JP2009269936A - Terminal-modified, alkali dissolvable polyimide and photosensitive resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a terminal-modified, alkali dissolvable polyimide having a good thermal stability and showing a good developing property, a positive type photosensitive composition containing the polyimide, and to provide a photosensitive film comprising the photosensitive resin composition. <P>SOLUTION: This alkali dissolvable polyimide has at least one functional group selected from a carboxyl group, an aromatic hydroxy group and a sulfonic group at the terminal of a polymer main chain. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

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

  When a general polyimide material is finely processed, an etching process using a photoresist is performed, which requires a large number of steps. Therefore, a photosensitive polyimide material that can directly form a pattern on the insulating layer polyimide itself has been attracting attention. In particular, there is a strong demand for a photosensitive resin composition that can be developed with an alkaline aqueous solution in consideration of safety during work and influence on the environment. In general, in the case of the negative type, the exposed portion is swollen by the developer, and it is difficult to perform high resolution fine processing. Therefore, fine processing by a positive type photosensitive system is strongly desired. In particular, an alkali-soluble polyimide that does not require a thermal process for imidization is strongly desired.

  In addition, conventional screen printing has problems such as a solvent removal process and double-sided processing, so that it is desired to form a photosensitive resin composition into a dry film from the viewpoint of an industrial process. ing.

In the positive photosensitive resin composition, the alkali solubility of the base polymer is extremely important for developability. Patent Document 1 discloses a polyimide having an alkali-soluble functional group introduced therein. Patent Document 2 discloses a photosensitive resin composition having an acidic group introduced at the end of a polymer main chain.
Japanese Patent Laid-Open No. 2007-100078 JP 2002-221794 A

  An object of the present invention is to provide an alkali-soluble polyimide having excellent thermal stability and developability, a photosensitive resin composition containing the polyimide, and a photosensitive film comprising the photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that an alkali having at least one functional group selected from the group consisting of a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group at the end of the polymer main chain. It has been found that a soluble polyimide solves the above-mentioned problems, and the present invention has been completed.

  The alkali-soluble polyimide of the present invention is characterized by having at least one functional group selected from the group consisting of a carboxyl group, an aromatic hydroxyl group and a sulfonic acid group at the terminal of the polymer main chain.

In the alkali-soluble polyimide of the present invention, the alkali-soluble polyimide is preferably represented by the following general formula (1). (In the formula, R ₁ and R ₃ represent a tetravalent organic group and may be the same or different. R _{4 and} R ₅ represent a hydrocarbon group having 1 to 30 carbon atoms. R ₂ Represents a divalent organic group having at least one alkali-soluble functional group, n satisfies 1 ≦ n ≦ 30, and x + y = 100 and 0.1 ≦ x / (x + y) ≦ 0.9. A and / or B is an organic group having at least one functional group selected from a carboxyl group, an aromatic hydroxyl group and a sulfonic acid group at the terminal.

  The photosensitive resin composition of this invention contains the said alkali-soluble polyimide and a photosensitive agent, It is characterized by the above-mentioned. In this case, it is preferable that the photosensitizer has a quinonediazide structure.

  In the photosensitive resin composition of this invention, it is preferable to contain a phosphorus compound. In this case, it is preferable that the phosphorus compound has a phosphate ester structure and / or a phosphazene structure.

  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. In this case, it is preferable to provide 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

  The alkali-soluble polyimide of the present invention has at least one functional group selected from the group consisting of a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group at the end of the polymer main chain. It is excellent.

The present invention will be specifically described below.
Polyimide precursors such as polyamic acid are known to have a significantly reduced molecular weight due to thermal history, and thermal stability can be improved by substantially imidizing the polyamic acid moiety. However, alkali solubility does not develop at the polyimide site. Thus, alkali solubility can be expressed by using a monomer having an alkali-soluble site. However, when the monomer having the alkali-soluble site is introduced into the polymer, Tg and elastic modulus tend to be improved. Yes, it tends to warp when forming a dry film. For this reason, in this invention, the functional group in this invention is introduce | transduced into the terminal, and alkali solubility is improved greatly, with curvature reduced when it was made into a dry film.

The terminal-modified alkali-soluble polyimide in the present invention is not limited as long as it has at least one functional group selected from the group consisting of a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group at the end of the polymer main chain. Among them, the alkali-soluble polyimide represented by the general formula (1) is preferable. (In the formula, R ₁ and R ₃ represent a tetravalent organic group and may be the same or different. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms. R ₂ is alkali-soluble. Represents a divalent organic group having at least one functional group, wherein x + y = 100 and 0.1 ≦ x / (x + y) ≦ 0.9, A and / or B is a carboxyl group at the end, aromatic An organic group having at least one functional group selected from a functional hydroxyl group and a sulfonic acid group.)

The terminal-modified alkali-soluble polyimide in the present invention includes a diamine having an acid dianhydride represented by the general formula (2) and the general formula (3) and an alkali-soluble functional group represented by the general formula (4), It is a polyimide obtained by polymerizing and cyclizing the silicone diamine represented by the formula (5).

R ₁ and R ₃ in the general formula (1) are tetravalent organic groups derived from acid dianhydrides represented by the general formulas (2) and (3), respectively, and are the same or different. May be.

  Specific examples of the acid dianhydrides represented by the general formulas (2) and (3) 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-tetracarboxylic acid Dianhydride, 1-carboxyme L-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5-dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydro Naphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, ethylene glycol bis (trimellitic acid monoester Acid anhydride) (hereinafter abbreviated as TMEG), p-phenylenebis (trimellitic acid monoester acid anhydride), and the like.

  Among these, from the viewpoint of low Tg of the obtained polyimide precursor, ODPA, TMEG, p-phenylenebis (trimellitic acid monoester anhydride), 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 Things are preferred.

R ₄ , R ₅ and n in the general formula (1) are an organic group derived from the silicone diamine represented by the general formula (5) and an integer satisfying 1 ≦ n ≦ 30.

In the general formula (5), R ₅ represents a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different.

Examples of the hydrocarbon group having 1 to 30 carbon atoms (R ₅ ) 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, A heterocyclic functional group having a thiophene, imidazole, oxazole, thiazole, tetrahydrofuran, dioxane structure; an aromatic hydrocarbon group containing a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring structure, and the like.

The hydrocarbon group having 1 to 30 carbon atoms (R ₅ ) 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, when the hydrocarbon group having 1 to 30 carbon atoms (R ₅ ) contains a hetero atom and / or a metal atom, even if R ₅ is directly bonded to the bonded hetero atom and / or metal atom, the hetero atom And / or may be bonded via a metal atom.

The carbon number of R _{5 in} the general formula (5) is preferably 1 or more and 20 or less in consideration of flame retardancy. From the viewpoint of solvent solubility of the polyimide to be produced, the number of carbon atoms 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, and N, N-dimethylacetamide. In the organic solvent, the property of being dissolved in the solvent at a concentration of 5% by weight or more.

R _{4 in the} general formula (5) 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 (5) 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 ₂ in the general formula (1) is a diamine having an alkali-soluble functional group represented by the general formula (4).

  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.

  The site derived from the diamine having an alkali-soluble functional group in the present invention is preferably 3% by weight or more and 50% by weight or less, assuming that the alkali-soluble polyimide is 100% by weight. If it is 3% by weight or more, sufficient alkali solubility tends to be exhibited, and if it is 50% by weight or less, warping during film tends to be sufficiently suppressed. 5 wt% or more and 30 wt% or less is more preferable, and 8 wt% or more and 20 wt% or less is particularly preferable.

  In the present invention, in addition to the diamine having an alkali-soluble functional group represented by the general formula (4) and the silicone diamine represented by the general formula (5), the performance of the obtained alkali-soluble polyimide is not adversely affected. In the range, other diamines can be included.

  Examples of such diamines include 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4- Diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4 4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4,4 ′ Diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-amino) Phenyl) 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) sulfone Enyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, and the like.

  Among these, APB is preferable from the viewpoint of low Tg of the polyimide precursor.

  The ratio of other diamines in the present invention is 10 mol% or less, assuming that all diamines are 100 mol%.

  A and / or B in the present invention is not limited as long as it is an organic group having at least one functional group selected from a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group at the terminal. Among these, a carboxyl group and an aromatic hydroxyl group are preferable from the viewpoint of developability.

  In the present invention, the alkali-soluble polyimide having a functional group selected from a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group is composed of a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group in the amine-terminated alkali-soluble polyimide and molecular structure. It can also be obtained by reacting with an acid anhydride having an acid anhydride or by reacting an alkali-soluble polyimide at the terminal of the acid anhydride with an amine compound having a carboxyl group, an aromatic hydroxyl group or a sulfonic acid group.

  Examples of the acid anhydride having a carboxyl group, an aromatic hydroxyl group, or a sulfonic acid group in the molecular structure include carboxyl group-containing acid anhydrides such as trimellitic acid anhydride.

  Examples of the amine compound having a carboxyl group, an aromatic hydroxyl group, or a sulfonic acid group in the molecular structure include 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid.

  About the introduction rate of the part derived from the functional group selected from a carboxyl group, an aromatic hydroxyl group, and a sulfonic acid group at the polymer main chain terminal, the obtained terminal alkali-soluble polyimide and / or polyimide precursor can be formed into a film. If it has a weight average molecular weight, it will not be limited. Among them, if it is 0.5 mol% or more, good developability is exhibited, and if it is 10 mol% or less, it has a weight average molecular weight that can be formed into a film. 1 mol% or more and 5 mol% or less are particularly preferable.

  The weight average molecular weight of the alkali-soluble polyimide and / or polyimide precursor of the present invention is preferably 5,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography using polystyrene having a known weight average molecular weight as a standard. The molecular weight is preferably 5000 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 8,000 to 500,000, particularly preferably from 10,000 to 300,000.

  Next, the method for producing an alkali-soluble polyimide according to the present invention will be described by taking as an example a method for synthesizing polyamic acid and then synthesizing an alkali-soluble polyimide.

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

  Next, a method for synthesizing a polyamic acid by reacting an acid dianhydride and a diamine will be described, followed by an example of a method of imidizing after adding a catalyst, and the production conditions of the polyimide according to the present invention explain.

  The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, acid dianhydride powder is gradually added thereto, and the mixture is stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours using a mechanical stirrer. In this case, the monomer concentration is 0.5 wt% or more and 95 wt% or less, preferably 1 wt% or more and 90 wt% or less. By performing polymerization in this monomer concentration range, a polyamic acid solution can be obtained.

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

  The reaction temperature in the production of the polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower in consideration of the reaction start and side reaction effects. The reaction temperature is preferably 15 ° C. or higher and 220 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower.

  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 the alkali-soluble polyimide according to the present invention by adding a catalyst to the polyamic acid (chemically) imidization will be described.

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

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

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

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

  In the production of the polyimide according to the present invention, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower in consideration of reaction initiation and catalyst activity. The reaction temperature is preferably 20 ° C. or higher and 220 ° C. or lower, more preferably 20 ° C. or higher and 200 ° C. or lower.

  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. Further, when a highly pure polyimide precursor is required, an extraction method by a carbon dioxide supercritical method is also possible.

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

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

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

  Examples of the photosensitive agent in the present invention include those whose structure changes due to light irradiation and whose solubility in a solvent changes. Examples of such compounds include compounds containing a quinonediazide structure, aromatic diazonium salt compounds, compounds having an azide structure, and the like. From the viewpoint of solubility contrast, a compound containing a quinonediazide structure is preferred.

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-4-sulfonic acid esters and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Of these, compound B-1 represented by formula (6) is particularly preferred.

  In the general formula (6), Q is a structure represented by the general formula (7) 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 (6) are represented by the general formula (7). 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 from the viewpoint of photosensitive contrast when the amount of the terminal-modified alkali-soluble polyimide according to the present invention is 100% by weight. % Or less, more preferably 5 wt% or more and 30 wt% or less. If it is 1% by weight or more, it is preferable because dissolution of the unexposed area tends to be sufficiently suppressed. Less than 50% by weight is preferable because the sensitivity tends to be sufficiently high.

  The phosphorus compound in the present invention is not limited as long as it is a compound containing a phosphorus atom in the structure. Examples of such compounds include phosphate ester compounds and phosphazene compounds.

  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 phosphate esters, triphenyl phosphates, tricresyl phosphates, trixylenyl phosphates, resorcinol bis (diphenyl phosphates) having an aliphatic organic group containing an oxygen atom as a substituent, such as TBXP. Examples thereof include phosphate ester compounds having an organic group as a substituent.

  Among these, TBXP and triisobutyl phosphate are preferable from the viewpoint of developability and warpage after curing.

Examples of the phosphazene compound include structures represented by general formula (8) and general formula (9).

R ₆ , R ₇ , R ₈ and R ₉ in the phosphazene compounds represented by the general formula (8) and the general formula (9) 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 polyimide. Among these, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable from the viewpoint of flame retardancy. Examples of such functional groups include phenyl groups such as a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group. And functional groups derived from nitrogen-containing heterocyclic compounds such as pyridine, imidazole, triazole, and tetrazole, and the like, and functional groups having a naphthyl group such as 1-naphthyl group and 2-naphthyl group. These compounds may be used alone or in combination of two or more as required. Among these, a compound having a phenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group is preferable because of availability.

  A in the phosphazene compound represented by the general formula (8) in the present invention is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, a is preferably 3 or more and 10 or less from the viewpoint of availability.

  In the phosphazene compound represented by the general formula (9) in the present invention, b is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

D and E in the phosphazene compound represented by the general formula (9) in the present invention are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, D is _{-N = P (OC 6 H 5} ) 3, -N = P (OC 6 H 5) 2, (OC 6 H 4 OH) 3, -N = P (OC 6 H 5) ( _{OC 6 H 4 OH) 2,} -N = P (OC 6 H 4 OH) 3, -N = P (O) OC 6 H 5, -N = P (O) (OC 6 H 4 OH) are preferred. E 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.

  The phosphorus compound in the present invention may be used alone or in combination of two or more.

  In the photosensitive resin composition according to the present invention, the addition amount of the phosphorus compound is preferably 50% by weight or less from the viewpoint of photosensitivity when the amount of the terminal-modified alkali-soluble polyimide is 100% by weight. From the viewpoint of flame retardancy of the cured product, it is preferably 45% by weight or less, more preferably 40% by weight or less.

  The photosensitive resin composition according to the present invention may contain a solvent capable of uniformly dissolving and / or dispersing the terminal-modified alkali-soluble polyimide, the photosensitive agent, and / or the phosphorus compound as necessary. As a solvent, the solvent used for the above-mentioned terminal-modified alkali-soluble 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 the terminal-modified alkali-soluble polyimide in the photosensitive resin composition is preferably 1% by weight or more and 90% by weight or less. The concentration of the terminal-modified alkali-soluble 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 copper-clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

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

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

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

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

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

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

  The terminal-modified alkali-soluble polyimide and the photosensitive resin composition according to the present invention exhibit good thermal stability, good developability, and chemical resistance when used as a cured product. Protective layer formation for printed wiring boards and circuit boards used for operation panels of various electronic devices, insulation layer formation for laminated substrates, silicon wafers used for semiconductor devices, semiconductor chips, members around semiconductor devices, semiconductor mounting It is used for film formation on electronic parts for use in protection, insulation and adhesion of industrial substrates, heat sinks, lead pins, semiconductors, etc. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

[Example]
<Reagent>
In Examples and Comparative Examples, silicone diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.), TMEG (manufactured by Shin Nippon Chemical Co., Ltd.), APB (Mitsui Chemicals) ), MBAA (manufactured by Wakayama Seika Co., Ltd.), Compound B-1, TBXP (manufactured by Daihachi Chemical Co., Ltd.), trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), toluene (manufactured by Wako Pure Chemical Industries, Ltd., organic synthesis) ), Γ-butyrolactone (made by Wako Pure Chemical Industries, special grade), triethylene glycol dimethyl ether (made by Wako Pure Chemical Industries), pyridine (made by Wako Pure Chemical Industries, for organic synthesis), γ-valerolactone (Wako Pure) Yakuhin Kogyo Co., Ltd., first grade) and sodium carbonate (Wako Pure Chemical Industries, Ltd.) were used for the reaction without any special purification.

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

  Moreover, the calibration curve for calculating the molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<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 150micrometer. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.

<Lamination conditions>
Lamination in the present invention was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 110 ° C., the press pressure was 2.0 MPa, and the press time was 2 minutes.

<Developability evaluation>
Evaluation of developability was carried out using a photosensitive dry film (photosensitive layer thickness of about 18 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. The time until the copper surface appeared in the exposed area was measured by development, and ○ for 120 seconds or less and x for longer development time.

<Thermal stability evaluation>
The thermal stability evaluation in the present invention is to manufacture polyimide by the above dry film manufacturing method, peel off the obtained dry film from the easily peelable PET film, measure GPC after dissolving in the above GPC measurement solvent, This was done by determining the rate of change from the molecular weight of the unheated polyimide.

[Example 1]
Under a nitrogen atmosphere, put MBAA (5.0 mmol), silicone diamine (KF-8010, 15.0 mmol), γ-butyrolactone (28.0 g), triethylene glycol dimethyl ether (12.0 g) into a separable flask, ODPA (21.3 mmol) was added and stirred at 80 ° C. for 2 hours. Subsequently, toluene (15.0 g), pyridine (11.8 mmol), and γ-valerolactone (7.5 mmol) were added, and a Dean-Stark apparatus and a reflux were attached, followed by heating and stirring at 180 ° C. for 2 hours. After cooling to 80 ° C., APB (3.0 mmol) and MBAA (5.0 mmol) were added, and after stirring for 10 minutes, trimellitic anhydride (1.6 mmol) and TMEG (6.2 mmol) were added. The mixture was stirred with heating at ° C for 2 hours. Subsequently, toluene (10.0 g) was added, and the mixture was heated and stirred at 180 ° C. for 1 hour. The solution of polyimide (1) was obtained by cooling to 140 ° C., adding γ-butyrolactone so that the polymer solid content concentration was 25% by weight, and cooling to room temperature. The weight average molecular weight was 38000.

  The thermal stability of the polyimide (1) was evaluated by the above-described thermal stability evaluation method. Table 1 shows.

  Compound B-1 (20% by weight) and TBXP (10% 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 above photosensitive film was laminated on a copper clad laminate under the above-mentioned laminating conditions. The resulting laminate is exposed using a positive mask at an irradiation dose of 1.0 J / cm ² , followed by alkali development with a 1 wt% aqueous sodium carbonate solution and rinsing with water, and after drying, a pattern is formed. Observed with an optical microscope. The results are shown in Table 2.

[Comparative Example 1]
Under a nitrogen atmosphere, put MBAA (5.0 mmol), silicone diamine (KF-8010, 15.0 mmol), γ-butyrolactone (28.0 g), triethylene glycol dimethyl ether (12.0 g) into a separable flask, ODPA (21.3 mmol) was added and stirred at 80 ° C. for 2 hours. Subsequently, toluene (15.0 g), pyridine (11.8 mmol), and γ-valerolactone (7.5 mmol) were added, and a Dean-Stark apparatus and a reflux were attached, followed by heating and stirring at 180 ° C. for 2 hours. After cooling to 80 ° C., APB (3.0 mmol) and MBAA (5.0 mmol) were added, and after stirring for 10 minutes, TMEG (7.6 mmol) was added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Subsequently, toluene (10.0 g) was added, and the mixture was heated and stirred at 180 ° C. for 1 hour. The solution was cooled to 140 ° C., γ-butyrolactone was added to a polymer solid content concentration of 25% by weight, and the solution was cooled to room temperature to obtain a polyimide solution. The weight average molecular weight was 39000. Thermal stability was evaluated in the same manner as in Example 1. Table 1 shows.

  Compound B-1 (20% by weight) and TBXP (10% by weight) were mixed with 100% by weight of polyimide to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
In a nitrogen atmosphere, a separable flask was charged with MBAA (10.0 mmol), silicone diamine (KF-8010, 15.0 mmol), APB (3.0 mmol), γ-butyrolactone (28.0 g), triethylene glycol dimethyl ether (12 0.0 g), ODPA (21.3 mmol), trimellitic anhydride (1.6 mmol) and TMEG (6.2 mmol) were added, followed by stirring at 80 ° C. for 8 hours. Γ-butyrolactone was added so that the polymer solid content concentration would be 25% by weight, and the solution was cooled to room temperature to obtain a polyamic acid solution. The weight average molecular weight was 35000. Thermal stability was evaluated in the same manner as in Example 1. Table 1 shows.

Compound B-1 (20% by weight) and TBXP (10% by weight) were mixed with 100% by weight of the polyamic acid to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability in the same manner as in Example 1.

  As shown in Tables 1 and 2, a photosensitive film having excellent thermal stability and developability can be obtained by using the terminal-modified alkali-soluble polyimide of the present invention. Moreover, by using the terminal-modified alkali-soluble polyimide of the present invention, the development time is greatly shortened, which is extremely useful industrially.

  The terminal-modified alkali solubility in the present invention, the photosensitive resin composition containing the polyimide exhibits good thermal stability as a photosensitive film and has good developability. Formation of protective layers on flexible wiring boards and circuit boards used for operation panels, etc., formation of insulating layers on laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks It is used for film formation on electronic components for use in protection, insulation and adhesion of lead pins, semiconductors, etc.

Claims (10)

  An alkali-soluble polyimide having at least one functional group selected from the group consisting of a carboxyl group, an aromatic hydroxyl group and a sulfonic acid group at the polymer main chain terminal. The alkali-soluble polyimide according to claim 1 is represented by the following general formula (1). (In the formula, R ₁ and R ₃ represent a tetravalent organic group and may be the same or different. R _{4 and} R ₅ represent a hydrocarbon group having 1 to 30 carbon atoms. R ₂ Represents a divalent organic group having at least one alkali-soluble functional group, n satisfies 1 ≦ n ≦ 30, and x + y = 100 and 0.1 ≦ x / (x + y) ≦ 0.9. A and / or B is an organic group having at least one functional group selected from a carboxyl group, an aromatic hydroxyl group and a sulfonic acid group at the terminal.

  A photosensitive resin composition comprising the alkali-soluble polyimide according to claim 1 and a photosensitive agent.   A photosensitive resin composition, wherein the photosensitive agent according to claim 3 has a quinonediazide structure.   The photosensitive resin composition according to claim 3, comprising a phosphorus compound.   6. The photosensitive resin composition, wherein the phosphorus compound according to claim 5 has a phosphate ester structure and / or a phosphazene structure.   A photosensitive film comprising the photosensitive resin composition according to claim 3.   A laminated film comprising: a carrier film; and the photosensitive film according to claim 7 provided on the carrier film.   The laminated film according to claim 8, further comprising a cover film formed on the photosensitive film.   A substrate having wiring, and a cover lay formed on the substrate so as to cover the wiring and made of the photosensitive film or laminated film according to any one of claims 7 to 9. A printed wiring board characterized by: