JPH0912994A - Bonding composition and bonding sheet - Google Patents
Bonding composition and bonding sheetInfo
- Publication number
- JPH0912994A JPH0912994A JP7159390A JP15939095A JPH0912994A JP H0912994 A JPH0912994 A JP H0912994A JP 7159390 A JP7159390 A JP 7159390A JP 15939095 A JP15939095 A JP 15939095A JP H0912994 A JPH0912994 A JP H0912994A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- epoxy resin
- bonding
- sheet
- curing agent
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- 239000004593 Epoxy Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 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 claims abstract description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims description 41
- 239000000853 adhesive Substances 0.000 claims description 40
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 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 abstract description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical group N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- -1 for example Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- PLQNDYUMLMVFCX-UHFFFAOYSA-N 1h-imidazol-2-ylmethanediol Chemical compound OC(O)C1=NC=CN1 PLQNDYUMLMVFCX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- GQVCNZBQZKXBMX-UHFFFAOYSA-N butan-2-one;toluene Chemical compound CCC(C)=O.CC1=CC=CC=C1 GQVCNZBQZKXBMX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- Adhesive Tapes (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、回路基板や電子部品な
どの製造等に利用される接着性組成物および接着性シー
トに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition and an adhesive sheet used for manufacturing circuit boards, electronic parts and the like.
【０００２】[0002]
【従来の技術】回路基板の製造、電子部品の回路基板へ
の接合にガラス−エポキシ樹脂系、ポリイミド樹脂系、
ポリエステル樹脂系等の熱圧着可能な電気絶縁性の接着
剤あるいは接着性シートが多用されているが、近年の電
子機器の高性能化と多様化に伴い、これらの接着剤、接
着性シートもいろいろな特性が要求されている。2. Description of the Related Art Glass-epoxy resin-based, polyimide resin-based, for manufacturing circuit boards and bonding electronic components to circuit boards,
Electrically insulating adhesives or adhesive sheets that can be thermocompression-bonded, such as polyester resin, are often used, but these adhesives and adhesive sheets are being used in various ways as the performance and diversification of electronic devices have increased in recent years. Characteristics are required.
【０００３】例えば、電源等の用途向けの回路基板に用
いられる接着性シートについては、電子部品の大電力化
による発熱の増大に伴い、高熱伝導化が要求され、特開
平５−１７９２１０号公報では、接着性シートに熱伝導
性のフィラーを充填することで、高熱伝導性を達成する
ことが開示されている。For example, an adhesive sheet used for a circuit board for applications such as a power source is required to have high thermal conductivity as the heat generated by the increase in electric power of electronic parts increases, and in Japanese Patent Laid-Open No. 5-179210. It is disclosed that high heat conductivity is achieved by filling the adhesive sheet with a heat conductive filler.
【０００４】しかし、フィラーを充填することは、接着
性シートの強度を発現する有機質バインダーの割合が低
下するので、接着性シートの強度が低下したり、柔軟性
が失われる問題がある。However, the filling of the filler lowers the ratio of the organic binder that exerts the strength of the adhesive sheet, so that there is a problem that the strength of the adhesive sheet is lowered or the flexibility is lost.
【０００５】接着性シートが適切な強度、柔軟性を有す
ることを目的に、高分子のエポキシ樹脂、いわゆるフェ
ノキシ樹脂をバインダーの一部として用いる方法が、特
開平６−１０８０１６号公報で開示されているものの、
これを用いて得られる回路基板の耐熱特性については充
分でないという問題がある。Japanese Patent Laid-Open No. 6-108016 discloses a method of using a high molecular weight epoxy resin, so-called phenoxy resin, as a part of a binder for the purpose of ensuring that the adhesive sheet has appropriate strength and flexibility. Though
There is a problem that the heat resistance of the circuit board obtained by using this is not sufficient.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、回路
基板等の製造に用いられる接着性シートに関し、接着前
は適切なシート強度と柔軟性を有し、接着後には優れた
耐熱性を有する接着性シート、及びそれを容易に得られ
る接着性組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention relates to an adhesive sheet used for manufacturing a circuit board or the like, which has appropriate sheet strength and flexibility before adhesion and excellent heat resistance after adhesion. An object of the present invention is to provide an adhesive sheet having the same and an adhesive composition that can easily obtain the same.
【０００７】[0007]
【課題を解決するための手段】本発明は、エポキシ当量
の異なるエポキシ樹脂の少なくとも２種以上からなるエ
ポキシ樹脂混合物と硬化剤とを含有する接着性組成物で
あって、前記エポキシ樹脂混合物の見掛けのエポキシ当
量が２５０以上１５００以下であることを特徴とする接
着性組成物である。The present invention is an adhesive composition containing an epoxy resin mixture comprising at least two epoxy resins having different epoxy equivalents and a curing agent, and the apparent appearance of the epoxy resin mixture. It has an epoxy equivalent of 250 or more and 1500 or less.
【０００８】本発明は、前記硬化剤が２位置にフェニル
基又はナフタレン基を有し、しかも４及び５位置にヒド
ロキシアルキル基を有するイミダゾールであることを特
徴とする前記の接着性組成物であり、より好ましくは、
前記イミダゾールが２フェニル４、５ジヒドロキシメチ
ルイミダゾールであることを特徴とする前記の接着性組
成物である。The present invention is the above adhesive composition, wherein the curing agent is an imidazole having a phenyl group or a naphthalene group at the 2-position and a hydroxyalkyl group at the 4- and 5-positions. , And more preferably,
The adhesive composition is characterized in that the imidazole is 2-phenyl4,5 dihydroxymethylimidazole.
【０００９】又、本発明は、前記エポキシ樹脂混合物を
構成するエポキシ樹脂のうち、最も大きなエポキシ当量
を有するエポキシ樹脂のエポキシ当量が２０００以上５
０００以下であることを特徴とする前記の接着性組成物
である。Further, according to the present invention, among the epoxy resins constituting the epoxy resin mixture, the epoxy resin having the largest epoxy equivalent has an epoxy equivalent of 2000 or more and 5 or more.
The adhesive composition is characterized in that it is 000 or less.
【００１０】更に、本発明は、前記の接着性組成物から
なり、厚みが２０μｍ以上３００μｍ以下の接着性シー
トである。Furthermore, the present invention is an adhesive sheet comprising the above-mentioned adhesive composition and having a thickness of 20 μm or more and 300 μm or less.
【００１１】以下、本発明について、より詳細に説明す
る。The present invention will be described in more detail below.
【００１２】本発明者らは、上述の問題解決を図り鋭意
検討した結果、見掛けのエポキシ当量が特定の範囲にあ
るエポキシ樹脂混合物を選択する時に、それを硬化した
後の硬化体の耐熱性が向上することを実験的に見いだ
し、本発明に至ったものである。As a result of intensive investigations aimed at solving the above-mentioned problems, the present inventors have found that when an epoxy resin mixture having an apparent epoxy equivalent in a specific range is selected, the heat resistance of the cured product after curing the epoxy resin mixture is high. It has been experimentally found to be improved, and the present invention has been achieved.
【００１３】エポキシ当量の異なるエポキシ樹脂の少な
くとも２種以上を混合して得られるエポキシ樹脂混合物
の見掛けのエポキシ当量が２５０以上１５００以下であ
る。ここで、見掛けのエポキシ当量は、２種以上のエポ
キシ樹脂のそれぞれのエポキシ当量の重量基準での配合
割合で重しを付けた平均値である。例えば、エポキシ当
量がＥ１のエポキシ樹脂をＷ１グラムとエポキシ当量が
Ｅ２のエポキシ樹脂Ｗ２グラムを混合して得られるエポ
キシ樹脂混合物のエポキシ当量Ｅは、次の式で算出され
る。Ｅ＝Ｅ１＊（Ｗ１／Ｗ）＋Ｅ２＊（Ｗ２／Ｗ）ここ
で、Ｗ＝Ｗ１＋Ｗ２である。見掛け上同じエポキシ当量
を有していても、エポキシ当量の異なるエポキシ樹脂の
２種以上を混合する場合には、エポキシ樹脂を単独で用
いる場合に較べて、シート強度と柔軟性が向上、更に硬
化体の耐熱性が向上する。この理由については不明であ
るが、次のように解釈できる。The epoxy resin mixture obtained by mixing at least two kinds of epoxy resins having different epoxy equivalents has an apparent epoxy equivalent of 250 or more and 1500 or less. Here, the apparent epoxy equivalent is an average value obtained by weighting the respective epoxy equivalents of two or more kinds of epoxy resins with a mixing ratio on a weight basis. For example, the epoxy equivalent E of an epoxy resin mixture obtained by mixing W1 grams of an epoxy resin having an epoxy equivalent of E1 and W2 grams of an epoxy resin having an epoxy equivalent of E2 is calculated by the following formula. E = E1 * (W1 / W) + E2 * (W2 / W) where W = W1 + W2. Even if they have the same epoxy equivalents, when two or more epoxy resins with different epoxy equivalents are mixed, the sheet strength and flexibility are improved compared to the case where the epoxy resins are used alone, and further curing The heat resistance of the body is improved. The reason for this is unknown, but it can be interpreted as follows.
【００１４】即ち、見掛けのエポキシ当量が同一であっ
ても、異なるエポキシ当量を有するエポキシ樹脂の２種
以上を混合する場合には、エポキシ当量が見掛けの値よ
りも大きく高分子量のエポキシ樹脂が存在するので、シ
ート強度が増加するし柔軟性も向上する。一方、硬化体
の耐熱性に関しては、エポキシ当量が見掛けの値よりも
小さな低分子量のエポキシ樹脂が存在することが架橋構
造を効果的に発達させ、耐熱性を向上する。That is, when two or more epoxy resins having different epoxy equivalents are mixed even if the apparent epoxy equivalents are the same, the epoxy equivalent is larger than the apparent value and a high molecular weight epoxy resin is present. Therefore, the sheet strength is increased and the flexibility is also improved. On the other hand, regarding the heat resistance of the cured product, the presence of a low molecular weight epoxy resin having an epoxy equivalent smaller than the apparent value effectively develops a crosslinked structure and improves the heat resistance.
【００１５】エポキシ当量が異なるエポキシ樹脂を少な
くとも２種以上含むエポキシ樹脂混合体の見掛けのエポ
キシ当量が２５０未満の場合には、強い接着力が得られ
るものの、逆に接着性シートを作製する際にキャリヤー
シート等からの剥離が容易でなくなる。又、１５００を
越える場合には硬化体の耐熱性が充分でない。両者のバ
ランスから、２５０以上１５００以下が選択される。特
に、３００以上１０００以下が、両者のバランスがとれ
るので、より好ましい。When the apparent epoxy equivalent of the epoxy resin mixture containing at least two kinds of epoxy resins having different epoxy equivalents is less than 250, a strong adhesive force is obtained, but conversely, when an adhesive sheet is produced. Peeling from the carrier sheet or the like becomes difficult. When it exceeds 1500, the heat resistance of the cured product is not sufficient. 250 or more and 1500 or less are selected from the balance of both. In particular, 300 or more and 1000 or less are more preferable because both can be balanced.
【００１６】エポキシ樹脂混合物を構成するエポキシ樹
脂のうち、最も大きなエポキシ当量を有するエポキシ樹
脂のエポキシ当量については、２０００以上５０００以
下である。該エポキシ当量が２０００未満のエポキシ樹
脂を用いた場合には、強い接着力が得られるものの、得
られる接着性シートの柔軟性やシートの強度が必ずしも
充分でなくなり、本発明の目的を達することができな
い。一方、市販エポキシ樹脂のエポキシ当量は１３０〜
５０００であり、５０００を越えるエポキシ当量を有す
るエポキシ樹脂を工業的に、安価に入手するのは容易で
ない。Among the epoxy resins constituting the epoxy resin mixture, the epoxy equivalent of the epoxy resin having the largest epoxy equivalent is 2000 or more and 5000 or less. When an epoxy resin having an epoxy equivalent of less than 2000 is used, a strong adhesive force can be obtained, but the flexibility and the strength of the obtained adhesive sheet are not always sufficient, and the object of the present invention can be achieved. Can not. On the other hand, the epoxy equivalent of commercially available epoxy resin is 130-
It is not easy to industrially and inexpensively obtain an epoxy resin having an epoxy equivalent of 5000 or more than 5000.
【００１７】本発明のエポキシ樹脂としては、ビスフェ
ノールＡ型、ビスフェノールＦ型、ナフトール型、それ
らの臭素等ハロゲン置換したものやグリシジルアルコー
ルとのエーテル結合体等の骨格を有するものが公知であ
るが、本発明においてはいずれをも用いることができ
る。又、前記の骨格を有するエポキシ樹脂は、シリコー
ンゴム単位、ポリイミドで代表されるイミド単位、ポリ
エステルに由来するエステル単位、ポリアクリル誘導体
等に由来するカルボキシル基及び炭素炭素一重結合等が
部分的に含まれていても差し支えない。As the epoxy resin of the present invention, bisphenol A type, bisphenol F type, naphthol type, those substituted with halogen such as bromine, and those having a skeleton such as an ether bond with glycidyl alcohol are known. Any of these can be used in the present invention. Further, the epoxy resin having the above skeleton partially contains a silicone rubber unit, an imide unit represented by polyimide, an ester unit derived from polyester, a carboxyl group derived from a polyacrylic derivative and a carbon-carbon single bond. It does not matter even if it is.
【００１８】本発明における硬化剤は、エポキシ樹脂と
混合したのみではエポキシ樹脂を硬化させず、しかも加
熱後にエポキシ樹脂を硬化させる特性（いわゆる潜在性
硬化性）を有するものでなければならない。即ち、エポ
キシ樹脂は加熱前においては未硬化状態（Ｂステージ状
態という）を保つことが重要である。加熱条件として
は、例えば回路基板製造においては、１８０℃、３０Kg
/cm2、１時間の熱圧着条件が一般的である。The curing agent in the present invention must have the property of not curing the epoxy resin only by mixing it with the epoxy resin, and also of curing the epoxy resin after heating (so-called latent curability). That is, it is important that the epoxy resin is kept in an uncured state (called a B stage state) before heating. The heating conditions are, for example, 180 ° C. and 30 kg in the manufacture of circuit boards.
A thermocompression bonding condition of / cm 2 for 1 hour is common.
【００１９】前記の潜在性硬化性を有する硬化剤として
は、ジシアンジアミドが一般的であるが、その硬化体
は、例えば２６０℃、１時間の条件での、耐熱性試験で
膨れを生じる。更に、イミダゾール類が公知であるが、
汎用のイミダゾール、例えば２メチル４エチルイミダゾ
ールでは硬化が早く、Ｂステージ状態のままで保存が出
来ない。このために、イミダゾールを嵩高い置換基によ
り、エポキシ樹脂あるいはその溶剤、さらには添加され
る樹脂等への溶解性を低下させることで、反応性を減少
させる措置が講じられる。この様なイミダゾールとし
て、２フェニル４メチル５ヒドロキシメチルイミダゾー
ルがあげられるが、得られる硬化体の耐熱性が悪いとい
う欠点を有している。Dicyandiamide is generally used as a curing agent having the latent curability described above, but the cured product thereof swells in a heat resistance test under the conditions of, for example, 260 ° C. and 1 hour. Further, although imidazoles are known,
General-purpose imidazole, such as 2-methyl-4-ethylimidazole, cures quickly and cannot be stored in the B stage state. For this reason, measures are taken to reduce the reactivity of the imidazole by reducing the solubility of the imidazole in the epoxy resin or the solvent thereof, the resin to be added, and the like by the bulky substituent. As such an imidazole, 2 phenyl 4 methyl 5 hydroxymethyl imidazole can be mentioned, but it has a drawback that the obtained cured product has poor heat resistance.
【００２０】本発明者らは、いろいろな硬化剤について
実験的に検討し、２位置にフェニル基又はナフタレン基
を有し、しかも４及び５位置にヒドロキシアルキル基を
有するイミダゾールが、とりわけ２フェニル４、５ジヒ
ドロキシメチルイミダゾールが優れた潜在性硬化性を有
することを見いだし、本発明に至ったものである。The present inventors have experimentally studied various curing agents, and imidazole having a phenyl group or a naphthalene group at the 2-position and a hydroxyalkyl group at the 4- and 5-positions, especially 2phenyl-4. It was found that 5 dihydroxymethylimidazole has an excellent latent curability, and the present invention has been completed.
【００２１】即ち、４及び５位置の両方の位置にヒドロ
キシアルキル基を導入することで、従来の４又は５位置
のいずれかにヒドロキシアルキル基を有する硬化剤の場
合に較べて、硬化時に架橋点を増やすことができ、硬化
体の耐熱性を向上することができる。しかし、ヒドロキ
シル基を４及び５位置の両方に導入した場合には、エポ
キシ樹脂への溶解性が高いためか反応性も高くなり、潜
在性硬化剤として安定性が悪いという欠点を有する。本
発明者らは、上記欠点を改善するために嵩高い官能基を
導入するという考えに基づき更に検討した結果、２位置
にフェニル基若しくはナフタレン基を導入することで、
潜在性硬化性を付与することができること、加えて、４
及び５位置にヒドロキシアルキル基を導入することで硬
化体の耐熱性が向上できることを見いだしたものであ
る。尚、４及び５位置のヒドロキシアルキル基のアルキ
ル部分の長さは短い方が、硬化体の耐熱性、強度の面か
ら好ましいし、４位置のヒドロキシアルキル基のアルキ
ル部分の長さと５位置のヒドロキシアルキル基のアルキ
ル部分の長さとは一致しても、しなくても構わない。
又、ヒドロキシアルキル基の中でのヒドロキシ基の導入
位置は、一般的にアルキル基の末端が選択されるが、本
発明ではこれに限定されるものではない。That is, by introducing a hydroxyalkyl group at both the 4 and 5 positions, the cross-linking point at the time of curing is increased as compared with the conventional curing agent having a hydroxyalkyl group at either the 4 or 5 position. Can be increased, and the heat resistance of the cured product can be improved. However, when a hydroxyl group is introduced into both the 4th and 5th positions, the reactivity becomes high probably due to the high solubility in the epoxy resin, and there is a drawback that the latent curing agent has poor stability. The present inventors further studied based on the idea of introducing a bulky functional group to improve the above-mentioned drawbacks, and as a result, by introducing a phenyl group or a naphthalene group at the 2-position,
In addition to the ability to impart latent curability, 4
It was found that the heat resistance of the cured product can be improved by introducing a hydroxyalkyl group at the 5 and 5 positions. It is preferable that the length of the alkyl moiety of the 4- and 5-position hydroxyalkyl groups is shorter from the viewpoint of heat resistance and strength of the cured product. It may or may not match the length of the alkyl portion of the alkyl group.
Further, the introduction position of the hydroxy group in the hydroxyalkyl group is generally selected at the terminal of the alkyl group, but the present invention is not limited to this.
【００２２】上記の樹脂及び硬化剤を含有する接着性組
成物よりなる接着性シートは、ＰＥＴフィルム等のキャ
リアーシート上にドクターブレード法、押し出し法、ロ
ールコーター法等の一般的なシート化方法により得るこ
とができる。接着性シートの厚みは、２０μｍ以上３０
０μｍ以下である。２０μｍ未満のものは、充分に均質
なシートを安定して得ることができないし、３００μｍ
を越えるものは、熱抵抗性が悪くなり、回路基板の製造
用途で実用的価値が見いだせなくなる。An adhesive sheet made of an adhesive composition containing the above resin and a curing agent is formed on a carrier sheet such as a PET film by a general sheet forming method such as a doctor blade method, an extrusion method or a roll coater method. Obtainable. The thickness of the adhesive sheet is 20 μm or more and 30
0 μm or less. If it is less than 20 μm, a sufficiently homogeneous sheet cannot be stably obtained, and 300 μm
Those having a heat resistance of more than 50% have poor thermal resistance and cannot be of practical value for use in manufacturing circuit boards.
【００２３】本発明の接着性組成物及び接着性シート
は、Ｂステージ状態を保つ限り、前記樹脂以外の樹脂、
充填材或いは各種の添加剤を含有することができる。前
記樹脂以外の樹脂としては、エポキシ官能基をもち硬化
可能なものであれば良く、単官能、２官能、３官能以上
のエポキシ基を有するものなどなんでも良い。As long as the adhesive composition and adhesive sheet of the present invention are kept in the B stage state,
It may contain a filler or various additives. As the resin other than the above resins, any resin having an epoxy functional group and capable of being cured may be used, and any resin having a monofunctional, bifunctional, trifunctional or higher functional epoxy group may be used.
【００２４】前記の充填材としては、用途に応じて、例
えば金、銀、銅、アルミニウム、ニッケル、黒鉛を含む
炭素、窒化チタン、炭化ケイ素等の導電性のもの、酸化
アルミニウム、窒化アルミニウム、窒化硼素、酸化ケイ
素、窒化ケイ素、炭化硼素、酸化チタン、ダイアモンド
等の高熱伝導性のもの等を用いることができる。これら
の充填材は、例えばグリシドキシプロピルトリメトキシ
シラン等のカップリング剤で処理することもある。As the above-mentioned filler, for example, gold, silver, copper, aluminum, nickel, carbon containing graphite, conductive materials such as titanium nitride and silicon carbide, aluminum oxide, aluminum nitride, and nitride are used depending on the application. Materials having high thermal conductivity such as boron, silicon oxide, silicon nitride, boron carbide, titanium oxide and diamond can be used. These fillers may be treated with a coupling agent such as glycidoxypropyltrimethoxysilane.
【００２５】回路基板製造用の接着性シートでは、高熱
伝導性を得る目的で、前記充填材の中より電気絶縁性の
酸化アルミニウム、酸化ケイ素、窒化硼素、窒化アルミ
ニウム等が高度に充填される。その配合割合は、２５重
量％〜９５重量％である。２５重量％未満では充填材の
特性が充分に発揮しがたく、９５重量％を越えると強度
が低下し、シートを保てなくなる。好ましくは５０重量
％〜８５重量％が選択される。In the adhesive sheet for manufacturing a circuit board, electrically insulating aluminum oxide, silicon oxide, boron nitride, aluminum nitride or the like is highly filled from the above-mentioned filler for the purpose of obtaining high thermal conductivity. The blending ratio is 25% by weight to 95% by weight. If it is less than 25% by weight, the characteristics of the filler are not sufficiently exhibited, and if it exceeds 95% by weight, the strength is lowered and the sheet cannot be kept. Preferably 50% to 85% by weight is selected.
【００２６】各種添加剤としては、消泡剤、難燃剤、キ
レート化剤、抗酸化剤、老化防止剤、ワックス、分散助
剤、レベリング剤、防錆剤、更には、溶剤を組み合わせ
使用することができる。溶剤としてはトルエン、キシレ
ンで代表される芳香族炭化水素、メチルエチルケトン、
アセトン等のケトン類、又蒸発速度の調整及び構造粘性
を下げる目的でセルソルブ系等が用いられる。As various additives, a defoaming agent, a flame retardant, a chelating agent, an antioxidant, an antiaging agent, a wax, a dispersion aid, a leveling agent, an anticorrosive agent, and a solvent may be used in combination. You can As the solvent, toluene, aromatic hydrocarbon represented by xylene, methyl ethyl ketone,
Ketones such as acetone, or a cellosolve system or the like is used for the purpose of adjusting the evaporation rate and lowering the structural viscosity.
【００２７】以下、実施例をもって、本発明を更に詳細
に説明する。Hereinafter, the present invention will be described in more detail with reference to Examples.
〔実施例１〜１０、比較例１〜３〕いろいろなエポキシ
当量のエポキシ樹脂を表１の割合となるように配合し、
その１００部をトルエン−メチルエチルケトン混合溶媒
（トルエン／メチルエチルケトン＝８０／２０）１００
部に、８０℃で加熱溶解した。室温に冷却後、酸化アル
ミニウム粉（平均粒径２．５μｍ）を３００部、シラン
カップリング剤（日本ユニカー社製、Ａ−１８７）３部
及び２フェニル４、５ジヒドロキシメチルイミダゾール
等の硬化剤を２部を加え、３本ロールに通し混練した。
又、一部においては、エポキシ当量の異なる３種のエポ
キシ樹脂を用いたり、エポキシ樹脂単独の場合等につい
ても検討した。得られたスラリーについてはその安定性
を調べた後、ドクターブレード法により、ＰＥＴフィル
ム上に所定の厚みで塗工し、送風乾燥機中で溶媒を除去
することで接着性シートを得た。この接着性シートにつ
いて、ＰＥＴフィルムからの離形性と柔軟性を評価し
た。次に、上記の接着シートを厚さ１．５ｍｍのアルミ
ニウム板と厚さ３５μｍの銅箔との間に挟み、１８０
℃、３０Ｋｇ／ｃｍ2で１時間加圧プレスし、回路基板
を作製した。この回路基板について、２６０℃で１時間
の加熱の前後の絶縁耐圧を測定した。以上の結果を表１
に纏めて示した。[Examples 1 to 10 and Comparative Examples 1 to 3] Epoxy resins having various epoxy equivalents were mixed in the proportions shown in Table 1,
100 parts thereof was mixed with 100 parts of toluene-methyl ethyl ketone mixed solvent (toluene / methyl ethyl ketone = 80/20).
Part, heated and dissolved at 80 ° C. After cooling to room temperature, 300 parts of aluminum oxide powder (average particle size 2.5 μm), 3 parts of a silane coupling agent (manufactured by Nippon Unicar Co., A-187) and a curing agent such as 2 phenyl 4,5 dihydroxymethylimidazole. Two parts were added and the mixture was passed through a three-roll mill and kneaded.
In addition, in some cases, three kinds of epoxy resins having different epoxy equivalents were used, or the case where the epoxy resin was used alone was examined. After the stability of the obtained slurry was examined, it was applied on a PET film with a predetermined thickness by the doctor blade method, and the solvent was removed in a blow dryer to obtain an adhesive sheet. This adhesive sheet was evaluated for releasability from the PET film and flexibility. Next, the above adhesive sheet was sandwiched between an aluminum plate having a thickness of 1.5 mm and a copper foil having a thickness of 35 μm,
A circuit board was produced by press-pressing at 30 ° C. and 30 kg / cm 2 for 1 hour. The dielectric strength of this circuit board was measured before and after heating at 260 ° C. for 1 hour. Table 1 shows the above results.
It is summarized and shown.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明の接着性組成物を用いれば、接着
前は適切なシート強度と柔軟性を有し、接着後には優れ
た耐熱性を有し、回路基板の製造等に用いられる接着性
シートを容易に、安定して得ることができる。EFFECTS OF THE INVENTION The adhesive composition of the present invention has suitable sheet strength and flexibility before adhesion and excellent heat resistance after adhesion, and is used for the manufacture of circuit boards. The elastic sheet can be easily and stably obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加藤 和男 東京都町田市旭町３丁目５番１号 電気化 学工業株式会社総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Kato 3-5-1, Asahimachi, Machida-shi, Tokyo Denka Kagaku Kogyo Co., Ltd.
Claims (5)
なくとも２種以上からなるエポキシ樹脂混合物と硬化剤
とを含有する接着性組成物であって、前記エポキシ樹脂
混合物の見掛けのエポキシ当量が２５０以上１５００以
下であることを特徴とする接着性組成物。1. An adhesive composition comprising an epoxy resin mixture comprising at least two epoxy resins having different epoxy equivalents and a curing agent, wherein the epoxy resin mixture has an apparent epoxy equivalent of 250 or more and 1500 or less. An adhesive composition comprising:
されることを特徴とする請求項１記載の接着性組成物。 【化１】 （但し、化学式中のＲＯＨ、Ｒ’ＯＨはヒドロキシアル
キル基であり、Ｘはフェニル基又はナフタレン基であ
る。）2. The adhesive composition according to claim 1, wherein the curing agent is represented by the following chemical formula (1). Embedded image (However, ROH and R'OH in the chemical formula are hydroxyalkyl groups, and X is a phenyl group or a naphthalene group.)
て、ＲＯＨ及びＲ’ＯＨがいずれもヒドロキシメチル基
であり、しかもＸがフェニル基であることを特徴とする
請求項２記載の接着性組成物。3. The adhesive property according to claim 2, wherein in the chemical formula (1), the curing agent is a hydroxymethyl group for both ROH and R′OH, and X is a phenyl group. Composition.
キシ樹脂のうち、最も大きなエポキシ当量を有するエポ
キシ樹脂のエポキシ当量が２０００以上５０００以下で
あることを特徴とする請求項１記載の接着性組成物。4. The adhesive composition according to claim 1, wherein among the epoxy resins constituting the epoxy resin mixture, the epoxy resin having the largest epoxy equivalent has an epoxy equivalent of 2000 or more and 5000 or less.
項４記載の接着性組成物からなることを特徴とする接着
性シート。5. An adhesive sheet comprising the adhesive composition according to claim 1, claim 2, claim 3 or claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15939095A JP3594363B2 (en) | 1995-06-26 | 1995-06-26 | Adhesive composition and adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15939095A JP3594363B2 (en) | 1995-06-26 | 1995-06-26 | Adhesive composition and adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0912994A true JPH0912994A (en) | 1997-01-14 |
| JP3594363B2 JP3594363B2 (en) | 2004-11-24 |
Family
ID=15692745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15939095A Expired - Fee Related JP3594363B2 (en) | 1995-06-26 | 1995-06-26 | Adhesive composition and adhesive sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3594363B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092297A (en) * | 2010-09-30 | 2012-05-17 | Nippon Steel Chem Co Ltd | Adhesive resin composition, its cured product and adhesive film |
-
1995
- 1995-06-26 JP JP15939095A patent/JP3594363B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012092297A (en) * | 2010-09-30 | 2012-05-17 | Nippon Steel Chem Co Ltd | Adhesive resin composition, its cured product and adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3594363B2 (en) | 2004-11-24 |
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