TW201022312A - Polyamideimine resin, said resin composition, flame retardancy adhesive agent composition and adhesive sheet, covering film, printing wiring board made from said composition - Google Patents

Abstract

The purpose of the present invention is to provide a polyamideimine resin which simultaneously satisfies heat resistance, adherence property and insulating reliability, solvent solubility, and is adaptable to the use of printing wiring board of heat resistance adhesive agent. Further, also provided is a flame retardancy adhesive agent composition having no halogen, which not only formed by the components being able to resolve in general use solvent and represents property of stability, but also could be used in flexibility printing wiring board and the like to represent excellent flame retardancy, heat resistance of soldering, adherence property and electrical insulating property. The solution mean of the present invention is a polyamideimine resin obtained by reacting the acid components of following (a) to (c) with diisocyanate having aromatic ring or diamine, in which is characterized in that the ratios of each acid component are (a) 3 to 10 mol%, (b) 10 to 80 mol%, (c) 10 to 87 mol% respectively while all of the acid components of said polyamideimine resin is set as 100 mol%: (a) acrylonitrile-butadiene rubber having carboxyl group at two terminal ends; (b) aliphatic dicarboxylic acid with 4 - 12 carbon numbers; (c) anhydrate of polycarbonxyl containing aromatic ring.

Description

• 201022312 VI. Description of the Invention: [Technical Field] The present invention relates to a polyamidoximine resin and a thermosetting resin composition using the same, and more particularly to a binder resin composition It has excellent flexibility, heat resistance, solvent solubility, insulation and adhesion, and is suitable for copper clad laminate or cover layer, adhesive sheet, copper foil with resin, protective film layer ink, prepreg Wait for the printed wiring board. Further, the present invention relates to a printed wiring board, in particular, a flexible printed wiring board which is excellent in flexibility, and which has excellent performance, and is excellent in flame retardancy, solder heat resistance, adhesion, and electrical insulation. A flame-retardant adhesive composition, and a printed wiring board using a copper clad laminate, an adhesive sheet, a cover film, a resin-attached copper foil, a prepreg, and a protective film layer ink using the composition. [Prior Art] Since the polyamidimide resin is composed of an aromatic monomer, it exhibits the same heat resistance, chemical resistance, flaw resistance and abrasion resistance as those of the polyimide resin. In addition, it is superior to polyamidimide because it has a high boiling point such as N-methyl-2-pyrrolidone and exhibits solubility in a specific guanamine solvent, and has been applied to a molding material or a heat resistant insulating coating. Wait. However, the aromatic polyamidoximine resin is the same as a general polyamidene resin, and generally has a high modulus of elasticity, is hard and brittle, and has low solubility in a solvent having a low boiling point. It is difficult to use the softness of the adhesive or the like or the drying property of the solvent as an essential use. However, flexible printed wiring boards have been widely used for electronic device components that seek flexibility or space saving, for example, liquid crystal displays, plasma displays, etc. -4- 201022312 component substrate for display devices; or mobile phones, digital Further expansion of the use of a substrate relay cable such as a camera or a portable game machine, an operation switching unit substrate, and the like has been expected. In the adhesive used for such an application, an epoxy resin or an acrylic resin is conventionally used, and in recent years, in order to increase the density of the wiring or to lead-free solder, the heat resistance is insufficient, and the heat resistance is different from those of the resin. Agents, polyamidene resins have been explored. In order to solve the disadvantages of the conventional polyimine-based resin having high modulus of elasticity, hardness and brittleness, difficulty in adhesion, and dissolution in only a high-boiling solvent, it has been explored to combine long-chain monomers or oligomers with poly-pyrene. The amine resin is copolymerized. For example, in Patent Documents 1 and 2, a polyoxynitride-modified polyimide-based resin has been disclosed in a method of imparting flexibility and low elastic modulus. However, in order to impart flexibility and low elastic modulus, the polyoxyalkylene-modified polyimide-based resin must use a very expensive starting material having a dimethyloxane bond, which is not economically viable. Further, as the amount of polyoxyalkylene copolymerization increases, there is a problem that the adhesiveness and solubility of the resin are lowered. In Patent Documents 3 and 4, although the solution to this problem has revealed the use of a composition of a polycarbonate-modified polyimine-based resin to improve the disadvantages of low solubility or economy, but for sufficient flexibility In the case of low elastic modulus, it is necessary to increase the amount of modification of the polycarbonate. In this case, the chemical resistance or the heat and humidity resistance tends to be lowered. Further, Patent Document 5 discloses a method of copolymerizing a polyhydric alcohol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol with a polyamidoximine resin. However, these modified polyamidoximines are copolymerized with a long-chain polyol by a heat-resistant urethane bond, and the heat resistance is lowered to the problem of 201022312. Further, in Patent Document 6, a method of copolymerizing a dimer acid with a polyamidoximine has been disclosed. In this method, 'a certain degree of flexibility is possible, because the molecular weight of the dimer acid is low'. In order to find sufficient flexibility, it is necessary to increase the amount of copolymerization, in which case 'because of the aroma in the resin The proportion of the group base is significantly lowered and the heat resistance is lowered. Further, by increasing the amount of introduction into the resin, the glass transition temperature is lowered, and there is a problem that the adhesion is lowered or the solubility is lowered. In Patent Documents 7 and 8, a method of copolymerizing acrylonitrile butadiene having a carboxyl group at both ends of a molecule and a polyamidoximine resin has been disclosed. According to this method, it is possible to improve adhesion to some extent when flexibility is imparted, and in order to find sufficient adhesion by this method, it is necessary to increase the amount of copolymerization of acrylonitrile butadiene, and as a result, The insulation reliability is lowered, and the solvent solubility is also lowered, which makes it difficult to dissolve other than the high boiling point solvent such as N-methyl-2-pyrrolidone. In order to be suitable for use, the adhesive must be dissolved in a low boiling point solvent such as dimethylacetamide or toluene. In the use of printed wiring boards, it is desirable to have superior heat resistance, flexibility, insulation reliability, adhesion. The emergence of resins for solvent and solvent solubility. Nowadays, flexible wiring boards have been widely used in electronic device components requiring flexibility or space saving, for example, component mounting substrates for display devices such as liquid crystal displays and plasma displays; or mobile phones and digital cameras. A substrate relay cable such as a portable game machine or a personal computer, an operation switching unit substrate, and the like. In recent years, these electronic device components have been increasingly miniaturized and densified, and there has been a strong demand for fine patterning and high performance of flexible printed wiring boards, particularly flame retardancy, solder heat resistance, adhesion, and electric power. Insulation, etc. 201022312 Further improvement has gradually become necessary. The flame retardancy of these electronic machine components is aimed at ensuring the safety of fires, and conventional bromine-based flame retardants have been used as flame retardant imparting agents. However, the environmental impact of social issues has been considered important. The bromine-based halides have the concern of producing corrosive hydrogen halide gas over time, or the same gas when burning, Dioxin Worries about substances that cause adverse effects on the human body, such as furan. Therefore, in order to increase the tendency to suppress the use of halides, a halogen-free flame retardant adhesive is being sought. According to the above-mentioned background, there has recently been proposed a method of using a ruthenium compound such as a phosphorus compound or a metal hydrate, a nitrogen-containing compound or the like in place of a halide flame retardant to make it difficult to ignite. However, although the non-halogen flame retardant does not contain harmful halogens, it is necessary to have a large amount of flame retardant because the flame retardant effect is deteriorated as compared with the halogen flame retardant. Since the addition of a large amount of the flame retardant causes the outflow of the flame retardant or the deterioration of the mechanical properties of the adhesive, it is difficult to coexist with the flame retardancy and various characteristics. Further, the above-mentioned metal hydrate or the like is required to uniformly disperse the cerium material in the binder composition, and the step is increased as compared with the case where the cerium-free material is not contained, and the economical efficiency is increased. Will be worse. In addition, since the ruthenium material will settle, the non-uniformity of the composition of the binder will easily occur, and the usable period of the composition paint is short, and quality management is difficult. When the coating film is formed, it becomes difficult to form a film. Even in the processed surface of the flexible printed wiring board, there are various problems such as a flow of an etchant or the like, which causes a decrease in performance. In the case of a phosphorus compound, a phosphate ester which is often used as a flame retardant is easily hydrolyzed, and when a phosphate ester is used as a flame retardant, it is required to be produced under high-humidity conditions, such as 201022312 9 to 1 1 . The solvent resistance is to lower the fat, the hardener, the oxygen, and the laminate formed by using the oxidized product is composed of a copper foil, and it is easy to obtain a flame retardant of 260 ° C. The resin constituting the hardener disclosed herein is required. The compound of the group and the epoxy tree are a layered product, and the practical phosphorus content is as low as about 3% (the structure of the patent document is difficult to evaluate, and the solubility change of the solvent is not obtained in order to reduce the flame retardancy. It is necessary to pay attention to the amount and structure of the addition. For example, a resin composition containing a phosphate ester has been proposed in the patent literature, and the phosphoric acid ion component at a high temperature has a low electrical insulating property and a low adhesiveness, and cannot be satisfactorily characterized. A flame retardant resin composition containing an epoxy phosphine (Patent Document 12) has been proposed to improve the chemical resistance of the phosphine. However, in the evaluation of the flame retardancy of the group of plates, the test piece is the most The outer surface oxygen has a small contact surface with the composition, and a structure capable of accommodating UL-94V0 is formed. In addition, the solder heat resistance is also lowered. 1 The performance of the flexible printed wiring board is improved, and the object cannot be said to have sufficient heat resistance. In addition, it has been proposed that an epoxy resin containing phosphorus and a product containing a compound (Patent Document 13) can solve the problem of additive phosphating by reacting a reaction type grease, thereby causing electrical characteristics. However, the problem of lowering etc. However, the mass % of the phosphorus-containing epoxy resin used for the flexible printed wiring board cannot obtain sufficient flame retardancy. In the group 13), in order to easily obtain the flame retardant burning as described above Sex, not enough to be fully flame retardant. Further, when the phosphorus content is increased and the phosphorus content is increased, the crosslinking structure of the epoxy equivalent is deteriorated, and the heat resistance is deteriorated; or the problem of the difference is caused. In addition to the above, there are many proposals for the incombustibility of using a reactive phosphorus compound or a phosphorus-containing epoxy resin. For example, a binder composition containing a phosphorus-based flame retardant, a 201022312 thermoplastic resin, and a thermosetting resin has been proposed. (Patent Document 14); a coating layer comprising a nitrogen-containing compound, an epoxy resin, an epoxy compound containing a phosphorus atom, and a binder composition containing a curing agent (Patent Document 15). However, in any of the examples, it can be seen that all of the inorganic-based ruthenium filler materials have been added, and the ruthenium-free filler material cannot satisfy various characteristics such as flame retardancy and heat resistance. The addition of the ruthenium material has the problem as described above, and in Patent Document 14, the solder heat resistance is insufficient despite the addition of the ruthenium filler material. Also, in Patent Document 15, since the addition type phosphate ester has been added, it is resistant to water. The solution is worse. As described above, in the case of a halogen-free flame-retardant adhesive, it is still difficult to combine the flame retardancy and various characteristics. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2000-34131 No. JP-A No. 2001-339131 Patent Document 1 1 : Japanese Patent Laid-Open No. 2 0 0 1 - 3 Japanese Patent Laid-Open Publication No. JP-A No. 2001-200247A Patent Publication No. JP-A No. 2001----------- Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Solubility agent can be heat-resistant adhesive use for printed wiring board or the like, polyimide resins suitable to yet have unreached. An object of the present invention is to solve the above problems and problems of the prior art, and to provide a polyamide tyrosine resin suitable for use in a printed wiring board or the like and a binder resin composition using the φ resin. Further, there is provided a flame-retardant adhesive composition which is non-halogen-free and does not contain a ruthenium-filled material, and which exhibits stability characteristics not only by being formed of all components soluble in a general-purpose solvent, but also can be used for flexibility. A printed wiring board or the like exhibits excellent flame retardancy, solder heat resistance, adhesion, and electrical insulation. Further, a copper clad laminate, an adhesive sheet, a cover film, and a prepreg using the composition are provided. A printed wiring board such as a copper foil of a resin or a protective film layer ink. φ Technical means for solving the problem The inventors of the present invention have completed the present invention in order to solve the above problems. That is, the present invention is formed by the following constitutions: (1) A polyamidoximine resin which reacts the following acid components of (a) to (c) with a diisocyanate or diamine having an aromatic ring. The obtained polyamidoximine resin is characterized in that the ratio of each of the acid components in the case where the total acid component of the polyamidoximine resin is 100% by mole is (a) 3 to 10 mol%, (b) 10 to 80 mol%, (c) 10 to 87 mol%; (a) acrylonitrile-butadiene rubber having carboxyl groups at both ends, -10-201022312 (b) aliphatic dicarboxylic acid having 4 to 12 carbon atoms An acid, (c) an acid anhydride of a polycarboxylic acid having an aromatic ring. (2) The polyamidoquinone imine resin disclosed in the above (1) is obtained by dissolving 10% by mass or more of the polyamidoquinone imide resin at 60% by mass in ethanol. And a mixed solvent of at least one solvent selected from the group consisting of toluene, xylene and methyl ethyl ketone and 40% by mass of dimethylacetamide. (3) A polyamidoquinone imide resin composition, wherein the thermosetting component @ is added to the polyamidoximine resin disclosed in (2). (4) A polyamidoximine resin composition according to (3), wherein the thermosetting component is an epoxy resin. (5) A printed wiring board which is used as an adhesive in the polyamidoximine resin disclosed in (3) or (4). (6) A flame retardant adhesive composition comprising (A) a polyamidoximine resin, (B) a phosphorus-containing epoxy resin, (C) a phosphorus compound, and (A) a polyamidoxime The imine resin is a polyamidoximine imine resin obtained by reacting the following acid components of (a) to (c) with a diisocyanate or diamine having an φ aromatic ring, characterized in that the polyamidoximine The ratio of each acid component in the case where the total acid component of the resin is 10 〇 111 〇 1% is (〇3 to 1〇111〇1%, (13) 10 to 80 mol%, and (c) 10 to 87 mol%. The phosphorus content of the total mass of the components (A) to (C) is 2.0 to 5.0% by mass; (a) the acrylonitrile-butadiene rubber having a carboxyl group at both ends, and (b) the carbon number is 4 to 12 An aliphatic dicarboxylic acid, (c) an acid anhydride of a polycarboxylic acid having an aromatic ring. (7) A flame retardant adhesive composition disclosed in (6), wherein (C) phosphorus-11-201022312 is a phosphazene (phosphazene) and/or a phosphinic acid derivative. (8) A flame retardant adhesive composition disclosed in (6), which further contains (D) an epoxy resin hardener. (9) Revealed in the (6) Flame retardant adhesive composition Further, it further contains (E) a phosphorus-free epoxy resin. (10) A flame retardant adhesive composition disclosed in (6), which further contains (F) a decane coupling agent. (1 1 ) (6) The flame-retardant adhesive group φ of any one of (6), which dissolves all of the components (A) to (F) at a solid concentration of 25% by mass at 25 ° C. In the solvent of any one of (6) to (10), the flame retardant adhesive of any one of (6) to (10) is disclosed in any one of (6) to (10). In the composition, the phosphorus content of the total mass of the components (A) to (F) is 2.0 to 5.0% by mass. (13) An adhesive sheet which will be disclosed in the (6) to (10) Any one of the flame retardant adhesive compositions as an adhesive layer, and having an adhesive layer formed of a flame retardant adhesive composition disclosed in any one of φ on the peelable protective film layer (14) A cover film which is formed by an adhesive layer formed of a flame retardant adhesive composition disclosed in any one of (6) to (10) and an insulating plastic. (15) A flexible printed wiring board comprising an insulating layer formed using the flame retardant adhesive composition disclosed in any one of (6) to (10). Since the polyamidoximine resin of the present invention is in a specific range, an acrylonitrile-butadiene rubber having a carboxyl group at both ends and an aliphatic dicarboxylic acid having a carbon number of 4 to 12 are polymerized at a total of -12 to 201022312. As the acid component, not only the low-boiling solvent but also the adhesion of the polyamidoximine resin itself is remarkably improved. Therefore, it is possible to simultaneously satisfy the conventional heat resistance/flexibility/adhesiveness/insulation reliability/solvent solubility, and it is possible to provide a heat-resistant adhesive suitable for a printed wiring board. In addition, the flame retardant adhesive composition of the present invention is non-halogen, and does not contain an inorganic ruthenium filler such as aluminum hydroxide, which can achieve the flame retardancy of UL94 VTM-0, and because it is all soluble in general use. The composition of the solvent is formed, and there is no concern about the problem of dispersion of the composition, and the stability is excellent, and the film production of the stability property is easy. Further, since it is a composition which is dissolved in a low-boiling general-purpose solvent, it is easy to dry and is suitable as a flame retardant adhesive. Further, when the flame retardant adhesive composition of the present invention is used as an adhesive for a printed wiring board, it exhibits excellent flame retardancy, solder heat resistance, adhesion, and electrical insulation. Further, even when it is placed under high temperature and high humidity and is in a state of being wet, it is possible to exhibit solder heat resistance which is not superior to the conventional one. φ In addition, high adhesion can be maintained even after PCT test under high temperature and high humidity conditions. Furthermore, the cover layer provided on the circuit can also exhibit high migration resistance. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Polyamidoximine resin The polyamidoximine resin of the present invention is a polyamine obtained by reacting the following acid components of (a) to (C) with a diisocyanate or diamine having an aromatic ring. The proportion of each of the acid components in the case where the total acid component of the polyamidoximine resin is -100223% is (a) 3 to 10 mol%, (b) 10 to 80 mol. %, (c) 10 to 87 mol%; (a) acrylonitrile-butadiene rubber having a carboxyl group at both ends, (b) an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, (c) having an aromatic ring An acid anhydride of a polycarboxylic acid. ❿

In the present invention, (a) an acrylonitrile-butadiene rubber having a carboxyl group at both terminals is used to impart flexibility or adhesion to a polyamidoximine resin, and to carry out all the acid components of 3 to 1〇111〇1. % copolymer. Preferably, it is 3 to 8111 〇 1%, and if the amount of copolymerization is less than 3 mol%, flexibility or adhesiveness cannot be found; if it exceeds 10 mol%, solubility reliability and solubility to a solvent having a low boiling point are lowered. The tendency. In the present invention, (a) the acrylonitrile-butadiene rubber having a carboxyl group at both terminals has an acrylonitrile moiety and a butadiene moiety, and the weight average molecular weight is preferably from 500 to 5,000. When the molecular weight is smaller than this range, flexibility or adhesiveness cannot be achieved; and if the molecular weight is large, it becomes difficult to copolymerize in the polyamidoximine resin. Further, the proportion of the acrylonitrile moiety is preferably in the range of 10 to 50% by mass. When the amount is less than 1% by mass, the solubility to a solvent having a low boiling point tends to decrease, and when it exceeds 50% by mass, the reliability of insulation tends to be lowered. The commercially available acrylonitrile-butyl rubber having a carboxyl group at both ends of the above properties may, for example, be Hypro (trade name) CTBN series of Emerald Performance Materials. However, if only the component (a) is copolymerized, flexibility or adhesion and solubility are insufficient. In order to improve flexibility, adhesiveness and solvent solubility, (b) an aliphatic dicarboxylic acid having a carbon number of 4 to 12 and a polyamidoximine resin are copolymerized in the present invention in the range of -14 to 201022312. The copolymerization amount is a copolymerization of 10 to 80 mol% of all the acid components, preferably 20 to 60 mol%. When it is less than 10 mol%, sufficient adhesiveness and flexibility are not obtained, and the effect of improving solubility is also small. In the case of more than 80 mol%, the heat resistance is lowered due to a decrease in the proportion of the aromatic structure in the polyamide amide resin. As described above, there is a limit to the amount of introduction of the acrylonitrile-butadiene rubber having a carboxyl group at both ends of the component (a), and only the component (a) cannot be found to have sufficient adhesiveness or flexibility, and it is impossible to find a pair. The solubility of a low boiling point solvent is therefore necessary to copolymerize the component (b). Here, the carbon number of the dicarboxylic acid of the component (b) also includes the number of carbons of the carboxylic acid moiety. Therefore, for example, in the case of sebacic acid, it is set to 10. Further, in the case where the carbon number is larger than 12, the portion having a low polarity in the polyamide amide imide resin is increased, and the solubility or adhesiveness of the resin is lowered. In the present invention, (b) the aliphatic dicarboxylic acid having 4 to 12 carbon atoms may, for example, be a linear aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid having a branched structure. For example, the linear structure may be exemplified by succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.; In the branched structure, the above-mentioned dicarboxylic acid such as 2-methylsuccinic acid may have a hydrocarbon substituent, and these aliphatic dicarboxylic acids may be used singly or in combination of several kinds. In the present invention, the acid anhydride of the polycarboxylic acid having the (c) aromatic ring which forms the quinone ring formation function, for example, trimellitic anhydride, pyromellitic dianhydride, ethylene glycol double dehydrated trimellitate , propylene glycol double-dehydrated trimellitic acid ester, 1,4-butanediol double-dehydrated trimellitic acid ester, hexanediol double-dehydrated trimellitic acid ester, polyethylene glycol double-dehydrated trimellitic acid ester, polypropylene glycol Double dehydration partial 201022312, alkanediol bis-dehydrated trimellitate such as trimesic acid ester; 3,3,,4,4,-benzophenonetetracarboxylic dianhydride, 3,3',4,4 '-Biphenyltetracarboxylic dianhydride, i,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine four Carboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, m-triphenyl-3,3',4 , 4'-tetracarboxylic dianhydride, 4,4,-oxodiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(2,3- Or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 0 hexafluoro-2,2-bis[4-(2 , 3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldifluorene An oxane dianhydride or the like; these acid anhydrides may be used singly or in combination of several kinds. In addition to the components (a) to (c) which have been described, the acid component of the present invention is an acid or an alicyclic acid anhydride or an alicyclic dicarboxylic acid, which is an acid component which does not impair the effects of the present invention. acid. For example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and hexahydrogenation can be mentioned. Pyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-φ tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3-( 1,2),5, 6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-( 1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane 1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2),3,4-tetracarboxylic dianhydride, 1- Propylcyclohexane-1-(1,2), 3,4-tetracarboxylic dianhydride, 1,3-dipropylzero hexane-1·(2,3),3-(2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride , 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2 , 3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo [2.2.1] g-17 - 201022312 院-2,3,5, 6-tetradecanoic acid dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6- Tetracarboxylic dianhydride, bicyclo [2.2.2] octane · 2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride, cyclohexane The carboxylic acid or the like can be used singly or in combination of several kinds. Based on the viewpoint of the heat resistance of the obtained polyamidoximine resin and the flame retardancy of the binder resin composition using the same, Among these components, these components are preferably 20 mol% or less. As the diisocyanate or diamine having an aromatic ring used in the present invention, as the diisocyanate, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4 may be mentioned. , 2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2,· or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyl Diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6 , 2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'- Diisocyanate, diphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylindole-4,4'-diisocyanate, toluene- 2,4-diisocyanate, toluene-2,6-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'·[ 2,2'-double ( 4-phenoxyphenyl)propane]diisocyanate 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate, etc.; diamine corresponds to such diisocyanate Diamine. These diisocyanates or diamines may be used singly or in combination of several kinds. -17- 201022312 The isocyanate or amine component can be used in an aliphatic or alicyclic structure to the extent that the effects of the present invention are not impaired. For example, a diisocyanate or a diamine of any one of the components listed in the preceding paragraph can be hydrogenated. Further, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, iota, 3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and ethylidene diisocyanate may also be mentioned. Propyl diisocyanate, hexyl diisocyanate, and diamines corresponding thereto. In the polyamidoximine resin of the present invention, it is possible to copolymerize a compound having three or more functional groups for the purpose of improving heat resistance. For example, a polyfunctional carboxylic acid such as trimesic acid, a dicarboxylic acid having a hydroxyl group such as 5-hydroxyisophthalic acid, or a dicarboxylic acid having an amine group such as 5-aminoisophthalic acid; A tablet having three or more hydroxyl groups, such as glycerin or polyglycerol, or a compound having three or more amine groups such as tris(2-aminoethyl)amine, and among these compounds, based on the viewpoint of reactivity and solubility, It is preferably a dicarboxylic acid having a hydroxyl group such as 5-hydroxyisophthalic acid or a compound having three or more amine groups such as tris(2-aminoethyl)amine, which is relative to an acid component or an amine component. The amount is preferably 20 mol% or less. If it exceeds 20 mol%, it is feared that the crosslinking point will increase, or gelation will occur during the production of polyamide, or insoluble matter may be formed. In the polyamidoximine resin of the present invention, the acrylonitrile-butadiene rubber or the aliphatic dicarboxylic acid having 4 to 12 carbon atoms is imparted with flexibility or adhesion to the extent that the effects of the present invention are not impaired. As the component, a polyester, a polyether, a polycarbonate, a dimer acid, a polyoxyalkylene or the like can be used. In this case, when the amount of the copolymerization of the polyamidimide resin is large, the effect of the present invention which is concerned with heat resistance, solubility, and adhesion is impaired, and relative to the entire acid component or the amine component, These components are preferably 10 mol% or less. -18 - 201022312 The method of obtaining the polyamidoximine resin of the present invention is produced by the following conventional method: a method of producing an acid component and an isocyanate component (isocyanate) Method: A method in which a lysine is reacted with an amine component to form a valine acid, followed by a ring closure method (direct method), or a method in which a compound having an acid anhydride and an acid chloride is reacted with a diamine. Industrially, the isocyanate process is advantageous. The polymerization of the polyamidoximine resin is obtained by dissolving and heating the acid component and the isocyanate or the amine component in a solvent. At this time, the ratio of the acid component to the isocyanate or amine component is preferably 100: 91 to 100: 109. If it exceeds this range, the molecular weight is not sufficiently increased, and there is a concern that mechanical strength will be insufficient or gelation will occur during polymerization. Further, from the viewpoint of the stability of the resin and the resin coating, the quinone ring portion of the polyamidoximine resin obtained according to the present invention is preferably a closed loop of 90% or more. Therefore, in the polymerization of the polyamide amidoxime resin, it is necessary to sufficiently react, and a method of increasing the reaction temperature or adding a catalyst can be mentioned. The solvent which can be used for the polymerization of the polyamidoximine resin of the present invention may, for example, be N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolium diketone or dimethyl sulfoxide. Dimethylformamide, oxime-ethyl-2-pyrrolidone, dimethylacetamide, cyclohexanone, cyclopentanone, tetrahydrofuran, and the like. Among these solvents, 'based on the viewpoint of low boiling point and good polymerization efficiency, dimethyl hydrazine acid is preferred. Further, after the polymerization, the concentration of the nonvolatile matter or the viscosity of the solution is adjusted by diluting with a solvent for polymerization or other low boiling point solvent I. Examples of the low boiling point solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexagram, Gengyuan, and octane; and alcohol solvents such as methanol, ethanol, propanol, and decyl alcohol. ; acetone, methyl ethyl ketone, methyl iso-19- 201022312 ketone solvent such as butyl ketone, cyclohexanone, cyclopentanone; ether solvent such as diethyl ether or tetrahydrofuran; ethyl acetate, acetic acid An ester solvent such as butyl ester or isobutyl acetate. Further, in order to accelerate the reaction, an alkali metal such as sodium fluoride, potassium fluoride or sodium methoxide; triethylene glycol diamine, triethylamine, diethanolamine or 1,8-diazabicyclo[5,4 can be used. , a catalyst such as 0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-decene or a catalyst such as dibutyltin dilaurate. 2. Polyimine ylidene resin composition g The polyamidoximine resin obtained according to the present invention can be used as an adhesive (thermosetting resin composition) by adding a thermosetting component. When the thermosetting resin composition is used as an adhesive, it is preferred to lower the drying temperature, and in order to dry the drying reaction in order to prevent the curing reaction from proceeding, it is preferred that the resin solution contains a low drying property. Boiling point solvent. Examples of the low boiling point solvent suitable for the adhesive (thermosetting resin composition) include ethanol, toluene, xylene, and methyl ethyl ketone. The drying property and the advantage are preferably 10% by mass or more. The polyamidoximine resin is dissolved in a mixed solvent containing 40 parts by mass of a solvent composed of such a solvent and a mixed solvent containing 40% by mass of dimethylacetamide. By having such a solubility, it is possible to form an adhesive (thermosetting resin composition) by adding a thermosetting component, not only having excellent drying properties, but also not being dissolved by the solvent of the thermosetting component, and is superior. It is used as a thermosetting resin composition for stability over time and storage stability. Here, the dissolution system in the present invention means a state in which the solution is kept transparent and the solid matter is not precipitated in an environment of 25 ° C for 24 hours or more, and the viscosity of the solution rises less than 1.5 times. -20- 201022312 The polyamidoximine resin obtained according to the present invention is used for a printed wiring board, especially in the case of a flexible printed wiring board in which flexibility is necessary, and the logarithmic viscosity of a polyamide amide resin Preferably, it is 2 dl/g or more, the glass transition temperature is preferably 80 ° C or more, and the tensile modulus is preferably less than 2000 MPa. When the logarithmic viscosity is less than 2.2 dl/g, since the molecular weight of the polyamidoximine resin is low, the problem of a decrease in mechanical strength may occur; the glass transition temperature is lower than 8 (in the case of TC, a polyfluorene may be formed). The problem of insufficient heat resistance of the amine imine resin; in the case where the tensile modulus of elasticity is 2000 MP on Q, since the resin is hard and brittle, the adhesion strength may be lowered, or the coating may be formed in the coating or drying step. The problem of curling on the film or the substrate. The thermosetting component which can be used for the polyamidoximine resin obtained according to the present invention may, for example, be an epoxy resin, an isocyanate compound, a melamine resin or an isocyanate compound. In the phenol resin, the maleic anhydride imide compound, etc., the epoxy compound is preferably used based on the physical properties of the cured coating film or the processing suitability. For example, the epoxy resin may be a product of Japan Epoxy Q Resin (stock). a bisphenol A type epoxy resin such as jER828 and 1001; a hydrogenated bisphenol A type epoxy resin manufactured by Dongdu Chemical Co., Ltd. under the trade name ST-2004, 2007; Dongdu Huacheng ( Bisphenol F-type epoxy resin, such as YDF-170, 2004, etc.; brominated bisphenol A epoxy resin, such as YDB-400 and 600, manufactured by Toho Chemical Co., Ltd.; Japan Epoxy Resin The product name of the (share) company, jER 152, 154, and the product name EPPN-2 manufactured by Nippon Kayaku Co., Ltd. (M, phenol novolac type epoxy resin, such as DEN-43 8 manufactured by BREN' Dow Chemical Co., Ltd.; Dongdu Huacheng (share) system trade name YDCN-702, 703, Nippon Chemical Co., Ltd. -21- 201022312 The trade name is EOCN-125S, 103S, 104S and other o-cresol novolac epoxy resin; Dongdu Huacheng ( Epoxy resin having a trade name of YD-1 7 1 manufactured by the company); epoxy resin having a cyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by DIC; Shell Epoxy (share) trade name Eponl031S' Ciba Specialty Chemicals (shares) trade name ARALDITE0163, NagaseChemtex (shares) trade names DENACOL EX-611, EX-614, EX-622, EX-512, EX- 521, EX-421, EX-411, EX-321, etc. The product name of the oxy (share) system is EPIC OAT6 04, the product name of the company is YH-434, and the product name of the Mitsubishi Gas Chemical (share) is TETRAD-X, TETRAD-C, and Nippon Chemical Co., Ltd. The product name is GAN, the amine type epoxy resin such as ELM-120 manufactured by Sumitomo Chemical Co., Ltd.; the heterocyclic epoxy resin such as ARALDITE PT810 manufactured by Ciba Specialty Chemicals Co., Ltd.; Daicel Chemical Industry (shares) product name: CELLOXIDE 2021, EHPE3150, UCC company's ERL4234 and other alicyclic epoxy resin; ® Dainippon Ink Chemical Industry Co., Ltd. product name EPIKURON EXA-15 14 and other bisphenol S type Epoxy resin; triepoxypropyl isocyanate of TEPIC, etc. manufactured by Nissan Chemical Industry Co., Ltd.; and bis- xylenol type epoxy resin such as YX-40 00 manufactured by Shell Epoxy Co., Ltd.; A bisphenol type epoxy resin, such as YL-6056, manufactured by Shell Epoxy Co., Ltd.; these epoxy resins may be used alone or in combination of two or more. Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy-22-201022312 tree, oxygen ring type halogenated non-phenolic phenolic resin, tree polyoxygen is a cyclic oxyamine Ring, lipid 2 tree, oxygen, cyclone type, aldehyde, hydrazine, sol, resin, compatibility with solvent, solvent resistance, chemical resistance, and polyami oxime imine resin obtained according to the present invention The viewpoint of improving moisture resistance is preferred. The solvent solution of the polyamidoximine resin of the present invention and the epoxy resin has excellent adhesion and can firmly adhere the polyimide film to the copper foil. The obtained copper polyimine film laminate has superior solder heat resistance and superior insulation reliability (resistance to @migration) in the case of use as a cover layer on a circuit. For this reason, it is considered that in a specific range, a polyamidoquinone imine resin in which an acrylonitrile-butadiene rubber is copolymerized with an aliphatic dicarboxylic acid having 4 to 12 carbon atoms is improved by introduction of an aliphatic group. Solvent solubility, while the chain length of the aliphatic group is not short or long, moderately dispersed in polyamidoquinone, by adhesion due to acrylonitrile-butadiene rubber, aliphatic dicarboxylic acid The introduction of a soft amine and a highly polar amine group will increase the adhesion multiply. An epoxy resin hardener or a hardening accelerator can be added to the thermosetting resin composition using the polyamidoquinone φ amine resin of the present invention insofar as the properties are not impaired. The curing agent is not particularly limited as long as it is a compound which reacts with an epoxy resin, and examples thereof include an amine curing agent, a compound having a phenolic hydroxyl group, a compound having a carboxylic acid, and a compound having an acid anhydride. The curing catalyst is not particularly limited as long as it accelerates the reaction of the epoxy resin with the polyamide and the above-mentioned hardener. For example, 2MZ, 2E4MZ, and Ci® manufactured by Shikoku Chemicals Co., Ltd. Z, CnZ ' 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C, iZ-CN ' 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, -23- 201022312 2MZ-AZINE, 2E4MZ-AZINE > MMZ-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, etc. imidazole derivatives; 胍 胍, 胍 胍 wells, etc.; diamine diphenylmethane, meta-phenylene diamine, between Polyamines such as xylene diamine, diamine diphenyl hydrazine, dicyanodiamide, urea, urea derivatives, melamine, polybasic hydrazine, etc.; such organic acid salts and/or epoxy addition compounds; Amine salt of boron trifluoride, ethyldiamine-S-three tillage, 2,4-diamino-S-three tillage, 2,4-diamino-6-dimethylphenyl-S-three Three-tillage derivatives such as cultivating; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyl-dimethylamine, pyridine 'N-methyl-morpholine, hexyl -methyl)melamine, 2,4,6-tris(dimethylaminophenol) Tetramethylguanidine, DBU (1,8-diazabicyclo[5,4,0]-7-undecene), DBN (1,5-diazabicyclo[4,3,0]- Tertiary amines such as 5-decene; such organic acid salts and/or tetraphenylborate; polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, Organic phosphines such as tris-2-cyanoethyl phosphine; tri-n-butyl bromide (2,5-dihydroxyphenyl) iron, cetyl tributyl sulphate, tetraphenyl quaternary tetraphenyl a quaternary phosphonium salt of a boric acid ester or the like: a quaternary ammonium salt such as benzyltrimethylammonium chloride or phenyltributylphosphonium chloride; the above polycarboxylic anhydride, diphenylphosphonium tetrafluoroborate Ester, triphenylsulfonium hexafluoroammonium, 2,4,6-triphenylthiopyranofluorohexafluorophosphate, Irgacure 2 6 1 (manufactured by Ciba Specialty Chemicals Co., Ltd.), 〇pt〇mer-SP-170 Photocationic polymerization catalysts such as ADEKA (manufactured by ADEKA Co., Ltd.); molar reactants such as styrene-maleic anhydride resin, phenyl isocyanate and dimethylamine, or toluene diisocyanate, isophorone isocyanate, etc. A molar reaction of an organic polyisocyanate with dimethylamine or the like. These hardeners and hardening accelerators may be used singly or in combination of two or more. -24-201022312 An inorganic or organic material can be added to the thermosetting resin composition using the polyamidoximine resin of the present invention as long as it does not impair the characteristics. For example, inorganic tantalum can be used: cerium oxide (Si〇2), aluminum oxide (Al2〇3), titanium dioxide (Ti〇2), tantalum oxide (Ta205), zirconium dioxide (Zr02), tantalum nitride (Si3N4) ), barium titanate (Ba0.Ti02), barium carbonate (BaC03), lead titanate (PZT), lead zirconate titanate (PLZT), gallium oxide (Ga2〇3), spinel (spinel, MgO ·Α12〇3), mullite (Mullite, 3Al2〇3 -2Si02), cordierite (2MgO ·2Α12〇3 *5Si02), talc (3Mg0.4Si02.H20), aluminum titanate (Ti02-Al203), Bismuth-containing dioxide pin (Y203-Zr02), barium strontium silicate (Ba0*8Si02), boron nitride (BN), calcium carbonate (CaC03), calcium sulfate (CaS04), zinc oxide (ZnO), magnesium titanate ( MgO*Ti02), barium sulfate (BaS04), organic bentonite, carbon (C), etc., these inorganic materials may be used singly or in combination of two or more. In the case of adding such a material, it is necessary to have a working step of dispersing, and depending on the use of the resin composition of the present invention, it is added because it has the possibility of not impairing the flexibility or processability of the original resin composition. In the case of dip, it is preferred to adjust the type of dip used or the amount added. The flame retardant can be added to the thermosetting resin composition using the polyamidoximine resin of the present invention as long as it does not impair the characteristics. The non-halogen-based flame retardant is preferably a non-halogen-based flame retardant as long as it is an environmentally-friendly one, as long as the non-halogen-based flame retardant used in the present invention is dissolved in the polyamidoximine resin composition. The limitation 'but the viewpoint of hydrolysis resistance, heat resistance or prevention of the escape of the flame retardant on the surface of the coating film is preferably a phosphazene phosphinic acid derivative. These flame retardants may be used singly or in combination of 2 to 25 to 201022312 or more. For example, the phosphazene may be a cyclic phenoxyphosphazene such as SPE-1® manufactured by Otsuka Chemical Co., Ltd., or a cyclic hydroxyphenoxy acid such as SPH-100 manufactured by Otsuka Chemical Co., Ltd. Cyclic cyanophenoxyphosphazene, such as FP-3 00, manufactured by Fushimi Pharmaceutical Co., Ltd., may be listed as chain phenoxyphosphazene, crosslinked phenoxyphosphazene, etc. However, since the chain phosphazene has a substituent at the molecular end, in general, the phosphorus content is lowered as compared with the cyclic phosphazene. Therefore, in the present invention, a cyclic phosphazene is preferred, and a cyclic trimer and/or a tetramer phosphazene is more preferred. In addition, since the non-reactive phosphazene will flow out over the surface over time, or under excessive use conditions, free phosphorus may be dissolved by the influence of hydrolysis or the like, or the insulating property may be lowered by the decomposition product. Preferably, a reactive phosphazene having a functional group reactive with an epoxy resin is selected. Specific examples thereof include a cyclic hydroxyphenoxyphosphazene having a hydroxyl group and the like. For example, the phosphinic acid derivative may be exemplified by: HCA (9,10-dihydroxy-9-sideoxy-10-phosphonium phenanthrene-10-oxide) of Sanguang (share), HCA-HQ (10-(2,5) -dihydroxyphenyl)-l〇-hydrogen-9-sideoxy-10-phosphate phenanthrene-10-oxide), 10-(2,5-dihydroxynaphthyl)-10-hydrogen-9-side oxygen- Phenanthrene 10-phosphate 'BCA ( 10-benzyl-10-hydrogen-9-sideoxy-10-phosphate phenanthrene-10.oxide), phenylphosphinic acid, diphenylphosphinic acid, etc. . In addition to the non-halogen-based flame retardant described above, other non-halogen-based flame retardants may be used insofar as the low bending property, heat resistance, and outflow property are not impaired. For example, a phosphorus-containing epoxy resin such as a copolymerized HC A skeleton, a phosphorus-containing polyester resin, a condensed phosphate ester of meta-hydroxybenzene diphenyl phosphate, or the like can be cited; however, it is not resistant to such non-halogen-based flame retardation. It is limited by the agent, and it can also be used by combining two types of -26-201022312 or more. 3. Flame-retardant adhesive composition The flame-retardant adhesive composition of the present invention is characterized by (A) polyamidoximine resin, (B) phosphorus-containing epoxy resin, (C) phosphorus compound, The phosphorus content is 2.0 to 5.0% by mass based on the total mass of (A) to (C). (A) Polyacrylamide imine resin (A) The polyamidoximine resin used in the present invention is the above-mentioned polyamidoximine resin, which has the following acid components and aromatics (a) to (c) The ratio of each of the acid components in the case where the polyacrylamide quinone imine resin obtained by the reaction of the diisocyanate or the diamine of the ring is 100 mol% of the total acid component of the polyamidoximine resin is (a) 3 to 10 mol%, (b) 10 to 80 mol%, and (c) 10 to 87 mol%. (a) an acrylonitrile-butadiene rubber having a carboxyl group at both ends, (b) an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and (c) an acid anhydride of a polycarboxylic acid having an aromatic ring. (A) Polyamidoximine resin can be used as an adhesive (thermosetting resin composition) by adding a thermosetting component to form a solvent solution. When the thermosetting resin composition is used as an adhesive, the drying temperature is lowered, and in order to prevent the curing reaction from proceeding excessively during drying, it is preferred to contain a solvent having a low dryness and a low boiling point in the resin solution. Examples of the low boiling point solvent suitable for the adhesive (thermosetting resin composition) include ethanol, toluene, xylene, and methyl ethyl ketone. In order to find dryness and superiority, it is preferably contained in an amount of 60% by mass or more. In the mixed solvent of at least one solvent selected from the group consisting of such solvents, the polyamidoximine resin is dissolved in 10 -27 to 201022312% by mass or more. By having such solubility, not only superior drying properties are added 'the following (B) phosphorus-containing epoxy resin, (C) phosphorus compound, (D) epoxy resin hardener, (E) phosphorus-free ring When the oxygen resin or the (F) decane coupling agent is used as an adhesive (thermosetting resin composition), it is excellent in stability and storage stability as a thermosetting resin composition. Here, the dissolution in the present invention means a state in which the solution is kept transparent and the solid matter is not precipitated in an environment of 25 ° C for 24 hours or more and the viscosity of the solution between the φ is increased by less than 1.5 times. The polyamidoximine resin of the present invention has a logarithmic viscosity of preferably 0.2 dl/g or more, a glass transition temperature of preferably 80 to 200 ° C, and a tensile modulus of elasticity of preferably less than 2000 MPa. In the case where the logarithmic viscosity is less than 2.2 dl/g, the following problem will occur: since the molecular weight of the polyamidoximine resin is low, the mechanical strength will be lowered; and the glass transition temperature is lower than 80 °C. The heat resistance of the amidoxime resin will be insufficient; if the tensile modulus of elasticity is 2000MP or more, since the resin is hard and brittle, the adhesive strength will become weak, or the crimping in the coating or drying step will occur. . In addition, when the glass transition temperature is higher than 200 ° C, the flexible printed wiring board is attached to the adherend, and the temperature of the heat lamination (hot press-bonding) is increased in order to be sufficiently bonded. The workability and workability will be lowered, and the solvent solubility will be deteriorated. In the present invention, the (A) polyamidoximine resin is dissolved in a solvent together with the following components (B) to (F), and the flame retardant adhesive composition has excellent adhesion and can be firmly adhered thereto. Adhesive polyimide film and copper foil. The obtained copper polyimine film laminate has superior solder heat resistance and superior insulation reliability (resistant to -28-201022312 mobility) when used as a coating on a circuit. The reason for this is considered to be that, in a specific range, the introduction of the aliphatic group is improved by the copolymerization of the acrylonitrile-butadiene rubber and the polyamidoximine resin of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms. Solvent solubility, while the chain length of the aliphatic group is not short or long, moderately dispersed in polyamidoquinone, by adhesion caused by acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid The introduction of a soft amine and a highly polar amine group will increase the adhesion multiply. (B) Phosphorus-containing epoxy resin (B) The phosphorus-containing epoxy resin used in the present invention is an epoxy resin obtained by using a reactive phosphorus compound to obtain a phosphorus atom by a chemical bond, and preferably has two or more rings in one molecule. Examples of the oxy group include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type, or a hydrogenated epoxy resin, and a phenol novolac type epoxy resin. Epoxy propyl ether epoxy resin such as cresol novolac type epoxy resin, epoxy propyl hexahydrophthalate or glycidyl diacrylate ; epoxidized propyl propyl isocyanate, tetra-epoxypropyl diamine diphenylmethane and other epoxy propyl amines; epoxy resin; epoxidized polybutadiene, epoxidized soybean oil and other linear fat. Oxygen resin, etc. Further, examples of the reactive phosphorus compound used in the phosphorus-containing epoxy resin include 9,10-dihydroxy-9-sideoxy-10-phosphonium phenoxy-10-oxide (manufactured by Sanko Co., Ltd., trade name) :1^人), 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-sideoxy-10-phosphate phenanthrene-10-oxide (Sanguang (share) system, trade name: HCA-HQ And the like, by reacting with the above epoxy resin, a phosphorus-containing epoxy resin can be obtained. For example, EPIKURONEXA9710 (made by DIC (share), phosphorus content: 3 mass%), -29-201022312 EXA9748 (DIC (share), phosphorus content: 4.5% by mass), ( Dongdu Huacheng (share) system, phosphorus content: 3% by mass). The blending amount of the phosphorus-containing epoxy resin used herein is preferably from 3 to 160 parts by mass to from 5 to 120 parts by mass, more preferably more than 1 part by mass of the (A) polyamidoximine resin. 1〇~80 parts by mass. When the amount of the epoxy resin is less than 1 part by mass, the flame retardancy is deteriorated. When the amount of the epoxy resin is large, the heat resistance and the adhesiveness are deteriorated, or the mechanical properties are lowered, and the sheet is easily broken. φ ( C ) Phosphorus compound ‘ Although the (C) phosphorus compound used in the present invention is not particularly based on hydrolysis resistance, heat resistance, and outflow, a phosphazene acid derivative is preferred. These flame retardants may be used singly or in combination. The phosphazene compound is represented by the following formula (1) or (2) (the same or different elements represent hydrogen, a hydroxyl group, an amine group, an alkyl group, or an aryl group). For example, the organic group may be an alcohol group or a benzene group. The oxy 'allyloxy group, hydroxyphenoxy group or the like, η is an integer of from 3 to 25). FX305 invention f, better if phosphorus is more than 200 strength, phosphine 2, medium, X, organic, cyanobenzene

(2) X - -P=N- I Lx J η For example, the commercial product of such a phosphazene may be a cyclic phenoxy oxime chemical (stock), trade name: Spb_i〇〇, SPE-100) Nitrile (large, cyclic -30-201022312 cyanophenoxyphosphazene (made by Fushimi Pharmaceutical Co., Ltd., trade name: FP-3 00), cyclic hydroxyphenoxyphosphazene (Otsuka Chemical Co., Ltd.) In addition, the addition type phosphazene has a time-lapse outflow, and under the severe use conditions, the free phosphorus is eluted by the influence of hydrolysis or the like, and the electrical insulation property is lowered. Therefore, a reactive phosphazene having a functional group reactive with an epoxy resin is preferably selected. Specific examples thereof include a cyclic hydroxyphenoxyphosphazene having a phenolic hydroxyl group, and the like. The phosphinic acid derivative of the phenanthroline type is, for example, 9,10-dihydroxy-9-sideoxy-10-phenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA), 10-benzyl-10-hydrogen-9-sideoxy-10-phosphate phenanthrene-10-oxide (manufactured by Sanguang Co., Ltd., trade name: BCA), etc. Among the substances, HCA has reactivity with an epoxy resin, and when it has an outflow, the temperature resistance and the high humidity resistance are deteriorated, and the blending amount is appropriately selected in consideration of the properties. In the range of damage to flame retardancy, solder heat resistance, and outflow, if necessary, other phosphorus compounds may be used alone or in combination of two or more. The phosphorus content of the flame retardant adhesive composition of the present invention is 2.0. ～5.0% by mass, preferably 2.2 to 4.5% by mass, still more preferably 2.5 to 4.0% by mass, and if the phosphorus content is less than 2.0% by mass, good flame retardancy is not obtained; if it exceeds 5·0 When the mass is %, heat resistance, adhesiveness, and electrical insulating properties tend to be lowered. (D) Epoxy resin hardener-31-201022312 As long as the (D) epoxy resin hardener used in the present invention is generally used as an epoxy resin The hardening agent is not particularly limited. For example, the (D) epoxy resin curing agent may, for example, be a polyamine curing agent, a sour liver curing agent, a boron trifluoride amine salt, or a resin. For example, a polyamine hardener can Listed: diethylenetriamine, tetraethylenetetramine, tetraethyleneamine, isophorone diamine, diamine diphenylmethane, meta-phenylenediamine, m-xylenediamine, diamine diphenyl maple, Polyamines such as dicyandiamide, urea, urea derivatives, melamine, polyalkali, etc., organic acid salts and/or epoxy addition compounds, etc., for example, an acid anhydride hardener : phthalic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, six Hydrogenated pyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3-( 1,2), 5, 6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane 1-en-3-yl(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-b (1,2), 3,4-tetracarboxylic dianhydride, 1_ Propylcyclohexane- l-(2,3),3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3),3-(2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1] W heptane-2,3,5,6-tetracarboxylic acid Anhydride, 1-propane Cyclohexane- l-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2,3)- Tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4,-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, Bicyclo[2_2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydroperbenzenetetracarboxylic anhydride, and the like. These hardeners may be used singly or in combination of two or more. When the total non-volatile content of the flame retardant adhesive composition is set to mass%, (D) the blending amount of the epoxy resin hardener is 0 to 5 mass% '-32-201022312, preferably 〇~3 mass %. When the blending amount exceeds 5% by mass, the heat resistance tends to be lowered. (Ε) Phosphorus-free epoxy resin The epoxy resin which does not contain phosphorus in the present invention is not particularly limited as long as it is an epoxy resin which does not contain phosphorus in the molecule. The epoxy resin may be denatured by using a decane, a urethane, a polyimide or a polyamine, or may contain a sulfur atom or a nitrogen atom in the molecular skeleton. For example, such an epoxy resin may be exemplified by a bisphenol fluorene type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type, or a hydrogenated product of such an epoxy resin, and a phenol novolac type epoxy resin. Epoxy propyl ether epoxy resin such as cresol novolac type epoxy resin, epoxy propyl hexahydrophthalate or glycidyl diacrylate, etc. a resin; a glycidyl propyl epoxy resin such as trisepoxypropyl isocyanate or tetraepoxypropyl diamine diphenylmethane; a linear aliphatic epoxy such as epoxidized polybutadiene or epoxidized soybean oil; Resin, etc. For example, such a commercial item may be bisphenol A type epoxy resin such as jER8 28, 1001 manufactured by Japan Epoxy Resin Co., Ltd., and ST-2004, 2007 manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin; bisphenol F type epoxy tree of YDF-170, 2004, etc., manufactured by Dongdu Chemical Co., Ltd.; Jap an Epoxy Resin (share), trade name jER 152, Dow A phenol novolac type epoxy resin manufactured by Chemical Co., Ltd. under the trade name DEN-43 8; the trade name of the company is YDCN-702, 703, and the product name of EOCN-125S, 103S manufactured by Nippon Chemical Co., Ltd. O-cresol novolac type epoxy resin such as 104S; epoxy resin having a cyclopentadiene skeleton such as HP-7200, HP-7200H, etc. manufactured by DIC (trade name); 33-201022312 YD-l 71 flexible epoxy resin; trade name Eponl031S manufactured by Shell Epoxy Co., Ltd., trade name ARALDITE0163 manufactured by Ciba Specialty Chemicals (share), Nagase Chemtex (share) DENACOL EX-611, EX-614, EX-622, EX-512, EX-521 Multi-functional epoxy resin such as EX-421, EX-411, EX-321, etc.; trade name EPICOAT604 manufactured by Shell Epoxy Co., Ltd., YH-434 manufactured by Dongdu Chemical Co., Ltd., Mitsubishi Gas Chemical ) The trade name TETRAD-X, TETRAD-C, the product name GAN of the Nippon Chemical Co., Ltd., and the amine type epoxy resin of the product name ELM-120 manufactured by Sumitomo Chemical Co., Ltd.; Ciba Specialty Chemicals ( a heterocyclic epoxy resin such as ARALDITE PT810 manufactured by the company, a condensed epoxy resin such as CELLOXIDE 2021, EHPE3150 manufactured by Daicel Chemical Industry Co., Ltd., and ERL4234 manufactured by UCC;

A bisphenol S type epoxy resin such as EPIKURON EXA-1514 manufactured by DIC (share); a triepoxypropyl isocyanate such as TEPIC manufactured by Nissan Chemical Industries Co., Ltd.; and a product made of oiled Shell Epoxy (share) name

a bisphenol type epoxy resin such as YX-4000; a bisphenol type epoxy resin such as YL-605 6 manufactured by Shell Epoxy (share A); these epoxy resins may be used alone. Or you can use 2 or more types. When the total non-volatile content of the flame retardant adhesive composition is 100% by mass, the blending amount of the (E) phosphorus-free epoxy resin is 0 to 20% by mass, preferably 0 to 15% by mass. . When the blending amount exceeds 20% by mass, there is a tendency that sufficient flame retardancy cannot be obtained. (F) decane coupling agent, as long as the (F) decane coupling agent used in the present invention is a conventional decane coupling-34-201022312 mixture as an adhesive The agent is not particularly limited. Specific examples thereof include an amino decane, a mercapto decane, a vinyl decane, an epoxy decane, a methacryl decane, an isocyanate decane, a ketimine decane or a mixture or reactant thereof, or A compound obtained by reacting a decane coupling agent with a polyisocyanate or the like. For example, such a decane coupling agent may be exemplified by 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxydecane, and 3-aminopropylethylidene. Diethoxy decane, bistrimethoxy sulfonyl propylamine, bis tri φ ethoxylated alkyl propylamine, bismethoxydimethoxy decyl propylamine, bisethoxydiethoxy hydrazinopropylamine, N-2-( Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3- Amino decane such as amine propyl triethoxy decane, N-2-(aminoethyl)-3-amine propylethyldiethoxy decane; γ-mercaptopropyltrimethoxy decane, γ-锍a fluorenyl group such as propyltriethoxydecane, γ-mercaptopropylmethyldimethoxydecane, γ-mercaptopropylmethyldiethoxydecane, γ-mercaptopropylethyldiethoxydecane Decane; vinyl methoxy decane, vinyl triethoxy oxime, vinyl decane such as tris(2-methoxyethoxy) vinyl decane; γ·glycidoxypropyltrimethoxy Decane, γ-glycidoxypropyl dimethyl ethoxy decane, γ-epoxy Propoxypropylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-( Epoxy decane such as 3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-methylpropenyl methoxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Methyl decyl decane, such as decane, 3-methylpropenyl methoxypropylmethyldiethoxy decane, 3-methyl propylene oxypropyl triethoxy decane, etc.; isocyanate propyl triethoxy a decane counon such as decane, isocyanate propyl-35-201022312 octylmethoxy decane, etc.; ketone imidized propyltriyl decane, ketimine propyl triethoxy decane, etc. Use one alone, or you can use 2 on it. Among these decane coupling agents, since the epoxy decane has a reactive oxy group, it can be combined with (A) a polyamidoximine resin, (B) an epoxy resin, and (D) an epoxy resin hardener. (E) a reaction in which a phosphorus-free cycloaliphatic or the like is reacted, and the total non-volatile content of the flame-retardant adhesive composition is set to 1% by mass based on the viewpoint of improvement in heat resistance and moist heat resistance, (F) The blending amount of the decane coupling agent is 0 to 3% by mass, and is 0 to 2% by mass. When the blending amount exceeds 3% by mass, the heat resistance tends to decrease. The components (A) to (F) used in the present invention are preferably at a solid concentration of 25% by mass at 25 ° C, and are all dissolved in dimethyl acetamide, ethanol, lutylene, methyl ethyl ketone. In any of the solvents. Therefore, if the uniform dispersion step of ruthenium is not required, problems such as the above-mentioned problems of ignorance, non-uniformity, reduction in the usable period of the paint, and low chemical resistance can be avoided. Further, in the present invention, a hardening accelerator can be used as necessary. The accelerator is used to accelerate various components which can react with the epoxy resin, and is not limited as long as it is a hardening accelerator which does not contain a halogen atom. Examples of the hardening accelerator include a third-stage amine, a fourth-order ammonium salt, an imidazole, and an octanoate. These may be used alone or in combination of two or more. For the flame-retardant resin composition of the present invention, Does not impair its characteristics of methoxy: this is better with the oxygen tree of cyclophosphine. The quality is better, and the benzene or the dispersing agent of the organic bismuth and the inorganic cerium can be added to the benzene and the sulphate. However, since the processing property or performance of the printed wiring board is lowered by the addition, it is necessary to fully consider the type or amount of the use or the filling material. The components (A) to (F) used in the present invention are dissolved in an organic solvent. The composition is used as a solution and adjusted for use. The organic solvent may, for example, be dimethylacetamide, ethanol, methanol, toluene, xylene, methyl ethyl ketone, dimethylformamide, cyclohexanone, N-methyl-2-pyrrolidone, isopropyl Examples of the alcohol, acetone, and the like include dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone. These solvents may be used alone or in combination of two or more. When the composition is dissolved in an organic solvent and used, when the solvent is dried, since the hardening reaction does not proceed completely, it is desirable to lower the drying temperature. Therefore, it is preferred to contain a large amount of low-boiling solvent which is excellent in drying property in the resin solution. Examples of the low boiling point solvent suitable for the solution of the composition include ethanol, toluene, xylene, methyl ethyl ketone, etc., and in order to find dryness and advantages, it is preferable that the composition is dissolved in 50% or more. The total concentration (solid content concentration) of the components (A) to (F) in the above-mentioned adhesive solution is usually 10 to 45 mass in a mixed solvent of a solvent selected from the group consisting of such solvents. %, preferably 15 to 40% by mass, still more preferably 20 to 35% by mass. If the concentration is less than 1% by mass, the thickness of the adhesive will be thinner, and the heat resistance and adhesion strength will be lowered. If the mass is greater than 45 mass%, the uniform coating will become excessive as the viscosity of the solution becomes too high. difficult. 4. Adhesive sheet-37-201022312 The adhesive sheet for an electronic component of the present invention refers to a non-flammable adhesive composition of the present invention as an adhesive layer, and has at least one layer of a peelable protective film. Layer structure. For example, the two-layer structure of the protective film layer/adhesive layer or the three-layer structure of the protective film layer/adhesive layer/protective film layer conforms thereto. Here, the protective film layer is not particularly limited as long as it can be peeled off without impairing the form of the adhesive layer, and examples thereof include polyethylene, polyester, polyolefin, polymethylpentene, polyvinyl chloride, and poly. a plastic film such as vinylidene fluoride or polyphenylene sulfide; a film which is coated with such a plastic film by using a decane or a fluoride; a paper laminated with such a protective film layer; and a peeling or coating having a peeling Paper of resin, etc. In addition, it is possible to use metals, ceramics, and the like, and it is advantageous not only for protection against surface insulation and environmental resistance, but also for new functions such as heat release, electromagnetic shielding, reinforcement, and recognition. The adhesive sheet is produced by applying the adhesive solution in which the flame retardant adhesive composition of the present invention is dissolved in a solvent to the film having mold release property, preferably at a temperature of 50 to 200 ° C, preferably 70 to 160 ° C, further preferably dried at 1 〇〇 to 130 ° C for about 2 to 10 minutes to form an adhesive layer. The thickness of the above adhesive layer after drying is 5 to 40 μm, preferably 10 to 25 μm. Further, in the case of a three-layer structure, a release protective film is further laminated and laminated. 5. Cover film The cover film of the present invention is formed by forming a flame retardant adhesive composition of the present invention as an adhesive layer, a two-layer structure of an insulating plastic film layer/adhesive layer, or by insulation. The three-layer structure of the plastic film layer/adhesive layer/protective film layer is formed. The so-called insulating plastic film is Poly-Asian-38-201022312 Amine, polyester, polyphenylene sulfide, polyether mill, polyetheretherketone, aromatic polyamine, polycarbonate, polyarylate, etc. A film having a thickness of 5 to 200 μm may be laminated to a plurality of films selected from such an insulating plastic film. The protective film can be used as the protective film of the above adhesive sheet. The method for producing a cover film is to apply an adhesive solution in which a flame retardant adhesive composition of the present invention is dissolved in a solvent to the above-mentioned insulating plastic film at a temperature of 50 to 200 ° C, preferably 70 °. At 160 ° C, further U is more preferably dried at 1 〇〇 to 13 ° ° C for about 2 to 10 minutes to form an adhesive layer. The thickness of the above adhesive layer after drying is 5 to 40 μm, preferably 10 to 25 μM. Further, in the case of a three-layer structure for storage or the like, a release protective film is further laminated and laminated. 6. Flexible printed wiring board The flexible printed wiring board of the present invention means that the flame retardant adhesive composition of the present invention is used as an adhesive layer, and the adhesive layer is used to bond an insulating plastic film with copper. Foil structure. For example, it may be exemplified by having the adhesive layer provided on one side or both sides of the insulating film, and the flexibility of one or two layers of copper foil adhered to one or two layers of the adhesive layer. Printed wiring board. For the copper foil, a rolled copper foil or an electrolytic copper foil which is conventionally used for a flexible printed wiring board can be used. The insulating plastic film can use the above-mentioned matter as the insulating plastic film of the above-mentioned cover film. The method for producing a flexible printed wiring board is characterized in that an adhesive solution in which a flame retardant adhesive composition of the present invention is dissolved in a solvent is applied onto the above-mentioned insulating plastic film, preferably at a temperature of 50 to 200 ° C. Further, at 70 to 160 ° C, more preferably at 100 to 130 ° C, and dried for about 2 to 10 minutes to form -39-201022312 Adhesive layer, the thickness of the above adhesive layer after drying is 5 to 40 μm, preferably It is 10~25 μπι. Next, by laminating a copper foil on the adhesive layer and performing thermal lamination at a temperature of 80 to 150 ° C, preferably 110 to 130 ° C, a laminate can be obtained. From the viewpoint of heat resistance, the Tg of the polyamidoximine resin used in the present invention is high, and if the laminating temperature is lower than 100 ° C, it will not be smoothly heat-bonded; if it is 150 ° C When it is high, there is a tendency that workability will be lowered. The flexible printed wiring board can be obtained by further heat-hardening at 120 to 200 ° C, preferably 140 to 170 ° C, to completely cure the adhesive. Even if the flexible printed wiring board obtained by the present invention is immersed in a solder bath of 1300 ° C for 30 seconds, almost any one of appearance abnormalities such as peeling, swelling, and discoloration does not occur, and it is possible to exhibit superiority. Solder heat resistance. In addition, after being allowed to stand for 24 hours in an environment of 40 ° C and a relative humidity of 90%, even if it was quickly immersed in a solder bath of 300 ° C for 30 seconds, appearance abnormalities such as peeling, swelling, and discoloration did not occur. The solder heat resistance technique of any of the phenomena cannot be easily accomplished. EXAMPLES Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited by the examples. 1. For the polyamidoximine resin and the resin characteristics of the resin composition, the following method was used for measurement and evaluation (log viscosity). At 30 ° C, the Ubbelohde viscosity tube was used to determine that it would be dried. The solid polymer was 〇5 g of a solution dissolved in 10 ml of NMP. -40-201022312 (stretching elastic modulus) The obtained polyamidoximine resin solution was applied to a copper foil so that the film thickness after drying became 20 μm, and it was dried at 150 ° C by a hot air dryer. After drying for 10 minutes, it was dried at 200 ° C for 5 hours in an oxidation-free oven, and the copper foil was removed by etching to form a polyimide film of a polyimide film, and a film having a width of 10 mm was formed from the film. The rectangular shape was measured at a tensile speed of 20 mm/min using TENSILON manufactured by Toyo Baldwin Co., Ltd.*> 玻璃 (glass transition temperature) The dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement and Control Co., Ltd. was used at a frequency of 110 Hz. The measurement of the dynamic viscoelasticity of the polyimide film which is the same as that of the elastic modulus of the tensile modulus is determined by the inflection point of the storage elastic modulus. (Solubility) The polyacetamide quinone imide resin film used for the tensile modulus measurement was dissolved in 40 parts by mass of the mixed dimethyl acetamide and toluene in such a manner that the nonvolatile content was 10% by mass. 60 parts by mass of solvent. In the environment of 25 °C, the solution was transparent, and the solid matter was not precipitated for 24 hours, and the completely dissolved one was recorded as 〇, and the non-completely dissolved one was recorded as X. (Adjustment of the binder resin composition) The epoxy resin (jER 152, phenol novolac type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) was added to the non-volatile resin 1 〇〇g of the obtained polyamidoximine resin solution. 50 g of a toluene solution containing 30% by mass of a component and 4 g of a methyl ethyl ketone solution having a nonvolatile content of 15% by mass of 4,4,-diamine diphenyl maple (SEIKACURE-S, manufactured by Wakayama Seika Co., Ltd.) to obtain a binder resin composition. -41- 201022312 Things. (Adhesive strength) The adhesive resin composition was applied to a polyimide film (APICAL®) having a thickness of 25 μm by a film thickness of 15 μm after drying, and was dried at 1 30 ° C by a hot air dryer. The solvent was dried for 5 minutes. Thereafter, it was bonded to an electrolytic copper foil (18 μηι thickness, USLP, manufactured by Nippon Seisakusho Co., Ltd.) at 130 ° C, and further hardened by heating at 1, 70 ° C for 3 hours. Then, the obtained copper clad laminate was cut into a width of 1.0 mm, and TENSILON manufactured by Toyo Baldwin Co., Ltd. was used at room temperature, and peeled at 90° at a tensile speed of 50 mm/min to measure the peel strength. (Solder heat resistance) The state in which the copper clad laminate having the adhesion was measured was floated in a 300 ° C side tin bath for 60 seconds. Those who have not peeled off or swelled are denoted as 〇, and others are denoted as X. (Insulation reliability: migration resistance) A comb-type pattern (circuit) of φ line pitch of 50 μm was prepared on a two-layer CCL (trade name: VYLOFLEX) manufactured by Toyobo Co., Ltd., and washed with 3% hydrochloric acid, followed by washing with water. The adhesive resin composition was applied over the entire surface of the obtained resin so that the film thickness after drying was 2 μm, and the adhesive layer was heat-hardened at 170 ° C for 180 minutes. Thereafter, a DC voltage of 50 V is applied, and an insulation resistance 値 after 500 hrs exceeding 1 χ 108 Ω is denoted as 〇, which is less than 1 χ 1 〇 8 Ω or a dendritic crystal is observed as X in the wiring. Example 1 (Polyacrylamide imine resin 1): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a thermometer of 4 bottles - 42 - 201022312, 'feeding trimellitic anhydride l 5.67 g (0.55) Mol), azelaic acid 80.09g (0.40mol), acrylonitrile butadiene rubber with carboxylic acid at both ends (CTBN 1 3 00x 13 , number average molecular weight 3500, proportion of acrylonitrile site 26wt%) 175g (0.05mol 4,4'-diphenylmethane diisocyanate 252.75 g (1.0 mol), dimethylacetamide 5 2 6 g, and the temperature was raised to 1 ° C under a nitrogen gas stream, and the reaction was carried out for 2 hours. Next, by adding 117 g of dimethylacetamide and further reacting at 150 ° C for 5 hours, 439 g of toluene and 146 g of dimethylacetamide were added, and then diluted, and cooled to room temperature, and φ was brown. Turbid polyamidoximine resin solution 1. The results obtained by measuring the logarithmic viscosity, the glass transition temperature, and the tensile modulus of elasticity of the polymer obtained from the resin solution are shown in Table 1. Further, as described above, the binder resin composition is adjusted from the polyamidoximine resin solution, and the copper-clad laminate is produced using the binder resin composition, and the adhesion strength and solder heat resistance are evaluated for the copper-clad laminate. . In addition, the method disclosed in the preceding paragraph is utilized to evaluate the migration resistance as a necessary characteristic of the cover layer. The results obtained are shown in Table 1. φ Example 2 (polyamidiamine resin 2): In a 2 liter separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a 4-bottle of a thermometer, 142.18 g (0.74 mol) of trimellitic anhydride was fed. 40.45g (0.20mol) of azelaic acid, acrylonitrile butadiene rubber (CTBN 1 300M3 ) with both ends being citric acid 210.0g (0.06mol), 4,4'·diphenylmethane diisocyanate 125.13g (0.5mol ), toluene diisocyanate 87.08 g (0.5 mol) and 517 g of dimethylacetamide were heated to 10 ° C under a nitrogen gas stream, and reacted for 2 hours. Then, after reacting at 150 ° C for 5 hours, toluene 43 lg and 25 g of dimethylacetamide were added, and then diluted to -43 - 201022312, and cooled to room temperature to obtain a brown, completely turbid polyamine.醯Imine resin solution 2. In the same manner as in Example 1, the obtained measurement results and evaluation results are shown in Table 1 » Example 3 (polyamidiamine resin 3): equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer 4 bottles of a 2 liter separable flask, feeding trimellitic anhydride 10 5.67 g (0.55 mol), dodecanedioic acid 92.12 g (0.4 mol), acrylonitrile butadiene rubber with carboxylic acid at both ends (匚Ding 81^1300><13) 1758 (0.05111〇1), 4,4'-diphenylmethane diisocyanate 250.25g (1.0 mol), dimethylacetamide 53 5g, heated to 100 under nitrogen gas flow At °C, the reaction was carried out for 2 hours. Next, after reacting at 150 ° C for 5 hours, 594 g of toluene and 119 g of dimethylacetamide were added, followed by dilution, and the mixture was cooled to room temperature to obtain a brown, completely turbid polyamidoximine resin solution 3 . The same manner as in Example 1 was carried out, and the obtained measurement results and evaluation results are shown in Table 1. Example 4 (polyamimidoximine resin 4): 105.67 g (0.55 mol) of trimellitic anhydride was fed into a 2-liter separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a 4-bottle of a thermometer. 58.46 g (0.4 mol) of diacid, acrylonitrile butadiene rubber (CTBN 1 3 00 xl3) 175 g (0.05 mol) and 4,4,-diphenylmethane diisocyanate 250.25 g (l. Omol) and 501 g of dimethylacetamide were reacted for 2 hours under a nitrogen gas stream to a temperature of 1 ° C. Then, after reacting at 150 ° C for 5 hours, 418 g of toluene and 251 g of dimethylacetamide were added, followed by dilution, and the mixture was cooled to room temperature to obtain a brown color completely free of -44-201022312 turbid polyamine. Amine resin solution 4. The same manner as in Example 1 was carried out, and the obtained measurement results and evaluation results are shown in Table 1. Example 5 (polyamidiamine resin 5): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a 4-bottle of a thermometer, trimellitic anhydride 67.25 g (0.35 mol), 癸二121.34 g (0.60 mol) of acid, acrylonitrile butadiene rubber (CTBN130〇xl3) 175 g (0.05 mol) and 4,4'-diphenylmethane diisocyanate 252.75 g (1. Omol) 5, g of dimethylacetamide, heated to 1 ° C under a nitrogen stream, and reacted for 2 hours. Further, after reacting at 150 ° C for 5 hours, 438 g of toluene and 63 g of dimethylacetamide were added, followed by dilution, and the mixture was cooled to room temperature to obtain a brown, completely turbid polyami oxime imine resin solution 5 . The same manner as in Example 1 was carried out, and the obtained measurement results and evaluation results were not shown in Table 1. Comparative Example 1 (Polyacrylamide imine resin 6): φ In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a 4-bottle of a thermometer, 89.15 g (0.58 mol) of trimellitic anhydride was fed. 64.72g (0.40m〇l) of acid, acrylonitrile butadiene rubber (CTBN130〇xl3) with carboxylic acid at both ends, 56g (0.02mol), 4,4,-diphenylmethane diisocyanate 201.2g (lmol), 423.3 1 g of dimethylacetamide, and the temperature was raised to 1 Torr (TC) under a nitrogen gas stream for 2 hours. Then, after reacting at 150 ° C for 5 hours, 353 g of toluene and 212 g of dimethylacetamide were added. After dilution, it was cooled to room temperature to obtain a brown, completely turbid, polyamidoximine resin solution 6. -45 - 201022312 The same procedure as in Example 1 was carried out, and the obtained measurement results and evaluation results were not observed. Table 1. Comparative Example 2 (Polyacrylamide imine resin 7): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a 4-bottle of a thermometer, 172.92 g (0.90 mol) of trimellitic anhydride was fed. , azelaic acid 10.11g (0.05mol), both ends of the citrate (CTBN130〇xl3) 175g (0.05mol), 4,4'-diphenylmethane diisocyanate 247.75g (0.99mol), dimethylglycolamine 518g, heated to l〇〇 °C under nitrogen gas, react 2 hours. Then, by reacting at 150 ° C for 5 hours, 431 g of toluene and 295 g of dimethylacetamide were added and diluted, and cooled to room temperature to obtain a brown polyamidimide resin solution. 7 showed turbidity. The same procedure as in Example 1 was carried out, and the obtained measurement results and evaluation results were not shown in Table 1. Comparative Example 3 (Polyacrylamide yimimide resin 8): equipped with a stirrer, a cooling tube, and a nitrogen gas In a separable flask with 4 bottles of inlet tube and thermometer, 9.61 g (0.05 mol) of trimellitic anhydride, 182.02 g (0.90 mol) of sebacic acid, and acrylonitrile butadiene rubber with carboxylic acid at both ends (CTBN130〇) Xl3) 175g (0.05mol), 4,4'-diphenylmethane diisocyanate 25 2.7 5g (1.0m〇l), dimethylacetamide 5 29g, heated to 100 °C under nitrogen gas, react 2 After further reacting for 5 hours at 150 ° C, toluene 44 lg and dimethylacetamide 2 64 g were added. The mixture was diluted and cooled to room temperature to obtain a brown, turbid, polyamidoximine resin solution 8. The same procedure as in Example 1 was carried out, and the obtained measurement results and evaluation results of -46-201022312 are shown in the table. 2»Comparative Example 4 (Polyimide yimimide resin 9): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a 4-bottle of a thermometer, 105.67 g (0.55 mol) of trimellitic anhydride was fed. Acrylonitrile butadiene rubber (CTBN130〇xl3) 175g (0.05mol), eicosanedioic acid (made by Okamura Oil Co., Ltd.) 137g (40mol), 4,4'-diphenylmethane diisocyanate 125.13 g (0.5 mol), 87.08 g (0.5 mol) of toluene diisocyanate and 542 g of dimethylacetamide were heated to 1 ° C under a nitrogen gas stream, and reacted for 2 hours. Next, after reacting at 150 ° C for 5 hours, 452 g of toluene and 271 g of dimethylacetamide were added, and then diluted to cool to room temperature 'because the solubility of the polyamidoximine resin was insufficient, the resin solution Obviously become turbid, and the subsequent measurement results and evaluation are suspended. Comparative Example 5 (polyamimidoximine resin 10): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a 4-bottle of a thermometer, 86.4 g (0.45 mol) of trimellitic anhydride and azelaic acid were fed. 80.09 g (0.40 mol), acrylonitrile butadiene rubber (CTBN 1300x13) 525 g (0.15 mol), 4,4'-diphenylmethane diisocyanate 252.75 g (1.0 mol), dimethyl group 8 54 g of acetamide was heated to 100 ° C under a nitrogen gas stream, and reacted for 2 hours. Then, by adding 190 g of dimethylacetamide and further reacting at 150 ° C for 5 hours, 712 g of toluene and 237 g of dimethylacetamide were added, diluted, and cooled to room temperature to obtain a brown color and slightly blurred. Polyamidoximine resin solution 1 〇. The same manner as in Example 1 was carried out, and the obtained measurement results and evaluation results were not shown in Table 2. -47- 201022312 Comparative Example 6 (polyamidoximine resin 11): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube, and a 4-bottle of a thermometer, 182.4 g of trimellitic anhydride was fed (〇.95 mol). ), acrylonitrile butadiene rubber (CTBN 1 300xl3) 175g (0.05mol), 4,4'-diphenylmethane diisocyanate 252.75g (1.0111〇1), dimethylacetamide 5198, the temperature was raised to 100 ° under a nitrogen gas stream (:, the reaction was carried out for 2 hours. Then, by adding 115 g of dimethylacetamide, and further reacting at 150 ° C for 5 hours, 433 g of toluene and dimethyl φ B were added. After 144 g of guanamine was diluted, it was cooled to room temperature to obtain a brown, completely turbid polyami oxime imide resin solution 11. The solution was slightly foggy. The same procedure as in Example 1 was carried out, and the obtained measurement was carried out. The results and evaluation results are shown in Table 2. Comparative Example 7 (polyamidiamine resin 12): In a separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a 4-bottle of a thermometer, trimellitic anhydride 91.2 was fed. g ( 0.4 7 5 mol ), both ends are carboxylic acid C Nitrile butadiene rubber (CTBN 1 300 xl3) l75g ▲ (0.05mol), 1,4-cyclohexanedicarboxylic acid 81.7g (0.475mol), isophor Φ ketone diisocyanate 222g (1.0 mol), 1, 8-Diazabicyclo[5,4,0]-7-undecene 1.52 g (0.01 mol), dimethylglycolamine 482 g' was heated to 100 ° C under a nitrogen gas stream, and reacted for 2 hours. After reacting at 150 ° C for 5 hours, 'diethyl acetamide 24 lg and toluene 402 g were added, diluted, and cooled to room temperature to obtain a yellow and turbid polyami oxime imine resin solution 1 2. The same manner as in Example 1 was carried out, and the obtained measurement results and evaluation results are shown in Table 2. · -48- 201022312 Table 1 Example 1 2 3 4 5 Resin Polyimine Amine Resin Resin. No 1 2 3 4 5 Logarithmic viscosity 0.52 0.70 0.51 0.55 0.43 Tg(°C) 145 155 135 150 115 Tensile modulus (MPa) 950 1100 900 1000 800 Solubility 〇0 〇0 〇 Composition adhesion strength (N/cm) 16.5 16 16 15.5 13 Solder heat resistance 迁移 migration resistance 〇0 〇0 〇 Table 2

Comparative Example 1 2 3 4 5 6 7 Resin Polyamidimide Tree Si.N0 6 7 8 9 10 11 12 Logarithmic Viscosity 0.38 0.40 0.40 • 0.41 0.52 0.31 Tg (°C) 165 170 85 - 135 180 80 Tensile Modulus of elasticity (MPa) 1300 1200 700 - 800 1200 650 Solubility 〇X 〇XXX 〇 Composition adhesion strength (N/cm) 10 8 14 - 14.5 6.5 8 Solder heat resistance X 〇〇〇〇〇 Immigration resistance XXX 〇X As described above, it is known that a polyamine amidoxime having an aliphatic component of carbon number 4 to 12 and an acrylonitrile butadiene rubber component is introduced in a specific range, which not only improves the polyamidoquinone imine The solubility of the low-boiling solvent and the adhesion are also remarkably improved. The binder composition of the present invention has superior solder heat resistance or migration resistance and is suitable for use in printed wiring boards. On the other hand, in Comparative Example 1, since the acrylonitrile butadiene rubber component -49 - 201022312 was small, adhesiveness and solder heat resistance were inferior; in Comparative Example 2, since the aliphatic component was small, solubility and adhesiveness were poor, and resin Performance has not been played. In Comparative Example 3, since the aliphatic component was increased and the guanamine component was also increased at the same time, the water absorption of the resin was high, and the migration resistance was poor. In Comparative Example 4, the aliphatic chain length was too long; In 5, 'the acrylonitrile butadiene rubber component was excessive; in Comparative Example 6, since the aliphatic component having no carbon number of 4 to 12 was not obtained, the solubility of each was remarkably remarkable. In Comparative Example 7, 'there is a disadvantage that the reactivity is low. When the alicyclic component can be introduced, the solubility is improved, but the adhesiveness is deteriorated and the migration resistance is poor. 2. For the flame retardant resin composition, the adhesive sheet, the cover film, and the flexible printed wiring board. The measurement system disclosed in the examples was measured by the following method. Further, the parts in the examples are simply parts by mass. &lt;Logarithmic viscosity&gt; A solution of the dried solid polymer 〇.5 g dissolved in 100 ml of NMP was measured at 30 ° C using an Ubbelohde viscosity tube. &lt;Stretching Elastic Modulus&gt; The obtained polyamidoximine resin solution was applied onto a copper foil so that the film thickness after drying became 20 μm, and dried at 150 ° C by a hot air dryer. After 10 minutes, it was dried at 200 ° C for 5 hours in an oxidizing-free oven, and the urethane was removed to remove the copper foil to form a polyimide film of a polyimide film, and a thin rectangle having a width of 10 mm was formed from the film. The measurement was carried out at a tensile speed of 20 mm/min using TENSILON manufactured by Toyo Baldwin Co., Ltd. &lt;Glass transfer temperature) -50- 201022312 The dynamic viscoelasticity measurement 丨DVA-22 0 was measured by IT measurement and control company, and the dynamic viscoelasticity was measured at a frequency of 110 Hz to determine the inflection point of the storage elastic modulus. . &lt;Solubility&gt; The film of the polyamidoximine resin used for the elastic modulus measurement was dissolved in 40 parts by mass of mixed diethylamine and ethanol, toluene, etc., so that the nonvolatile content was 10% by mass. Xylene and methylethyl constitute a solvent of 60 parts by mass of a solvent selected from the group. Under the environment, leave it for 24 hours to check if the solution is transparent or if it is not precipitated. (Judgement: the solution is transparent, and no solid matter is precipitated, which is complete; X: undissolved matter, or precipitation of confirmed solid matter &lt; Synthesis Example 1 to 5 of polyamidoximine resin; Comparative Synthesis Example 1 - The same procedure as in Example 1 was carried out to carry out the production of polyamidoquinone tree synthesis examples 1 to 5 and comparative synthesis examples 1 to 6. The polyamidoximine resin thus obtained was subjected to the same. The results of the physical properties and the evaluation of the properties are shown in Table 3. The dissolution of the product by the pull of methyl ketone 2 5 〇 C shape 6 &gt; The way of the fat shows -51- 2 1X 3202 1X20 Comparison] Synthesis Example 6, σ\ »0 O Dimethyl B _ 30% by mass VO rn 1 浒 E- Run § (N »0 Ο ο (Ν rH X Comparative Synthesis Example 5 〇\ CO o 〇νο ο Ο ν〇X Π±Ππ 〇〇〇&lt; 〇 ov〇00 cn ο ο m 〇m ^ &lt;π ν〇^Τί o 1—^ Ο ^Η Γ〇to ο ο 00 〇 (Ν ^ &lt;π o ι〇00 ο inchο ο X m ^ &lt;|Π家o rH § ο ο ο 宕X Synthesis Example 5 mo ο ο 00 〇 Synthesis Example 4 »〇〇yn ο ο ο 〇 Synthesis Example 3 Om c&gt; ο 窆〇 Synthesis Example 2 VO o Bu ο ο τ-Η 〇 Synthesis Example I to Ο o Sun K) m Wang · 11 &lt;rj (Ν m ο ο Ον 〇 trimellitic anhydride filling II Π3 azelaic acid twelve Alkanedioic acid dimer acid NBR &gt;-HI 5 Polymer solvent Non-volatile content concentration BS iff ^-s Logarithmic viscosity tensile modulus (Mpa) Soluble acid component isocyanate 璀mm 浚Resin properties and characteristics Lithium chain w _璀Μ式-3⁄4 避经碱辄H1#.:Ial 填充避缄IKMisfrs^u-^VICMminhliE— § 201022312 &lt;Various components of the adhesive composition&gt; (B) Phosphorus-containing epoxy resin (1) EXA- 9710 : DIC (share) phosphorus-containing epoxy resin (epoxy equivalent: 490, phosphorus content: 3.0% by mass) of methyl ethyl ketone dissolved matter (nonvolatile content: 70% by mass) (C) phosphorus compound ( 1) HCA: Sanguang (share) phenanthrene-based organic phosphate compound, 9,10-dihydroxy-9-sideoxy-10-phosphonium phenoxy-10-oxide (phosphorus content: 14.3 mass%) (2) BCA: Sanguang (share) phenanthrene organic phosphate compound, 10-benzyl-10-hydrogen-9-side oxygen-10-phosphate phenanthrene-10·oxide (phosphorus content: 10.1 mass %) (3) SPH-1 00: Oxygen oxyphosphazene (amount of phosphorus: 1 2 · 5 mass %) manufactured by Otsuka Chemical Co., Ltd. (D) Epoxy resin hardener DDS : 4,4'- Diamine diphenyl φ (E) phosphorus-free epoxy resin jER 152 : Japan Epoxy Resin (stock) phenol novolac epoxy resin (epoxy equivalent 175 ) (F ) decane coupling agent KBM-4 03: Shin-Etsu Chemical Industry Co., Ltd. 3-glycidoxypropyltrimethoxydecane (epoxy equivalent 283) &lt;Example 6 &gt; Solution of (A) Polyamidoximine Resin Resin obtained in Synthesis Example 1 The solution of the above-mentioned various components was added to obtain the -53-201022312 solution of the adhesive composition 1 of Example 6. That is, in a glass bottle, 173.3 parts of the solution of the (A) polyamidoximine resin obtained in Synthesis Example 1, 22.9 parts of EXA-9710, and 64.0 parts of the BCA nonvolatile content concentration of 25% by mass were fed. a solution of dimethyl acetamide, 20.0 parts of a methyl ethyl ketone solution having a non-volatile content of 30% by mass of SPH-100, 12.0 parts of a toluene solution having a nonvolatile content of 50% by mass of jER 152, and 20.0 parts of DDS. a methyl ethyl ketone solution having a nonvolatile content of 15% by mass, 5.0 parts of KBM-4 03, a nonvolatile content of 20% by mass of φ toluene solution, and 16.1 parts of a diluent solvent (dimethylacetamide / toluene = 20) /80), a solution of the binder composition of Example 6 having a nonvolatile content concentration of 30% by mass was obtained. The blend ratio of the solid content in which the total solid content was set to 1% by mass is shown in Table 4. Using the adhesive solution obtained in Example 6, an adhesive sheet, a cover film, and a flexible printed wiring board were produced. The manufacturing methods of these are shown below. &lt;Adhesive sheet&gt; _ The adhesive solution obtained in Example 6 was applied to the polyester film subjected to the release treatment so that the thickness after drying was 25 μm, and was placed in a blown oven at 1 3 (The adhesive sheet in an unhardened or semi-hardened state was produced by drying in TC for 3 minutes. &lt;covering film&gt; The composition of the binder composition obtained in Example 6 was obtained by making the thickness after drying to 25 μm. It was coated on a 25 μm polyimine film (manufactured by Kaneka Co., Ltd., APICAL 25 NPI), and dried in a blowing oven at 130 ° C for 3 minutes to form an unhardened or semi-hardened cover film. -54- 201022312 &lt;Flexible Printed Wiring Board&gt; The solution of the binder composition obtained in Example 6 was applied to a 25 μm polyimide film (Kaneka Co., Ltd., APICAL 25 NPI) so that the thickness after drying was 16 μm. The film was dried in a blown oven at 130 ° C for 3 minutes to form an adhesive film in an unhardened or semi-hardened state. A vacuum compression laminator manufactured by Nasec Co., Ltd. was used at a lamination temperature of 130 ° C and a pressure of 3 MPa. The adhesive coated surface of the adhesive film obtained in this manner and the electrolytic copper foil (thickness φ 18 μm, USLP manufactured by Nippon Electrolysis Co., Ltd.) or rolled copper foil (thickness 18 μm, bismuth ore) were carried out under the conditions of a time of 20 seconds. The surface of the roughened surface of the metal ruthenium was heat-pressed. The flexible printed wiring board was further heat-hardened for 3 hours under TC (TC). According to the evaluation items shown below, the above method was carried out. Evaluation of the obtained adhesive sheet, the cover film, and the flexible printed wiring board. <Peel strength> According to JIS C6471, a circuit having a pattern width of 1 mm 上述 is formed on the flexible wiring board, and RTM100 manufactured by Toyo Baldwin Co., Ltd. is used. The tensile test of the copper foil was carried out at a tensile speed of 50 mm/min in a 90° direction of the wiring board at 25° C., and the peel strength of 90° was measured. (Judgement) ◎ : 15 N/cm or more; : 1 lN/cm or more, less than 15 N/cm; △: 6 N/cm or more, less than 1 lN/cm; X: less than 6 N/cm. &lt;Solder heat resistance&gt; (1) Normal state: According to Jis C6471, cut the above flexible printed wiring board -55- 201022312 A test piece was prepared by cutting into a square of 25 mm, and the test piece was immersed in a solder bath of the east or more for 30 seconds. The temperature at which any one of the appearance and the discoloration did not occur in the test piece was measured. : 33 (above TC; 〇: above 300 °C, below 3 30 °C; X: below 3 0 01. (2) Moisture absorption: After the test piece prepared in the above normal state was placed in 24 at 40 ° C and a relative humidity of 90%, the test piece was quickly immersed in a solder bath of 280 ° C or more. Zhongzhong. The temperature at which an appearance abnormality such as peeling, swelling, or discoloration did not occur in the test piece was measured. (Judgment) ◎ : 300X: or more; 〇 : 2 80 °C or more, less than 300 °C; X: less than 2 80 °C. &lt;Flameability&gt; The solution of the obtained binder composition was applied to a 12.5 μm polyruthenium film (Kaneka Co., Ltd., APICAL 12.5ΝΡΙ) by a thickness of 16 μm after drying. In a double-sided air oven, after drying at 130 ° C for 3 minutes, it was added at 170 ° C for 3 hours to prepare a test. Flammability according to UL-94 VTM flame retardant specifications. (Judgment) ◎: In accordance with UL94 VTM-0, the burning of the test piece is better than one; 〇: in accordance with UL94 VTM-0, the burning of the test piece is one; 3 00 °C peeling, 30 seconds in the phase of the phase In the example, the imide is thin, and it is difficult to evaluate the heat hardening by half or more -56-201022312 X: Not meeting UL94 VTM-0. &lt;Insulation reliability: migration resistance&gt; A comb-type pattern having a line pitch of 70 μm was formed on a two-layer CCL (trade name: VYLOFLEX) manufactured by Toyobo Co., Ltd. The solution of the binder composition obtained in Example 6 was applied to the circuit by drying the film thickness after drying to 2 5 μϊ, and dried in a blowing oven at 130 ° C for 3 minutes. 1 Heat-hardened at 70 ° C for 3 hours to prepare a sample having a cover layer. Thereafter, a direct current voltage of 50 V was applied at 85 ° C and a relative humidity of 85%, and the migration resistance was measured. (Judgement) 〇 : The insulation resistance 値 after 500 hr exceeds 1 χ 108 Ω, and the growth of dendritic crystals is not confirmed; X: The insulation resistance 値 after 500 hr is less than 1 χ 108 Ω, or the growth of dendrites has been confirmed. &lt;Peel strength after PCT treatment&gt; The flexible printed wiring board was cut to have a sample width of 5 mm, and an autoclave made of Tomy Seiko Co., Ltd. was used at a temperature of 121 ° C and a humidity of 100. A 40-hour PCT test was carried out under conditions of a pressure of 2 atm. According to JIS C6471, a tensile test of a copper foil was carried out at a tensile speed of 50 mm/min in a 90° direction at 25 ° C using a RTM100 manufactured by Toyo Baldwin Co., Ltd., and the 90° peel strength was measured. (Judgment) ◎ : lON/cm or more; 〇: 6 N/cm or more and less than 10 N/cm; Δ: 4 N/cm or more and less than 6 N/cm; X: less than 4 N/cm. • 57-$ $201022312 The results obtained by the above evaluation methods are shown in Table 4, Table 5 ° &lt;Examples 7 to 13, Comparative Examples 8 to 16&gt; 'The same as the flame retardant adhesive of Example 6. For the composition, the solutions obtained in Synthesis Examples 1 to 5 of (A) polyamidoximine resin and Comparative Synthesis Examples 1 to 6 were blended, and various components (B) to (F) were blended, and a diluent solvent (dimethyl) was used. The flammable adhesive composition of Examples 7 to 13 and Comparative Examples 8 to 16 which were adjusted to have a nonvolatile content concentration of 30% was obtained by using acetamide/toluene = 20/80. With respect to each of the obtained binder compositions, the blend ratio of the solid component in which the solid content was 100% by mass is shown in Tables 4 and 5. Further, each of the components (B) to (F) is dissolved in a solvent in advance and used as a solution. Hereinafter, the concentration of the nonvolatile component and the solvent composition of the respective components (B) to (F) are shown. HC A : concentration of nonvolatile matter of 25% by mass, dimethylacetamide solution BC A : concentration of nonvolatile matter of 25% by mass, dimethyl acetamide solution SPH-100: concentration of nonvolatile matter of 30% by mass, methyl group Ethyl ketone solution DDS: non-volatile content concentration 15% by mass, methyl ethyl ketone solution jERl 52 : non-volatile content concentration 50% by mass, toluene solution KBM-403: non-volatile content concentration 20% by mass, toluene solution is the same as Example 6 For the adhesive compositions of Examples 7 to 13 and Comparative Examples 8 to 16, an adhesive sheet, a cover film, and a flexible printed wiring board were also produced, and the evaluation was carried out in the same manner as in Example 6. The results are shown in Tables 4 and 5. -58- 201022312 辑 UK 2 CN m 卜 m Os 00 CN ◎ ◎ ◎ 〇〇 ◎ Example 12 卜 (N &lt; N m 寸 00 CN 〇 ◎ 〇 ◎ 〇〇 Example 11 v〇v〇Ό mv〇00 〇 ◎ 〇〇〇 ◎ Example 10 Bu cn &lt; N m 00 ri 〇 ◎ 〇〇〇〇 Example 9 m (N CN cs 00 o 卜 〇 ◎ 〇 ◎ 〇〇 Example 8 卜 CN m (N m 00 &lt;N ◎ ◎ ◎ ◎ 〇 ◎ Example 7 Tt vn fH 00 00 &lt;N 〇 ◎ ◎ ◎ Example 6 (NV 〇Ό m 00 r4 ◎ ◎ ◎ 〇〇 ◎ Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 | Synthesis Example 5 IeXA-9710 |hca ) BCA | SPH-100 DDS jER152 ΚΒΜ-403 Phosphorus content in the flame retardant adhesive composition (%) Peel strength (N/cm) Normal Hygroscopicity and flame retardancy (UL94, VTM-0) Peel strength after migration PCT treatment_m) Adhesive composition Polyurethane imide resin (A) Epoxy resin containing disc (9) Phosphorus compound (c) Epoxy resin hardener (D) Phosphorus-free epoxy resin (E) Decane coupling agent (F) Solder heat resistance (.〇 ] Composition characteristics - 6ln_ ο 3 2 02 1X 20 s谳Comparative name 2) Bu CS m &lt;N m 00 &lt; NX ◎ X 〇〇X Comparative example 15 卜 CS cn cn 00 &lt;N 1 1 Comparative example 14 卜CN m &lt;N m 00 &lt;N &lt;] ◎ X Ο 〇X m Τ&quot;Η 镒JJ JA 卜&lt;N m &lt;N m inch 00 CN &lt;] Ο &lt; Ο 〇X &lt; Ν *-Η 镒JJ JA 卜 (N (N inch 00 H ◎ Ο X Ο 〇〇 Comparative Example 1J 卜 (N m cs 00 r4 &lt; ◎ &lt; 〇〇X Comparative Example ίο m 〇〇Γ^Ι rn 〇 〇XXXX Comparative Example 9 m inch cn »n 〇XX 〇XX Comparative Example 8 v〇VO m σ\ iH O) ◎ ◎ 〇X 〇Ο Synthesis Example 2 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Comparative Synthesis Example 4 Comparative Synthesis Example 5 Comparative Synthesis Example 6 EXA-9710 HCA BCA SPH-100 DDS jER152 KBM-403 Phosphorus content in flame retardant adhesive composition (%) Peel strength (N/cm) m Platinum moisture flammable (UL94, VTM-0) Peel strength after migration resistance PCT treatment_m) Adhesive composition Polyamide resin ( A) Phosphorus-containing epoxy resin (B) mt^KC) Epoxy resin hardener (D) Phosphorus-free epoxy resin (E) Sand fiber mixture (F) Solder heat resistance (. 〇1 1 1 .09 201022312 As described above, the cover film and flexible printed device of the present invention are superior in terms of excellent peel strength, solder heat resistance, flame retardancy, and migration resistance to high temperature and high humidity conditions. The above characteristics. The heat resistance of Youxi can withstand 330 °C, and as in Examples 6-8 and 13, it can withstand 300 °C after moisture absorption. The phosphorus content of Comparative Example 8 is lower than 2.0. The mass% is different from the application, and the flame retardancy is deteriorated. The phosphorus content of Comparative Example 9 was larger than 5.0% by mass, and the solder heat resistance and migration resistance were deteriorated outside the range of the application φ. In Comparative Example 10, the (B) phosphorus-containing epoxy resin was not contained, and the solder heat resistance, flame retardancy, and migration resistance were deteriorated outside the scope of the application. In Comparative Example 11, the polybutylamine resin outside the scope of the patent application in which (b) the aliphatic group having a carbon number of 4 to 12 was less than 1 〇 mol% was used, and the peel strength was deteriorated. In Comparative Example 12, the use of (b) an aliphatic amine having a carbon number of 4 to 12 in an amount of more than 80 mol% of the polyamidoxime which is outside the scope of the patent application is deteriorated, and the heat resistance of the solder after moisture absorption is deteriorated. Comparative Example 13 used (b) a polyamidoximine resin outside the scope of the aliphatic patent having a carbon number of 12, and a peel strength comparative example 14 using (a) an acrylonitrile-butyl group having a carboxyl group at both ends. Polyamide amine imide resin with a ratio of less than 3 mol%, peeling bow difference. Comparative Example 15 is a material with significantly improved adhesion, laminated with a flexible printing plate (temperature 130 ° C , pressure 3MPa, time can not be hot-pressed, can not be evaluated. Wire plate system, as it, welding shows, [characteristics] patents patent patented carboxylic acid imine tree carboxylic acid imine tree dicarboxyl The acid is deteriorated. The diene rubber is changed to the brush wire for 20 seconds. -61- .201022312 Comparative Example 16 is a non-copolymerization (b) polycondensation of an aliphatic dicarboxylic acid having a carbon number of 4 to 12. Amidoxime resin has poor peel strength. INDUSTRIAL APPLICABILITY The polyamidoximine resin of the present invention, further comprising a thermosetting agent, a resin composition for a copper clad laminate or a cover layer, an adhesive sheet, a copper foil with a resin, and protection In addition to a printed wiring board such as a film layer ink or a prepreg, it can be used in a wide range of fields such as electronic devices such as paints and coating agents. Further, the flame retardant adhesive composition of the present invention is non-halogen, and has an excellent environment and excellent workability, and is suitable for the production of a flexible printed wiring board. Further, it can be used as an adhesive layer, a cover film, an insulating layer of a flexible printed wiring board, or the like. [Simple description of the diagram] None. [Main component symbol description] -62-

Claims (1)

201022312 VII. Patent application scope: 1. A polyamidoquinone imine resin which is obtained by reacting the following acid components of (a) to (c) with a diisocyanate or diamine having an aromatic ring. The imine resin is characterized in that the ratio of each of the acid components in the case where the total acid component of the polyamidoximine resin is 100% by mole is (a) 3 to 10 mol%, (b) 10 to 80 mol%. , (c) 1 0 to 8 7 mo 1 % ; (a) acrylonitrile-butadiene rubber having a carboxyl group at both ends, (b) an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, (c) having an aromatic An anhydride of a polycarboxylic acid of the ring. 2. The polyamidoximine resin according to claim 1 of the patent application is prepared by dissolving 10% by mass or more of the polyamidoquinone imide resin at 60% by mass at 25 ° C. A mixed solvent of at least one solvent selected from the group consisting of ethanol, toluene, xylene and methyl ethyl ketone and 40% by mass of dimethylacetamide. A polyamidoquinone imide resin composition which is a thermosetting component added to a polyamidoximine resin as disclosed in claim 2 of the patent application. 4. The polyamidoquinone imide resin composition of claim 3, wherein the thermosetting component is an epoxy resin. Five kinds of printed wiring boards are used as an adhesive as the adhesive composition of the polyamidamine imine resin of the third or fourth aspect of the patent application. 6. A flame retardant adhesive composition comprising (A) a polyamidoximine resin, (B) a phosphorus-containing epoxy resin, (C) a phosphorus compound, (A) a polyamidoxime The amine resin is a polyamidoximine resin obtained by reacting an acid component of the following (a) to (c) with a diisocyanate or a diamine having an aromatic ring, which is characterized by the polyamidoximine resin. All the acid-63-201022312 is divided into 100% by mole. The ratio of each acid component is (a) 3 to 10 mol% ' (b) 10 to 80 mol%, (c) 10 to 87 mol%, relative to ( A) The phosphorus content of the total mass of the components (C) is 2.0 to 5.0% by mass; (a) acrylonitrile-butadiene rubber having a carboxyl group at both ends, and (b) an aliphatic group having a carbon number of 4 to 12 A carboxylic acid, (C) an acid anhydride of a polycarboxylic acid having an aromatic ring. 7. The flame retardant adhesive composition of claim 6, wherein the (C) phosphorus compound is a phosphazene and/or a phosphinic acid derivative. 8. A flame retardant adhesive composition according to item 6 of the patent application, which further comprises (D) an epoxy resin hardener. 9. The flame retardant adhesive composition of claim 6 further contains (E) a phosphorus-free epoxy resin. 10. A flame retardant adhesive composition according to claim 6 of the patent application, which further comprises a (F) decane coupling agent. 11. The flame retardant adhesive composition according to any one of claims 6 to 10, wherein the components (A) to (F) having a solid concentration of 25% by mass are contained at 25 ° C. It is dissolved in any of dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone. The flame retardant adhesive composition according to any one of the items (6) to (10), wherein the phosphorus content of the total mass of the components (A) to (F) is 2.0 to 5.0% by mass. An adhesive sheet comprising a pressure-sensitive adhesive layer formed of a flame retardant adhesive composition according to any one of claims 6 to 10 and a peelable protective film layer, which is adhered One or two sides of the agent layer -64-, 201022312, with a peelable protective film layer. A cover film comprising a pressure-sensitive adhesive layer formed of a flame retardant adhesive composition according to any one of claims 6 to 10 and an insulating plastic film layer. A flexible printed wiring board comprising an insulating layer formed using the flame retardant adhesive composition according to any one of claims 6 to 10. -65- 201022312 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 ^ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: -Ρ=Ν· (1) (2)