JPWO2010038644A1 - Polyamideimide resin, resin composition, flame-retardant adhesive composition, adhesive sheet comprising the composition, coverlay film, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide-imide resin that satisfies heat resistance, adhesiveness, insulation reliability, and solvent solubility at the same time and is suitable for a heat-resistant adhesive for printed wiring boards. In addition, it is non-halogen and consists of components that are all soluble in general-purpose solvents and exhibits stable characteristics, as well as excellent flame resistance, solder heat resistance, adhesion, and electrical insulation when used for flexible printed wiring boards. Provided is a flame retardant adhesive composition capable of exhibiting properties. PROBLEM TO BE SOLVED: A polyamideimide resin obtained by reacting an acid component (a) to (c) below with a diisocyanate or diamine having an aromatic ring, wherein the total acid component of the polyamideimide resin is 100 mol% (A) 3-10 mol%, (b) 10-80 mol%, (c) 10-87 mol%, The polyamideimide resin characterized by the above-mentioned. (A) Acrylonitrile-butadiene rubber having carboxyl groups at both ends (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Acid anhydride of polycarboxylic acid having aromatic ring

Description

The present invention relates to a polyamide-imide resin and a thermosetting resin composition using the resin. More specifically, the present invention is excellent in flexibility, heat resistance, solvent solubility, insulation, and adhesiveness, and is a copper-clad laminate. The present invention relates to an adhesive resin composition suitable for printed wiring boards such as coverlays, coverlays, adhesive sheets, copper foils with resin, overcoat inks, and prepregs.
In addition, the present invention exhibits excellent performance in printed wiring boards, particularly flexible printed wiring boards that require flexibility, and has excellent flame resistance, solder heat resistance, adhesion, and electrical insulation. The present invention relates to an agent composition, and a printed wiring board such as a copper-clad laminate, an adhesive sheet, a coverlay film, a copper foil with resin, a prepreg, and an overcoat ink using the composition.

  Conventionally, polyamide-imide resins are made of aromatic monomers, exhibiting properties such as heat resistance, chemical resistance, and abrasion resistance that are comparable to polyimide, and are superior to polyimide, such as N-methyl-2-pyrrolidone. Since it has solubility in a special amide solvent at its boiling point, it is applied to molding materials and heat-resistant insulating paints. However, similar to general polyimide resins, aromatic polyamideimide resins generally have high elastic modulus and are hard and have low solubility in low-boiling solvents. It was difficult to use for applications that require easy drying.

  By the way, a flexible printed wiring board is an electronic device component that requires flexibility and space saving, for example, a device substrate for a display device such as a liquid crystal display or a plasma display, or a substrate relay such as a mobile phone, a digital camera, or a portable game machine. Widely used in cables, operation switch board, etc., further expansion of applications is expected.

  Conventionally, epoxy resins and acrylic resins have been used as adhesives for such applications, but heat resistance is insufficient to meet the recent trend toward higher wiring density and lead-free solder orientation. Thus, polyimide resins have been studied as adhesives having heat resistance instead of them. In order to solve the drawbacks of conventional polyimide resins with high elasticity, hard and brittle, difficult to develop adhesive properties and only soluble in high boiling solvents, long-chain monomers and oligomers are copolymerized with polyimide resins. Consideration has been made. For example, Patent Documents 1 and 2 disclose polysiloxane-modified polyimide resins as techniques for imparting flexibility and reducing elastic modulus.

However, polysiloxane-modified polyimide resins are inferior in economic efficiency because it is necessary to use a very expensive starting material having a dimethylsiloxane bond for imparting flexibility and lowering the elastic modulus. Further, there is a problem that the adhesiveness and solubility of the resin are lowered with an increase in the copolymerization amount of polysiloxane.
As a solution to this problem, Patent Document 3 and Patent Document 4 disclose a composition using a polycarbonate-modified polyimide resin, which has improved defects such as low solubility and economy, but is sufficient. In order to reduce the elasticity and the low elastic modulus, it is necessary to increase the amount of polycarbonate modification. In this case, chemical resistance and heat-and-moisture resistance tend to decrease.

  Patent Document 5 discloses a method in which a polyol such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol is copolymerized with a polyamideimide resin. However, these modified polyamideimides have a problem that heat resistance is lowered because long-chain polyols are copolymerized with urethane bonds having poor heat resistance.

  Patent Document 6 discloses a method of copolymerizing dimer acid with polyamideimide. Even in this method, flexibility can be imparted to some extent, but since the molecular weight of dimer acid is relatively low, it is necessary to increase the amount of copolymerization in order to express sufficient flexibility. Since the ratio of the aromatic group in the resin is remarkably lowered, the heat resistance is lowered. Moreover, there is a problem that the glass transition temperature is lowered by increasing the amount introduced into the resin, and the adhesiveness and solubility are lowered.

  Patent Documents 7 and 8 disclose a method of copolymerizing acrylonitrile butadiene having a carboxyl group at both molecular ends with a polyamideimide resin. Even with this method, it is possible to impart flexibility and improve the adhesiveness to some extent, but in order to develop sufficient adhesiveness by this method, it is necessary to increase the copolymerization amount of acrylonitrile butadiene, As a result, the insulation reliability is lowered, and the solubility in the solvent is lowered, so that it is difficult to dissolve other than high boiling point solvents such as N-methyl-2-pyrrolidone. In order to be suitably used as an adhesive, it is necessary to dissolve in a low boiling point solvent such as dimethylacetamide and toluene. For printed wiring board applications, heat resistance, flexibility, insulation reliability, adhesiveness In addition, the appearance of a resin excellent in all solvent solubility is desired.

  Currently, flexible printed wiring boards are electronic device parts that require flexibility and space saving, for example, device mounting substrates for display devices such as liquid crystal displays and plasma displays, mobile phones, digital cameras, portable game machines, personal computers, etc. Widely used for inter-board relay cables, operation switch board, etc. In recent years, these electronic device parts have been increasingly miniaturized and densified, and the demand for fine patterning and high performance of flexible printed wiring boards has been increasing, especially flame resistance, solder heat resistance, Further improvement in adhesiveness, electrical insulation and the like is required.

  The flame retardancy of these electronic device parts is intended to ensure safety against fire, and conventionally bromine-based flame retardants have been used as flame retardant imparting agents. However, while the environmental impact is regarded as an important social issue, halogen compounds mainly composed of bromine may generate corrosive hydrogen halide gas with the passage of time. There is a risk of generating substances that adversely affect the human body, such as furan. For this reason, the movement which suppresses use of a halogen compound increases and the halogen-free flame-retardant adhesive agent is calculated | required.

  Due to the above-described background, recently, a flame retardant method using a phosphorus compound, a filler such as a metal hydrate, a nitrogen-containing compound, or the like has been proposed as a flame retardant that is replaced with a halogen compound. However, although non-halogen flame retardants do not contain harmful halogens, they tend to require a large amount of flame retardants because they are inferior in flame retardancy compared to halogen flame retardants. Addition of a large amount of flame retardant causes bleed out of the flame retardant and deterioration of the mechanical properties of the adhesive, and thus it is difficult to achieve both flame retardancy and various properties.

  Furthermore, the filler such as the metal hydrate described above requires a step for uniformly dispersing the filler in the adhesive composition, and the number of steps is increased compared to the case where the filler is not included. Inferior. In addition, since the filler settles, the composition of the adhesive composition tends to be non-uniform, the varnish usable period of the composition is short and quality control is difficult, and it is difficult to make a thin film when creating a coating film. Even on the processed surface of the flexible printed wiring board, there are various problems such as deterioration in performance due to outflow into a chemical such as an etching solution.

  Even in phosphorus compounds, many phosphoric esters that are frequently used as flame retardants are susceptible to hydrolysis. When phosphoric esters are used as flame retardants, attention must be paid to their addition amount and structure. For example, although a resin composition containing a phosphate ester is proposed in Patent Documents 9 to 11 and the like, a phosphate ion component is produced under high-temperature and high-humidity conditions, resulting in a decrease in electrical insulation, adhesion, and solvent resistance. However, satisfactory characteristics cannot be obtained.

  For such problems, a flame retardant resin composition containing an epoxy resin, a curing agent, and phosphine oxide (Patent Document 12) has been proposed, and chemical resistance has been improved by using phosphine oxide. . However, in the flame retardancy evaluation of a laminate comprising the composition, the test piece is composed of a copper foil on the outermost surface, and the flame-retardant UL-94V0 can be easily obtained with few contact surfaces between oxygen and the composition. It has become. In addition, solder heat resistance is as low as 260 ° C., and high performance of flexible printed wiring boards is demanded today. The composition disclosed here has sufficient heat resistance and flame retardancy. I can't say that.

Also, a resin composition (Patent Document 13) containing a phosphorus-containing epoxy resin and a curing agent has been proposed, and it was a problem with an additive-type phosphorus compound by reacting a reactive phosphorus compound with an epoxy resin. Problems such as deterioration of electrical characteristics due to bleed-out from the laminate can be solved. However, since the phosphorus content of the phosphorus-containing epoxy resin that is practically used for the flexible printed wiring board is as low as about 3% by mass, sufficient flame retardancy cannot be obtained. The composition (Patent Document 13) also has sufficient flame retardancy because it is evaluated for flame retardancy in such a configuration that flame retardancy can be easily obtained as described above. Absent. In addition, when the phosphorus content is increased to improve flame retardancy, the epoxy group equivalent is reduced, a sufficient cross-linked structure cannot be obtained, and the heat resistance is poor, and the solubility in a solvent is poor. Occurs.
In addition to the above, there are many proposals for flame retardancy using a reactive phosphorus compound and a phosphorus-containing epoxy resin. For example, an adhesive composition containing a phosphorus-based flame retardant, a thermoplastic resin, and a thermosetting resin (Patent Document 14) ), A coverlay made of an adhesive composition containing a nitrogen-containing compound, an epoxy resin, a phosphorus atom-containing non-epoxy compound, and a curing agent (Patent Document 15). However, in any of the examples, an inorganic filler is added, and it can be seen that various properties such as flame retardancy and heat resistance cannot be satisfied without the filler. The addition of the filler has the above-mentioned problems, and in Patent Document 14, although the filler is added, the solder heat resistance is insufficient. Since an ester is added, the hydrolysis resistance is poor.
As described above, it is difficult for halogen-free flame retardant adhesives to achieve both flame retardancy and various properties.

Japanese Patent Laid-Open No. 5-25452 JP 7-304950 A Japanese Patent Laid-Open No. 11-12500 Japanese Patent No. 3928329 Japanese Patent No. 3729291 JP-A-3-54690 JP 2003-289594 A Japanese Patent No. 3931387 JP 2000-345035 A JP 2001-339131 A JP 2001-339132 A JP 2001-200140 A JP 2001-288247 A JP 2002-146310 A JP 2004-87923 A

As described above, the conventional technology is suitable as a heat-resistant adhesive that can be used for applications such as a printed wiring board that simultaneously satisfies heat resistance, flexibility, adhesion, insulation reliability, and solvent solubility. A polyimide resin was not obtained. An object of the present invention is to solve the above-described problems of the prior art and provide a polyamide-imide resin suitable for uses such as a printed wiring board and an adhesive resin composition using the resin.
In addition, it is non-halogen, does not contain fillers, etc., and is composed of all soluble components in general-purpose solvents and exhibits stable characteristics. It also has excellent flame resistance and solder heat resistance when used for flexible printed wiring boards. It is to provide a flame retardant adhesive composition capable of exhibiting properties, adhesiveness, and electrical insulation, and further, a copper-clad laminate, an adhesive sheet, a coverlay film, a prepreg using the composition, The object is to provide printed wiring boards such as copper foil with resin, overcoat ink and the like.

As a result of intensive studies in order to solve the above problems, the present inventors have finally completed the present invention. That is, this invention consists of the following structures.
(1)
The following (a) to (c) are polyamideimide resins obtained by reacting an acid component with a diisocyanate or diamine having an aromatic ring, and each acid component when the total acid component of the polyamideimide resin is 100 mol% (A) 3 to 10 mol%, (b) 10 to 80 mol%, and (c) 10 to 87 mol%. (A) Acrylonitrile-butadiene having carboxyl groups at both ends Rubber (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Acid anhydride of polycarboxylic acid having aromatic ring (2)
In the above (1), the polyamideimide resin is dissolved in a mixed solvent consisting of 60 masses of at least one solvent selected from the group consisting of ethanol, toluene, xylene and methylethylketone and 40 masses of dimethylacetamide at 25 ° C. at 10 mass% or more. The polyamide-imide resin described.
(3)
A polyamide-imide resin composition obtained by adding a thermosetting component to the polyamide-imide resin described in (2).
(4)
The polyamideimide resin composition according to (3), wherein the thermosetting component is an epoxy resin.
(5)
A printed wiring board using the polyamideimide resin composition according to (3) or (4) as an adhesive.
(6)
(A) Polyamidoimide resin, (B) Phosphorus-containing epoxy resin, (C) Phosphorus compound, and (A) Polyamidoimide resin having the following acid components and aromatic rings (a) to (c) or It is a polyamide-imide resin obtained by reacting with a diamine, and the ratio of each acid component when the total acid component of the polyamide-imide resin is 100 mol% is (a) 3 to 10 mol%, (b) 10 Flame retardancy characterized in that it is ˜80 mol%, (c) 10 to 87 mol%, and the phosphorus content relative to the total mass of the components (A) to (C) is 2.0 to 5.0 mass%. Adhesive composition.
(A) Acrylonitrile-butadiene rubber having carboxyl groups at both ends (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Polycarboxylic acid anhydride having an aromatic ring (7)
(C) The flame retardant adhesive composition as described in 6 above, wherein the phosphorus compound is a phosphazene and / or phosphinic acid derivative.
(8)
(D) The flame retardant adhesive composition according to 6 or 7, further comprising an epoxy resin curing agent.
(9)
(E) The flame retardant adhesive composition according to any one of the above 6 to 8, which contains an epoxy resin containing no phosphorus.
(10)
(F) The flame-retardant adhesive composition according to any one of 6 to 9, further comprising a silane coupling agent.
(11)
The components (A) to (F) are all dissolved in any solvent of dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone at 25 ° C. and a solid content concentration of 25% by mass. Flame retardant adhesive composition.
(12)
The flame-retardant adhesive composition according to any one of 6 to 11, wherein the phosphorus content relative to the total mass of the components (A) to (F) is 2.0 to 5.0 mass%.
(13)
The flame retardant adhesive composition according to any one of 6 to 12 above is used as an adhesive layer, and the adhesive layer composed of the flame retardant adhesive composition according to any one of the above is laminated on a peelable protective film. An adhesive sheet having a layer.
(14)
The coverlay film formed by laminating | stacking the adhesive bond layer and insulating plastic film which consist of a flame-retardant adhesive composition in any one of said 6-12.
(15)
The flexible printed wiring board containing the insulating layer formed using the flame-retardant adhesive composition in any one of said 6-12.

Since the polyamide-imide resin of the present invention is copolymerized in a specific range with an acrylonitrile-butadiene rubber having a carboxyl group at both ends as an acid component and an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, a low-boiling solvent In addition, the adhesion of the polyamide-imide resin itself is remarkably improved. Therefore, heat resistance, flexibility, adhesiveness, insulation reliability, and solvent solubility, which were difficult to be satisfied at the same time, can be satisfied at the same time. Can be provided.
Further, the flame retardant adhesive composition of the present invention is non-halogen, can achieve the flame resistance of UL94 VTM-0 without containing an inorganic filler such as aluminum hydroxide, and is all soluble in general-purpose solvents. Therefore, it is easy to produce a thin film having excellent stability and stable characteristics without worrying about problems related to dispersion of the composition. Furthermore, since it is a composition dissolved in a low-boiling general-purpose solvent, it is easy to dry and suitable as a flame-retardant adhesive.
Furthermore, when the flame retardant adhesive composition of the present invention is used as an adhesive for printed wiring boards, it exhibits excellent flame retardancy, solder heat resistance, adhesion, and electrical insulation. Moreover, even in a state where it is left to stand under high temperature and high humidity to absorb moisture, it can exhibit superior solder heat resistance. Moreover, high adhesiveness can be maintained even after the PCT test under high temperature and high humidity conditions. Furthermore, the coverlay provided on the circuit can exhibit high migration resistance.

The present invention will be described in detail below.
1. Polyamideimide resin The polyamideimide resin of the present invention is a polyamideimide resin obtained by reacting the following acid components (a) to (c) with a diisocyanate or diamine having an aromatic ring, and the total acid of the polyamideimide resin: The ratio of each acid component when a component is 100 mol% is (a) 3 to 10 mol%, (b) 10 to 80 mol%, and (c) 10 to 87 mol%.
(A) Acrylonitrile-butadiene rubber having carboxyl groups at both ends (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Acid anhydride of polycarboxylic acid having an aromatic ring

The (a) acrylonitrile-butadiene rubber having carboxyl groups at both ends in the present invention is copolymerized in an amount of 3 to 10 mol% of the total acid component in order to impart flexibility and adhesiveness to the polyamideimide resin. Preferably, it is 3 to 8 mol%, and if the copolymerization amount is less than 3 mol%, flexibility and adhesiveness cannot be expressed, and if it exceeds 10 mol%, the insulation reliability and the solubility in low-boiling solvents tend to decrease. There is.
The (a) acrylonitrile-butadiene rubber having carboxyl groups at both ends in the present invention preferably has an acrylonitrile moiety and a butadiene moiety, and has a weight average molecular weight of 500 to 5,000. If the molecular weight is smaller than this range, flexibility and adhesiveness cannot be expressed, and if the molecular weight is large, it is difficult to copolymerize in the polyamideimide resin. Moreover, it is preferable that the ratio of an acrylonitrile site | part is the range of 10-50 mass%. If the amount is less than 10% by mass, the solubility in a low-boiling solvent tends to decrease, and if it exceeds 50% by mass, the insulation reliability tends to decrease.
Examples of the acrylonitrile butadiene rubber having a carboxyl group at the terminal end satisfying these requirements include Hypro (trade name) CTBN series of Emerald Performance Materials. However, just copolymerizing the component (a) does not provide sufficient flexibility, adhesion and solubility.

In the present invention, (b) the aliphatic dicarboxylic acid having 4 to 12 carbon atoms is copolymerized in order to improve the flexibility, adhesiveness and solvent solubility of the polyamideimide resin. The amount of copolymerization is 10 to 80 mol% of the total acid component, and preferably 20 to 60 mol%. When the amount is less than 10 mol%, sufficient adhesion and flexibility cannot be obtained, and the effect of improving the solubility is small. When it exceeds 80 mol%, the ratio of the aromatic structure in the polyamide-imide resin is lowered, so that the heat resistance is lowered.
As already mentioned, the amount of (a) component acrylonitrile-butadiene rubber having carboxyl groups at both ends is limited, and the component (a) alone has sufficient adhesiveness and flexibility, and further to a low boiling point solvent. The solubility of can not be expressed. Therefore, it is necessary to copolymerize the component (b).

  Here, the carbon number of the dicarboxylic acid of the component (b) is the number including the carbon of the carboxylic acid moiety, and is assumed to be 10 in the case of sebacic acid, for example. Moreover, when this carbon number is larger than 12, a part with low polarity will increase in a polyamideimide resin, and the problem that the solubility and adhesiveness of resin will fall will arise.

  Examples of (b) the aliphatic dicarboxylic acid having 4 to 12 carbon atoms in the present invention include linear aliphatic dicarboxylic acids and aliphatic dicarboxylic acids having a branched structure. For example, as a linear structure, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, undecadioic acid, dodecanedioic acid, etc. have a branched structure And those having a hydrocarbon substituent in the above dicarboxylic acid such as 2-methylsuccinic acid, and these may be used alone or in combination.

  Examples of acid anhydrides of polycarboxylic acids having an aromatic ring that play a role in imide ring formation in the present invention include trimellitic acid anhydride, pyromellitic dianhydride, ethylene glycol bisanhydro trimellitate. , Propylene glycol bisanhydro trimellitate, 1,4-butanediol bis anhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene glycol bis anhydro trimellitate Alkylene glycol bisanhydro trimellitate, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1, , 5,6-Naphthalenetetracarboxylic Dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, m-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid 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, 1,1, 1,3,3,3-hexafluoro-2,2-bis [4- ( , 3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, etc. These may be used alone or in combination.

  As the acid component of the present invention, in addition to the components (a) to (c) already described, other acid components to the extent that the effects of the present invention are not impaired, aliphatic or alicyclic acid anhydrides and alicyclic rings Group dicarboxylic acids can be used. For example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, hexahydropyromellitic acid 2 Anhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic acid bis Anhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1, 2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3) , 3,4-Tetracarboxylic acid 1,3-dipropylcyclohexane-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] heptane-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 , 6-tetracarboxylic dianhydride, hexahydroterephthalic trimellitic anhydride, include cyclohexane dicarboxylic acid, etc., they may be used alone, it may be used in union plurality. These components are preferably 20 mol% or less in the acid component from the viewpoint of the heat resistance of the polyamideimide resin obtained and the flame retardancy of the adhesive resin composition using the polyamideimide resin.

  Examples of the diisocyanate or diamine having an aromatic ring used in the present invention include 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'-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'-diethyldiphenylmethane-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'-G Cyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene- 2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2bis (4-phenoxyphenyl) Propane] diisocyanate, 3,3 ′ or 2,2′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′- or 2,2′-diethylbiphenyl-4,4′-diisocyanate, 3,3′- Dimethoxy bifu Nyl-4,4′-diisocyanate, 3,3′-diethoxybiphenyl-4,4′-diisocyanate and the like include diamines corresponding to these diisocyanates, and these may be used alone. You can also use multiple combinations.

  An aliphatic or alicyclic structure can be used as the isocyanate or amine component to the extent that the effects of the present invention are not impaired. For example, diisocyanate or diamine obtained by hydrogenating any of the components listed in the previous section can be used. Further, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4 ′ dicyclohexylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, and diamines corresponding to them are also included.

  The polyamide-imide resin of the present invention can be copolymerized with a compound having 3 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, a dicarboxylic acid having an amino group such as 5-aminoisophthalic acid, a glycerol, a polyglycerin or the like having 3 or more hydroxyl groups And those having three or more amino groups such as tris (2-aminoethyl) amine, among which dicarboxylic acid having a hydroxyl group such as 5-hydroxyisophthalic acid, tris ( Those having 3 or more amino groups such as 2-aminoethyl) amine are preferred, and the amount thereof is preferably 20 mol% or less based on the acid component or amine component. If it exceeds 20 mol%, the number of cross-linking points increases, which may cause gelation during the production of polyamide or generate insoluble matter.

  The polyamide-imide resin of the present invention includes polyester, poly (polyethylene), poly (polyethylene) rubber as a component for imparting flexibility and adhesion other than acrylonitrile-butadiene rubber and aliphatic dicarboxylic acids having 4 to 12 carbon atoms, to the extent that the effects of the present invention are not impaired. Ether, polycarbonate, dimer acid, polysiloxane and the like can be used. In that case, if the amount of copolymerization to the polyamide-imide resin is large, the effects of the present invention such as heat resistance, solubility, and adhesiveness may be impaired. Therefore, these components are based on the total acid component or amine component. It is preferable that it is 10 mol% or less.

As a method for obtaining the polyamideimide resin of the present invention, a method of producing from an acid component and an isocyanate component (isocyanate method), or a method of reacting an acid component and an amine component to form an amic acid, followed by ring closure ( Direct method) or a known method such as a method of reacting a compound having an acid anhydride and an acid chloride with a diamine. Industrially, the isocyanate method is advantageous.
Polymerization of the polyamide-imide resin can be obtained by dissolving the acid component and the isocyanate or amine component in a solvent and heating. At this time, the ratio of the acid component to the isocyanate or amine component is preferably 100: 91 to 100: 109. If it is out of this range, the molecular weight may not be sufficiently increased, resulting in insufficient mechanical strength or gelation during polymerization. Moreover, it is preferable that the imide ring part of the polyamideimide resin obtained by this invention is 90% or more closed from the surface of resin and resin varnish stability. For that purpose, it is necessary to make it fully react at the time of superposition | polymerization of a polyamidoimide resin, and there exists a method of raising reaction temperature or adding a catalyst.

  Solvents that can be used for polymerization of the polyamideimide resin of the present invention include, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidinone, dimethyl sulfoxide, dimethylformamide, N-ethyl-2-pyrrolidone, dimethyl Examples include acetamide, cyclohexanone, cyclopentanone, and tetrahydrofuran. Among them, dimethylacetamide is preferred because of its low boiling point and good polymerization efficiency. Further, after the polymerization, it can be diluted with a solvent used for the polymerization or other low-boiling solvent to adjust the concentration of non-volatile components and the solution viscosity.

  Low boiling solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane and octane, alcoholic solvents such as methanol, ethanol, propanol, butanol and isopropanol, acetone, methyl ethyl ketone and methyl isobutyl. Examples thereof include ketone solvents such as ketone, cyclohexanone and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate.

  In order to accelerate the reaction, alkali metals such as sodium fluoride, potassium fluoride, sodium methoxide, triethylenediamine, triethylamine, diethanolamine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] -5-nonene, or a catalyst such as dibutyltin dilaurate can be used.

2. Polyamideimide resin composition The polyamideimide resin solution obtained by 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, the resin solution contains a low-boiling solvent with good drying properties in order to lower the drying temperature and prevent the curing reaction from proceeding during drying. It is preferable. Examples of the low boiling point solvent suitable for the adhesive (thermosetting resin composition) include ethanol, toluene, xylene, methyl ethyl ketone, and the like. To find superiority in drying properties, at least one selected from the group consisting of these is used. It is preferable that 10% by mass or more of the polyamideimide resin is dissolved in a mixed solvent containing 60 masses of the solvent and 40 masses of dimethylacetamide. By having this solubility, not only is it excellent in drying properties, but when an adhesive (thermosetting resin composition) is added by adding a thermosetting component, it is not insolubilized by the solvent of the thermosetting component, Moreover, it is excellent in temporal stability and storage stability as a thermosetting resin composition.

  Here, dissolution in the present invention means that the solution is transparent in a 25 ° C. atmosphere and a solid is not deposited for 24 hours or more, and the viscosity increase of the solution during that time is less than 1.5 times. Indicates that there is.

  When the polyamideimide resin obtained by the present invention is used for a printed wiring board, particularly a flexible printed wiring board requiring flexibility, the polyamideimide resin has a logarithmic viscosity of 0.2 dl / g or more and a glass transition temperature of 80 ° C. As described above, the tensile modulus is preferably less than 2000 MPa. When the logarithmic viscosity is less than 0.2 dl / g, the polyamideimide resin has a low molecular weight, so that the mechanical strength is lowered. When the glass transition temperature is less than 80 ° C., the heat resistance of the polyamideimide resin is reduced. When the tensile modulus is 2000 MPa or more, the resin is hard and brittle, resulting in low adhesive strength, and curling of the coating film and substrate in the coating and drying process. May be.

  Examples of the thermosetting component that can be used in the thermosetting resin composition using the polyamideimide resin obtained by the present invention include an epoxy resin, an isocyanate compound, a melamine resin, a cyanate compound, a phenol resin, and a maleimide compound. Of these, epoxy compounds are preferred from the viewpoint of physical properties and processability of the cured coating film. Examples of the epoxy resin include bisphenol A type epoxy resins such as trade names jER828 and 1001 manufactured by Japan Epoxy Resin Co., Ltd., and hydrogenated bisphenol A type epoxies such as product names ST-2004 and 2007 manufactured by Tohto Kasei Co., Ltd. Resin, bisphenol F type epoxy resin such as trade name YDF-170, 2004 made by Toto Kasei Co., Ltd., brominated bisphenol A type epoxy resin such as trade name YDB-400, 600 made by Toto Kasei Co., Ltd., Japan Epoxy Phenol novolac type epoxy resins such as trade names jER152 and 154 manufactured by Resin Co., Ltd., trade names EPPN-201 and BREN manufactured by Nippon Kayaku Co., Ltd., and trade names DEN-438 manufactured by Dow Chemical Co., Ltd. Product name YDCN-702, 703, manufactured by Nippon Kayaku Co., Ltd. Product name EOCN-125S, 103S, 104S O-cresol novolac type epoxy resin, flexible epoxy resin such as trade name YD-171 manufactured by Tohto Kasei Co., Ltd., and cyclopentadiene skeleton such as trade names HP-7200 and HP-7200H manufactured by DIC Corporation Epoxy resin having the product name Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., product name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., and product names Denacol EX-611 and EX-614 manufactured by Nagase Chemtech Co., Ltd. , EX-622, EX-512, EX-521, EX-421, EX-411, EX-321 and other functional epoxy resins, product name Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., Toto Kasei Co., Ltd. Trade name YH-434 manufactured by Mitsubishi Gas Chemical Co., Ltd. Trade names TETRAD-X and TETRAD-C manufactured by Nippon Kayaku Co., Ltd. Trade names manufactured by Sumitomo Chemical Co., Ltd. Amine type epoxy resins such as LM-120, trade name Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Celoxide 2021, EHPE 3150 manufactured by Daicel Chemical Industries, Ltd., manufactured by UCC Alicyclic epoxy resin such as ERL4234, bisphenol S type epoxy resin such as trade name Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc., triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd., Bixylenol type epoxy resin such as YY-4000 made by Yuka Shell Epoxy Co., Ltd., Bisphenol type epoxy resin such as YL-6056 made by Yuka Shell Epoxy Co., Ltd., etc. Or two or more types may be used in combination.

  Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolac type epoxy resin, amine type epoxy resin are It is a non-halogen type, and is preferable in terms of improvement in compatibility with the polyamideimide resin obtained by the present invention, solvent resistance, chemical resistance, and moisture resistance.

  The solvent solution of the polyamideimide resin and the epoxy resin of the present invention is excellent in adhesiveness, and can firmly bond the polyimide film and the copper foil. The obtained copper polyimide film laminate is excellent in solder heat resistance, and is excellent in insulation reliability (migration resistance) when used as a coverlay on a circuit. The reason for this is that, in the polyamideimide resin obtained by copolymerizing acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid having 4 to 12 carbon atoms in a specific range, introduction of an aliphatic group improves solvent solubility, and The chain length is neither short nor long, and is moderately dispersed in the polyamide-imide, so it is synergistically bonded by the adhesion of acrylonitrile-butadiene rubber, the flexibility of aliphatic dicarboxylic acid and the introduction of highly polar amide groups. This is considered to improve the performance.

An epoxy resin curing agent or curing accelerator can be added to the thermosetting resin composition using the polyamide-imide resin of the present invention as long as the properties are not impaired. The curing agent is not particularly limited as long as it is a compound that 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 between the epoxy resin, the polyamide-imide resin, and the curing agent. For example, 2MZ, 2E4MZ, C ₁₁ Z, C ₁₇ manufactured by Shikoku Kasei Kogyo Co., Ltd. Z, 2PZ, 1B2MZ, 2MZ- CN, 2E4MZ-CN, C 11 Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C 11 Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2PZ, 2P4BHZ and other imidazole derivatives, acetoguanamine, benzoguanamine and other guanamines, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives ,melamine, Polyamines such as polybasic hydrazides, their organic acid salts and / or epoxy adducts, amine complexes of boron trifluoride, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino- Triazine derivatives such as 6-xylyl-S-triazine, trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-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-nonene), organic acid salts thereof and / or tetraphenylboroe , Polyvinylphenol, polyvinylphenol bromide, organic phosphines such as tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride Quaternary phosphonium salts such as tetraphenylphosphonium tetraphenylboroate, quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, the polycarboxylic acid anhydride, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoro Antimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacu -261 (manufactured by Ciba Specialty Chemicals Co., Ltd.), photocationic polymerization catalyst such as Optoma-SP-170 (manufactured by ADEKA Co., Ltd.), styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine And an equimolar reaction product of organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine. These curing agents and curing accelerators can be used alone or in combination of two or more.

An inorganic or organic filler can be added to the thermosetting resin composition using the polyamide-imide resin of the present invention as long as the characteristics are not impaired. Examples of the inorganic filler include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ). , Barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (PLZT) Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (2MgO.2Al ₂ O ₃ .5SiO ₂ ), talc (3MgO.4SiO ₂ .H ₂ O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , silicate barium (BaO · 8SiO _2), Boron (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO), magnesium titanate (MgO · TiO _2), barium sulfate (BaSO _4), organic bentonite, carbon (C) These may be used alone or in combination of two or more. When these fillers are added, a dispersion work step is required, and depending on the use of the resin composition of the present invention, the flexibility and workability originally possessed by the resin composition are impaired. Since there is a possibility, when adding a filler, it is preferable to adjust the kind and amount of filler to be used.

  A flame retardant can be added to the thermosetting resin composition using the polyamideimide resin of the present invention as long as the characteristics are not impaired. The flame retardant is preferably non-halogen based in consideration of the environment, and as the non-halogen flame retardant used in the present invention, any flame retardant may be used as long as it is soluble in the above polyamideimide resin composition. Although there is no limitation, phosphazene and phosphinic acid derivatives are preferable from the viewpoint of hydrolysis resistance, heat resistance, and prevention of bleed-out of flame retardant to the coating film surface. You may use these individually or in combination of 2 or more types.

  As phosphazenes, for example, cyclic phenoxyphosphazenes such as trade name SPE-100 manufactured by Otsuka Chemical Co., Ltd., cyclic cyanophenoxyphosphazenes such as trade name FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd., manufactured by Otsuka Chemical Co., Ltd. In addition, cyclic phenoxy phosphazenes such as SPH-100, chain phenoxy phosphazenes, cross-linked phenoxy phosphazenes, and the like are listed. However, chain phosphazenes generally have phosphorus groups compared to emotional phosphazenes because they have substituents at the molecular ends. The content is reduced. Accordingly, in the present invention, cyclic phosphazenes are preferable, and cyclic trimers and / or tetrameric phosphazenes are more preferable.

  In addition, non-reactive phosphazenes may cause bleeding on the surface over time, elute free phosphorus under the influence of hydrolysis under severe use conditions, or the degradation characteristics may deteriorate due to decomposition products. Therefore, most preferably, a reactive phosphazene having a functional group that reacts with the epoxy resin is selected. Specific examples thereof include cyclic hydroxyphenoxyphosphazene having a hydroxyl group.

  Examples of phosphinic acid derivatives include HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and HCA-HQ (10- (2,5-dihydroxyphenyl)- 10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, BCA ( 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), phenylphosphinic acid, diphenylphosphinic acid and the like.

  In addition to the above non-halogen flame retardants, other non-halogen flame retardants may be used in combination as required as long as the low warpage, heat resistance, and bleeding are not impaired. Examples thereof include phosphorus-containing epoxy resins copolymerized with an HCA skeleton, phosphorus-containing polyester resins, and condensed phosphate esters such as resorcyl diphenyl phosphate. However, the present invention is not limited to these, and two or more types may be combined. You may use.

3. Flame-retardant adhesive composition The flame-retardant adhesive composition of the present invention comprises (A) a polyamideimide resin, (B) a phosphorus-containing epoxy resin, (C) a phosphorus compound, and (A) to (C). The phosphorus content relative to the total mass of the components is 2.0 to 5.0 mass%.
(A) Polyamideimide resin (A) Polyamideimide resin used in the present invention is the above-mentioned polyamideimide resin, and the following (a) to (c) acid components are reacted with a diisocyanate or diamine having an aromatic ring. The ratio of each acid component when the total acid component of the polyamideimide resin is 100 mol% 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 (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Acid anhydride of polycarboxylic acid having an aromatic ring

(A) Polyamideimide resin can be used as an adhesive (thermosetting resin composition) by adding a thermosetting component to a solvent solution. When the thermosetting resin composition is used as an adhesive, the resin solution contains a low-boiling solvent with good drying properties in order to lower the drying temperature and prevent the curing reaction from proceeding much during drying. It is preferable. Examples of the low boiling point solvent suitable for the adhesive (thermosetting resin composition) include ethanol, toluene, xylene, methyl ethyl ketone, and the like. To find superiority in drying properties, at least one selected from the group consisting of these is used. It is preferable that 10% by mass or more of the polyamideimide resin is dissolved in a mixed solvent containing 60% by mass or more of various types of solvents.
By having this solubility, not only is the drying property excellent, but also the following (B) phosphorus-containing epoxy resin, (C) phosphorus compound, (D) epoxy resin curing agent, (E) epoxy resin not containing phosphorus, (F) When a silane coupling agent or the like is added to form an adhesive (thermosetting resin composition), the thermosetting resin composition has excellent temporal stability and storage stability.

  Here, dissolution in the present invention means that the solution is transparent in a 25 ° C. atmosphere and a solid is not deposited for 24 hours or more, and the viscosity increase of the solution during that time is less than 1.5 times. Indicates that there is.

  The polyamideimide resin in the present invention preferably has a logarithmic viscosity of 0.2 dl / g or more, a glass transition temperature of 80 to 200 ° C., and a tensile modulus of less than 2000 MPa. When the logarithmic viscosity is less than 0.2 dl / g, the polyamideimide resin has a low molecular weight, so that the mechanical strength is lowered. When the glass transition temperature is less than 80 ° C., the heat resistance of the polyamideimide resin is reduced. If the tensile elastic modulus is 2000 MPa or more, the resin is hard and brittle, the adhesive strength is lowered, and curling may occur in the coating or drying process. Moreover, when the glass transition temperature is higher than 200 ° C., when laminating adherends as a flexible printed wiring board, the temperature for heat laminating (thermocompression bonding) for sufficient bonding becomes high, and productivity and workability decrease. In addition, the solvent solubility is poor.

  The (A) polyamideimide resin in the present invention is dissolved in a solvent together with the following components (B) to (F), and as a flame retardant adhesive composition, it has excellent adhesiveness and strengthens the polyimide film and the copper foil. Can be glued. The obtained copper polyimide film laminate is excellent in solder heat resistance and, when used as a coverlay on a circuit, is excellent in insulation reliability (migration resistance). The reason for this is that, in the polyamideimide resin obtained by copolymerizing acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid having 4 to 12 carbon atoms in a specific range, introduction of an aliphatic group improves solvent solubility, and The chain length is neither short nor long, and is moderately dispersed in the polyamide-imide, so it is synergistically bonded by the adhesion of acrylonitrile-butadiene rubber, the flexibility of aliphatic dicarboxylic acid and the introduction of highly polar amide groups. This is considered to improve the performance.

(B) Phosphorus-containing epoxy resin (B) The phosphorus-containing epoxy resin used in the present invention is an epoxy resin in which a phosphorus atom is incorporated by a chemical bond using a reactive phosphorus compound, and two or more epoxy groups are contained in one molecule. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type, or those hydrogenated thereto, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. glycidyl ether type epoxy resins Glycidyl ester epoxy resins such as glycidyl hexahydrophthalate and dimer acid glycidyl ester, glycidyl amine epoxy resins such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, And linear aliphatic epoxy resins such as poxylated soybean oil.

  Examples of the reactive phosphorus compound used in the phosphorus-containing epoxy resin include 9,10-dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA), 10 -(2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ) A phosphorus-containing epoxy resin is obtained by reacting with. As these commercially available products, for example, Epicron EXA9710 (manufactured by DIC Corporation, phosphorus content: 3% by mass), EXA9748 (manufactured by DIC Corporation, phosphorus content: 4.5% by mass), FX305 (Tohto Kasei) Co., Ltd., phosphorus content: 3% by mass) and the like.

  The compounding quantity of the phosphorus containing epoxy resin used by this invention is 1-200 mass parts with respect to 100 mass parts of (A) polyamideimide resin, Preferably it is 3-160 mass parts, More preferably, it is 5-120 masses. Part, more preferably 10 to 80 parts by weight. When the amount of the phosphorus-containing epoxy resin is less than 1 part by mass, the flame retardancy is inferior, and when the amount is more than 200 parts by mass, the heat resistance and adhesiveness are inferior, and the mechanical strength is lowered and the sheet is easily cracked. Become.

(C) Phosphorus Compound The (C) phosphorus compound used in the present invention is not particularly limited, but phosphazene and phosphinic acid derivatives are preferred from the viewpoints of hydrolysis resistance, heat resistance and bleed out. These may be used alone or in combination of two or more.

  The phosphazene compound is represented by the following general formula (1) or (2) (wherein X is the same or different and represents hydrogen, a hydroxyl group, an amino group, an alkyl group, an aryl group, an organic group, and examples of the organic group include: And an alcohol group, a phenoxy group, an allyl group, a cyanophenoxy group, a hydroxyphenoxy group, and the like, and n is an integer of 3 to 25).

  Examples of commercially available products of these phosphazenes include cyclic phenoxyphosphazenes (manufactured by Otsuka Chemical Co., Ltd., trade names: SPB-100, SPE-100), cyclic cyanophenoxyphosphazenes (manufactured by Fushimi Pharmaceutical Co., Ltd., trade names: FP). -300), cyclic hydroxyphenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name: SPH-100), and the like.

  In addition, additive-type phosphazenes bleed out over time, and under the severe conditions of use, free phosphorus may be eluted under the influence of hydrolysis and the like, and the electrical insulation properties may be lowered. Accordingly, a reactive phosphazene having a functional group that reacts with an epoxy resin is preferably selected. Specific examples include cyclic hydroxyphenoxyphosphazene having a phenolic hydroxyl group.

The phosphinic acid derivative is preferably a phenanthrene-type phosphinic acid derivative. For example, 9,10-dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA), 10- Examples include benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: BCA).
Among the phosphinic acid derivatives described above, HCA has reactivity with epoxy resin, but causes bleed-out and may be inferior in high-temperature and high-humidity resistance. Therefore, the blending amount is appropriately selected in consideration of performance.
In addition to the above phosphorus compounds, other phosphorus compounds may be used singly or in combination of two or more as necessary within the range not impairing flame retardancy, solder heat resistance and bleed out.

  The phosphorus content in the flame retardant adhesive composition of the present invention is 2.0 to 5.0% by mass, preferably 2.2 to 4.5% by mass, and more preferably 2.5 to 4%. 0.0% by mass. When the phosphorus content is less than 2.0% by mass, good flame retardancy cannot be obtained, and when it exceeds 5.0% by mass, heat resistance, adhesiveness, and electrical insulation tend to be lowered.

(D) Epoxy resin curing agent The (D) epoxy resin curing agent used in the present invention is not particularly limited as long as it is normally used as a curing agent for epoxy resins. As this (D) epoxy resin hardening | curing agent, a polyamine type hardening | curing agent, an acid anhydride type hardening | curing agent, a boron trifluoride amine complex salt, a phenol resin etc. are mentioned, for example. Examples of polyamine curing agents include diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, isophoronediamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, Examples thereof include polyamines such as basic hydrazide, organic acid salts and / or epoxy adducts thereof. Examples of the acid anhydride-based curing agent include phthalic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutane. Tetracarboxylic dianhydride, hexahydropyromellitic 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- Ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-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] 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] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane- 2,3,5,6-tetracarboxylic dianhydride, bicyclo [2. .2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydroterephthalic trimellitic anhydride, and the like. The above curing agents may be used alone or in combination of two or more.

  (D) The compounding quantity of an epoxy resin hardening | curing agent is 0-5 mass% when the whole non volatile matter of a flame-retardant adhesive composition is 100 mass%, Preferably it is 0-3 mass%. When the blending amount exceeds 5% by mass, the heat resistance tends to decrease.

(E) Epoxy resin not containing phosphorus The (E) epoxy resin not containing phosphorus used in the present invention is not particularly limited as long as it is an epoxy resin containing no phosphorus atom in its molecule. This epoxy resin may be modified with silicone, urethane, polyimide, polyamide or the like, and may contain a sulfur atom, a nitrogen atom or the like in the molecular skeleton.

  Examples of such an epoxy resin include glycidyl ethers such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type, or those hydrogenated thereto, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and the like. Epoxy resin, glycidyl ester epoxy resin such as glycidyl ester of hexahydrophthalic acid, dimer acid glycidyl ester, glycidyl amine epoxy resin such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, epoxidized soybean oil, etc. Examples thereof include linear aliphatic epoxy resins. Examples of these commercially available products include bisphenol A type epoxy resins such as trade names jER828 and 1001 manufactured by Japan Epoxy Resins Co., Ltd., and hydrogenated bisphenol A such as trade names ST-2004 and 2007 manufactured by Tohto Kasei Co., Ltd. Type epoxy resin, product name YDF-170 manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin such as 2004, product name jER152 manufactured by Japan Epoxy Resin Co., Ltd., product name DEN-438 manufactured by Dow Chemical Co., Ltd. Phenol novolac type epoxy resins, trade names YDCN-702, 703 manufactured by Toto Kasei Co., Ltd., trade names EOCN-125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd., DIC ( Epoxy resins having a cyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Tohsei Kasei Co., Ltd. Flexible epoxy resin such as YD-171, trade name Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name manufactured by Nagase Chemtech Co., Ltd. Multifunctional epoxy resins such as Denacol EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, and EX-321, trade names made by Yuka Shell Epoxy Co., Ltd. Epicoat 604, trade name YH-434 manufactured by Tohto Kasei Co., Ltd., trade names TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., trade names GAN manufactured by Nippon Kayaku Co., Ltd., Sumitomo Chemical Co., Ltd. Amine type epoxy resin such as ELM-120, manufactured by Ciba Specialty Chemicals Co., Ltd., and epoxy resin containing heterocycle such as Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd. Alichemical epoxy resins such as the product names Celoxide 2021 and EHPE3150 manufactured by Le Chemical Industry Co., Ltd., ERL4234 manufactured by UCC, bisphenol S-type epoxy resins such as the product name Epicron EXA-1514 manufactured by DIC Corporation, Nissan Chemical Co., Ltd. Triglycidyl isocyanurate such as TEPIC manufactured by Kogyo Co., Ltd., bixylenol type epoxy resins such as trade name YX-4000 manufactured by Yuka Shell Epoxy Co., Ltd., trade name YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd. Bisphenol-type epoxy resins, etc. may be used, and these may be used alone or in combination of two or more.

  (E) The compounding quantity of the epoxy resin which does not contain phosphorus is 0 to 20% by mass, preferably 0 to 15% by mass, when the nonvolatile content of the flame retardant adhesive composition is 100% by mass. . When the blending amount exceeds 20% by mass, sufficient flame retardancy tends not to be obtained.

(F) Silane Coupling Agent The (F) silane coupling agent used in the present invention is not particularly limited as long as it is a conventionally known silane coupling agent as an adhesion-imparting agent. Specific examples thereof include aminosilane and mercaptosilane. , Vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with polyisocyanate.

  Examples of such silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, and bistrimethoxysilylpropylamine. Bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3- Aminosilanes such as aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane, and γ-mercapto Mercaptosilanes such as propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylethyldiethoxysilane, vinyltrimethoxysilane, vinyl Vinylsilanes such as triethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- Epoxy silanes such as (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Methacrylic silane such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, isocyanatepropyltriethoxysilane, isocyanatepropyltri Examples thereof include isocyanate silanes such as methoxysilane, ketimine silanes such as ketiminated propyltrimethoxysilane and ketiminated propyltriethoxysilane, and these may be used alone or in combination of two or more.

  Of these silane coupling agents, epoxy silane has a reactive epoxy group, and therefore does not contain (A) polyamide-imide resin, (B) phosphorus-containing epoxy resin, (D) epoxy resin curing agent, and (E) phosphorus. Since it can react with an epoxy resin or the like, it is preferable in terms of improving heat resistance and heat and humidity resistance.

(F) The compounding quantity of a silane coupling agent is 0-3 mass% when the whole non volatile matter of a flame-retardant resin composition is 100 mass%, Preferably it is 0-2 mass%. If 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 all dissolved in a solvent of dimethylacetamide, ethanol, toluene, xylene, or methyl ethyl ketone at 25 ° C. and a solid content concentration of 25% by mass. This eliminates the need for a uniform dispersion step such as a filler, and avoids the above-mentioned problems such as economy, non-uniformity, reduction in varnish service life, and chemical resistance. I can do it.

  Moreover, in this invention, a hardening accelerator can be used as needed. A hardening accelerator is used in order to accelerate | stimulate reaction with various components which can react with an epoxy resin and an epoxy resin, and if it does not contain a halogen atom, it will not specifically limit. Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, phosphines, imidazoles, octylates, etc., and these may be used alone or in combination of two or more.

Fillers such as organic fillers and inorganic fillers and dispersants thereof can be added to the flame-retardant resin composition of the present invention within a range that does not impair the characteristics, but processing of printed wiring boards by adding them Therefore, it is necessary to fully consider its use and the type and amount of filler.

  The components (A) to (F) used in the present invention are used by dissolving in an organic solvent and preparing the composition as a solution. Examples of the organic solvent include dimethylacetamide, ethanol, methanol, toluene, xylene, methyl ethyl ketone, dimethylformamide, cyclohexanone, N-methyl-2-pyrrolidone, isopropanol, acetone and the like, preferably dimethylacetamide, ethanol, toluene, Examples include xylene and methyl ethyl ketone. These organic solvents may be used alone or in combination of two or more.

  When the composition is used after being dissolved in an organic solvent, it is desired to lower the drying temperature in order not to allow the curing reaction to proceed much when the solvent is dried. Therefore, it is preferable that the resin solution contains a lot of low-boiling solvents with good drying properties. Examples of the low boiling point solvent suitable for the solution of the composition include ethanol, toluene, xylene, methyl ethyl ketone, and the like. In order to find an advantage in drying properties, 50 masses of one kind of solvent selected from the group consisting of these is used. It is preferable that 30% by mass or more of the composition is dissolved in a mixed solvent containing at least%.

  The total concentration (solid content concentration) of the components (A) to (F) in the adhesive solution is usually 10 to 45% by mass, preferably 15 to 40% by mass, and more preferably 20 to 20% by mass. 35% by mass. When the concentration is less than 10% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are reduced. When the concentration is greater than 45% by mass, the solution viscosity becomes too high, and the coating is performed uniformly. It becomes difficult.

4). Adhesive sheet The adhesive sheet for electronic parts of the present invention refers to a composition having the flame retardant adhesive composition of the present invention as an adhesive layer and having at least one peelable protective film layer. . For example, a two-layer structure of protective film layer / adhesive layer or a three-layer structure of protective film layer / adhesive layer / protective film layer corresponds to this. The protective film layer here is not particularly limited as long as it can be peeled without impairing the form of the adhesive layer. For example, plastics such as polyethylene, polyester, polyolefin, polymethylpentene, polyvinyl chloride, polyvinylidene fluoride, and polyphenylene sulfide. Examples thereof include films and films obtained by coating these with silicone or a fluorine compound, papers laminated with these, papers impregnated or coated with a releasable resin, and the like. In addition, metal, ceramics, etc. can be used, and there is an advantage that new functions such as heat dissipation, electromagnetic shielding, reinforcement, identification, etc. can be added as well as protection for the purpose of surface insulation and environmental resistance. is there.

  The method for producing an adhesive sheet is obtained by applying an adhesive solution obtained by dissolving the flame retardant adhesive composition of the present invention in a solvent to the above-described film having releasability, and a temperature of 50 to 200 ° C., preferably The adhesive layer is formed by drying at 70 to 160 ° C., more preferably 100 to 130 ° C., for about 2 to 10 minutes. The thickness of the adhesive layer after drying is 5 to 40 μm, preferably 10 to 25 μm. In the case of a three-layer structure, a releasable protective film is further laminated and laminated.

5). Coverlay film The coverlay film of the present invention is composed of the flame retardant adhesive composition of the present invention as an adhesive layer and is composed of two layers of an insulating plastic film layer / adhesive layer, or an insulating plastic film layer / adhesion. It consists of a three-layer structure of agent layer / protective film layer. The insulating plastic film is a film having a thickness of 5 to 200 μm made of plastic such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, and the like. A film may be laminated. What was demonstrated as a protective film of the adhesive agent sheet mentioned above can be used for a protective film.

  The coverlay film is produced by applying an adhesive solution obtained by dissolving the flame retardant adhesive composition of the present invention in a solvent to the insulating plastic film described above, and a temperature of 50 to 200 ° C., preferably 70 to The adhesive layer is formed by drying at 160 ° C., more preferably 100 to 130 ° C., for about 2 to 10 minutes. The thickness of the adhesive layer after drying is 5 to 40 μm, preferably 10 to 25 μm. For storage and the like, when a three-layer structure is used, a releasable protective film is further laminated and laminated.

6). Flexible printed wiring board The flexible printed wiring board of the present invention refers to one having a configuration in which the flame-retardant adhesive composition of the present invention is used as an adhesive layer, and an insulating plastic film and a copper foil are bonded together by the adhesive layer. . For example, a flexible printed wiring board having the adhesive layer provided on one side or both sides of an insulating film, and one or two layers of copper foil to which one or two layers of the adhesive layer are bonded is mentioned. It is done. As the copper foil, a rolled copper foil or an electrolytic copper foil conventionally used for flexible printed wiring boards can be used. What was demonstrated as an insulating plastic film of the coverlay film mentioned above can be used for an insulating plastic film.

  In the method for producing a flexible printed wiring board, an adhesive solution obtained by dissolving the flame retardant adhesive composition of the present invention in a solvent is applied to the insulating plastic film described above, and the temperature is 50 to 200 ° C., preferably 70. It is dried at ˜160 ° C., more preferably 100 to 130 ° C. for about 2 to 10 minutes, to form an adhesive layer. The thickness of the adhesive layer after drying is 5 to 40 μm, preferably 10 to 25 μm. Next, a copper foil is disposed on the adhesive layer and heat laminated at a temperature of 80 to 150 ° C., preferably 110 to 130 ° C., to obtain a laminate. The polyamide-imide resin used in the present invention has a high Tg from the viewpoint of heat resistance, and when the lamination temperature is lower than 100 ° C., it cannot be thermocompression bonded well, but when it exceeds 150 ° C., the workability tends to be lowered. The laminate is further heated and cured at 120 to 200 ° C., preferably 140 to 170 ° C., whereby the adhesive is completely cured to obtain a flexible printed wiring board.

  The flexible printed wiring board obtained by the present invention has excellent solder heat resistance so that none of appearance abnormalities such as peeling, swelling, and discoloration occurs even when immersed in a solder bath at 330 ° C. for 30 seconds. it can. Also, after leaving it to stand in an atmosphere of 40 ° C. and 90% relative humidity for 24 hours to absorb moisture, even if it is immediately immersed in a 300 ° C. solder bath for 30 seconds, abnormal appearance such as peeling, swelling and discoloration will occur. The solder heat resistance that does not occur in either case cannot be easily achieved by the prior art.

In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to the examples.
1. Regarding the polyamideimide resin and the general resin composition, the characteristics of the resins in the examples were measured and evaluated by the following methods.
(Logarithmic viscosity)
A solution obtained by dissolving 0.5 g of dried solid polymer in 100 ml of NMP was measured at 30 ° C. using an Ubbelohde viscosity tube.

(Tensile modulus)
The obtained polyamideimide resin solution was applied onto a copper foil so that the film thickness after drying was 20 μm, dried at 150 ° C. for 10 minutes with a hot air dryer, and then at 200 ° C. for 5 hours in an inert oven. By drying and removing the copper foil by etching, a polyamide-imide resin film is prepared, a strip having a width of 10 mm is made from these films, and a tensile speed of 20 mm / min is measured using Tensilon of Toyo Baldwin. did.

(Glass-transition temperature)
The same polyamidoimide resin film as that used for the measurement of the tensile elastic modulus was measured for dynamic viscoelasticity at a frequency of 110 Hz using a dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement Control Co., Ltd., and its storage elasticity It was calculated from the inflection point of the rate.

(Solubility)
The same polyamideimide resin film as that used for the measurement of the tensile modulus was dissolved in a solvent in which 40 parts by mass of dimethylacetamide and 60 parts by mass of toluene were mixed so that the nonvolatile content would be 10% by mass. A state where the solution was transparent and no solid matter was deposited in a 25 ° C. atmosphere was maintained for 24 hours.

(Adjustment of adhesive resin composition)
To 100 g of the resulting polyamideimide resin solution, 50 g of a toluene solution with a non-volatile content of 30% by mass of an epoxy resin (jER152, a phenol novolak type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) and 4,4′-diaminodiphenylsulfone (Seika Wakayama) 4 g of a methyl ethyl ketone solution having a nonvolatile content of 15% by mass of SEIKACURE-S) manufactured by Kasei Co., Ltd. was added to obtain an adhesive resin composition.

(Adhesive strength)
The adhesive resin composition was applied to a polyimide film (apical NPI) having a thickness of 25 μm so that the film thickness after drying was 15 μm, and the solvent was dried at 130 ° C. for 5 minutes in a hot air dryer. Thereafter, it was bonded to a treated surface of electrolytic copper foil (USP manufactured by Nihon Electrolytic Co., Ltd.) at 130 ° C., and further cured by heating at 170 ° C. for 3 hours.
Next, the obtained copper-clad laminate was cut into a width of 1.0 mm, peeled at 90 ° using a Tensilon manufactured by Toyo Baldwin Co., Ltd. at room temperature, and the peel strength was measured.

(Solder heat resistance)
The state when the copper-clad laminate whose adhesion was measured was floated in a 300 ° C. solder bath for 60 seconds was observed. The thing without peeling and swelling was set as (circle) and the other than that was set as *.

(Insulation reliability: migration resistance)
A comb pattern (circuit) having a line spacing of 50 μm was formed on a two-layer CCL (trade name Viroflex) manufactured by Toyobo Co., Ltd., washed with 3% hydrochloric acid, and then washed with water and dried. The entire surface of the obtained circuit was coated with the adhesive resin composition so that the film thickness after drying was 20 μm, and the adhesive layer was cured by heating at 170 ° C. for 180 minutes. Thereafter, a DC voltage of 50 V was applied, and when the insulation resistance value after 500 hours was higher than 1 × 10 ⁸ Ω, it was rated as ○, and when it was below or when dendrite was seen between the wirings, it was marked as ×.

Example 1 (polyamideimide resin 1):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, trimellitic anhydride 105.67 g (0.55 mol), sebacic acid 80.09 g (0.40 mol), both ends Carboxylic acid acrylonitrile butadiene rubber (CTBN 1300 × 13, number average molecular weight 3,500, acrylonitrile part ratio 26 wt%) 175 g (0.05 mol), 4,4′-diphenylmethane diisocyanate 252.75 g (1.0 mol), dimethylacetamide 526 g Was heated to 100 ° C. under a nitrogen stream and allowed to react for 2 hours. Next, 117 g of dimethylacetamide was added and further reacted at 150 ° C. for 5 hours, and then diluted by adding 439 g of toluene and 146 g of dimethylacetamide and cooled to room temperature. 1 was obtained.
Table 1 shows the results obtained by measuring the logarithmic viscosity, glass transition temperature, and tensile modulus of the polymer obtained from the resin solution.
In addition, as described above, an adhesive resin composition is prepared from a polyamideimide resin solution, and a copper-clad laminate is manufactured using the adhesive resin composition. Sex was evaluated. Moreover, the migration resistance which is a necessary characteristic as a coverlay was evaluated by the method described in the previous section. The obtained results are shown in Table 1.

Example 2 (Polyamideimide resin 2):
In a four-necked 2 liter separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 142.18 g (0.74 mol) trimellitic anhydride, 40.45 g (0.20 mol) sebacic acid, 210.0 g (0.06 mol) of acrylonitrile butadiene rubber (CTBN 1300 × 13) having carboxylic acid at both ends, 125.13 g (0.5 mol) of 4,4′-diphenylmethane diisocyanate, 87.08 g (0.5 mol) of tolylene diisocyanate 517 g of dimethylacetamide was charged, heated to 100 ° C. under a nitrogen stream, and reacted for 2 hours. Next, after reacting at 150 ° C. for 5 hours, 431 g of toluene and 258 g of dimethylacetamide were added for dilution, and the mixture was cooled to room temperature to obtain a polyamideimide resin solution 2 that was brown but had no turbidity.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Example 3 (polyamideimide resin 3):
In a four-necked 2 liter separable flask equipped with a stirrer, cooling tube, nitrogen inlet tube and thermometer, 105.67 g (0.55 mol) trimellitic anhydride and 92.12 g (0.4 mol) dodecanedioic acid , 175 g (0.05 mol) of acrylonitrile butadiene rubber having a carboxylic acid at both ends (CTBN 1300 × 13), 250.25 g (1.0 mol) of 4,4′-diphenylmethane diisocyanate, and 535 g of dimethylacetamide up to 100 ° C. in a nitrogen stream The temperature was raised and reacted for 2 hours. Next, after reacting at 150 ° C. for 5 hours, 594 g of toluene and 119 g of dimethylacetamide were added for dilution, and the mixture was cooled to room temperature to obtain a polyamideimide resin solution 3 which was brown but had no turbidity.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Example 4 (polyamideimide resin 4):
In a four-necked 2 liter separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 105.67 g (0.55 mol) trimellitic anhydride, 58.46 g (0.4 mol) adipic acid, Charged with 175 g (0.05 mol) of acrylonitrile butadiene rubber (CTBN1300 × 13) with carboxylic acid at both ends, 250.25 g (1.0 mol) of 4,4′-diphenylmethane diisocyanate and 501 g of dimethylacetamide, and heated to 100 ° C. under a nitrogen stream. Allow to warm and react for 2 hours. Next, after reacting at 150 ° C. for 5 hours, 418 g of toluene and 251 g of dimethylacetamide were added for dilution, and the mixture was cooled to room temperature to obtain a polyamideimide resin solution 4 which was brown but had no turbidity.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Example 5 (polyamideimide resin 5):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 67.25 g (0.35 mol) of trimellitic anhydride, 121.34 g (0.60 mol) of sebacic acid, both ends Is charged with 175 g (0.05 mol) of acrylonitrile butadiene rubber (CTBN1300 × 13), 4,4′-diphenylmethane diisocyanate 252 g (1.0 mol), and 526 g of dimethylacetamide, and heated to 100 ° C. under a nitrogen stream. The reaction was performed for 2 hours. After further reacting at 150 ° C. for 5 hours, 438 g of toluene and 263 g of dimethylacetamide were added and diluted, and cooled to room temperature to obtain a polyamideimide resin solution 5 which was brown but had no turbidity.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Comparative Example 1 (polyamideimide resin 6):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 89.15 g (0.58 mol) trimellitic anhydride, 64.72 g (0.40 mol) sebacic acid, both ends Is charged with 56 g (0.02 mol) of acrylonitrile butadiene rubber (CTBN1300 × 13) of carboxylic acid, 201.2 g (1 mol) of 4,4′-diphenylmethane diisocyanate and 423.31 g of dimethylacetamide, and heated to 100 ° C. under a nitrogen stream. The reaction was performed for 2 hours. Next, after reacting at 150 ° C. for 5 hours, 353 g of toluene and 212 g of dimethylacetamide were added for dilution, and the mixture was cooled to room temperature to obtain a polyamideimide resin solution 6 which was brown but had no turbidity.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Comparative example 2 (polyamideimide resin 7):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 172.92 g (0.90 mol) of trimellitic anhydride, 10.11 g (0.05 mol) of sebacic acid, both ends Is carboxylic acid acrylonitrile butadiene rubber (CTBN1300 × 13) 175g (0.05mol), 4,4'-diphenylmethane diisocyanate 247.75g (0.99mol) and dimethylacetamide 518g, and heated up to 100 ° C under nitrogen flow The reaction was performed for 2 hours. Next, after reacting at 150 ° C. for 5 hours, 431 g of toluene and 259 g of dimethylacetamide were added for dilution, and the mixture was cooled to room temperature, whereby a brown polyamideimide resin solution 7 was obtained, but it was cloudy.
The measurement results and evaluation results obtained in the same manner as Example 1 are shown in Table 1.

Comparative Example 3 (polyamideimide resin 8):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 9.61 g (0.05 mol) of trimellitic anhydride, 182.02 g (0.90 mol) of sebacic acid, both ends Is charged with 175 g (0.05 mol) of acrylonitrile butadiene rubber (CTBN 1300 × 13), 4,4′-diphenylmethane diisocyanate 252 g (1.0 mol), and 529 g of dimethylacetamide, and heated to 100 ° C. in a nitrogen stream. The reaction was performed for 2 hours. Furthermore, after making it react at 150 degreeC for 5 hours, 441 g of toluene and 264 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the polyamideimide resin solution 8 which is brown, but without turbidity.
The measurement results and evaluation results obtained in the same manner as in Example 1 are shown in Table 2.

Comparative example 4 (polyamideimide resin 9):
In a four-necked separable flask equipped with a stirrer, cooling tube, nitrogen inlet tube and thermometer, trimellitic anhydride 105.67 g (0.55 mol), both ends of carboxylic acid acrylonitrile butadiene rubber (CTBN 1300 × 13 175 g (0.05 mol), eisacodioic acid (Okamura Yushi Co., Ltd.) 137 g (40 mol), 4,4'-diphenylmethane diisocyanate 125.13 g (0.5 mol), tolylene diisocyanate 87.08 g (0.5 mol), 542 g of dimethylacetamide was charged, heated to 100 ° C. under a nitrogen 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 diluted, and cooled to room temperature. However, the solubility of the polyamideimide resin was insufficient, and the resin solution was extremely cloudy. Subsequent measurement results and evaluation were discontinued.

Comparative example 5 (polyamideimide resin 10):
In a four-necked separable flask equipped with a stirrer, a condenser tube, a nitrogen inlet tube and a thermometer, 86.4 g (0.45 mol) of trimellitic anhydride, 80.09 g (0.40 mol) of sebacic acid, both ends Is charged with 525 g (0.15 mol) of acrylonitrile butadiene rubber (CTBN 1300 × 13), 4,4′-diphenylmethane diisocyanate 252.75 g (1.0 mol), and 854 g of dimethylacetamide, and heated to 100 ° C. in a nitrogen stream. The reaction was performed for 2 hours. Next, 190 g of dimethylacetamide was added, and further reacted at 150 ° C. for 5 hours. Then, 712 g of toluene and 237 g of dimethylacetamide were added, diluted, and cooled to room temperature, so that a polyamideimide resin solution 10 having a brown and slightly dull color was obtained. Obtained.
The measurement results and evaluation results obtained in the same manner as in Example 1 are shown in Table 2.

Comparative Example 6 (polyamideimide resin 11):
In a four-necked separable flask equipped with a stirrer, cooling tube, nitrogen inlet tube and thermometer, 182.4 g (0.95 mol) of trimellitic anhydride and carboxylic acid acrylonitrile butadiene rubber (CTBN 1300 × 13) ) 175 g (0.05 mol), 4,4′-diphenylmethane diisocyanate 252.75 g (1.0 mol), and 519 g of dimethylacetamide were heated to 100 ° C. in a nitrogen stream and reacted for 2 hours. Next, 115 g of dimethylacetamide was added and further reacted at 150 ° C. for 5 hours, and then diluted by adding 433 g of toluene and 144 g of dimethylacetamide, and cooled to room temperature, thereby obtaining a brown polyamideimide resin solution 11. The solution was a little muddy.
The measurement results and evaluation results obtained in the same manner as in Example 1 are shown in Table 2.

Comparative Example 7 (polyamideimide resin 12):
In a four-necked separable flask equipped with a stirrer, cooling tube, nitrogen inlet tube and thermometer, 91.2 g (0.475 mol) trimellitic anhydride and carboxylic acid acrylonitrile butadiene rubber (CTBN1300 × 13) 175 g (0.05 mol), 1,4-cyclohexanedicarboxylic acid 81.7 g (0.475 mol), isophorone diisocyanate 222 g (1.0 mol), 1,8-diazabicyclo [5,4,0] -7-undecene 1 .52 g (0.01 mol) and 482 g of dimethylacetamide were charged, the temperature was raised to 100 ° C. in a nitrogen stream, and the reaction was allowed to proceed for 2 hours. Furthermore, after making it react at 150 degreeC for 5 hours, 241 g of dimethylacetamide and 402 g of toluene were added and diluted, and it cooled to room temperature, and obtained the polyamide-imide resin solution 12 which is yellow and has no turbidity.
The measurement results and evaluation results obtained in the same manner as in Example 1 are shown in Table 2.

As described above, the polyamideimide in which the aliphatic component having 4 to 12 carbon atoms and the acrylonitrile butadiene rubber component are introduced in a specific range not only improves the solubility of the polyamideimide in the low boiling point solvent, but also has an adhesive property. Thus, it can be seen that the adhesive composition of the present invention is excellent in solder heat resistance and migration resistance and is suitable for use as a printed wiring board.
On the other hand, in Comparative Example 1, since there are few acrylonitrile butadiene rubber components, adhesiveness and solder heat resistance are bad, and in Comparative Example 2, since there are few aliphatic components, solubility and adhesiveness are bad, and resin performance is not exhibited. In Comparative Example 3, since there are many aliphatic components and many amide components, the water absorption of the resin becomes high and the migration resistance is poor. In Comparative Example 4, the aliphatic chain length is too long. In No. 5, since there are too many acrylonitrile butadiene rubber components, since Comparative Example 6 does not have an aliphatic component having 4 to 12 carbon atoms, the solubility is remarkably poor. In Comparative Example 7, there is a defect that the reactivity is low, and if the alicyclic component can be introduced, the solubility is improved, but the adhesion is poor and the migration resistance is poor.

2. The measured value described in the Example about a flame-retardant resin composition, an adhesive sheet, a coverlay film, and a flexible printed wiring board is measured by the following method. In the examples, the term “parts” means parts by mass.
<Logarithmic viscosity>
A solution obtained by dissolving 0.5 g of dried solid polymer in 100 ml of NMP was measured at 30 ° C. using an Ubbelohde viscosity tube.

<Tensile modulus>
The obtained polyamideimide resin solution was applied onto a copper foil so that the film thickness after drying was 20 μm, dried at 150 ° C. for 10 minutes with a hot air dryer, and then at 200 ° C. for 5 hours in an inert oven. Drying and removing the copper foil by etching to create polyamideimide resin films, making strips with a width of 10 mm from these films, measured using a Tensilon of Toyo Baldwin Co., Ltd., at a tensile rate of 20 mm / min did.

<Glass transition temperature>
The same polyamidoimide resin film as that used for the measurement of the tensile elastic modulus was measured for dynamic viscoelasticity at a frequency of 110 Hz using a dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement Control Co., and its storage elasticity. It was calculated from the inflection point of the rate.

<Solubility>
The same polyamideimide resin film as that used for measurement of the tensile modulus was mixed with 40 parts by mass of dimethylacetamide and 60 parts by mass of one kind of solvent selected from the group consisting of ethanol, toluene, xylene, and methyl ethyl ketone. The solution was dissolved so that the nonvolatile content was 10% by mass. It was allowed to stand in an atmosphere at 25 ° C. for 24 hours, and it was examined whether the solution was transparent and solid matter was not precipitated.
(Judgment) ○: The solution was transparent and completely dissolved without precipitation of solid matter. ×: The solution did not dissolve or the precipitation of solid matter was observed.

<Synthesis Examples 1 to 5 of Polyamideimide Resin, Comparative Synthesis Examples 1 to 6>
In the same manner as in Example 1, Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 6 of polyamideimide resin were prepared. Table 3 shows the physical property values and characteristic evaluation results of the polyamideimide resin thus obtained.

<Various components of adhesive composition>
(B) Phosphorus-containing epoxy resin (1) EXA-9710: Methyl ethyl ketone-dissolved product (nonvolatile content concentration 70% by mass) of phosphorus-containing epoxy resin (epoxy equivalent: 490, phosphorus content: 3.0% by mass) manufactured by Dic Corporation )
(C) Phosphorus compound (1) HCA: Sanko Co., Ltd. phenanthrene type organophosphate compound, 9,10-dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (phosphorus content: 14.3 mass%) )
(2) BCA: Phenanthrene-type organophosphate compound manufactured by Sanko Co., Ltd., 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (phosphorus content: 10.1% by mass)
(3) SPH-100: Cyclic hydroxyphenoxyphosphazene (phosphorus content: 12.5% by mass) manufactured by Otsuka Chemical Co., Ltd.
(D) Epoxy resin curing agent DDS: 4,4′-diaminodiphenylsulfone (E) Epoxy resin not containing phosphorus jER152: Phenol novolac epoxy resin (epoxy equivalent 175) manufactured by Japan Epoxy Resin Co., Ltd.
(F) Silane coupling agent KBM-403: Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyltrimethoxysilane (epoxy equivalent 283)

<Example 6>
The above-mentioned various components were added to the solution of the (A) polyamideimide resin obtained in Synthesis Example 1 to obtain a solution of the adhesive composition 1 of Example 6.
That is, 173.3 parts of the solution of the (A) polyamideimide resin obtained in Synthesis Example 1, 22.9 parts of EXA-9710, and 64. of a dimethylacetamide solution with a non-volatile concentration of 25% by mass of BCA in a glass bottle. 0 parts, 20.0 parts of a methyl ethyl ketone solution with a non-volatile content of 30% by mass of SPH-100, 12.0 parts of a toluene solution of 50% by mass of non-volatile of jER152, and a methyl ethyl ketone solution with a non-volatile content of 15% by mass of DDS 20.0 parts, 5.0 parts of a toluene solution of KBM-403 with a nonvolatile content concentration of 20% by mass, 16.1 parts of a diluent solvent (dimethylacetamide / toluene = 20/80) were charged, and the nonvolatile content concentration was 30% by mass. The adhesive composition solution of Example 6 was obtained. Table 4 shows the mixing ratio of the solid content with the total solid content being 100% by mass.

  Using the adhesive solution obtained in Example 6, an adhesive sheet, a coverlay film, and a flexible printed wiring board were produced. These production methods are shown below.

<Adhesive sheet>
It apply | coated so that the thickness after drying might be set to 25 micrometers on the polyester film which performed the mold release process using the adhesive composition solution obtained in Example 6, and it dried in a ventilation oven at 130 degreeC for 3 minutes. An uncured or semi-cured adhesive sheet was produced.

<Coverlay film>
The solution of the adhesive composition obtained in Example 6 was applied on a 25 μm polyimide film (manufactured by Kaneka Corporation, Apical 25 NPI) so that the thickness after drying was 25 μm, and was blown at 130 ° C. for 3 minutes. An uncured or semi-cured coverlay film was prepared by drying in an oven.

<Flexible printed wiring board>
The solution of the adhesive composition obtained in Example 6 was applied on a 25 μm polyimide film (manufactured by Kaneka Corporation, Apical 25 NPI) so that the thickness after drying was 16 μm, and was blown at 130 ° C. for 3 minutes. An uncured or semi-cured film with an adhesive was prepared by drying in an oven. The adhesive-coated surface of the film with adhesive obtained in this way and the roughened surface of the electrolytic copper foil (thickness 18 μm, USLP made by Nippon Electrolytic Co., Ltd.) or rolled copper foil (thickness 18 μm, Nikko metallic BHY) Were subjected to thermocompression bonding under the conditions of a laminating temperature of 130 ° C., a pressure of 3 MPa, and a time of 20 seconds using a vacuum press laminator manufactured by Nasek Corporation. This was further heat-cured at 170 ° C. for 3 hours to prepare a flexible printed wiring board.

  The adhesive sheet, coverlay film, and flexible printed wiring board obtained as described above were evaluated according to the evaluation items as shown below.

<Peel strength>
In accordance with JIS C6471, a circuit with a pattern width of 1 mm is formed on the flexible printed wiring board, and a copper foil is placed in the direction of 90 ° of the wiring board in an atmosphere of 25 ° C. using RTM100 manufactured by Toyo Baldwin. A tensile test was performed at a pulling speed of 50 mm / min, and a 90 ° peel strength was measured.
(Determination) A: 15 N / cm or more B: 11 N / cm or more and less than 15 N / cm Δ: 6 N / cm or more and less than 11 N / cm X: Less than 6 N / cm

<Solder heat resistance>
(1) Normal state: In accordance with JIS C6471, a test piece was prepared by cutting the flexible printed wiring board into 25 mm squares, and the test piece was immersed in a solder bath at 300 ° C. or higher for 30 seconds. The temperature at which none of the appearance abnormalities such as peeling, swelling, and discoloration occurred on the test piece was measured.
(Judgment) A: 330 ° C. or higher ○: 300 ° C. or higher and lower than 330 ° C. x: Less than 300 ° C. The specimen was allowed to stand for 24 hours and then immediately immersed in a solder bath at 280 ° C. or higher for 30 seconds. The temperature at which none of the appearance abnormalities such as peeling, swelling, and discoloration occurred on the test piece was measured.
(Judgment) A: 300 ° C. or higher ○: 280 ° C. or higher and lower than 300 ° C.

<Flame retardance>
The solution of the adhesive composition obtained in Example 6 was applied to both sides of a 12.5 μm polyimide film (manufactured by Kaneka Corporation, Apical 12.5 NPI) so that the thickness after drying was 16 μm. After drying in a blowing oven at 3 ° C. for 3 minutes, a sample was prepared by heat curing at 170 ° C. for 3 hours. Flame retardancy was evaluated in accordance with UL-94 VTM flame retardancy standards.
(Judgment) (double-circle): It is equivalent to UL94 VTM-0 and the sample piece burned less than half.
◯: Equivalent to UL94 VTM-0, with sample pieces combusting more than half.
X: Not satisfying UL94 VTM-0

<Insulation reliability: Migration resistance>
A comb pattern having a line spacing of 70 μm was formed on a two-layer CCL (trade name Viroflex) manufactured by Toyobo. A solution of the adhesive composition obtained in Example 6 was applied onto this circuit so that the thickness after drying was 25 μm, dried at 130 ° C. for 3 minutes in a blowing oven, and then at 170 ° C. for 3 hours. Then, a sample provided with a coverlay was prepared by heat curing. Thereafter, a DC voltage of 50 V was applied under conditions of a temperature of 85 ° C. and a relative humidity of 85%, and migration resistance was measured.
(Judgment) ◯: The insulation resistance value after 500 hr exceeded 1 × 10 ⁸ Ω, and no dendrite growth was observed.
×: When the insulation resistance value after 500 hours is less than 1 × 10 ⁸ Ω, or when dendrite growth is observed.

<Peel strength after PCT treatment>
After cutting the flexible printed wiring board so that the sample width is 5 mm and creating a sample, a PCT test is performed for 40 hours under conditions of a temperature of 121 ° C., a humidity of 100%, and a pressure of 2 atm using an autoclave manufactured by Tommy Seiko Co., Ltd. It was. In accordance with JIS C6471, using a RTM100 manufactured by Toyo Baldwin, a copper foil was subjected to a tensile test in a direction of 90 ° of the wiring board at a pulling speed of 50 mm / min in an atmosphere of 25 ° C. ° Peel strength was measured.
(Determination) A: 10 N / cm or more B: 6 N / cm or more and less than 10 N / cm Δ: 4 N / cm or more and less than 6 N / cm ×: less than 4 N / cm

  Tables 4 and 5 show the results obtained by the above evaluation methods.

<Examples 7 to 13 and Comparative Examples 8 to 16>
Similarly to the flame-retardant adhesive composition of Example 6, (A) Polyamideimide resin synthesis examples 1 to 5 and comparative synthesis examples 1 to 6 were used to prepare various components (B) to ( F) was blended, and flame retardant adhesive compositions of Examples 7 to 13 and Comparative Examples 8 to 16 that were adjusted to a non-volatile concentration of 30% with a diluent solvent (dimethylacetamide / toluene = 20/80) were obtained. . Tables 4 and 5 show the blending ratio of the solid content with the total solid content being 100% by mass for each of the obtained adhesive compositions. Various components (B) to (F) were previously dissolved in a solvent and used as a solution. Nonvolatile content concentrations and solvent compositions of various components (B) to (F) are shown below.
HCA: Nonvolatile content concentration 25% by mass, dimethylacetamide solution BCA: Nonvolatile content concentration 25% by mass, dimethylacetamide solution SPH-100: Nonvolatile content concentration 30% by mass, methyl ethyl ketone solution DDS: Nonvolatile content concentration 15% by mass, methyl ethyl ketone solution jER152: Nonvolatile content concentration 50% by mass, toluene solution KBM-403 Nonvolatile content concentration 20% by mass, toluene solution

  Similarly to Example 6, the adhesive compositions of Examples 7 to 13 and Comparative Examples 8 to 16 were also produced as adhesive sheets, coverlay films, and flexible printed wiring boards, and evaluated in the same manner as in Example 6. . The results are shown in Tables 4 and 5.

  As described above, the coverlay film and flexible printed wiring board of the present invention are excellent in peel strength, solder heat resistance, flame retardancy and migration resistance, and are excellent in the above characteristics even after being processed under high temperature and high humidity conditions. . In particular, the solder heat resistance can withstand 330 ° C., and as shown in Examples 6 to 8 and 13, the unprecedented excellent characteristics that can withstand 300 ° C. even after moisture absorption. Indicates.

The phosphorus content of Comparative Example 8 is less than 2.0% by mass and outside the scope of the claims, and the flame retardancy is poor.
The phosphorus content of Comparative Example 9 is greater than 5.0% by mass, outside the scope of the claims, and is inferior in solder heat resistance and migration resistance.
Comparative Example 10 does not contain (B) the phosphorus-containing epoxy resin, and is outside the scope of the claims, and is inferior in solder heat resistance, flame retardancy, and migration resistance.
Comparative Example 11 uses a polyamideimide resin outside the scope of claim (b) in which the proportion of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms is less than 10 mol%, and the peel strength is inferior.
Comparative Example 12 uses a polyamideimide resin outside the scope of claims where the proportion of (b) the aliphatic dicarboxylic acid having 4 to 12 carbon atoms is more than 80 mol%, and the solder heat resistance after moisture absorption is poor. .
Comparative Example 13 uses a polyamideimide resin outside the scope of claim (b) using an aliphatic dicarboxylic acid having a carbon number greater than 12, and the peel strength is inferior.
Comparative Example 14 uses a polyamideimide resin in which the ratio of (a) acrylonitrile-butadiene rubber having carboxyl groups at both ends is less than 3 mol%, and the peel strength is inferior.
Comparative Example 15 was extremely inferior in adhesiveness, and could not be thermocompression-bonded and evaluated under the lamination conditions (temperature 130 ° C., pressure 3 MPa, time 20 seconds) for creating a flexible printed wiring board.
Comparative Example 16 uses (b) a polyamideimide resin outside the scope of claims, which is not copolymerized with an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and has a poor peel strength.

The polyamide-imide resin of the present invention and an adhesive resin composition further added with a thermosetting agent are useful for printed wiring boards such as copper-clad laminates, coverlays, adhesive sheets, copper foils with resin, overcoat inks, and prepregs. In addition, it can be used in a wide range of electronic devices as paints, coating agents, and the like.
The flame-retardant adhesive composition of the present invention is non-halogen, is environmentally friendly, has excellent workability, and is suitable for the production of flexible printed wiring boards. Furthermore, the flame retardant adhesive composition of the present invention can be used as an adhesive sheet, a coverlay film, an insulating layer of a flexible printed wiring board, and the like.

Claims (15)

The following (a) to (c) are polyamideimide resins obtained by reacting an acid component with a diisocyanate or diamine having an aromatic ring, and each acid component when the total acid component of the polyamideimide resin is 100 mol% The ratio of is (a) 3-10 mol%, (b) 10-80 mol%, (c) 10-87 mol%, The polyamideimide resin characterized by the above-mentioned.
(A) Acrylonitrile-butadiene rubber having carboxyl groups at both ends (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Acid anhydride of polycarboxylic acid having an aromatic ring   The polyamide-imide resin is dissolved in a mixed solvent composed of 60 masses of at least one solvent selected from the group consisting of ethanol, toluene, xylene, and methyl ethyl ketone and 40 masses of dimethylacetamide at 25 ° C at 10 mass% or more. Polyamideimide resin.   The polyamide-imide resin composition which added the thermosetting component to the polyamide-imide resin of Claim 2.   The polyamide-imide resin composition according to claim 3, wherein the thermosetting component is an epoxy resin.   A printed wiring board using the polyamideimide resin composition according to claim 3 or 4 as an adhesive. (A) Polyamidoimide resin, (B) Phosphorus-containing epoxy resin, (C) Phosphorus compound, and (A) Polyamidoimide resin having the following acid components and aromatic rings (a) to (c) or It is a polyamide-imide resin obtained by reacting with a diamine, and the ratio of each acid component when the total acid component of the polyamide-imide resin is 100 mol% is (a) 3 to 10 mol%, (b) 10 Flame retardancy characterized in that it is ˜80 mol%, (c) 10 to 87 mol%, and the phosphorus content relative to the total mass of the components (A) to (C) is 2.0 to 5.0 mass%. Adhesive composition.
(A) Acrylonitrile-butadiene rubber having carboxyl groups at both ends (b) Aliphatic dicarboxylic acid having 4 to 12 carbon atoms (c) Polycarboxylic acid anhydride having an aromatic ring   (C) The flame retardant adhesive composition according to claim 6, wherein the phosphorus compound is a phosphazene and / or phosphinic acid derivative.   (D) The flame retardant adhesive composition according to claim 6 or 7, further comprising an epoxy resin curing agent.   (E) The flame retardant adhesive composition according to any one of claims 6 to 8, further comprising an epoxy resin containing no phosphorus.   (F) The flame retardant adhesive composition according to any one of claims 6 to 9, further comprising a silane coupling agent.   The components (A) to (F) are all dissolved in any solvent of dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone at 25 ° C and a solid content concentration of 25% by mass. Flame retardant adhesive composition.   The flame-retardant adhesive composition according to any one of claims 6 to 11, wherein a phosphorus content relative to a total mass of the components (A) to (F) is 2.0 to 5.0 mass%.   It is an adhesive sheet by which the adhesive bond layer which consists of a flame-retardant adhesive composition in any one of Claims 6-12, and the peelable protective film layer are laminated | stacked, Comprising: One side or both surfaces of an adhesive bond layer An adhesive sheet having a protective film layer that can be peeled off.   The coverlay film formed by laminating | stacking the adhesive bond layer and insulating plastic film layer which consist of a flame-retardant adhesive composition in any one of Claims 6-12. The flexible printed wiring board containing the insulating layer formed using the flame-retardant adhesive composition in any one of Claims 6-12.