WO2015151960A1 - プリント配線板用接着剤組成物、積層板およびフレキシブルプリント配線板 - Google Patents
プリント配線板用接着剤組成物、積層板およびフレキシブルプリント配線板 Download PDFInfo
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- WO2015151960A1 WO2015151960A1 PCT/JP2015/059127 JP2015059127W WO2015151960A1 WO 2015151960 A1 WO2015151960 A1 WO 2015151960A1 JP 2015059127 W JP2015059127 W JP 2015059127W WO 2015151960 A1 WO2015151960 A1 WO 2015151960A1
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- printed wiring
- adhesive composition
- wiring board
- component
- acid
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- 0 *C1CC2(*)OC2(*)CC1 Chemical compound *C1CC2(*)OC2(*)CC1 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
Definitions
- 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.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- acrylic films are being used as plastic films that are base materials.
- an epoxy resin adhesive having a good adhesive property 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.
- 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.
- 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.
- a circuit is formed from a laminated board for printed wiring board.
- an etching solution is used to partially remove the metal foil layer.
- the adhesive must satisfy not only adhesiveness but also chemical resistance in addition to low-temperature curability and colorless transparency.
- 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%.
- Patent Document 2 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. .
- Patent Document 1 describes that the adhesive is cured by heating at a temperature of 80 to 180 ° C. for 1 to 30 hours.
- 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.
- the composition of patent document 2 shows the outstanding transparency and adhesiveness compared with the conventional adhesive agent for printed wiring boards.
- aromatic amine curing agents or phenol resin curing agents are used as curing agents. Amine curing agents tend to cause coloration.
- 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.
- 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.
- the printed wiring board adhesive composition includes an alicyclic epoxy compound (A), a hydride of an ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin (B), and an elastomer (C).
- the hydride (B) of the ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin has an acid value of 300 to 350 mgKOH / g and is 50 parts by weight based on 100 parts by weight of the alicyclic epoxy compound (A).
- the elastomer (C) is an adhesive composition for printed wiring boards having a glass transition temperature of ⁇ 35 ° C. to 5 ° C. and a Hazen unit color number of 300 or less.
- the laminate according to one aspect of the present invention is a laminate in which a plastic film and an adhesive layer for a printed wiring board including the above-mentioned adhesive composition for a printed wiring board are provided on the plastic film.
- a flexible printed wiring board according to an aspect of the present invention is a flexible printed wiring board provided with the above laminated board.
- the adhesive composition of the present embodiment comprises an alicyclic epoxy compound (A) (hereinafter also referred to as component (A)), an ⁇ , ⁇ -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.
- component (A) an alicyclic epoxy compound (hereinafter also referred to as component (A)
- component (B) an ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin having an acid value of 300 to 350 mgKOH / g Hydride
- component (C) elastomer having a glass transition temperature of ⁇ 35 ° C. to
- 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.
- 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 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.
- R 1 to R 4 each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- ALK represents an alkylene group having 1 to 4 carbon atoms
- 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
- 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 Methyl (3,4-epoxy-3-methyl)
- component (A) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (commercially available as “Celoxide 2021P” in terms 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 ( RENESSENZ) is preferred.
- 3,4-epoxy) cyclohexanecarboxylate commercially available as “Celoxide 2021P” in terms 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),
- epoxy resins may be used in combination with the component (A) without departing from the purpose and effect of the present embodiment.
- 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).
- Component (B) is a hydride obtained by further subjecting a raw material rosin to an addition reaction of an ⁇ , ⁇ -unsaturated dicarboxylic acid with a hydrogenation treatment.
- Component (B) is isolated from (I) Diels-Alder reaction product of ⁇ , ⁇ -unsaturated dicarboxylic acids and rosins, or (II) isolated from 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.
- rosins examples 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.
- 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 ⁇ , ⁇ -unsaturated dicarboxylic acid include maleic anhydride, maleic acid, fumaric acid and the like.
- ⁇ , ⁇ -unsaturated dicarboxylic acid is preferably maleic anhydride from the viewpoint of reaction stability and yield.
- the amount of ⁇ , ⁇ -unsaturated dicarboxylic acid used is usually 15 parts by weight or more based on 100 parts by weight of rosins from the viewpoint of solubility of the obtained component (B) in an organic solvent, preferably 17.5 parts by weight or more.
- the amount of ⁇ , ⁇ -unsaturated dicarboxylic acid used is usually 25 parts by weight or less, preferably 23.5 parts by weight or less.
- the conditions for reacting rosins with ⁇ , ⁇ -unsaturated dicarboxylic acids are not particularly limited.
- the reaction between rosins and ⁇ , ⁇ -unsaturated dicarboxylic acid is usually performed by adding ⁇ , ⁇ -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 ⁇ , ⁇ -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.
- 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 ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin may contain a resin acid derived from a raw material.
- 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.
- the hydrogenation catalyst examples 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 ⁇ , ⁇ -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 ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin.
- an organic solvent may be used as a solvent as necessary.
- it is preferable that the obtained component (B) is refine
- Resin acid derived from raw material rosin such as abietic acid is simultaneously hydrogenated by hydrogenation treatment. Thereby, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, etc. are produced
- component (B) contains 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 shall apply 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).
- Component (B) may be blended in an amount of 50 parts by weight or more, preferably 60 parts by weight or more, based on 100 parts by weight of component (A). 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.
- 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.
- 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.
- Component (C) is not particularly limited as long as it has a glass transition temperature (in accordance with JIS K-7244-1) of ⁇ 35 ° C. to 5 ° C.
- the glass transition temperature may be ⁇ 35 ° C. or higher, preferably ⁇ 30 ° C. or higher, more preferably ⁇ 25 ° C. or higher.
- the glass transition temperature may be 5 ° C. or lower, preferably ⁇ 5 ° C. or lower, more preferably ⁇ 15 ° C. or lower.
- the adhesive composition tends to have poor chemical resistance during the etching process.
- a glass transition temperature exceeds 5 degreeC the softness
- the color tone of the component (C) may be as long as the Hazen unit color number is 300 or less, preferably 200 or less, more preferably 150 or less, from the viewpoint of the transparency of the resulting adhesive layer.
- the component (C) showing the glass transition temperature may be, for example, an acrylic elastomer or a polyurethane elastomer.
- component (C) When component (C) is an acrylic elastomer, 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, ⁇ - 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.
- the component (C) comprises an epoxy group-containing monomer (C1) as a main component of an acrylate ester or an ⁇ -substituted acrylate ester (c1) (hereinafter referred to as component (c1)).
- 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)).
- 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).
- component (c3) examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and the like which do not have a hydroxyl group other than the components (c1) to (c2).
- component (c4) there are many other components (c1) to (c3) such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. 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.
- other vinyl monomers such as vinyl chloride, vinylidene chloride, styrene, acrylonitrile, vinyl acetate and the like may be copolymerized.
- acrylic elastomer of component (C) to be obtained polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyoctyl acrylate, methyl acrylate-styrene copolymer, acrylic Examples thereof include polyacrylate copolymers such as methyl acrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile-acrylic acid copolymer, and butyl acrylate-ethyl acrylate-acrylonitrile copolymer.
- 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 commercially available products include “Taisan Resin SG-70L” and “Taisan Resin WS-023 EK30” (manufactured by Nagase ChemteX Corporation).
- such a 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).
- content of a component (C) is less than 200 weight part, there exists a tendency for adhesiveness to fall adhesive composition.
- 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 component (C) is not particularly limited.
- the number average molecular weight of the component (C) is about 150,000 to 300,000.
- component (C) is a polyurethane elastomer
- 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)).
- 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 groups such as versatic acid glycid
- 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.
- isophorone diisocyanate is preferable from the viewpoint of colorless transparency of the adhesive layer.
- other diisocyanates may be used in combination as long as they do not depart from the purpose and effect of the present embodiment.
- 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.
- 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.
- a chain elongation 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-
- Illustrative examples include imidazoles such as 4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like.
- component (C) an organic solvent (D) described later (hereinafter also referred to as component (D)) may be used without any particular limitation.
- Component (C) can be produced by, for example, the following two methods.
- Method 1 Two-step method: A polyol and an excess of a 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.
- component (C) obtained examples include polycarbonate polyurethane, polyether polyester polyurethane, polyether carbonate polyurethane, polycaprolactone polyurethane, aliphatic polyurethane, and aromatic polyurethane.
- a component (C) is polyether polyester polyurethane.
- commercially available polyether polyester polyurethanes include “TAJ-642” (manufactured by Arakawa Chemical Industries, Ltd.).
- such a component (C) is preferably contained in an amount of 200 parts by weight or more, more preferably 230 parts by weight or more with respect to the component (A). It is more preferable. Moreover, it is preferable that such a component (C) is contained so that it may become 750 weight part or less with respect to a component (A), and it is more preferable that it is contained so that it may become 710 weight part or less.
- 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.
- 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.
- 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).
- 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.
- 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.
- 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.
- 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).
- Epoxy curing acceleration is preferably used at a ratio of about 0.05 to 5% by weight with respect to the total amount of component (A) and component (B).
- a mold release agent 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.
- the adhesive composition of the present embodiment includes component (A) (alicyclic epoxy compound (A)), component (B) ( ⁇ , ⁇ -unsaturated dicarboxylic acid having an acid value of 300 to 350 mgKOH / g.
- component (B) alicyclic epoxy compound (A)
- component (B) ⁇ , ⁇ -unsaturated dicarboxylic acid having an acid value of 300 to 350 mgKOH / g.
- the acid-modified rosin hydride (B)) and the component (C) glass transition temperature of ⁇ 35 ° C. to 5 ° C. and Hazen unit color number of 300 or less, respectively
- Such an adhesive composition simultaneously satisfies low-temperature curability, colorless transparency, adhesiveness, and chemical resistance as compared with the conventional adhesive composition for printed wiring boards.
- the adhesive composition is suitable for flexible printed wiring boards for display and optical applications, and more specifically, the adhesive composition is for touch panel substrates, electronic paper substrates, and flexible displays. Suitable for substrates, reflective films, metal mesh films, etc. In addition, the adhesive composition is also suitable for IC cards and IC tag substrates, laminates for electromagnetic wave shields, and the like.
- Adhesive sheets and laminates for printed wiring boards 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.
- the plastic film is not particularly limited, and any known film can be used without limitation depending on the application.
- Specific examples of the plastic film include polyester films such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), acrylic films, and cycloolefin polymer films.
- PEN polyethylene naphthalate
- PET polyethylene terephthalate
- acrylic films acrylic films
- cycloolefin polymer films 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 method for producing the adhesive sheet is not particularly limited.
- the adhesive sheet is formed by, for example, applying the adhesive composition for printed wiring boards of the above-described embodiment on a plastic film as a base material so that the film thickness upon curing is about 5 to 50 ⁇ m. It can be produced by pre-drying at about 120 ° C. for about 30 seconds to 5 minutes.
- 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.
- 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.
- the metal foil may be laminated on a printed wiring board adhesive layer (laminate method), vapor-deposited (vapor deposition method), or sputtered (sputter method).
- a laminated board 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, in the laminated board for a printed wiring board, the printed wiring board adhesive layer 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 ones 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.
- 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.
- An ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin comprising an alicyclic epoxy compound (A), a hydride (B) of an ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin, and an elastomer (C)
- 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 based on 100 parts by weight of the alicyclic epoxy compound (A).
- An adhesive composition for printed wiring boards having a glass transition temperature of ⁇ 35 ° C. to 5 ° C. and a Hazen unit color number of 300 or less.
- the elastomer (C) is an acrylic elastomer and is a polyacrylic ester 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).
- the alicyclic epoxy compound (A) includes at least one of an epoxycyclohexane compound represented by the following general formula (1) and a caprolactone adduct thereof: (1) to (4)
- the ⁇ , ⁇ -unsaturated dicarboxylic acid-modified rosin hydride (B) is at least one selected from the group consisting of maleic anhydride, maleic acid and fumaric acid, (1) to (6)
- a laminate comprising a plastic film and an adhesive layer for printed wiring board comprising the adhesive composition for printed wiring board according to any one of (1) to (10) provided on the plastic film .
- a flexible printed wiring board comprising the laminate according to any one of (11) to (13).
- ⁇ Curing agent> Component (B): hydride (B) of ⁇ , ⁇ -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 tone: Hazen unit color number 150)
- Rikacid Liquid alicyclic acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Rikacid
- ⁇ 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 (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 Corp., 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 °
- 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. Thereafter, xylene was distilled off to obtain B-1. Table 1 shows the physical properties of B-1.
- 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.
- Example 2 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.
- peel strength For the peel strength, the peel strength between the copper foil and the plastic film was measured according to 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.
- 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.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
以下、本発明のプリント配線板用接着剤組成物(以下、接着剤組成物ともいう)の一実施形態について説明する。本実施形態の接着剤組成物は、脂環式エポキシ化合物(A)(以下、成分(A)ともいう)、酸価が300~350mgKOH/gである、α,β-不飽和ジカルボン酸変性ロジンの水素化物(B)(以下、成分(B)ともいう)、およびガラス転移温度が-35℃~5℃であり、ハーゼン単位色数が300以下であるエラストマー(C)(以下、成分(C)ともいう)をそれぞれ特定量含有する。以下、それぞれについて説明する。
成分(A)は、格別限定なく、各種公知のものを使用できる。一例を挙げると、成分(A)は、無色透明性、低温硬化性および耐薬品性の点から、下記一般式(1)で表されるエポキシシクロヘキサン化合物、または、そのカプロラクトン付加物の少なくもいずれか一方である。
成分(B)は、原料のロジン類にα,β-不飽和ジカルボン酸を付加反応させたものをさらに水素化処理した水素化物である。成分(B)は、(I)α,β-不飽和ジカルボン酸類とロジン類とのディールス・アルダー反応物を水素化する方法や、(II)当該ディールス・アルダー反応物から公知の方法で単離した変性樹脂酸(米国特許2628226号参照)を水素化する方法、(III)ロジン類から公知の方法で単離したレボピマル酸(J.Am.Chem.Soc.70,334(1948)参照)とα,β-不飽和ジカルボン酸類とのディールス・アルダー反応物を水素化する方法等によって得られ得る。これらの中でも、方法(I)が、工業的には簡便な方法である。
成分(C)は、硬化後の接着剤層に柔軟性を付与するとともに、ポリエステルなどのプラスチックフィルムとの接着性も高める目的で使用される。
(方法1)二段法:ポリオールと過剰のジイソシアネート化合物とを、温度70~150℃程度、3~10時間程度反応させて、高分子ポリオールの末端にイソシアネート基を有するプレポリマーを調製し、次いでこれを適当な溶媒中で鎖伸長剤および必要により鎖長停止剤と反応させる方法。
(方法2)一段法:ポリオール、ジイソシアネート化合物、鎖伸長剤および必要により鎖長停止剤を一度に反応させる方法。
これらの中でも、均一なポリマー溶液を得るには、方法1が好ましい。
以下、本発明の積層板の一実施形態として、接着剤シートおよびプリント配線板用積層板について説明する。本実施形態の接着剤シート(積層板の一例)は、プラスチックフィルムと、プラスチックフィルム上に、上記した実施形態のプリント配線板用接着剤組成物を含むプリント配線板用接着剤層が設けられた、接着剤シートである。
以下、本発明のフレキシブルプリント配線板の一実施形態について説明する。本実施形態のフレキシブルプリント配線板は、上記したプリント配線板用積層板(積層板の一例)を備える。フレキシブルプリント配線板は、たとえばプリント配線板用積層板の金属箔面を、エッチング処理により部分除去し、回路を形成したものである。このようなフレキシブルプリント配線板は、タッチパネル用基板、電子ペーパー用基板、フレキシブルディスプレイ用基板等のディスプレイ用基板として好適に利用できる。
<エポキシ樹脂>
(成分(A):脂環式エポキシ化合物(A))
A-1:3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート((株)ダイセル製、商品名「セロキサイド2021P」 構造は以下に示される)
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)
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」)
(成分(B):酸価が300~350mgKOH/gであるα,β-不飽和ジカルボン酸変性ロジンの水素化物(B))
B-1:マレイン化ロジン水素化物(酸価:330mgKOH/g、色調:ハーゼン単位色数150)
B-2:マレイン化ロジン水素化物(酸価:316mgKOH/g、色調:ハーゼン単位色数150)
(その他の硬化剤)
B-3:マレイン化ロジン水素化物(酸価:358mgKOH/g、色調:ハーゼン単位色数200)
B-4:マレイン化ロジン水素化物(酸価:270mgKOH/g、色調:ハーゼン単位色数150)
リカシッド:液状脂環式酸無水物(新日本理化(株)製、商品名「リカシッド MH-700」、色調:ハーゼン単位色数50)
タマノル:フェノールノボラック樹脂(荒川化学工業(株)製、商品名「タマノル759」、色調:ガードナー色数3)
b2:調製例1の工程2で得られたマレイン化ロジン
ガスカミン:メタキシレンジアミンとスチレンの付加反応物(三菱ガス化学(株)製、商品名「ガスカミン240」、色調:ハーゼン単位色数500)
(成分(C):ガラス転移温度が-35~5℃であり、ハーゼン単位色数が300以下であるエラストマー(C))
C-1:ポリエーテルポリエステルポリウレタン(荒川化学工業(株)製、商品名「TAJ-642」、固形分35%(酢酸エチル/IPA)、ガラス転移温度:-25℃、色調:ハーゼン単位色数150))
C-2:アクリル酸エステル共重合体(ナガセケムテックス(株)製、商品名「テイサンレジンSG-70L」、濃度12.5%、ガラス転移温度:-17℃、色調:ハーゼン単位色数50)
C-3:アクリル酸エステル共重合体(ナガセケムテックス(株)製、商品名「テイサンレジンWS-023 EK30」、濃度30%、ガラス転移温度:-10℃、色調:ハーゼン単位色数200)
(その他のエラストマー)
E-1:ポリエーテルポリエステルポリウレタン(荒川化学工業(株)製、商品名「TSP-2548」、固形分30%(酢酸エチル/IPA)、ガラス転移温度:-30℃、色調:ガードナー色数3)
E-2:ポリエーテルポリウレタン(荒川化学工業(株)製、商品名「PU-419L」、固形分30%(メチルエチルケトン/IPA)、ガラス転移温度:-55℃、色調:ハーゼン単位色数150)
E-3:ポリエステルポリウレタン(荒川化学工業(株)製、商品名「PU-536」、固形分30%(トルエン/IPA)、ガラス転移温度:-40℃、色調:ハーゼン単位色数150)
E-4:アクリル酸エステル共重合体(ナガセケムテックス(株)製、商品名「テイサンレジンSG-P3」、濃度15%(MEK)、ガラス転移温度:15℃、色調:ハーゼン単位色数500)
E-5:アクリル酸エステル共重合体(ナガセケムテックス(株)製、商品名「テイサンレジンSG-600TEA」、濃度15%(トルエン/酢酸エチル)、ガラス転移温度:-37℃、色調:ハーゼン単位色数500)
E-6:アクリル酸エステル共重合体(ナガセケムテックス(株)製、商品名「テイサンレジンSG-708-6」、濃度20%(MEK)、ガラス転移温度:6℃、色調:ハーゼン単位色数500)
NBR:カルボキシNBR(JSR(株)製、商品名「XER-32C」、色調:ガードナー色数10)
上記した成分(B)(B-1~B-4)の調製方法を以下に示す。
(調製例1:B-1)
工程(1):精製
未精製のガムロジン(酸価171mgKOH/g、ガードナー色数6、中国産)を減圧蒸留容器に仕込み、窒素シール下に0.4kPaの減圧下で蒸留し、精製ロジン(b1)(酸価177mgKOH/g、ガードナー色数3)を得た。
次いで、別の減圧蒸留容器に精製ロジン(b1)700gと無水マレイン酸154gを仕込み、窒素気流下に攪拌しながら220℃で4時間反応させた後、4kPaの減圧下に未反応物を除去することによって、マレイン化ロジン(b2)(酸価335mgKOH/g、ガードナー色数8)を得た。
次いで、マレイン化ロジン(b2)500gと触媒として5%パラジウムカーボン(含水率50%)6.0gを1リットル回転式オートクレーブに仕込み、系内の酸素を除去した後、水素にて10MPaに加圧し、220℃まで昇温し、同温度で3時間水素化反応させることにより、粗ロジン生成物(b3)を得た。
次いで、粗ロジン生成物(b3)400gとキシレン200gを反応容器に仕込み、加熱下に溶解させた後、触媒ろ過を行った。その後、キシレンを留去することによって、B-1を得た。B-1の物性を表1に示す。
調製例1の工程(2)における無水マレイン酸の使用量を表1に示されるように変更した以外は調製例1と同様の方法により、B-2~B-4を得た。B-2~B-4の物性を表1に示す。
(実施例1)
エポキシ樹脂A-1を100.0g、硬化剤B-1を139.0g、エラストマーC-1を1604.0g(固形分:561.4g)およびメチルエチルケトンを139.0g加えて、均一に溶解して接着剤組成物を調製した。接着剤組成物中に存在するエポキシ基1当量に対して、エポキシ樹脂A-1中のカルボキシル基は1当量である。
使用したエポキシ樹脂、硬化剤およびエラストマーを表2に示されるものに変更した以外は、実施例1と同様の方法により、接着剤組成物を調製した。
実施例1~12および比較例1~20で得た接着剤組成物を50μmのポリエスエルフィルム(東洋紡(株)製 商品名「コスモシャインA4100」)にロールコーターで乾燥後の厚さが12μmになるように塗布し、90℃の乾燥機で3分間予備乾燥し、接着剤シートを得た。
実施例1~12および比較例1~20で得た接着剤組成物を使用して得た接着剤シートの接着剤層と、18μmの銅箔(古河サーキットフォイル(株)製 商品名「F2-WS」)の鏡面とを重ね合わせて100℃のラミネートロールで圧着した。その後、オーブンで60℃、4日間加熱し、接着剤層を硬化させてプリント配線板用積層板を得た。得られたプリント配線板用積層板の剥離強度、耐薬品性および透明性を以下の条件で測定した。結果を表2に示す。
剥離強度は、JIS C-6481に準拠して、銅箔とプラスチックフィルムとの剥離強度を測定した。数値が大きいほど、剥離強度は良好である。
(耐薬品性)
プリント配線板用積層板の試験片を室温にてエッチング液(塩化第二鉄40%水溶液)に1時間浸漬し、銅箔を溶解させた後、色差計でb*値を測定した。b*の数値が小さいほど、耐薬品性は高い。
(透明性)
プリント配線板用積層板の試験片を室温にて塩化第二鉄40%水溶液に1時間浸漬し、銅箔を溶解させた後、ヘイズメーターでヘイズ値(JIS K 7105に準拠)を測定した。数値が小さいほど、透明性は高い。
得られたプリント配線板用積層板ついて、銅箔の一部をエッチング液(塩化第二鉄40%水溶液)を用いたエッチング処理により除去して、ライン/スペース=50μm/50μmの銅回路を形成することにより、フレキシブルプリント配線板を作製し得ることを確認した。
Claims (14)
- 脂環式エポキシ化合物(A)と、α,β-不飽和ジカルボン酸変性ロジンの水素化物(B)と、エラストマー(C)とを含み、
前記α,β-不飽和ジカルボン酸変性ロジンの水素化物(B)は、酸価が300~350mgKOH/gであり、100重量部の前記脂環式エポキシ化合物(A)に対して50~220重量部含まれ、
前記エラストマー(C)は、
ガラス転移温度が-35℃~5℃であり、
ハーゼン単位色数が300以下である、プリント配線板用接着剤組成物。 - 前記エラストマー(C)は、アクリル系エラストマーであり、
ポリアクリル酸エステル系共重合体であり、
100重量部の前記脂環式エポキシ化合物(A)に対して200~750重量部含まれる、請求項1記載のプリント配線板用接着剤組成物。 - 前記エラストマー(C)は、ポリウレタンエラストマーであり、100重量部の前記脂環式エポキシ化合物(A)に対して200~750重量部含まれる、請求項1記載のプリント配線板用接着剤組成物。
- 前記ポリウレタンエラストマーは、ポリエーテルポリエステルポリウレタンである、請求項3記載のプリント配線板用接着剤組成物。
- 前記脂環式エポキシ化合物(A)は、3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、または、そのカプロラクトン付加物のうち少なくもいずれか一方を含む、請求項5記載のプリント配線板用接着剤組成物。
- 前記α,β-不飽和ジカルボン酸変性ロジンの水素化物(B)は、無水マレイン酸、マレイン酸およびフマル酸からなる群より選ばれる少なくとも1種である、請求項1~6のいずれか1項に記載のプリント配線板用接着剤組成物。
- 前記α,β-不飽和ジカルボン酸変性ロジンの水素化物(B)は、ハーゼン単位色数が200以下である、請求項1~7のいずれか1項に記載のプリント配線板用接着剤組成物。
- さらに、有機溶剤(D)を含む、請求項1~8のいずれか1項に記載のプリント配線板用接着剤組成物。
- 前記有機溶媒(D)は、沸点が120℃以下の有機溶剤である、請求項9記載のプリント配線板用接着剤組成物。
- プラスチックフィルムと、
前記プラスチックフィルム上に、請求項1~10のいずれか1項に記載のプリント配線板用接着剤組成物を含むプリント配線板用接着剤層が設けられた、積層板。 - 前記プリント配線板用接着剤層に、さらに金属箔が貼り合わされた、請求項11記載の積層板。
- プリント配線板用である、請求項11または12記載の積層板。
- 請求項11~13のいずれか1項に記載の積層板を備える、フレキシブルプリント配線板。
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WO2020157805A1 (ja) * | 2019-01-28 | 2020-08-06 | 日立化成株式会社 | 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法 |
JP2020145242A (ja) * | 2019-03-04 | 2020-09-10 | 太陽ホールディングス株式会社 | 硬化性樹脂組成物、ドライフィルム又はプリプレグ、硬化物、及び、配線板 |
EP3907252A1 (en) * | 2020-05-06 | 2021-11-10 | Henkel AG & Co. KGaA | Adhesive composition and cured product |
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CN106675489A (zh) * | 2016-10-26 | 2017-05-17 | 惠州市杜科新材料有限公司 | 一种用于玻璃、金属及塑料模内注射粘接的胶粘剂 |
CN108929403B (zh) * | 2017-05-25 | 2022-05-27 | 日油株式会社 | 粘结剂树脂、导电膏组合物、陶瓷用粘结剂树脂及陶瓷组合物 |
KR102444486B1 (ko) * | 2018-01-30 | 2022-09-19 | 쇼와덴코머티리얼즈가부시끼가이샤 | 접착제 조성물, 필름형 접착제, 접착 시트 및 반도체 장치의 제조 방법 |
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