JP2007070481A - Adhesive composition and flexible printed wiring board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-free flame-retardant adhesive excellent in adhesivity to various plastic films, adhesivity to metals including copper, aluminum and stainless steel and glass, heat resistance, moisture resistance, shelf-life, migration resistance, etc. <P>SOLUTION: An adhesive composition comprising a polyester(A), an epoxy compound(B) and a curing catalyst(C) is provided. In this composition, the polyester(A) contains a component of formula(I)[ wherein, R is -(CH<SB>2</SB>)<SB>n</SB>COOH or -(CH<SB>2</SB>)<SB>n</SB>OH; and n meets the relationship:1≤n≤20 ] and a component of formula(II) as copolymerization components. A flexible printed wiring board using the above adhesive composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive composition excellent in flame retardancy, solder heat resistance, migration resistance and adhesion. The adhesive composition exhibits an excellent effect when used for a flexible printed circuit board.

  In recent years, adhesives have been used in various fields, but due to diversification of usage purposes, adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, adhesion to glass, heat resistance There are demands for further improvements in performance, moisture resistance, shelf life, and the like. For example, an epoxy / acryl butadiene adhesive, an epoxy / polyvinyl butyral adhesive, or the like is used as an adhesive for a circuit board. When used as an adhesive for circuit boards including flexible printed wiring boards, solder heat resistance and adhesion in a high temperature atmosphere are required.

  On the other hand, polyester-based resins as structural plastics are used in a wide variety of fields because of the large design range of resin characteristics of the copolymer and recyclability.

  In particular, in order to cope with recent lead-free solder, an adhesive having higher heat resistance is required. In addition, a long pot life is required for storage until the circuit board is formed after the adhesive is applied to the adherend and dried. With conventional epoxy / acrylic butadiene adhesives and epoxy / polyvinyl butyral adhesives, the pot life is short, they must be stored at low temperatures, and metal and plastic film adhesion is not sufficient. There wasn't. Moreover, since these conventional adhesives have insufficient copper migration resistance, short circuits and discoloration of copper occur, and a sufficiently satisfactory adhesive cannot be obtained. In addition, polyester-based resins as structural plastics are used in a wide variety of fields because of the large design range of resin characteristics of the copolymer and recyclability.

  Since these resin compositions are inherently flammable, they require flame safety, that is, flame resistance, in addition to satisfying the general chemical and physical properties in a balanced manner when used as industrial materials. Often done. In particular, in many cases used for home appliances including flexible printed wiring boards, high flame retardancy such as “V-0 by UL standard” is required. In general, as a method of imparting flame retardancy to a resin, a method of adding a halogen-based organic compound as a flame retardant and further adding an antimony compound as a flame retardant assistant to the resin can be mentioned. However, it is also pointed out that this method generates corrosive halogen gas during combustion. Therefore, in recent years, in order to eliminate the adverse effects of these halogen-based flame retardants on the environment, it has been strongly desired to use a halogen-free flame retardant that does not contain halogen at all.

As for halogen-free flame retardant formulations, for example, the incorporation of phosphorus-based flame retardants and nitrogen-based flame retardants, introduction into the molecules of phosphorus-based compounds, and the like are known (see, for example, Patent Document 1). However, in order to impart flame retardancy with these additives, it must be blended in a large amount in the resin, not only the resin properties such as adhesiveness, heat resistance, solder resistance, etc., but also the flame retardant bleeds. The problem that goes out also arises.
JP 2001-2931 A JP 2002-332332 A

  The present invention relates to an adhesive, and for that purpose, adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, adhesion to glass, heat resistance, moisture resistance, shelf life, The object is to provide a non-halogen flame retardant adhesive having excellent migration resistance and the like.

（式中、Ｒは−（ＣＨ₂）_nＣＯＯＨ、或いはＲは−（ＣＨ₂）_nＯＨであり、ｎは１≦ｎ≦２０を示す。）
式（II）；

The inventors have excellent adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, adhesion to glass, heat resistance, moisture resistance, shelf life, migration resistance, etc. As a result of intensive studies to obtain an adhesive, the present invention has been achieved. That is, according to the present invention, in the adhesive composition comprising the polyester (A), the epoxy compound (B), and the curing catalyst (C), the polyester (A) is represented by the formula (I) and the formula (II). It is related with the adhesive composition characterized by containing a component as a copolymerization component, and a flexible printed wiring board using the same.
Formula (I);

(In the formula, R is — (CH ₂ ) _n COOH, or R is — (CH ₂ ) _n OH, and n represents 1 ≦ n ≦ 20.)
Formula (II);

  The present invention is a non-halogen resistant material that has excellent adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, adhesion to glass, heat resistance, moisture resistance, shelf life, migration resistance, etc. A flammable adhesive can be provided.

The adhesive composition of the present invention contains at least a polyester (A), an epoxy compound (B), and a curing catalyst (C).
The polyester (A) used as a constituent component of the adhesive composition of the present invention can be obtained by copolymerizing the component represented by the formula (I) into an acid component and / or an alcohol component. The amount of copolymerization at that time is preferably 3 mol% or more when the total acid component and the total alcohol component are each 100 mol%.
The polyester (A) is preferably copolymerized with a component represented by the formula (II). The amount of copolymerization is preferably 5 mol% or more in the acid component. Furthermore, it is preferable that the number average molecular weights of polyester (A) are 5000-50000.
When the component represented by the formula (I) in the polyester (A) is less than 3 mol% in the acid component and / or alcohol component, the number of functional groups in the polyester (A) that reacts with the epoxy compound (B) is Therefore, sufficient crosslinking density may not be obtained, and sufficient heat resistance may not be obtained. In order to obtain a sufficient crosslinking density, the amount is preferably 6 mol% or more. Moreover, when the compound represented by the formula (II) is less than 5 mol% in the acid component, sufficient flame retardancy satisfying high flame retardancy such as “V-0 by UL standard” is obtained. There is a risk of not. In order to obtain sufficient flame retardancy, it is preferably at least 10 mol%, more preferably at least 15 mol%. Moreover, when the polyester (A) has a number average molecular weight lower than 5000, the mechanical properties as an adhesive may be insufficient and sufficient adhesiveness and heat resistance may not be obtained. When the number average molecular weight is higher than 50000, when the adhesive is used after being dissolved in a solvent, the solution viscosity becomes too high, and there may be a problem that it cannot be actually used.

  As a method for copolymerizing the component of the formula (II) with the polyester (A), a conventionally known method can be used. For example, the component of formula (II) may be used as it is for esterification (exchange) reaction to carry out polycondensation, or esterified products of the formula (II) component such as ethylene glycol may be used. The acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide may be separately charged into the reaction system, and the Michael addition reaction may be simultaneously performed during the esterification (exchange) reaction.

  Examples of the acid component of the polyester (A) include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyldicarboxylic acid. Aromatic dibasic acids such as 4,4′-diphenyl ether dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, Examples include aliphatic or alicyclic dibasic acids such as 4-methyl-1,2-cyclohexanedicarboxylic acid and dimer acid, and aromatic tribasic acids such as trimellitic anhydride.

  Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1, 3-pentanediol, 1,4-cyclohexanedimethanol, neopentylhydroxypivalate, bisphenol A ethylene oxide adduct and propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct and propylene Oxado adduct, 1,9-nonanedio , 2-methyl-octanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecanedimethanol, and the like.

  Examples of the compound represented by the formula (I) include bis (2-carboxymethyl) isocyanurate, bis (2-carboxyethyl) isocyanurate, bis (2-hydroxymethyl) isocyanurate, and bis (2-hydroxyethyl) isocyanate. Examples include nurate.

Examples of the method for determining the composition of the polyester resin (A) used in the present invention include ¹ H-NMR and ¹³ C-NMR in which the polyester resin is dissolved in a solvent such as chloroform D, and measurement is performed after methanolysis of the polyester resin. Examples include quantification by gas chromatography. Of these, ¹ H-NMR is convenient and preferred.

  Specific examples of the epoxy compound (B) used in the adhesive composition of the present invention include glycidyl ether types such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolac glycidyl ether, and brominated bisphenol A diglycidyl ether. Glycidyl ester types such as glycidyl hexahydrophthalate and dimer acid glycidyl ester, glycidyl amine such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, or 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, large epoxidation Examples include alicyclic or aliphatic epoxides such as bean oil.

  Examples of the epoxy curing catalyst (C) used in the adhesive composition of the present invention include imidazole compounds, tertiary amines, triphenylphosphine, and cationic catalysts. It is preferable from the viewpoint.

  In addition, additives such as silane coupling agents and leveling agents, compounding agents such as silica, melamine cyanurate, melamine polyphosphate, melam polyphosphate, phosphazene compounds, aluminum hydroxide, magnesium hydroxide, etc. A flame retardant can be blended.

  The adhesive composition of the present invention is preferably used for flexible printed wiring board applications. For example, it is suitable as an adhesive that bonds a base material such as polyimide and copper foil, and an adhesive that bonds a cover film such as a polyimide film on a circuit surface to a flexible printed wiring board that has been processed by etching.

  Hereinafter, the present invention will be specifically illustrated by examples. In the examples, “parts” means “parts by weight”.

Synthesis example 1 of polyester (A)
In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 41.5 parts of terephthalic acid, 41.5 parts of isophthalic acid, 41.6 parts of itaconic acid, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide 64.8 parts, ethylene glycol 62.0 parts, 3methyl-1,5-pentanediol 118.0 parts, n-tributylamine 0.19 parts, antioxidant IRGANOX 1330 (Ciba 0.3 parts of Specialty Chemicals Co., Ltd.) was added, the temperature was gradually raised to 230 ° C. over 4 hours, and the esterification reaction was carried out while removing the distilled water out of the system. Subsequently, the mixture is cooled to 200 ° C., charged with 49.1 parts of bis (2-carboxyethyl) isocyanurate and 0.45 part of titanium tetrabutoxide and gradually raised to 220 ° C. over 2 hours. The esterification reaction was carried out while removing it outside the system. Subsequently, this was subjected to reduced pressure initial polymerization to 10 mmHg over 30 minutes and the temperature was raised to 240 ° C., and then the latter polymerization was performed at 1 mmHg or less for 40 minutes to obtain polyester. The characteristic values of the polyester thus obtained are shown in Table 1.
Each measurement evaluation item followed the following method.

(1) Measurement of reduced viscosity 0.1 g of polyester was dissolved in 25 cc of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscometer.
The unit is indicated by dl / g.
(2) Measurement of glass transition temperature It measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC).
(3) Measurement of Acid Value 0.2 g of polyester was dissolved in 20 ml of chloroform, and titrated with a 0.1N KOH ethanol solution to obtain the equivalent (equivalent / t) per ton of resin.

Polyester (A) Synthesis Example 2
In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 54.8 parts of terephthalic acid, 54.8 parts of isophthalic acid, 24.6 parts of bis (2-carboxyethyl) isocyanurate, ethylene glycol 26.8 parts, 3methyl-1,5 pentanediol 118.9 parts, and titanium tetrabutoxide 0.1 part were charged and gradually raised to 230 ° C. over 4 hours, while removing distilled water out of the system. An esterification reaction was performed. Subsequently, the mixture was cooled to 200 ° C., and 173.0 parts of a solution (formula (II) / ethylene glycol = 50/50 solid weight ratio (GHM manufactured by Sanko Co., Ltd.)) obtained by esterifying formula (II) with ethylene glycol was added. This was stirred and stirred at 220 ° C. for 5 minutes, and then the initial polymerization under reduced pressure was performed to 10 mmHg over 30 minutes, the temperature was raised to 240 ° C., and the latter polymerization was further performed at 1 mmHg or less for 40 minutes to obtain a polyester. The characteristic values of the polyester thus obtained are shown in Table 1.

Synthesis example 3 of polyester (A)
In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 16.6 parts of terephthalic acid, 66.4 parts of isophthalic acid, 41.6 parts of itaconic acid, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide 64.8 parts, ethylene glycol 62.0 parts, 1,9-nonanediol 160.0 parts, n-tributylamine 0.19 parts, antioxidant IRGANOX 1330 (Ciba Specialty 0.3 parts (made by Chemicals Co., Ltd.) was charged, and it raised gradually to 230 degreeC over 4 hours, and esterified by removing the distilled water out of the system. Subsequently, the mixture was cooled to 200 ° C., charged with 49.1 parts of bis (2-carboxyethyl) isocyanurate, 0.45 part of titanium tetrabutoxide, and 0.1 part of phenothiazine, and gradually increased to 220 ° C. over 2 hours. The esterification reaction was conducted while removing distilled water out of the system. Subsequently, this was subjected to reduced pressure initial polymerization to 10 mmHg over 30 minutes and the temperature was increased to 240 ° C., and further late polymerization was performed at 1 mmHg or less for 40 minutes. After returning to normal pressure, the mixture was then cooled to 200 ° C. in a nitrogen stream, 1.92 parts of trimellitic anhydride was added, and the mixture was stirred at 200 ° C. for 30 minutes to acid-modify the polyester terminal. . The characteristic values of the polyester thus obtained are shown in Table 1.

Polyester (A) Comparative Synthesis Example 1
In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, terephthalic acid 49.8, isophthalic acid part 93.0 parts, bis (2-carboxyethyl) isocyanurate 38.2 parts, ethylene glycol 62 0.03 parts, 3methyl-1,5-pentanediol (118.0 parts) and titanium tetrabutoxide (0.1 parts) were charged, and the temperature was gradually raised to 230 ° C. over 4 hours. The reaction was carried out. Subsequently, under reduced pressure initial polymerization was carried out to 10 mmHg over 30 minutes, the temperature was raised to 240 ° C., and further late polymerization was conducted at 1 mmHg or less for 40 minutes to obtain a polyester. The characteristic values of the polyester thus obtained are shown in Table 1.

Polyester (A) Comparative Synthesis Example 2
In a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 56.4 parts terephthalic acid, 56.4 parts isophthalic acid, 41.6 parts itaconic acid, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide 64.8 parts, ethylene glycol 62.0 parts, 3methyl-1,5-pentanediol 118.0 parts, n-tributylamine 0.19 parts, antioxidant IRGANOX 1330 (Ciba 0.3 parts of Specialty Chemicals Co., Ltd.) was added, the temperature was gradually raised to 230 ° C. over 4 hours, and the esterification reaction was carried out while removing the distilled water out of the system. Subsequently, the mixture was cooled to 200 ° C., charged with 0.45 part of titanium tetrabutoxide, stirred at 220 ° C. for 5 minutes, subjected to reduced pressure initial polymerization to 10 mmHg over 30 minutes, and the temperature was raised to 240 ° C. Late polymerization was carried out at 1 mmHg or less for 40 minutes to obtain a polyester. The characteristic values of the polyester thus obtained are shown in Table 1.

Example 1
Method for producing patterned copper-clad laminate As a 100 part polyester obtained in Polyester (A) Synthesis Example 1 and an epoxy compound (B), HP7200H (dicyclopentadiene) manufactured by Dainippon Ink & Chemicals, Inc. Type epoxy resin) was dissolved in 16 parts using methyl ethyl ketone so that the solid concentration would be 30%. Subsequently, 30 parts of aluminum hydroxide (Hijilite H-42M manufactured by Showa Denko KK) was added and dispersed. To this solution, 0.3 part of Soroku Kasei Kogyo Co., Ltd. Curazole 1B2PZ was added as a curing catalyst (C) and sufficiently stirred to obtain a desired adhesive solution.

The adhesive solution was applied to a 25 μm polyimide film so that the thickness after drying was 30 μm, and dried at 120 ° C. for 5 minutes. When the adhesive film thus obtained was bonded to a 30 μm rolled copper foil, the acid-treated surface of the rolled copper foil was in contact with the adhesive so that the temperature was 140 ° C., the pressure was 3 kg / cm ² , and the roll speed was 5 m. Bonding by roll lamination was performed under the conditions of / min. The obtained adhesion sample was cured by heat treatment at 150 ° C. In this way, a copper-clad laminate was obtained. This copper-clad laminate was patterned on the copper foil surface by conventional methods, such as photoresist coating, pattern exposure, development, copper foil pattern etching, and photoresist stripping process, so that the distance between copper wires was 0.1 mm. A copper-clad laminate was created.

Production method of flexible printed wiring board cover film Polyester (A) HP7200H (dicyclopentadiene type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.) using 100 parts of the polyester obtained in Synthesis Example 1 and epoxy compound (B) 16 parts) was dissolved with methyl ethyl ketone so that the solid concentration would be 30%. Subsequently, 20 parts of melam polyphosphate (PMP-200 manufactured by Nissan Chemical Co., Ltd.) was added and dispersed.

  To this solution, 0.3 part of UCAT-5002 manufactured by San Apro Co., Ltd. was added as a curing catalyst (C) and sufficiently stirred to obtain the intended adhesive solution. The adhesive solution was applied to a 25 μm polyimide film so that the thickness after drying was 30 μm, and dried at 120 ° C. for 5 times to obtain a flexible printed wiring board cover film.

Flexible printed wiring board production method The patterned copper-clad laminate and flexible printed wiring board cover film obtained by the above production method are bonded together by vacuum pressing at a temperature of 120 ° C. and a pressing pressure of 5 kg / cm ^{2 for} 30 seconds. It was. This sample was heat-treated at 150 ° C. for 4 hours to obtain the desired flexible printed wiring board. The flexible printed wiring board thus obtained was evaluated as follows.

Migration resistance test (conditions) Temperature 85 ° C, humidity 85%, DC 100V, 1000 hours (determination) ○: No short circuit, no discoloration ×: Short circuit or discoloration

Solder resistance test (conditions)
Normal state: The sample was dried at 120 ° C. for 30 minutes, and then immersed in a solder bath at 300 ° C. for 30 seconds with the cover film face up, and the presence or absence of swelling was observed.
Humidification: The sample was allowed to stand at 40 ° C. and 80% humidification for 2 days and then floated in a 260 ° C. solder bath for 30 seconds with the cover film face up, and the presence or absence of swelling was observed.
(Judgment) ○: No abnormality
×: Fully swollen

Peel strength test (conditions)
In an atmosphere of 25 ° C. and 100 ° C., a 90 ° peel test between a copper-clad laminate and a cover film patterned with a sample width of 1 cm and a tensile speed of 100 mm / min was performed.

Shelf life test (conditions)
The flexible printed wiring board cover film obtained as described above is allowed to stand in an atmosphere of 20 ° C. for 6 months, and the flexible printed wiring board cover film is bonded to the patterned copper-clad laminate by the above method, and similarly migration resistant. The test of solder resistance and peel strength was conducted in the same manner.
(Judgment)
Compare the initial evaluation result with the evaluation result after being left at 20 ° C for 6 months,
○: No degradation in performance ×: Table 4 shows the results of this performance degradation.

Flame retardant test (conditions)
An adhesive composition is applied to a 25 μm polyimide film so that the thickness after drying is 30 μm, dried at 120 ° C. for 5 minutes, and then heat-treated at 150 ° C. for 4 hours to cure the sample. did. This was evaluated using a test piece having a length of 125 mm and a width of 12.5 mm based on Subject No. 94 (UL94) standardized by US Underwriters Laboratories (UL).
(Decision) ○: Passed in flame retardant class V-0
X: What did not pass

Example 2
As shown in Table 2, the polyester resin obtained in Synthesis Example 2 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Example 3
As shown in Table 2, the polyester resin obtained in Synthesis Example 3 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Example 4
As shown in Table 2, the polyester resin obtained in Synthesis Example 1 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Example 5
As shown in Table 2, the polyester resin obtained in Synthesis Example 2 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Example 6
As shown in Table 2, the polyester resin obtained in Synthesis Example 3 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Example 7
As shown in Table 2, the polyester resin obtained in Synthesis Example 3 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 4.

Comparative Example 1
As shown in Table 3, the polyester resin obtained in Comparative Synthesis Example 1 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 5.
In Comparative Example 1, the polyester of Comparative Synthesis Example 1 is used for the polyester (A), and this polyester does not contain the compound represented by the formula (II) and is inferior in flame retardancy.

Comparative Example 2
As shown in Table 3, the polyester resin obtained in Comparative Synthesis Example 2 was blended in the same manner as in Example 1 to prepare a sample. Each evaluation of the obtained sample was performed in the same manner as in Example 1. The test results are shown in Table 5.
Comparative Example 2 uses the polyester of Comparative Synthesis Example 2 for polyester (A), and this polyester does not contain the compound represented by formula (I) and lacks crosslinkability. Inferior in adhesion, adhesion and solder resistance.

Comparative Example 3
Nippon Zeon Co., Ltd. Nipol 1072J 25 parts, Nippon Kayaku Co., Ltd. BREN-S 20 parts, Toto Kasei Co., Ltd. YDB400 20 parts, Toto Kasei Co., Ltd. YD014 30 parts, benzophenone tetracarboxylic 5 parts of acid dianhydride, 4 parts of Rikasid TMTA-C manufactured by Shin Nippon Rika Co., Ltd., 0.5 part of C ₁₁ Z-AZINE manufactured by Shikoku Fine Chemicals Co., Ltd. 2PHZ-CN 0 manufactured by Shikoku Fine Chemicals Co., Ltd. .5 parts and 30 parts of aluminum hydroxide (Hijilite H-42M manufactured by Showa Denko KK) were dissolved using methyl ethyl ketone so that the solid concentration was 40% to obtain an adhesive solution. A test was conducted in the same manner as in Example 1 using the adhesive solution thus obtained. The test results are shown in Table 5. Comparative Example 3 is an adhesive composition using a halogen-containing epoxy generally used conventionally, and the adhesive composition of the present invention is non-halo flame retardant while being equivalent to or more than a conventional halogen adhesive. It can be said that it has the performance of.

YDCN703: Toto Kasei Co., Ltd. o-cresol novolak type epoxy resin EXA-4850-1000: Dainippon Ink and Chemicals, Inc. FX-289B: Toto Kasei Co., Ltd. Phosphorus-containing epoxy resin
TETRAD-X: N, N, N ′, N′-tetraglycidyl m-xylenediamine UCAT5002 manufactured by Mitsubishi Gas Chemical Co., Ltd. 1,8-diazabicyclo (5,4,0) -U manufactured by San Apro Co., Ltd. Ndecene-7 tetraphenylborate salt EH-30: 2,4,6-tri (dimethylaminomethyl) manufactured by Cognis Japan Co., Ltd. Phenol MC-640: Nissan Chemical Co., Ltd. melamine cyanurate SP703: Shikoku Chemicals Industrial Co., Ltd. Phosphorus Flame Retardant CoatOSil 1770: β- (3,4 Epoxycyclohexyl) ethyltriethoxysilane

  The present invention is a non-halogen resistant material that has excellent adhesion to various plastic films, adhesion to metals such as copper, aluminum and stainless steel, adhesion to glass, heat resistance, moisture resistance, shelf life, migration resistance, etc. A flammable adhesive can be provided.

Claims (6)

In the adhesive composition comprising the polyester (A), the epoxy compound (B), and the curing catalyst (C), the component in which the polyester (A) is represented by the formulas (I) and (II) is used as a copolymerization component. An adhesive composition characterized by containing.
Formula (I);

(In the formula, R is — (CH ₂ ) _n COOH, or R is — (CH ₂ ) _n OH, and n represents 1 ≦ n ≦ 20.)
Formula (II);

  2. The adhesive composition according to claim 1, wherein the component represented by the formula (I) of the polyester (A) is contained in an amount of 3 mol% or more in the acid component and / or the alcohol component.   The adhesive composition according to claim 1 or 2, wherein the component represented by the formula (II) of the polyester (A) is contained in an acid component in an amount of 5 mol% or more.   The number average molecular weight of polyester (A) is 5000-50000, The adhesive composition in any one of Claims 1-3 characterized by the above-mentioned.   The adhesive composition according to claim 1, wherein the curing catalyst (C) is an amine catalyst.   The flexible printed wiring board which has a layer structure which bonded together the plastic film layer and the metal layer using the adhesive composition in any one of Claims 1-5.