JP5139837B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition having a high residual film ratio and excellent residue removability, and suitable for a printed wiring board coverlay, 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 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.

  When warping occurs during the formation of a dry film, it becomes a problem from the viewpoint of an industrial process. In general, it is known that warping is reduced when a resin containing a siloxane structure is used.

  When a positive photosensitive resin composition is used, generally, if the development time is shortened in order to reduce the amount of film loss in the unexposed area, a development residue remains in the exposed area of the development pattern to be originally removed, which is favorable. I can't get a pattern. On the other hand, if the development time is lengthened, the amount of film loss in the unexposed areas increases, the shape of the development pattern is significantly deteriorated, and the performance cannot be exhibited sufficiently. Furthermore, the alkali-soluble polyimide containing a siloxane structure has a problem that a development residue tends to remain.

  A photosensitive resin composition containing a phenol compound is disclosed for the above problems (Patent Documents 1 and 2). The photosensitive resin composition uses a polybenzoxazole precursor as a resin, uses an organic amine aqueous solution as a developer, and does not disclose any alkali-soluble polyimide. Moreover, this composition is an indication at the time of using with a varnish, and there is no disclosure about a dry film.

  On the other hand, a photosensitive resin composition containing an acidic compound such as acetic acid is disclosed (Patent Document 3). The resin composition is disclosure regarding storage stability and stable photosensitive properties, and there is no disclosure regarding development residue and the like. In addition, since a volatile compound such as acetic acid is used, there is a problem that the effect cannot be sufficiently exhibited when a dry film is formed.

As described above, in the dry film-shaped siloxane-containing alkali-soluble polyimide, it was difficult to remove the development residue while maintaining a high residual film ratio during development.
JP 2000-292913 A JP 2006-276094 A JP 2000-338664 A

  The present invention has been made in view of such points, and in a dry film shape, a positive photosensitive resin composition having a high residual film ratio and excellent residue removability, and a photosensitive film comprising the photosensitive resin composition The purpose is to provide.

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble polyimide containing 10% by weight or more of a siloxane structure, (B) a photosensitive agent having a quinonediazide structure, and (C) an acid dissociation constant (pKa at 25 ° C.). ) is Ri der 6 to 14, characterized in that it contains a compound containing an aromatic hydroxyl group.

  In the photosensitive resin composition of the present invention, the acid dissociation constant (pKa) of the compound (C) is preferably 8 or more and 12 or less.

In the photosensitive resin composition of this invention, it is preferable that the said compound (C) contains one aromatic hydroxyl group.

  In the photosensitive resin composition of this invention, it is preferable to contain (D) plasticizer. In this case, the plasticizer (D) is preferably a phosphate ester.

  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 on the photosensitive film.

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

  According to the photosensitive resin composition of the present invention, (A) an alkali-soluble polyimide containing 10% by weight or more of a siloxane structure, (B) a photosensitive agent having a quinonediazide structure, and (C) an acid dissociation constant at 25 ° C. (PKa) of 6 or more and 14 or less, a film having excellent resolution and residue removability while maintaining a high residual film ratio, and good warping of a dry film and good press-bonding property to a substrate, etc. Can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
First, (A) alkali-soluble polyimide will be described.
(A) Specific examples of acid dianhydrides used in alkali-soluble polyimides 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-cyclohexanetetra Carboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic 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, ODPA, TMEG, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran) from the viewpoint of the solvent solubility of polyimide and the pressure-bonding property to a substrate and the like. -3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydrides are preferred. Here, the solvent solubility means that polyimide has a property of being dissolved in a known organic solvent at a concentration of 5% by weight or more.

  (A) Examples of the diamine used in the alkali-soluble polyimide include diamines having an alkali-soluble functional group and other diamines.

  Next, the diamine having an alkali-soluble functional group 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. In the present invention, the aromatic hydroxyl group is a functional group derived from a compound in which the hydroxyl group is directly bonded to the aromatic ring. Specific examples include functional groups derived from compounds in which a hydroxyl group is directly bonded to a benzene ring, such as phenol, catechol, resorcinol, hydroquinone, 1-naphthol, and 2-naphthol.

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

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

  Other diamines include 1, n-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4. '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis ( Trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'- Bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-amino) Phenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4- Aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene (hereinafter abbreviated as APB), 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, and 1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane.

(A) The alkali-soluble polyimide containing 10% by weight or more of siloxane structure is not limited as long as it is a compound containing a siloxane structure. Among them, a siloxane structure derived from the silicone diamine represented by the general formula (1) is preferable.

  The structure of the said silicone diamine will not be limited if it is the structure of the said General formula (1). In the general formula (1), R represents a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. a represents an integer of 1 to 10, and b represents an integer of 1 to 20.

  Examples of the hydrocarbon group (R) having 1 to 20 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 a primary hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, a secondary hydrocarbon group such as an isobutyl group and an 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, or a phenanthrene ring structure.

  The hydrocarbon group (R) having 1 to 20 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. The metal atom in the present invention includes silicon and titanium.

  In addition, when the hydrocarbon group (R) having 1 to 20 carbon atoms contains a hetero atom and / or a metal atom, even if R is directly bonded to the bonded hetero atom and / or metal atom, the hetero atom and / or Alternatively, they may be bonded via a metal atom.

  The carbon number of R in the general formula (1) is preferably 1 or more and 20 or less in consideration of flame retardancy. From the viewpoint of the solubility of the polyimide to be produced, the number of carbon atoms is particularly preferably 1 or more and 10 or less.

  (A) In the alkali-soluble polyimide, solvent solubility means that the polyimide is at least one organic compound selected from γ-butyrolactone, 1-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. It means the property of being dissolved in a solvent at a concentration of 5% by weight or more.

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

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

  (A) Content of the siloxane structure in alkali-soluble polyimide will not be limited if it is 10 weight% or more. From the viewpoint of warpage and flame retardancy when formed into a dry film, it preferably has a siloxane structure of 10% by weight to 90% by weight, and more preferably 20% by weight to 80% by weight. In this case, the weight percent of the siloxane structure represents the weight percent of the alkali-soluble polyimide.

  (A) The terminal of alkali-soluble polyimide will not be specifically limited if it is a structure which does not affect performance. The terminal may be derived from an acid dianhydride or diamine used for producing a polyimide (precursor), or the terminal may be sealed with another acid anhydride, an amine compound or the like.

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

  Next, (A) the method for producing an alkali-soluble polyimide will be described by taking as an example a method for synthesizing polyamic acid and then synthesizing an alkali-soluble polyimide.

  A polyimide can be obtained by reacting an acid dianhydride and a diamine to synthesize a polyamic acid and then heating (heating imidization). It can also be obtained by reacting acid dianhydride and 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 polyamic acid by reacting acid dianhydride and diamine will be described, followed by an example of a method of imidizing after adding a catalyst, and (A) Production conditions of alkali-soluble polyimide Will be described.

  The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved 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, decalin; benzene, toluene, xylene, mesitylene, tetralin Aromatic hydrocarbon compounds having 6 to 10 carbon atoms; ester compounds having 3 to 6 carbon atoms such as methyl acetate, ethyl acetate, and γ-butyrolactone; chloroform, methylene chloride, 1,2-di Halogen-containing compounds having 1 to 10 carbon atoms such as loroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Compound; Sulfur-containing compounds such as dimethyl sulfoxide are exemplified. These may be one kind or a mixture of two or more kinds as necessary. Particularly preferable solvents include ester compounds having 3 to 6 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and nitrogen-containing compounds having 2 to 10 carbon atoms.

  These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

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

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

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

  (A) The imidization catalyst for producing the alkali-soluble polyimide is not particularly limited, but an acid anhydride such as acetic anhydride, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ- Examples thereof include lactone compounds such as coumarin and γ-phthalic acid, 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 is particularly preferable from the viewpoint of high reactivity.

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

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

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

  These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  (A) In the production of the alkali-soluble polyimide, the reaction temperature is preferably 15 ° C. or higher and 250 ° C. or lower. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

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

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

  (A) As a purification method of alkali-soluble polyimide, a method of removing insoluble acid dianhydride and diamine in the reaction solution by filtration under reduced pressure, pressure filtration or the like can be mentioned. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Furthermore, when a particularly high-purity polyimide is required, an extraction method using a carbon dioxide supercritical method is also possible.

  (A) A resin composition comprising an alkali-soluble polyimide and a solvent in which the polyimide can be uniformly dissolved and / or dispersed can be obtained.

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

  (A) The density | concentration of the (A) alkali-soluble polyimide in the resin composition containing an alkali-soluble polyimide and a solvent will not be restrict | limited especially if a resin molding is manufactured. The polyimide concentration is preferably 1% by weight or more from the viewpoint of the film thickness of the resin molded body to be produced, and the polyimide concentration 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.

  (B) The photosensitizer which has a quinonediazide structure will not be limited if it is a compound containing a quinonediazide structure.

Examples of the compound having a quinonediazide structure include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2-naphthoquinonediazidesulfonic acid. Amides are mentioned. 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, 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, B-1 or B-2 represented by the general formula (3) is particularly preferable.

  In the general formula (2), Q is a structure or a hydrogen atom represented by the general formula (3) or the general formula (4). As a photosensitive agent in the photosensitive resin composition according to the present invention, compound B-1 has a structure in which an average of 2.34 of the three Qs in the general formula (2) is represented by the general formula (3). It points to what is. Compound B-2 refers to one having an average of 2.3 of the three Qs in the general formula (2) having a structure represented by the general formula (4).

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

  (C) The compound having an acid dissociation constant (pKa) at 25 ° C. of 6 or more and 14 or less is not limited as long as the acid dissociation constant (pKa) at 25 ° C. is 6 or more and 14 or less. From the viewpoint of reducing the film thickness of the unexposed area, the acid dissociation constant (pKa) at 25 ° C. is preferably 8 or more and 12 or less. Examples of such a compound include aromatic hydroxyl group-containing compounds such as phenol and naphthol, benzenethiol compounds such as thiophenol, and compounds having a heterocyclic moiety such as 3-hydroxypyridine. Among these, an aromatic hydroxyl group-containing compound is preferable from the viewpoint of reducing the film thickness of the unexposed area.

  Examples of the aromatic hydroxyl group-containing compound include compounds containing 1 to 3 aromatic hydroxyl groups. Compounds containing one aromatic hydroxyl group include phenol, 1-naphthol, 2-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5 -Xylenol, 3,4-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 2-tert-butylphenol, 3- compounds having an aliphatic hydrocarbon group such as tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, cyclohexylphenol; -Benzylphenol, 4-benzylphenol Compounds having an aromatic hydrocarbon group such as alcohol, p-cumylphenol (hereinafter abbreviated as PCP); o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxy Examples thereof include compounds having an alkoxy group such as phenol, p-ethoxyphenol, o-propoxyphenol, m-propoxyphenol, and p-propoxyphenol. Examples of the compound containing two aromatic hydroxyl groups include resorcinol, hydroquinone, 4-ethylresorcinol, naphthoresorcinol, dihydroxybiphenyl, bisphenol A, and bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as BPS). Examples of the compound containing three aromatic hydroxyl groups include pyrogallol, 5-t-butyl pyrogallol, 4,4 ', 4 "-methylidynetrisphenol, etc. Among these, film reduction in unexposed areas. In view of the above, a compound having one aromatic hydroxyl group is particularly preferable.

  Among compounds having one aromatic hydroxyl group, a compound having an aliphatic hydrocarbon group, a compound having an aromatic hydrocarbon group, and the like tend to improve the warp of a dry film from which the compound is obtained, and thus this is particularly preferable. Among them, PCP and 4-benzylphenol are more preferable from the viewpoint of residue removability. The amount of (C) added in the present invention is preferably 0.01% by weight to 50% by weight. From the standpoint of residue removability and the remaining film ratio after development, 0.1 wt% or more and 20 wt% or less are more preferable. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed.

  The photosensitive resin composition comprises (A) an alkali-soluble resin containing 10% by weight or more of a siloxane structure, (B) a photosensitive agent, and (C) an acid dissociation constant (pKa) at 25 ° C. of 6 or more and 14 or less. It is preferable that a certain compound further contains (D) a plasticizer. (D) By containing a plasticizer, since Tg of a composition falls, since it exists in the tendency for the curvature at the time of dry film formation to reduce, it is preferable.

  The (D) plasticizer is not particularly limited as long as it imparts plasticity to the resin composition and can lower the Tg of the composition. Examples of such plasticizers include phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate (hereinafter abbreviated as TBXP); Ether compounds such as polyethylene glycol, polypropylene glycol and crown ether; methacryl group-containing compounds such as tetraethylene glycol dimethacrylate and polyethylene glycol dimethacrylate; acrylic group-containing compounds such as tetraethylene glycol diacrylate and polyethylene glycol diacrylate; dimethyl phthalate; Phthalic acid esters such as diethyl phthalate; Trimellitic acid esters such as tris (2-ethylhexyl) trimellitate ; Dimethyl adipate, aliphatic dibasic acid esters such as dibutyl adipate; isocyanuric acid ethylene glycol-modified triacrylate, etc. ε- caprolactone-modified tris (acryloyloxyethyl) isocyanurate. Of these, phosphoric acid esters, methacrylic group-containing compounds, isocyanuric acid ethylene glycol-modified triacrylate, and ε-caprolactone-modified tris (acryloxyethyl) isocyanurate are preferred from the viewpoint of warping after forming into a dry film.

  In consideration of sufficient plasticity, the amount of the plasticizer added is preferably 50% by weight or less when the amount of the (A) alkali-soluble resin is 100% by weight. Moreover, 20 weight% or less is more preferable from a flame-retardant viewpoint of a hardening body.

  If necessary, (A) alkali-soluble polyimide containing 10% by weight or more of siloxane structure, (B) photosensitive agent, and (C) acid dissociation constant (pKa) at 25 ° C. of 6 or more as required. A solvent capable of uniformly dissolving and / or dispersing the following compounds can be added. As a solvent, the solvent used for the above-mentioned polyimide resin composition can be used.

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

Next, the manufacturing method of a photosensitive film is demonstrated.
First, the photosensitive resin composition is coated on a substrate. 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 said photosensitive resin composition, the solution of the photosensitive resin composition is apply | coated on arbitrary base materials by arbitrary methods, and it is made into 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 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 according to the present invention include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a polyimide film. Among these, a flexible substrate is preferable from the viewpoint of bendability.

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

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

  After the light irradiation, the photosensitive film can be subjected to positive photolithography by dissolving the light irradiation site by alkali development. 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.

  Next, the printed wiring board is formed by baking the printed wiring board to which the photosensitive film is pressure-bonded. Firing is preferably performed at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoint of solvent removal, side reaction, decomposition, or the like. More preferably, it is 100 degreeC or more and 300 degrees C or less.

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

  Since the photosensitive resin composition has a high residual film ratio and good developability, in the electronics field, it forms a protective layer for printed wiring boards and circuit boards used for operation panels of various electronic devices, Insulating layer formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors themselves, etc. to electronic parts for use in protection and insulation and adhesion Used for film formation. Such protective films and insulating films are collectively referred to as a coverlay.

Next, examples for clarifying the effects of the present invention will be described.
<Reagent>
In Examples and Comparative Examples, silicone diamine (KF-8010) (manufactured by Shin-Etsu Chemical Co., Ltd.), MBAA (manufactured by Wakayama Seika Co., Ltd.), ODPA (manufactured by Wako Pure Chemical Industries, Ltd.), APB (Mitsui Chemicals) are used reagents. ), TMEG (manufactured by Shin Nippon Chemical Co., Ltd.), Compound B-1, Compound B-2, TBXP (manufactured by Daihachi Chemical Co., Ltd.), toluene (manufactured by Wako Pure Chemical Industries, Ltd., for organic synthesis), γ-butyrolactone ( Wako Pure Chemical Industries, special grade), pyridine (Wako Pure Chemical Industries, for organic synthesis), γ-valerolactone (Wako Pure Chemical Industries, first grade), PCP (Wako Pure Chemical Industries, special grade) , Isophthalic acid (manufactured by Wako Pure Chemical Industries, first grade), 4-benzylphenol, 1,1-diphenylpropane (manufactured by Wako Pure Chemical Industries, Ltd.), BPS (manufactured by Tokyo Chemical Industry Co., Ltd.) are subjected to special purification. Used in the reaction.

<Number average molecular weight measurement>
Gel permeation chromatography (GPC), which is a method for measuring the number average molecular weight, was measured under the following conditions. N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) was used as a solvent, and 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement). 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
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 of 100 micrometers. The coated film was dried at 95 ° C. for 30 minutes using a dryer (manufactured by ESPEC, SPH-201) 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 3.7 MPa, and the press time was 1 minute.

<Developability evaluation>
For evaluation of developability, a photosensitive dry film (thickness of photosensitive layer: about 14 μm) was laminated on a copper-clad laminate under the above-mentioned laminating conditions, and then a dose of 800 mJ / cm ² using a positive mask. Then, an alkaline development treatment with a 1% aqueous sodium hydroxide solution and rinsing with water were performed, and after drying, the pattern was evaluated with an optical microscope and a scanning electron microscope. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. By development, the copper surface appears in the exposed area and the remaining film ratio of the photosensitive layer in the unexposed area is 90% or more, and the case where it is 60% or more and less than 90% is evaluated as ◯. When it was inferior or the remaining film rate was less than 60%, it was set as x.

<Evaluation of warpage>
The evaluation of the warp of the dry film was performed by cutting the dry film into 5 cm squares and measuring the lift of the edge. Here, the warp of the dry film is good when the end float is 10 mm or less.

Example 1
Under a nitrogen atmosphere, silicone diamine (KF-8010, 45.0 mmol) and γ-butyrolactone (120 mL) were added to a separable flask, followed by ODPA (60.0 mmol), and the mixture was stirred at 80 ° C. for 2 hours. Subsequently, toluene (60 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and a Dean Stark apparatus and a reflux were attached, and the mixture was heated and stirred at 180 ° C. for 2 hours. After cooling to 80 ° C., APB (9.0 mmol) and MBAA (30 mmol) were added, and after stirring for 10 minutes, TMEG (25.8 mmol) was added, and the mixture was heated and stirred at 80 ° C. for 2 hours. Subsequently, toluene (15 mL) was added, and the mixture was stirred with heating at 180 ° C. for 2 hours. The mixture was cooled to 80 ° C., γ-butyrolactone was added so that the polymer solid content concentration was 30% by weight, and the mixture was cooled to room temperature to obtain a γ-butyrolactone solution of polyimide (1). The number average molecular weight of the polyimide (1) was 26600, and the content of the siloxane structure was 43% by weight.

  As shown in Table 1 below, with respect to 100% by weight of polyimide (1), compound B-1 (20% by weight), TBXP (10% by weight), PCP (3% by weight, pKa = 10.7) The mixture was mixed 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 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 exposure dose of 800 mJ / cm ² , followed by alkali development with a 1% aqueous sodium hydroxide solution and rinsing with water. And observed with a scanning electron microscope. A copper surface appeared in the exposed area of each dry film, and the remaining film ratio of the coverlay layer in the unexposed area was 90% or more. There was no development residue, and the warp of the dry film was 2 mm. The results are shown in Table 2 below.

(Example 2)
Compound B-2 (20 wt%), TBXP (10 wt%), PCP (3 wt%, pKa = 10.7) are mixed with 100 wt% of the polyimide (1) produced in Example 1, A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Example 3)
Compound B-1 (20% by weight), TBXP (10% by weight), 4-benzylphenol (3% by weight, pKa = 10.5) with respect to 100% by weight of the polyimide (1) produced in Example 1. The mixture was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

Example 4
Compound B-2 (20% by weight), TBXP (10% by weight), 4-benzylphenol (3% by weight, pKa = 10.5) with respect to 100% by weight of the polyimide (1) produced in Example 1 The mixture was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Example 5)
Compound B-1 (20 wt%), TBXP (10 wt%), BPS (3 wt%, pKa = 7.8) are mixed with 100 wt% of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Example 6)
Compound B-2 (20 wt%), TBXP (10 wt%), BPS (3 wt%, pKa = 7.8) were mixed with 100 wt% of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

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

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

(Comparative Example 3)
Compound B-1 (20% by weight), TBXP (10% by weight), isophthalic acid (3% by weight, pKa = 3.5) were mixed with 100% by weight of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Comparative Example 4)
Compound B-2 (20 wt%), TBXP (10 wt%), isophthalic acid (3 wt%, pKa = 3.5) were mixed with 100 wt% of the polyimide (1) produced in Example 1. A photosensitive resin composition was prepared. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Comparative Example 5)
Compound B-1 (20 wt%), TBXP (10 wt%), 1,1-diphenylpropane (3 wt%, pKa >> 14) with respect to 100 wt% of the polyimide (1) produced in Example 1 The mixture was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

(Comparative Example 6)
Compound B-2 (20 wt%), TBXP (10 wt%), 1,1-diphenylpropane (3 wt%, pKa >> 14) with respect to 100 wt% of the polyimide (1) produced in Example 1 The mixture was mixed to prepare a photosensitive resin composition. The photosensitive resin composition was evaluated for alkali developability and dry film warpage in the same manner as in Example 1. The results are shown in Table 2 below.

  As can be seen from Table 2, (C) a photosensitive film composed of a photosensitive resin composition to which a compound having an acid dissociation constant (pKa) at 25 ° C. of 6 to 14 is added (from Example 1). In Example 6), as compared with the photosensitive films constructed with the photosensitive resin composition not added (Comparative Example 1 and Comparative Example 2), the residue removability during development while maintaining a high residual film rate, Dry film warpage has been improved. Moreover, in the photosensitive film (Comparative Example 3 and Comparative Example 4) constructed by the photosensitive resin composition to which a compound having an acid dissociation constant (pKa) at 25 ° C. of less than 6 is added, the remaining film ratio may be decreased. I understand. Furthermore, in the photosensitive films (Comparative Example 5 and Comparative Example 6) composed of the photosensitive resin composition to which a compound having an acid dissociation constant (pKa) at 25 ° C. of greater than 14 was added, the effect of removing the development residue was observed. I can't. From the above, the photosensitive film composed of the photosensitive resin composition added with the compound having an acid dissociation constant (pKa) at 25 ° C. of 6 or more and 14 or less of the present invention maintains a high residual film ratio. The residue removability was improved, and the warp of the dry film was also good.

  The present invention is not limited to the embodiment described above, and can be implemented with various modifications. In the above embodiment, the numerical values, materials, and processing methods in the above description can be appropriately changed and implemented without departing from the scope of the present invention. Other modifications can be made without departing from the scope of the present invention.

  The photosensitive resin composition according to the present invention is a flexible wiring used as an operation panel of various electronic devices in the electronics field because it has a high residual film ratio, excellent residue removability, and good warpage as a photosensitive film. Protection of board and circuit board protection 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 It is used for film formation on electronic parts for use in insulation and adhesion.

Claims (9)

And alkali solubility polyimide (A) a siloxane structure containing more than 10 wt% state, and are a photosensitive agent, (C) an acid dissociation constant at 25 ° C. (pKa) of 6 to 14 with (B) a quinonediazide structure, A photosensitive resin composition comprising a compound containing an aromatic hydroxyl group .   The photosensitive resin composition according to claim 1, wherein the acid dissociation constant (pKa) of the compound (C) is 8 or more and 12 or less. The compound (C) according to claim 1 or claim 2 photosensitive resin composition according to characterized in that it contains one aromatic hydroxyl group. (D) The photosensitive resin composition in any one of Claims 1-3 containing a plasticizer. The photosensitive resin composition according to claim 4, wherein the plasticizer (D) is a phosphate ester. Photosensitive film, characterized in that they are composed of a photosensitive resin composition as claimed in any one of claims 5. A laminated film comprising: a carrier film; and the photosensitive film according to claim 6 provided on the carrier film. The laminated film according to claim 7 , further comprising a cover film 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 6 to 8. A printed wiring board characterized by: