TW200839442A - Photosensitive resin composition, and flexible print circuit board using the same - Google Patents

Abstract

Disclosed is a photosensitive resin composition comprising components (A), (B) and (C), wherein the component (A) is an alkali-soluble resin, the component (B) is at least one compound selected from the group consisting of a compound having a structure represented by the formula (1), a compound having an isocyanurate ring and an imide compound having one or two imide groups which is different from the compound of the component (A), and the component (C) is a quinonediazide compound. P=X (1) wherein P represents a phosphorus atom, wherein the number of covalent bonds is 5; X represents a nitrogen atom or an oxygen atom, wherein the number of covalent bonds is 3 when X represents a nitrogen atom, the number of covalent bonds is 2 when X represents an oxygen atom, and the phosphorus atom and the nitrogen or oxygen atom are bound to each other via a double bond.

Description

[Technical Field] The present invention relates to a photosensitive resin composition suitable for a cover layer of a flexible printed circuit board and a flexible printed circuit board using the same. [Prior Art] In recent years, in a flexible printed circuit board (hereinafter abbreviated as FPC) which is more developed, a material having excellent flexibility and flexibility is required as a substrate or a cover layer. In terms of the superiority of the process, the FPC cover layer is expected to be dry-filmed for lamination. Further, it is expected that the dry film has photosensitivity. The reason for this is that when the ordinary polyimide material is subjected to microfabrication, a photoresist is used for the etching treatment, so that a large number of steps are required. Therefore, a photosensitive polyimide material which can form a pattern directly on the polyimine itself as an insulating layer is attracting attention, and in consideration of safety during work and influence on the environment, an alkaline aqueous solution is strongly required. A photosensitive resin composition which is subjected to development treatment. Usually, when it is a negative type, the exposed portion is swollen by the developer, and it is difficult to perform fine processing with high resolution. Therefore, it is strongly desired to use a positive photosensitive system for microfabrication. When manufacturing an FPC using a dry film that does not have sensitivity, the dry film is mechanically stamped into a specific contour pattern, and after the alignment between the dry film and the circuit substrate, the stamped dry film is attached to the circuit. On the substrate. When a plurality of films are sensitized, after bonding the circuit substrate and the dry film, the dry film can be patterned into a desired pattern by photolithography, so that no mechanical pattern stamping and alignment with the circuit substrate are required. Wait for steps. 126625.doc 200839442 In addition, in the previous screen printing, there are processes that require solvent removal, and two processes required for double-sided curing. Therefore, in terms of industrial processes, photosensitivity is also expected. The resin composition was dry filmed. On the other hand, a polyimine which is excellent in flexibility and flexibility is used as a material of the cover layer. In general, (iv) imines have a heat resistance of more than t and excellent mechanical properties, and electrical properties such as low dielectric constant and high insulation are also different. Therefore, a highly heat-resistant resin such as polyimine is attracting attention as an insulating layer or a protective layer which is excellent in heat resistance, a barrier material, and particularly a solid element in the semiconductor industry. Kapton (registered trademark) or the like is known as the polyimine. However, since the Kapton film is insoluble in a solvent, a film cannot be produced using a polyimide varnish (for example, Non-Patent Document U. Therefore, in the case of using Kapton) After forming a film in the form of polylysine, the film is imidized and thinned by heating to a high temperature. The Kapt〇n film obtained in this manner is excellent in flexibility and bowing property, but on the other hand, Since the glass transition point is 400 ° C or more (for example, 'Non-Patent Document 2), it is not plastic, and it is difficult to use it as a dry film, that is, it is difficult to laminate on a circuit board. It is soluble in a solvent and is excellent in flexibility and flexibility. In the case of a polyimine, a polyimine having a rhodium skeleton introduced therein is proposed (for example, Patent Document 1). Further, a negative photosensitive cover layer is also proposed, and the cover layer is introduced with a xenon fire. A monomer such as a (fluorenyl) acrylate which is used as a reactive diluent to impart plasticity and photosensitivity to a skeleton (for example, Patent Document 2). Polyimine Or the reactive dilute 126625.doc 200839442 release agent, the glass transfer point is decreased by μ, so that it is difficult to carry out dry film formation of Kapt〇n. However, if the framework is introduced, the polyimine resin becomes It is also easy to burn, and the use of a monomer such as (meth) acrylate may also lower the flame retardancy. Further, as a positive photosensitive resin composition, it is also proposed to add a bismuth stack to the polyimide. A composition obtained from a nitrogen compound (for example, Patent Document 3). The photosensitive resin composition may be dried, but warpage occurs during dry film formation, plasticity is insufficient, and embedding on a wiring pattern substrate is achieved. In addition, it is difficult to use as a dry film, and it is formed as a positive photosensitive resin composition by adding a quinonediazide compound to a polybenzazole precursor or a polybenzoxazole precursor. Positive photosensitive resin composition (Patent Document 4). The above-mentioned precursor type can make the final film physical property superior, but the composition is formed due to the state of the precursor, so the storage stability is poor, and sometimes it is produced in processing. unfavorable Further, as a positive photosensitive resin composition containing a polyimine, a photosensitive resin composition containing a polyamidene having a sulfonic acid group and a naphthoquinonediazide compound is disclosed (Patent Document 5). Although the storage stability of the resin composition is improved, the polystyrene has a high Tg, so that it is difficult to be pressure-bonded to a substrate or the like. Further, the positive photosensitive resin composition which reduces the Tg of the polyimide. 'Disclosed a positive photosensitive dendrimer composition comprising a polyfluorene having a fluorene skeleton (Patent Document 6). As in the technique of the document, by introducing a oxalate skeleton, Poly The Tg of the amine is lowered, but the flame retardancy tends to be lowered. Moreover, the plasticity of the above composition is not sufficient, so that warpage occurs when the film is dried at 126625.doc 200839442, and it is difficult to use it as a photosensitive film. As a method of imparting flame retardancy to a resin composition, a method of adding a phosphorus compound to a resin composition is known (for example, Non-Patent Document 3). However, in order to express the flame retardancy by using a conventionally known technique, it is necessary to add a large amount of the phosphorus compound, and if this technique is applied to the photosensitive resin composition, the display property is deteriorated and the photosensitive property is lowered. Further, in order to improve the deterioration of the material properties of the mechanical properties such as the breaking strength, a technique of arranging a small amount of a specific phosphorus compound in the polyimide resin is known (for example, Patent Document 7). However, in this technique, the phosphorus compound does not exhibit flame retardancy, and the occurrence of warpage during dry film formation cannot be suppressed. A simple combination of the above-mentioned conventionally known techniques, for example, a composition obtained by adding a scaly compound to a polyimine imine having a cerium-oxygen skeleton introduced therein, warp when dry film formation, and wiring pattern The embedding property is insufficient, and since the polyimine which has a rhodium skeleton is introduced to have a flammable property, the flame retardancy of the dish compound cannot be sufficiently exhibited. Further, the positive-type photosensitive resin composition in which a quinonediazide compound is added to a polybenzamine is known, and even if the resin is a polyimine which has a rhodium-oxygen skeleton introduced therein, it is warped upon dry film formation. song. In order to improve the warpage and to add a monomer such as a (meth) acrylate which is conventionally known as a reactive diluent, warpage is improved, but flame retardancy is impaired. As described above, it is difficult to simultaneously impart the warpage suppression property at the time of dry film formation, the embedding property or adhesion to the wiring pattern substrate, the photosensitivity or developability, and the flame retardancy. Sex. [Non-Patent Document 1] The latest polyamidomine~Basic and Application~(NTS) Page 4 I26625.doc 200839442 [Non-Patent Document 2] Electronic Packaging Technology 2〇〇3年2月(v〇U9 ^^.2 [Page 5] [Non-Patent Document 3] Flame-retardant technology (NTS) using a non-virtual-based flame-retardant material, page 28 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-35440 (Patent Document 2) Japanese Patent JP-A-2003-140339 [Patent Document 3] Japanese Patent No. 2906637 (Patent Document 4) Japanese Patent No. 3078175 (Patent Document 5) Japanese Patent Laid-Open Publication No. 2004-23 No. 591 (Patent Document 6) International Publication No. 2003/060010 [Patent Document 7] Japanese Patent No. 295 5712 SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive dry film and a flexible printed circuit board using the same, which is positive The photosensitive dry film has the following characteristics which are difficult to be obtained by the conventional photosensitive resin composition, that is, it does not cause warpage during dry film formation, and has lamination property and embedding property which are easily pressed against a substrate or the like. The development characteristics are good and have flame retardancy. In order to solve the above problems, the inventors of the present invention have found that the photosensitive resin composition having the following characteristics can suppress the softness during the dry film formation and can simultaneously impart embedding property to the wiring pattern substrate or The photosensitive resin composition is characterized in that it contains (A) component, (B) component, and (c) component, and the component (A) is the adhesiveness, the photosensitivity, the developability, and the flame retardance. The alkali-soluble resin, the component (B) is a compound selected from the group consisting of a compound having a structure of the formula (1), a compound having a hetero-cyanuric acid ring, and a component other than the component (126625.doc 200839442 and the above (A). The present invention is completed by at least one compound of a group consisting of two quinone imine-based quinone imine compounds, which is a quinonediazide compound. Therefore, the photosensitive resin composition of the present invention can be used, and a photosensitive dry film, a photosensitive laminated film, and a cover layer and a flexible printed circuit board using the same can be provided.

(In the formula, P represents a phosphorus atom, and the number of covalent bonds is 5. χ represents a nitrogen atom or an oxygen atom, and when X is a nitrogen atom, the number of covalent bonds is 3, and when it is an oxygen atom, the number of covalent bonds is 2. The phosphorus atom is bonded to a nitrogen atom or an oxygen atom by a double bond.) The present inventors have found that a specific compound has both a warpage improving effect of dry film formation, embedding property to a wiring pattern, adhesion, and flame retardancy. Further, it has been found that by combining them with a quinonediazide compound, both photosensitivity and developability can be exhibited. Further, it has been found that the specific compound and the quinonediazide compound are blended in a resin composition such as a soluble polyimine to form a photosensitive resin composition, and it is possible to completely satisfy the absence of (four) (suppression of distortion) and the layer. A positive photosensitive dry film having pressure, photosensitivity, and flame retardancy, thereby completing the present invention. Specifically, the structure of the component (7)) in the photosensitive resin composition of the present invention includes a functional group capable of exhibiting a surface roughness improving effect of a dry film, and a phosphorus atom or nitrogen which exhibits flame retardancy. atom. Further, in the structure of the component (c) in the photosensitive resin composition of the present invention, a nitrogen atom having a flame retardancy can be exhibited, and at the same time, one or more m groups having a large volume, specifically, naphthalene 8匕 can be obtained. Azido or benzoquinone has a relatively two-layer 126625.doc -11 - 200839442 murine base. As a result of intensive studies, the inventors have found that by combining the component (8) with the component (C), the phosphorus atom or the nitrogen atom of the component (b) and the nitrogen atom of the component (6) can exhibit sufficient flame retardancy. In addition, it is amazing that when the combination of the component (B) and the component (C) is carried out, the component (B) does not impair the surface properties of the dry film, and the flame retardancy can be imparted. . Further, it has been found that by combining the component (8) with the component (C), it is possible to impart flame retardancy to a polyamidene resin having a stone-oxygen skeleton which has been difficult to achieve flame retardant. It is presumed that the flame retardancy and the light film improvement effect of the dry film can be simultaneously achieved in that each of the molecules of the component (B) has a phosphorus atom or a nitrogen atom which imparts flame retardancy, and can exhibit a dry film. A functional group that warps to improve the effect. Further, it has been found that when a phosphate having an aliphatic organic group is used, sensitivity (sensitivity) is excellent, and developability (reducing development time or reducing development residue floating foam, etc.) is also improved. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. The photosensitive resin composition of the present invention is characterized by comprising (A) a component, a component (B), and a component (C), wherein the component (A) is an alkali-soluble resin, and the component (B) is selected from the group consisting of a compound having a structure represented by the formula (1), a compound having a hetero-cyanuric acid ring, and at least one compound of a group consisting of a quinone imine compound having one or two quinone imine groups other than the above components, The above component (C) is a quinonediazide compound. Thereby, it is possible to provide a positive photosensitive property which does not cause warpage during dry film formation, has lamination property or adhesiveness, is excellent in photosensitivity or developability, and has flame retardancy. 126625.doc -12- 200839442 Further, in addition, a flexible printed circuit board having a cover layer formed using a positive photosensitive dry film can be provided. p=x Formula (1) (wherein P represents a squamous atom' has a number of covalent bonds of 5. X represents a nitrogen atom or an oxygen atom. When X is a nitrogen atom, the number of covalent bonds is 3, and when X is an oxygen atom, The number of covalent bonds is 2. The subunit is bonded to the nitrogen atom or the oxygen atom by a double bond. /, First, the component (A) is described. The test resin used in the present invention is soluble in the test solution. The resin is not limited, and examples of the resin include a primary bond and/or a known tree-salt which is soluble in alkali ▲ soil such as a county, an aromatic trans group, or a reductive acid group. Resin, from the viewpoint of heat resistance, fortunately, the solubility of polyethylenimine, poly-aracine, and polybenzoquinone saliva = dissolved t-mercapto' is from the viewpoint of dry film formation. More preferably, it is a polyacrylamide w and a polyimide precursor, and a test amine is particularly preferred. The solvent-soluble polyamine used in the present invention may, for example, be a diamine or a tetracarboxylic acid. An anhydride is obtained as a raw material. As a structure of the test-soluble polyimine, it is good for the car to have a solubility and/or a basis. The carboxyl group is used as a monoamine, and an aromatic diamine, an aliphatic diamine, an alicyclic di-anthracene, or an alicyclic group can be used to introduce a (four) and/or a mercapto group, and the amine can be used as an amine. The oxoxane skeleton can be calcined with a Jk group. For the fragrant sulphur-amines, there can be mentioned: o-phenylenediamine, m-phenylenediamine, p-benzene 126625.doc -13- 200839442 diamine, 3,3' -diaminodiphenyl-, 4,4'-diaminodiphenyl ether, 3,4,-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4,-di Aminodiphenylmethane, 4,4匕diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4,-diaminodiphenyldifluoromethane, 3,3 Bis-diamine diphenyl stone, 3,4,-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3,-diaminodiphenyl sulfide, 3,4, -diaminodiphenyl sulfide, 4,4'diaminodiphenyl sulfide, 3,3,-diaminodiphenyl ketone, 3,4'diaminodiphenyl ketone, 4,4, -diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2-(3,4,-diaminodiphenyl)propane, 2,2-bis (4 -aminophenyl)propane, 2,2-bis(3-aminobenzene) Hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-double ( 3-aminophenoxy)benzene, u-bis(4-aminophenoxy)benzene, 3,3'-[1,4-phenylene-bis(1-methylethylidene)] Aniline, 3,4414-phenylphenyl-bis(1-methylethylidene)]diphenylamine, 4,4,1[1,4-phenylene-bis(1-methylethylidene)] Aniline, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2- Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-( 3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, Bis[4-(4-aminophenoxy)phenyl]sulfone, and i,3-bis(4-aminophenoxy) as 1,η·bis(4-aminophenoxy)alkane Propane, 14-diaminophenoxy)butane, I% bis(4-aminophenoxy) heptane. As the aliphatic diamine, i, 2, diaminoethane, i, 3, diaminopropyl, 1,4-diaminobutane, hydrazine, % diaminopentane, ^ Diaminohexanone, I7.diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 126625.doc -14-200839442 1,1〇-diamine Decane, U1 <Aminoundecane. The compound shown by the formula (19) can be enumerated as a month of the month. [Chem. 18]

The diamine having a slow group may, for example, be a compound represented by the formula (2). [Chem. 19]

hoocV^cv^^coohh2N order χχΗ2

COOH h2n^)«

NH 2

HOOC ^h2 h2 nh2 chcx, cchcooh h2 h2 h2n H2 COOH , C'CH NH2 (2 0 ) In the formula 20, 3,3,_dicarboxy·4,4,-diaminobenzophenone is preferred. , 3,5-diaminobenzoic acid, and the like. Examples of the diamine having a hydroxyl group include i,2-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, and 1,3-diamino-4-hydroxybenzene. , 4-diamino-6-hydroxybenzene, 1,5-diamino-6-hydroxybenzene, L3-diamino-4,6-dihydroxy stupid, 1,2-diamino-3,5 - dihydroxy stupid, 4-(3,5-diaminophenyloxy) arbitrarily, 3-(3,5·diaminophenoxy)phenol, 2-(3,5-diaminophenoxy Base) benzene 126625.doc -15- 200839442

Phenol, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3,-diamino-4,4,-di-biphenyl, 2,2-bis (4- 3-aminophenyl)propane, 2,2-bis(4-carbyl-3-aminophenyl)hexafluoropropanone, bis(4-yl-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-diaminopyrimidinyl)methyl]phenol, p. , 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)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)one, 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. The diamine sulfoxane is a compound represented by the formula (21). [Chem. 20]

(21) (Chemical group 6 represents a hydrocarbon group of 1 or more and 20 or less. a represents an integer of 1 or more and 1〇 or less. b represents an integer of 1 or more and 2〇 or less.) Hydrocarbon group having an inverse number of 1 or more and 2 or less (r6) is not particularly limited, and examples thereof include an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, a functional group having a bad structure, and a group in which the group is combined. The aliphatic saturated hydrocarbon group may, for example, be a primary hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, or an isobutyl group or an isopentyl group, etc. II2665.doc •16-200839442 hydrocarbon group, A tertiary hydrocarbon group such as tributyl or the like. The above-mentioned aliphatic unsaturated hydrocarbon group 'is a hydrocarbon group having a vinyl group, a dipropyl group, a double bond, a hydrocarbon group having a triple bond such as an ethynyl group, and the like. Examples of the functional group of the above-mentioned soil-containing structure include a monocyclic functional group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group or a cyclooctyl group; and a polycyclic ring such as a decyl group or a gold group. Functional group; with pyrrole, furan, thiophene, imidazole, evil °!,? ? a heterocyclic functional group having a tetrahydrofuran or a dioxane structure; an aromatic hydrocarbon group containing a benzene φ ring naphthalene ring, an anthracene ring ring, or a phenanthrene ring structure. The above hydrocarbon group (R6) having the above carbon number may contain a (tetra)atom hetero atom and a metal atom. The (4) in the present invention may be exemplified by gas, chlorine, bromine or iodine. Further, the hetero atom in the present invention may, for example, be oxygen, sulfur, nitrogen or phosphorus. Further, examples of the metal atom in the present invention include ruthenium and titanium. Further, in the case where the hydrocarbon group (Re) having a carbon number of 20 or more and 丨 or more contains a hetero atom and/or a metal atom, & may be directly bonded to the bonded hetero atom and/or metal atom, or may be via a hetero atom. And / or metal atoms and bonding. • Considering the flame retardancy, the carbon number of the formula (21) is preferably 1 or more and 20 or less. From the viewpoint of solvent solubility of the produced polyimine, the carbon number is particularly preferably 1 or more and 1 Torr or less. The most noble hydrocarbon group (r6) is a methyl group. • Considering the flame retardancy, the formula (9) is 10 or more. From the viewpoint of solvent solubility of the produced polyimine, & is preferably 2 or more and 8 or less, more preferably 3 or more and 6 or less. In view of flame retardancy, the formula is 20 or more. From the viewpoint of solvent solubility of the produced polyimine, b is preferably 1 or more and 126625.doc -17·200839442, more preferably 1 or more and 12 or less. Further, the diamine components may be used singly or in combination. The tetracarboxylic dianhydride used in the present invention may, for example, be aromatic tetramethicone anhydride, alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic dianhydride. As the two needles of the Fangxiang tetracarboxylic acid, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2,,3,3,-biphenyltetracarboxylic acid are mentioned. Dihydride, 2,3,3,4'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-di Carboxyphenyl)propane dianhydride, 1,1 bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1 bis(3,4-dicarboxyphenyl)ethane dianhydride 'double ( 2,3_Dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10- Perylene tetracarboxylic acid monoanhydride, bis(3,4-dihydrophenyl)ether two needles, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,3',4'- Benzophenone tetracarboxylic dianhydride, 2,3,2,3,2-dibenzophenone tetradecanoic acid anhydride, 2,3,3',4'-diphenyltetracarboxylic acid dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Formic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetradecanoic acid dianhydride, 2,3 ,6,7-tetrachloronaphthalene-1,4,5,8-four Formic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)methylbenzene Pyrane dianhydride, bis(3,4-dicarboxyphenyl)diphenylnonane dianhydride, 14-bis(3,4-dicarboxyphenyldimethyl decyl) phthalic anhydride, 1,3-double (3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl] Propane dianhydride, 4,4-bis (3,4-126625.doc -18- 200839442 dicarboxyphenoxy)diphenyl sulfide dianhydride. Also, the aromatic tetrazide secret # μ with an ester group, the formazan anhydride can impart flexibility to the alkali-soluble polyimine, and can also accept the alkali solubility of the imine, and impart inhibition during development. The effect of the stains, etc., therefore, contains b, a carboxylic acid-containing aromatic tetracarboxylic dianhydride, in the saponin of the wild. As the base of the i-supply, the earthworms know the tetracarboxylic acid dianhydride, and the bis(2-per hexafluoroisopropyl)benzoquinone ('1; Diacetate ester), 1,3-bis(2-_ hexafluoroisopropyl)benzene bis(p-benzotriazide diester, bis-p-benzoic anhydride i 2 , hydrazine to phthalic anhydride 1,2 _Ethylene diester, bis-p-triphenyl propylene dicarboxylate, bis-p-trimellitic acid ^1,3' ... K anhydride butyl succinate, trimellitic anhydride 1,5-pentane diester, trimellitic anhydride i ,6·hexanediester, trimellitic anhydride 1,7-heptanediester, double low cage, double diammonium dimethyl anhydride, dioctyl octyl ester, double bias anhydride 1,9-decane diester, double Phenylene phthalate, monomethyl phthalic anhydride 1,10-decane diester, bis-paraformic anhydride 1,12-dodecane di-, oxime, bi-dimerization of the tricarboxylic anhydride 1,16-undecyl ester, Bis-p-benzoic anhydride i, I, octadecane diester. It can be introduced into the 5-soluble polyimine when it is introduced into the 5-soluble polyimine, and is preferably an anhydride of the formula (6). The double bias of T is the three-field dicarboxylic anhydride to benzoic acid S. [Chem. 21] 9

Ester, or double-plumbing as shown in formula (7) - anhydride, 2-ethane II 126625.doc -19- 200839442 [Chem. 22]

Examples of the alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, I, 2,3,4-butanetetracarboxylic dianhydride, hydrazine, and 5·cyclooctadiene-1. 2,5,6-tetracarboxylic dianhydride, 5-carboxymethylbicyclo[2.2.1]heptane_2,3,6-trimethyl

Acid-2,3:5,6-dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6.3'5-anhydride, bicyclo[2.2.2]-octene_2 , 3,5,6-tetradecanoic acid dianhydride, S(2,5-monooxytetrahydro-3-indolylmethyl-3-cyclohexene-L2-dicarboxylic anhydride, tetrahydrofuran-2,3, 4,5-tetracarboxylic dianhydride, 4_(2,5-dioxotetrafuran I group > 1,2,3,4-tetrahydronaphthalic anhydride, decalin-1,4,5,8 -tetracarboxylic dianhydride, 4,8-dimethylhexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclodecane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine -2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis (exobicyclo[2·2·1]glycan-2,3-diindole The acid anhydride is 飒. The tetracarboxylic dianhydride components may be used singly or in combination. From the viewpoints of the solubility of the polyimine in an organic solvent and the adhesion to a substrate or the like, it is preferable that ··Bis(3, cardio-dicarboxyphenyl) phthalic anhydride bis-p-benzoic anhydride ethylene glycol ester, bis-p-trimellitic anhydride p-benzodiazepine, heart (2,5-dioxotetrahydrofuran)), 2 , 3, tetrahydroanthracene]yi 2 f anhydride 5_(2,5-dioxytetrahydrofuranyl>3_mercapto_3_cyclohexene u-di-nic anhydride. 126625. Doc -20- 200839442 The alkali-soluble polyimine used in the present invention is preferably a polyphosphonium diamine, a diamine having an alkali-soluble functional group, and/or the like, as shown in the formula (5). A polyimine formed by polymerization and cyclization of a diamine and an acid dianhydride.

(wherein R 3 and Rs represent a tetravalent organic group, and may be the same or different. The hydrocarbon group having an inverse number of 1 or more and 2 Å or less is represented by a group. I represents a divalent organic group having at least one of the test functional groups. An integer of 1 or more and 1 〇 or less is represented. b represents an integer of 1 or more and 20 or less. & represents a tetravalent organic group having an ester structure, and 8 represents a divalent organic group. A, β, and γ are at least 1 or more, and 〇 〇1$β/(α+β+γ)$〇·9.) Further, from the viewpoint of flame retardancy, when the portion derived from all diamines is loo mol%, it is used in the present invention. The content of the polydiimide from the other diamine is preferably 35 mol% or less. The diamine derived from R4 in the present invention is not limited as long as it has one of the above-mentioned test functional groups. Further, the diamine derived from Rs in the present invention is indefinitely determined if it is the above diamine. The acid dianhydride used in the present invention is not limited as long as it is an acid dianhydride which can react with a polyoxylamine, a diamine having a test functional group, and/or another diamine. . In the formula (5), R5 is a tetravalent organic group derived from the above tetracarboxylic acid 126625.doc * 21 - 200839442 dianhydride, and may be the same or different. The terminal of the polyimine used in the present invention is not particularly limited as long as it does not affect the performance. The terminal of the acid dianhydride or diamine used in the production of the polyimine may be blocked by other acid anhydrides, amine compounds or the like.

The number average molecular weight of the polyimine used in the present invention is preferably from 1,000 to 1,000,000 in terms of the flame retardancy, the viscosity of the resin composition containing the polyimide, and the moldability. Here, the number average molecule 1 means a molecular weight measured by gel permeation chromatography using polystyrene having a known number average molecular weight as a standard. The above molecular weight is more preferably 5,000 or more and 500,000 or less, and most preferably 1 〇〇〇〇 or more and 3 〇 (10) (10) or less. The copolymerized form of the polyimine used in the present invention may be either a block structure or a random structure. In the present invention, the α, p, and 丫 constituting the copolymerization component are at least those of the above-mentioned poly(oxygen diamine) which are required to be bonded to a substrate or the like. The part is sufficiently large to express the crimpability of the μ substrate. Further, the value of ιβ/(α+ρ+γ) is 〇9 or less, and the ratio of the portion derived from the diamine having the test functional group required for the solubility test is sufficiently large to exhibit alkali solubility. The value of β/(α+β+γ) is preferably 0.02 or more and 0.8 or less, and more preferably 〇〇3 or more and 〇67 or less, from the viewpoint of the balance of the pressure-sensitive properties of the alkali-soluble cerium to the substrate. . The polyimine of the present invention can be obtained by reacting a two-needle with a diamine to synthesize a poly-proline, followed by heating (an anthraquinone). X can also be obtained by reacting acid di liver with two 126625.doc -22-200839442 amines, synthesizing poly-proline, and then adding a catalyst to polyiminate into polyamid (Chemical oxime imidization). Among them, in terms of being able to complete the imidization at a lower temperature, chemical ruthenium is preferred. Further, it is also preferred that the acid dianhydride and the diamine are reacted in a non-equal molar ratio to synthesize the H acid, and then the catalyst is added to carry out the ruthenium imidization (chemical oxime imidization). And preparing a polyimine block, and then reacting the remaining acid dianhydride and/or diamine in such a manner as to finally reach a substantially equal molar ratio, so that the poly-proline block is grown and then Amination (chemical oxime imidization), and synthesis of block polyimine. In order to explain in more detail, first, a method of synthesizing imidate by reacting an acid dianhydride with a diamine will be described. Then, a method of ruthenium imidizing the polyamic acid by adding a catalyst is as follows. For example, the production conditions of the polyimine used in the present invention will be described. The method for producing the polyamic acid is not particularly limited, and a known method can be applied. More specifically, it can be obtained using the following method. First, the diamine is dissolved and/or dispersed in a polymerization solvent, and the acid di野 powder is slowly added thereto, and stirred for 5 to 96 hours using a mechanical stirrer, preferably for 0.5 to 30 hours. The monomer concentration at this time is 5% by mass or more and 7% by mass or less, preferably 1% by mass or more and 90% by mass or less. The polyaminic acid solution can be obtained by carrying out polymerization in the concentration range of the monomer. The reaction solvent used in the production of the above polyamic acid may be a carbon number of 2 or more and 6 or less, such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane or ethylene glycol dimethyl ether. Ether compound; a ketone compound having a carbon number of 2 or more and 6 or less such as methyl or methyl ethyl ketone; n-pentane, ring 126625.doc -23- 200839442 decane, n-hexane, cyclohexane, sulfhydryl a saturated tobacco compound having a carbon number of 5 or more and 1 Torr or less, such as cyclohexane or decahydronaphthalene; a benzene having a carbon number of 6 or more and 1 or less, such as benzene, toluene, xylene, tridecylbenzene or tetrahydronaphthalene; a hydrocarbon compound, an ester compound having a carbon number of not less than 6 or less, such as methyl acetate, ethyl acetate or butyrolactone; a carbon number of 1 or less such as chloroform, dichloromethane or 1,2-dichloroethane; Above 10 or less of the tooth-containing compound; acetonitrile, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, Ν-methyl-2-pyrrolidone, etc. a nitrogen-containing compound of 10 or less; a sulfur-containing compound such as dimethyl arsenic. These may be used singly or in combination of two or more kinds. Particularly preferred > granules include a vinegar compound having a carbon number of 3 or more and 6 or less, an aromatic hydrocarbon compound having a carbon number of 6 or more and 10 or less, and a nitrogen-containing compound having a carbon number of 2 or more and 10 or less. These may be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like. The reaction temperature at which the polyglycolic acid is produced is preferably less than 2 5 Torr. If it is 0 C or more, the reaction can be started, and if it is 25 Å. 〇 Below, # There will be no side effects such as side reactions. It is preferably 15 t or more and 220 ° C or less, more preferably 20 C or more and 200 ° C or less. The best is 2 〇 °c or more and 100 ° C or less. The time required for the reaction of the polyamic acid varies depending on the purpose or the reaction conditions, and is usually within 96 hours, and particularly preferably in the range of from 3 minutes to 3 hours. In the following, a method in which a polyamine is added to a polyamic acid to carry out (chemical) ruthenium imidization to obtain an alkali-soluble polyimine used in the present invention will be described. 126625.doc -24- 200839442 The ruthenium-imidation catalyst used in the production of the alkali-soluble polyimine used in the present invention is not particularly limited, and examples thereof include an acid anhydride such as acetic anhydride. , γ· butyl vinegar, γ-te window acid, 酜 g g, γ-coumarin, γ-laclaconoid lactone compound, pyridine, quinoline, Ν_曱基吗琳, 三乙A tertiary amine such as an amine. Further, one type may be used as needed or a mixture of two or more types may be used. Among them, in particular, from the viewpoint of the degree of reactivity, a mixture of γ-valerolactone and pyridine is particularly preferable. _ When the polyamic acid is 10 〇 mass ❶ / 醯, the amount of the ruthenium imidization catalyst is preferably 50% by mass or less, more preferably 3 〇 ❶ / q or less. More preferably, it is 10% by mass or less, and most preferably 5% by mass or less. As the reaction solvent, the same one as the reaction solvent used for the production of polyamic acid can be used. At this time, the polyaminic acid solution can be used directly. Further, a solvent different from the user who produces the polyamic acid can also be used. Examples of the reaction solvent include ether compounds having a carbon number of 2 or more and 6 φ or less such as dimethyl ether, diethyl ether, mercaptoether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether; acetone and methyl ethyl a ketone compound having a carbon number of 2 or more and 6 or less; a carbon number of n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane or decalin is 5 or more and 1 or less a saturated hydrocarbon compound, an aromatic hydrocarbon compound having a carbon number of 6 or more and 10 or less, such as benzene, toluene, dimethyl benzene, mesitylene, and tetrahydronaphthalene; carbon such as methyl acetate, ethyl acetate or cesium butyrolactone; An ester compound having a number of 3 or more and 6 or less; a carbon number of chloroform, such as 'dichlorodecane or 1,2-dichloroethane, containing less than 1 以上 from the compound · acetonitrile, hydrazine, hydrazine-dimethyl ketone Nitrogen-containing compounds having a carbon number of 2 or more and 1 or less, such as guanamine, hydrazine, hydrazine, dimethylacetamide, ν•methyl-2-pyrrolidone, etc., II & A 126625.doc -25- 200839442 Sulfur-containing compounds such as sulfones. These may be used singly or in combination of two or more. The solvent is preferably an ester compound having a carbon number of 3 or more and 6 or less, an aromatic hydrocarbon compound having a carbon number of 6 or more and 1 or less, and a nitrogen-containing compound having a carbon number of 2 or more and 10 or less. These may be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like. The production of the polyimine used in the invention is preferably carried out at a reaction temperature of 15 ° C or more and 250 t or less. If it is 15. Above 〇, you can open φ to start the reaction 'again' if it is 250. Below, the catalyst will not be deactivated. Preferably, it is 20C or more and 220 ° C or less, more preferably 2 (rc or more 2 〇 (rc or less.) Water which can be formed by the hydrazine imidization reaction, and a solvent which azeotropes with water, such as toluene or two The toluene is discharged together to the outside of the reaction system, and the obtained reaction liquid can be directly used as a polyimide varnish. The time required for the reaction varies depending on the purpose or reaction conditions, and is usually within 96 hours, particularly preferably at 3 The reaction is carried out in the range of 〇 minute to 3 hours. • The recovery of the polyimine after the completion of the production can be carried out by distilling off the solvent in the reaction solution under reduced pressure. The method of using the polyimine may be a method of removing insoluble acid dianhydride and monoamine in the reaction solution by filtration under reduced pressure, pressure filtration, etc. Further, a so-called reprecipitation purification method, that is, a reaction solution, may be carried out. It is added to a poor solvent to precipitate it. In particular, when a polypyrimidine having a particularly high purity is required, an extraction method using a carbon dioxide supercritical method can also be carried out. Using the polyimine used in the present invention, it can be obtained. Dissolve The resin composition of 126625.doc -26- 200839442, that is, the solvent can uniformly dissolve and/or disperse the above polyimine. The resin composition containing the polyimine used in the present invention is constituted. The solvent "is not limited as long as the polyimine used in the present invention is uniformly dissolved and/or dispersed. The solvent used in the polymerization is also preferably used. As such a solvent, there are mentioned: An ether compound having a carbon number of 2 or more and 6 or less such as methyl ether, dibutyl scale, mercapto diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone a ketone compound having a carbon number of 2 or more and 6 or less; a saturated hydrocarbon compound having 5 or more carbon atoms or less, such as n-pentane, cyclopentane, n-hexanol, cyclohexane, methylcyclohexane or decalin An aromatic hydrocarbon compound having a carbon number of 6 or more and 1 Torr or less such as benzene, toluene, xylene, mesitylene or tetrahydronaphthalene; carbon number such as ruthenium acetate, ethyl acetate or γ-butyrolactone; 3 or more ester compounds of 6 or less, gas imitation, dichloromethane, 1, 2_2 a chlorine-containing compound having a carbon number of 1 or more and 1 Torr or less; acetonitrile, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidone A nitrogen-containing compound having a carbon number of 2 or more and 1 Torr or less, a sulfur-containing compound such as a methionite, etc. Further, such a mixture may be used as a 'or a mixture of two or more. For dissolution of the polyimine. From the point of view of sex, 'preferably Ν-methyl-2-U pirone, γ-butane vinegar, hydrazine, hydrazine-dimercaptocarboxamide, hydrazine, hydrazine-dimercaptoacetamide The concentration of the polyimine in the resin composition composed of the polyimine and the solvent used in the present invention is not particularly limited as long as the concentration of the resin molded body can be produced. From the viewpoint of the film thickness of the body, the concentration of the polyanilin is preferably 1% by mass or more, and the polyetherimide is considered in terms of the uniformity of the film thickness of the resin molding 126625.doc -27-200839442. The concentration is preferably 9 〇 Berry / 〇 below. From the viewpoint of the film thickness of the obtained resin molded body, it is more preferably 2% by mass or more and 8% by mass or less. The structure of the alkali-soluble polyimine or the polyimide precursor used in the present invention is not particularly limited, and mechanical properties such as ductility, flexibility, and steep bending at the time of film formation, and dry film are considered. The warping effect of the time of the change is better, and it is better to have the skeleton of the Shi Xi oxygen house. The warpage improvement effect at the time of dry film formation can be achieved by blending (Β) into a knife, and the low elastic modulus and low Tg which are produced by the rhodium skeleton are more effective in improving warpage. From the viewpoint of warpage and flame retardancy at the time of dry film formation, the alkali-soluble polyimine or polyimine precursor is preferably an anthracene having a mass of 1% by mass or more and 9% by mass or less. The structure is more preferably a ruthenium oxide structure having a mass% or less of 2% by mass or less. The terminus of the polyimine precursor of the present invention is not particularly limited as long as it does not affect the tenth energy, and may be an acid used from the manufacture of the polyimide precursor. The terminal of the diamine may be blocked by other acid livers, amine compounds, etc. Further, the polyimide precursor of the resin composition of the present invention may be used for the above-mentioned test polyimine. The diamine is synthesized with tetracarboxylic dianhydride. The 'polyimine imine precursor has a carboxyl group in the molecule, so even if a diamine having a (d) or a diamine having a hydroxy group is not used as a raw material, it is also a solubility tester' It is soluble in an organic solvent. The (Β) component is described below. The (Β) component is a compound selected from the group consisting of a compound having the structure represented by the formula (1), having a 126625.doc -28-200839442 heterodimeric acid, and the above At least one compound of the group consisting of yttrium imine compounds containing one or two quinone imine groups other than the component (A) P = x Formula (1) (wherein P represents a phosphorus atom, and the number of covalent bonds thereof 5 is a nitrogen atom or an oxygen atom, and X is a nitrogen atom. The number of bonds is 3, and when it is an oxygen atom, the number of covalent bonds is 2. The phosphorus atom is bonded to a nitrogen atom or an oxygen atom by a double bond.) As the phosphoric acid compound, an acid selected from the formula (7) or the formula (3) can be used. At least one of a group consisting of an ester compound, or a phosphine oxide compound represented by the formula (4), and a phosphorus-nitrogen compound of the formula (10): adding the phosphating human 舲 ^ ^ 里 ^ ^ " The warpage during dry film formation can be reduced, and the lamination property of the f wiring pattern substrate can be improved, and the flame retardancy can be imparted to the user's shirt. [Chem. 24] Reference 9 R" Ri 〇(2) (wherein Rl is a monovalent organic group [Chemical 25] plural R! Each may be the same or different

Ri (the ruler in the formula! is the same as the formula (3)). Multiple hearts can be the same or not. 126625.doc -29· 200839442 [Chem. 26]

R2 (4) (wherein R2 is a monovalent organic group.) [Chem. 27]

咢13 Ο I

(17) [28]

^15 〇 I P I 〇 ^16

B q (18) These compounds have good thermal stability and do not decompose even when heated at a high temperature of 200 ° C or more together with the resin of the component (A), and do not cause decomposition of the component (A). Further, considering the flame retardancy when combined with the component (C), the compound represented by the formula (3) is particularly preferable because it has a particularly high flame retarding effect. The phosphate compound represented by the formula (2) used in the present invention is not limited as long as it is a phosphate compound having an aliphatic organic group having 1 or more and 30 or less carbon atoms. When the number of carbon atoms is 1 or more, it is preferable to improve the surface curvature and the embedding property when the film is dried, and it is preferable. When the carbon number is not more than 5%, the flame retardant is exhibited. The tendency of sex is better, and in view of the effect of improving the warpage of the dry film, it is preferred that the center of the formula (2) is selected from the group consisting of methyl, ethyl, butyl, isobutyl, An organic group of 2-ethylhexyl, butoxyethyl, phenyl, tolyl, xylyl or aminophenyl. In addition, in view of thermal stability and effect of warpage improvement of dry film, Preferably, R2 in the formula (4) is an organic group selected from the group consisting of hydrogen, dihydroxyphenyl, dibutyl-benzyl, and an organic group containing a (meth) acrylate. Further, in consideration of the resin varnish The compatibility and the effect of improving the warpage during dry film formation, and R2 is preferably hydrogen. Examples of such a compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triisobutyl phosphate. a phosphate ester having an aliphatic hydrocarbon group as a substituent, such as tris(2-ethylhexyl) phosphate, and tris(butoxyethyl) phosphate, etc. A phosphate ester or the like having an aliphatic organic group as an oxygen atom as a substituent. From the viewpoint of non-volatilization at the time of calcination, preferred is tributyl phosphate, mono-phosphate, butyrate, and bis(2-ethylhexyl). And the ester of the phosphate ester compound used in the present invention may be used alone or in combination of two or more. The combination of flammability and warping improvement effect at the same time is better, and it is better to combine the two kinds, 彳(4): a combination of diced acid tributyl vinegar and squaric acid tris(butoxyethyl) ester, Combination of tris(2-ethylhexyl) phosphate with tris(butoxyethyl) phosphate, combination of tributyl phosphate and tris(2-ethylhexyl) phosphate, triisobutyl phosphate and phosphoric acid tri A combination of butoxyethyl esters, etc. 126625.doc -31 - 200839442 In the case of a phosphoric acid having an aliphatic organic group, the aliphatic organic group has a bond, and the structure of the group is opened. The development time is shortened and the effect of development collapse (floating; end) is reduced by v. Therefore, it is preferable that The aliphatic-containing organic group has a _ structure of a cleavage acid ester. Compared with the eve of the eve, the compound of the human body is exemplified by tris(butoxyhexyl) phosphate. Two or more types are used in combination, and more preferably, at least the aliphatic organic group has a phosphate ester having a bond φ. The preferred combination can be listed as I: tributyl phosphate and tris(butoxyethyl) phosphate a combination of S, a combination of tributyl acrylate and tris(butoxyethyl) acrylate, etc. In the photosensitive resin composition of the present invention, the amount of the (A) alkali-soluble resin is 100 mass. In the case of the sensitization, etc., the amount of the phosphate compound added is preferably 5% by mass or less. From the viewpoint of heat resistance of the cured body, it is preferably 45% by mass or less. Good is 4% by mass or less. Φ As the compound having a heterodiisocyanate ring, a compound of the formula (8) can be preferably used. The addition of the compound having an iso-cyanocyanate ring is also preferable in terms of flame retardancy and improvement in warpage at the time of dry film formation as in the above-mentioned _ phosphate compound. β [化29]

126625.doc -32 - 200839442 (wherein R9 is a mussel organic group. The plural I groups may be the same or different.) h is a monovalent organic group. The Hf organic group is, for example, an organic group having a carboxyl group or an organic group having an ester group. Such an i-valent organic group is, for example, an organic group represented by the formula (22). Further, from the viewpoint of compatibility with a solvent for a resin or a varnish, an organic group having an ester group is preferred. [化30]

-CH2CH2〇^c2H4-〇~C2H4-〇-C2H5 (22) In view of the effect of warpage improvement of the dry film, r9 in the formula W is preferably selected from the organic groups represented by the formula (1)). Further, considering the adhesion to copper, the structure of the 乂 乂 is a structure represented by the formula (12) or the formula (13), and more preferably the structure of the formula (9)::. Further, it is preferred that the ? in the formula (9) is hydrogen. also'. To the warpage improvement effect, it is in the formula (13).较_CH2CH2〇|r" (1 (wherein Ru is selected from the formula (12) [Chem. 32] The organic group in the formula (13) ^12 C=CH2 2) (wherein, R !2 is an organic group selected from hydrogen and methyl groups [Chem. 33]

QR 3) 126625.doc • 33 · 200839442 (wherein c is an integer of 2 to 5. In the formula, 1^2 is the same organic group as in the formula (12).) (A) used in the present invention A compound represented by the formula (9) can be preferably used as the quinone imine compound having one or two subfeet groups other than the component. The addition of the quinone imine compound containing one or two quinone imine groups is also preferable from the viewpoint of the flame retardancy and the improvement of warpage at the time of dry film formation as in the above-mentioned acid vinegar compound. [34]

(wherein R1G is a monovalent or divalent organic group. (5) is t or 2. γ represents an organic group represented by the formula (1〇).) [Chem. 35]

When m is 2, R1G is a divalent organic group. In this case, the quinone imine compound can be obtained by a condensation reaction of a diamine and a dicarboxylic anhydride. At this time, a divalent organic group having a suitable diamine is introduced. As the diamine, for example, an aromatic diamine, an aliphatic diamine or an alicyclic diamine used in the synthesis of the above-mentioned soluble polyimine can be used. Among them, in terms of improving warpage, it is more difficult to have an aliphatic diamine. More preferably, the aliphatic carbon number is 2 to 6, 2-diaminoethane, 1,3-diaminopropane, diaminobutane, 1,5-diaminopentane, 126625.doc -34- 200839442 1,6-diaminohexane, 1,3-bis(4-aminophenoxy)propane, hydrazine, bis-('aminophenoxy)butane, 1,5 - bis(4-aminophenoxy)heptane. Namely, rig is preferably an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a group represented by the formula (23). [化36]

(23) (wherein d represents an integer from 3 to 5.) When m is 1, "is an organic group." The valence organic group may, for example, be an alkyl group or an alkoxy group. Examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples of the alkoxy group include an oxyethylene group, a polyoxyethylene group, an oxypropylene group, an oxypropylene group, a butyl oxide group, and a polyoxybutylene group. Γ Γ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Ruler' base. For example, the monovalent organic group represented by the formula (13) is a compound represented by the formula (24). [化37]

Ο 〇 H2C=C-C~〇^c-c2-n

ο o h2c=c-c~〇x~c2-n h2

(2 4) 126625.doc 200839442 Such a compound is preferred because it is excellent in flame retardancy. The components (B) can be used singly or in combination. From the viewpoint of flame retardancy and warpage of the dry film, it is preferred that the phosphate compound is combined with a compound having an iso-cyanocyanate ring, or the phosphate compound and the component (A) contain one or two. A combination of quinone imine based quinone imine compounds. In this case, it is preferred that the compounding is preferably carried out with respect to 1 part by mass of the phosphate compound, or a compound having an iso-cyanuric acid ring or a component other than the component (A) containing one or two quinone imine groups. The quinone imine compound is from 50 parts by mass to 200 parts by mass. The component (B) is particularly preferably selected from the group consisting of the formula (25), the formula (26), the formula (27), the formula (28), and the formula (29) in view of flame retardancy and warpage of the dry film. At least one compound of the group consisting of the compounds. [化38]

(wherein Rl7 is an organic group selected from hydrogen or methyl. The plurality of Rl7 may be the same or different.) [Chem. 39]

126625.doc -36- 200839442 [化40]

R 18' Λ 〇 9 〇,f '〇 ^18 [化41]

R18=—〇Η2〇Η2〇-〇-(ΟΗ2)5 一〇~〇C=CH Η (27) 叻〇-c2h4s◦~ Ο / 3 R17

Ο rR17 0-p-〇 0

R 17 (28) (wherein, R!7 has the same meaning as in formula (25). A plurality of Ri7s may be the same). The component (8) is preferably in an amount of 5 parts by mass or less based on (10) parts by mass of the component (A). More preferably, it is less than 3 parts by mass. Particularly preferably, it is 20 parts by mass or less. In the case of the addition range, the film is excellent in ductility and flexibility, and alkali solubility is also good. The ?, Ru, Ri5, and r16 of the phosphorus-nitrogen compound of the formula (17) and the formula (10) used in the present invention are not limited as long as the carbon number is 3 or more and 2 Å or less. If the carbon number is 3 or more, it is preferable to exhibit flame retardancy. If the carbon number is 3 Å or less, it is preferable to use the test resin ▲2. Among them, in terms of the flame retardancy, it is particularly preferable that the carbon number is 6 or more and 18 is from the point where the heart is compounded from the base of the compound. Examples of such a functional group include a functional group having a naphthyl group such as a phenyl group, a 2-phenyl group, a 4-phenyl group or a 4-phenyl group having a phenyl group such as a phenyl group.咐: base, naiwang two wow, four sigma sitting, etc. 126625.doc •37· 200839442 Containing functional groups of rat heterocyclic compounds. These compounds may be used as needed, or two or more types may be used in combination. Among them, a compound having a phenyl group, a 4, phenyl group is preferred in terms of ease of obtaining. The p in the dish-form nitrogen compound represented by the formula (17) used 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, it exhibits resistance, and when it is 25 or less, it has high solubility in an organic solvent. Among them, especially in terms of the ease of obtaining, what is better? For 3 or more _ below.

The q in the phosphorus-nitrogen compound represented by the formula (18) used in the present invention is not limited to 3 or more loooo or less. When it is 3 or more, it exhibits flame retardancy, and when it is 10000 or less, solubility in an organic solvent is high. Among them, especially in terms of the ease of obtaining, it is preferable. It is 3 or more and 100 or less. In the phosphorus-nitrogen-based compound represented by the formula (18) used in the present invention, A and B are not limited as long as they have an organic group having 3 or more carbon atoms. Among them, A car father is -n=P(〇C6H5)3, -N=P(〇C6H5)2, (oc6h4oh)3, -N=P(〇C6H5)(OC6H4OH)2, -N=P (OC6H4OH)3, -N=p(o)〇c6H5, -n=p(o)(〇c6h4oh). B is preferably -P(〇C6H5)4, -P(OC6H5)3(〇C6H4OH), -P(0C6H5)2(0C6H40H)2, -p(oc6h5)(0C6H40H)3, -P(〇c6H4OH 4,·ρ(〇)(〇(:6Η5)2, -p(〇)(〇C6H4OH)2, -P(〇)(〇C6H5)(〇C6H4〇H), etc. Photosensitive property of the present invention In the resin composition, when the amount of the fluorinated resin (A) is 100% by mass, the amount of the phosphorus-nitrogen compound added is preferably 50% by mass or less from the viewpoint of photosensitivity and the like. From the viewpoint of heat resistance of 126625.doc -38 - 200839442, it is preferably 45 mass% or less, more preferably 40 mass% or less. In the photosensitive resin composition of the present invention, the formula (1) a compound shown, and/or a compound having an iso-cyanocyanate ring, and/or a ruthenium imine compound (B) containing one or two quinone imine groups other than the component (A), by The bismuth component is combined to exhibit the south flame retardancy. The following describes the component (C). The resin composition of the present invention exhibits photosensitivity by using the S-quinonediazide compound of the component (C). Combining component (c) with component (B) above The photosensitive resin composition of the present invention exhibits high flame retardancy. Examples of the quinonediazide compound include i,2-benzoquinonediazidesulfonate and 1,2-benzoquinone. Azidosulfonamide, naphthoquinonediazide, hydrazine, and 1,2-naphthoquinonediazide, among which, from the viewpoint of inhibiting the solubility, it is preferably 12- Naphthoquinone diazide sulfonate. As 込2·naphthoquinonediazide sulfonate, as shown in formula (14) and formula (15), the substitution position of the group is the fourth position, 2 -naphthoquinonediazide-4_supply acid=: and the 5th position, 2_naphthalene g-quinonediazide_5_sulfonate, any of which can be used, and the viewpoint of flame retardancy In general, it is preferred that 1,2-naphthoquinone dinitrein S is intended. c [42]

126625.doc •39- 200839442 [Chem. 43]

(1 5) 1,2-naphthoquinonediazidesulfonate can be obtained by esterifying a compound having a phenolic hydroxyl group as a raw material and sulfonic acid. For example, it can be obtained by using a phenolic hydroxyl group having a functional group of im〇1 and 1,2-naphthoquinonediazide_4_sulfonic acid or its anthracene in a suitable solvent such as acetone. The chloride or its sulfonate is mixed or mixed with the sulfonic acid group at the 5th position, 2? naphthoquinonediazide-5-sulfonic acid or its hydrazine compound or its sulfonate. At this time, an alkaline catalyst such as triethylamine can be used. From the viewpoint of suppressing the solubility and the alkali solubility after exposure, the esterification ratio of the sulfonic acid is preferably 〇·6〇 or more and 98 or less. Examples of the 1,2-naphthoquinone-quinonediazide-removed g-g-g-types include tri-perylene-benzoic benzophenones, tetra-n-phenylene benzophenones, pentahydroxybenzophenones, and hexahydroxy-di Benzophenones, ((tetra)phenylporines, 1,2, (tetra), diazide sisters S. As a tri-perylene-benzophenone-based naphthalene-dihydrogenated vinegar, for example, 2 ,3,4-trihydroxybenzophenone g 〆T Ming-1,2-na-8 than two feng squirrels · 4_ tyros acid ester, 2,3,4. trisyl benzophenone (tetra), 2-naphthalene Stuffed diazide-5-shihuang warm vinegar/2,4,6. trihydroxybenzophenone+2.naphthoquinonediazide_4_sulfonic acid acetophenone heart naphthalene diazide, sour Etc. A base - as a tetra-based diphenylmethyl group eve #, · Nai Sft - 璺 续 续 酸 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 40- 200839442 2,2,4,3f-tetraweisylbenzophenone-1,2-naphthoquinone-quinonediazide-4-tartaric acid vinegar, 2,2,4,3'-tetrazide Phenyl ketone ketone 1,2-naphthoquinone quinone diazide-5 - tartaric acid S, 2,3,4,4'-tetrakilylbenzophenone-1,2-naphthoquinone quinonediazide -4_石黄酸醋, 2,3,4,4f-tetrasyldibenzoquinone-1,2-naphthoquinonequinodizide-5 · Xanthate S, 2,3,4,2'-tetracyclyldibenzophenone-1,2-naphthoquinone-quinonediazide-4-carnitine, 2,3,4,2 Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-indole, 2-naphthalene醌Diazide-4-sulfonate, 2,3,4,4,-tetrahydroxy-3,-nonyloxybenzophenone-; i, 2-naphthoquinonediazide-5-sulfonate Et al. 1,2-naphthoquinonediazide carboxylic acid esters of pentahydroxybenzophenones, 玎 · 2,3,4,2',6*-penta-dibenzophenone-naphthalene g-kun Azide-4 -barnadate, 253,4,2,6'-pentahydroxybenzophenone-i,2-naphthoquinonediazide-5-sulfonate, etc. as hexahydroxydiphenyl 1,2-naphthoquinonediazide sulfonate of ketones, which can be exemplified by 2,4,6,3',4',5'-hexahydroxybenzophenone-1,2-naphthoquinone Nitro-4-sulfonate, .////', :^-hexahydroxybenzophenone, naphthoquinone, diazide, sulfonate, 3,4,5,3',4',5 '-Hexahydroxybenzophenone_1,2-naphthoquinonediazide-4-sulfonate, ^/^.'/'.•-hexahydroxybenzophenone-^naphthoquinonediazide- Sulfonate, etc. The 1,2-naphthoquinonediazide reductive ester of a hydrocarbon is exemplified by: bis-P,4-dihydroxyphenyl)decane-indole, 2-naphthoquinonediazide sulfonate, double ( 2,4-Dihydroxyphenyl)decane_1,2-naphthoquinonediazide, bis(p-hydroxyphenyl)decane-1,2-naphthoquinonediazide-4·sulfonate , bis(p-hydroxyphenyl)decane_ 1,2-naphthoquinonediazide-5-sulfonate, m-tris(p-hydroxyphenyl)ethane, in naphthalene 126625.doc •41 · 200839442 酉甓 甓 _ _ _ _ _ ι ι ι ι ι ι 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓 甓Phenyl)methane-12-naphthoquinonediazide-4-carvate, bis(2,3,4-trihydroxyphenyl)methane_i,2-naphthoquinonediazide_5-sulfonic acid S , 2,2,-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-4-sulfonic acid vinegar, 2,2,·bis (2,3,4 -trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonic acid vinegar, 1,1,3·tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenyl Propane·1,2-naphthoquinonediazide-4sulfonate, 1,1,3-tris(2,5·dimethyl-4-hydroxyphenyl)-3-phenylpropanone-1,2 -naphthoquinonediazide-5-acid Ester, 4,4'-[1-[4-[1-[4-phenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide 4-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2- Naphthoquinonediazide_5_sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)_2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate , bis(2,5-dimethyl-4-hydroxybenylphenylcarbamate-1,2-naphthalene-diazide-5-carvate, 3,3,3,,3,-tetra Base-1,1'-spirobi-5,6,7,5,6,7,6-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3 ,,3,tetradecyl-l,l,·spirobi- 5,6,7,5,6,7,-hexaol_ 1,2-naphthoquinonediazide_5_sulfonate , 2,2,4-trimethyl-7,2',4,trihydroxyflavan-1,2-naphthoquinonediazide_4_sulfonic acid|, 2,2,4-trimethyl -7,2,,4,-trihydroxyflavan-1,2-naphthoquinonediazide sulfonate, and the like. As the 1,2-naphthoquinonediazide compound, in addition to the above, for example, a compound represented by the formula (29) may be mentioned. [化44]

126625.doc •42- 200839442

〇一Q (2 9 ) (Q is the same as formula (14) and formula (15).) In terms of inhibition of solvency, compared with sulfonic acid vinegar, the photosensitive contrast ratio is "2-naphthoquinone". 2 4 酉 酉 二 二 二 -4- 续 续 续 续 续 续 萘 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = Its compound [Chem. 45]). Q-0

(4) (!6) (wherein Q is independently hydrogen, or de+, from equation (14) or Π5). Among them, a plurality of / called organic base. One of the Qs is one selected from the formula (10) or / (), and the flame retarding effect of the σ 4 is superior to that of the other - naphthoquinone quinone compound. Among them, the compound of the 12-naphthoquinonediazide·4·sulfonic acid vine having the substitution of the Q-form (14) and the fourth-position is represented by the Q-form (14), and the resistivity is particularly excellent, so that it is preferable. . 126625.doc -43- 200839442 The component (c) is preferably from 9% by mass to 50% by mass, more preferably from 5% by mass to 4% by mass, based on 100% by mass of the component (VIII). Particularly preferably, it is 15 mass% or more and 3 mass% or less. Within this range, the flame retardancy and photosensitivity are relatively good. The amount of the component (B) and the component (c) is preferably 5 parts by mass or more and 6 parts by mass or less based on the total amount of the component (B) and the component (A). More preferably, it is 50 parts by mass or less. Particularly preferably, it is 2 parts by mass or more and 4 parts by mass or less. The ratio of the component (B) to the component (c) is preferably 0.4 or more and 4 or less, more preferably 0.5 or more and 3 or less. Particularly preferably 0.75 or more and 2 or less. In this range, the flame retardancy and the photosensitivity are excellent, and the warpage at the time of dry film formation can be suppressed, and the embedding property to the substrate is also good. The component (D) is described below. It is also preferred to add a component (D), that is, a polyether compound, to the photosensitive resin composition of the present invention. Examples of the polyether compound include a linear polyether or a cyclic crown ether. The polyether is, for example, a compound having an oxyethylene chain, a propylene oxide chain, or a butyl oxide chain. Among them, a compound having an oxyethylene chain is particularly effective for improving warpage at the time of dry film formation, and is preferably a crown ether. , for example, 12-crown-4 ether, 15-crown-5-ether, 18-crown-6-ether, etc. In order to improve the adhesion of the copper surface to the wiring of the wiring pattern substrate, the polyether compound Preferred are compounds having a quinone H group at the end. As having an oxyethylene chain, and having an end Polyether compound of OH group 126625.doc • 44 - 200839442 Examples of materials include polyethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc. As the propylene oxide chain, the terminal has OH The compound of the group may be a polypropylene glycol such as J-propanol, dipropylene glycol, tripropylene glycol or tetrapropylene glycol. Examples of the compound having a butyl oxide chain and having a fluorene H group at the terminal include butanediol and dibutylene glycol. Polybutanediol such as tributyl diol or tetrabutyl diol.

In view of the warpage of the dry film, polyethylene glycol is preferred among these. Among the polyethylene glycols, a compound having a mass of 300 to 1 Torr has a better light-curing effect and is more compatible with a tree sap/month paint, and is therefore preferred. Further, from the viewpoint of simultaneously achieving the effect of improving the warpage and suppressing the scattering of the components remaining in the film after heating, the molecular weight is more preferably 4 Å to 8 Å. Specifically, polyethylene glycol having a molecular weight of about 6 Å is preferred. Moreover, in order to further improve the warpage and developability at the time of dry film formation, it is also preferable to add a plasticizer (7)) as a plasticizer to the photosensitive resin composition of the present invention having a phosphorus-nitrogen group. The component (E) which is a plasticizer in the squamous-containing photosensitive sulphate composition used in the present invention is not suitable for imparting plasticity to the resin composition and lowering the Tg of the composition. Specially limited. Examples of such a plasticizer include tricresyl phosphate, tris(xylylene) phosphate, tributyl phosphate, triisobutyl phosphate, tris(2-ethylhexyl) phosphate, and tributyloxy phosphate. Base) θ is an equivalent phosphate; an ether compound such as ethylene glycol, polypropylene glycol, crown ether; tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate 126625.doc -45 · 200839442 酉曰, etc. a compound containing a methacrylonitrile group; a compound containing an acrylonitrile group such as tetraethylene glycol diacrylate or a polyethylene glycol diacrylate; an phthalic acid such as dimethyl phthalate phthalate or an adjacent ortho-dicarboxylic acid Dicarboxylic acid trimellitic acid tris(2-ethylhexyl) vinegar and other trimellitic acid _; adipic acid dimethyl ketone, adipic acid-butyl ester and other aliphatic dibasic acid ester; Ester-modified triacrylic acid _, ε_ caprolactone modified tris(acrylic oxyethyl) iso-cyanuric acid vinegar and the like. Among them, 'in terms of the surface curvature after dry filming', it is better to fill the acid vinegar, the methacrylic oxime-containing compound, the iso-ethylene cyanate modified triacrylate vinegar, ε-hexene Vinegar modified tris(propylene oxyethyl) iso-cyanuric acid. In view of sufficient plasticity, when the amount of the (A) alkali-soluble resin is 1% by mass, the plasticizer in the (4) nitrogen-based photosensitive resin composition used in the present invention is (E) The amount of the component added is preferably 3% by mass.

under. Further, from the viewpoint of the flame retardancy of the hardened body, it is more preferably 2% by mass or less. In the photosensitive resin composition of the present invention, a known additive may be added as needed within the range of the amount and quality without departing from the effects of the present invention. Specifically, examples of the additive include an adhesion promoter, a surfactant, an antioxidant, an ultraviolet inhibitor, a light stabilizer, a plasticizer, a hydrazine, a filler, a pigment, a dye, a foaming agent, and a consumer. A foaming agent, a dehydrating agent, an antistatic agent, an antibacterial agent, an antifungal agent, a leveling agent, a dispersing agent, an ethylenically unsaturated compound, and the like. The photosensitive resin composition of the present invention is obtained by mixing (A) component, (B) component, and (C) component in any solvent. As the solvent, a solvent used in the above polyimine resin composition can be used. Further, if necessary, the component (D) or the component (8) may be added to the photosensitive resin composition of the present invention at 126625.doc -46-200839442. The resulting solution can be mixed and used as a coating liquid. X, the photosensitive tree of the present invention, and the mouth of the mouth is applied to the substrate, and then the mixture is applied to a specific substrate.

The circuit board can be manufactured using the photosensitive resin composition of this invention. In the case of manufacturing a circuit board, the photosensitive resin composition is laminated on a substrate having wiring, and the photosensitive resin composition layer is subjected to pattern exposure, and the water is dissolved in the fourth (four) water. The resin composition layer after the exposure was subjected to development treatment. The substrate having a wiring is, for example, a hard substrate such as a glass epoxy substrate or a maleimide glass substrate, or a substrate having flexibility such as a polyimide film. The router. Among them, the photosensitive resin composition of the present invention is particularly suitably used as a cover layer of a flexible printed circuit board having a wiring on a flexible substrate such as a polyimide film, and the photosensitive resin composition of the present invention is used as a scratch In the case of a cover layer of a printed circuit board, for example, the photosensitive resin composition of the present invention can be attached to a substrate having a wiring in a state of being made into a dry film. When a dry film composed of the photosensitive resin composition of the present invention is used, the solution of the photosensitive resin composition is applied to any carrier film such as a polyethylene terephthalate film or a metal film by any method. After drying, it was dried and dried to form a laminate film having a carrier film and a dry film. Further, at least one of the antifouling film or the protective film ' such as a low-density polyethylene film may be provided on the dry film to form a laminated film. The dry film may be laminated on a substrate having wiring by any method such as thermal lamination, hot pressing, hot vacuum lamination, or hot vacuum pressing. Thus, a flexible printed circuit board can be produced, and 126625.doc-47-200839442 is provided with a substrate and a cover layer having wiring, and the cover layer is formed on the substrate so as to cover the wiring. Further, it is composed of a substance formed by exposing and developing the photosensitive resin composition of the present invention. First, the photosensitive resin composition of the present invention is applied onto a substrate. As the substrate, if it is a substrate which is not damaged when a photosensitive dry film is formed, it is infinitely flawless. Examples of such a substrate include a stone wafer, a glass, a ceramic, a heat resistant resin, a carrier film, and the like. The carrier film in the present invention may, for example, be a polyethylene terephthalate film or a metal film. The heat-resistant resin and the carrier film are preferred in terms of the handling property, and a polyethylene terephthalate film is particularly preferable from the viewpoint of the releasability after pressure-bonding to the substrate. The coating method may, for example, be bar coating, roll coating, die coating, blade coating, dip coating, blade coating, spray coating, flow coating, spin coating, slit coating, brush coating or the like. After coating, a heat treatment called pre-baking may be performed using a hot plate or the like as needed. In the case of using the photosensitive I* raw film composed of the photosensitive composition of the present invention, the solution of the photosensitive resin composition is applied to any substrate by any method, and then dried. The film is dried to form a laminated film having, for example, a carrier film and a photosensitive film. Further, at least one layer of an antifouling or shingling cover film may be provided on the photosensitive film to form a laminated film. The cover film in the laminated film used in the present invention may, for example, be a photosensitive film made of low-density polyethylene or the like. The film thickness of the coating layer formed by the above methods is not particularly limited, and in terms of circuit characteristics, etc., it is preferably 4 μηι to 50 μηι, more preferably 126 126625.doc -48- 200839442 μιη ~40 μπι, especially good is 8 arrays ~ 3 〇 _. The photosensitive film composed of the resin composition of the present invention can be used for a printed circuit board which can be obtained by crimping on a substrate having wiring by covering the above wiring The photosensitive thin film is subjected to inspection and development, and is obtained by firing. The substrate having wiring as the printed circuit board used in the present invention may be a hard substrate such as a bad oxygen glass substrate or a cis-succinimide glass substrate, or a polyimide film. Such as a flexible substrate. Among them, a flexible substrate is preferred from the viewpoint of being bendable. * The method for producing a printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. As such a production method, hot pressing, hot lamination, hot vacuum pressing, and hot vacuum are performed in a state where the wiring side of the substrate having the wiring is brought into contact with the photosensitive film of the present invention. A method such as lamination. Among them, from the viewpoint of the embedding property of the photosensitive film to the wiring, it is preferable that the thermal film is subjected to hot pressing and hot vacuum lamination.加热 When the photosensitive film is laminated on the substrate having the wiring, the heating temperature j is the temperature at which the photosensitive film can be adhered to the substrate, and the viewpoint of the substrate is infinite. In view of the decomposition of the photosensitive film or the field reaction, it is preferably 3 (rc or more, C or less. More preferably, it is 50 ° C or less and 15 or less (rc or less). The photosensitive resin composition of the present invention can be used. After the light is irradiated, it can be used for the positive type of material patterned by the photolithography method by the inspection development = the light-dissolving portion. 126625.doc -49- 200839442 There is no special light source for light irradiation. Limitations include high pressure mercury lamps, ultra high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, fluorescent lamps, crane lamps, argon lasers, and money lasers. Among them, high pressure mercury lamps are preferred. Ultra high pressure mercury lamp.

The aqueous solution to be used for development is not limited as long as it is a bath that can dissolve the light-irradiated portion. Examples of such a solution include sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium acid solution and an aqueous sodium hydroxide solution are preferred. As the developing method, there are listed: jet development, impregnation development, stirring development, and the like. The film or the positive pattern obtained on the substrate by these methods may be subjected to heat treatment as needed. The heating temperature is preferably 10 (rc or more, 3 〇〇 or less. More preferably, it is more than (10)^: The following is better than (10) above 2 〇〇 ° C. The heat treatment by this range The photosensitive resin composition of the present invention can exhibit high flame retardancy. It can be heated in any of an air environment or a nitrogen atmosphere. Further, there is no special heating method: an oven can be used. Heating is carried out in a baking furnace, a hot plate, etc. From the viewpoint of removing the solvent, or by side reaction or decomposition, the photosensitive film of the present invention is pressure-bonded and then cultured, preferably at a temperature of 4 〇 n: The calcination is carried out at the following temperature. More preferably, the crucible is not more than 300 ° C. The gas atmosphere in the above-mentioned calcination reaction can be carried out in an air environment of 1 μ. In the production of the above printed circuit board, the above-mentioned culture The time required for the calcination varies depending on the reaction conditions, and is usually within 24 hours from 126625.doc -50 to 200839442, and it is particularly preferred to carry out calcination in the range of from 丨hour to 8 hours.

The photosensitive resin composition of the present invention can sufficiently suppress warpage when forming a photosensitive film, and has good developability, and exhibits chemical resistance when formed into a cured body. a printed circuit board for operating panels or the like of various electronic devices, or a protective layer for a circuit substrate; an insulating layer for forming a laminated substrate; for forming a film on the electronic component described below for use in an electronic device field The electronic component is protected, and the like, and the like, the semiconductor wafer used in the electronic component semiconductor device, the semiconductor wafer, the semiconductor device member, the semiconductor substrate, the heat sink, and the bow pin, The semiconductor itself and so on. Hereinafter, an embodiment adopted to clarify the effects of the present invention will be described. < Brief Description> The abbreviation of the reagent used in the present invention is disclosed. • Acid dianhydride tender: oxygen bis-phthalic acid dianhydride (double (3, 4. two county anhydride) TAHQ; bis-p-trimellitic anhydride terephthalate TMEG: 譬 low 岔 - double partial dimethyl anhydride Ethylenediester•Diamine MBAA·3,3,Disulphate·4,4ί_Diaminobenzophenone·1,3_bis(3-aminophenoxybenzene) 126625.doc •51 - 200839442 • (B) component TBP: tributyl phosphate TOP: tris(2-ethylhexyl) phosphate TBXP: tris(butoxyethyl) phosphate TIBP: triisobutyl phosphate RDP: resorcinol double ( ATP: tributyl citrate CR741: bisphenol A bis(diphenyl phosphate) HCA : 9,10-dihydro _9_oxa-10-disphenanthrene 〇 _Oxide M-325 : ε-Caprolactone modified tris(propylene oxyethyl) isomeric cyanurate Μ-140: Ν-propylene oxiranyl ethyl hexahydro phthalate imine CDP: Toluene diphenyl phosphate • Compound (C): (C): refers to three of the general formula (16) (the average of 23 is the structure represented by the general formula (14). Compound C-2: Refers to three of the general formula (16) (wherein an average of 2.34 is a structure not represented by the general formula (15). _ <Reagents> Examples The reagents used in the comparative examples can be used for the reaction without special purification, such as polyoxydiamine (KF-8 〇1〇X Shin-Etsu Chemical Co., Ltd.), MBAA (Wakayama Refinery) Co., Ltd. manufacturing), ODPA (manufactured by Wako Pure Chemical Industries Co., Ltd.), APB (manufactured by Ishii Chemical Co., Ltd.), TMEG (manufactured by Shinsho Chemical Co., Ltd.), Compound B-1, Compound B-2, TBP (Dauba Chemical Co., Ltd. has 126625.doc -52-200839442 limited company manufacturing), TOP (made by Daiba Chemical Co., Ltd.), TBXP (made by Daiba Chemical Co., Ltd.), TIBP (manufactured by Ajinomoto Fine Chemical Co., Ltd.) , resorcinol bis(diphenyl phosphate) (manufactured by Ajinomoto Fine Chemical Co., Ltd., hereinafter referred to as RDP), tributyl citrate (manufactured by Pfizer Chemical Co., Ltd., hereinafter referred to as ATC), ε- Ester-modified tris(acrylic oxyethyl)isocyanate (Aronix®-325, manufactured by Toagosei Co., Ltd., hereinafter referred to as M-325), phosphorus-nitrogen-based compound (SPB_100, SPH-100) , Otsuka Chemical Co., Ltd. ), toluene (manufactured by Wako Pure Chemical Industries Co., Ltd., for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries Co., Ltd., special grade), pyridine (manufactured by Wako Pure Chemical Industries Co., Ltd., for organic synthesis) ), γ-valerolactone (manufactured by Wako Pure Chemical Industries Co., Ltd., Level 1). [Soluble Polyimine Synthesis Example 1] A 1 liter separable three-necked flask equipped with a stirrer was attached to a cooling tube with a ball valve equipped with a water meter. Under a nitrogen stream, 268.52 g of γ-butyrolactone (manufactured by Wako Pure Chemical Co., Ltd.) and 31.02 g (100 mmol) of oxydiphthalic dianhydride (manufactured by Manac Co., Ltd.) were placed in a flask. 68.5 5 g (75 mmol) of 1,3-bis(3-aminopropyl)polydecane (molecular weight: 914 / manufactured by Shin-Etsu Chemical Co., Ltd.), 7.61 g (50 mmol) of 3,5- Diaminobenzoic acid (manufactured by Alddch Co., Ltd.) was stirred at room temperature for 2 hours. 1.5 g (15 mmol) of γ-valerolactone, 2.4 g (30 mmol) of σ ratio bite, and 50 g of toluene were placed in the flask, and the temperature was raised to 180 ° C to remove the total benzene-water The ingredients were boiled and stirred at 180 rpm for 2 hours. After being placed at room temperature, 126625.doc -53 - 200839442 After cooling, put 2G.62 g (5G mmol) of bis-p-benzoic anhydride U2-ethylene diacetate (manufactured by Nippon Chemical and Chemical Co., Ltd.), 7·3ΐ g (25-faced 1'3 bis(4-aminophenyloxy)benzene (manufactured by Wakayama Seiki Co., Ltd.), 166.21 g of γ-butyrolactone, and stirred at room temperature for 2 hours. • 180 C, removing the azeotrope component of toluene-water, and stirring at 180 rpm for 2 hours, then left to cool. The polymer concentration of the obtained polyimine solution was 25% by mass. Amine varnish is used as a varnish containing the component (A). The polyimide varnish is applied to an easily peelable enamel having a thickness of 25 μm using a knife coater (Τ10〇-Η25/Mitsubishi Chemical Polyester Film Co., Ltd.) After the above, it was dried in an oven at 95 C/30 minutes, and then peeled off to obtain a film, which was obtained by measuring the film using a tensile tester (AUT® GRAPH AGS_Η/Tokyo Manufacturing Co., Ltd.). The ductility is 5〇°/〇 or more (the test piece is 24 μηη thick, 15 mm×100 mm) [Preparation example] _ The components of the composition shown in Table 1 are prepared in proportions not shown in Table 1. Further, 'the compound (a) shown by the following formula (30) or the following formula (31) is not used. Compound (b), as a ((:) component of a quinonediazide compound. Compound (a) is a, cx, a'-tris(4-hydroxyphenylethyl_4_isopropyl-benzene (1) M〇1), an ester of 3-diazo 3,4-dihydro-4-oxonaphthalenesulfonic acid (2·3 m〇l). Compound (b) is α,α,α'-three (4) -hydroxyphenyl)-1-ethyl-4-isopropyl-benzene (1 mol) and 4·diazo-4,5-dihydro-5-oxonaphthalene d•sulfonic acid (2.34^οΐ) Ester. [Chem. 46] 126625.doc -54- 200839442

ο Q

Q - 〇

(a) 3. ~? , CH

(In the formula 30, 〇, Q (Q knife illusion is independent of hydrogen or one of the valences of the selected formula (14)

(The Q knife in Formula 31 is independently hydrogen or the valence organic group selected from the formula (1)). As the component (B), (1) bisphenol a bis (diphenyl phosphate) is used (CR741/Da Ba Chemical Co., Ltd.) Co., Ltd.), (η) 9,1〇-dihydro_9_oxa-1〇-phosphaphenanthrene-10-oxide (manufactured by HCA/Sanguang Co., Ltd.), (called) and ^ Modified tris(propylene oxyethyl) iso-cyanate (Aronix Μ _ 3 2 5 / manufactured by Donglian Synthetic Co., Ltd.), (iv) N- propylene oxide hexahydrophthalic acid醯imine (manufactured by Ar〇nix M-140/East Asia Synthetic Co., Ltd.), (v) tris (butoxyethyl) _ (TBXP/Da Ba Chemical Co., Ltd.), (vi) toluene phosphate Phenyl ester (CDP/Da Ba Chemical Co., Ltd.). Further, as component (A), component (B), and component (C), 126625.doc •55·200839442 was added, and (vii) polyethylene glycol diacrylate (η=4) (ΝΚ ester 4G) was used. /Xinzhongcun Chemical Manufacturing), (viii) resorcinol bis(xyl phosphate) (ΡΧ200/Da Ba Chemical Co., Ltd.), (ix) polyethylene glycol with a molecular weight of 600 (Wako Pure Chemical Co., Ltd.) Made by the company). [Table 1] Ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Varnish containing the component (A) 400 400 400 400 400 400 400 400 400 400 400 (B) (〇15 (i)15, (ϋ)1〇(i)15, (iii)10 (1)5, (vi)10 (iii)15 (1)15, (ii)l〇(015 , (ii) l〇(iv)15 (1)15, (iv)10 (1)10, (iii)5 (v)15 (C) Ca)15 (a)15 (a)15 (4)20 (a)20 (b)15 ( a) 20 (8) 20 (a) 15 (8) 20 (a) 20 Adding component (10) 3 Component Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Unit: Parts by mass (8) Varnishes for ingredients 400 400 400 400 400 400 400 400 400 (B) (i) l〇_ (C) (a) 30 (a) 30 (8) 30 (a) 30 (8) 20 (4) 20 Add ingredients (vii) 10 (viii) 15 ( Ix) 5 (viii) 15 (viiii) 15 (vii) 10 Evaluation by the following method. <Quantitative average molecular weight determination> Determination of the number average molecular weight, ie, gel permeation chromatography (GPC) The measurement was carried out under the following conditions. The measurement, that is, using N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) as a solvent, and adding 24.8 mmol/L of one hydrated evolutionary lithium before the measurement (and pure light) Produced by Pharmaceutical Industries, with a purity of 99.5%) and 63. 2 mmol/L of acid (made by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography). Column: Shodex KD-806M (Showa Denko) Made by the company)

Flow rate: 1 · 0 mL / min Column temperature: 40 ° C Pump: PU-2080 Plus (manufactured by JASCO) -56- 126625.doc 200839442 Detector: RI-2031 Plus (RI: differential refractometer; manufactured by JASCO UV-2075 Plus (UV-VIS: UV-Vis Spectrometer; manufactured by JASCO) Further, a standard polystyrene (manufactured by Tosoh Corporation) was used to prepare a calibration curve for calculating the above molecular weight. <Measurement of film thickness> The film thickness of the cured body was measured using a film thickness meter (manufactured by Mitutoyo Co., Ltd., ID-C112B). <Dry film production method> The photosensitive resin composition of the present invention was applied by a doctor blade method using a film coater (FILMCOATER) (manufactured by TESTER SANGYO Co., Ltd., PI1210). Specifically, the photosensitive resin composition was dropped onto an easily peelable PET film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., DIAFOIL, T100-H25), and applied at a gap of 200 μm. The coated film was dried at 95 ° C for 30 minutes using a drier (manufactured by ESPEC Co., Ltd., SPHH-101), whereby a photosensitive dry film was obtained. <Warring> After applying the photosensitive resin composition of the present invention to a PET film (T100-H25/Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 25 μm, using a knife coater, Drying in an oven at 95 ° C / 30 minutes gave a photosensitive dry film. The coated portion was cut out to a size of 20 cm x 20 cm as a test film, and the melody was visually evaluated. The case where no warpage occurred was recorded as ◎, and the case where the slight warpage occurred was recorded as 〇, and warpage occurred, and the film curl 126625.doc -57- 200839442 was recorded as a roll. <Flame retardancy test> The flame retardancy test was carried out in the following order. The photosensitive resin composition was applied to one side of a film of KaPt〇n (registered trademark) (manufactured by EN-100/Du Pont-. T〇ray Co., Ltd.) at 95 ° C by the above coating method. The photosensitive resin composition was applied to the opposite surface at 95 ° while drying for 30 minutes. Under the squeaking of the squeegee clock, the photosensitive resin composition was applied to both sides of a Kapton film, and then a calciner (manufactured by Koyo Lindberg Co., Ltd.) was used at 120. (: calcination was carried out for 60 minutes, followed by baking at 20 °C for 6 minutes to thereby harden the photosensitive resin composition to obtain a hardened body. The hardened body was cut out to 20 cm X 5 cm, and the flame retardancy was evaluated by the UL94 VTM test. The sample after the residual flame time of each sample is 1 sec or less, and the sample which is not burned to the mark of 12.5 is recorded as VTM_0 (or 〇), and the residual flame time of each sample is 1 〇 second or more or burned to 12 The flame retardancy of the sample of the mark at 5 cm is denoted by X. <Lamination property> φ The photosensitive resin composition of the present invention is applied to a PET film having a thickness of 25 μm using a knife coater (Τ100·η25/Mitsubishi Chemical Polyester Film Co., Ltd.) was dried in an oven at 95 ° C / 30 minutes to obtain a photosensitive dry film having a film thickness of 24 μm. • The thickness was 18 Km. The copper foil (F3-WS/glossy surface) was polished on the entire surface of the polishing roll (#200) and the entire surface of the sandblasting brush, using al-70〇 (manufactured by Asahi Kasei Co., Ltd.), and the residual heat of the substrate was 60 ° C. The photosensitive dry film obtained by laminating the pressure at a temperature of 14 (rCT, 〇·34 MPa, 〇·5 m/min, peeling off PET film. The case where only the pET film was peeled off was denoted by 〇, and the case where the pET film and the photosensitive 126625.doc -58-200839442 film were peeled off was denoted by x. "Photosensitivity" was obtained using the laminate property evaluation The copper foil laminated with the photosensitive film is evaluated as follows. Further, since it is difficult to evaluate the peeling of the PET film and the photosensitive film, it is not laminated on the copper foil and directly sensitized. The dry film was subjected to the following evaluation. Contact exposure was performed using an ultra-high-pressure mercury lamp (manufactured by HMW-201KB/Oak Co., Ltd.) using a positive-type mask. The exposure amount was 1,300 mJ/cm2. The method is as follows: using a sodium carbonate/water mixture having a concentration of 3%, and developing at a developing temperature of 4 Torr, a jetting pressure of 〇·2 Mpa, and a developing gate of 40 and the like. The obtained pattern was observed by an optical microscope at room temperature. The pattern obtained by forming a circular aperture pattern of 100 μm was denoted by 〇, and the case where a circular aperture pattern of 1 无法 could not be formed was denoted as X. Table 2]

Example 1 Appreciation Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Implementation Implementation 11Π Implementation Π1 Warp 〇〇 ◎ 〇 ◎ ◎ 〇〇\7 4 ^ ◎ \T\ l\J 〇1X4 1 χ ◎ Flame retardant 〇〇〇〇〇〇〇〇〇〇〇 laminate 〇〇〇〇〇〇〇〇〇〇〇 photosensitive 〇〇〇〇〇〇〇〇〇〇〇 comparison Comparison, comparison, comparison, comparison, comparison, comparison, *, !0, case, case, case, case, case, case, case, case XX 〇V-/ X Lamination XX 〇〇X 〇〇X 〇Photosensitive 〇 〇〇 〇〇 〇〇〇 X

[Polyimine Synthesis Example 2] 126625.doc -59- 200839442 A 1 liter separable three-necked flask equipped with a stirrer was attached to a cooling tube with a ball valve equipped with a water meter. Under a nitrogen stream, 341.64 g of γ-butyrolactone (manufactured by Wako Pure Chemical Co., Ltd.) and 31 〇 2 g (100 mmol) of oxydiphthalic dianhydride (manufactured by Manac Co., Ltd.) were added to the flask. 68.55 g (75 mmol) of 1,3-bis(3-aminopropyl) polyoxoxime (molecular weight: 914 / manufactured by Shin-Etsu Chemical Co., Ltd.), i4 31 g (50 mmol) of 3,3 '-Dicarboxy-4,4,diaminodiphenylmethane (manufactured by Wakayama Seiki Co., Ltd.), and stirred at room temperature for 2 hours. 1.5 g (15 mmol) of γ-valerolactone, 2.4 g (30 mmol) of bite, and 50 g of decane were added to the flask and the temperature was raised to 18 Torr. Thereafter, the azeotropic component of toluene-water was removed and stirred at 180 rpm for 2 hours. After standing to cool at room temperature, 20.62 g (50 mmol) of trimellitic anhydride ι, 2-ethylene diester (manufactured by Nippon Chemical and Chemical Co., Ltd.) and 7·3 ι g (25 mm 〇1) were added. 3-(3-aminophenoxy)benzene (manufactured by Wakayama Seiki Co., Ltd.) 67.59 g of γ-butyrolactone was stirred at room temperature for 2 hours. Thereafter, the temperature was raised to 180 C, and the azeotropic component of toluene-water was removed, and the mixture was stirred at 18 rpm for 2 hours, and then left to cool. The polymer concentration of the obtained polyimine solution was about 25 mass%. The obtained polyimide varnish was used as the varnish containing the ingredients' for evaluation of Example 12 and Example 13. In Example 12, the varnish containing the component disclosed in Synthesis Example 2 was replaced with the varnish containing the component (A) of Example 5, and evaluation was carried out in the same manner as in Example 5. As a result, the warpage was ◎, the flame retardancy was 〇, the lamination property was 〇, and the photosensitivity was 〇. In the shell target example 13, the varnish containing the component (A) 126625.doc-60-200839442 disclosed in the polyimine synthesis example 2 was used, and the varnish containing the component (A) of the example u was replaced. The evaluation was carried out in the same manner as in Example ,, and the result was ◎, the flame retardancy was 〇, the lamination property was 〇, and the photosensitivity was 〇. From the above, it was confirmed that the photosensitive films (Examples to Examples 13) obtained by using the photosensitive resin composition of the present invention were all excellent in warpage, flame retardancy, laminate properties, and photosensitivity. On the other hand, the photosensitive films of Comparative Example 4, Comparative Example 6, Comparative Example 7, and Comparative Example 9 were inferior in flame retardancy, and the warpage or lamination property of the photosensitive films of Comparative Example 5 and Comparative Example 8 was poor. Poor. In Examples 14 to 21 and Comparative Examples 1 to 24 below, the evaluation was carried out by the following evaluation conditions. <Laminating Condition> The lamination in the present invention is carried out using a vacuum press (manufactured by Nikko Seisakusho Co., Ltd.). The pressing was carried out under the conditions of a pressing temperature of 11 (TC, a pressing pressure of 丨.23 Mpa, and a pressing time of 5 minutes. <evaluation evaluation> The warpage was evaluated in the following manner: when manufacturing a photosensitive dry film of A4 size In the case where the edge portion is not present in a portion where the lift is more than 5 mm, the case where the portion exceeding 5 mm is generated is referred to as X. <Developability Evaluation> The developability is evaluated in the following manner: A photosensitive dry film (the thickness of the photosensitive layer is about 20 μm), which is laminated on a copper-clad laminate by the above lamination conditions, and then irradiated at a dose of 1·〇J/cm 2 using a positive mask. Exposure, followed by 'developing with a 3% aqueous solution of sodium hydroxide, 126625.doc •61- 200839442 Rinse with water, dry and evaluate the pattern using an optical microscope. The mask uses a circle with a direct control of 100 μηι a pattern (interval of 1 〇〇μηη). The case where the copper surface is exposed at the exposed portion and the thickness of the photosensitive layer of the unexposed portion is 18 μm or more is recorded as ◎, and the photosensitive layer of the unexposed portion is used. The film thickness is 15 μηι or more and The case of up to 18 μm is denoted by 〇, and the case where the resolution is poor or the film thickness is less than 15 μm is referred to as X. <Vacuum indentation evaluation> Using a photosensitive dry film by using The lamination conditions were carried out by laminating the copper-made electric 50 μm 'line at a pitch of 50 μm, and the thickness of the copper wiring was 12 μm), and then the obtained laminate was cut, and the cross section was observed using an electron microscope. It is noted that there is no insufficient embedding and the flatness of the surface of the cover layer is good. The case where the embedding was insufficient and the void was observed was denoted as X 〇 [Example 14] Under a nitrogen atmosphere, 'ΜΒΑΑ(30·0 mmol), polyoxo-diamine (!(^-8010, 30.0 mmol), ΑΡΒ (15.0 mmol), γ-butyrolactone (100 mL) was added to a separable flask, followed by hydrazine DPA (60.0 mmol), and stirred at room temperature for 2 hours. Then, toluene (3 〇 mL) was added. , pyridine (34.13 mmol), γ-valerolactone (22.47 mmol), heated and stirred at 180 ° C for 2 hours using a Dean-Stark apparatus and a reflux vessel. After cooling to 120 ° C, ΑΡΒ (15·0) was added. (mmol), stirring for 10 minutes, then adding 〇dpa (30.0 mmol), heating and stirring at 120 ° C for 2 hours. Then, adding toluene (10 mL), heating at 180 ° C for 2 hours, cooling to 140. °C, adding 丫-butyrolactone to make the solid content concentration of the polymer reach 30% by mass, and cooling to a temperature of 126625.doc -62-200839442, thereby obtaining γ-butene of polyimine (1) The ester solution. The mass average molecular weight and the mass (content ratio) (%) of the site derived from the oxylate structure are shown in the following Table 3. Further, the polyimide, the sensation The blending amount of the photo-agent and the phosphate ester is shown in the following Table 4. Further, the blending amounts of the following examples and comparative examples are also shown in Table 4 below. In 100% by mass of the polyimine (1), A photosensitive resin composition was prepared by mixing the compound c-2 (2% by mass %), TBP (i5 mass%), and ugly (15% by mass). By the above coating method, The salty secret fat composition obtained by the above method was applied onto an easily peelable PET film and dried at 95 for 3 ' minutes to thereby obtain a photosensitive dry film. The warpage of the dry film was 〇. The photosensitive dry film was laminated on a copper circuit (a steel wire width of 50 μm, a line spacing of 5 μm, and a copper wiring thickness of 12 μm). The laminated body obtained was cut and observed using an electron microscope. In the cross section, the photosensitive dry film was found to be embedded in a copper circuit without voids, and the surface of the coating layer was also flat. # Applying the above-mentioned positive photosensitive resin composition to Kapton by the above coating method (registered) On the trademark), it is dried at 95 for 3 minutes, and then coated on the opposite side. Said positive-type photosensitive resin composition was dried at 95 ° C for 30 minutes thereby to obtain a coated Kapton positive-type photosensitive resin composition (registered trademark) coated with a positive type photosensitive resin composition

KaPt〇n (W-continued trademark) was fired in a hot air towel at a temperature of 12 G ° C in a microwave oven at a temperature of 12 ° C. for 2 minutes, thereby obtaining a hardened body. The flame retardancy of the above hardened body was evaluated by UL94 ^ 4 test. The results are shown in Table 5 below. 126625.doc -63- 200839442 The above photosensitive film was laminated on a copper box laminate by the above lamination conditions. Using a positive mask, expose the obtained two-layer body with U "em2 exposure. Then, use a 3% aqueous solution of sodium hydroxide to test the development process. Use water to rinse, dry and use. Observe the pattern with an optical microscope. The copper surface is exposed at the exposed portion of each dry film, and the thickness of the coating layer of the unexposed portion is 15 μm or more (2 μm μη). [Example 15]

The photosensitive resin composition was prepared by mixing the compound C-2 (20% by mass), Τ0Ρ (15% by mass), and ΤΒχρ〇5 in 100% by mass of the polyimine (1) produced in Example 14 Things. The warpage, flame retardancy, embedding property, and developability of the photosensitive resin composition were evaluated in the same manner as in Example 14. The results are shown in Table 5 below. [Example 16] In 100% by mass of the polyimine (1) produced in Example 14, the compound C-2 (20% by mass), butyl hydrazine > (15% by mass) and ΤΒχρ (ΐ5) were mixed. The photosensitive resin composition was prepared by mass%). In the same manner as in Example 14, δ was used to evaluate the taste, flame retardancy, embedding property, and alkali developability of the above-mentioned photosensitive resin composition. The results are shown in Table 5 below. [Example 17] In a separable flask, μβαα (3〇〇mmol), polyoxydiamine (KF-8010, 45·0 mmol), γ·butyrolactone (1〇) were placed under a nitrogen atmosphere. 〇mL), then hydrazine DPA (60.0 mmol) was added and stirred at room temperature for 2 hours. Then, toluene (30 kL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added using a Dean-Stark apparatus and a reflux apparatus at 18 Torr. 126 126625.doc -64- 200839442 Heated and dropped for 2 hours. After cooling to i2 (rc, add ApB (15 〇mm〇l) 'scrambled for 10 minutes, then add 〇DpA (3〇〇匪〇1), heat and mix at 120C for 2 hours. Then add toluene (I Stirring, stirring at 180 °C for 2 hours. Cooling to (10), adding 丫-butyrolactone so that the solid content of the polya is 3 3% by mass, and cooling to room temperature, thereby obtaining poly fluorene. The γ-butyrolactone solution of the amine (2). The mass average molecular weight and the mass (content ratio) (%) of the site derived from the siloxane structure are shown in Table 3 below. In the amine (2), the photosensitive resin composition was prepared by mixing the compound c_1 (2% by mass) and tbxp (15% by mass), and the above-mentioned photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in the following Table 5. [Comparative Example 10] In 1% by mass of the polyimine (1) produced in Example 14, mixed The photosensitive resin composition was prepared by using the compound C-2 (20% by mass). The photosensitive resin composition was evaluated in the same manner as in Example 14. The results are shown in the following Table 5. [Comparative Example 11] In 100% by mass of the polyimine (1) produced in Example 14, A photosensitive resin composition was prepared by using a compound C-2 (2% by mass) and an aromatic group-containing scaly acid: RDP (30% by mass). The above photosensitive resin was evaluated in the same manner as in Example '. The composition of the composition was: flammability, embedding property, and alkali developability. The results are shown in the following Table 5. '', [Comparative Example 12] The polyimine produced in Example 14 at 100% by mass In (1), a photosensitive resin composition is prepared by mixing 126625.doc -65-200839442 compound C-2 (20% by mass) and an ordinary plasticizer, atc (four) mass phrase, in the same manner as in the embodiment (4). Method 'Evaluation of warpage, flame retardancy, embedding property, and alkali developability of the above-mentioned photosensitive resin composition. The results are shown in the following Table 5. [Comparative Example 13] Example 17 in 100 mass / 〇 A photosensitive resin composition was prepared by preparing a mixture of a raw material C 1 (20 bury / Å) in the production of t-merine (7). In the same manner, the surface curvature, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated. The results are shown in Table 5 below. [Comparative Example 14] Example at 100 Å/〇 丨In the polyimine (2) produced, a photosensitive resin composition is prepared by mixing a compound CM (2% by mass) and an aqueous vinegar having an aromatic group, that is, Rdp (30% by mass). The warpage, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 14. The results are shown in Table 5 below. [Comparative Example 15] The mass was 100 mg. /. The polyacrylonitrile (2) produced in Example 17 was mixed. A photosensitive resin composition was prepared by using a compound C-1 (20% by mass) and an ordinary plasticizer, ATc (3 Å mass / 0). The warpage, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 14. The results are shown in Table 5 below. According to Table 5, a photosensitive film (Comparative Example W, Comparative Example 13) composed of a photosensitive resin composition to which the phosphate compound used in the present invention was not added, and an aromatic phosphate compound were added thereto. Sense 126625.doc -66-200839442 Photosensitive film composition (Comparative Example 11 and Comparative Example 14) composed of a photosensitive resin composition, a photosensitive resin composition containing the acid ester compound used in the present invention The photosensitive film (Examples 14 to 17) thus constituted maintained flame retardancy and improved warpage and embedding property. Further, the photosensitive film (Comparative Example 12 and Comparative Example 15) composed of the photosensitive resin composition to which the ordinary plasticizer was added exhibited improved warpage and embedding property, but the flame retardancy was lowered. According to the above, the photosensitive film composed of the photosensitive resin composition to which the acid-filling compound used in the present invention is added maintains the flame retardancy, and the warpage and the embedding property at the time of dry film formation are improved, and The developability is also relatively good. [Table 3] The number average molecular weight, composition, and the content of the decane structure of the polyimine. The average molecular weight composition The content of the decane structure (%) Polyimine (1) 37000 [ODPA+MBAA+Si +APB][ODPA+APB] 35.5 Polyimine (2) 33000 [ODPA+MBAA+Si][ODPA+APB] 47.8 [Table 4] Composition of Positive Photosensitive Resin Composition Polyimine Sensitizer Phosphoric Acid Ester species mass % Species mass % Species mass % Example 14 Polyimine (1) 100 C-2 20 TBP, TBXP 30 Example 15 Polyimine (1) 100 C-2 20 TOP, TBXP 30 Example 16 Polyimine (1) 100 C-2 20 TIBP, TBXP 30 Example 17 Polyimine (2) 100 C-1 20 TBXP 15 Comparative Example 10 Polyimine (1) 100 C-2 20 None 0 Comparative Example 11 Polyimine (1) 100 C-2 20 RDP 30 Comparative Example 12 Polyimine (1) 100 C-2 20 ATC 30 • 67· 126625.doc 200839442 Comparative Example 13 Polyimine ( 2) :100 C-1 : 20 None! 0 Comparative Example 14 Polyimine (2) 1 100 C-1 : 20 RDP | 30 Comparative Example 15 Polyimine (2) 1 1〇〇ci I 20 ATC 30 [Table 5] Photosensitivity made of a positive photosensitive resin composition Film Properties Soft Film Thickness (μιη) Flame Retardant Insertability Developability Example 14 〇20 VTM-0 〇◎ Example 15 〇20 VTM-0 〇◎ Example 16 〇20 VTM-0 〇◎ Example 17 〇 21 VTM-0 〇〇 Comparative Example 10 X 20 VTM-0 X 〇 Comparative Example 11 X 20 VTM-0 X 〇 Comparative Example 12 〇 20 X 〇〇 Comparative Example 13 X 21 VTM-0 X 〇 Comparative Example 14 X 21 VTM-0 X 〇Comparative Example 15 〇20 X 〇〇 [Example 18] Under a nitrogen atmosphere, MBAA (30.0 mmol) and polyoxymethylene diamine (KF-8010, 30·0) were placed in a separable flask. Methyl), hydrazine (15.0 mmol), γ-butyl vinegar (100 mL), followed by ODPA (60.0 mmol) and stirred at room temperature for 2 hours. Then, toluene (30 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and the mixture was heated and stirred at 180 ° C for 2 hours using a Dean-Stark apparatus and a reflux apparatus. After cooling to 120 ° C, hydrazine (15.0 mmol) was added and stirred for 10 minutes, then TMEG (31.8 mmol) was added, and the mixture was stirred under heating at 120 ° C for 2 hours. Then, toluene (10 mL) was added, and the mixture was stirred under heating at 180 ° C for 2 hours. After cooling to 140 ° C, γ-butyrolactone was added to bring the polymer solid concentration to 30% by mass, and it was cooled to room temperature, whereby a ruthenium-butyrolactone solution of polyimine (3) was obtained. The number average molecular weight of the polyimine (3) was 37,000, and the value of β/(α + β + γ) of the formula (5) was 0.33. 126625.doc •68- 200839442 In 100% by mass of polyimine (3), compound C-2 (20% by mass), TBP (15% by volume) and TBXP (15% by mass) were mixed to prepare photosensitivity. Resin composition. The photosensitive resin composition obtained in this manner was applied onto an easily peelable PET film by the above-mentioned coating method, and dried at 95 ° C for 30 minutes, whereby a photosensitive dry film was obtained. The warpage of the dry film is 〇. The photosensitive dry film was laminated on a copper circuit (copper line width of 50 μm, line spacing of 50 μm, and copper wiring thickness of 12 μm) by the lamination conditions described above. The laminate obtained by the cutting was observed by an electron microscope, and it was found that the above-mentioned photosensitive dry film was embedded in a copper circuit without voids, and the surface of the cover layer was also flat. The positive photosensitive resin composition is applied to Kapton (registered trademark) by the above-mentioned coating method, and dried at 95 ° C for 30 minutes, and then the positive photosensitive resin composition is applied to the opposite surface. Kapton (registered trademark) coated with a positive photosensitive resin composition, and Kapton (registered trademark) coated with a positive photosensitive resin composition in a baking furnace were obtained by drying at 95 ° C for 3 minutes. In the medium and air environment, take 12 〇. The crucible was calcined for 60 minutes, and then calcined at 20 (rc for 6 minutes to obtain a hardened body. The flame retardancy of the hardened body was evaluated by the UL94 VTM test. The results are shown in Table 2 below. The blending amounts of the imine, the sensitizer, and the scaly acid are shown in the following Table 6. Further, the blending amounts of the following examples and comparative examples are also shown in Table 6 below. The photosensitive film was laminated on a copper foil laminate. Using a positive mask, the obtained laminate was exposed to an irradiation dose of 1 〇J/cm 2 , and then a 3% aqueous solution of sodium hydroxide was introduced into 126625. Doc -69- 200839442 The development process is carried out, rinsed with water, dried and observed with an optical microscope. The exposed surface of each dry film is exposed to the copper surface, and the thickness of the unexposed portion of the cover layer is 15 μm or more (20 [Example 19] In 100% by mass of the polyimine (3) produced in Example 18, compound C-2 (20 mass% / 〇), butyl hydrazine (15 mass%), and A photosensitive resin composition was prepared by using ΤΒΧΡ (15% by mass). The same as in Example 18. Method 'Evaluation of lightness, flame retardancy, entanglement property, and alkali developability of the above-mentioned photosensitive resin composition. The results are shown in the following Table 7. [Example 20] It was produced in 100% by mass of Example 18 In the polyimine (3), a photosensitive resin composition was prepared by mixing a compound (: -1 (20% by mass)) and hydrazine (30% by mass). The above photosensitivity was evaluated in the same manner as in Example 18. The warpage, flame retardancy, embedding property, and alkali developability of the resin composition. The results are shown in the following Table 7. [Example 21] In a separable flask, 〇DPA (20.0 mmol) was placed under a nitrogen atmosphere. , polyfluorene diamine (KF-8010, 15.0 mmol), γ-butyrolactone (40 mL), stirred at 80 ° C for 2 hours, then added toluene (15 mL), pyridine (11.4 mmol) , γ-valerolactone (7.5 mmol), heated and stirred at 180 ° C for 2 hours using a Dean-Stark apparatus and a reflux vessel. After cooling to 80X:, ΑΡΒ (3·0 mmol), ΜΒΑΑ (10·) 0 mmol), then TMEG (8.6 mmol) was added, and the mixture was stirred under heating at 8 °C for 1 hour. Then, toluene (5 mL) was added, and the mixture was heated and stirred at 180 ° C for 2 hours. Cool to 140 ° C, add 126625.doc -70-200839442 into the inside of the 曰, so that the solid content of the t complex reached 3 〇 mass%, cooled to room temperature, thereby obtaining polyimine ( 4) γ-butyrolactone solution. The number average molecular weight is 25000, and the value of β/(α+β+γ) is 〇.54. In 100 mass% of the polyimine (4), the mixed compound匕1 (2〇% by mass), ΤΙΒΡ (35 mass). / 〇) and TBXP (15% by mass) to prepare a photosensitive resin composition. The warpage, flame retardancy, and embedding property of the above-mentioned photosensitive resin composition were evaluated in the same manner as in Example 18. Further, as for the alkali developability, developability was evaluated in the same manner as in Example 18 except that a sodium hydroxide aqueous solution having a concentration of 1% was used as the developer. The results are shown in Table 7 below. [Comparative Example 16] A photosensitive resin composition was prepared by mixing the compound C-2 (20% by mass) in 100% by mass of the polyimine (3) produced in Example 18. The warpage, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. [Comparative Example 17] In 100% by mass of the polyimine (3) produced in Example 18, the compound C-2 (20% by mass) and the phosphate having an aromatic group, that is, RDP (30 lb) were mixed. /)) to prepare a photosensitive resin composition. The warpage, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. [Comparative Example 18] In 1% by mass of the polyimine (3) produced in Example 18, the mixed material C 2 (20 畺 / 〇), and the ordinary plasticizer, that is, the quality 126625. Doc 200839442%), a photosensitive resin composition was prepared. The buckling, flame retardancy, post-entry property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. [Comparative Example 19] A photosensitive resin composition was prepared by mixing Compound 01 (20% by mass) in 100% by mass of the polyimine (3) produced in Example 18. The lightness, flame retardancy, embedding property, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. [Comparative Example 20] In 100% by mass of the polyimine produced in Example 18, a compound C1 (20% by mass) and an aromatic group-containing phosphate, RDP (30% by mass), were mixed to prepare a photosensitive film. Resin composition. In the same manner as in Example 18, the above-mentioned photosensitive resin composition was evaluated for warpage, flame retardancy, and developability. The results are shown in Table 7 below. [Comparative Example 21]

[Comparative Example 22]

In the same manner as in Example 18, a photosensitive resin composition was prepared. The warpage of the above-mentioned photosensitive resin composition was evaluated, and the flame retardancy, embedding property, and alkali developability of 126625.doc • 72-200839442 were evaluated. The results are shown in Table 7 below. [Comparative Example 23] The compound C-1 (20% by mass) and the phosphoric acid group having an aromatic group, that is, RDP (in the case of 1% by mass of the polyimine (4) produced in Example 21) 50% by mass), a photosensitive resin composition was prepared. The warpage, flame retardancy, embedding property, and alkali developability of the above-mentioned photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. [Comparative Example 24] In 100% by mass of the polyimine (4) produced in Example 21, compound Cl (20% by mass) and a common plasticizer, ATC (5% by mass), were mixed. A photosensitive resin composition was prepared. The warpage, flame retardancy, dispersibility, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 18. The results are shown in Table 7 below. According to Table 7, it is understood that the photosensitive film (Comparative Example 16, Comparative Example 19, Comparative Example 22) composed of the photosensitive resin composition to which the phosphate compound of the present invention is not added, and the addition of the aromatic phosphate compound A photosensitive film composed of a photosensitive resin composition to which the phosphate compound of the present invention is added is compared with a photosensitive film (Comparative Example 17, Comparative Example 20, and Comparative Example 23) composed of the photosensitive resin composition ( In the examples "to the embodiment 21", the flame retardancy was maintained, and the warpage and the embedding property were improved. Further, a photosensitive film composed of a photosensitive resin composition to which a general plasticizer was added was observed (Comparative Example) 18. Comparative Example 2 1. Comparative Example 24), although the curvature and the embedding property were improved, the flame retardancy was lowered. According to the above, the photosensitive resin composition to which the phosphoric acid compound of the present invention was added was composed of 126625. The photosensitive film of doc-73-200839442 still maintains flame retardancy, and the warpage and embedding property at the time of dry film formation are improved, and the developability is also good. [Table 6] Positive photosensitive resin combination Composition Polyimine sensitizer Phosphate type mass% % Species % % by mass Example 18 Polyimine (3) 100 C-2 20 ΤΒΡ, ΤΒΧΡ 30 Example 19 Polyimine (3) 100 C -2 20 TOP, ΤΒΧΡ 30 Example 20 Polyimine (3) 100 C-1 20 ΤΒΧΡ 30 Example 21 Polyimine (4) 100 C-1 20 ΤΙΒΡ, ΤΒΧΡ 50 Comparative Example 16 Polyimine (3) 100 C-2 20 No 0 Comparative Example 17 Polyimine (3) 100 C-2 20 RDP 30 Comparative Example 18 Polyimine (3) 100 C-2 20 ATC 30 Comparative Example 19 Polysaccharide Amine (3) 100 C-1 20 No 0 Comparative Example 20 Polyimine (3) 100 C-1 20 RDP 30 Comparative Example 21 Polyimine (3) 100 C-1 20 ATC 30 Comparative Example 22 Polyfluorene Imine (4) 100 C-1 20 No 0 Comparative Example 23 Polyimine (4) 100 C-1 20 RDP 50 Comparative Example 24 Polyimine (4) 100 C-1 20 ATC 50

[Table 7] Physical properties of photosensitive film produced from positive photosensitive resin composition

Flexural film thickness (μιη) Flame retardant embedding developability Example 18 〇20 VTM-0 〇◎ Example 19 〇20 VTM-0 〇◎ Example 20 〇20 VTM-0 〇〇Example 21 〇20 VTM -0 〇 ◎ Comparative Example 16 X 21 VTM-0 X 〇 Comparative Example 17 X 20 VTM-0 X 〇 Comparative Example 18 〇 20 X 〇〇 Comparative Example 19 X 20 VTM-0 X 〇 Comparative Example 20 X 21 VTM-0 X 〇 Comparative Example 21 〇 20 X 〇〇 Comparative Example 22 〇 20 XX 〇 Comparative Example 23 X 20 VTM-0 XX Comparative Example 24 X 20 X 〇X In the following Examples 22 to 25 and Comparative Example 25, a film was used. The thickness is about 15 μηη -74- 126625.doc 200839442 Condition, the developability is evaluated in the following manner. <Evaluation of developability> - Flattening developability by the following method: using a photosensitive dry film (e photosensitive layer of the photosensitive layer, spoon is 15 μm), and laminating it on a copper foil layer by the above lamination conditions ^ After the upper, use a positive mask, exposure of a 〇 J / cm2 exposure, dust, using a 10% solution of 1% or 3% sodium hydroxide 7jc solution for development and treatment, rinse with water, After drying, the pattern was evaluated using an optical microscope. A circular pattern having a diameter of 100 μm (with a spacing of 100 pm) was used on the mask. The film thickness of the photosensitive layer exposed at the exposed portion and the unexposed portion was developed by development. In the case of 13 μm or more, the film thickness of the photosensitive layer in the unexposed portion is 10 μm or more and less than 13 μπι, and the case where the resolution is poor or the film thickness is not The case of 丨〇μπι is denoted by X. [Example 22] In a gas-fired environment, ruthenium (30.0 mmol) and polyoxydeoxy diamine (kf-8010, 45_0 mmol) were placed in a separable roasting pot. Γ-butyrolactone (120 mL) was added to 〇dpa (60.0 mmol) and stirred at room temperature for 2 hours. Further, toluene (60 mL), pyridine (34.13 mmol), and γ-valerolactone (22.47 mmol) were added, and the mixture was heated and stirred at 180 ° C for 2 hours using a 〇6 & 11-81 & 1± apparatus and a reflux device. After cooling to 120 ° C, hydrazine (15.0 mmol) was added and stirred for 1 hr, then TmeG (30.0 mmol) was added, and the mixture was heated and stirred at 120 ° C for 2 hours. Then, toluene (15 mL) was added. The mixture was heated and stirred at 180 ° C for 2 hours, cooled to 140 ° C, and γ-butyrolactone was added to bring the polymer solid concentration to 30% by mass, and cooled to room temperature, thereby obtaining a polyimine (5). Γ-butyrolactone solution. The number average molecular weight and the mass (%) of the portion derived from the decane structure of 126625.doc •75-200839442 are shown in the following Table 8. 100% by mass of polyimine ( 5) A photosensitive resin composition was prepared by mixing the compound C-1 (20% by mass), SPB-100 (20% by mass), and M-325 (30% by mass), and the composition thereof is shown in Table 9 below. The photosensitive resin composition obtained in this manner was applied onto the easily peelable PET film by the above-described coating method, and dried at 95°. The photosensitive dry film was obtained. The warpage of the dry film was 〇. 0 The above-mentioned photosensitive dry film was laminated on a copper circuit by the above lamination conditions (the copper wire width was 50 μm, and the line spacing was 5 〇 μηι, The thickness of the copper wiring was 12 μm. The laminated body obtained by cutting was observed by an electron microscope. The photosensitive dry film was found to be embedded in a copper circuit without voids, and the surface of the overlying layer was also flat. The positive photosensitive resin composition was applied to Kapton (registered trademark) at 95 by the above coating method. The underside was dried for 3 minutes, and then the above-mentioned positive photosensitive resin composition was applied to the opposite side, and dried at 95 ° C for 30 minutes. Thus, a positive photosensitive resin composition was applied thereto.

Kapton (registered trademark), Kapton (registered trademark) coated with a positive photosensitive resin composition in a baking furnace, air-cooled at 12 Torr for 60 minutes, followed by 2 Torr (TC baking for 6 minutes) Thus, a hardened body was obtained. The flame retardancy of the hardened body was evaluated by a muscle 94 VTM test. The results are shown in Table 10 below. The above photosensitive film was laminated on a copper foil by the above lamination conditions. On the laminate board, using a positive mask, the obtained laminate is exposed by an irradiation dose of 1·〇J/cm2, and then, using a sodium hydroxide aqueous solution having a concentration of 3%, 126625.doc • 76-200839442 The alkali development treatment was carried out by rinsing with water, and after drying, the pattern was observed using an optical microscope. The exposed surface of each dry film was exposed to a copper surface, and the thickness of the coating layer of the unexposed portion was 13 μm or more. [Example 23] Nitrogen gas Under the environment, put in a separable flask, polyoxydiamine, cadaveric-8010, 45.0 mmol), γ-butyrolactone (120 mL), then add ODPA (60.0 mmol), and mix at room temperature. hour. Then, toluene (60 mL), σ specific bite (34·13 mmol), and γ-pental vinegar (22.47 mmol) were added, and the mixture was heated and stirred at 180 ° C for 2 hours using a Dean-Stark apparatus and a reflux. After cooling to 120 ° C, hydrazine (9·0 mmol) and MBA (30 mmol) were added and stirred for 10 minutes, then TMEG (25.8 mmol) was added, and the mixture was stirred and heated at 120 ° C for 2 hours. Then, toluene (15 mL) was added, and the mixture was stirred under heating at 180 ° C for 2 hours. After cooling to 140 ° C, γ-butyrolactone was added to bring the solid content of the polymer to 30% by mass, and the mixture was cooled to room temperature, whereby a γ-butyrolactone solution of polyimine (6) was obtained. The number average molecular weight and the mass (%) of the portion derived from the oxime structure are shown in Table 8 below. A photosensitive resin composition was prepared by mixing the compound 02 (20% by mass) and SPB-100 (20% by mass) in 100% by mass of the polyimine (6). The composition is shown in Table 9 below. The warpage, flame retardancy, and pressure-bonding property to the substrate of the photosensitive resin composition were evaluated in the same manner as in Example 22. As for the alkali developability, it was evaluated using a 1% aqueous sodium hydroxide solution. The results are shown in Table 10 below. [Example 24] 126625.doc -77- 200839442 In 100% by mass of the polyimine (6) produced in Example 23, compound C_2 (20% by mass), SPB_100 (20% by volume), ΤΒχρ were mixed. (% by mass), a photosensitive resin composition was prepared. The composition is shown in Table 9 below. The warpage, flame retardancy, pressure-bonding property to the substrate, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 22. The results are shown in Table 10 below. [Example 25] In 100% by mass of the polyimine (6) produced in Example 23, compound C-2 (20% by mass), SPH_100 (20 f amount 0/〇), tBXP (1〇) were mixed. A photosensitive resin composition was prepared by mass / 〇). The composition is shown in Table 9 below. In the same manner as in Example 22, the warpage resistance of the photosensitive resin composition, the pressure-bonding property to the substrate, and the developability were evaluated. The results are shown in Table 10 below. [Comparative Example 25] A photosensitive resin composition was prepared by mixing the compound C-2 (20% by mass) in the polyimine (6) produced in Example 23 of 1% by mass. The composition is shown in Table 9 below. The warpage, flame retardancy, pressure-bonding property to the substrate, and alkali developability of the photosensitive resin composition were evaluated in the same manner as in Example 22. The results are shown in Table 1 below. [Table 8] The number average molecular weight, composition, and the content of the decane structure of the polyimine 126625.doc • 78- 200839442 The number average molecular weight composition of the siloxane structure (%) Polyimide (5) 35000 [ODPA+1.5Si+MBAA][TMEG+0.5APB] 46 Polyimine (6) 17400 [ODPA+1.5Si][0.86TMEG+MBAA+0.3APB] 48.04 [Table 9] Positive photosensitive resin combination Composition of the composition Polyimine sensitizer Phosphorus-nitrogen compound plasticizer Type mass% Type i% by mass Type ί% by mass 丨% by mass Example 22 Polyimine (5) 100 C-1 i 20 SPB-100丨20 M-325 ! 30 Example 23 Polyimine (6) 100 C-2 20 SPB-100 ; 20 none 0 Example 24 Polyimine (6) 100 C-2 : 20 SPB-100 | 20 TBXP: 10 Example 25 Polyimine (6) 100 C-2 | 20 SPH-100; 20 TBXP : 10 Comparative Example 25 Polyimine (6) 100 C-2 ; 20 None \ 0 None;

[Table 10] Physical properties of the photosensitive film produced from the positive photosensitive resin composition, film thickness (μιη), flame retardancy, adhesion to the substrate i, developability Example 22 〇16 VTM-0 ο i ◎ Example 23 〇17 VTM-0 〇 ◎ Example 24 〇17 VTM-0 〇 ◎ Example 25 〇16 VTM-0 ο 1 ◎ Comparative Example 25 〇17 XX : 〇 According to the results of Table 10, it is known that Comparative Example 2 of the phosphorus-nitrogen-based compound of the invention The flame-retardant properties of the photosensitive resin compositions of Examples 22 to 25 to which the nitrogen-absorbing compound of the present invention was added were improved. Further, it is understood that the developability is also improved. According to the above, the photosensitive film composed of the photosensitive resin composition to which the nitrogen-containing compound of the present invention is added has improved flame retardancy and developability. Further, it was found that the pressure-bonding property to the substrate was also good. [Industrial Applicability] When the photosensitive resin composition of the present invention is formed into a photosensitive film, it can be sufficiently -79·126625.doc 200839442 to suppress light curvature, excellent in embedding property and adhesion to a substrate, and developability It is relatively good and has flame retardancy after hardening, so it can be applied to a photosensitive dry film or a cover layer, and can be used for the following purposes: flexibility for forming an operation panel or the like for various electronic machines in the field of electronic equipment. a protective layer of a circuit board or a circuit substrate; an insulating layer for forming a laminated substrate; a film for forming an electronic component for protecting the electronic component, for insulating, and the like, and the electronic component A germanium wafer, a semiconductor wafer, a semiconductor device peripheral member, a semiconductor substrate, a heat sink, a lead pin, a semiconductor itself, or the like used in a semiconductor device.

126625.doc -80-

Claims (1)

200839442 X. Patent application scope: 1 . A photosensitive resin composition comprising a component, a (Β) component, and (C) component, wherein the (Α) component is an alkali-soluble resin, and the (Β) component is a group consisting of a compound having the structure represented by the formula (1), a compound having an iso-cyanuric acid ring, and a group of quinone imine compounds having one or two quinone imine groups other than the above (Α) component At least one compound, the above (C) component is a quinonediazide compound; ρ = χ where (1) where t ' represents a filling atom, the number of covalent bonds is 5; χ represents a nitrogen atom or an oxygen atom, and X is a nitrogen atom When the number of covalent bonds is 3, when it is an oxygen atom, the number of covalent bonds is 2; the phosphorus atom is bonded to a nitrogen atom or an oxygen atom by a double bond). 2. As requested! The photosensitive resin composition wherein the component (1) of the above formula (1) is an acid-filled vinegar compound of the formula (2) or the formula (3), or a phosphine oxide compound as shown; > 1 J [Chemical Formula 1] 9 Rf0 十〇-% 0 ( 2 ) (wherein Ri is 1 仏 organic group, and multiple R1 can be the same); 3 9 Ftj—O-p-Ο δ 126625.doc 200839442 (wherein Ri is the same as the above formula (2), and plural & respectively may be the same or different); [Chemical 3] (wherein R2 is a monovalent organic group). The photosensitive resin composition of claim 1 or 2, wherein the component (A) is an alkali-soluble polyimine or a polyimide precursor, and has an austenite-fired skeleton. 4. The photosensitive resin composition of claim 3, wherein the above-mentioned oxoxane skeleton is contained in an amount of 1% by mass or more based on the mass of the alkali-soluble polyimine or the polyimide precursor. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A) is an alkali-soluble polyimine and is a φ polyimine resin having a carboxyl group and/or a hydroxyl group. The photosensitive resin composition according to any one of claims 1 to 5, wherein the β (Α) component is an alkali-soluble polyimine represented by the following formula (5); (wherein, Rs represents a tetravalent organic group, which may be the same or different; R 126625.doc 200839442 represents a hydrocarbon group having a carbon number of 1 or more and 20 or less; and r4 represents a divalent organic group having at least one test functional group; ; a represents an integer of 1 or more and 1〇 or less; b represents an integer of 1 or more and 20 or less; r7 represents 4 having an ester structure; [Bei organic group & 8 represents a divalent organic group; and 〇 1, 0, and 7 are at least 1 or more, Χ〇.01$β/(α+β+γ)$〇.9;). 7. The photosensitive resin composition of claim 6, wherein the component (a) is an alkali-soluble polyimine represented by the above formula (5), and the formula satisfies 〇·〇3$β/(α+β +γ)$〇·67 〇 8. The photosensitive resin composition according to claim 6 or 7, wherein the above r7 is a functional group derived from an acid dianhydride represented by the following formula (6) or (7); [Chemical 5] Ρ 0 〇〇 ( 6) 〇[Chemical 6] Q 9 〇0 /. Λ α 〇 (7) 0 The photosensitive resin composition of the above formula (2) or the above formula (3), isobutyl, 2-ethylhexyl 9 Wherein the component (B) comprises the scaly vinegar compound represented by the above formula (2) or (3), and the upper R1 is selected from the group consisting of methyl, ethyl, τ, butane ethyl, phenyl, and phenyl , 126625.doc 200839442 The organic group of the group consisting of xylyl and aminophenyl. The photosensitive resin composition according to any one of claims 2 to 8, wherein the component (B) contains the phosphate compound represented by the above formula (2), and the carbon number of the first formula in the formula (2) is The aliphatic organic group of 1 or more and 30 or less may be the same or different. The photosensitive resin composition according to any one of claims 2 to 10, wherein the component (B) contains the acid ester compound represented by the above formula (2), and the I in the above formula (2) is selected from the group consisting of Any of the group consisting of decyl, ethyl, butyl, isobutyl, 2-ethylhexyl, and butoxyethyl. The photosensitive resin composition according to any one of claims 2 to 11, wherein the component (B) comprises a phosphate compound represented by the above formula (2), and the carbon number of the first formula in the formula (2) is The aliphatic organic group of 2 or more and 3 or less may be the same or different, and the aliphatic organic group has an ether structure. The photosensitive resin composition according to any one of claims 2 to 12, wherein the component (B) contains a phosphate compound represented by the above formula or formula (3), and contains two or more phosphate compounds. . The photosensitive resin composition according to any one of claims 9 to 13, wherein the component (B) contains the phosphate compound represented by the above formula (2), and R! in the above formula (2) is butoxy Ethyl. The photosensitive resin composition according to any one of claims 1 to 14, wherein the (B) component (B) is contained in an amount of (10) or less per part of the component (A). 16·If you ask for help! The photosensitive resin composition of any one of the above-mentioned item (B), wherein the component (B) contains a compound having a hetero-cyanuric acid ring, and the compound having a heterocyclic cyanide ring as described above contains the compound of the formula (8). Organic base; [Chem. 7] (wherein R 9 is a monovalent organic group, and a plurality of I's may be the same). , or not The photosensitive resin composition of any one of the above-mentioned items, wherein the (B) component contains a quinone imine compound, and the quinone imine compound contains the organic group represented by (9); 8] (wherein 'Rl〇 is a monovalent or divalent organic group, m is 1 or 2, and Y represents an organic group represented by the formula (1〇)) [Chemical 9] Force» ... 18· as requested in the case to 17 The photosensitive resin composition according to any one of the above, wherein the component (B) comprises a phosphine oxide compound, and r2 in the above formula (4) is selected from the group consisting of hydrogen, dihydroxyphenyl, dibutylhydroxybenzyl and (methyl) An organic group of a group consisting of an organic group of an acrylic acid group. The photosensitive resin composition according to any one of the preceding claims, wherein, in the compound having an iso-cyanocyanate ring, R9 in the above formula (8) is a formula (U). Organic group; [Chemical 10] ^ - CH2CH2〇|Rl1 (1 n • (wherein R11 is an organic group selected from formula (12) or formula (13)); [11] • r12 -c= Ch2 (i 2) (wherein Ru is hydrogen or methyl); [Chemical 12] Ο R-|2 —(CH2)c~〇-C-C"CH2 ( j 3 ) (wherein c is 2 The photosensitive resin composition of any one of Claims 1 to 19, wherein, in the above-mentioned quinone imine compound, the above formula (9) The photosensitive resin composition of any one of Claims 1 to 20, wherein the above-mentioned (C) component is a formula. (14) or a compound of the formula (15), [Chemical 13] Ο (14) 126625.doc 200839442 [Chem. 14] The photosensitive resin composition of claim 21, wherein the compound having the above-described formula or the organic group represented by the formula (10) is a compound obtained by esterifying a compound having a divalent hydroxyl group by a continuous acid, Further, the esterification ratio of any of the organic groups represented by the above formula (丨4) or formula (丨5) per compound having a phenolic hydroxyl group is from 0.60 to 0.98. The photosensitive resin composition according to any one of claims 1 to 22, wherein the component (C) contains the quinonediazide compound represented by the formula (16); 〇-Q 〇-Q (16) (wherein Q is each independently hydrogen or an organic group selected from the above formula (14) or the formula ""; wherein at least one of the plurality of Qs is selected from the above formula (14) or an organic group of the formula (15). There is a polyether compound as the component (D). The photosensitive resin composition according to any one of claims 1 to 23, which contains 126625.doc 200839442. 25. The photosensitive resin composition of claim 24, wherein the above-mentioned poly The ether compound has an oxyethylene chain. The photosensitive resin composition of claim 24 or 25, wherein the polyether compound has a hydroxyl group at the terminal. The photosensitive resin composition of any one of Claims 1 to 26, wherein the component (B) represented by the above formula (1) is a phosphorus-nitrogen compound of the following formula (17) or formula (8). At least one of them; [Chemical 16] 汴 13 0 -P=N-- Ο «Μ L Jp '---1(17) [Chem. 17] A* ^15 O -B ~P=N- 〇R 16 q (1 8 ) (Rs Ru'R", ;66 is an organic group having a carbon number of 3 or more and 2〇 or less. P is an integer of 3 or more and 25 or less, 9 is an integer of 3 or more and 10000 or less, and A and B are an organic group having 3 or more carbon atoms. The photosensitive resin composition of claim 27, wherein r13, r14, Rl5, and Ri6 in the above-mentioned phosphorus-nitrogen compound 126625.doc 200839442 have an aromatic ring. The photosensitive resin composition of claim 27 or 28 which contains (7) a plasticizer. The photosensitive resin composition of claim 29, wherein the plasticizer comprises a compound selected from the group consisting of a phosphate ester, an ether compound, a methacrylic group-containing compound, a propylene group-containing compound, and a phthalate ester. , aliphatic dibasic acid ester, aromatic condensed phosphate ester, modified ethylene glycol cyanide modified three Any of a group consisting of acrylic vinegar and ε-caprolactone-modified tris(propylene oxyethyl)isophthalate. A photosensitive film comprising the photosensitive resin composition according to any one of claims 1 to 30. The photosensitive film of claim 31, which comprises the alkali-soluble polyimine according to any one of claims 6 to 8. A laminated film comprising a carrier film and a photosensitive film according to claim 31 or 32 provided on the carrier film. The laminate film according to claim 33, comprising a cover film formed on the photosensitive film. A coating layer obtained by using the photosensitive film or laminate film according to any one of claims 31 to 34. 36. A printed circuit board, comprising: a substrate and a cover layer; the substrate has a wiring; the cover layer is formed on the substrate in such a manner as to cover the wiring, and is used as requested (4) To obtain the photosensitive film or laminated film of the middle-end. The cover layer, the cover layer 37. A printed circuit board, characterized in that 126625.doc 200839442 is used as claimed in any one of claims 1 to 30. The photosensitive resin composition of the present invention is obtained by being applied to a substrate having wiring. 126625.doc 10- 200839442 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the representative figure is a simple description: φ VIII. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: R^-〇^P^〇-R^ 〇(2) (3) 126625.doc