inventors presume as follows. In general, the positive photosensitive resin composition tends to have low adhesion to the substrate, and soaking of the plating solution occurs. For this reason, nitrogen-containing heterocyclic compounds having two or more nitrogen atoms have been proposed for the purpose of improving adhesion, but conventional nitrogen-containing heterocyclic compounds also improve adhesion during development, so the film thickness is large. In some cases or when the developer concentration is low, there is a tendency for a residue to be formed, resulting in poor development. However, the nitrogen-containing heterocyclic compound according to the present invention exhibits good adhesion because no residue is produced during development even when the film thickness is large or the developer concentration is low, and the plating solution does not soak. It is estimated that plating resistance was developed while maintaining the properties. The case where the film thickness is thick in the present invention is a thickness that can completely cover a conductor such as a printed wiring board, and is 12 μm or more. The case where the concentration of the developer in the present invention is low is a weak alkaline aqueous solution, more specifically, an aqueous solution of sodium carbonate or potassium carbonate of 10% by mass or less.

  The addition amount of the nitrogen-containing heterocyclic compound is preferably 30 parts by mass or less and 0.1 parts by mass or more from the viewpoint of plating resistance with respect to 100 parts by mass of the (A) alkali-soluble resin. From the viewpoint of developability, 20 parts by mass or less is more preferable, and 10 parts by mass or less is more preferable. If it is 0.1 mass part or more, plating tolerance will become favorable.

(D) Phosphorus Compound The photosensitive resin composition according to the present invention may contain (D) a phosphorus compound. (D) Since a flame retardance tends to improve by containing a phosphorus compound, it is preferable to contain a phosphorus compound.

  The phosphorus compound is not limited as long as it is a compound containing a phosphorus atom in the structure. Among them, a phosphoric acid ester compound, a phosphazene compound and the like are preferably used.

  Examples of the phosphoric acid ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, phosphate ester having tris (2-ethylhexyl) phosphate as a substituent, tris (butoxyethyl) phosphate ( Aromatics such as phosphates, triphenyl phosphates, tricresyl phosphates, trixylenyl phosphates, resorcinol bis (diphenyl phosphates) having an aliphatic organic group containing an oxygen atom as a substituent, such as TBEP (hereinafter abbreviated as TBEP) Examples thereof include phosphate ester compounds having an organic group as a substituent. Among these, TBEP and triisobutyl phosphate are preferable from the viewpoint of developability.

  Examples of the phosphazene compound include structures represented by the following general formula (12) and the following general formula (13).

R ₇ , R ₈ , R ₉ , and R ₁₀ in the phosphazene compound represented by the general formula (12) and the general formula (13) are not limited as long as they are organic groups having 1 to 20 carbon atoms. . A carbon number of 1 or more is preferable because flame retardancy tends to be exhibited. A carbon number of 20 or less is preferred because it tends to be compatible with the polyimide precursor. 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. As such a functional group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-cyanophenyl Group, functional group having a phenyl group such as 3-cyanophenyl group and 4-cyanophenyl group, functional group having a naphthyl group such as 1-naphthyl group and 2-naphthyl group, pyridine, imidazole, triazole, tetrazole and the like. And functional groups derived from nitrogen heterocyclic compounds. These compounds may be used alone or in combination of two or more as required. Among these, a compound having a phenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group is preferable because of availability.

  V in the phosphazene compound represented by the general formula (12) is not limited as long as it is an integer of 3 to 25. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is particularly preferably 3 or more and 10 or less in view of availability.

  W in the phosphazene compound represented by the general formula (13) is not limited as long as it is an integer of 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

A and B in the phosphazene compound represented by the general formula (13) are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, A is _{-N = P (OC 6 H 5} ) 3, -N = P (OC 6 H 5) 2 (OC 6 H 4 OH), - N = P (OC 6 H 5) (OC 6 _{H 4 OH) 2, -N =} P (OC 6 H 4 OH) 3, -N = P (O) (OC 6 H 5), - N = P (O) (OC 6 H 4 OH) are preferred. B is _{-P (OC 6 H 5) 4} , -P (OC 6 H 5) 3 (OC 6 H 4 OH), - P (OC 6 H 5) 2 (OC 6 H 4 OH) 2, -P ( _{OC 6 H 5) (OC 6} H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 OH) _2, such as _{-P (O) (OC 6 H} 5) (OC 6 H 4 OH) are preferred. A phosphorus compound may be used alone or in combination of two or more.

  The addition amount of the phosphorus compound is preferably 50 parts by mass or less and 0.1 parts by mass or more from the viewpoint of photosensitivity with respect to 100 parts by mass of the polyimide precursor. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is preferable, and 40 parts by mass or less is more preferable. If it is 0.1 mass part or more, since a flame retardance will fully express, it is preferable.

(E) Solvent In the photosensitive resin composition of the present invention, a polyimide precursor, a compound having a quinonediazide structure, a heterocyclic compound containing one nitrogen atom, and / or a phosphorus compound are uniformly dissolved and / or as required. Alternatively, a solvent that can be dispersed can be included. As a solvent, the solvent used for the above-mentioned polyimide precursor resin composition can be used.

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

<Method for producing photosensitive film>
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 which concerns on this invention, it dries after apply | coating the solution of the photosensitive resin composition on arbitrary base materials by arbitrary methods, and a dry film For example, a laminated film having a carrier film and a photosensitive film is obtained.

  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 according to the present invention to a substrate having wiring so as to cover the wiring, performing alkali development, and baking.

  Examples of the substrate having wiring in the printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper-clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  The method for forming the printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. As such a forming method, a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating or the like in a state where the wiring side of the substrate having the wiring and the photosensitive film according to the present invention are in contact with each other. Etc. 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 at the time of laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can adhere to the substrate. From the viewpoint of adhesion to the substrate and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  The surface treatment of the substrate having the wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

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

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

  Subsequently, a printed wiring board is formed by baking the printed wiring board which pressure-bonded the photosensitive film which concerns on this invention. 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 performed 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, and particularly preferably in the range of 1 to 8 hours.

  The photosensitive resin composition according to the present invention has little warpage after curing, 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 semiconductor devices, insulation layer formation for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting boards, heat sinks, lead pins It is used for film formation on electronic parts for use in protection, insulation and adhesion of the semiconductor itself. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

(Example)
Next, examples performed for clarifying the effects of the present invention will be described. In addition, this invention is not restrict | limited at all by the following examples.

<Reagent>
In the following Examples and Comparative Examples, silicone diamine (trade name: KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.), TMEG (trade name: TMEG-100, manufactured by Shin Nippon Chemical Co., Ltd.), APB (Mitsui) are used as reagents. Chemicals, trade name: APB-N), compound B, TBEP (manufactured by Wako Pure Chemical Industries), phosphazene compound (trade name: FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd.), ethyl picolinate (manufactured by Aldrich) , Ethyl nicotinate (manufactured by Aldrich), diethyl 3,4-pyridinedicarboxylate (manufactured by Aldrich), 2-ethyl-4-methylimidazole (hereinafter abbreviated as 2E4MZ) (manufactured by Shikoku Kasei Kogyo Co., Ltd.), toluene ( Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (Wako Pure Chemical Industries), triethylene glycol dimethyl ether (Wako Pure Chemical) Co. Gosha), sodium carbonate (Wako Pure Chemical Industries, Ltd.), sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) is without performing any special purification, was used for the reaction.

<Weight average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the weight average molecular weight, was measured under the following conditions. Using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) as a solvent, 24.8 mmol / L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement) 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
A calibration curve for calculating the weight average 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 photosensitive resin composition was dropped onto an easily peelable PET film (Mitsubishi Chemical Polyester Film Co., Ltd., DIAFOIL, T100H25) and coated with a clearance of 150 μm. 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 2.0 MPa, and the press time was 1 minute.

<Pretreatment method of copper clad laminate>
As a pretreatment method of the copper clad laminate in the present invention, a sodium persulfate treatment (15% by mass or immersion in a sodium sulfate aqueous solution for 1 minute), followed by washing with water and drying at 50 ° C. was used.

<Curing body manufacturing method>
The method for producing a cured product is the method of laminating the photosensitive dry film produced by the above-mentioned coating method on the copper-clad laminate treated by the above-mentioned pretreatment method by the above-mentioned laminating method, and firing the furnace (manufactured by Koyo Lindberg) ) Was used to perform firing. 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 carried out using a photosensitive dry film (photosensitive layer thickness of about 25 μm) on a copper clad laminate under the above laminating conditions, and then using a positive mask to give an irradiation dose of 1.0 J / Exposure was performed at cm ² , followed by alkali development with an aqueous sodium carbonate solution and rinsing with water, and after drying, the pattern was evaluated with an optical microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. When the copper surface appears without any residue in the exposed area due to development and the film thickness of the photosensitive layer in the unexposed area is 20 μm or more, the case where the resolution is inferior or the film thickness is less than 20 μm It was.

<Measurement of warpage after firing>
The method for measuring warpage after firing was obtained by laminating the obtained photosensitive dry film on Kapton (registered trademark) under the above laminating conditions and then firing under the above calcining conditions. The film was cut into 5 cm squares, and those having a floating height of 10 mm or less at the end were marked with ◯, and those having a floating height above that were marked with ×.

<Electroless nickel plating resistance evaluation>
As plating resistance, electroless nickel plating resistance evaluation was performed. After laminating the photosensitive dry film produced by the above method on the copper clad laminate subjected to the above pretreatment method under the above laminating conditions, a 400 μm diameter circular pattern is formed under the above developing conditions, followed by baking. It was. Using the developed and fired samples, the nickel 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 is immersed in a 10% by mass 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: The coverlay was immersed in a 10% by mass sulfuric acid aqueous solution at room temperature for 30 seconds.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Pre-dip: The coverlay is immersed in a 10% by mass hydrochloric acid aqueous solution at room temperature for 30 seconds.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Activator: The coverlay is immersed in an activator solution (trade name: ICP Nicolon Axela manufactured by Okuno Pharmaceutical Co., Ltd.) at room temperature for 30 seconds.
Rinse: The coverlay is immersed in purified water at room temperature for 1 minute.
Nickel plating: The coverlay was immersed in a nickel plating solution (trade name: ICP Nicolon GM-M, ICP Nicolon GM-1 manufactured by Okuno Pharmaceutical Co., Ltd.) at 80 ° C. for 5 minutes.
Water washing: The coverlay is immersed in purified water at 30 ° C. for 1 minute.

[Example 1]
In a separable flask under a nitrogen atmosphere, γ-butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), silicone diamine (KF-8010, 19.54 mmol), TMEG-100 (40.00 mmol) was added, a Dean-Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 30 minutes. After removing toluene, which is an azeotropic solvent, the mixture was cooled to 25 ° C., silicone diamine (KF-8010, 4.89 mmol) and APB-N (15.56 mmol) were added, and the mixture was stirred at 25 ° C. for 5 hours. After stirring, a mixed solvent of γ-butyrolactone / triethylene glycol dimethyl ether was added so that the polymer solid content concentration was 30% by mass to obtain a solution of the polyimide precursor (1). The weight average molecular weight was 31600.

  Compound B (20 parts by mass), TBEP (10 parts by mass), and ethyl picolinate (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor (1) to prepare a photosensitive resin composition. The photosensitive resin composition thus obtained was coated on an easily peelable PET film by the above-described coating method and dried at 95 ° C. for 30 minutes to obtain a photosensitive dry film. The composition of the photosensitive resin composition is shown in Table 1 below.

The above photosensitive film was laminated on a copper clad laminate under the above-mentioned laminating conditions. The obtained laminate is exposed using a positive mask at an irradiation amount of 1.0 J / cm ² , followed by alkali development with a 1% by mass aqueous sodium carbonate solution (30 ° C.) and rinsing with water, After drying, the pattern was observed with an optical microscope. The copper surface appeared without residue in the exposed area, and the film thickness of the coverlay layer in the unexposed area was 20 μm or more, which was good. The evaluation results are shown in Table 2 below.

  The above photosensitive film was laminated on Kapton (registered trademark) under the above-mentioned laminating conditions, and the obtained film was baked under the above-mentioned baking conditions, and the film was cut into 5 cm square and the warpage was measured. The floating height of the end portion was within 10 mm and was ◯. The evaluation results are shown in Table 2 below.

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 1.0 J / cm ² using a positive mask, Subsequently, an alkali development treatment with a 1% by mass aqueous sodium carbonate solution (30 ° C.) and rinsing with water were performed to form a circular pattern with a diameter of 400 μm and firing was performed. The above-mentioned nickel plating resistance evaluation was performed on the coverlay. The plating solution soaked, peeled off, and swollen from the circular holes, and was good. The evaluation results are shown in Table 2 below.

[Example 2]
Compound 100 (20 parts by mass), TBEP (10 parts by mass), ethyl picolinate (1 part by mass), FP-100 (7 parts by mass) with respect to 100 parts by mass of the polyimide precursor (1) produced in Example 1 ) Was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated in the same manner as in Example 1 for alkali developability, warpage after firing, and nickel plating resistance. The composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

[Example 3]
Compound 100 (20 parts by mass), TBEP (10 parts by mass), ethyl nicotinate (1 part by mass), FP-100 (7 parts by mass) with respect to 100 parts by mass of the polyimide precursor (1) produced in Example 1 ) Was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated in the same manner as in Example 1 for alkali developability, warpage after firing, and nickel plating resistance. The composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

[Example 4]
Compound 100 (20 parts by mass), TBEP (10 parts by mass), diethyl 3,4-pyridinedicarboxylate (1 part by mass), FP- with respect to 100 parts by mass of the polyimide precursor (1) produced in Example 1 100 (7 mass parts) was mixed and the photosensitive resin composition was adjusted. The photosensitive resin composition was evaluated in the same manner as in Example 1 for alkali developability, warpage after firing, and nickel plating resistance. The composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

[Comparative Example 1]
Compound B (20 parts by mass), TBEP (10 parts by mass), and FP-100 (7 parts by mass) are mixed with 100 parts by mass of the polyimide precursor produced in Example 1 to prepare a photosensitive resin composition. did. The photosensitive resin composition was evaluated in the same manner as in Example 1 for alkali developability, warpage after firing, and nickel plating resistance. The composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

[Comparative Example 2]
Compound B (20 parts by mass) and TBEP (10 parts by mass), 2E4MZ (1 part by mass), and FP-100 (7 parts by mass) are mixed with 100 parts by mass of the polyimide precursor produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated in the same manner as in Example 1 for alkali developability, warpage after firing, and nickel plating resistance. The composition of the photosensitive resin composition is shown in Table 1 below, and the evaluation results are shown in Table 2 below.

  As shown in Table 2, in Examples 1 to 4, the developability is good and the nickel plating resistance is improved even when the film thickness is comparable, as compared with Comparative Example 1 and Comparative Example 2. Recognize. From the above, it can be seen that the photosensitive film made of the photosensitive resin composition of the present invention has nickel plating resistance, warpage, and good developability.

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

Claims (12)

  At least any one selected from the group consisting of an alkali-soluble resin, a compound having a quinonediazide structure, and a pyrrole structure, isoxazole structure, thiazole structure, isothiazole structure, pyridine structure, indole structure, quinoline structure, and isoquinoline structure And a nitrogen-containing heterocyclic compound having one structure.   The photosensitive resin composition according to claim 1, wherein the nitrogen-containing heterocyclic compound has a pyrrole structure and / or a pyridine structure.   The nitrogen-containing heterocyclic compound has a pyridine structure, and has at least one functional group selected from the group consisting of a carboxyl group and a functional group derived from a carboxyl group in a molecular structure. The photosensitive resin composition of Claim 2.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin is an alkali-soluble polyimide and / or a polyimide precursor. The alkali-soluble resin 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 repeating structural units, respectively. The photosensitive resin composition in any one of Claims 1-4.

(In formulas (1) and (2), R ₁ and R ₆ are tetravalent organic groups having 1 to 50 carbon atoms, R ₂ is a divalent organic group having 1 to 30 carbon atoms, and R _5. Is a divalent organic group having 1 to 80 carbon atoms, R ₃ is a monovalent organic group having 1 to 30 carbon atoms, and n is an integer of 1 to 30.)   The photosensitive resin composition according to claim 1, further comprising a phosphorus compound.   The photosensitive resin composition according to claim 6, wherein the phosphorus compound is a compound having a phosphate ester structure and / or a phosphazene structure.   A photosensitive film comprising the photosensitive resin composition according to claim 1.   A photosensitive film obtained by heat-treating the photosensitive resin composition according to claim 1.   A laminated film comprising: a carrier film; and the photosensitive film according to claim 9 provided on the carrier film.   The laminated film according to claim 10, further comprising a cover film formed on the photosensitive film.   It is formed on the base material so as to cover the wiring, and has a wiring film and the photosensitive film according to claim 8 or claim 9 or the laminated film according to claim 10 or claim 11. A printed wiring board comprising a coverlay.