JP6274306B2 - Adhesive composition for printed wiring board, laminate and flexible printed wiring board - Google Patents

Description

  The present invention relates to an adhesive composition for a printed wiring board, a laminated board, and a printed wiring board. More specifically, the present invention is excellent in transparency, for example, an adhesive composition for a printed wiring board, a laminate and a laminate that can be suitably used as a display substrate such as a touch panel substrate, an electronic paper substrate, and a flexible display substrate. The present invention relates to a printed wiring board.

  A flexible printed wiring board is generally a laminated board for printed wiring boards in which a metal film such as copper foil is bonded to a plastic film made of polyimide, liquid crystal polymer or the like having excellent heat resistance and electrical insulation via an adhesive. Is being used. In recent years, flexible printed wiring boards have been used for display units such as displays, and are required to be colorless and transparent. In response to such market demand, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and colorless and transparent films such as acrylic films are being used as plastic films that are base materials.

  When bonding the plastic film and the metal foil, an epoxy resin adhesive having good adhesiveness is widely used. The adhesive is generally composed of an epoxy resin, a curing agent, and an elastomer, and is cured to give not only adhesiveness to the film but also flexibility. The adhesive is applied to a plastic film in the form of a liquid or varnish dissolved in an organic solvent, and then cured while volatilizing the organic solvent by heating. However, the above-described polyester film and acrylic film have poor heat resistance as compared with the polyimide film and liquid crystal polymer film, and it is necessary to cure the adhesive at a low temperature. Therefore, low temperature curability is required for the adhesive to be used. In order to cure the adhesive at a low temperature, an aliphatic amine or aromatic amine is used as the curing agent. However, when these amines are used, the adhesive layer is easily colored during curing.

  Moreover, in order to produce a flexible printed wiring board, a circuit is formed from the laminated board for printed wiring boards. At that time, an etching solution is used to partially remove the metal foil layer. In this case, if the low-temperature curing between the adhesive and the plastic film is insufficient, the uncured portion of the adhesive layer is colored by the etching solution. Therefore, the adhesive must satisfy not only adhesiveness but also chemical resistance in addition to low-temperature curability and colorless transparency.

  As a technique for solving these problems, Patent Document 1 includes a polyamide resin, a phenol resin, and an epoxy resin as adhesive components, and the haze of the flexible insulating film after removing the copper foil by etching is 5 to 5. A laminate for a flexible printed circuit board, which is 50%, has been proposed.

  In order to solve the above problems, Patent Document 2 by the present applicant discloses that a methoxy group-containing silane-modified epoxy resin, a carboxyl group, a glass transition point of 20 ° C. or less, and an acid value of 2 to 10 (mgKOH / g), an adhesive composition containing an acrylic polymer having a number average molecular weight of 150,000 to 300,000 (the polymer imparts adhesion and flexibility to the film) and a curing agent for epoxy resin has been proposed. .

JP 2003-309336 A JP 2007-332337 A

  Patent Document 1 describes that the adhesive is cured by heating at a temperature of 80 ° C. to 180 ° C. for 1 to 30 hours. However, the film to which the adhesive is applied is a polyimide film, and a colorless transparent film such as a polyester film or a polyacrylic film has not been studied. Moreover, the composition of patent document 2 shows the outstanding transparency and adhesiveness compared with the conventional adhesive agent for printed wiring boards. However, aromatic amine curing agents or phenol resin curing agents are used as curing agents. Amine curing agents tend to cause coloration. Moreover, the phenol resin-based curing agent needs to be cured for a long time at a high temperature of 100 ° C. or higher, and the low-temperature curability is not sufficient.

  The present invention has been made in view of the above-described conventional problems, and simultaneously satisfies low-temperature curability, colorless transparency, adhesiveness, and chemical resistance as compared with conventional adhesive compositions for printed wiring boards. An object is to provide an adhesive composition for a printed wiring board, a laminate using the adhesive composition for a printed wiring board, and a flexible printed wiring board.

  As a result of intensive studies, the present inventors have solved the above problems by using an adhesive composition containing specific amounts of a predetermined alicyclic epoxy compound, a rosin hydride, and an elastomer. The present invention was completed.

  That is, the printed wiring board adhesive composition according to one aspect of the present invention includes an alicyclic epoxy compound (A), a hydride of an α, β-unsaturated dicarboxylic acid-modified rosin (B), and an elastomer (C). The hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin has an acid value of 300 to 350 mgKOH / g, and is 50 per 100 parts by weight of the alicyclic epoxy compound (A). -220 weight part is contained, and the said elastomer (C) is the adhesive composition for printed wiring boards whose glass transition temperature is -35 degreeC-5 degreeC and whose Hazen unit color number is 300 or less.

  Moreover, the laminated board by 1 aspect of this invention is a laminated board by which the adhesive layer for printed wiring boards containing the said adhesive composition for printed wiring boards was provided on the said plastic film and the said plastic film.

  Furthermore, the flexible printed wiring board by 1 aspect of this invention is a flexible printed wiring board provided with the said laminated board.

[Adhesive composition for printed wiring board]
Hereinafter, an embodiment of the adhesive composition for printed wiring boards of the present invention (hereinafter also referred to as an adhesive composition) will be described. The adhesive composition of the present embodiment includes an alicyclic epoxy compound (A) (hereinafter also referred to as component (A)), an α, β-unsaturated dicarboxylic acid-modified rosin having an acid value of 300 to 350 mgKOH / g. Hydride (B) (hereinafter also referred to as component (B)), and elastomer (C) having a glass transition temperature of −35 ° C. to 5 ° C. and a Hazen unit color number of 300 or less (hereinafter referred to as component (C) )))) In a specific amount. Each will be described below.

（式中、Ｒ¹およびＲ²はそれぞれ水素原子または炭素数１〜４のアルキル基を示し、Ｘはエポキシ基含有置換基を示す）(Alicyclic epoxy compound (A))
As the component (A), various known ones can be used without any particular limitation. For example, the component (A) is an epoxycyclohexane compound represented by the following general formula (1) or at least any of its caprolactone adducts from the viewpoint of colorless transparency, low-temperature curability and chemical resistance. On the other hand.

(Wherein R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an epoxy group-containing substituent)

（式中、Ｒ¹〜Ｒ⁴はそれぞれ水素原子または炭素数１〜４のアルキル基を示し、ＡＬＫは炭素数１〜４のアルキレン基を示す）

（式中、Ｒ¹、Ｒ²、Ｒ⁵〜Ｒ⁷はそれぞれ水素原子または炭素数１〜４のアルキル基を示す）More specifically, the component (A) may be at least one of an epoxycyclohexane compound represented by the following general formula (2) or general formula (3) or a caprolactone adduct thereof.

(Wherein R ^{1 to} R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ALK represents an alkylene group having 1 to 4 carbon atoms)

(Wherein R ¹ , R ² and R ^{5 to} R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

  More specifically, component (A) is bis (3,4-epoxycyclohexyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate Bis (3,4-epoxycyclohexylmethyl) piperate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxycyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexyl Methyl (6-methyl-3,4-epoxy) cyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl (3,4-epoxy-2-methyl) cyclohexanecarboxylate; 3,4-epoxy-3- Methylcyclohexyl Tyr (3,4-epoxy-3-methyl) cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl (3,4-epoxy-5-methyl) cyclohexanecarboxylate and their caprolactone adducts, limonene di Examples thereof include oxide and vinylcyclohexene dioxide. Two or more of these may be used in combination. Any of these can be synthesized by a conventional method. Among these, component (A) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (as a commercial product, “Celoxide 2021P” from the viewpoint of colorless transparency, low-temperature curability and chemical resistance. ”(Manufactured by Daicel Corporation) or its caprolactone adduct (commercially available products are“ Celoxide 2081 ”,“ Celoxide 2083 ”(manufactured by Daicel Corporation) and limonene dioxide (commercially available products are“ Limonene Dioxide ”( RENESSENZ) is preferred.

  In addition, other epoxy resins may be used in combination with the component (A) without departing from the purpose and effect of the present embodiment. There are no particular limitations on the other epoxy resins, and various known ones can be used. Examples of the other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, glycidyl ether type epoxy resins such as brominated epoxy resins, and heterocyclic epoxy resins. Two or more of these may be used in combination. The amount of other epoxy resin used is not particularly limited. The other epoxy resin is usually used in an amount of less than 30% by weight based on the component (A).

(Hydride of α, β-unsaturated dicarboxylic acid modified rosin (B))
Component (B) is a hydride obtained by subjecting a raw material rosin to an addition reaction of an α, β-unsaturated dicarboxylic acid and further a hydrogenation treatment. Component (B) is isolated from (I) the Diels-Alder reaction product of α, β-unsaturated dicarboxylic acids and rosins, or (II) isolated from the Diels-Alder reaction product by a known method. A modified resin acid (see US Pat. No. 2,628,226), (III) levopimaric acid isolated from rosins by a known method (see J. Am. Chem. Soc. 70, 334 (1948)) and It can be obtained by a method of hydrogenating a Diels-Alder reaction product with an α, β-unsaturated dicarboxylic acid. Among these, the method (I) is an industrially simple method.

  Examples of rosins that are raw materials for the component (B) include gum rosin, wood rosin, tall oil rosin and the like. The method for purifying rosins is not particularly limited. From the color tone of the resulting adhesive composition, rosins that have been purified by a vacuum distillation method, a steam distillation method, an extraction method, a recrystallization method, or the like are preferably used.

  When purifying, an organic solvent is appropriately used. Specifically, the organic solvent includes aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as n-hexane, n-heptane and isooctane; cyclohexane and decalin And alicyclic hydrocarbons and the like. Two or more of these organic solvents may be used in combination.

  Examples of the α, β-unsaturated dicarboxylic acid include maleic anhydride, maleic acid, fumaric acid and the like. Among these, the α, β-unsaturated dicarboxylic acid is preferably maleic anhydride from the viewpoint of reaction stability and yield. The amount of α, β-unsaturated dicarboxylic acid used is usually 15 parts by weight or more, preferably 100 parts by weight of rosins, from the viewpoint of solubility of the obtained component (B) in an organic solvent. 17.5 parts by weight or more. The amount of α, β-unsaturated dicarboxylic acid used is usually 25 parts by weight or less, preferably 23.5 parts by weight or less.

  Conditions for reacting rosins with α, β-unsaturated dicarboxylic acids are not particularly limited. For example, the reaction between rosins and α, β-unsaturated dicarboxylic acid is usually performed by adding α, β-unsaturated dicarboxylic acid to the above ratio to rosins melted under heating. Conditions for reacting at a temperature of about 180 to 240 ° C. for about 1 to 9 hours are employed. The reaction between the rosin and the α, β-unsaturated dicarboxylic acid is preferably carried out while blowing an inert gas such as nitrogen into the sealed reaction system in order to improve the color tone of the adhesive composition. Is called. In the reaction, a known catalyst such as a Lewis acid such as zinc chloride, iron chloride or tin chloride, or a Bronsted acid such as paratoluenesulfonic acid or methanesulfonic acid may be used. The amount of these catalysts used is usually about 0.01 to 10% by weight based on rosins.

  The obtained α, β-unsaturated dicarboxylic acid-modified rosin may contain a raw material-derived resin acid. However, the content of the resin acid derived from the raw material is preferably 40 to 60% by weight from the viewpoint of solubility in an organic solvent.

  Component (B) can be obtained by hydrogenating the α, β-unsaturated dicarboxylic acid-modified rosin by various known methods. Specifically, in the hydrogenation treatment, α, β-unsaturated dicarboxylic acid-modified rosin is heated in the presence of a hydrogenation catalyst at a temperature of about 100 to 300 ° C. (preferably 150 to 260 ° C.) and a hydrogen pressure of 1 to 25 MPa. It is carried out by reacting at a degree (preferably 5 to 20 MPa). Examples of the hydrogenation catalyst include supported catalysts such as palladium carbon, rhodium carbon, ruthenium carbon and platinum carbon; metal powders such as nickel and platinum; iodides such as iodine and iron iodide. The amount of the hydrogenation catalyst used is usually 0.01% by weight or more, preferably 0.10% by weight or more based on the α, β-unsaturated dicarboxylic acid-modified rosin. The amount of the hydrogenation catalyst used is usually about 10.0% by weight or less, preferably 5.0% by weight or less based on the α, β-unsaturated dicarboxylic acid-modified rosin. In the hydrogenation treatment, an organic solvent may be used as a solvent as necessary. In addition, it is preferable that the obtained component (B) is refine | purified by the purification method of rosins mentioned above from the point of heat resistance and chemical-resistance improvement.

  By the hydrogenation treatment, the resin acid derived from the raw material rosin such as abietic acid is simultaneously hydrogenated. Thereby, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc. are produced | generated. Therefore, the obtained component (B) not only has a good color tone, but also increases the wettability of the adhesive composition to the adherend and the adhesiveness to the metal foil. Moreover, the adhesive composition using such a component (B) can form a colorless and transparent adhesive layer.

  In addition, the content of resin acid hydrides (dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc.) contained in component (B) is the total from the viewpoint of solubility in organic solvents and adhesion to metal foil. It is preferably 20 to 60% by weight.

  The color tone of the obtained component (B) is not particularly limited. The color tone of component (B) is preferably a Hazen unit color number (according to JIS K0071-1; the same applies hereinafter) of 200 or less, more preferably a Hazen unit color, from the viewpoint of the transparency of the resulting adhesive layer. The number is 150 or less.

  The acid value of component (B) is usually about 300 mgKOH / g or more, preferably 320 mgKOH / g or more. Moreover, the acid value of a component (B) is about 350 mgKOH / g or less normally, and it is preferable that it is 345 mgKOH / g or less. The acid value component (B) is easily soluble in various organic solvents. Moreover, the laminated board for printed wiring boards obtained using the adhesive composition of this embodiment is easy to improve chemical resistance. The acid value can be calculated by dissolving component (B) in a mixed solvent of acetone / potassium hydroxide and titrating a solution obtained by adding a small amount of a phenolphthalein solution with hydrochloric acid (JIS K- 0070).

  The compounding amount (in terms of solid content) of the component (B) may be 50 parts by weight or more with respect to 100 parts by weight of the component (A), and preferably 60 parts by weight or more. Moreover, the compounding quantity of a component (B) should just be 220 weight part or less with respect to 100 weight part of component (A), and it is preferable that it is 210 weight part or less. If it is out of the range, the component (A) or the component (B) remains in the adhesive layer after the crosslinking reaction, and the chemical resistance tends to be lowered. Moreover, the compounding quantity of a component (B) is the carboxy equivalent (total of a tertiary carboxy group and an anhydrous ring) in a component (B) with respect to 1 equivalent of epoxy groups which exist in a component (A), and, normally About 0.1 equivalent or more is preferable, and 0.5 equivalent or more is more preferable. Moreover, the compounding quantity of a component (B) has preferable about 2.0 equivalent or less with respect to 1 equivalent of epoxy groups which exist in a component (A), and 1.5 equivalent or less is more preferable.

(Elastomer (C))
The component (C) is used for the purpose of imparting flexibility to the cured adhesive layer and enhancing the adhesion to a plastic film such as polyester.

  The component (C) is not particularly limited as long as the glass transition temperature (based on JIS K-7244-1) is -35 ° C to 5 ° C. The glass transition temperature should just be -35 degreeC or more, Preferably it is -30 degreeC or more, More preferably, it is -25 degreeC or more. Moreover, the glass transition temperature should just be 5 degrees C or less, Preferably it is -5 degrees C or less, More preferably, it is -15 degrees C or less. When the glass transition temperature is less than -35 ° C, the adhesive composition tends to have poor chemical resistance during the etching process. Moreover, when a glass transition temperature exceeds 5 degreeC, the softness | flexibility of the adhesive bond layer after hardening and adhesiveness with a plastic film are easy to fall.

  Further, the color tone of component (C) may be as long as the Hazen unit color number is 300 or less, preferably 200 or less, and more preferably 150 or less, from the viewpoint of the transparency of the resulting adhesive layer.

  The component (C) exhibiting the glass transition temperature may be, for example, an acrylic elastomer or a polyurethane elastomer.

  When the component (C) is an acrylic elastomer, the component (C) has at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, and (1) an acrylate ester, α- A polymer comprising a substituted acrylate ester as a main component and containing at least one of the functional groups as a crosslinking point, or (2) a monomer having at least one monomer having the functional group as the main component And a graft polymerized polymer. Specifically, the component (C) is composed of an epoxy group-containing monomer (a monomer component (C1) (hereinafter referred to as the component (c1)) as a main component. c2) (hereinafter referred to as component (c2)), carboxyl group-containing monomer (c3) (hereinafter referred to as component (c3)), and hydroxyl group-containing monomer (c4) (hereinafter referred to as component (c4)). Examples thereof include those obtained by copolymerization of monomers having at least one functional group.

  Examples of the component (c1) include monomers having no epoxy group, carboxyl group and hydroxyl group, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and octyl acrylate. Examples of the component (c2) include glycidyl ethers such as vinyl glycidyl ether and allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and the like which do not have a carboxyl group and a hydroxyl group other than the component (c1). Examples of the component (c3) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and the like that do not have a hydroxyl group other than the components (c1) to (c2). As the component (c4), there are many other than components (c1) to (c3) such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and the like. Examples thereof include dimethacrylates of monohydric alcohols, alkoxy acrylates such as methoxymethyl acrylate, and the like. Two or more of these may be used in combination. Furthermore, if necessary, other vinyl monomers such as vinyl chloride, vinylidene chloride, styrene, acrylonitrile, vinyl acetate and the like may be copolymerized.

  Examples of the resulting component (C) acrylic elastomer include polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyoctyl acrylate, methyl acrylate-styrene copolymer, acrylic Examples thereof include polyacrylic acid ester copolymers such as methyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile-acrylic acid copolymer, and butyl acrylate-ethyl acrylate-acrylonitrile copolymer. Among these, the component (C) is preferably a butyl acrylate-ethyl acrylate-acrylonitrile copolymer so that the adhesive composition can be satisfactorily bonded to a plastic film or a metal foil. Examples of the commercially available products include “Taisan Resin SG-70L” and “Taisan Resin WS-023 EK30” (manufactured by Nagase ChemteX Corporation).

  When the component (C) is an acrylic elastomer, such a component (C) is preferably contained in an amount of 200 parts by weight or more, and 230 parts by weight or more with respect to 100 parts by weight of the component (A). It is more preferable that it is contained in. Further, such component (C) is preferably contained so as to be 750 parts by weight or less, more preferably 710 parts by weight or less, relative to 100 parts by weight of component (A). When content of a component (C) is less than 200 weight part, there exists a tendency for adhesiveness to fall adhesive composition. On the other hand, when the content of the component (C) exceeds 750 parts by weight, the chemical resistance of the adhesive composition tends to decrease.

  When the component (C) is an acrylic elastomer, the number average molecular weight of the component (C) is not particularly limited. As an example, the number average molecular weight of the component (C) is about 150,000 to 300,000.

  On the other hand, when the component (C) is a polyurethane elastomer, such a component (C) includes, for example, a high molecular weight polyol (c5) (hereinafter also referred to as component (c5)), a diisocyanate compound (c6) (hereinafter referred to as component). (Also referred to as (c6)) and a chain extender (c7) (hereinafter also referred to as component (c7)).

  Specifically, the component (c5) is a polyether polyol such as a polymer or copolymer such as ethylene oxide, propylene oxide, and tetrahydrofuran; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, diethylene glycol, triethylene glycol , Various known and unsaturated glycols such as dipropylene glycol, alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, and monocarboxylic acid glycides such as versatic acid glycidyl ester Diester diols obtained by reducing dimer acid, dimer acid, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, Polyester polyols obtained by dehydrating and condensing dibasic acids such as suberic acid, azelaic acid and sebacic acid, or the corresponding acid anhydrides and dimer acids; ring-opening polymerization of cyclic ester compounds such as ε-caprolactone Examples of polycaprolactone polyols obtained from the above; other known polymer polyols used in the production of polyurethane such as polycarbonate polyols, polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, etc. The The polyether polyester polyol can be obtained by addition polymerization of a polyester polyol with ethylene oxide, propylene oxide, tetrahydrofuran or the like.

  Specific examples of the component (c6) include aromatic, aliphatic and alicyclic diisocyanates. More specifically, component (c6) comprises 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate. Tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4 , 4-Trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophoro Diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, dimer diisocyanate and the like. Two or more of these may be used in appropriate combination. Among these, isophorone diisocyanate is preferable from the viewpoint of colorless transparency of the adhesive layer. In addition to these, other diisocyanates may be used in combination as long as they do not depart from the purpose and effect of the present embodiment. As other diisocyanates, various known ones can be used without any particular limitation. Other diisocyanates may be used in combination so as to be less than about 30% by weight with respect to component (c6), for example.

  Specific examples of the component (c7) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, dimeramineamine and other polyamines, 2-hydroxyethyl Diamines having a hydroxyl group in the molecule such as ethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, Furthermore, the said low molecular glycols etc. are illustrated. Two or more of these may be used in appropriate combination. Among these, isophoronediamine is preferable from the viewpoint of colorless transparency of the adhesive layer.

  As a raw material for the component (C), a chain extension terminator (c8) (hereinafter also referred to as component (c8)) is added to the reaction components (component (c5) to component (c7)) as necessary. Also good. Specific examples of the component (c8) include dialkylamines such as di-n-butylamine, dihydroxyalkylamines such as diethanolamine, alcohols such as ethanol and isopropyl alcohol, imidazole, 2-isopropylimidazole, 2-ethyl- Examples include imidazoles such as 4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like.

  In the production of the component (C), an organic solvent (D) described later (hereinafter also referred to as component (D)) may be used without any particular limitation.

It does not specifically limit as a manufacturing method of a component (C). Component (C) can be produced by, for example, the following two methods.
(Method 1) Two-stage method: A polyol and excess diisocyanate compound are reacted at a temperature of about 70 to 150 ° C. for about 3 to 10 hours to prepare a prepolymer having an isocyanate group at the terminal of the polymer polyol, A method of reacting this in a suitable solvent with a chain extender and optionally a chain length terminator.
(Method 2) One-step method: a method in which a polyol, a diisocyanate compound, a chain extender and, if necessary, a chain length terminator are reacted at once.
Among these, the method 1 is preferable for obtaining a uniform polymer solution.

  Examples of the component (C) to be obtained include polycarbonate polyurethane, polyether polyester polyurethane, polyether carbonate polyurethane, polycaprolactone polyurethane, aliphatic polyurethane, and aromatic polyurethane. Among these, since an adhesive composition can adhere | attach with a plastic film and metal foil favorably, it is preferable that a component (C) is polyether polyester polyurethane. As a commercial item of polyether polyester polyurethane, “TAJ-642” (manufactured by Arakawa Chemical Industries, Ltd.) and the like are exemplified.

When the component (C) is a polyurethane elastomer, such a component (C) is preferably contained so as to be 200 parts by weight or more with respect to 100 parts by weight of the component (A), and is 230 parts by weight or more. It is more preferable that it is contained in. Further, such component (C) is preferably contained so as to be 750 parts by weight or less, more preferably 710 parts by weight or less, relative to 100 parts by weight of component (A). When content of a component (C) is less than 200 weight part, there exists a tendency for adhesiveness to fall adhesive composition. On the other hand, when the content of the component (C) exceeds 750 parts by weight, the chemical resistance of the adhesive composition tends to decrease.

  The number average molecular weight of the obtained component (C) is preferably 7,500 or more, and more preferably 10,000 or more. The number average molecular weight of the component (C) is preferably 30,000 or less, and more preferably 25,000 or less. With such a number average molecular weight, the component (C) is easily compatible with the component (A) and the component (B), and the adhesive composition adheres to the plastic film or metal foil after being cured. Is easy to secure.

  In addition, a component (C) may be used together with another elastomer in the range which does not deviate from the objective and effect of this embodiment. As other elastomers, specifically, the above-mentioned acrylic polymer, acrylonitrile butadiene polymer, styrene butadiene polymer, butadiene methyl acrylate acrylonitrile polymer, butadiene polymer, carboxyl group-containing acrylonitrile butadiene polymer, vinyl group-containing acrylonitrile butadiene polymer, silicone polymer, Examples include polyvinyl butyral, polyester, and polyimide. Two or more of these may be used in combination. The amount of other elastomer used is usually less than about 30% by weight of component (C).

  Returning to the description of the entire adhesive composition, the adhesive composition of the present embodiment preferably contains an organic solvent (D) (hereinafter also referred to as component (D)) in order to be applied to a plastic film. Specific examples of the component (D) include alcohols such as methanol, ethanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dioxane and tetrahydrofuran; hexane, cyclohexane, Aliphatic hydrocarbons such as methylcyclohexane; Esters such as ethyl acetate and butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Non-protons such as dimethyl sulfoxide, N-methyl-2-pyrrolidone and dimethylformamide An example is a polar solvent. Two or more of these may be used in combination. Among these, in order to cure the adhesive at a low temperature using a film having poor heat resistance, the component (D) is preferably a low boiling organic solvent having a boiling point of 120 ° C. or lower. More specifically, component (D) is preferably methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, toluene or the like.

In the adhesive composition of the present embodiment, an epoxy curing accelerator may be appropriately added without departing from the purpose and effect of the present embodiment. Specific examples of the epoxy curing accelerator include 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl). ) Tertiary amines such as phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenyl Organic phosphines such as phosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenyl Tetraphenyl boron salts such rate and the like. Epoxy curing accelerator, based on the total amount of components (A) and (B), is preferably used in a proportion of about 0.05 to 5 wt%.

  In the adhesive composition of the present embodiment, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, and an antifungal agent as necessary, as long as the effects of the present embodiment are not impaired. An agent, a leveling agent, an antifoaming agent, a coloring agent, a stabilizer, a coupling agent and the like may be blended.

As described above, the adhesive composition of the present embodiment includes component (A) (alicyclic epoxy compound (A)) and component (B) (α, β-unsaturated dicarboxylic acid having an acid value of 300 to 350 mgKOH / g. Acid-modified rosin hydride (B)) and component (C) (elastomer (C) having a glass transition temperature of −35 ° C. to 5 ° C. and a Hazen unit color number of 300 or less ) are contained in specific amounts. . Such an adhesive composition simultaneously satisfies low-temperature curability, colorless transparency, adhesiveness and chemical resistance as compared with conventional adhesive compositions for printed wiring boards. Therefore, the adhesive composition of this embodiment is suitable for flexible printed wiring boards for display applications and optical applications. More specifically, the adhesive composition is suitable for a touch panel substrate, an electronic paper substrate, a flexible display substrate, a reflective film, a metal mesh film, and the like. In addition, the adhesive composition is also suitable for IC cards and IC tag substrates, electromagnetic wave shielding laminates, and the like.

[Adhesive sheets and laminates for printed wiring boards]
Hereinafter, an adhesive sheet and a laminate for a printed wiring board will be described as an embodiment of the laminate of the present invention. The adhesive sheet (an example of a laminated board) of this embodiment was provided with an adhesive layer for a printed wiring board containing the adhesive composition for a printed wiring board of the above-described embodiment on a plastic film and the plastic film. It is an adhesive sheet.

  It does not restrict | limit especially as a plastic film, According to a use, a well-known thing can be used without a restriction | limiting. Specific examples of the plastic film include polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), acrylic films, and cycloolefin polymer films. Among these, it is preferable that a plastic film is a polyester film from the balance of colorless transparency and chemical resistance. What is necessary is just to set the thickness of a plastic film suitably according to a use.

  The manufacturing method of an adhesive sheet is not specifically limited. The adhesive sheet is, for example, coated on the plastic film as the base material with the adhesive composition for a printed wiring board according to the above-described embodiment so that the film thickness upon curing is about 5 to 50 μm. It can be produced by pre-drying at about 120 ° C. for about 30 seconds to 5 minutes.

  Moreover, the adhesive sheet of this embodiment may be a laminated board in which a metal foil is further provided on the printed wiring board adhesive layer coated with the printed wiring board composition of the above-described embodiment. Such a laminated board is suitable as a laminated board for printed wiring boards. The method for providing the metal foil on the printed wiring board adhesive layer is not particularly limited. As an example, the metal foil may be laminated on a printed wiring board adhesive layer (laminate method), vapor-deposited (vapor deposition method), or sputtered (sputter method).

  When a metal foil is provided by a laminating method, a laminate for a printed wiring board is produced, for example, by superposing a metal foil on a printed wiring board adhesive layer and thermocompression bonding with a laminating roll heated to about 40 to 120 ° C. obtain. The laminated board for printed wiring boards of this embodiment has an adhesive layer made of the above resin composition. Therefore, the printed wiring board adhesive layer of the laminated board for printed wiring board can be cured at a low temperature in about 0.5 to 10 days at a temperature of about 40 to 70 ° C., for example.

  The metal foil is not particularly limited, and various known foils can be used. Specific examples of the metal foil include gold foil, ITO foil, silver foil, copper foil, nichrome foil, and aluminum foil. Among these, the metal foil is preferably a copper foil from the viewpoint of excellent conductivity and corrosion resistance in the use of the flexible printed wiring board.

  The laminate for a printed wiring board thus obtained has not only excellent adhesiveness but also chemical resistance, and further exhibits excellent permeability by partially removing the metal foil by etching treatment. It will be a thing.

[About flexible printed wiring boards]
Hereinafter, an embodiment of the flexible printed wiring board of the present invention will be described. The flexible printed wiring board of this embodiment includes the above-described laminated board for printed wiring board (an example of a laminated board). The flexible printed wiring board is obtained by, for example, partially removing the metal foil surface of the laminated board for printed wiring board by an etching process to form a circuit. Such a flexible printed wiring board can be suitably used as a display substrate such as a touch panel substrate, an electronic paper substrate, or a flexible display substrate.

  The embodiment of the present invention has been described above. The present invention is not particularly limited to the above embodiment. The above-described embodiments mainly describe the invention having the following configuration.

(1) An alicyclic epoxy compound (A), a hydride (B) of an α, β-unsaturated dicarboxylic acid-modified rosin, and an elastomer (C), the α, β-unsaturated dicarboxylic acid-modified rosin The hydride (B) has an acid value of 300 to 350 mgKOH / g and is contained in an amount of 50 to 220 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). The adhesive composition for printed wiring boards whose glass transition temperature is -35 degreeC-5 degreeC and whose Hazen unit color number is 300 or less.

(2) The elastomer (C) is an acrylic elastomer, is a polyacrylate copolymer, and is contained in an amount of 200 to 750 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). , (1) Symbol placement of the printed wiring board adhesive composition.

(3) The adhesive for printed wiring boards according to (1), wherein the elastomer (C) is a polyurethane elastomer and is contained in an amount of 200 to 750 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). Composition.

(4) The adhesive composition for printed wiring boards according to (3), wherein the polyurethane elastomer is a polyether polyester polyurethane.

（式中、Ｒ¹およびＲ²はそれぞれ水素原子または炭素数１〜４のアルキル基を示し、Ｘはエポキシ基含有置換基を示す）(5) The alicyclic epoxy compound (A) includes at least one of an epoxycyclohexane compound represented by the following general formula (1) or a caprolactone adduct thereof, (1) to (4) The adhesive composition for printed wiring boards according to any one of 1).

(Wherein R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an epoxy group-containing substituent)

(6) The alicyclic epoxy compound (A) contains at least one of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate or a caprolactone adduct thereof. ) Adhesive composition for printed wiring boards.

(7) The hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin is at least one selected from the group consisting of maleic anhydride, maleic acid and fumaric acid (1) to (6) The adhesive composition for printed wiring boards according to any one of the above.

(8) The adhesive for printed wiring boards according to any one of (1) to (7), wherein the hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin has a Hazen unit color number of 200 or less. Agent composition.

(9) The adhesive composition for printed wiring boards according to any one of (1) to (8), further comprising an organic solvent (D).

(10) The adhesive composition for printed wiring boards according to (9), wherein the organic solvent (D) is an organic solvent having a boiling point of 120 ° C. or lower.

(11) A laminate comprising a plastic film and an adhesive layer for a printed wiring board comprising the adhesive composition for a printed wiring board according to any one of (1) to (10) on the plastic film. .

(12) The laminated board according to (11), wherein a metal foil is further bonded to the adhesive layer for a printed wiring board.

(13) The laminated board according to (11) or (12), which is for a printed wiring board.

(14) A flexible printed wiring board comprising the laminate according to any one of (11) to (13).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

Ａ−２：Ａ−１のカプロラクトン付加物（（株）ダイセル製、商品名「セロキサイド２０８１」）
Ａ−３：リモネンジオキサイド（ＲＥＮＥＳＳＥＮＺ社製、商品名「リモネンジオキサイド」 構造は以下に示される）

（その他のエポキシ樹脂）
ＪＥＲ：ビスフェノールＡ型エポキシ樹脂（三菱化学（株）製、商品名「ＪＥＲ８２８」）
ＹＤＰＮ：フェノールノボラック型エポキシ樹脂（新日鐵住金（株）製、商品名「ＹＤＰＮ−６３８」）The raw materials used are shown below.
<Epoxy resin>
(Component (A): Alicyclic epoxy compound (A))
A-1: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (manufactured by Daicel Corporation, trade name “Celoxide 2021P” The structure is shown below)

A-2: Caprolactone adduct of A-1 (manufactured by Daicel Corporation, trade name “Celoxide 2081”)
A-3: Limonene dioxide (RENESSENZ, trade name “limonene dioxide” The structure is shown below)

(Other epoxy resins)
JER: Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, trade name “JER828”)
YDPN: phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “YDPN-638”)

<Curing agent>
(Component (B): hydride (B) of an α, β-unsaturated dicarboxylic acid-modified rosin having an acid value of 300 to 350 mgKOH / g)
B-1: Maleated rosin hydride (acid value: 330 mg KOH / g, color tone: Hazen unit color number 150)
B-2: Maleated rosin hydride (acid value: 316 mg KOH / g, color tone: Hazen unit color number 150)
(Other curing agents)
B-3: Maleated rosin hydride (acid value: 358 mg KOH / g, color tone: Hazen unit color number 200)
B-4: Maleated rosin hydride (acid value: 270 mg KOH / g, color: Hazen unit color number 150)
Rikacid: liquid alicyclic acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Rikacid MH-700”, color tone: Hazen unit color number 50)
Tamanol: phenol novolac resin (Arakawa Chemical Industries, trade name "Tamanol 759", color tone: Gardner color number 3)
b2: Maleinized rosin obtained in Step 2 of Preparation Example 1 Gascamine: Addition reaction product of metaxylenediamine and styrene (Mitsubishi Gas Chemical Co., Ltd., trade name “Gascamin 240”, color tone: Hazen unit color number 500)

<Elastomer>
(Component (C): Elastomer (C) having a glass transition temperature of −35 to 5 ° C. and a Hazen unit color number of 300 or less)
C-1: Polyether polyester polyurethane (manufactured by Arakawa Chemical Industries, Ltd., trade name “TAJ-642”, solid content 35% (ethyl acetate / IPA), glass transition temperature: −25 ° C., color tone: Hazen unit color number 150))
C-2: Acrylate ester copolymer (manufactured by Nagase ChemteX Corporation, trade name “Taisan Resin SG-70L”, concentration 12.5%, glass transition temperature: −17 ° C., color tone: Hazen unit color number 50 )
C-3: Acrylate ester copolymer (manufactured by Nagase ChemteX Corp., trade name “Taisan Resin WS-023 EK30”, concentration 30%, glass transition temperature: −10 ° C., color tone: Hazen unit color number 200)
(Other elastomers)
E-1: Polyether polyester polyurethane (manufactured by Arakawa Chemical Industries, Ltd., trade name “TSP-2548”, solid content 30% (ethyl acetate / IPA), glass transition temperature: −30 ° C., color tone: Gardner color number 3 )
E-2: Polyether polyurethane (trade name “PU-419L”, manufactured by Arakawa Chemical Industries, Ltd., solid content 30% (methyl ethyl ketone / IPA), glass transition temperature: −55 ° C., color tone: Hazen unit color number 150)
E-3: Polyester polyurethane (Arakawa Chemical Industries, Ltd., trade name “PU-536”, solid content 30% (toluene / IPA), glass transition temperature: −40 ° C., color tone: Hazen unit color number 150)
E-4: Acrylate ester copolymer (manufactured by Nagase ChemteX Corp., trade name “Taisan Resin SG-P3”, concentration 15% (MEK), glass transition temperature: 15 ° C., color tone: Hazen unit color number 500 )
E-5: Acrylate ester copolymer (manufactured by Nagase ChemteX Corporation, trade name “Taisan Resin SG-600TEA”, concentration 15% (toluene / ethyl acetate), glass transition temperature: −37 ° C., color tone: Hazen Number of unit colors 500)
E-6: Acrylate ester copolymer (manufactured by Nagase ChemteX Corp., trade name “Taisan Resin SG-708-6”, concentration 20% (MEK), glass transition temperature: 6 ° C., color tone: Hazen unit color Number 500)
NBR: Carboxy NBR (manufactured by JSR Corporation, trade name “XER-32C”, color tone: Gardner color number 10)

<Preparation of component (B)>
The preparation method of above-described component (B) (B-1 to B-4) is shown below.
(Preparation Example 1: B-1)
Step (1): Purification An unpurified gum rosin (acid value 171 mg KOH / g, Gardner color number 6, produced in China) is charged into a vacuum distillation vessel, distilled under a vacuum of 0.4 kPa under a nitrogen seal, and purified rosin (b1 ) (Acid value 177 mg KOH / g, Gardner color number 3).

Step (2): Diels-Alder Reaction Next, 700 g of purified rosin (b1) and 154 g of maleic anhydride were charged into another vacuum distillation vessel and reacted at 220 ° C. for 4 hours with stirring under a nitrogen stream. By removing unreacted substances under reduced pressure, maleated rosin (b2) (acid value 335 mgKOH / g, Gardner color number 8) was obtained.

Step (3): Hydrogenation Reaction Next, 500 g of maleated rosin (b2) and 6.0 g of 5% palladium carbon (water content 50%) as a catalyst were charged into a 1 liter rotary autoclave and oxygen in the system was removed. The crude rosin product (b3) was obtained by pressurizing to 10 MPa with hydrogen, raising the temperature to 220 ° C., and performing a hydrogenation reaction at the same temperature for 3 hours.

Step (4): Purification Next, 400 g of the crude rosin product (b3) and 200 g of xylene were charged into a reaction vessel and dissolved under heating, followed by catalyst filtration. Then, B-1 was obtained by distilling off xylene. Table 1 shows the physical properties of B-1.

(Preparation Examples 2 to 4: B-2 to B-4)
B-2 to B-4 were obtained in the same manner as in Preparation Example 1, except that the amount of maleic anhydride used in Step (2) of Preparation Example 1 was changed as shown in Table 1. Table 1 shows the physical properties of B-2 to B-4.

<Manufacture of adhesive composition>
Example 1
Add 100.0 g of epoxy resin A-1, 139.0 g of curing agent B-1, 1604.0 g of elastomer C-1 (solid content: 561.4 g) and 139.0 g of methyl ethyl ketone, and dissolve uniformly. An adhesive composition was prepared. The carboxyl group in the epoxy resin A-1 is 1 equivalent with respect to 1 equivalent of the epoxy group present in the adhesive composition.

(Examples 2 to 12, Comparative Examples 1 to 20)
An adhesive composition was prepared in the same manner as in Example 1 except that the epoxy resin, curing agent and elastomer used were changed to those shown in Table 2.

<Manufacture of adhesive sheet>
The adhesive compositions obtained in Examples 1-12 and Comparative Examples 1-20 were applied to a 50 μm polyester film (trade name “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) with a roll coater to a thickness of 12 μm after drying. Then, it was preliminarily dried for 3 minutes with a 90 ° C. dryer to obtain an adhesive sheet.

<Manufacture of laminated boards for printed wiring boards>
Adhesive layers of adhesive sheets obtained by using the adhesive compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 20, and 18 μm copper foil (trade name “F2− manufactured by Furukawa Circuit Foil Co., Ltd.) The mirror surface of WS ") was superposed and pressure-bonded with a laminating roll at 100 ° C. Then, it heated at 60 degreeC for 4 days in oven, the adhesive bond layer was hardened, and the laminated board for printed wiring boards was obtained. The peel strength, chemical resistance, and transparency of the obtained printed wiring board laminate were measured under the following conditions. The results are shown in Table 2.

(Peel strength)
The peel strength measured the peel strength between the copper foil and the plastic film in accordance with JIS C-6481. The larger the value, the better the peel strength.
(chemical resistance)
The test piece of the laminated board for printed wiring boards was immersed in an etching solution (40% aqueous ferric chloride solution) at room temperature for 1 hour to dissolve the copper foil, and then the b * value was measured with a color difference meter. The smaller the value of b *, the higher the chemical resistance.
(transparency)
The test piece of the laminated board for printed wiring boards was immersed in a 40% ferric chloride aqueous solution at room temperature for 1 hour to dissolve the copper foil, and then the haze value (conforming to JIS K 7105) was measured with a haze meter. The smaller the value, the higher the transparency.

  As shown in Table 2, it was found that the adhesive compositions of Examples 1 to 12 were cured under a low temperature condition of 60 ° C. for 4 days. Moreover, it turned out that the laminated board for printed wiring boards obtained using the adhesive composition of Examples 1-12 is excellent not only in peeling strength but in the chemical resistance and transparency of an adhesive bond layer.

<Production of flexible printed wiring board>
About the obtained laminated board for printed wiring boards, a part of the copper foil is removed by an etching process using an etching solution (40% ferric chloride aqueous solution) to form a copper circuit of line / space = 50 μm / 50 μm. As a result, it was confirmed that a flexible printed wiring board could be produced.

Claims (14)

An alicyclic epoxy compound (A), a hydride (B) of an α, β-unsaturated dicarboxylic acid-modified rosin, and an elastomer (C),
The hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin has an acid value of 300 to 350 mgKOH / g, and 50 to 220 weight with respect to 100 parts by weight of the alicyclic epoxy compound (A). Part included,
The elastomer (C) is
The glass transition temperature is -35 ° C to 5 ° C,
The adhesive composition for printed wiring boards whose Hazen unit color number is 300 or less. The elastomer (C) is an acrylic elastomer,
A polyacrylate copolymer,
The adhesive composition for printed wiring boards according to claim 1, which is contained in an amount of 200 to 750 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A).   The said elastomer (C) is a polyurethane elastomer, The adhesive composition for printed wiring boards of Claim 1 contained by 200-750 weight part with respect to 100 weight part of said alicyclic epoxy compounds (A).   The adhesive composition for printed wiring boards according to claim 3, wherein the polyurethane elastomer is polyether polyester polyurethane. The alicyclic epoxy compound (A) includes at least one of an epoxycyclohexane compound represented by the following general formula (1) or a caprolactone adduct thereof. The adhesive composition for printed wiring boards as described in the paragraph.

(Wherein R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an epoxy group-containing substituent)   The said alicyclic epoxy compound (A) contains 3, 4- epoxy cyclohexyl methyl (3,4- epoxy) cyclohexane carboxylate or at least any one among the caprolactone adducts of Claim 5. An adhesive composition for printed wiring boards. The α, β-unsaturated dicarboxylic acid used to obtain the hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin is at least one selected from the group consisting of maleic anhydride, maleic acid and fumaric acid. The adhesive composition for printed wiring boards according to any one of claims 1 to 6, which is a seed.   The adhesive composition for printed wiring boards according to any one of claims 1 to 7, wherein the hydride (B) of the α, β-unsaturated dicarboxylic acid-modified rosin has a Hazen unit color number of 200 or less. .   Furthermore, the adhesive composition for printed wiring boards of any one of Claims 1-8 containing an organic solvent (D).   The said organic solvent (D) is an adhesive composition for printed wiring boards of Claim 9 which is an organic solvent whose boiling point is 120 degrees C or less. Plastic film,
The laminated board in which the adhesive layer for printed wiring boards containing the adhesive composition for printed wiring boards of any one of Claims 1-10 was provided on the said plastic film.   The laminate according to claim 11, wherein a metal foil is further bonded to the adhesive layer for a printed wiring board.   The laminated board according to claim 11 or 12, which is for a printed wiring board.   A flexible printed wiring board provided with the laminated board of any one of Claims 11-13.