JPH02133487A - Adhesive resin composition - Google Patents
Adhesive resin compositionInfo
- Publication number
- JPH02133487A JPH02133487A JP28587688A JP28587688A JPH02133487A JP H02133487 A JPH02133487 A JP H02133487A JP 28587688 A JP28587688 A JP 28587688A JP 28587688 A JP28587688 A JP 28587688A JP H02133487 A JPH02133487 A JP H02133487A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- copper foil
- adhesive
- adhesive resin
- polyimide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000004840 adhesive resin Substances 0.000 title claims abstract description 20
- 229920006223 adhesive resin Polymers 0.000 title claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 229920001225 polyester resin Polymers 0.000 claims description 19
- 239000004645 polyester resin Substances 0.000 claims description 19
- 239000011889 copper foil Substances 0.000 abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 43
- 229920001721 polyimide Polymers 0.000 abstract description 40
- 238000005476 soldering Methods 0.000 abstract description 14
- -1 polyethylene terephthalate adipate Polymers 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000004642 Polyimide Substances 0.000 abstract description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001634 Copolyester Polymers 0.000 abstract description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 description 42
- 239000000853 adhesive Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 18
- 229910000679 solder Inorganic materials 0.000 description 10
- 239000004831 Hot glue Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XSSOJMFOKGTAFU-UHFFFAOYSA-N 3-[2-(2-prop-2-enoxyethoxy)ethoxy]prop-1-ene Chemical compound C=CCOCCOCCOCC=C XSSOJMFOKGTAFU-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920013646 Hycar Polymers 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- FDADMSDCHGXBHS-UHFFFAOYSA-N copper;ethene Chemical compound [Cu].C=C FDADMSDCHGXBHS-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、飽和共重合ポリエステル樹脂と架橋性モノマ
ーおよび/またはオリゴマーからなる接着性樹脂組成物
に関し、さらに詳しくは、ポリイミドをベースフィルム
とするフレキシブルプリント基板における銅箔とポリイ
ミドフィルムとの接着、あるいは該基板とオーバーレイ
フィルムとの接着に特に好適な接着性樹脂組成物に関す
る。Detailed Description of the Invention [Industrial Application Field] The present invention relates to an adhesive resin composition comprising a saturated copolymerized polyester resin and a crosslinkable monomer and/or oligomer, and more particularly relates to an adhesive resin composition comprising a polyimide base film. The present invention relates to an adhesive resin composition particularly suitable for adhesion between a copper foil and a polyimide film in a flexible printed board, or for adhesion between the board and an overlay film.
近年、電子機器が軽量小形化、高性能化するにつれて、
通常の絶縁被覆電線に替わって、基板上に金属箔の配線
部を形成した回路基板が、テレビジョン受信機、オーデ
ィオ機器などの民生用電子機器、計測器、電子計算機な
どの電子機器、自動車、航空機などの各種配線部こ多用
されるに至っている。In recent years, as electronic devices have become lighter, smaller, and more sophisticated,
Instead of ordinary insulated wires, circuit boards with metal foil wiring formed on the board are used in consumer electronic equipment such as television receivers and audio equipment, electronic equipment such as measuring instruments and computers, automobiles, etc. It has come to be widely used in various wiring parts such as in aircraft.
このような用途に使用される回路基板として、高分子材
料からなるフィルムと銅箔とがら構成された可撓性を有
するいわゆるフレキシブルプリント基板が多用されてい
る。当該基板には、銅箔表面を化学的なエツチングなど
の手段により、必要部分のみを残して、配線パターンが
形成される。As a circuit board used for such purposes, a so-called flexible printed circuit board, which has flexibility and is composed of a film made of a polymer material and a copper foil, is often used. A wiring pattern is formed on the substrate by means such as chemical etching on the surface of the copper foil, leaving only the necessary portions.
現在、このフレキシブルプリント基板は、銅箔とポリエ
チレンテレフタレートフィルムあるいはポリイミドフィ
ルムなどの可撓性絶縁フィルムとを、フィルム状接着剤
を使用してラミネートする方法、銅箔または可撓性絶縁
フィルム上に接着剤を塗布し、加圧下に加熱接着せしめ
る方法、あるいはエポキシ樹脂含浸ガラス布(プリプレ
グ)を銅箔と加圧下に加熱接着せしめる方法などにより
製造されている。Currently, this flexible printed circuit board is produced by laminating copper foil and a flexible insulating film such as polyethylene terephthalate film or polyimide film using a film adhesive, or by bonding the copper foil or flexible insulating film onto the copper foil or flexible insulating film. They are manufactured by applying an agent and heat bonding under pressure, or by heat bonding an epoxy resin-impregnated glass cloth (prepreg) to copper foil under pressure.
ところで、近年、プリント配線板などの電子部品には、
耐熱性、耐熱老化性、電気絶縁性、耐薬品性、引裂強さ
などに、それぞれ高度の性能が要求されてきており、特
にそれらの実装時には、自動半田付は工程を経る場合が
多いため、半田耐熱性などの耐熱特性に関しては、可撓
性絶縁フィルムの耐熱性だけではな(、銅箔との接着剤
層にも高度の耐熱性が要求されている。By the way, in recent years, electronic components such as printed wiring boards,
High performance is required in terms of heat resistance, heat aging resistance, electrical insulation, chemical resistance, tear strength, etc. Especially when mounting these, automatic soldering often requires a process. Regarding heat resistance properties such as solder heat resistance, not only the heat resistance of the flexible insulating film (but also the adhesive layer with the copper foil is required to have a high degree of heat resistance.
可撓性絶縁フィルムの耐熱性等に関しては、ポリエチレ
ンテレフタレートフィルムは、安価であるが耐熱性に劣
り、半田付は工程でフィルムの軟化、ふくれ、銅箔との
剥離などの問題が生じる場合があり、また、エポキシ樹
脂含浸ガラス布は、半田付は工程で変色したり、極薄で
可撓性の良好なものを製造しにくく、しかも高価である
などの開閉点を有している。Regarding the heat resistance of flexible insulating films, polyethylene terephthalate film is inexpensive but has poor heat resistance, and problems such as softening, blistering, and peeling of the film from the copper foil may occur during the soldering process. In addition, epoxy resin-impregnated glass cloth has switching points such as discoloration during the soldering process, difficulty in manufacturing extremely thin and flexible products, and high cost.
これに対し、ポリイミドフィルムは、優れた耐熱性、電
気的特性、耐化学薬品性などを有するため、フレキシブ
ルプリント基板用ベースフィルムとして多用されている
。On the other hand, polyimide films have excellent heat resistance, electrical properties, chemical resistance, etc., and are therefore frequently used as base films for flexible printed circuit boards.
ところが、ポリイミドフィルムは、−船釣特性として接
着性が悪いため、充分な剥離強度を得ることが困難であ
り、特に半田付は工程や繰り返し屈曲による銅箔の剥離
が問題となる。However, polyimide films have poor adhesion properties, making it difficult to obtain sufficient peel strength, and peeling of the copper foil during soldering processes and repeated bending is particularly problematic.
そこで、接着性を改善するために、各種の接着剤が開発
されている。フレキシプリント基板の銅箔とポリイミド
フィルムあるいは、フレキシプリント基板とオーバーレ
イフィルムの接着を行なうには、銅箔とポリイミドフィ
ルムの双方に接着する接着剤が必要である。従来、この
ような接着剤として、六フッ化プロピレンー四フッ化エ
チレン共重合体(デュポン社製”Teflon″FEP
など)などのフッ素系樹脂、エポキシ−ノボラック系樹
脂(ダウ・ケミカル社製DEN438など)、シリコー
ン樹脂(ダウ・コーニング社製DC282など)、ニト
リル−フェノール系樹脂CB、 F、グツ:2リッチ社
製Plastilock 605など)、ポリエステル
系才封月旨fUSM社製Bostic 7151+ B
oscodur 1など)、アクリル系樹脂(B、F、
グツドリッチ社製Hycar 2679X6、ローム・
アンド・ハース社製Phoplex LC40、UCC
社製Dear 370など)が知られている(工業材料
、vol、2+、No、IO,p、28,1981)。Therefore, various adhesives have been developed to improve adhesive properties. To bond the copper foil and polyimide film of a flexible printed circuit board or the flexible printed circuit board and an overlay film, an adhesive that adheres to both the copper foil and the polyimide film is required. Conventionally, as such adhesive, hexafluoropropylene-tetrafluoroethylene copolymer ("Teflon" FEP manufactured by DuPont) has been used.
etc.), epoxy-novolac resins (DOW Chemical Co., Ltd. DEN438, etc.), silicone resins (Dow Corning Co., Ltd. DC282, etc.), nitrile-phenolic resins CB, F, Gutsu: 2 Rich Co., Ltd. Plastilock 605, etc.), polyester-based product Bostic 7151+ B manufactured by USM
oscodur 1, etc.), acrylic resins (B, F,
Gutdrich Hycar 2679X6, Rohm
& Haas Phoplex LC40, UCC
Dear 370 manufactured by Kogyo Corporation, etc.) are known (Industrial Materials, vol. 2+, No., IO, p. 28, 1981).
上記の接着剤を使用した場合、ポリイミドフィルムと銅
箔の初期接着力は、シリコーン樹脂系接着剤を使用した
系を除けば、1.0kg/cm以上の接着力を示し、ま
た、例λば、290°Cの半田浴に10秒間浸漬した場
合にも、ポリイミドフィルムや銅箔のふ(れ、シ1離が
認められず、半田耐熱性についても優れた特性を有して
いる。When the above adhesives are used, the initial adhesive strength between polyimide film and copper foil is 1.0 kg/cm or more, except for systems using silicone resin adhesives, and for example λ Even when immersed in a 290°C solder bath for 10 seconds, no bulging or peeling of the polyimide film or copper foil was observed, and it also has excellent soldering heat resistance.
ところが、上記の接着剤は、接着を完了せしめるのに高
温と長時間を必要するものが多(、例えば、エポキシ−
ノボラック系樹脂の場合においては、接着剤の硬化反応
を完了せしめるために180°Cないし200℃の高温
で30分から60分間の熱圧着を行なう必要がある。こ
のため、ポリイミドフィルムと銅箔の接着は基本的にバ
ッチ処理となり、フレキシブルプリント基板を連続的に
生産しようとする場合、接着工程が律速段階とになり、
生産性の向上に限界がある
一方、六フッ化プロピレンー四フッ化エチレン共重合体
を接着剤として使用する場合には、ポリイミドフィルム
と銅箔間に六フッ化プロビレ〉・−四フッ化エチレン共
重合体のフィルムを挾み、290°Cないし320’C
で熱圧着するだけで接着が可能であり、フレキシブルプ
リント基板の連続的な生産に適する反面、接着処理温度
がより高温になるために、部分的に銅箔の酸化が進行す
るなどの問題点を抱えている。However, many of the above adhesives require high temperatures and long periods of time to complete adhesion (for example, epoxy
In the case of novolak resin, it is necessary to carry out thermocompression bonding at a high temperature of 180° C. to 200° C. for 30 to 60 minutes in order to complete the curing reaction of the adhesive. For this reason, bonding polyimide film and copper foil is basically a batch process, and when trying to continuously produce flexible printed circuit boards, the bonding process becomes the rate-limiting step.
While there is a limit to productivity improvement, when using a hexafluoropropylene-tetrafluoroethylene copolymer as an adhesive, it is necessary to Sandwich the polymer film and heat at 290°C to 320'C.
Bonding can be done simply by thermocompression, making it suitable for the continuous production of flexible printed circuit boards. However, because the bonding process temperature is higher, there are problems such as partial oxidation of the copper foil. I'm holding it.
最近、ポリイミドフィルムに熱可塑性ポリイミドフィル
ム(三井東圧社製Larc−TPI )を介して銅箔を
接着することが提案されているが(機能材料、1985
年9月号p、 22−30 ) 、熱可塑性ポリイミド
の融着温度が350℃と高温であるため、銅箔の酸化劣
化や熱膨張率の差異に起因するカールなどの問題が予想
される。Recently, it has been proposed to bond copper foil to a polyimide film via a thermoplastic polyimide film (Larc-TPI manufactured by Mitsui Toatsu Co., Ltd.) (Functional Materials, 1985).
Since the fusing temperature of thermoplastic polyimide is as high as 350° C., problems such as oxidative deterioration of the copper foil and curling due to differences in coefficient of thermal expansion are expected.
ポリイミドフィルムと銅箔の接着剤としては、この他に
、エポキシ崩脂−ボリアミン系接着剤や、ポリオール−
イソシアネート系などのポリウレタン系接着剤なども種
々検討されているが、接着剤の硬化反応を完了せしめる
には、上記同様に高温と長時間、もしくは室温近辺の温
度であっても長時間を要するため、接着工程はバッチ処
理とならざるを得ない。Other adhesives for polyimide film and copper foil include epoxy fat-polyamine adhesives and polyol-based adhesives.
Various polyurethane-based adhesives such as isocyanate-based adhesives are being considered, but as above, it requires high temperatures and long periods of time, or even at temperatures around room temperature, to complete the curing reaction of the adhesives. , the adhesion process must be a batch process.
触媒などの添加によって、硬化所要時間を短縮せしめる
方法も知られているが、短時間で硬化を完了せしめると
、接着剤層に硬化歪みが残留し、その結果、フレキシブ
ルプリント基板がカーリングするなどの問題が発生する
場合がある。It is also known to shorten the curing time by adding catalysts, etc. However, if curing is completed in a short time, curing distortion remains in the adhesive layer, resulting in problems such as curling of the flexible printed circuit board. Problems may occur.
方、一般に被接着物間の接着を比較的低温で、しかも短
時間で行なうことのできる接着剤としてホットメルト接
着剤が知られている。On the other hand, hot melt adhesives are generally known as adhesives that can bond objects together at relatively low temperatures and in a short time.
ホットメルト接着剤の種類としては、エチレンのポモポ
リマーおよびコポリマー、スチレンブロックコポリマー
(熱可塑性エラストマー)、ボッアミド系、ナイロン系
、ポリエステル系、ブチルゴム系などが知られており、
粘首付与剤としては、ロジンおよびそのエステル誘導体
、水添ロジンおよびそのエステル誘導体、石油系炭化水
素樹脂、可剤剤としては、パラフィンワックス類、酸化
防止剤としては、ヒンダードフェノール類、亜リン酸塩
類などが使用されている。Known types of hot melt adhesives include ethylene pomopolymers and copolymers, styrene block copolymers (thermoplastic elastomers), boramid adhesives, nylon adhesives, polyester adhesives, and butyl rubber adhesives.
Viscosifying agents include rosin and its ester derivatives, hydrogenated rosin and its ester derivatives, petroleum-based hydrocarbon resins, additives include paraffin waxes, and antioxidants include hindered phenols and phosphorus. Acid salts are used.
このホットメルト接着剤をポリイミドフィルムと銅箔の
接着に応用することが考えられる。例えば、エチレン−
酢酸ビニル共重合体系ホットメルト接着剤やエチレン−
エチルアクリレート系ホットメルト接着剤の溶融物をポ
リイミドフィルムに約30μmの厚みに塗布し、銅箔と
100°Cないし170℃で1分間圧着すれば、銅箔と
ポリイミドフィルムの接着が可能である。そして、この
場合、初期接着力が1.0kg/cm以上の接着力を有
するものを容易に形成することが可能である。It is conceivable to apply this hot melt adhesive to bonding polyimide film and copper foil. For example, ethylene-
Vinyl acetate copolymer hot melt adhesives and ethylene
Copper foil and polyimide film can be bonded by applying a melted ethyl acrylate hot-melt adhesive to a thickness of about 30 μm on a polyimide film and pressing it against a copper foil at 100°C to 170°C for 1 minute. In this case, it is possible to easily form a material having an initial adhesive strength of 1.0 kg/cm or more.
ところが、上記のホットメルト接着剤により形成したポ
リイミドフィルム銅箔積層体は、例えば、280°Cの
半田浴に5秒間1すると、ポリイミドフィルムと銅箔が
剥離してしまうという問題がある。However, the polyimide film copper foil laminate formed using the above hot melt adhesive has a problem in that the polyimide film and the copper foil peel off when placed in a solder bath at 280° C. for 5 seconds, for example.
以上説明したように、銅箔とポリイミドフィルムの接着
には、接着強度と半田耐熱性の改善を目的として多くの
接着剤が提案されており、利用されている。ところが、
熱硬化性接着剤の多くは硬化に高温と長時間を要するた
め、接着工程がバッチ処理となり生産性が悪く、また、
熱可塑性接着剤も高温での圧着を必要とし、銅箔の酸化
や基板のカールを引き起こすなどの問題を有している。As explained above, many adhesives have been proposed and used for adhering copper foil and polyimide film with the aim of improving adhesive strength and solder heat resistance. However,
Many thermosetting adhesives require high temperatures and long periods of time to cure, so the bonding process is a batch process, resulting in poor productivity.
Thermoplastic adhesives also require pressure bonding at high temperatures and have problems such as oxidation of the copper foil and curling of the substrate.
一方、ホットメルト接着剤は、比較的低温で、しかも短
時間で接着を行なうことができ、初期接着力も良好では
あるものの、半田耐熱性が極めて悪い。On the other hand, hot melt adhesives can be bonded at a relatively low temperature and in a short time, and have good initial adhesive strength, but have extremely poor soldering heat resistance.
このように、従来、短時間での接着が可能で、初期接着
力が太き(、しかも半田耐熱性にも便れる接着剤は知ら
れていない。As described above, there has been no known adhesive that can be bonded in a short time, has a strong initial adhesive strength (and also has good soldering heat resistance).
[発明が解決しようとする課題]
本発明の目的は、比較的低温かつ短時間での接着が可能
で、初期接着力が大きく、しがも半田耐熱性に優れた接
着性樹脂組成物を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide an adhesive resin composition that can be bonded at a relatively low temperature and in a short time, has a large initial adhesive strength, and has excellent soldering heat resistance. It's about doing.
さらに、本発明の目的は、ポリイミドをベースフィルム
とするフレキシブルプリント基板の銅箔とポリイミドフ
ィルム、あるいは該基板とオーバーレイフィルムとの接
着用として好適な接着性樹脂組成物を提供することにあ
る。A further object of the present invention is to provide an adhesive resin composition suitable for adhesion between a copper foil and a polyimide film of a flexible printed board having a polyimide base film, or between the board and an overlay film.
本発明者らは、前記従来技術の有する問題点を解決する
ために鋭意研究した結果、飽和共重合ポリエステル樹脂
に、分子内に複数個の不飽和結合を有するモノマーおよ
び/またはオリゴマーを添加した樹脂組成物が、ポリイ
ミドフィルムと銅箔の接着剤として、比較的低温かつ短
時間での接着が可能で、初期接着力に優れ、しかも半田
耐熱i生に優れていることを見出した。本発明は、それ
らの知見に基づいて完成するに至ったものである。As a result of intensive research to solve the problems of the above-mentioned conventional technology, the present inventors have discovered a resin in which a monomer and/or oligomer having multiple unsaturated bonds in the molecule is added to a saturated copolymerized polyester resin. It has been found that the composition can be used as an adhesive for polyimide film and copper foil to bond at relatively low temperatures and in a short time, has excellent initial adhesive strength, and has excellent solder heat resistance. The present invention has been completed based on these findings.
[課題を解決するための手段]
すなわち、本発明の要旨は、飽和共重合ポリエステル樹
脂に、分子内に複数個の不飽和結合を有するモノマーお
よび/またはオリゴマーを添加してなる接着性樹脂組成
物にある。[Means for Solving the Problems] That is, the gist of the present invention is to provide an adhesive resin composition obtained by adding a monomer and/or oligomer having a plurality of unsaturated bonds in the molecule to a saturated copolymerized polyester resin. It is in.
以下、本発明の構成等について詳述する。Hereinafter, the configuration of the present invention will be explained in detail.
(飽和共重合ポリエステル樹脂)
本発明で用いる飽和共重合ポリエステル樹脂は、多価カ
ルボン酸と多価アルコールの重縮合反応によって合成さ
れるものであって、具体的には、テレフタル酸、イソフ
タル酸、アジピン酸、アゼライン酸、セバシン酸などの
多価カルボン酸と、エチレングリコール、1,4−ブタ
ンジオール、1,6−ヘキサンジオール、ジエチレング
リコール、ポリエチレングリコールなどの多価アルコー
ルをモノマーとし、これらのモノマー成分を組合わせて
重縮合して得られる共重合体である。(Saturated copolymerized polyester resin) The saturated copolymerized polyester resin used in the present invention is synthesized by a polycondensation reaction of a polycarboxylic acid and a polyhydric alcohol, and specifically includes terephthalic acid, isophthalic acid, The monomer components are polycarboxylic acids such as adipic acid, azelaic acid, and sebacic acid, and polyhydric alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and polyethylene glycol. It is a copolymer obtained by polycondensing a combination of
これらの飽和共重合ポリエステル樹脂としては、ポリエ
チレンテレフタレートやポリブチレンテレフタレートな
どの飽和ホモポリエステルの成分の一部を他成分で置き
換え、ランダム共重合させたものが代表的なものであり
、例えば、ポリエチレンテレフタレート・セバケート、
ポリエチレンテレフタレート・アジペート、ポリエチレ
ンテレフタレート・イソフタレート、ポリブチレンテレ
フタレート・イソフタレートなどが挙げられる。Typical of these saturated copolymerized polyester resins are those in which some of the components of saturated homopolyesters such as polyethylene terephthalate and polybutylene terephthalate are replaced with other components and randomly copolymerized, such as polyethylene terephthalate.・Sevakate,
Examples include polyethylene terephthalate/adipate, polyethylene terephthalate/isophthalate, and polybutylene terephthalate/isophthalate.
本発明では、これらの飽和共重合ポリエステル樹脂とし
て、市販のものを使用することができる。また、2種以
上の樹脂を組合わせて使用してもよい。In the present invention, commercially available saturated copolyester resins can be used. Furthermore, two or more types of resins may be used in combination.
(分子内に複数個の不飽和結合を有するモノマーおよび
オリゴマー)
本発明で用いる分子内に複数個の不飽和結合を有するモ
ノマーとしては、例えば、エチレングリコールジアクリ
レート、1.4−ブタンジオールジメタクリレート、ト
リメチロールプロパントリアクリレート、ポリエチレン
グリコールジメタクリレート、シアヌル酸トリアクリレ
ート、トリアクリルホルマールなどのアクリル酸エステ
ルまたはメタクリル酸エステル系モノマー、トリアリル
シアヌレート、トリアリルイソシアヌレート、トリメリ
ット酸トリアリル、ジエチレングリコールジアリルエー
テルなどのアリル系化合物などを挙げることができる。(Monomers and oligomers having multiple unsaturated bonds in the molecule) Monomers having multiple unsaturated bonds in the molecule used in the present invention include, for example, ethylene glycol diacrylate, 1,4-butanediol dimethacrylate, , trimethylolpropane triacrylate, polyethylene glycol dimethacrylate, cyanuric acid triacrylate, acrylic ester or methacrylic ester monomers such as triacrylic formal, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diethylene glycol diallyl ether Examples include allyl compounds such as.
また、本発明で用いる分子内に複数個の不飽和結合を有
するオリゴマーとしては、例えば、アクリル変性ビスフ
ェノール誘導体、アクリル変性ノボラック樹脂誘導体、
アクリル変性エステルオリゴマー類、アリリデンペンタ
エリスリトール誘導体、ジアリリデンペンタエリスリト
ール誘導体、アクリル変性ジアリリデンペンタエリトー
ル誘導体などを挙げることができる。Further, examples of oligomers having multiple unsaturated bonds in the molecule used in the present invention include acrylic-modified bisphenol derivatives, acrylic-modified novolac resin derivatives,
Examples include acrylic modified ester oligomers, arylidene pentaerythritol derivatives, diarylidene pentaerythritol derivatives, and acrylic modified diarylidene pentaerythritol derivatives.
これらのモノマーおよびオリゴマーは、それぞれ単独で
、あるいは複数種を徂合わせて使用することができる。These monomers and oligomers can be used alone or in combination.
(配合割合)
飽和共重合ポリエステル樹脂と分子内に複数個の不飽和
結合を有するモノマーおよび/またはオリゴマーの配合
割合は、特に限定されないが、初期接着力および半田耐
熱性の観点から、飽和共重合ポリエステル樹脂99〜5
0重量部に対し前記モノマーおよび/またはオリゴマー
1〜50重量部の配合割合が好ましく、さらに好ましく
は、飽和共重合ポリエステル樹脂95〜7o重量部に対
し、前記モノマーおよび/またはオリゴマー5〜30重
量部の配合割合である。(Blending ratio) The blending ratio of the saturated copolymerized polyester resin and the monomer and/or oligomer having multiple unsaturated bonds in the molecule is not particularly limited, but from the viewpoint of initial adhesive strength and soldering heat resistance, the saturated copolymerized polyester resin Polyester resin 99-5
The blending ratio is preferably 1 to 50 parts by weight of the monomer and/or oligomer to 0 parts by weight, and more preferably 5 to 30 parts by weight of the monomer and/or oligomer to 95 to 7 parts by weight of the saturated copolymerized polyester resin. This is the blending ratio of
また、本発明の接着性樹脂組成物には、必要に応じて、
可塑剤、酸化防止剤などの添加剤を適宜添加することが
できる。In addition, the adhesive resin composition of the present invention may include, if necessary,
Additives such as plasticizers and antioxidants can be added as appropriate.
さらに、後述するように、ジクミルパーオキサイドなど
の有機過酸化物やベンゾフェノンなどの光重合開始剤を
添加することができる。Furthermore, as described later, an organic peroxide such as dicumyl peroxide or a photopolymerization initiator such as benzophenone can be added.
(使用方法)
本発明の接着性樹脂組成物をポリイミドをベースフィル
ムとするフレキシブルプリント基板用接着剤として使用
するには、ポリイミドフィルム上に該樹脂組成物を加熱
溶融して塗布するか、あるいは該樹脂組成物の有機溶媒
溶液を塗布し、乾燥せしめる方法などにより、樹脂組成
物層を形成し、次いで、当該樹脂組成物層上に銅箔を熱
プレスなどの方法で一熱圧着せしめる。熱圧着の条件は
、使用する飽和共重合ポリエステルの軟化点または融点
にもよるが、100〜210’C1好ましくは100〜
180°C1さらに好ましくは100〜160℃の温度
で、好ましくは1〜20分、さらに好ましくは5〜15
分の時間で圧着せしめる。(Method of Use) In order to use the adhesive resin composition of the present invention as an adhesive for flexible printed circuit boards using polyimide as a base film, the resin composition is heated and melted and applied onto a polyimide film, or A resin composition layer is formed by applying and drying a solution of a resin composition in an organic solvent, and then a copper foil is thermally pressed onto the resin composition layer by a method such as a hot press. The conditions for thermocompression bonding depend on the softening point or melting point of the saturated copolymer polyester used, but are preferably 100 to 210'C1.
180°C1, more preferably at a temperature of 100 to 160°C, preferably for 1 to 20 minutes, even more preferably for 5 to 15 minutes.
It can be crimped in minutes.
本発明の接着性樹脂組成物は、前記の熱圧着法のみで接
着を完了せしめることが可能であり、この場合、加熱に
より遊離基などの活性種を発生する有機過酸化物などの
ラジカル重合開始剤を接着性樹脂組成物に予め有効量添
加しておくことが望ましい。The adhesive resin composition of the present invention can complete adhesion only by the above-mentioned thermocompression bonding method, and in this case, radical polymerization of organic peroxides, etc., which generate active species such as free radicals by heating, can be completed. It is desirable to add an effective amount of the agent to the adhesive resin composition in advance.
また、本発明の接着性樹脂組成物を用いて熱圧着した後
、ポリイミドフィルム面上から電離放射線を照射すれば
、初期接着力および半田耐熱性が一層優れたポリイミド
フィルム銅箔積層体を得ることができる。Further, by irradiating ionizing radiation from the surface of the polyimide film after thermocompression bonding using the adhesive resin composition of the present invention, a polyimide film copper foil laminate with even better initial adhesive strength and soldering heat resistance can be obtained. Can be done.
電離放射線としては、α線、β線(電子線)、γ線、X
線、紫外線などが使用可能であるが、工業的利用という
見地からは、β線(電子線)や紫外線の使用が望ましい
。また、紫外線を使用する場合には、紫外線照射により
遊機基を発生するベンゾフェノン、ベンゾフェノン誘導
体、アセトフェノン、アセトフェノン誘導体などの光重
合開始触媒を有効量添加することが好ましい。Ionizing radiation includes α rays, β rays (electron beams), γ rays, and
Rays, ultraviolet rays, etc. can be used, but from the standpoint of industrial use, it is desirable to use β rays (electron beams) and ultraviolet rays. When ultraviolet rays are used, it is preferable to add an effective amount of a photopolymerization initiation catalyst such as benzophenone, benzophenone derivatives, acetophenone, and acetophenone derivatives that generate free radicals upon irradiation with ultraviolet rays.
また、本発明の接着性樹脂組成物は、ポリイミドフィル
ム銅箔積層体のみならず、熱圧着等による接着が可能な
分野に適用することができる。Furthermore, the adhesive resin composition of the present invention can be applied not only to polyimide film copper foil laminates but also to fields where bonding by thermocompression bonding or the like is possible.
〔作 用]
本発明の飽和共重合ポリエステルと分子内に複数個の不
飽和結合を有するモノマーおよび/またはオリゴマーの
組成物をポリイミドフィルムと銅箔の接着剤として使用
した場合、初期接着力とともに半田耐熱性の優れたポリ
イミドフィルム銅箔積層体(フレキシブルプリント基板
)が得られる。熱圧着の条件も比較的低温かつ短時間で
あるため、銅箔の酸化劣化や基板のカーリングの発生な
どの問題もない。[Function] When the composition of the saturated copolymerized polyester of the present invention and a monomer and/or oligomer having a plurality of unsaturated bonds in the molecule is used as an adhesive between a polyimide film and a copper foil, the initial adhesion strength as well as the solder A polyimide film copper foil laminate (flexible printed circuit board) with excellent heat resistance is obtained. Since the thermocompression bonding conditions are relatively low temperature and short time, there are no problems such as oxidation deterioration of the copper foil or curling of the substrate.
飽和共重合ポリエステル樹脂のみをポリイミドフィルム
と銅箔の接着剤として使用した場合には、初期接着力に
は優れているけれども、半田引熱性の(!れたものは得
られない。また、分子内に複数個の不飽和結合を有する
モノマーおよび/またはオリゴマーだけをポリイミドフ
ィルムと竹筒の接着剤として使用した場合には、初期接
着性の侵れたポリイミドフィルム銅箔積層体が得られな
い。When only saturated copolymerized polyester resin is used as an adhesive between polyimide film and copper foil, although it has excellent initial adhesion strength, it does not have good soldering heat resistance. If only a monomer and/or oligomer having a plurality of unsaturated bonds is used as an adhesive between a polyimide film and a bamboo tube, a polyimide film copper foil laminate with deteriorated initial adhesiveness cannot be obtained.
このように、両成分を組合わせることにより、特有の効
果を奏するのである。In this way, a unique effect is produced by combining both components.
本発明によれば、従来の接着剤で問題となっていた接着
工程に要する時間を大幅に短縮することが可能で、例え
ば、電子線照射によって接着を完了せしめる場合には、
熱圧着の工程を含めても、従来の1/2ないし1/10
の短時間で接着工程を完了することができる。しかも、
熱圧着の温度も低温化できるため、例えば、ロールラミ
ネート工程(熱圧着工程)と電子線照射工程を連続した
ラインで行なうことも可能になり、生産性の向上ならび
に作業性の向上を図ることができる。According to the present invention, it is possible to significantly shorten the time required for the bonding process, which has been a problem with conventional adhesives. For example, when completing the bonding by electron beam irradiation,
Even including the thermocompression bonding process, it is 1/2 to 1/10 of the conventional price.
The bonding process can be completed in a short time. Moreover,
Since the temperature of thermocompression bonding can be lowered, for example, it is possible to carry out the roll lamination process (thermocompression bonding process) and the electron beam irradiation process in a continuous line, improving productivity and workability. can.
[実施例]
以下、実施例および比較例を挙げて本発明を具体的に説
明するが、本発明は、これらの実施例のみに限定される
ものではない。[Examples] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
[実施例1〜6]
ポリイミドフィルムとして東しデュポン((1)社製カ
プトン100H(商品名)、厚み25μmのフィルムを
用い、銅箔には、電解銅箔で厚み35μmのものを使用
した。[Examples 1 to 6] As the polyimide film, Kapton 100H (trade name) manufactured by DuPont Azuma ((1)) with a thickness of 25 μm was used, and as the copper foil, an electrolytic copper foil with a thickness of 35 μm was used.
第1表に示す飽和共重合ポリエステル(が脂と分子内に
複数個の不飽和結合を有するモノマーまたはオリゴマー
とをロールミキサーで、足台した後、得られた樹脂組成
物を前記ポリイミドフィルム上にホットアプリケーター
を使用して、7み35μmに塗布し、冷却間化せしめ、
接着剤層を形成した。有機過酸化物を添加した樹脂組成
物についても同様に調製し、接着剤層を形成した。After mixing the saturated copolymerized polyester shown in Table 1 with a monomer or oligomer having multiple unsaturated bonds in the molecule using a roll mixer, the resulting resin composition is placed on the polyimide film. Using a hot applicator, apply to a thickness of 35 μm and allow to cool.
An adhesive layer was formed. A resin composition to which an organic peroxide was added was similarly prepared to form an adhesive layer.
この接着剤層に前記銅箔を密着せしめ、150℃の熱プ
レスで圧着せしめた。さらに、電」「放射線の照射によ
って接着を完了せしめるものについては、熱プレスで圧
着せしめた積層体に加速電圧400kVの電子線をポリ
イミドフィルム面より照射した。熱プレス時間、電子線
照射1などの条件は第1表に示す。The copper foil was brought into close contact with this adhesive layer, and was pressed with a hot press at 150°C. Furthermore, for those in which the adhesion was completed by irradiation with electricity or radiation, an electron beam with an acceleration voltage of 400 kV was irradiated from the surface of the polyimide film onto the laminate that had been pressure-bonded using a heat press. The conditions are shown in Table 1.
接着後の積層体の物性評価は、剥離試験(補強板式)お
よび半田浴浸漬後(半田浴温度;28゜°C,浸漬時間
:30秒)の試料の観察により実東した。結果は第1表
に一括して示す。Physical properties of the laminate after bonding were evaluated by peeling test (reinforcing plate type) and observation of the sample after being immersed in a solder bath (solder bath temperature: 28° C., immersion time: 30 seconds). The results are summarized in Table 1.
[比較例1〜7]
比較のために、第2表に示す飽和共重合ポリエステル樹
脂、または分子内に複数個の不飽和結合を有するモノマ
ーあるいはオリゴマーをそれぞれ単独で使用し、同表に
示す条件でポリイミドフィルム銅箔積層体を得た。[Comparative Examples 1 to 7] For comparison, saturated copolymerized polyester resins shown in Table 2 or monomers or oligomers having multiple unsaturated bonds in the molecule were used alone, and the conditions shown in the same table were used. A polyimide film copper foil laminate was obtained.
これらの積層体についても実施例と同様に剥離試験およ
び半田浴浸漬試験を行なった。結果を第2表に一括して
示す。These laminates were also subjected to a peel test and a solder bath immersion test in the same manner as in the examples. The results are summarized in Table 2.
なお、実施例および比較例で使用した飽和共重合ポリエ
ステルは、次のとおりである。The saturated copolymerized polyesters used in Examples and Comparative Examples are as follows.
A、:軟化点115℃、ガラス転移点9°C,溶融粘度
2800ボイズ(200℃)の飽和共重合ポリエステル
樹脂(東し沖社製・商品名ケミット)
、へ2 :軟化点145°C、ガラス転移点47℃、極
限粘度0.5dl/gの飽和共重合ポリエステル樹脂(
東洋紡(…社製・商品名バイロン)
A3 :軟化点113℃、ガラス転移点23°C,、@
融粘度2300ボイス(2oo′c)の飽和共重合ポリ
エステル樹脂と軟化点145℃、ガラス転移点25°C
1溶融粘度1600ボイズ(200℃)の飽和共重合ポ
リエステル樹脂の75/254i比)の混合物(東し■
社製・商品名ケミット)
A4 :軟化点115℃、ガラス転移点24℃、極限粘
度0.3dl/gの飽和共重合ポリエステル樹脂(東洋
紡((1)社製・商品名バイロン)
(以下余白)
第1表から明らかなように、本発明の接着性樹脂組成物
を使用したポリイミドフィルム銅箔積層体は、初期接着
力が良好であるとともに、優れた半田耐熱性を有してい
る。これに対し、飽和共重1”)ポリエステル樹脂を単
独で使用した場合は、第2表に示すように初期接着力は
良好であるが、半田引熱性に劣るものであった。また、
複数個の不飽和結合を有するモノマーやオリゴマーを単
独で使用しても接着させることはできなかった。A: Saturated copolymer polyester resin with a softening point of 115°C, a glass transition point of 9°C, and a melt viscosity of 2800 voids (200°C) (manufactured by Higashishioki Co., Ltd., trade name: Chemit), H2: Softening point of 145°C, Saturated copolymerized polyester resin with a glass transition point of 47°C and an intrinsic viscosity of 0.5 dl/g (
Toyobo (manufactured by... company, product name Byron) A3: Softening point 113°C, glass transition point 23°C, @
Saturated copolymerized polyester resin with a melt viscosity of 2300 voices (2oo'c), a softening point of 145°C, and a glass transition point of 25°C.
1 A mixture of 75/254i ratio of saturated copolymerized polyester resin with a melt viscosity of 1600 voids (200°C) (Toshi ■
A4: Saturated copolymer polyester resin (manufactured by Toyobo (1), product name Vylon) with a softening point of 115°C, a glass transition point of 24°C, and an intrinsic viscosity of 0.3 dl/g (manufactured by Toyobo Co., Ltd. (1), product name Vylon) (blank below) As is clear from Table 1, the polyimide film copper foil laminate using the adhesive resin composition of the present invention has good initial adhesive strength and excellent soldering heat resistance. On the other hand, when a saturated copolymer (1") polyester resin was used alone, as shown in Table 2, the initial adhesion was good, but the soldering heat resistance was poor.
Even if monomers or oligomers having multiple unsaturated bonds were used alone, they could not be bonded.
[発明の効果]
本発明の接着性樹脂組成物は、被接着物間に介在させ、
熱圧着等により比較的低温かつ短時間での接着が可能で
、初期接着力が太き(、しかも半田耐熱性に優れている
。[Effect of the invention] The adhesive resin composition of the present invention can be interposed between objects to be adhered,
Bonding can be done at relatively low temperatures and in a short time using thermocompression bonding, etc., and the initial adhesive strength is strong (and it has excellent solder heat resistance).
この接着性樹脂組成物は、特に、ポリイミドをベースフ
ィルムとするフレキシブルプリント基板の銅箔とポリイ
ミドフィルム、あるいは該基板とオーバーレイフィルム
との接着用として好適であり、接着工程に要する時間を
大幅に短縮することが可能で、しかも、熱圧着の温度も
低温化できるため、生産性の向上ならびに作業性の向上
を区ることかできる。また、銅箔の酸化劣化や基板のカ
ーリングの発生などの問題を解決することができる。This adhesive resin composition is particularly suitable for bonding the copper foil and polyimide film of a flexible printed circuit board with a polyimide base film, or the substrate and an overlay film, and significantly reduces the time required for the bonding process. Moreover, since the temperature of thermocompression bonding can be lowered, it is possible to improve productivity and workability. Further, problems such as oxidative deterioration of the copper foil and curling of the substrate can be solved.
Claims (1)
の不飽和結合を有するモノマーおよび/またはオリゴマ
ーを添加してなる接着性樹脂組成物。(1) An adhesive resin composition obtained by adding a monomer and/or oligomer having a plurality of unsaturated bonds in the molecule to a saturated copolymerized polyester resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28587688A JPH02133487A (en) | 1988-11-14 | 1988-11-14 | Adhesive resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28587688A JPH02133487A (en) | 1988-11-14 | 1988-11-14 | Adhesive resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02133487A true JPH02133487A (en) | 1990-05-22 |
Family
ID=17697174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28587688A Pending JPH02133487A (en) | 1988-11-14 | 1988-11-14 | Adhesive resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02133487A (en) |
-
1988
- 1988-11-14 JP JP28587688A patent/JPH02133487A/en active Pending
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