JP4576140B2 - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
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- JP4576140B2 JP4576140B2 JP2004089504A JP2004089504A JP4576140B2 JP 4576140 B2 JP4576140 B2 JP 4576140B2 JP 2004089504 A JP2004089504 A JP 2004089504A JP 2004089504 A JP2004089504 A JP 2004089504A JP 4576140 B2 JP4576140 B2 JP 4576140B2
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- 239000000853 adhesive Substances 0.000 title claims description 67
- 230000001070 adhesive effect Effects 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 40
- 229920001187 thermosetting polymer Polymers 0.000 claims description 32
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 16
- 229920000058 polyacrylate Polymers 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920003987 resole Polymers 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 239000002966 varnish Substances 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- -1 isodecyl Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002683 reaction inhibitor Substances 0.000 description 3
- 239000011134 resol-type phenolic resin Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 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
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は接着剤組成物および接着シートに関し、さらに詳細には、感熱接着剤組成物および接着シートで、フレキシブル印刷回路基板（ＦＰＣ）などの接着に使用されるものに関する。 The present invention relates to an adhesive composition and an adhesive sheet, and more particularly to a heat-sensitive adhesive composition and an adhesive sheet that are used for bonding a flexible printed circuit board (FPC) or the like.
電子機器には、ＦＰＣが広く利用されている。 ＦＰＣの接着は、（１）ポリイミド樹脂、ポリアミドイミド樹脂などの耐熱性基材上に接着剤を介して銅やアルミニウムなどの導電性金属箔を積層し、ＦＰＣを作る過程、（２）ＦＰＣをアルミニウム、ＳＵＳ、ポリイミドなどの補強板に接着する過程で行われる。 FPC is widely used for electronic devices. Adhesion of FPC consists of (1) the process of making FPC by laminating conductive metal foils such as copper and aluminum on a heat-resistant substrate such as polyimide resin and polyamideimide resin, and (2) FPC This is performed in the process of bonding to a reinforcing plate such as aluminum, SUS, or polyimide.
これらに利用される接着剤には、従来アクリロニトリルブタジエンゴム（ＮＢＲ）を熱可塑性成分として含有するエポキシ系熱硬化性接着剤組成物、アクリルゴムを熱可塑性成分として含有するエポキシ系熱硬化性接着剤組成物が多く用いられてきた（例えば、特許文献１を参照）。しかし、当該エポキシ系熱硬化接着剤組成物は、ポリイミドフィルムヘの接着性が低いという問題があった。一方、熱可塑性成分としてアクリル系樹脂を用いたエポキシ系熱硬化型接着剤組成物も提案されている（特許文献２を参照）。 The adhesives used for these include an epoxy thermosetting adhesive composition that conventionally contains acrylonitrile butadiene rubber (NBR) as a thermoplastic component, and an epoxy thermosetting adhesive that contains acrylic rubber as a thermoplastic component. Many compositions have been used (see, for example, Patent Document 1). However, the epoxy thermosetting adhesive composition has a problem of low adhesion to the polyimide film. On the other hand, an epoxy thermosetting adhesive composition using an acrylic resin as a thermoplastic component has also been proposed (see Patent Document 2).
前記特許文献２に開示されたカルボキシル基含有アクリルポリマー／エポキシ系熱硬化性接着剤組成物は、接着力や耐熱性は十分満足できるものであるが、常温での経時的な架橋反応を抑制するためにアミン類や酸系の反応抑制剤の使用が必須である。かかる反応抑制剤は、加熱時にはエポキシの熱硬化を促進させるが、接着工程でエポキシとの反応によりガスが発生し、気泡が生じる。この気泡は、接着シートのふくれやハガレの原因になる。このため、高温で長時間の加熱圧着が必要であった。 The carboxyl group-containing acrylic polymer / epoxy thermosetting adhesive composition disclosed in Patent Document 2 is sufficiently satisfactory in adhesive strength and heat resistance, but suppresses the cross-linking reaction over time at room temperature. Therefore, it is essential to use amines and acid-based reaction inhibitors. Such a reaction inhibitor promotes thermal curing of the epoxy during heating, but gas is generated due to reaction with the epoxy in the bonding process, and bubbles are generated. These bubbles cause blistering and peeling of the adhesive sheet. For this reason, it has been necessary to perform thermocompression bonding at a high temperature for a long time.
近年、ＦＰＣの製造工程では製造効率化のため、短時間の加熱圧着の要望が高く、これを満足する接着剤が切望されていた。
本発明の目的は、接着性および耐熱性に優れ、加熱圧着が短時間で完了可能な熱硬化型接着剤組成物および接着シートを提供することにある。 An object of the present invention is to provide a thermosetting adhesive composition and an adhesive sheet that are excellent in adhesiveness and heat resistance and that can complete thermocompression bonding in a short time.
本発明者らは、前記課題を解決すべく鋭意検討した結果、特定の組成のポリマーに特定量のレゾール型フェノール樹脂とエポキシ樹脂を組み合わせることでその目的を達成することができることを見出し、本発明を完成させるに至った。すなわち、本発明の熱硬化型接着剤組成物は、熱可塑性成分および熱硬化性成分を含有してなる熱硬化型接着剤組成物において、前記熱可塑性成分は、下記モノマー成分：
（ａ）ブチルアクリレートを４５〜８５重量％、
（ｂ）アクリロニトリルを１０〜５０重量％、および
（ｃ）アクリル酸を０．１〜１０重量％、
を含有するアクリルポリマーであり、前記熱硬化性成分は、前記アクリルポリマー１００重量部に対して、エポキシ樹脂０．１〜２０重量部およびレゾール型フェノール樹脂１〜２０重量部を配合してなり、かつ、硬化促進剤および反応抑制剤のいずれも含有しないものであることを特徴とする。
As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by combining a polymer having a specific composition with a specific amount of a resol type phenol resin and an epoxy resin. It came to complete. That is, the thermosetting adhesive composition of the present invention is a thermosetting adhesive composition comprising a thermoplastic component and a thermosetting component, wherein the thermoplastic component is the following monomer component:
(A) 45 to 85% by weight of butyl acrylate,
(B) acrylonitrile and 10 to 50 wt%, and (c) 0.1 to 10 wt% of acrylic acid,
The thermosetting component is formed by blending 0.1 to 20 parts by weight of an epoxy resin and 1 to 20 parts by weight of a resol type phenol resin with respect to 100 parts by weight of the acrylic polymer. And it is what contains neither a hardening accelerator nor a reaction inhibitor.
前記エポキシ樹脂は、分子内に２個以上のエポキシ基を含有し、エポキシ当量が１００〜１０００のものであることが好ましい。 The epoxy resin preferably contains two or more epoxy groups in the molecule and has an epoxy equivalent of 100 to 1,000.
また、本発明の接着シートは、基材上に、前記熱硬化型接着剤組成物からなる接着層を設けたものであることを特徴とする。 The adhesive sheet of the present invention is characterized in that an adhesive layer made of the thermosetting adhesive composition is provided on a base material.
本発明の接着剤組成物によれば、従来のアクリル系接着剤組成物では熱硬化性や耐熱性が十分発揮できなかった低含有量の熱硬化性成分を配合することにより、接着性および耐熱性を保持したままで、加熱圧着時間が短縮された熱硬化型接着剤組成物を提供することができる。かかる接着剤組成物の効果は、特定のアクリルモノマー成分を特定の割合で使用し、かつアクリルポリマーに対して特定のエポキシ樹脂およびフェノール樹脂を所定量配合することにより、より有効に発揮することができる。 According to the adhesive composition of the present invention, the adhesive and heat resistance can be obtained by blending a low content of thermosetting component, which has not been able to sufficiently exhibit thermosetting and heat resistance in the conventional acrylic adhesive composition. Thus, it is possible to provide a thermosetting adhesive composition in which the thermocompression bonding time is shortened while maintaining the properties. The effect of such an adhesive composition can be exhibited more effectively by using a specific acrylic monomer component in a specific ratio and blending a specific amount of a specific epoxy resin and phenol resin with the acrylic polymer. it can.
また、本発明の接着シートによれば、前記本発明の接着剤組成物を接着層として有することにより、比較的短時間で圧着しうる優れた作業性と、ポリイミド系樹脂や金属材料に対しても良好な接着性、耐熱性を有し、電子部品の固定用途に適したものとなる。 In addition, according to the adhesive sheet of the present invention, by having the adhesive composition of the present invention as an adhesive layer, excellent workability that can be pressure-bonded in a relatively short time, and for polyimide resins and metal materials In addition, it has good adhesion and heat resistance, and is suitable for fixing electronic parts.
本発明は、カルボキシル基含有アクリルポリマー１００重量部に対し、エポキシ樹脂０．１〜２０重量部およびレゾール型フェノール樹脂１〜２０重量部を配合してなる熱硬化型接着剤組成物を提供するものである。 The present invention provides a thermosetting adhesive composition comprising 0.1 to 20 parts by weight of an epoxy resin and 1 to 20 parts by weight of a resol type phenolic resin based on 100 parts by weight of a carboxyl group-containing acrylic polymer. It is.
本発明の熱硬化型接着剤組成物において用いられるカルボキシル基含有アクリルポリマーは、基本的には、アクリル系モノマーを主とし、これと少量のカルボキシル基を有するモノマーから構成されるものであれば良く、通常の溶液重合、エマルジョン重合、懸濁重合、塊状重合のいずれで調製されたものであってもよい。 The carboxyl group-containing acrylic polymer used in the thermosetting adhesive composition of the present invention may be basically composed of an acrylic monomer and a monomer having a small amount of carboxyl groups. It may be prepared by any of ordinary solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
本発明において、カルボキシル基含有アクリルポリマーは、（ａ）炭素数２〜１２のアルキル基を有するアクリレートの１種または２種以上を４５〜８５重量％、（ｂ）アクリロニトリルもしくはメタクリロニトリルまたはそれらの混合物を１０〜５０重量％、および（ｃ）カルボキシル基含有ビニルモノマーの１種または２種以上を０．１〜１０重量％、を含有する。 In the present invention, the carboxyl group-containing acrylic polymer is (a) 45 to 85% by weight of one or more acrylates having an alkyl group having 2 to 12 carbon atoms, (b) acrylonitrile or methacrylonitrile, or those The mixture contains 10 to 50% by weight, and (c) one or more carboxyl group-containing vinyl monomers are contained in an amount of 0.1 to 10% by weight.
このうち、（ａ）成分である炭素数２〜１２のアルキル基を有するアクリレートは熱硬化型接着剤組成物に柔軟性を付与するものであり、アクリルポリマー中に４５〜８５重量％、好ましくは５０〜８０重量％配合する。４５重量％未満の場合は、柔軟性が損なわれることもあり、また逆に８５重量％を超える場合は、加熱圧着時のはみ出しが発生することもあるので好ましくない。 Among these, the acrylate having an alkyl group having 2 to 12 carbon atoms as component (a) imparts flexibility to the thermosetting adhesive composition, and is 45 to 85% by weight in the acrylic polymer, preferably 50-80% by weight is blended. When the amount is less than 45% by weight, flexibility may be impaired. On the other hand, when it exceeds 85% by weight, protrusion at the time of thermocompression bonding may occur, which is not preferable.
前記アクリレートの具体的な化合物としては、エチルアクリレート、ブチルアクリレート、イソペンチルアクリレート、ｎ−ヘキシルアクリレート、イソオクチルアクリレート、２−エチルヘキシルアクリレート、ｎ−オクチルアクリレート、イソノニルアクリレート、ｎ−デシルアクリレート、イソデシルアクリレートなどがあげられ、これらの１種以上が使用される。 Specific examples of the acrylate include ethyl acrylate, butyl acrylate, isopentyl acrylate, n-hexyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, n-decyl acrylate, and isodecyl. An acrylate etc. are mention | raise | lifted and 1 or more types of these are used.
また、（ｂ）成分であるアクリロニトリルもしくはメタクリロニトリルまたはそれらの混合物は耐熱性、接着性を付与するものであり、アクリルポリマー中に１０〜５０重量％、好ましくは１５〜４５重量％配合する。１０重量％未満では耐熱性が劣る傾向があり、５０重量％を超えると柔軟性が減少する傾向がある。 The component (b), acrylonitrile or methacrylonitrile, or a mixture thereof imparts heat resistance and adhesion, and is blended in the acrylic polymer in an amount of 10 to 50% by weight, preferably 15 to 45% by weight. If it is less than 10% by weight, the heat resistance tends to be inferior, and if it exceeds 50% by weight, the flexibility tends to decrease.
さらに、（ｃ）成分であるカルボキシル基含有ビニルモノマーまたはそれらの混合物は、接着性を付与し、また、架橋点となるものであり、アクリルポリマー中に０．１〜１０重量％、好ましくは０．１〜５重量％配合する。０．１重量％未満では架橋効果が少なく、１０重量％を超えると架橋しすぎ、接着力が低下する場合がある。 Furthermore, the carboxyl group-containing vinyl monomer (c) component or a mixture thereof provides adhesion and becomes a crosslinking point, and is 0.1 to 10% by weight, preferably 0, in the acrylic polymer. .1 to 5% by weight is blended. If the amount is less than 0.1% by weight, the crosslinking effect is small.
前記ビニルモノマーの具体的な化合物としては、アクリル酸、メタクリル酸、イタコン酸またはそれらの混合物などがあげられる。 Specific examples of the vinyl monomer include acrylic acid, methacrylic acid, itaconic acid or a mixture thereof.
本発明におけるレゾール型フェノール樹脂は、熱硬化性、耐熱性、エポキシ樹脂の硬化剤の特性を有し、その好ましい例として、ビスフェノールＡ；ｐ−ｔ−ブチルフェノール、オクチルフェノールなどのアルキルフェノール；ｐ−フェニルフェノール、クレゾールなどを原料として調製したレゾール型フェノール樹脂があげられる。 The resol type phenol resin in the present invention has thermosetting, heat resistance, and epoxy resin curing agent characteristics. Preferred examples thereof include bisphenol A; alkylphenols such as pt-butylphenol and octylphenol; p-phenylphenol. And a resol type phenolic resin prepared using cresol or the like as a raw material.
前記レゾール型フェノール樹脂の配合量は、カルボキシル基含有アクリルポリマー１００重量部に対し、１〜２０重量部である。１重量部未満では組成物の熱硬化性が不足し、目的とする特性が得られない。２０重量部を超えると、組成物の接着力が低下することがある。 The compounding quantity of the said resol type phenol resin is 1-20 weight part with respect to 100 weight part of carboxyl group-containing acrylic polymers. If it is less than 1 part by weight, the thermosetting property of the composition is insufficient, and the desired properties cannot be obtained. If it exceeds 20 parts by weight, the adhesive strength of the composition may be lowered.
本発明で用いるエポキシ樹脂は、本組成物の接着性に寄与するものであり、好ましいエポキシ樹脂としては、エポキシ基を２個以上含有し、そのエポキシ当量が１００〜１０００のものであり、具体的には、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、脂肪族エポキシ樹脂、グリシジルアミン型エポキシ樹脂などがあげられる。エポキシ当量が１００〜１０００のものを利用した場合は優れた接着力が得られるが、エポキシ当量１００未満のものを用いた場合は接着力が低く、逆にエポキシ当量１０００を超えるものを用いた場合は反応性が低く、熱硬化性が不足するのでいずれも好ましくない。また、上記条件を満たすフェノール樹脂、エポキシ樹脂を組み合わせた形のエポキシ変性フェノール樹脂を用いてもよい。 The epoxy resin used in the present invention contributes to the adhesiveness of the present composition. Preferred epoxy resins contain two or more epoxy groups and have an epoxy equivalent of 100 to 1,000. Examples thereof include bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic epoxy resin, glycidylamine type epoxy resin and the like. When an epoxy equivalent having an epoxy equivalent of 100 to 1000 is used, excellent adhesive strength can be obtained, but when an epoxy equivalent of less than 100 is used, the adhesive strength is low, and conversely when an epoxy equivalent exceeding 1000 is used. Is not preferred because of low reactivity and lack of thermosetting. Moreover, you may use the epoxy-modified phenol resin of the form which combined the phenol resin and epoxy resin which satisfy | fill the said conditions.
前記エポキシ樹脂の配合量は、カルボキシル基含有アクリルポリマー１００重量部に対し、０．１〜２０重量部である。０．１重量部未満では十分な接着力を発揮できず、２０重量部を超えると短時間の加熱圧着では気泡が発生する場合がある。 The compounding quantity of the said epoxy resin is 0.1-20 weight part with respect to 100 weight part of carboxyl group-containing acrylic polymers. If the amount is less than 0.1 parts by weight, sufficient adhesive force cannot be exhibited. If the amount exceeds 20 parts by weight, bubbles may be generated by short-time thermocompression bonding.
本発明では、上記配合物以外に老化防止剤、各種充填材、顔料などを特性に影響を与えない範囲で配合することができる。 In the present invention, an anti-aging agent, various fillers, pigments and the like can be blended in addition to the above blend in a range that does not affect the characteristics.
本発明の熱硬化型接着剤組成物の調製は、前記熱硬化性成分と熱可塑性成分を、前記所定範囲となるように溶剤に溶解または分散してワニスとすることにより行うことができる。必要に応じ、さらに前記公知の配合成分を加えることもできる。ワニス化の溶剤としては、たとえば、メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロヘキサノン、トルエン、酢酸エチル、メタノール、エタノールなどを使用することができる。 The thermosetting adhesive composition of the present invention can be prepared by dissolving or dispersing the thermosetting component and the thermoplastic component in a solvent so as to be in the predetermined range to obtain a varnish. If necessary, the known ingredients can be added. As the varnishing solvent, for example, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, toluene, ethyl acetate, methanol, ethanol and the like can be used.
本発明の接着シートは、たとえば、剥離ライナーとして用いられる剥離処理フィルムを基材とし、当該基材上に、本発明の熱硬化型接着剤組成物を塗布した後、加熱して溶剤を除去し、接着層を形成することにより作成することができる。 The adhesive sheet of the present invention has, for example, a release-treated film used as a release liner as a base material, and after applying the thermosetting adhesive composition of the present invention on the base material, the solvent is removed by heating. It can be created by forming an adhesive layer.
また、本発明の接着シートは、たとえば、ポリイミドフィルム、ポリエステルフィルム、ポリテトラフルオロエチレンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルサルフォンフィルムなどのプラスチックフィルム基材を使用して、この基材の片面または両面に本発明の熱硬化型接着剤組成物の層を貼り合わせた構造の基材付の接着シートとすることもできる。 Moreover, the adhesive sheet of the present invention uses, for example, a plastic film substrate such as a polyimide film, a polyester film, a polytetrafluoroethylene film, a polyether ether ketone film, a polyether sulfone film, and the like on one side of the substrate. Or it can also be set as the adhesive sheet with a base material of the structure which bonded the layer of the thermosetting type adhesive composition of this invention on both surfaces.
このようにして製造される接着シートの接着層は、通常、厚さ１０〜２００μｍ程度とするのが好ましい。また、得られた接着シートはシート状やテープ状などとして使用することができる。 In general, the adhesive layer of the adhesive sheet thus produced preferably has a thickness of about 10 to 200 μm. Moreover, the obtained adhesive sheet can be used as a sheet form or a tape form.
本発明の接着シートの加熱圧着時間は、圧着後の接着シートに気泡やフクレが生じないように、加熱温度、加熱時間および圧力を適宜設定すればよい。接着層の厚さが２５μｍ程度の場合、通常１２０〜１８０℃、０．２〜３ＭＰａで０．１〜３．０分である。 What is necessary is just to set the heating temperature, heating time, and pressure suitably for the heat-pressing time of the adhesive sheet of this invention so that a bubble and a swelling may not arise in the adhesive sheet after pressure bonding. When the thickness of the adhesive layer is about 25 μm, it is usually 0.1 to 3.0 minutes at 120 to 180 ° C. and 0.2 to 3 MPa.
（実施例）
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。
(Example)
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
アクリルポリマー１００重量部、レゾール型フェノール樹脂１０重量部およびエポキシ樹脂１５重量部を、溶剤メチルエチルケトン（ＭＥＫ）に固形分２０重量％になるように溶解し、接着剤組成物のワニスを得た。用いた原料は、下記に記載の通りである。
Example 1
100 parts by weight of an acrylic polymer, 10 parts by weight of a resol type phenol resin, and 15 parts by weight of an epoxy resin were dissolved in a solvent methyl ethyl ketone (MEK) so as to have a solid content of 20% by weight to obtain a varnish of an adhesive composition. The raw materials used are as described below.
アクリルポリマー：ブチルアクリレート（ＢＡ）／アクリロニトリル（ＡＮ）／アクリル酸（ＡＡ）＝６５／３０／５（重量比）
レゾール型フェノール樹脂：荒川化学（株）製、タマノールＡＳ
エポキシ樹脂：ジャパンエポキシレジン製、エピコート＃１００１、ビスフェノールＡ型、エポキシ当量 ４５０〜５００
得られたワニスを、乾燥後の厚さが２５μｍになるように剥離紙に塗布し、乾燥させて接着シートを得た。
Acrylic polymer: butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 65/30/5 (weight ratio)
Resol-type phenolic resin: Amanagawa Chemical Co., Ltd., Tamanol AS
Epoxy resin: manufactured by Japan Epoxy Resin, Epicoat # 1001, bisphenol A type, epoxy equivalent 450-500
The obtained varnish was applied to release paper so that the thickness after drying was 25 μm and dried to obtain an adhesive sheet.
実施例２
実施例１において、レゾール型フェノール樹脂として住友ベークライト（株）製、ＰＲ−５１２８３を１０重量部、およびエポキシ樹脂として三菱ガス化学（株）製、テトラッドＣ（エポキシ当量１０３）を０．３重量部用いること以外は実施例１と同様にして、接着剤組成物のワニス（固形分２０重量％）を得た。得られたワニスを、乾燥後の厚さが２５μｍになるように剥離紙に塗布し、乾燥させて接着シートを得た。
Example 2
In Example 1, 10 parts by weight of PR-51283 manufactured by Sumitomo Bakelite Co., Ltd. as a resol type phenol resin, and 0.3 parts by weight of Tetrad C (epoxy equivalent 103) manufactured by Mitsubishi Gas Chemical Co., Ltd. as an epoxy resin A varnish (solid content 20% by weight) of the adhesive composition was obtained in the same manner as Example 1 except that it was used. The obtained varnish was applied to release paper so that the thickness after drying was 25 μm and dried to obtain an adhesive sheet.
比較例１
実施例１において、レゾール型フェノール樹脂の代わりにイミダゾール系硬化促進剤を１重量部用いること以外は実施例１と同様にして、接着剤組成物のワニス（固形分２０重量％）を得た。得られたワニスを、乾燥後の厚さが２５μｍになるように剥離紙に塗布し、乾燥させて接着シートを得た。
Comparative Example 1
In Example 1, an adhesive composition varnish (solid content 20% by weight) was obtained in the same manner as in Example 1 except that 1 part by weight of an imidazole curing accelerator was used in place of the resol type phenol resin. The obtained varnish was applied to release paper so that the thickness after drying was 25 μm and dried to obtain an adhesive sheet.
比較例２
実施例１において、レゾール型フェノール樹脂を３０重量部、およびエポキシ樹脂を１５重量部用いること以外は実施例１と同様にして、接着剤組成物のワニス（固形分２０重量％）を得た。得られたワニスを、乾燥後の厚さが２５μｍになるように剥離紙に塗布し、乾燥させて接着シートを得た。
Comparative Example 2
In Example 1, a varnish (solid content 20% by weight) of the adhesive composition was obtained in the same manner as in Example 1 except that 30 parts by weight of the resol type phenol resin and 15 parts by weight of the epoxy resin were used. The obtained varnish was applied to release paper so that the thickness after drying was 25 μm and dried to obtain an adhesive sheet.
試験
＜接着力＞
実施例１および２ならびに比較例１および２で得られた接着シートを、１００μｍ厚ＦＰＣ（ポリイミドを基材に用いたフレキシブルプリント基板）と０．５ｍｍ厚アルミ板との間に挟み、１６０℃で６０秒、０．５ＭＰａの圧力で加熱圧着後、１６０℃で２時間加熱硬化させた。このサンプルを１ｃｍ幅に切断し、試験片とした。接着力は、テンシロンを用いて、前記試験片を９０°方向に引張り速度５０ｍｍ／分にて引き剥がし、その時の抵抗値（Ｎ／ｃｍ）を接着力とした。結果を表１に示す。
Test <Adhesive strength>
The adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were sandwiched between a 100 μm thick FPC (flexible printed circuit board using polyimide as a base material) and a 0.5 mm thick aluminum plate at 160 ° C. After thermocompression bonding at a pressure of 0.5 MPa for 60 seconds, it was cured by heating at 160 ° C. for 2 hours. This sample was cut to a width of 1 cm to obtain a test piece. The adhesive strength was determined by using Tensilon to peel off the test piece in the 90 ° direction at a pulling speed of 50 mm / min, and using the resistance value (N / cm) at that time as the adhesive strength. The results are shown in Table 1.
＜加熱圧着後の状態＞
実施例１および２ならびに比較例１および２で得られた接着シートを、１００μｍ厚ＦＰＣに１６０℃で６０秒、０．５ＭＰａの圧力で加熱圧着させ、接着シートの外観異常の有無を観察した。結果を表１に示す。
<State after thermocompression bonding>
The adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were thermocompression bonded to a 100 μm-thick FPC at 160 ° C. for 60 seconds at a pressure of 0.5 MPa, and the presence or absence of abnormal appearance of the adhesive sheets was observed. The results are shown in Table 1.
表１より、実施例１および２の各熱硬化型接着シートは、ポリイミドフィルムや金属に対する接着性に優れていることがわかる。加熱圧着時間も短時間で十分である。これに対して、比較例１および２の各熱硬化型接着シートは、上記加熱圧着条件ではフクレが発生し、接着力に劣っていることがわかる。比較例の接着シートは、さらなる加熱圧着時間を要する。 From Table 1, it can be seen that the thermosetting adhesive sheets of Examples 1 and 2 are excellent in adhesion to polyimide films and metals. A short time for the thermocompression bonding is sufficient. On the other hand, it can be seen that the thermosetting adhesive sheets of Comparative Examples 1 and 2 generate blisters under the above-mentioned thermocompression bonding conditions and have poor adhesive strength. The adhesive sheet of the comparative example requires further heat pressing time.
Claims (3)
（ａ）ブチルアクリレートを４５〜８５重量％、
（ｂ）アクリロニトリルを１０〜５０重量％、および
（ｃ）アクリル酸を０．１〜１０重量％、
を含有するアクリルポリマーであり、
前記熱硬化性成分は、前記アクリルポリマー１００重量部に対して、エポキシ樹脂０．１〜２０重量部およびレゾール型フェノール樹脂１〜２０重量部を配合してなり、かつ、硬化促進剤および反応抑制剤のいずれも含有しないものであることを特徴とする熱硬化型接着剤組成物。 In the thermosetting adhesive composition comprising a thermoplastic component and a thermosetting component, the thermoplastic component is the following monomer component:
(A) 45 to 85% by weight of butyl acrylate,
(B) acrylonitrile and 10 to 50 wt%, and (c) 0.1 to 10 wt% of acrylic acid,
An acrylic polymer containing
The thermosetting component comprises 0.1 to 20 parts by weight of an epoxy resin and 1 to 20 parts by weight of a resol type phenol resin with respect to 100 parts by weight of the acrylic polymer. A thermosetting adhesive composition characterized by not containing any of the agents.
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| JP5258466B2 (en) * | 2008-09-08 | 2013-08-07 | 日東電工株式会社 | Thermosetting adhesive composition, thermosetting adhesive tape or sheet, and flexible circuit board |
| CN102471645B (en) * | 2009-07-09 | 2013-11-06 | 日东电工株式会社 | Heat-curable adhesive tape or sheet and flexible printed circuit board |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03255186A (en) * | 1990-03-05 | 1991-11-14 | Hitachi Chem Co Ltd | Adhesive composition for flexible printed wiring board, base material for flexible printed wiring board made by using it, and flexible printed wiring board |
| JPH0551569A (en) * | 1991-08-27 | 1993-03-02 | Sekisui Chem Co Ltd | Heat-sensitive adhesive composition and adhesive sheet |
| JPH05171126A (en) * | 1991-12-26 | 1993-07-09 | Sumitomo Chem Co Ltd | Acrylic adhesive composition |
| JP2005139387A (en) * | 2003-11-10 | 2005-06-02 | Shin Etsu Chem Co Ltd | Acrylic adhesive sheet |
| JP2005179622A (en) * | 2003-12-15 | 2005-07-07 | Kyodo Chem Co Ltd | Acrylic adhesive composition |
| JP2005239830A (en) * | 2004-02-25 | 2005-09-08 | Nitto Denko Corp | Thermosetting pressure-sensitive adhesive composition and thermosetting pressure-sensitive adhesive tape or sheet |
| JP2005247910A (en) * | 2004-03-02 | 2005-09-15 | Nitto Denko Corp | Thermosetting hardenable adhesive tape or sheet and method for producing the same |
-
2004
- 2004-03-25 JP JP2004089504A patent/JP4576140B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03255186A (en) * | 1990-03-05 | 1991-11-14 | Hitachi Chem Co Ltd | Adhesive composition for flexible printed wiring board, base material for flexible printed wiring board made by using it, and flexible printed wiring board |
| JPH0551569A (en) * | 1991-08-27 | 1993-03-02 | Sekisui Chem Co Ltd | Heat-sensitive adhesive composition and adhesive sheet |
| JPH05171126A (en) * | 1991-12-26 | 1993-07-09 | Sumitomo Chem Co Ltd | Acrylic adhesive composition |
| JP2005139387A (en) * | 2003-11-10 | 2005-06-02 | Shin Etsu Chem Co Ltd | Acrylic adhesive sheet |
| JP2005179622A (en) * | 2003-12-15 | 2005-07-07 | Kyodo Chem Co Ltd | Acrylic adhesive composition |
| JP2005239830A (en) * | 2004-02-25 | 2005-09-08 | Nitto Denko Corp | Thermosetting pressure-sensitive adhesive composition and thermosetting pressure-sensitive adhesive tape or sheet |
| JP2005247910A (en) * | 2004-03-02 | 2005-09-15 | Nitto Denko Corp | Thermosetting hardenable adhesive tape or sheet and method for producing the same |
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