WO2014147903A1 - Adhesive composition, and coverlay film and flexible copper-clad laminate using same - Google Patents

Adhesive composition, and coverlay film and flexible copper-clad laminate using same Download PDF

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Publication number
WO2014147903A1
WO2014147903A1 PCT/JP2013/083245 JP2013083245W WO2014147903A1 WO 2014147903 A1 WO2014147903 A1 WO 2014147903A1 JP 2013083245 W JP2013083245 W JP 2013083245W WO 2014147903 A1 WO2014147903 A1 WO 2014147903A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
styrene
film
epoxy resin
adhesive
Prior art date
Application number
PCT/JP2013/083245
Other languages
French (fr)
Japanese (ja)
Inventor
祐弥 沖村
成志 山田
Original Assignee
東亞合成株式会社
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Application filed by 東亞合成株式会社 filed Critical 東亞合成株式会社
Priority to JP2015506553A priority Critical patent/JPWO2014147903A1/en
Publication of WO2014147903A1 publication Critical patent/WO2014147903A1/en

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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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/748—Releasability
    • 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
    • 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
    • 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
    • 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
    • C09J2425/00—Presence of styrenic polymer
    • 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
    • C09J2453/00—Presence of block copolymer
    • 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
    • C09J2463/00—Presence of epoxy resin
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer

Definitions

  • the present invention relates to an adhesive composition which is excellent in adhesiveness and dielectric properties and suitable for the manufacture of electronic parts, particularly related products of flexible printed wiring boards (hereinafter also referred to as “FPC”).
  • the present invention also relates to a coverlay film, a flexible copper-clad laminate and a bonding sheet obtained using this adhesive composition.
  • the flexible printed wiring board can be mounted three-dimensionally and in a high density even in a limited space, its application is expanding.
  • related products for flexible printed wiring boards have been diversified, and the demand for such products has increased.
  • flexible copper-clad laminate in which copper foil is bonded to polyimide film flexible printed wiring board in which electronic circuit is formed on flexible copper-clad laminate, flexible printed wiring board and reinforcing plate are bonded together
  • a flexible printed wiring board with a reinforcing plate, a flexible copper-clad laminate, or a multilayer board in which flexible printed wiring boards are stacked and joined For example, when manufacturing a flexible copper-clad laminate, a polyimide film and a copper foil are bonded together. For this purpose, an adhesive is usually used.
  • cover lay film when manufacturing a flexible printed wiring board, a film called “cover lay film” is usually used to protect the wiring portion.
  • This coverlay film includes an insulating resin layer and an adhesive layer formed on the surface thereof, and a polyimide resin composition is widely used for forming the insulating resin layer.
  • a flexible printed wiring board is manufactured by affixing a coverlay film on the surface which has a wiring part using an adhesive layer through an adhesive layer, for example. At this time, the adhesive layer of the cover lay film needs to have strong adhesion to both the wiring portion and the film base layer.
  • the printed wiring board a build-up type multilayer printed wiring board in which conductor layers and organic insulating layers are alternately laminated on the surface of the substrate is known.
  • an insulating adhesive layer forming material called a “bonding sheet” is used to join the conductor layer and the organic insulating layer.
  • the insulating adhesive layer must have strong adhesiveness to both the wiring part and the constituent material (copper etc.) of the conductor forming the circuit and the organic insulating layer (polyimide resin etc.). is there.
  • Patent Document 1 discloses an ethylene-acrylic acid ester copolymer rubber / epoxy resin adhesive.
  • Patent Document 2 discloses a glycidyl group-containing thermoplastic elastomer / epoxy resin adhesive.
  • Patent Document 3 discloses a styrene-maleic acid copolymer / epoxy resin adhesive.
  • the adhesive composition described in these documents realizes a rapid curing reaction by utilizing the reactivity between the carboxyl group of the rubber or elastomer component and the epoxy resin, and is excellent in adhesiveness. Widely used.
  • Patent Document 4 discloses an epoxy resin composition containing an epoxy resin, a copolymer resin obtained by using an aromatic vinyl compound and maleic anhydride as essential components, and a specific phenol compound. It is disclosed.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an adhesive composition having good adhesion to an insulating film such as a polyimide film and having excellent dielectric properties.
  • an adhesive composition containing a carboxyl group-containing styrenic elastomer and an epoxy resin is excellent in adhesiveness and dielectric properties when the elastomer and the epoxy resin have a specific content.
  • the “adhesive layer” is applied when at least a part of the film including the carboxyl group-containing styrene elastomer (A) and the epoxy resin (B) begins to cure. It means a layer having a property that enables adhesion to the body or adhesion between at least two members made of the same material or different materials.
  • bonded part means a cured part made of a cured product formed after bonding, and “cured product” does not mean only complete curing, but at least partially has a crosslinked structure such as semi-cured. Including the state of having.
  • the adhesive composition according to the present invention is as follows. 1. An adhesive composition containing a carboxyl group-containing styrene elastomer (A) and an epoxy resin (B), wherein the content of the epoxy resin (B) is the carboxyl group-containing styrene elastomer (A) 100. An adhesive composition characterized by being 1 to 20 parts by mass relative to parts by mass and having a dielectric constant of a cured adhesive measured at a frequency of 1 GHz of less than 2.5. 2. 2. The adhesive composition according to 1 above, wherein the carboxyl group-containing styrene elastomer (A) has an acid value of 0.1 to 20 mg KOH / g. 3.
  • the carboxyl group-containing styrene elastomer (A) is a styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene. 1 or 2 above, wherein at least one styrene elastomer selected from the group consisting of ethylene-butylene-styrene block copolymer and styrene-ethylenepropylene-styrene block copolymer is modified with unsaturated carboxylic acid.
  • 6. A coverlay film, wherein an adhesive layer obtained by using the adhesive composition according to any one of 1 to 5 above is formed on one surface of a polyimide film or a liquid crystal polymer film. 7).
  • a flexible copper clad laminate comprising a copper foil bonded to at least one surface of a polyimide film or a liquid crystal polymer film using the adhesive composition according to any one of 1 to 5 above. 8).
  • 6. A bonding sheet, wherein an adhesive layer obtained by using the adhesive composition according to any one of 1 to 5 above is formed on one surface of a release film.
  • the adhesive composition of the present invention can form an adhesive part excellent in adhesiveness and dielectric properties to a flexible film such as a polyimide film.
  • the adhesive composition of the present invention has a good resin flow-out property during heat bonding. Therefore, the adhesive composition of this invention is suitable for manufacture of the related product of a flexible wiring board.
  • the adhesive composition of the present invention is an adhesive composition containing a predetermined amount of a carboxyl group-containing styrene elastomer (A) and an epoxy resin (B).
  • the carboxyl group in the carboxyl group-containing styrene-based elastomer reacts with the epoxy group in the epoxy resin (B) to develop adhesiveness and begin to form a cured product, High adhesion to the adherend can be obtained. Also, the heat resistance of the bonded portion can be obtained.
  • the components contained in the adhesive composition of the present invention will be specifically described.
  • the carboxyl group-containing styrenic elastomer (A) is one of the main components of the adhesive composition of the present invention. In addition to adhesiveness and flexibility of the cured product, dielectric It is a component that gives characteristics.
  • This carboxyl group-containing styrene-based elastomer is obtained by modifying a copolymer mainly composed of blocks and random structures of a conjugated diene compound and an aromatic vinyl compound, and a hydrogenated product thereof with an unsaturated carboxylic acid.
  • aromatic vinyl compound examples include styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene, p-tert-butylstyrene and the like.
  • conjugated diene compound examples include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
  • the modification of the carboxyl group-containing styrene elastomer (A) can be performed, for example, by copolymerizing an unsaturated carboxylic acid during the polymerization of the styrene elastomer. Moreover, it can also carry out by heating and kneading
  • the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride and the like.
  • the amount of modification with unsaturated carboxylic acid is usually 0.1 to 10% by mass.
  • the acid value of the carboxyl group-containing styrene elastomer (A) is preferably 0.1 to 20 mgKOH / g, more preferably 0.5 to 18 mgKOH / g, and 1.0 to 15 mgKOH / g. More preferably.
  • the acid value is less than 0.1 mgKOH / g, the adhesive composition may be insufficiently cured, and good adhesiveness, heat resistance, and resin flowability may not be obtained.
  • the acid value exceeds 20 mgKOH / g, the adhesive strength and the dielectric properties may be deteriorated.
  • the weight average molecular weight of the carboxyl group-containing styrene elastomer (A) is preferably 1 to 500,000, more preferably 3 to 300,000, and further preferably 50,000 to 200,000.
  • the weight average molecular weight is in the range of 1 to 500,000, excellent adhesion and dielectric properties can be exhibited.
  • the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as “GPC”) into polystyrene.
  • carboxyl group-containing styrene elastomer (A) examples include styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer.
  • examples thereof include a polymer, a styrene-ethylenebutylene-styrene block copolymer, a styrene-ethylenepropylene-styrene block copolymer, and the like modified with an unsaturated carboxylic acid.
  • a styrene-ethylenebutylene-styrene block copolymer and a styrene-ethylenepropylene-styrene block copolymer are preferable from the viewpoint of adhesiveness and dielectric properties.
  • the mass ratio of styrene / ethylenebutylene in the styrene-ethylenebutylene-styrene block copolymer and the mass ratio of styrene / ethylenepropylene in the styrene-ethylenepropylene-styrene block copolymer were 10/90 to 50/50. Preferably there is. If the said mass ratio is in this range, it can be set as the adhesive composition which has the outstanding dielectric characteristic.
  • the epoxy resin (B) used in the present invention plays a role for developing the heat resistance and high adhesiveness of the cured adhesive.
  • epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, or those hydrogenated to them; orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid Glycidyl ester epoxy resins such as glycidyl ester, tetrahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, trimellitic acid triglycidyl ester; ethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether, 1,4-butanediol diglycidyl ether,
  • epoxy resins include brominated bisphenol A type epoxy resins, phosphorus-containing epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, naphthalene skeleton-containing epoxy resins, anthracene type epoxy resins, tertiary butylcatechol type epoxy resins, triphenylmethane Type epoxy resin, tetraphenylethane type epoxy resin, biphenyl type epoxy resin, bisphenol S type epoxy resin and the like can be used.
  • an epoxy resin having an alicyclic skeleton such as dicyclopentadiene is preferable because an adhesive composition having excellent dielectric properties can be obtained.
  • the epoxy resin used in the present invention preferably has two or more epoxy groups in one molecule. This is because a cross-linked structure can be formed by reaction with the carboxyl group-containing styrene-based elastomer and high heat resistance can be expressed. When an epoxy resin having one epoxy group is used, sufficient heat resistance may not be obtained because the degree of crosslinking with the carboxyl group-containing styrene elastomer is low.
  • the content of the epoxy resin (B) needs to be 1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing styrene elastomer (A).
  • the content is preferably 3 to 15 parts by mass. If the content is less than 1 part by mass, sufficient adhesion and heat resistance may not be obtained. On the other hand, when the content exceeds 20 parts by mass, the peel adhesion strength may be lowered, or the dielectric constant of the cured product may be increased.
  • the adhesive composition according to the present invention contains a predetermined amount of carboxyl group-containing styrene elastomer (A) and epoxy resin (B), and the dielectric constant ( ⁇ ) of the cured adhesive measured at a frequency of 1 GHz is 2.5. It is characterized by being less than. If the said dielectric constant is less than 2.5, it is suitable for the utilization to the related product of a flexible printed wiring board.
  • the dielectric loss tangent (tan ⁇ ) of the cured adhesive product measured at a frequency of 1 GHz is preferably less than 0.01. If the said dielectric loss tangent is less than 0.01, the related product of the flexible printed wiring board which is excellent in a dielectric characteristic can be manufactured.
  • the dielectric constant and dielectric loss tangent can be adjusted according to the proportion of the carboxyl group-containing styrene elastomer (A) and epoxy resin (B) in the adhesive composition, adhesive compositions having various configurations can be used depending on the application. Can be set. In addition, the measuring method of a dielectric constant and a dielectric loss tangent is mentioned later.
  • the adhesive composition of the present invention is a thermoplastic resin other than the carboxyl group-containing styrene-based elastomer (A), a tackifier, Containing flame retardants, curing accelerators, coupling agents, heat aging inhibitors, leveling agents, antifoaming agents, inorganic fillers, pigments, solvents, etc. to the extent that they do not affect the function of the adhesive composition. Can do.
  • thermoplastic resins examples include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, and polyvinyl resins.
  • tackifiers examples include coumarone / indene resin, terpene resin, terpene / phenol resin, rosin resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, Examples thereof include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
  • the flame retardant may be either an organic flame retardant or an inorganic flame retardant.
  • the organic flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium amidophosphate, carbamate phosphate, and carbamate polyphosphate ,
  • inorganic flame retardant examples include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. Two or more of these flame retardants can be used in combination.
  • the curing accelerator is used for the purpose of accelerating the reaction between the carboxyl group-containing styrenic elastomer and the epoxy resin, and is a tertiary amine-based curing accelerator, a tertiary amine salt-based curing accelerator, and an imidazole system.
  • a curing accelerator or the like can be used.
  • Tertiary amine curing accelerators include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N'- Examples thereof include dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo [5.4.0] undecene.
  • Tertiary amine salt curing accelerators include formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenol of 1,8-diazabicyclo [5.4.0] undecene Examples include novolak resin salts and 1,5-diazabicyclo [4.3.0] nonene formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenol novolac resin salt. It is done.
  • imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-methyl
  • the content of the curing accelerator may be used in a range of 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B). preferable. Particularly preferred is a range of 2 to 5 parts by mass. When the content of the curing accelerator is in the range of 1 to 10 parts by mass, excellent adhesion and heat resistance are obtained.
  • the coupling agent examples include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltri
  • silane coupling agents such as ethoxysilane and imidazolesilane
  • titanate coupling agents such as ethoxysilane and imidazolesilane
  • aluminate coupling agents such as aluminate coupling agents
  • zirconium coupling agents these may be used alone or in
  • heat aging inhibitor examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propione.
  • -Phenolic antioxidants such as tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; dilauryl-3,3'-thiodipropionate Sulfur antioxidants such as dimyristyl-3,3′-dithiopropionate; phosphorus antioxidants such as trisnonylphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite It is done. These may be used alone or in combination of two or more.
  • examples of the inorganic filler include powders made of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, copper, silver, and the like. These may be used alone or in combination of two or more.
  • the adhesive composition of the present invention can be produced by mixing the carboxyl group-containing styrene elastomer (A), the epoxy resin (B) and other components. Since the adhesive composition of the present invention is preferably used in the state of a solution or a dispersion, a solvent is also usually used. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol.
  • the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and isophorone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene and mesitylene; methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, Esters such as 3-methoxybutyl acetate; hexane, heptane, cyclohexane, methylcyclohex Aliphatic hydrocarbons such as emissions and the like. These solvents may be used alone or in combination of two or more.
  • the adhesive composition of the present invention is a solution or dispersion containing a solvent, coating on an adherend and formation of an adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be easily formed. Can get to.
  • the solid content concentration is preferably in the range of 3 to 80% by mass, more preferably in the range of 10 to 50% by mass, from the viewpoint of workability including film-forming properties. is there. If the solid content concentration exceeds 80% by mass, the viscosity of the solution becomes too high, and it may be difficult to coat uniformly.
  • Suitable adherends using the adhesive composition of the present invention include polymer materials such as polyimide resins, polyether ether ketone resins, polyphenylene sulfide resins, aramid resins, and liquid crystal polymers; inorganic materials such as copper, aluminum, and stainless steel. Is an object.
  • the shape of the adherend is not particularly limited. And two members which consist of the same material or different materials as a to-be-adhered body are adhere
  • coverlay film of the present invention is characterized in that the adhesive layer obtained by using the adhesive composition of the present invention is formed on one surface of a polyimide film or a liquid crystal polymer film. . Since the adhesive composition of the present invention is particularly excellent in adhesiveness with a polyimide resin, the coverlay film of the present invention is a film in which it is difficult to peel off the adhesive layer and the polyimide film.
  • the structure of the polyimide film or the liquid crystal polymer film is not particularly limited as long as it has electrical insulation, and is a film made of only a polyimide resin or a liquid crystal polymer, or a film made of the resin and an additive. Surface treatment may be performed on the side on which the adhesive layer is formed.
  • the thickness of the polyimide film or liquid crystal polymer film is usually 10 to 125 ⁇ m.
  • the thickness of the adhesive layer is usually 5 to 45 ⁇ m, preferably 10 to 35 ⁇ m.
  • the cover lay film of the present invention for example, after coating the surface of a polyimide film with an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B) and solvent.
  • an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B) and solvent.
  • the heating temperature at the time of drying is preferably 40 ° C. to 250 ° C., more preferably 70 ° C. to 170 ° C.
  • a film-coated film is subjected to hot air drying, far infrared heating, high frequency induction heating, or the like. This is done by passing it through.
  • a release film may be laminated on the surface of the adhesive layer for storage or the like.
  • the release film known ones such as a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a silicone release treated paper, a polyolefin resin coated paper, a TPX film, and a fluorine resin film are used.
  • the flexible copper-clad laminate of the present invention is characterized in that a polyimide film or a liquid crystal polymer film and a copper foil are bonded together using the adhesive composition of the present invention. That is, the flexible copper-clad laminate of the present invention is composed of a polyimide film or a liquid crystal polymer film, an adhesive layer formed of an adhesive composition, and a copper foil in this order. The adhesive layer and the copper foil may be formed on both sides of the polyimide film or the liquid crystal polymer film. Since the adhesive composition of the present invention is excellent in adhesiveness with articles containing copper, the flexible copper-clad laminate of the present invention is excellent in stability as an integrated product.
  • the composition of the polyimide film or the liquid crystal polymer film can be the same as the polyimide film or the liquid crystal polymer film in the cover lay film of the present invention.
  • the adhesive layer it is preferable that most of the adhesive composition undergoes a crosslinking reaction to form a cured product.
  • the thickness of the adhesive layer is usually 5 to 45 ⁇ m, preferably 5 to 18 ⁇ m.
  • the said copper foil is not specifically limited, Electrolytic copper foil, rolled copper foil, etc. can be used.
  • an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B) and solvent is applied to the surface of a polyimide film. And then dried in the same manner as in the case of the cover lay film of the present invention, and then the surface of the coated film and the copper foil are brought into surface contact with each other, heat laminated at 80 ° C. to 150 ° C., and There is a method of curing the coating film by after cure.
  • the after-curing conditions can be, for example, 100 ° C. to 200 ° C., 30 minutes to 4 hours.
  • Bonding sheet The bonding sheet of the present invention is characterized in that an adhesive layer obtained by using the adhesive composition of the present invention is formed on the surface of a release film.
  • the aspect provided with an adhesive layer between two release films may be sufficient as the bonding sheet
  • the release film known ones such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin-coated paper, TPX film, and fluorine resin film are used.
  • the thickness of the releasable film is usually 20 to 100 ⁇ m.
  • the thickness of the adhesive layer is usually 5 to 100 ⁇ m, preferably 10 to 60 ⁇ m.
  • an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B), and solvent is applied to the surface of a release film. Thereafter, there is a method of drying in the same manner as in the case of the coverlay film of the present invention.
  • this laminate (polyimide film / adhesive layer / copper foil) was thermocompression bonded at 180 ° C. and a pressure of 3 MPa for 30 minutes to obtain a flexible copper-clad laminate.
  • the flexible copper-clad laminate was cut to produce an adhesive test piece having a predetermined size.
  • 180 ° peel adhesion strength (N / mm when peeling the copper foil of the adhesive test piece from the polyimide film at 23 ° C. and a tensile speed of 50 mm / min in accordance with JIS C 6481. ) was measured.
  • the width of the adhesion test piece at the time of measurement was 10 mm.
  • solder heat resistance Based on JIS C 6481, the test was done on the following conditions.
  • the said adhesion test piece was cut
  • this laminate (polyimide film / adhesive layer / copper foil) was thermocompression bonded for 30 minutes at 180 ° C. and under a pressure of 3 MPa.
  • the maximum outflow length of the adhesive layer from the polyimide hole at this time was measured. It was judged that the smaller the outflow length, the better, and the larger the outflow length, the poorer resin flowability.
  • a release polyethylene terephthalate film having a thickness of 38 ⁇ m was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on the surface thereof. Subsequently, this film with a coating film was left still in an oven and dried at 90 ° C. for 3 minutes to form a coating film (adhesive layer) having a thickness of 50 ⁇ m to obtain a bonding sheet. Next, this bonding sheet was left in an oven and heat-treated at 180 ° C. for 30 minutes. Then, the said release film was peeled off and the test piece (15x80 mm) was produced.
  • the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the cured adhesive were measured using a PNA-L network analyzer N5230A (manufactured by Agilent) under the conditions of a cavity resonator perturbation method at 23 ° C. and a frequency of 1 GHz. .
  • Styrene elastomer (1) Styrene elastomer a1 A trade name “Tuftec M1913” (maleic acid-modified styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 10 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
  • Styrene elastomer a2 A trade name “Tuftec M1911” (maleic acid-modified styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 2 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
  • Styrene elastomer ⁇ The product name “Tuftec H1041” (styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 0 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
  • Epoxy resin b1 The product name "EPICLON HP-7200" (dicyclopentadiene skeleton-containing epoxy resin) manufactured by DIC was used.
  • Epoxy resin b2 The product name “EPICLON N-655EXP” (cresol novolac epoxy resin) manufactured by DIC was used.
  • Epoxy resin b3 The product name “jER828” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation was used.
  • Curing accelerator A trade name “Curazole C11-Z” (imidazole curing accelerator) manufactured by Shikoku Kasei Co., Ltd. was used.
  • Inorganic filler A trade name “Excellica SE-1” (silica) manufactured by Tokuyama Corporation was used.
  • Tackifier A product name “Clearon P105” (terpene resin) manufactured by Yasuhara Chemical Co., Ltd. was used.
  • Comparative Examples 1 and 2 are inferior in adhesiveness and dielectric properties because the content of the epoxy resin (B) deviates from the upper limit of the range of the present invention.
  • the comparative example 3 is inferior to adhesiveness, solder heat resistance, and resin flow-out property.
  • the adhesive composition of the present invention exhibits excellent adhesion to a polyimide film or the like, it is suitable for production of related products of flexible printed wiring boards. And the coverlay film, flexible copper clad laminated board, and bonding sheet which are obtained using the adhesive composition of the present invention are all excellent in appearance and dielectric properties.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Adhesive Tapes (AREA)

Abstract

Provided is an adhesive composition having good adhesiveness to polyimide film and other such insulating films and having excellent dielectric properties. An adhesive composition containing: a styrenic elastomer (A) containing a carboxyl group; and an epoxy resin (B); the adhesive composition being characterized in that the content of the epoxy resin (B) is 1-20 parts by mass per 100 parts by mass of the styrenic elastomer (A) containing a carboxyl group, and the dielectric constant of the cured adhesive measured at a frequency of 1 GHz is less than 2.5.

Description

接着剤組成物並びにこれを用いたカバーレイフィルム及びフレキシブル銅張積層板Adhesive composition, coverlay film and flexible copper-clad laminate using the same
　本発明は、接着性及び誘電特性に優れ、電子部品、特に、フレキシブルプリント配線板（以下「ＦＰＣ」ともいう）の関連製品の製造に適した接着剤組成物に関するものである。また、本発明は、この接着剤組成物を用いて得られたカバーレイフィルム、フレキシブル銅張積層板及びボンディングシートに関する。 The present invention relates to an adhesive composition which is excellent in adhesiveness and dielectric properties and suitable for the manufacture of electronic parts, particularly related products of flexible printed wiring boards (hereinafter also referred to as “FPC”). The present invention also relates to a coverlay film, a flexible copper-clad laminate and a bonding sheet obtained using this adhesive composition.
　フレキシブルプリント配線板は、限られたスペースでも立体的かつ高密度の実装が可能であるため、その用途が拡大しつつある。そして、近年、電子機器の小型化、軽量化等に伴い、フレキシブルプリント配線板の関連製品は多様化して、その需要が増大している。このような関連製品としては、ポリイミドフィルムに銅箔を貼り合わせたフレキシブル銅張積層板、フレキシブル銅張積層板に電子回路を形成したフレキシブルプリント配線板、フレキシブルプリント配線板と補強板を貼り合せた補強板付きフレキシブルプリント配線板、フレキシブル銅張積層板或いはフレキシブルプリント配線板を重ねて接合した多層板等があり、例えば、フレキシブル銅張積層板を製造する場合、ポリイミドフィルムと銅箔とを接着させるために、通常、接着剤が用いられる。 Since the flexible printed wiring board can be mounted three-dimensionally and in a high density even in a limited space, its application is expanding. In recent years, with the reduction in size and weight of electronic devices, related products for flexible printed wiring boards have been diversified, and the demand for such products has increased. As such related products, flexible copper-clad laminate in which copper foil is bonded to polyimide film, flexible printed wiring board in which electronic circuit is formed on flexible copper-clad laminate, flexible printed wiring board and reinforcing plate are bonded together There are a flexible printed wiring board with a reinforcing plate, a flexible copper-clad laminate, or a multilayer board in which flexible printed wiring boards are stacked and joined. For example, when manufacturing a flexible copper-clad laminate, a polyimide film and a copper foil are bonded together. For this purpose, an adhesive is usually used.
　また、フレキシブルプリント配線板を製造する場合、配線部分を保護するために、通常、「カバーレイフィルム」と呼ばれるフィルムが用いられる。このカバーレイフィルムは、絶縁樹脂層と、その表面に形成された接着剤層とを備え、絶縁樹脂層の形成には、ポリイミド樹脂組成物が広く用いられている。そして、例えば、熱プレス等を利用して、配線部分を有する面に、接着剤層を介してカバーレイフィルムを貼り付けることにより、フレキシブルプリント配線板が製造される。このとき、カバーレイフィルムの接着剤層は、配線部分及びフィルム基層の両方に対して、強固な接着性が必要である。 Also, when manufacturing a flexible printed wiring board, a film called “cover lay film” is usually used to protect the wiring portion. This coverlay film includes an insulating resin layer and an adhesive layer formed on the surface thereof, and a polyimide resin composition is widely used for forming the insulating resin layer. And a flexible printed wiring board is manufactured by affixing a coverlay film on the surface which has a wiring part using an adhesive layer through an adhesive layer, for example. At this time, the adhesive layer of the cover lay film needs to have strong adhesion to both the wiring portion and the film base layer.
　また、プリント配線板としては、基板の表面に、導体層と有機絶縁層とを交互に積層するビルドアップ方式の多層プリント配線板が知られている。このような多層プリント配線板を製造する場合、導体層及び有機絶縁層を接合するために、「ボンディングシート」と呼ばれる、絶縁接着層形成材料が用いられる。絶縁接着層には、配線部分への埋め込み性や回路を形成している導体部の構成材料（銅等）及び有機絶縁層（ポリイミド樹脂等）の両方に対して、強固な接着性が必要である。 Further, as the printed wiring board, a build-up type multilayer printed wiring board in which conductor layers and organic insulating layers are alternately laminated on the surface of the substrate is known. When manufacturing such a multilayer printed wiring board, an insulating adhesive layer forming material called a “bonding sheet” is used to join the conductor layer and the organic insulating layer. The insulating adhesive layer must have strong adhesiveness to both the wiring part and the constituent material (copper etc.) of the conductor forming the circuit and the organic insulating layer (polyimide resin etc.). is there.
　このようなＦＰＣ関連製品に使用される接着剤としては、エポキシ樹脂と高い反応性を有する熱可塑性樹脂を含有するエポキシ系接着剤組成物が提案されている。例えば、特許文献１には、エチレン－アクリル酸エステル共重合ゴム／エポキシ樹脂系接着剤が開示されている。また、特許文献２には、グリシジル基含有熱可塑性エラストマー／エポキシ樹脂系接着剤が開示されている。更に、特許文献３には、スチレン－マレイン酸共重合体／エポキシ樹脂系接着剤が開示されている。これらの文献に記載されている接着剤組成物は、ゴムやエラストマー成分のカルボキシル基とエポキシ樹脂との反応性を利用することにより、速やかな硬化反応を実現し、接着性にも優れているため、広く利用されている。 As an adhesive used for such FPC-related products, an epoxy adhesive composition containing a thermoplastic resin having high reactivity with an epoxy resin has been proposed. For example, Patent Document 1 discloses an ethylene-acrylic acid ester copolymer rubber / epoxy resin adhesive. Patent Document 2 discloses a glycidyl group-containing thermoplastic elastomer / epoxy resin adhesive. Further, Patent Document 3 discloses a styrene-maleic acid copolymer / epoxy resin adhesive. The adhesive composition described in these documents realizes a rapid curing reaction by utilizing the reactivity between the carboxyl group of the rubber or elastomer component and the epoxy resin, and is excellent in adhesiveness. Widely used.
　また、近年需要が急速に拡大している携帯電話や、情報機器端末などの移動体通信機器においては、大量のデータを高速で処理する必要があるため、信号の高周波数化が進んでいる。信号速度の高速化と、信号の高周波数化に伴い、ＦＰＣ関連製品に用いる接着剤には低誘電率及び低誘電正接化といった誘電特性の向上が望まれている。このような誘電特性の要求に応えるため、例えば、特許文献４にはエポキシ樹脂、芳香族ビニル化合物と無水マレイン酸を必須成分として得られる共重合樹脂及び特定のフェノール化合物を含むエポキシ樹脂組成物が開示されている。 In mobile communication devices such as mobile phones and information device terminals, for which demand has been rapidly expanding in recent years, it is necessary to process a large amount of data at high speed, and therefore, the frequency of signals is increasing. As the signal speed is increased and the signal frequency is increased, the adhesive used for FPC-related products is desired to have improved dielectric properties such as low dielectric constant and low dielectric loss tangent. In order to meet such requirements for dielectric properties, for example, Patent Document 4 discloses an epoxy resin composition containing an epoxy resin, a copolymer resin obtained by using an aromatic vinyl compound and maleic anhydride as essential components, and a specific phenol compound. It is disclosed.
特開平７－２３５７６７号公報Japanese Patent Laid-Open No. 7-235767 特開２００１－３５４９３６号公報JP 2001-354936 A 特開２００７－２１２１号公報Japanese Patent Laid-Open No. 2007-2121 特開平１０－１７６８５号公報Japanese Patent Laid-Open No. 10-1785
　しかしながら、前記の通り信号の高周波数化に伴い、特許文献１～４に記載された接着剤組成物では、極超短波のマイクロ波帯（１～３ＧＨｚ）における誘電特性が不十分であるという問題がある。 However, as described above, with the increase in the frequency of signals, the adhesive compositions described in Patent Documents 1 to 4 have a problem that the dielectric properties in the microwave band (1 to 3 GHz) of the ultra high frequency are insufficient. is there.
　本発明は、上記課題に鑑みなされたものであって、ポリイミドフィルム等の絶縁フィルムに対する接着性が良好であり、かつ、優れた誘電特性を有する接着剤組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide an adhesive composition having good adhesion to an insulating film such as a polyimide film and having excellent dielectric properties.
　本発明者らは、カルボキシル基含有スチレン系エラストマーとエポキシ樹脂とを含有する接着剤組成物において、前記エラストマーとエポキシ樹脂が特定の含有量である場合に、接着性及び誘電特性に優れることを見出し、本発明を完成させるに至った。
　なお、本明細書において、「接着性層」は、カルボキシル基含有スチレン系エラストマー（Ａ）及びエポキシ樹脂（Ｂ）を含む膜等の部分において、少なくとも一部が硬化し始めた段階で、被着体への接着、又は、同一材料若しくは異なる材料からなる少なくとも２つの部材同士の接着を可能としている性質を有する層を意味する。また、「接着部」は、接着後に形成された硬化物からなる硬化部を意味し、「硬化物」は、完全硬化のみを意味するものでなく、半硬化等、少なくとも一部に架橋構造を有する状態を含む。 The present inventors have found that an adhesive composition containing a carboxyl group-containing styrenic elastomer and an epoxy resin is excellent in adhesiveness and dielectric properties when the elastomer and the epoxy resin have a specific content. The present invention has been completed.
In the present specification, the “adhesive layer” is applied when at least a part of the film including the carboxyl group-containing styrene elastomer (A) and the epoxy resin (B) begins to cure. It means a layer having a property that enables adhesion to the body or adhesion between at least two members made of the same material or different materials. Further, “bonded part” means a cured part made of a cured product formed after bonding, and “cured product” does not mean only complete curing, but at least partially has a crosslinked structure such as semi-cured. Including the state of having.
　すなわち、本発明に係る接着剤組成物は以下の通りである。
１．カルボキシル基含有スチレン系エラストマー（Ａ）と、エポキシ樹脂（Ｂ）とを含有する接着剤組成物であって、前記エポキシ樹脂（Ｂ）の含有量は、前記カルボキシル基含有スチレン系エラストマー（Ａ）１００質量部に対して１～２０質量部であり、かつ、周波数１ＧＨｚで測定した接着剤硬化物の誘電率が２．５未満であることを特徴とする接着剤組成物。
２．上記カルボキシル基含有スチレン系エラストマー（Ａ）の酸価が、０．１～２０ｍｇＫＯＨ／ｇである上記１に記載の接着剤組成物。
３．上記カルボキシル基含有スチレン系エラストマー（Ａ）が、スチレン－ブタジエンブロック共重合体、スチレン－エチレンプロピレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－エチレンブチレン－スチレンブロック共重合体、スチレン－エチレンプロピレン－スチレンブロック共重合体からなる群より選択される少なくとも１つのスチレン系エラストマーを、不飽和カルボン酸で変性したものである上記１又は２に記載の接着剤組成物。
４．上記エポキシ樹脂（Ｂ）が、脂環骨格を有する多官能エポキシ樹脂である上記１～３のいずれかに記載の接着剤組成物。
５．周波数１ＧＨｚで測定した接着剤硬化物の誘電正接が、０．０１未満である上記１～４のいずれかに記載の接着剤組成物。
６．上記１～５のいずれかに記載の接着剤組成物を用いて得られた接着性層が、ポリイミドフィルム又は液晶ポリマーフィルムの一方の表面に形成されてなることを特徴とするカバーレイフィルム。
７．上記１～５のいずれかに記載の接着剤組成物を用いて、ポリイミドフィルム又は液晶ポリマーフィルムの少なくとも一方の表面に銅箔を貼り合わせてなることを特徴とするフレキシブル銅張積層板。
８．上記１～５のいずれかに記載の接着剤組成物を用いて得られた接着性層が、離型性フィルムの一方の表面に形成されてなることを特徴とするボンディングシート。 That is, the adhesive composition according to the present invention is as follows.
1. An adhesive composition containing a carboxyl group-containing styrene elastomer (A) and an epoxy resin (B), wherein the content of the epoxy resin (B) is the carboxyl group-containing styrene elastomer (A) 100. An adhesive composition characterized by being 1 to 20 parts by mass relative to parts by mass and having a dielectric constant of a cured adhesive measured at a frequency of 1 GHz of less than 2.5.
2. 2. The adhesive composition according to 1 above, wherein the carboxyl group-containing styrene elastomer (A) has an acid value of 0.1 to 20 mg KOH / g.
3. The carboxyl group-containing styrene elastomer (A) is a styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene. 1 or 2 above, wherein at least one styrene elastomer selected from the group consisting of ethylene-butylene-styrene block copolymer and styrene-ethylenepropylene-styrene block copolymer is modified with unsaturated carboxylic acid. The adhesive composition as described.
4). 4. The adhesive composition according to any one of 1 to 3 above, wherein the epoxy resin (B) is a polyfunctional epoxy resin having an alicyclic skeleton.
5. 5. The adhesive composition according to any one of 1 to 4 above, wherein the dielectric loss tangent of the cured adhesive product measured at a frequency of 1 GHz is less than 0.01.
6). 6. A coverlay film, wherein an adhesive layer obtained by using the adhesive composition according to any one of 1 to 5 above is formed on one surface of a polyimide film or a liquid crystal polymer film.
7). A flexible copper clad laminate comprising a copper foil bonded to at least one surface of a polyimide film or a liquid crystal polymer film using the adhesive composition according to any one of 1 to 5 above.
8). 6. A bonding sheet, wherein an adhesive layer obtained by using the adhesive composition according to any one of 1 to 5 above is formed on one surface of a release film.
　本発明の接着剤組成物は、ポリイミドフィルム等の可とう性フィルムに対する接着性及び誘電特性に優れた接着部を形成することができる。また、本発明の接着剤組成物は、加熱接着時の樹脂の流れ出し性も良好である。従って、本発明の接着剤組成物は、フレキシブル配線板の関連製品の製造に好適である。 The adhesive composition of the present invention can form an adhesive part excellent in adhesiveness and dielectric properties to a flexible film such as a polyimide film. In addition, the adhesive composition of the present invention has a good resin flow-out property during heat bonding. Therefore, the adhesive composition of this invention is suitable for manufacture of the related product of a flexible wiring board.
　本発明について、詳しく説明する。 The present invention will be described in detail.
１．接着剤組成物
　本発明の接着剤組成物は、カルボキシル基含有スチレン系エラストマー（Ａ）と、エポキシ樹脂（Ｂ）とを所定量含有する接着剤組成物である。本発明の接着剤組成物においては、カルボキシル基含有スチレン系エラストマー中のカルボキシル基と、エポキシ樹脂（Ｂ）中のエポキシ基とが反応することにより接着性を発現するとともに硬化物を形成し始め、被着体に対する高い接着性を得ることができる。また、接着部の耐熱性を得ることもできる。以下、本発明の接着剤組成物に含まれる成分について、具体的に説明する。 1. Adhesive Composition The adhesive composition of the present invention is an adhesive composition containing a predetermined amount of a carboxyl group-containing styrene elastomer (A) and an epoxy resin (B). In the adhesive composition of the present invention, the carboxyl group in the carboxyl group-containing styrene-based elastomer reacts with the epoxy group in the epoxy resin (B) to develop adhesiveness and begin to form a cured product, High adhesion to the adherend can be obtained. Also, the heat resistance of the bonded portion can be obtained. Hereinafter, the components contained in the adhesive composition of the present invention will be specifically described.
（Ａ）カルボキシル基含有スチレン系エラストマー
　カルボキシル基含有スチレン系エラストマー（Ａ）は、本発明の接着剤組成物の主要な成分の１つであり、接着性や硬化物の柔軟性に加えて、誘電特性を与える成分である。このカルボキシル基含有スチレン系エラストマーとは、共役ジエン化合物と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物を、不飽和カルボン酸で変性したものである。芳香族ビニル化合物としては、例えばスチレン、ｔ－ブチルスチレン、α－メチルスチレン、ｐ－メチルスチレン、ジビニルベンゼン、１，１－ジフェニルスチレン、Ｎ，Ｎ－ジエチル－ｐ－アミノエチルスチレン、ビニルトルエン、ｐ－第３ブチルスチレン等が挙げられる。また、共役ジエン化合物としては、例えば、ブタジエン、イソプレン、１，３－ペンタジエン、２，３－ジメチル－１，３－ブタジエン等を挙げることができる。 (A) Carboxyl group-containing styrenic elastomer The carboxyl group-containing styrenic elastomer (A) is one of the main components of the adhesive composition of the present invention. In addition to adhesiveness and flexibility of the cured product, dielectric It is a component that gives characteristics. This carboxyl group-containing styrene-based elastomer is obtained by modifying a copolymer mainly composed of blocks and random structures of a conjugated diene compound and an aromatic vinyl compound, and a hydrogenated product thereof with an unsaturated carboxylic acid. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
　カルボキシル基含有スチレン系エラストマー（Ａ）の変性は、例えば、スチレン系エラストマーの重合時に、不飽和カルボン酸を共重合させることにより行うことができる。また、スチレン系エラストマーと不飽和カルボン酸を有機パーオキサイドの存在下に加熱、混練することにより行うこともできる。不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、無水マレイン酸、無水イタコン酸、無水フマル酸等を挙げることができる。不飽和カルボン酸による変性量は、通常０．１～１０質量％である。 The modification of the carboxyl group-containing styrene elastomer (A) can be performed, for example, by copolymerizing an unsaturated carboxylic acid during the polymerization of the styrene elastomer. Moreover, it can also carry out by heating and kneading | mixing a styrene-type elastomer and unsaturated carboxylic acid in presence of an organic peroxide. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric anhydride and the like. The amount of modification with unsaturated carboxylic acid is usually 0.1 to 10% by mass.
　カルボキシル基含有スチレン系エラストマー（Ａ）の酸価は、０．１～２０ｍｇＫＯＨ／ｇであることが好ましく、０．５～１８ｍｇＫＯＨ／ｇであることがより好ましく、１．０～１５ｍｇＫＯＨ／ｇであることが更に好ましい。この酸価が０．１ｍｇＫＯＨ／ｇ未満であると、接着剤組成物の硬化が不十分となり、良好な接着性、耐熱性及び樹脂流れ出し性が得られない場合がある。一方、前記酸価が２０ｍｇＫＯＨ／ｇを超えると、接着強さ及び誘電特性が低下する場合がある。 The acid value of the carboxyl group-containing styrene elastomer (A) is preferably 0.1 to 20 mgKOH / g, more preferably 0.5 to 18 mgKOH / g, and 1.0 to 15 mgKOH / g. More preferably. When the acid value is less than 0.1 mgKOH / g, the adhesive composition may be insufficiently cured, and good adhesiveness, heat resistance, and resin flowability may not be obtained. On the other hand, when the acid value exceeds 20 mgKOH / g, the adhesive strength and the dielectric properties may be deteriorated.
　また、カルボキシル基含有スチレン系エラストマー（Ａ）の重量平均分子量は、１～５０万であることが好ましく、３～３０万であることがより好ましく、５～２０万であることが更に好ましい。重量平均分子量が１～５０万の範囲内であれば、優れた接着性及び誘電特性を発現することができる。なお、本明細書において、重量平均分子量とは、ゲル・パーミエーションクロマトグラフィー（以下「ＧＰＣ」ともいう）により測定した分子量をポリスチレン換算した値である。 Further, the weight average molecular weight of the carboxyl group-containing styrene elastomer (A) is preferably 1 to 500,000, more preferably 3 to 300,000, and further preferably 50,000 to 200,000. When the weight average molecular weight is in the range of 1 to 500,000, excellent adhesion and dielectric properties can be exhibited. In the present specification, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as “GPC”) into polystyrene.
　カルボキシル基含有スチレン系エラストマー（Ａ）の具体例としては、スチレン－ブタジエンブロック共重合体、スチレン－エチレンプロピレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレン－スチレンブロック共重合体等を、不飽和カルボン酸で変性したものが挙げられる。前記共重合体の中でも、接着性及び誘電特性の観点から、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレン－スチレンブロック共重合体が好ましい。また、スチレン－エチレンブチレン－スチレンブロック共重合体におけるスチレン／エチレンブチレンの質量比、及びスチレン－エチレンプロピレン－スチレンブロック共重合体におけるスチレン／エチレンプロピレンの質量比は、１０／９０～５０／５０であることが好ましい。当該質量比がこの範囲内であれば、優れた誘電特性を有する接着剤組成物とすることができる。 Specific examples of the carboxyl group-containing styrene elastomer (A) include styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer. Examples thereof include a polymer, a styrene-ethylenebutylene-styrene block copolymer, a styrene-ethylenepropylene-styrene block copolymer, and the like modified with an unsaturated carboxylic acid. Among the copolymers, a styrene-ethylenebutylene-styrene block copolymer and a styrene-ethylenepropylene-styrene block copolymer are preferable from the viewpoint of adhesiveness and dielectric properties. The mass ratio of styrene / ethylenebutylene in the styrene-ethylenebutylene-styrene block copolymer and the mass ratio of styrene / ethylenepropylene in the styrene-ethylenepropylene-styrene block copolymer were 10/90 to 50/50. Preferably there is. If the said mass ratio is in this range, it can be set as the adhesive composition which has the outstanding dielectric characteristic.
　次に本発明で用いられるエポキシ樹脂（Ｂ）について説明する。
　本発明で使用されるエポキシ樹脂（Ｂ）は、接着剤硬化物の耐熱性と高い接着性を発現するための役割を担っている。
　エポキシ樹脂の例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、又はそれらに水素添加したもの；オルトフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、ｐ－ヒドロキシ安息香酸グリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、トリメリット酸トリグリシジルエステル等のグリシジルエステル系エポキシ樹脂；エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、テトラフェニルグリシジルエーテルエタン、トリフェニルグリシジルエーテルエタン、ソルビトールのポリグリシジルエーテル、ポリグリセロールのポリグリシジルエーテル等のグリシジルエーテル系エポキシ樹脂；トリグリシジルイソシアヌレート、テトラグリシジルジアミノジフェニルメタン等のグリシジルアミン系エポキシ樹脂；エポキシ化ポリブタジエン、エポキシ化大豆油等の線状脂肪族エポキシ樹脂等が挙げられるが、これらに限定するものではない。また、フェノールノボラックエポキシ樹脂、ｏ－クレゾールノボラックエポキシ樹脂、ビスフェノールＡノボラックエポキシ樹脂等のノボラック型エポキシ樹脂も用いることができる。 Next, the epoxy resin (B) used in the present invention will be described.
The epoxy resin (B) used in the present invention plays a role for developing the heat resistance and high adhesiveness of the cured adhesive.
Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, or those hydrogenated to them; orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid Glycidyl ester epoxy resins such as glycidyl ester, tetrahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, trimellitic acid triglycidyl ester; ethylene glycol diglycidyl ether, propylene glycol Diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpro Triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, polyglycidyl ether of sorbitol, polyglycidyl ether of polyglycerol, etc .; triglycidyl isocyanurate, tetraglycidyl diamino Examples thereof include, but are not limited to, glycidylamine epoxy resins such as diphenylmethane; linear aliphatic epoxy resins such as epoxidized polybutadiene and epoxidized soybean oil. In addition, novolac type epoxy resins such as phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin and the like can also be used.
　更に、エポキシ樹脂の例として臭素化ビスフェノールＡ型エポキシ樹脂、リン含有エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、アントラセン型エポキシ樹脂、ターシャリーブチルカテコール型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等を用いることができる。これらの中でも、誘電特性に優れた接着剤組成物が得られることから、ジシクロペンタジエン等の脂環骨格を有するエポキシ樹脂が好ましい。 Examples of epoxy resins include brominated bisphenol A type epoxy resins, phosphorus-containing epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, naphthalene skeleton-containing epoxy resins, anthracene type epoxy resins, tertiary butylcatechol type epoxy resins, triphenylmethane Type epoxy resin, tetraphenylethane type epoxy resin, biphenyl type epoxy resin, bisphenol S type epoxy resin and the like can be used. Among these, an epoxy resin having an alicyclic skeleton such as dicyclopentadiene is preferable because an adhesive composition having excellent dielectric properties can be obtained.
　本発明に用いるエポキシ樹脂としては、一分子中に２個以上のエポキシ基を有するものが好ましい。カルボキシル基含有スチレン系エラストマーとの反応で架橋構造を形成し、高い耐熱性を発現させることができるからである。エポキシ基が１個のエポキシ樹脂を用いた場合、カルボキシル基含有スチレン系エラストマーとの架橋度が低いために十分な耐熱性が得られない場合がある。 The epoxy resin used in the present invention preferably has two or more epoxy groups in one molecule. This is because a cross-linked structure can be formed by reaction with the carboxyl group-containing styrene-based elastomer and high heat resistance can be expressed. When an epoxy resin having one epoxy group is used, sufficient heat resistance may not be obtained because the degree of crosslinking with the carboxyl group-containing styrene elastomer is low.
　上記エポキシ樹脂（Ｂ）の含有量は、上記カルボキシル基含有スチレン系エラストマー（Ａ）１００質量部に対して１～２０質量部であることが必要である。前記含有量は、３～１５質量部であることが好ましい。この含有量が１質量部未満であると、十分な接着性と耐熱性が得られない場合がある。一方、この含有量が２０質量部を超えると、はく離接着強さが低下したり、硬化物の誘電率が高くなったりする場合がある。 The content of the epoxy resin (B) needs to be 1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing styrene elastomer (A). The content is preferably 3 to 15 parts by mass. If the content is less than 1 part by mass, sufficient adhesion and heat resistance may not be obtained. On the other hand, when the content exceeds 20 parts by mass, the peel adhesion strength may be lowered, or the dielectric constant of the cured product may be increased.
　本発明に係る接着剤組成物は、カルボキシル基含有スチレン系エラストマー（Ａ）及びエポキシ樹脂（Ｂ）を所定量含有し、周波数１ＧＨｚで測定した接着剤硬化物の誘電率（ε）が２．５未満であることを特徴としている。当該誘電率が２．５未満であれば、フレキシブルプリント配線板の関連製品への利用に好適である。また、周波数１ＧＨｚで測定した接着剤硬化物の誘電正接（ｔａｎδ）が、０．０１未満であることが好ましい。当該誘電正接が０．０１未満であれば、誘電特性に優れるフレキシブルプリント配線板の関連製品を製造することができる。誘電率及び誘電正接は、接着剤組成物中のカルボキシル基含有スチレン系エラストマー（Ａ）及びエポキシ樹脂（Ｂ）の割合に応じて調整できるので、用途に応じて、種々の構成の接着剤組成物を設定することができる。なお、誘電率及び誘電正接の測定方法は後述する。 The adhesive composition according to the present invention contains a predetermined amount of carboxyl group-containing styrene elastomer (A) and epoxy resin (B), and the dielectric constant (ε) of the cured adhesive measured at a frequency of 1 GHz is 2.5. It is characterized by being less than. If the said dielectric constant is less than 2.5, it is suitable for the utilization to the related product of a flexible printed wiring board. The dielectric loss tangent (tan δ) of the cured adhesive product measured at a frequency of 1 GHz is preferably less than 0.01. If the said dielectric loss tangent is less than 0.01, the related product of the flexible printed wiring board which is excellent in a dielectric characteristic can be manufactured. Since the dielectric constant and dielectric loss tangent can be adjusted according to the proportion of the carboxyl group-containing styrene elastomer (A) and epoxy resin (B) in the adhesive composition, adhesive compositions having various configurations can be used depending on the application. Can be set. In addition, the measuring method of a dielectric constant and a dielectric loss tangent is mentioned later.
　本発明の接着剤組成物は、上記カルボキシル基含有スチレン系エラストマー（Ａ）及びエポキシ樹脂（Ｂ）に加えて、カルボキシル基含有スチレン系エラストマー（Ａ）以外の他の熱可塑性樹脂、粘着付与剤、難燃剤、硬化促進剤、カップリング剤、熱老化防止剤、レベリング剤、消泡剤、無機充填剤、顔料、及び溶剤等を、接着剤組成物の機能に影響を与えない程度に含有することができる。 In addition to the carboxyl group-containing styrene-based elastomer (A) and the epoxy resin (B), the adhesive composition of the present invention is a thermoplastic resin other than the carboxyl group-containing styrene-based elastomer (A), a tackifier, Containing flame retardants, curing accelerators, coupling agents, heat aging inhibitors, leveling agents, antifoaming agents, inorganic fillers, pigments, solvents, etc. to the extent that they do not affect the function of the adhesive composition. Can do.
　上記他の熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキシド樹脂、ポリウレタン樹脂、ポリアセタール樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂及びポリビニル系樹脂等が挙げられる。 Examples of the other thermoplastic resins include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, and polyvinyl resins.
　上記粘着付与剤としては、例えば、クマロン・インデン樹脂、テルペン樹脂、テルペン・フェノール樹脂、ロジン樹脂、ｐ－ｔ－ブチルフェノール・アセチレン樹脂、フェノール・ホルムアルデヒド樹脂、キシレン・ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、テレピン系樹脂等を挙げることができる。これらの粘着付与剤は、単独で用いてもよいし、２種以上を併用してもよい。 Examples of the tackifier include coumarone / indene resin, terpene resin, terpene / phenol resin, rosin resin, pt-butylphenol / acetylene resin, phenol / formaldehyde resin, xylene / formaldehyde resin, petroleum hydrocarbon resin, Examples thereof include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
　上記難燃剤は、有機系難燃剤及び無機系難燃剤のいずれでもよい。有機系難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート、トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタン等のリン系難燃剤；メラミン、メラム、メラミンシアヌレート等のトリアジン系化合物や、シアヌル酸化合物、イソシアヌル酸化合物、トリアゾール系化合物、テトラゾール化合物、ジアゾ化合物、尿素等の窒素系難燃剤；シリコーン化合物、シラン化合物等のケイ素系難燃剤等が挙げられる。また、無機系難燃剤としては、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム等の金属水酸化物；酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化ニッケル等の金属酸化物；炭酸亜鉛、炭酸マグネシウム、炭酸バリウム、ホウ酸亜鉛、水和ガラス等が挙げられる。これらの難燃剤は、２種以上を併用することができる。 The flame retardant may be either an organic flame retardant or an inorganic flame retardant. Examples of the organic flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium amidophosphate, carbamate phosphate, and carbamate polyphosphate , Aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , Titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, tetra Phosphorus flame retardants such as titanium diphenylphosphinate; triazine compounds such as melamine, melam, melamine cyanurate, and nitrogen-based flames such as cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea Examples of the flame retardant include silicon-based flame retardants such as silicone compounds and silane compounds. Examples of the inorganic flame retardant include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. Two or more of these flame retardants can be used in combination.
　上記硬化促進剤は、カルボキシル基含有スチレン系エラストマーとエポキシ樹脂との反応を促進させる目的で使用するものであり、第三級アミン系硬化促進剤、第三級アミン塩系硬化促進剤及びイミダゾール系硬化促進剤等を使用することができる。 The curing accelerator is used for the purpose of accelerating the reaction between the carboxyl group-containing styrenic elastomer and the epoxy resin, and is a tertiary amine-based curing accelerator, a tertiary amine salt-based curing accelerator, and an imidazole system. A curing accelerator or the like can be used.
　第三アミン系硬化促進剤としては、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、テトラメチルグアニジン、トリエタノールアミン、Ｎ，Ｎ’－ジメチルピペラジン、トリエチレンジアミン、１，８－ジアザビシクロ［５．４．０］ウンデセン等が挙げられる。 Tertiary amine curing accelerators include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N'- Examples thereof include dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo [5.4.0] undecene.
　第三アミン塩系硬化促進剤としては、１，８－ジアザビシクロ［５．４．０］ウンデセンの、ギ酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩や、１，５－ジアザビシクロ［４．３．０］ノネンの、ギ酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩等が挙げられる。 Tertiary amine salt curing accelerators include formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenol of 1,8-diazabicyclo [5.4.0] undecene Examples include novolak resin salts and 1,5-diazabicyclo [4.3.0] nonene formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenol novolac resin salt. It is done.
　イミダゾール系硬化促進剤としては、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－メチル－４－エチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等が挙げられる。 Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-e Le -s- triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy methyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, and the like.
　本発明の接着剤組成物が硬化促進剤を含有する場合、硬化促進剤の含有量は、エポキシ樹脂（Ｂ）１００質量部に対して、１～１０質量部の範囲に入るように用いることが好ましい。特に好ましくは、２～５質量部の範囲である。硬化促進剤の含有量が１～１０質量部の範囲であれば、優れた接着性及び耐熱性を有する。 When the adhesive composition of the present invention contains a curing accelerator, the content of the curing accelerator may be used in a range of 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B). preferable. Particularly preferred is a range of 2 to 5 parts by mass. When the content of the curing accelerator is in the range of 1 to 10 parts by mass, excellent adhesion and heat resistance are obtained.
　また、上記カップリング剤としては、ビニルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトシキシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネ－トプロピルトリエトキシシラン、イミダゾールシラン等のシラン系カップリング剤；チタネ－ト系カップリング剤；アルミネ－ト系カップリング剤；ジルコニウム系カップリング剤等が挙げられる。これらは、単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltri Examples thereof include silane coupling agents such as ethoxysilane and imidazolesilane; titanate coupling agents; aluminate coupling agents; zirconium coupling agents. These may be used alone or in combination of two or more.
　上記熱老化防止剤としては、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノ－ル、ｎ－オクタデシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネ－ト、テトラキス〔メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネ－ト〕メタン等のフェノ－ル系酸化防止剤；ジラウリル－３，３’－チオジプロピオネ－ト、ジミリスチル－３，３’－ジチオプロピオネ－ト等のイオウ系酸化防止剤；トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト等のリン系酸化防止剤等が挙げられる。これらは、単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the heat aging inhibitor include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propione. -Phenolic antioxidants such as tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; dilauryl-3,3'-thiodipropionate Sulfur antioxidants such as dimyristyl-3,3′-dithiopropionate; phosphorus antioxidants such as trisnonylphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite It is done. These may be used alone or in combination of two or more.
　上記無機充填剤としては、酸化チタン、酸化アルミニウム、酸化亜鉛、カ－ボンブラック、シリカ、銅、及び銀等からなる粉体が挙げられる。これらは、単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the inorganic filler include powders made of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, copper, silver, and the like. These may be used alone or in combination of two or more.
　本発明の接着剤組成物は、上記カルボキシル基含有スチレン系エラストマー（Ａ）、エポキシ樹脂（Ｂ）及びその他成分を混合することにより製造することができる。本発明の接着剤組成物は、溶液又は分散液の状態で好ましく用いられることから、通常は、溶剤も使用される。溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール、イソブチルアルコール、ｎ－ブチルアルコール、ベンジルアルコール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジアセトンアルコール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、イソホロン等のケトン類；トルエン、キシレン、エチルベンゼン、メシチレン等の芳香族炭化水素類；酢酸メチル、酢酸エチル、エチレングリコールモノメチルエーテルアセテ－ト、３－メトキシブチルアセテート等のエステル類；ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素類等が挙げられる。これらの溶剤は、単独で用いてよいし、２種以上を組み合わせて用いてもよい。本発明の接着剤組成物が溶剤を含む溶液又は分散液であると、被着体への塗工及び接着性層の形成を円滑に行うことができ、所望の厚さの接着性層を容易に得ることができる。 The adhesive composition of the present invention can be produced by mixing the carboxyl group-containing styrene elastomer (A), the epoxy resin (B) and other components. Since the adhesive composition of the present invention is preferably used in the state of a solution or a dispersion, a solvent is also usually used. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and isophorone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene and mesitylene; methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, Esters such as 3-methoxybutyl acetate; hexane, heptane, cyclohexane, methylcyclohex Aliphatic hydrocarbons such as emissions and the like. These solvents may be used alone or in combination of two or more. When the adhesive composition of the present invention is a solution or dispersion containing a solvent, coating on an adherend and formation of an adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be easily formed. Can get to.
　本発明の接着剤組成物が溶剤を含む場合、塗膜形成性を含む作業性等の観点から、固形分濃度は、好ましくは３～８０質量％、より好ましくは１０～５０質量％の範囲である。固形分濃度が８０質量％を超えると、溶液の粘度が高くなり過ぎて、均一に塗工し難くなる場合がある。 When the adhesive composition of the present invention contains a solvent, the solid content concentration is preferably in the range of 3 to 80% by mass, more preferably in the range of 10 to 50% by mass, from the viewpoint of workability including film-forming properties. is there. If the solid content concentration exceeds 80% by mass, the viscosity of the solution becomes too high, and it may be difficult to coat uniformly.
　本発明の接着剤組成物による好適な被着体は、ポリイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンサルファイド樹脂、アラミド樹脂、液晶ポリマー等の高分子材料；銅、アルミニウム、ステンレス等の無機材料等からなる物体である。被着体の形状は、特に限定されない。そして、被着体としての、同一材料又は異なる材料からなる２つの部材同士を、本発明の接着剤組成物により接着させて、一体化した複合化物を製造することができる。また、以下のカバーレイフィルム、ボンディングシートのように、接着性を有する接着性層を有する製品を製造することができる。 Suitable adherends using the adhesive composition of the present invention include polymer materials such as polyimide resins, polyether ether ketone resins, polyphenylene sulfide resins, aramid resins, and liquid crystal polymers; inorganic materials such as copper, aluminum, and stainless steel. Is an object. The shape of the adherend is not particularly limited. And two members which consist of the same material or different materials as a to-be-adhered body are adhere | attached with the adhesive composition of this invention, and the integrated composite can be manufactured. Moreover, the product which has an adhesive layer which has adhesiveness like the following cover-lay films and bonding sheets can be manufactured.
２．カバーレイフィルム
　本発明のカバーレイフィルムは、上記本発明の接着剤組成物を用いて得られた接着性層が、ポリイミドフィルム又は液晶ポリマーフィルムの一方の表面に形成されていることを特徴とする。上記本発明の接着剤組成物は、特にポリイミド系樹脂との接着性に優れるので、本発明のカバーレイフィルムは、接着性層及びポリイミドフィルムの剥離が困難なフィルムである。 2. Coverlay film The coverlay film of the present invention is characterized in that the adhesive layer obtained by using the adhesive composition of the present invention is formed on one surface of a polyimide film or a liquid crystal polymer film. . Since the adhesive composition of the present invention is particularly excellent in adhesiveness with a polyimide resin, the coverlay film of the present invention is a film in which it is difficult to peel off the adhesive layer and the polyimide film.
　上記ポリイミドフィルム又は液晶ポリマーフィルムの構成は、電気的絶縁性を有するものであれば、特に限定されず、ポリイミド樹脂若しくは液晶ポリマーのみからなるフィルム、又は当該樹脂及び添加剤からなるフィルム等とすることができ、接着性層が形成される側には、表面処理が施されていてもよい。
　上記ポリイミドフィルム又は液晶ポリマーフィルムの厚さは、通常、１０～１２５μｍである。また、上記接着性層の厚さは、通常、５～４５μｍであり、好ましくは１０～３５μｍである。 The structure of the polyimide film or the liquid crystal polymer film is not particularly limited as long as it has electrical insulation, and is a film made of only a polyimide resin or a liquid crystal polymer, or a film made of the resin and an additive. Surface treatment may be performed on the side on which the adhesive layer is formed.
The thickness of the polyimide film or liquid crystal polymer film is usually 10 to 125 μm. The thickness of the adhesive layer is usually 5 to 45 μm, preferably 10 to 35 μm.
　本発明のカバーレイフィルムを製造する方法としては、例えば、ポリイミドフィルムの表面に、上記カルボキシル基含有スチレン系エラストマー（Ａ）、エポキシ樹脂（Ｂ）及び溶剤を含む接着剤組成物を塗工した後、溶剤を除去するために２～１０分間程度加熱乾燥する方法がある。乾燥の際の加熱温度は、好ましくは４０℃～２５０℃、より好ましくは７０℃～１７０℃であり、通常、塗膜付きフィルムを、熱風乾燥、遠赤外線加熱、高周波誘導加熱等がなされる炉の中を通過させることにより行われる。なお、必要に応じて、接着性層の表面には、保管等のため、離型性フィルムを積層してもよい。前記離型性フィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、シリコーン離型処理紙、ポリオレフィン樹脂コート紙、ＴＰＸフィルム、フッ素系樹脂フィルム等の公知のものが用いられる。 As a method for producing the cover lay film of the present invention, for example, after coating the surface of a polyimide film with an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B) and solvent. In order to remove the solvent, there is a method of heating and drying for about 2 to 10 minutes. The heating temperature at the time of drying is preferably 40 ° C. to 250 ° C., more preferably 70 ° C. to 170 ° C. Usually, a film-coated film is subjected to hot air drying, far infrared heating, high frequency induction heating, or the like. This is done by passing it through. If necessary, a release film may be laminated on the surface of the adhesive layer for storage or the like. As the release film, known ones such as a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a silicone release treated paper, a polyolefin resin coated paper, a TPX film, and a fluorine resin film are used.
３．フレキシブル銅張積層板
　本発明のフレキシブル銅張積層板は、上記本発明の接着剤組成物を用いて、ポリイミドフィルム又は液晶ポリマーフィルムと銅箔とが貼り合わされていることを特徴とする。即ち、本発明のフレキシブル銅張積層板は、ポリイミドフィルム又は液晶ポリマーフィルム、接着性組成物により形成された接着層及び銅箔の順に構成されたものである。なお、接着層及び銅箔は、ポリイミドフィルム又は液晶ポリマーフィルムの両面に形成されていてもよい。上記本発明の接着剤組成物は、銅を含む物品との接着性に優れるので、本発明のフレキシブル銅張積層板は、一体化物として安定性に優れる。 3. Flexible copper-clad laminate The flexible copper-clad laminate of the present invention is characterized in that a polyimide film or a liquid crystal polymer film and a copper foil are bonded together using the adhesive composition of the present invention. That is, the flexible copper-clad laminate of the present invention is composed of a polyimide film or a liquid crystal polymer film, an adhesive layer formed of an adhesive composition, and a copper foil in this order. The adhesive layer and the copper foil may be formed on both sides of the polyimide film or the liquid crystal polymer film. Since the adhesive composition of the present invention is excellent in adhesiveness with articles containing copper, the flexible copper-clad laminate of the present invention is excellent in stability as an integrated product.
　上記ポリイミドフィルム又は液晶ポリマーフィルムの構成は、上記本発明のカバーレイフィルムにおけるポリイミドフィルム又は液晶ポリマーフィルムと同じとすることができる。
　上記接着層は、上記接着剤組成物の大部分が架橋反応して硬化物を形成していることが好ましい。
　上記接着層の厚さは、通常、５～４５μｍであり、好ましくは５～１８μｍである。
　また、上記銅箔は、特に限定されず、電解銅箔、圧延銅箔等を用いることができる。 The composition of the polyimide film or the liquid crystal polymer film can be the same as the polyimide film or the liquid crystal polymer film in the cover lay film of the present invention.
In the adhesive layer, it is preferable that most of the adhesive composition undergoes a crosslinking reaction to form a cured product.
The thickness of the adhesive layer is usually 5 to 45 μm, preferably 5 to 18 μm.
Moreover, the said copper foil is not specifically limited, Electrolytic copper foil, rolled copper foil, etc. can be used.
　本発明のフレキシブル銅張積層板を製造する方法としては、例えば、ポリイミドフィルムの表面に、上記カルボキシル基含有スチレン系エラストマー（Ａ）、エポキシ樹脂（Ｂ）及び溶剤を含む接着剤組成物を塗工した後、上記本発明のカバーレイフィルムの場合と同様にして乾燥し、次いで、塗膜付きフィルムの塗膜表面と銅箔とを面接触させ、８０℃～１５０℃で熱ラミネートを行い、更にアフターキュアにより塗膜を硬化する方法がある。アフターキュアの条件は、例えば、１００℃～２００℃、３０分～４時間とすることができる。 As a method for producing the flexible copper-clad laminate of the present invention, for example, an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B) and solvent is applied to the surface of a polyimide film. And then dried in the same manner as in the case of the cover lay film of the present invention, and then the surface of the coated film and the copper foil are brought into surface contact with each other, heat laminated at 80 ° C. to 150 ° C., and There is a method of curing the coating film by after cure. The after-curing conditions can be, for example, 100 ° C. to 200 ° C., 30 minutes to 4 hours.
４．ボンディングシート
　本発明のボンディングシートは、上記本発明の接着剤組成物を用いて得られた接着性層が、離型性フィルムの表面に形成されていることを特徴とする。なお、本発明のボンディングシートは、２枚の離型性フィルムの間に接着性層を備える態様であってもよい。 4). Bonding sheet The bonding sheet of the present invention is characterized in that an adhesive layer obtained by using the adhesive composition of the present invention is formed on the surface of a release film. In addition, the aspect provided with an adhesive layer between two release films may be sufficient as the bonding sheet | seat of this invention.
　上記離型性フィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、シリコーン離型処理紙、ポリオレフィン樹脂コート紙、ＴＰＸフィルム、フッ素系樹脂フィルム等の公知のものが用いられる。
　上記離型性フィルムの厚さは、通常、２０～１００μｍである。また、上記接着性層の厚さは、通常、５～１００μｍであり、好ましくは１０～６０μｍである。 As the release film, known ones such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin-coated paper, TPX film, and fluorine resin film are used.
The thickness of the releasable film is usually 20 to 100 μm. The thickness of the adhesive layer is usually 5 to 100 μm, preferably 10 to 60 μm.
　本発明のボンディングシートを製造する方法としては、例えば、離型性フィルムの表面に、上記カルボキシル基含有スチレン系エラストマー（Ａ）、エポキシ樹脂（Ｂ）及び溶剤を含む接着剤組成物を塗工した後、上記本発明のカバーレイフィルムの場合と同様にして乾燥する方法がある。 As a method for producing the bonding sheet of the present invention, for example, an adhesive composition containing the carboxyl group-containing styrene elastomer (A), epoxy resin (B), and solvent is applied to the surface of a release film. Thereafter, there is a method of drying in the same manner as in the case of the coverlay film of the present invention.
　本発明を、実施例に基づいてより具体的に説明するが、本発明は、これに限定されるものではない。なお、下記において、部及び％は、特に断らない限り、質量基準である。 The present invention will be described more specifically based on examples, but the present invention is not limited thereto. In the following, parts and% are based on mass unless otherwise specified.
１．評価方法
（１）分子量
　装置：アライアンス２６９５（Waters社製）
　カラム：ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｈ　２本、ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ２５００　２本、（東ソー社製）
　カラム温度：　４０℃
　溶離液：　テトラヒドロフラン　０．３５ｍｌ／ｍｉｎ
　検出器：　ＲＩ
　ＧＰＣにより測定した分子量をポリスチレンの分子量を基準にして換算した。 1. Evaluation method (1) Molecular weight Apparatus: Alliance 2695 (manufactured by Waters)
Column: 2 TSKgel SuperMultipore HZ-H, 2 TSKgel SuperHZ2500 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran 0.35ml / min
Detector: RI
The molecular weight measured by GPC was converted based on the molecular weight of polystyrene.
（２）はく離接着強さ
　厚さ２５μｍポリイミドフィルムを用意し、その表面に、表１に記載の液状接着剤組成物を、ロ－ル塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、９０℃で３分間乾燥させて厚さ２０μｍの被膜（接着性層）を形成し、カバーレイフィルムを得た。その後、厚さ３５μｍの圧延銅箔を、カバーレイフィルムの接着性層の表面に面接触するように重ね合わせ、１２０℃、圧力０．４ＭＰａ、及び速度０．５ｍ／分の条件でラミネ－トを行った。次いで、この積層体（ポリイミドフィルム／接着性層／銅箔）を１８０℃、及び圧力３ＭＰａの条件で３０分間加熱圧着し、フレキシブル銅張積層板を得た。このフレキシブル銅張積層板を切断して、所定の大きさの接着試験片を作製した。
　接着性を評価するために、ＪＩＳ　Ｃ　６４８１に準拠し、２３℃及び引張速度５０ｍｍ／分の条件で、接着試験片の銅箔をポリイミドフィルムから剥がすときの１８０゜はく離接着強さ（Ｎ／ｍｍ）を測定した。測定時の接着試験片の幅は１０ｍｍとした。 (2) Peeling adhesive strength A polyimide film having a thickness of 25 μm was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on the surface thereof. Subsequently, this film with a coating film was left still in an oven and dried at 90 ° C. for 3 minutes to form a coating film (adhesive layer) having a thickness of 20 μm to obtain a coverlay film. Thereafter, a rolled copper foil having a thickness of 35 μm is laminated so as to be in surface contact with the surface of the adhesive layer of the cover lay film, and laminated at 120 ° C., a pressure of 0.4 MPa, and a speed of 0.5 m / min. Went. Next, this laminate (polyimide film / adhesive layer / copper foil) was thermocompression bonded at 180 ° C. and a pressure of 3 MPa for 30 minutes to obtain a flexible copper-clad laminate. The flexible copper-clad laminate was cut to produce an adhesive test piece having a predetermined size.
In order to evaluate the adhesiveness, 180 ° peel adhesion strength (N / mm when peeling the copper foil of the adhesive test piece from the polyimide film at 23 ° C. and a tensile speed of 50 mm / min in accordance with JIS C 6481. ) Was measured. The width of the adhesion test piece at the time of measurement was 10 mm.
（３）はんだ耐熱性
　ＪＩＳ　Ｃ　６４８１に準拠し、次の条件で試験を行った。上記接着試験片を２５ｍｍ角に裁断し、１２０℃、３０分の加熱処理を行った。その後、ポリイミドフィルムの面を上にして、所定温度のはんだ浴に１０秒間浮かべて、接着試験片表面の発泡状態を観察した。この時、接着試験片に発泡が観察されない温度の上限を、はんだ耐熱性の温度とした。 (3) Solder heat resistance Based on JIS C 6481, the test was done on the following conditions. The said adhesion test piece was cut | judged to 25 square mm, and 120 degreeC and the heat processing for 30 minutes were performed. Thereafter, the surface of the polyimide film was faced up and floated in a solder bath at a predetermined temperature for 10 seconds, and the foaming state on the surface of the adhesion test piece was observed. At this time, the upper limit of the temperature at which foaming was not observed in the adhesion test piece was defined as the solder heat resistance temperature.
（４）樹脂流れ出し性
　厚さ２５μｍポリイミドフィルムを用意し、その表面に、表１に記載の液状接着剤組成物を、ロ－ル塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、９０℃で３分間乾燥させて厚さ２０μｍの被膜（接着性層）を形成し、カバーレイフィルムを得た。このカバーレイフィルムの接着性層の表面に６ｍｍφのパンチ穴を開けて、厚さ３５μｍの圧延銅箔を重ね合わせ、１２０℃、圧力０．４ＭＰａ、及び速度０．５ｍ／分の条件でラミネ－トを行った。次いで、この積層体（ポリイミドフィルム／接着性層／銅箔）を１８０℃、及び圧力３ＭＰａの条件で３０分間加熱圧着した。この時のポリイミド穴部からの接着性層の最大流出長さを測定した。流出長さが小さいものが良好で、大きいものほど樹脂流れ出し性が劣ると判断した。 (4) Resin flow-out property A polyimide film having a thickness of 25 μm was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on the surface thereof. Subsequently, this film with a coating film was left still in an oven and dried at 90 ° C. for 3 minutes to form a coating film (adhesive layer) having a thickness of 20 μm to obtain a coverlay film. A 6 mmφ punch hole is formed on the surface of the adhesive layer of the coverlay film, and a rolled copper foil having a thickness of 35 μm is overlaid, and laminating is performed at 120 ° C., a pressure of 0.4 MPa, and a speed of 0.5 m / min. Went. Next, this laminate (polyimide film / adhesive layer / copper foil) was thermocompression bonded for 30 minutes at 180 ° C. and under a pressure of 3 MPa. The maximum outflow length of the adhesive layer from the polyimide hole at this time was measured. It was judged that the smaller the outflow length, the better, and the larger the outflow length, the poorer resin flowability.
（５）誘電率及び誘電正接
　厚さ３８μｍ離型ポリエチレンテレフタレートフィルムを用意し、その表面に、表１に記載の液状接着剤組成物を、ロ－ル塗布した。次いで、この塗膜付きフィルムをオーブン内に静置して、９０℃で３分間乾燥させて厚さ５０μｍの被膜（接着性層）を形成し、ボンディングシートを得た。次に、このボンディングシートをオーブン内に静置して、１８０℃で３０分間加熱処理をした。その後、前記離型フィルムを剥がして、試験片（１５×８０ｍｍ）を作製した。
　接着剤硬化物の誘電率（ε）及び誘電正接（ｔａｎδ）は、ＰＮＡ－Ｌ ネットワークアナライザーＮ５２３０Ａ（アジレント社製）を使用し、空洞共振器摂動法で、２３℃、周波数１ＧＨｚの条件で測定した。 (5) Dielectric constant and dielectric loss tangent A release polyethylene terephthalate film having a thickness of 38 μm was prepared, and the liquid adhesive composition shown in Table 1 was roll-coated on the surface thereof. Subsequently, this film with a coating film was left still in an oven and dried at 90 ° C. for 3 minutes to form a coating film (adhesive layer) having a thickness of 50 μm to obtain a bonding sheet. Next, this bonding sheet was left in an oven and heat-treated at 180 ° C. for 30 minutes. Then, the said release film was peeled off and the test piece (15x80 mm) was produced.
The dielectric constant (ε) and dielectric loss tangent (tan δ) of the cured adhesive were measured using a PNA-L network analyzer N5230A (manufactured by Agilent) under the conditions of a cavity resonator perturbation method at 23 ° C. and a frequency of 1 GHz. .
２．接着剤組成物の原料
２－１．スチレン系エラストマー
（１）スチレン系エラストマーａ１
　旭化成ケミカルズ社製の商品名「タフテックＭ１９１３」（マレイン酸変性スチレン－エチレンブチレン－スチレンブロック共重合体）を用いた。この共重合体の酸価は１０ｍｇＫＯＨ／ｇであり、スチレン／エチレンブチレン比は３０／７０であり、重量平均分子量は１５万である。
（２）スチレン系エラストマーａ２
　旭化成ケミカルズ社製の商品名「タフテックＭ１９１１」（マレイン酸変性スチレン－エチレンブチレン－スチレンブロック共重合体）を用いた。この共重合体の酸価は２ｍｇＫＯＨ／ｇであり、スチレン／エチレンブチレン比は３０／７０であり、重量平均分子量は１５万である。
（３）スチレン系エラストマーα
　旭化成ケミカルズ社製の商品名「タフテックＨ１０４１」（スチレン－エチレンブチレン－スチレンブロック共重合体）を用いた。この共重合体の酸価は０ｍｇＫＯＨ／ｇであり、スチレン／エチレンブチレン比は３０／７０であり、重量平均分子量は１５万である。 2. 2. Raw material for adhesive composition 2-1. Styrene elastomer (1) Styrene elastomer a1
A trade name “Tuftec M1913” (maleic acid-modified styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 10 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
(2) Styrene elastomer a2
A trade name “Tuftec M1911” (maleic acid-modified styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 2 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
(3) Styrene elastomer α
The product name “Tuftec H1041” (styrene-ethylenebutylene-styrene block copolymer) manufactured by Asahi Kasei Chemicals Corporation was used. The copolymer has an acid value of 0 mg KOH / g, a styrene / ethylene butylene ratio of 30/70, and a weight average molecular weight of 150,000.
２－２．エポキシ樹脂
（１）エポキシ樹脂ｂ１
　ＤＩＣ社製　商品名「ＥＰＩＣＬＯＮ ＨＰ-７２００」（ジシクロペンタジエン骨格含有エポキシ樹脂）を用いた。
（２）エポキシ樹脂ｂ２
　ＤＩＣ社製　商品名「ＥＰＩＣＬＯＮ Ｎ-６５５ＥＸＰ」（クレゾールノボラックエポキシ樹脂）を用いた。
（３）エポキシ樹脂ｂ３
　三菱化学社製　商品名「ｊＥＲ８２８」（ビスフェノールＡ型エポキシ樹脂）を用いた。 2-2. Epoxy resin (1) Epoxy resin b1
The product name "EPICLON HP-7200" (dicyclopentadiene skeleton-containing epoxy resin) manufactured by DIC was used.
(2) Epoxy resin b2
The product name “EPICLON N-655EXP” (cresol novolac epoxy resin) manufactured by DIC was used.
(3) Epoxy resin b3
The product name “jER828” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation was used.
２－３．その他
（１）硬化促進剤
　四国化成社製　商品名「キュアゾールＣ１１－Ｚ」（イミダゾール系硬化促進剤）を用いた。
（２）無機充填剤
　トクヤマ社製　商品名「エクセリカＳＥ-１」（シリカ）を用いた。
（３）粘着付与剤
　ヤスハラケミカル社製　商品名「クリアロンＰ１０５」（テルペン樹脂）を用いた。
（４）溶剤
　トルエン及びメチルエチルケトンからなる混合溶剤（質量比＝９０：１０）を用いた。 2-3. Others (1) Curing accelerator A trade name “Curazole C11-Z” (imidazole curing accelerator) manufactured by Shikoku Kasei Co., Ltd. was used.
(2) Inorganic filler A trade name “Excellica SE-1” (silica) manufactured by Tokuyama Corporation was used.
(3) Tackifier A product name “Clearon P105” (terpene resin) manufactured by Yasuhara Chemical Co., Ltd. was used.
(4) Solvent A mixed solvent composed of toluene and methyl ethyl ketone (mass ratio = 90: 10) was used.
３．接着剤組成物の製造及び評価
　実施例１～７、比較例１～３
　撹拌装置付き１０００ｍｌフラスコに、上記の原料を表１に示す割合で添加し、室温下で６時間撹拌して溶解することにより、固形分濃度２０％の液状接着剤組成物を調製した。得られた液状接着剤組成物を用いて、上記の各種評価を行った。 3. Production and Evaluation of Adhesive Composition Examples 1 to 7 and Comparative Examples 1 to 3
The above-mentioned raw materials were added to a 1000 ml flask equipped with a stirrer at the ratio shown in Table 1, and the mixture was stirred and dissolved at room temperature for 6 hours to prepare a liquid adhesive composition having a solid content concentration of 20%. Various evaluations described above were performed using the obtained liquid adhesive composition.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１の結果から、実施例１～７の接着剤組成物は、すべての特性において優れたものであることが分かる。一方、比較例１及び２は、エポキシ樹脂（Ｂ）の含有量が本発明の範囲の上限から外れるため、接着性や誘電特性に劣る。また、比較例３は、スチレン系エラストマーがカルボキシル基を有しないため、接着性、はんだ耐熱性及び樹脂流れ出し性に劣る。 From the results of Table 1 above, it can be seen that the adhesive compositions of Examples 1 to 7 are excellent in all properties. On the other hand, Comparative Examples 1 and 2 are inferior in adhesiveness and dielectric properties because the content of the epoxy resin (B) deviates from the upper limit of the range of the present invention. Moreover, since the styrene-type elastomer does not have a carboxyl group, the comparative example 3 is inferior to adhesiveness, solder heat resistance, and resin flow-out property.
　本発明の接着剤組成物は、ポリイミドフィルム等に対して優れた接着性を発現するため、フレキシブルプリント配線板の関連製品の製造に好適である。そして、本発明の接着剤組成物を用いて得られるカバーレイフィルム、フレキシブル銅張積層板及びボンディングシートは、いずれも、外観及び誘電特性に優れる。 Since the adhesive composition of the present invention exhibits excellent adhesion to a polyimide film or the like, it is suitable for production of related products of flexible printed wiring boards. And the coverlay film, flexible copper clad laminated board, and bonding sheet which are obtained using the adhesive composition of the present invention are all excellent in appearance and dielectric properties.

Claims (8)

  1. 　カルボキシル基含有スチレン系エラストマー（Ａ）と、エポキシ樹脂（Ｂ）とを含有する接着剤組成物であって、
    　前記エポキシ樹脂（Ｂ）の含有量は、前記カルボキシル基含有スチレン系エラストマー（Ａ）１００質量部に対して１～２０質量部であり、かつ、周波数１ＧＨｚで測定した接着剤硬化物の誘電率が２．５未満であることを特徴とする接着剤組成物。     An adhesive composition containing a carboxyl group-containing styrenic elastomer (A) and an epoxy resin (B),
    The content of the epoxy resin (B) is 1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing styrene elastomer (A), and the dielectric constant of the cured adhesive measured at a frequency of 1 GHz is An adhesive composition characterized by being less than 2.5.
  2. 　上記カルボキシル基含有スチレン系エラストマー（Ａ）の酸価が、０．１～２０ｍｇＫＯＨ／ｇである請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the carboxyl group-containing styrene elastomer (A) has an acid value of 0.1 to 20 mgKOH / g.
  3. 　上記カルボキシル基含有スチレン系エラストマー（Ａ）が、スチレン－ブタジエンブロック共重合体、スチレン－エチレンプロピレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－エチレンブチレン－スチレンブロック共重合体、スチレン－エチレンプロピレン－スチレンブロック共重合体からなる群より選択される少なくとも１つのスチレン系エラストマーを、不飽和カルボン酸で変性したものである請求項１又は２に記載の接着剤組成物。 The carboxyl group-containing styrene elastomer (A) is a styrene-butadiene block copolymer, styrene-ethylenepropylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene. 3. At least one styrenic elastomer selected from the group consisting of an ethylene-butylene-styrene block copolymer and a styrene-ethylenepropylene-styrene block copolymer is modified with an unsaturated carboxylic acid. The adhesive composition described in 1.
  4. 　上記エポキシ樹脂（Ｂ）が、脂環骨格を有する多官能エポキシ樹脂である請求項１～３のいずれか１項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 3, wherein the epoxy resin (B) is a polyfunctional epoxy resin having an alicyclic skeleton.
  5. 　周波数１ＧＨｚで測定した接着剤硬化物の誘電正接が、０．０１未満である請求項１～４のいずれか１項に記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 4, wherein a dielectric loss tangent of the cured adhesive product measured at a frequency of 1 GHz is less than 0.01.
  6. 　請求項１～５のいずれか１項に記載の接着剤組成物を用いて得られた接着性層が、ポリイミドフィルム又は液晶ポリマーフィルムの一方の表面に形成されてなることを特徴とするカバーレイフィルム。 6. A coverlay, wherein the adhesive layer obtained by using the adhesive composition according to any one of claims 1 to 5 is formed on one surface of a polyimide film or a liquid crystal polymer film. the film.
  7. 　請求項１～５のいずれか１項に記載の接着剤組成物を用いて、ポリイミドフィルム又は液晶ポリマーフィルムの少なくとも一方の表面に銅箔を貼り合わせてなることを特徴とするフレキシブル銅張積層板。 A flexible copper clad laminate comprising a copper foil bonded to at least one surface of a polyimide film or a liquid crystal polymer film using the adhesive composition according to any one of claims 1 to 5. .
  8. 　請求項１～５のいずれか１項に記載の接着剤組成物を用いて得られた接着性層が、離型性フィルムの一方の表面に形成されてなることを特徴とするボンディングシート。 A bonding sheet, wherein an adhesive layer obtained by using the adhesive composition according to any one of claims 1 to 5 is formed on one surface of a release film.
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