JPH0621155B2 - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH0621155B2 JPH0621155B2 JP61257074A JP25707486A JPH0621155B2 JP H0621155 B2 JPH0621155 B2 JP H0621155B2 JP 61257074 A JP61257074 A JP 61257074A JP 25707486 A JP25707486 A JP 25707486A JP H0621155 B2 JPH0621155 B2 JP H0621155B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- hydroxyl group
- weight
- reaction
- diene polymer
- 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.)
- Expired - Lifetime
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 37
- 229920000647 polyepoxide Polymers 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 150000001993 dienes Chemical class 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000004678 hydrides Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920001195 polyisoprene Polymers 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 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 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- -1 dipropylenediamine Chemical compound 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はエポキシ樹脂組成物に関し、詳しくは硬化した
際に可撓性を有するエポキシ樹脂となりうる組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition, and more particularly to a composition capable of becoming a flexible epoxy resin when cured.
一般に、すぐれた諸性質を持つエポキシ樹脂は、接着
剤，成形材料等として重用されているが、可撓性に劣る
ため衝撃等によって亀裂を生じたり、破壊しやすいとい
う欠点がある。Generally, an epoxy resin having excellent properties is often used as an adhesive, a molding material, etc., but it is inferior in flexibility and has a drawback that it is easily cracked or broken by an impact or the like.
従来から、エポキシ樹脂に可撓性を付与するために、未
硬化のエポキシ樹脂を硬化させるに際して、硬化剤とと
もにポリエチレングリコールのジグリシジルエーテルや
１，４−ブタンジオールを可撓性付与剤として添加する
ことが行なわれてきた。しかしながら、このようにして
得られる硬化エポキシ樹脂は、ある程度の可撓性は有す
るものの、エポキシ樹脂と他の特性、たとえば電気特性
等を阻害するという結果を招来していた。Conventionally, in order to impart flexibility to an epoxy resin, when curing an uncured epoxy resin, a diglycidyl ether of polyethylene glycol or 1,4-butanediol is added as a flexibility-imparting agent together with a curing agent. Things have been done. However, although the cured epoxy resin thus obtained has a certain degree of flexibility, it results in impairing the epoxy resin and other properties such as electrical properties.
〔問題点を解決するための手段〕 本発明者らは、上記したエポキシ樹脂の従来の欠点を改
良すべく鋭意研究を重ねた。その結果、可撓性付与剤と
して水酸基含有液状ジエン系重合体の水素化物を用いる
ことにより、エポキシ樹脂の他の特性を失わずにすぐれ
た可撓性を有する硬化エポキシ樹脂が得られることを見
出し、本発明を完成した。[Means for Solving Problems] The inventors of the present invention have conducted extensive studies to improve the above-mentioned conventional drawbacks of epoxy resins. As a result, it was found that by using a hydride of a hydroxyl group-containing liquid diene polymer as a flexibility-imparting agent, a cured epoxy resin having excellent flexibility can be obtained without losing other properties of the epoxy resin. The present invention has been completed.
すなわち本発明は、（Ａ）未硬化のエポキシ樹脂、
（Ｂ）ポリアミン，ポリアミドおよび二塩基性酸または
その無水物から選ばれた硬化剤および（Ｃ）分子末端に
水酸基を有する液状ジエン系重合体の水素化物（以下、
単に水酸基含有液状ジエン系重合体と省略することもあ
る。）を主成分とするエポキシ樹脂組成物を提供するも
のである。That is, the present invention provides (A) an uncured epoxy resin,
(B) a curing agent selected from polyamines, polyamides and dibasic acids or anhydrides thereof, and (C) a hydride of a liquid diene polymer having a hydroxyl group at the molecular end (hereinafter,
It may be simply referred to as a hydroxyl group-containing liquid diene polymer. ) Is provided as the main component of the epoxy resin composition.
本発明において使用する未硬化の前記エポキシ樹脂とし
ては、公知のものを任意に選択することができ、１分子
当り少なくとも２個のエポキシ基を有し、たとえば臭素
化エポキシ樹脂、エポキシ樹脂ノボラック樹脂、ビスフ
ェノールＡ−エピクロルヒドリン樹脂、多官能性エポキ
シ樹脂、脂肪族エポキシ樹脂、脂環式エポキシ樹脂等を
使用することができる。これらエポキシ樹脂の代表的な
例は、ビスフェノールとエピクロルヒドリンとの反応に
より得られ、次の一般式で表される樹脂であって、 一般にｎは２または３以下、エポキシ当量１７０〜３０
０を有するものが好ましい。さらに、これらのエポキシ
樹脂に炭素数３〜１０の脂肪族アルコールグリシジルエ
ーテルたとえばブチルグリシジルエーテル、アリルグリ
シジルエーテル等の希釈剤および他の市販のエポキシ希
釈剤を加えることも可能である。希釈剤は、通常、エポ
キシ樹脂の２０重量部以下の配合量で使用することがで
きる。As the uncured epoxy resin used in the present invention, any known epoxy resin can be arbitrarily selected, and has at least two epoxy groups per molecule, for example, brominated epoxy resin, epoxy resin novolac resin, Bisphenol A-epichlorohydrin resin, polyfunctional epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and the like can be used. A typical example of these epoxy resins is a resin obtained by the reaction of bisphenol and epichlorohydrin, which is represented by the following general formula: Generally, n is 2 or 3 or less, epoxy equivalent 170 to 30
Those having 0 are preferred. Further, diluents such as aliphatic alcohol glycidyl ether having 3 to 10 carbon atoms such as butyl glycidyl ether and allyl glycidyl ether and other commercially available epoxy diluents can be added to these epoxy resins. The diluent can be used usually in an amount of 20 parts by weight or less of the epoxy resin.
次に本発明においては、分子末端に水酸基を有する液状
ジエン系重合体の水素化物を可撓性付与剤として用いる
が、ここで水酸基含有液状ジエン系重合体としては、数
平均分子量が３００〜２５０００、好ましくは５００〜
１００００の液状ジエン系重合体が充当される。ここで
水酸基の含有量は通常0.1〜１０mel／ｇ、好ましくは0.
3〜７mel／ｇである。Next, in the present invention, a hydride of a liquid diene polymer having a hydroxyl group at the molecular end is used as a flexibility-imparting agent. Here, the hydroxyl group-containing liquid diene polymer has a number average molecular weight of 300 to 25,000. , Preferably 500-
10,000 liquid diene-based polymers are applied. Here, the content of hydroxyl group is usually 0.1 to 10 mel / g, preferably 0.
It is 3 to 7 mel / g.
これらの液状ジエン系重合体としては炭素数４〜１２の
ジエン重合体、ジエン共重合体、さらにはこれらのジエ
ンモノマーと炭素数２〜２２のα−オレフィン性付加重
合性モノマーとの共重合体などがある。具体的にはブタ
ジエンホモポリマー，イソプレンホモポリマー，ブタジ
エン−スチレンコポリマー，ブタジエン−イソプレコポ
リマー，ブタジエン−アクリロニトリルコポリマー，ブ
タジエン−２−エチルヘキシルアクリレートコポリマ
ー，ブタジエン−ｎ−オクタデシルアクリレートコポリ
マーなどを例示することができる。これら液状ジエン系
重合体は、例えば液状反応媒体中で共役ジエンモノマー
を過酸化水素の存在下、加熱反応させることにより製造
することができる。この水酸基含有液状ジエン系重合体
を、ルテニウム，ニッケル，コバルト，鉄，パラジウ
ム，白金，ロジウム等を含有する水素化接触を用いて、
溶媒存在下、または不存在下で水素化することによっ
て、水酸基含有液状ジエン系重合体の水素化物を得るこ
とができる。As these liquid diene polymers, diene polymers having 4 to 12 carbon atoms, diene copolymers, and copolymers of these diene monomers and α-olefin addition polymerizable monomers having 2 to 22 carbon atoms and so on. Specific examples include butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprecopolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer, butadiene-n-octadecyl acrylate copolymer. . These liquid diene polymers can be produced, for example, by reacting a conjugated diene monomer in a liquid reaction medium in the presence of hydrogen peroxide with heating. This hydroxyl group-containing liquid diene polymer is subjected to hydrogenation contact containing ruthenium, nickel, cobalt, iron, palladium, platinum, rhodium, etc.
By hydrogenating in the presence or absence of a solvent, a hydrogenated product of a hydroxyl group-containing liquid diene polymer can be obtained.
かくして得られる水酸基含有液状ジエン系重合体の水素
化物は、数平均分子量３００〜２５０００、好ましくは
５００〜１００００のものであり、水酸基の含有量は0.
1〜１０mequ／ｇ、好ましくは0.3〜７mequ／ｇである。The hydride of the hydroxyl group-containing liquid diene polymer thus obtained has a number average molecular weight of 300 to 25,000, preferably 500 to 10,000, and the hydroxyl group content is 0.
It is 1-10 mequ / g, preferably 0.3-7 mequ / g.
また、その水素化比率が５０〜１００％、特に７０％以
上のものが好ましい。Further, the hydrogenation ratio thereof is preferably 50 to 100%, particularly preferably 70% or more.
なお、上記水素化率とは次式により定義される。水素化
率（％）＝（１−水素化物１分子当りの二重結合数／液
状ジエン系重合体１分子当りの二重結合数）×１００ 本発明において、可撓性付与剤として用いる水酸含有液
状ジエン系重合体の水素化物の使用量については、通
常、未硬化エポキシ１００重量部に対して１〜１００重
量部、好ましくは１０〜６０重量部である。１重量部未
満では硬化したエポキシ樹脂に充分な可撓性を付与する
ことができず、また１００重量部を越えると得られる硬
化エポキシ樹脂の機械的強度が低下する場合がある。The hydrogenation rate is defined by the following equation. Hydrogenation rate (%) = (1-number of double bonds per molecule of hydride / number of double bonds per molecule of liquid diene polymer) × 100 Hydroxyl acid used as a flexibility-imparting agent in the present invention The amount of the hydride of the contained liquid diene polymer used is usually 1 to 100 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the uncured epoxy. If it is less than 1 part by weight, sufficient flexibility cannot be imparted to the cured epoxy resin, and if it exceeds 100 parts by weight, the mechanical strength of the obtained cured epoxy resin may be lowered.
次に、本発明において用いる前記エポキシ樹脂の硬化剤
は、ポリアミン，ポリアミドおよび二塩基性酸またはそ
の無水物があげられる。ポリアミンの例としては、ジエ
チレントリアミン，トリエチレンテトラミン，テトラエ
チレンペンタミン，ジプロピレンジアミン，ジエチルア
ミノプロピルアミン，Ｎ−アミノエチルピペラジン，イ
ソホロンジアミン，ｍ−キシレンジアミン，メタフェニ
レンジアミン，ジアミノフェニルメタン，ジアミノジフ
ェニルスルホンなどがあげられる。ポリアミドはダイマ
ー酸とポリアミンとの縮合により生成するものが用いら
れ、二塩基性酸としては、無水フタウ酸，無水トリメリ
ット酸，無水ピロメリット酸，無水ベンゾフェノンテト
ラカルボン酸，エチレグリコールビス（アンヒドロトリ
メリテート），グリセロールトリス（アンヒドロトリメ
リテート）があげられる。これらの使用量については特
に制限はなく、要するに未硬化のエポキシ樹脂が、硬化
するに充分な量であればよい。一般的には、未硬化エポ
キシ樹脂１００重量部に対して 0.5〜５００重量部、好
ましくは１〜２５０重量部である。Next, examples of the curing agent for the epoxy resin used in the present invention include polyamines, polyamides and dibasic acids or their anhydrides. Examples of polyamines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, m-xylenediamine, metaphenylenediamine, diaminophenylmethane, diaminodiphenylsulfone. And so on. As the polyamide, one produced by condensation of dimer acid and polyamine is used, and as the dibasic acid, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydro) Examples include trimellitate) and glycerol tris (anhydro trimellitate). The amount of these used is not particularly limited, and in short, it is sufficient that the uncured epoxy resin is an amount sufficient for curing. Generally, it is 0.5 to 500 parts by weight, preferably 1 to 250 parts by weight, based on 100 parts by weight of the uncured epoxy resin.
上記の如き原料を主成分とし、さらに必要に応じて各種
の添加剤を適量配合することによって本発明のエポキシ
樹脂組成物が製造される。The epoxy resin composition of the present invention is produced by using the above-mentioned raw materials as a main component and, if necessary, adding various kinds of additives in appropriate amounts.
このようにして得られる本発明の組成物は、適当な条件
で硬化処理することにより硬化体となる。硬化処理する
際の条件は特に制限はないが、通常は０〜２００℃，好
ましくは２０〜１８０℃の温度にて、０．０１〜５００
時間，好ましくは０．０５〜２００時間程度加熱すれば
よい。なお、常温下で長時間放置することによって硬化
させることもできる。The composition of the present invention thus obtained becomes a cured product by being subjected to a curing treatment under appropriate conditions. The conditions for the curing treatment are not particularly limited, but usually 0.01 to 500 at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C.
The heating may be performed for a time, preferably about 0.05 to 200 hours. It is also possible to cure by leaving it at room temperature for a long time.
次に、本発明を実施例いよりさらに詳しく説明する。 Next, the present invention will be described in more detail with reference to Examples.
製造例１ 分子鎖末端に水酸基を有する液状ポリブタジエンの調
製 １のステンレス製耐圧反応容器に、ブタジエン２００
ｇ，濃度５０重量％の過酸化水素２０ｇおよび２−ブチ
ルアルコール２００ｇを仕込み、温度１２０℃，最大圧
力１８kg／cm2G，反応時間２時間の条件で反応を行なっ
た。反応終了後、分液ロートに反応混合物を入れ、６０
０ｇの水を添加して振とうし、３時間静置した後油層を
分取した。この油層から溶媒，低沸点成分を１mmHg，１
００℃，２時間の条件で留去し、分子鎖末端に水酸基を
有する液状ポリブタジエン（収率６４重量％）を得た。
このものの数平均分子量は２３６０，水酸基含有量は
０．８５meq／ｇであった。Production Example 1 Preparation of Liquid Polybutadiene Having Hydroxyl Group at Terminal of Molecular Chain
g, 20 g of hydrogen peroxide having a concentration of 50% by weight and 200 g of 2-butyl alcohol were charged, and the reaction was carried out under the conditions of a temperature of 120 ° C., a maximum pressure of 18 kg / cm 2 G and a reaction time of 2 hours. After completion of the reaction, put the reaction mixture in a separating funnel and
After adding 0 g of water and shaking, the mixture was allowed to stand for 3 hours, and then the oil layer was separated. From this oil layer, the solvent and low boiling point components are 1 mmHg, 1
It was distilled off under the conditions of 00 ° C. for 2 hours to obtain liquid polybutadiene having a hydroxyl group at the terminal of the molecular chain (yield 64% by weight).
This product had a number average molecular weight of 2,360 and a hydroxyl group content of 0.85 meq / g.
分子鎖末端に水酸基を有する液状ポリブタジエンの水
素化物の調製 上述の如くして得た分子鎖末端に水酸基を有する液状ポ
リブタジエン１００ｇ，ルテニウム含量５重量％のルテ
ニウム−カーボン触媒２０ｇおよび溶媒としてシクロヘ
キサン１００ｇを仕込み、５０kg／cm2Gの水素圧下で１
４０℃にて４時間水素化反応を行なった。反応終了後、
０．４５μのメンブランフィルターを通して反応溶液か
ら触媒を分離除去した後、２mmHg，１１０℃，２時間の
条件で溶媒を留去した。その結果、分子鎖末端に水酸基
を有する液状ポリブタジエンの水素化物が得られた。こ
のものの数平均分子量は２４２０，水酸基含有量は０．
８４meq／ｇ，水素化率は９８％であった。Preparation of Hydrogenated Liquid Polybutadiene Having Hydroxyl Group at Terminal of Molecular Chain 100 g of liquid polybutadiene having hydroxyl group at the terminal of molecular chain obtained above, 20 g of ruthenium-carbon catalyst having a ruthenium content of 5% by weight and 100 g of cyclohexane as a solvent were charged. , Under a hydrogen pressure of 50 kg / cm 2 G 1
The hydrogenation reaction was carried out at 40 ° C. for 4 hours. After the reaction,
After the catalyst was separated and removed from the reaction solution through a 0.45 µ membrane filter, the solvent was distilled off under the conditions of 2 mmHg, 110 ° C and 2 hours. As a result, a hydride of liquid polybutadiene having a hydroxyl group at the terminal of the molecular chain was obtained. This compound has a number average molecular weight of 2420 and a hydroxyl group content of 0.
It was 84 meq / g and the hydrogenation rate was 98%.
製造例２ 分子鎖末端に水酸基を有する液状ポリイソプレンの調
製 １のステンレス製耐圧反応容器に、イソプレン２００
ｇ，濃度５０重量％の過酸化水素水２０ｇおよび２−ブ
チルアルコール２００ｇを仕込み、温度１２０℃，最大
圧力９kg／cm2G，反応時間２時間の条件で反応を行なっ
た。反応終了後、分液ロートに反応混合物を入れ、６０
０ｇの水を添加して振とうし、３時間静置した後油層を
分取した。この油層から溶媒，低沸点成分を１mmHg，１
００℃，２時間の条件で留去し、分子鎖末端に水酸基を
有する液状ポリイソプレン（収率６７重量％）を得た。
このものの数平均分子量は２２３０，水酸基含有量は
０．９１meq／ｇであった。Production Example 2 Preparation of Liquid Polyisoprene Having Hydroxyl Group at Terminal of Molecular Chain In the stainless pressure-resistant reaction vessel of 1, isoprene 200 was added.
g, 20 g of hydrogen peroxide solution having a concentration of 50% by weight and 200 g of 2-butyl alcohol were charged, and the reaction was carried out under the conditions of a temperature of 120 ° C., a maximum pressure of 9 kg / cm 2 G and a reaction time of 2 hours. After completion of the reaction, put the reaction mixture in a separating funnel and
After adding 0 g of water and shaking, the mixture was allowed to stand for 3 hours, and then the oil layer was separated. From this oil layer, the solvent and low boiling point components are 1 mmHg, 1
It was distilled off under the conditions of 00 ° C. for 2 hours to obtain liquid polyisoprene (yield 67% by weight) having a hydroxyl group at the molecular chain terminal.
This product had a number average molecular weight of 2,230 and a hydroxyl group content of 0.91 meq / g.
分子鎖末端に水酸基を有する液状ポリイソプレンの水
素化物の調製 上述の如くして得た分子鎖末端に水酸基を有する液状ポ
リイソプレン１００ｇ，ルテニウム含量５重量％のルテ
ニウム−カーボン触媒２０ｇおよび溶媒としてシクロヘ
キサン１００ｇを仕込み、５０kg／cm2Gの水素圧下で１
４０℃にて４時間水素化反応を行なった。反応終了後、
０．４５μのメンブランフィルターを通して反応溶液か
ら触媒を分離除去した後、２mmHg，１１０℃，２時間の
条件で溶媒を留去した。その結果、分子鎖末端に水酸基
を有する液状ポリイソプレンの水素化物が得られた。こ
のものの数平均分子量は２３００，水酸基含有量は０．
９０meq／ｇ，水素化率は９９％であった。Preparation of Hydrogenated Liquid Polyisoprene Having Hydroxyl Group at Terminal of Molecular Chain 100 g of liquid polyisoprene having hydroxyl group at terminal of molecule obtained as described above, 20 g of ruthenium-carbon catalyst having 5% by weight of ruthenium content and 100 g of cyclohexane as solvent , And under hydrogen pressure of 50 kg / cm 2 G, 1
The hydrogenation reaction was carried out at 40 ° C. for 4 hours. After the reaction,
After the catalyst was separated and removed from the reaction solution through a 0.45 µ membrane filter, the solvent was distilled off under the conditions of 2 mmHg, 110 ° C and 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at the molecular chain end was obtained. This product has a number average molecular weight of 2,300 and a hydroxyl group content of 0.
It was 90 meq / g and the hydrogenation rate was 99%.
実施例１〜３および比較例１〜３ 第１表に示した成分を表示量容器に採取し、１１０℃で
２分間撹拌混合し、すばやく脱泡した後、シリコーン製
の型に流し込み、オーブン中で１１０℃で３時間硬化処
理をしてエポキシ樹脂硬化体を製造した。得られたエポ
キシ樹脂の硬化体の物性を第１表に示す。Examples 1 to 3 and Comparative Examples 1 to 3 The components shown in Table 1 were sampled in labeled containers, stirred and mixed at 110 ° C. for 2 minutes, quickly degassed, and then poured into a silicone mold and placed in an oven. And cured at 110 ° C. for 3 hours to produce an epoxy resin cured product. The physical properties of the obtained cured epoxy resin are shown in Table 1.
〔発明の効果〕 叙上の如くして得られたエポキシ樹脂組成物は、適当な
硬化処理を施すことにより、可撓性のすぐれた硬化体と
なるものである。 [Effects of the Invention] The epoxy resin composition obtained as described above becomes a cured product having excellent flexibility when subjected to an appropriate curing treatment.
本発明では可撓性付与剤として、水酸基含有液状ジエン
系重合体の水素化物を用いているため、得られるエポキ
シ樹脂の硬化体は、従来のように可撓性付与剤としてポ
リエチレングリコールのジグシジルエーテルや１，４−
ブタンジオールを用いた場合に比べ、エポキシ樹脂の持
つ電気特性が阻害されることなく、可撓性が付与される
ものである。したがって、本発明のエポキシ樹脂組成物
は、プリント基板などの成形材料、接着剤などに有用で
ある。In the present invention, since the hydrogenation product of the hydroxyl group-containing liquid diene polymer is used as the flexibility-imparting agent, the cured product of the obtained epoxy resin has a conventional flexibility-imparting agent of diglycidyl polyethylene glycol. Ether or 1,4-
As compared with the case of using butanediol, flexibility is imparted without impairing the electrical characteristics of the epoxy resin. Therefore, the epoxy resin composition of the present invention is useful as a molding material for printed boards, adhesives, and the like.
Claims (2)
アミン，ポリアミドおよび二塩基性酸またはその無水物
から選ばれた硬化剤および（Ｃ）分子末端に水酸基を有
する液状ジエン系重合体の水素化物を主成分とするエポ
キシ樹脂組成物。1. A curing agent selected from (A) uncured epoxy resin, (B) polyamine, polyamide and dibasic acid or its anhydride, and (C) a liquid diene polymer having a hydroxyl group at the molecular end. An epoxy resin composition containing the above hydride as a main component.
て、（Ｂ）硬化剤０．５〜５００重量部および（Ｃ）分
子末端に水酸基を有する液状ジエン系重合体の水素化物
１〜１００重量部を配合してなる特許請求の範囲第１項
記載の組成物。2. A hydrogenated product of a liquid diene polymer having 0.5 to 500 parts by weight of a curing agent (B) and (C) a hydroxyl group at a molecular end, relative to 100 parts by weight of an epoxy resin (A). The composition according to claim 1, wherein the composition is mixed in parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257074A JPH0621155B2 (en) | 1986-10-30 | 1986-10-30 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257074A JPH0621155B2 (en) | 1986-10-30 | 1986-10-30 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112616A JPS63112616A (en) | 1988-05-17 |
| JPH0621155B2 true JPH0621155B2 (en) | 1994-03-23 |
Family
ID=17301382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61257074A Expired - Lifetime JPH0621155B2 (en) | 1986-10-30 | 1986-10-30 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0621155B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2668703B2 (en) * | 1988-05-18 | 1997-10-27 | 日本ゼオン株式会社 | Adhesive for electric circuit laminate |
| JP5000238B2 (en) * | 2006-09-01 | 2012-08-15 | 株式会社ダイセル | Active energy ray-curable sealant and optical semiconductor device using the sealant |
| JP5226224B2 (en) * | 2007-01-31 | 2013-07-03 | 株式会社ダイセル | Curable resin composition and optical waveguide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4929400A (en) * | 1972-07-17 | 1974-03-15 | ||
| JPS50142633A (en) * | 1974-05-08 | 1975-11-17 | ||
| JPS624745A (en) * | 1985-06-29 | 1987-01-10 | Japan Synthetic Rubber Co Ltd | Flexibilizer for epoxy resin |
| JPS6220521A (en) * | 1985-07-18 | 1987-01-29 | Mitsui Petrochem Ind Ltd | Epoxy resin composition |
-
1986
- 1986-10-30 JP JP61257074A patent/JPH0621155B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63112616A (en) | 1988-05-17 |
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