JPS63308030A - Curing agent for epoxy resin - Google Patents
Curing agent for epoxy resinInfo
- Publication number
- JPS63308030A JPS63308030A JP14450987A JP14450987A JPS63308030A JP S63308030 A JPS63308030 A JP S63308030A JP 14450987 A JP14450987 A JP 14450987A JP 14450987 A JP14450987 A JP 14450987A JP S63308030 A JPS63308030 A JP S63308030A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- phenylimidazole
- epoxy resin
- curing agent
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- -1 imidazoline compound Chemical class 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- MGKYTHGPWULLHG-UHFFFAOYSA-N 1-ethyl-2-phenylimidazole Chemical compound CCN1C=CN=C1C1=CC=CC=C1 MGKYTHGPWULLHG-UHFFFAOYSA-N 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 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 10
- 239000000047 product Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- UQWBCJHVNOKNTG-UHFFFAOYSA-N 1-butyl-2-phenylimidazole Chemical compound CCCCN1C=CN=C1C1=CC=CC=C1 UQWBCJHVNOKNTG-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 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
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 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
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 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
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- DFPGBRPWDZFIPP-UHFFFAOYSA-N n'-butylethane-1,2-diamine Chemical compound CCCCNCCN DFPGBRPWDZFIPP-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- RIMLLIQKCLPVPC-UHFFFAOYSA-N phenol;phosphorous acid Chemical compound OP(O)O.OC1=CC=CC=C1 RIMLLIQKCLPVPC-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XQYMIMUDVJCMLU-UHFFFAOYSA-N phenoxyperoxybenzene Chemical compound C=1C=CC=CC=1OOOC1=CC=CC=C1 XQYMIMUDVJCMLU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000002912 waste gas Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
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用硬化剤に関する。[Detailed description of the invention] Industrial applications The present invention relates to a curing agent for epoxy resins.
従来の技術および
本発明が解決しようとする問題点
エポキシ樹脂の硬化剤として２−メチルイミダゾール、
２−エチル−４−メチルイミダゾール、２−フェニルイ
ミダゾール、１−メチル−２−メチルイミダゾール、な
どのイミダゾール化合物が用いられているが、これらイ
ミダゾール化合物は比較的融点の高い結晶でありかつエ
ポキシ樹脂との相溶性に欠けるため、エポキシ樹脂との
均一な配合が困難であるという欠点を有している。Prior art and problems to be solved by the present invention 2-methylimidazole,
Imidazole compounds such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 1-methyl-2-methylimidazole are used, but these imidazole compounds are crystals with relatively high melting points and are compatible with epoxy resins. It has the disadvantage that it is difficult to mix uniformly with an epoxy resin because of its lack of compatibility.
また近年電子、電気部品等に上記イミダゾール化合物を
硬化剤とするエポキシ樹脂組成物の成型物を使用するこ
とが提案されているが、これら用途での問題点としては
耐水性、耐薬品性が充分でないという点が挙げられる。In addition, in recent years, it has been proposed to use molded epoxy resin compositions using the imidazole compound as a curing agent for electronic and electrical parts, but the problem with these applications is that they do not have sufficient water resistance or chemical resistance. The point is that it is not.
問題点を解決するための手段
本発明者等はこのような欠点を解消すべく克明な試験研
究を重ねた結果、一般式［Ｉ］（ｎ＋は炭素数１〜６の
アルキル基を示す。Ｒ”は水素または炭素数ｌ〜４のア
ルキル基を示す。）で表わされる１−アルキル−２−フ
ェニルイミダゾールはエポキシ樹脂との相溶性に優れ、
かつ室温で低粘度の液性を示すため、エポキシ樹脂との
配合性に優れ、このものを含有するエポキシ樹脂組成物
は、良好な可使時間、硬化性を示（２、またその硬化生
成物は良好な耐水性、耐薬品性を示すことを見出した。Means for Solving the Problems The inventors of the present invention have repeatedly carried out extensive testing and research in order to solve these drawbacks, and as a result, we have found that the general formula [I] (n+ represents an alkyl group having 1 to 6 carbon atoms.R 1-alkyl-2-phenylimidazole represented by "represents hydrogen or an alkyl group having 1 to 4 carbon atoms" has excellent compatibility with epoxy resins,
In addition, since it exhibits low viscosity liquid properties at room temperature, it has excellent compatibility with epoxy resins, and epoxy resin compositions containing it exhibit good pot life and curability (2, and its cured products It has been found that this material exhibits good water resistance and chemical resistance.
すなわち、本発明は一般式［Ｉ］
（Ｒ１は炭素数１〜６のアルキル基を示す。Ｒ″は水素
または炭素数１〜４のアルキル基を示す。）で表わされ
るｌ−アルキル−２−フェニルイミダゾールを含有する
ことを特徴とするエポキシ樹脂用硬化剤に関する。That is, the present invention provides l-alkyl-2- represented by the general formula [I] (R1 represents an alkyl group having 1 to 6 carbon atoms. R'' represents hydrogen or an alkyl group having 1 to 4 carbon atoms). The present invention relates to a curing agent for epoxy resin characterized by containing phenylimidazole.
一般式［Ｉ］中、Ｒ１は炭素数１〜６の側鎖を有してい
てもよいアルキル基、例えばメチル、エチル、プロピル
、イソプロピル、ブチル、イソブチル、第２ブチル、第
３ブチル、ペンチル、イソペンチル、ネオペンチル、ヘ
キシル等である。In the general formula [I], R1 is an alkyl group optionally having a side chain having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary-butyl, pentyl, These include isopentyl, neopentyl, hexyl, etc.
一般式［Ｉ］中、Ｒ″は水素、あるいは炭素数１〜４の
側鎖を有していてもよいアルキル基、例えばメチル、エ
チル、プロピル、イソプロピル、ブチル、イソブチル、
第２ブヂル、第３ブヂル等である。In the general formula [I], R'' is hydrogen or an alkyl group which may have a side chain having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
They are the 2nd Bujiru, the 3rd Bujiru, etc.
また、−・般式［Ｉ］において、Ｒ２がアルキル基であ
る場合は、フェニル基のオルト、メタ、バラいずれの位
置にあってもよい。Moreover, in the general formula [I], when R2 is an alkyl group, it may be located at any of the ortho, meta, and distal positions of the phenyl group.
本発明において使用される、１−アルキル−２−フェニ
ルイミダゾールの具体例としてはｌ−メチル−２−フェ
ニルイミダゾール、ｌ−エチル−２−フェニルイミダゾ
ール、ｌ−プロピル−２−フェニルイミダゾール、１−
ブチル−２−フェニルイミダゾール、ｌ−イソブチル−
２−フェニルイミダゾール、１−エチル−２−（ｐ−メ
チルフェニル）イミダゾール、■−エチルー２−（ｏ−
ブチルフェニル）イミダゾールなどがあげられる。Specific examples of 1-alkyl-2-phenylimidazole used in the present invention include l-methyl-2-phenylimidazole, l-ethyl-2-phenylimidazole, l-propyl-2-phenylimidazole, 1-
Butyl-2-phenylimidazole, l-isobutyl-
2-phenylimidazole, 1-ethyl-2-(p-methylphenyl)imidazole, ■-ethyl-2-(o-
Examples include butylphenyl)imidazole.
本発明の硬化剤を利用しうるエポキシ樹脂としては一分
子当たり平均−個以上のエポキシ基を有する化合物、例
えば、ビスフェノールＡ型エポキシ樹脂、フェノールノ
ボラック型エポキシ樹脂、クレゾールノボラック型エポ
キシ樹脂、脂肪族グリシジルエーテル型エポキシ樹脂、
脂環式エポキシ樹脂、複素環型エポキシ樹脂等が挙げら
れるがこれらに限定されるものではない。また上記エポ
キシ樹脂とフェニルグリシジルエーテル、ブチルグリシ
ジルエーテル、フェノキシエーテル系モノエポキサイド
などのモノエポキシ化合物を適宜併用したものであって
むさしつかえはない。Epoxy resins that can be used with the curing agent of the present invention include compounds having an average of - or more epoxy groups per molecule, such as bisphenol A epoxy resins, phenol novolac epoxy resins, cresol novolak epoxy resins, aliphatic glycidyl ether type epoxy resin,
Examples include, but are not limited to, alicyclic epoxy resins and heterocyclic epoxy resins. It is also not difficult to use the above-mentioned epoxy resin in combination with a monoepoxy compound such as phenyl glycidyl ether, butyl glycidyl ether, phenoxy ether monoepoxide, or the like.
本発明において使用されるｌ−アルキル−２−フェニル
イミダゾール化合物の使用量はエポキシ樹脂１００重量
部に対して０．１〜２０重量部、好ましくは１〜ｌＯ重
量部である。即ち０．１重量部以下では硬化に長時間を
要し２０重量部以上では耐水性が低下するため好ましく
ない。またこのものを含有するエポキシ樹脂組成物の硬
化温度は６０〜２５０℃であり、好ましくは１００〜２
００℃の範囲である。The amount of the l-alkyl-2-phenylimidazole compound used in the present invention is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the epoxy resin. That is, if it is less than 0.1 part by weight, it takes a long time to cure, and if it is more than 20 parts by weight, the water resistance decreases, which is not preferable. The curing temperature of the epoxy resin composition containing this product is 60 to 250°C, preferably 100 to 250°C.
It is in the range of 00°C.
また、本発明の一般式［Ｉ］で表される１−アルキル−
２−フェニルイミダゾール化合物は他の硬化剤、例えば
フタル酸無水物、テトラヒドロフタル酸無水物、４−メ
チル−ヘキサヒドロフタル酸無水物、メチル−３，６−
ニンドメチレンテトラヒドロフタル酸無水物、ピロメリ
ット酸無水物、トリメリット酸無水物などのポリカルボ
ン酸無水物、メタフェニレンジアミン、ンアミノジフェ
ニルメタンなどの芳香族アミン、フェノール樹脂、ノボ
ラック樹脂、ジシアンジアミド、トリフェニルホスファ
イトフェノールメルカプタン、第４級アンモニウム塩な
どと併用しても使用できる。この場合、本発明の一般式
［Ｉ］で表される１−アルキル−２−フェニルイミダゾ
ール化合物の使用量はエポキシ樹Ｎ￥１１００重量部に
対して０．１−１０重量部である。Furthermore, 1-alkyl- represented by the general formula [I] of the present invention
The 2-phenylimidazole compound can be used with other curing agents, such as phthalic anhydride, tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-
Polycarboxylic acid anhydrides such as nindomethylenetetrahydrophthalic anhydride, pyromellitic anhydride, and trimellitic anhydride, aromatic amines such as metaphenylenediamine and aminodiphenylmethane, phenolic resins, novolak resins, dicyandiamide, triphenyl It can also be used in combination with phosphite phenol mercaptan, quaternary ammonium salts, etc. In this case, the amount of the 1-alkyl-2-phenylimidazole compound represented by the general formula [I] of the present invention used is 0.1 to 10 parts by weight per 1,100 parts by weight of the epoxy resin.
本発明の一般式［Ｉ］で表される１−アルキル−２−フ
ェニルイミダゾール化合物は特開昭５９−８４８７３や
特願昭６１−３７６４６の明細書記載の方法により一般
式［Ｉ］
％式％［］
（式中、Ｒ１は前記に同じ）
で表されるＮ−アルキル−エチレンジアミンと一般式［
■コ
（式中、Ｒ１は前記に同じ）
で表わされるニトリル化合物から得られるイミダシリン
化合物を、脱水素触媒を用いて脱水素することにより容
易に得られる。かかるイミダシリン化合物は一般式［Ｉ
Ｖ］
に１
（式中、Ｒ１およびＲ′は前記に同じ）で表される化合
物である。The 1-alkyl-2-phenylimidazole compound represented by the general formula [I] of the present invention can be prepared by the method described in the specification of JP-A-59-84873 and Japanese Patent Application No. 61-37646. [] (wherein R1 is the same as above) and N-alkyl-ethylenediamine represented by the general formula [
It can be easily obtained by dehydrogenating an imidacilline compound obtained from a nitrile compound represented by (3) (wherein R1 is the same as above) using a dehydrogenation catalyst. Such imidacilline compounds have the general formula [I
V] is a compound represented by 1 (in the formula, R1 and R' are the same as above).
前記イミダシリン化合物の脱水素反応条件は特に限定的
ではなく、公知の条件を採用できる。脱水素触媒として
はラネーニッケル、安定化ニッケル、ギ酸ニッケルなど
が挙げられ、イミダシリン化合物に対して１−１０重量
％用いることができる。また反応温度は好適には１５０
〜２５０℃である。The conditions for the dehydrogenation reaction of the imidacilline compound are not particularly limited, and known conditions can be employed. Examples of the dehydrogenation catalyst include Raney nickel, stabilized nickel, and nickel formate, which can be used in an amount of 1 to 10% by weight based on the imidacillin compound. The reaction temperature is preferably 150
~250°C.
本発明の１−アルキル−２−フェニルイミダゾニルを含
有するエポキシ樹脂組成物は顔料、可塑剤、充填剤、あ
るいはモノエポキシドのごとき稀釈剤と併用しても使用
できる。The 1-alkyl-2-phenylimidazonyl-containing epoxy resin compositions of the present invention can be used in combination with pigments, plasticizers, fillers, or diluents such as monoepoxides.
また本エポキシ樹脂組成物は抵抗器、コンデンサ、ダイ
オード、トランジスタ、などの絶縁封止用塗料、接着剤
、注型材料や、エポキシ樹脂組成物を適当な繊維物質に
含浸させて得られる積層物（含浸エポキシ）の製造等に
使用することができる。In addition, this epoxy resin composition can be used as coatings, adhesives, and casting materials for insulating sealing of resistors, capacitors, diodes, transistors, etc., as well as laminates obtained by impregnating suitable fiber materials with the epoxy resin composition. It can be used for the production of impregnated epoxy.
以下本発明を実施例に基づいて説明する。The present invention will be explained below based on examples.
合成例Ｉ
Ｎ−エチルエチレンジアミン２８５９、ベンゾニトリル
３３３ｇ、酢酸亜鉛２１ｇを１７２のオートクレーブに
仕込み、温度２２０〜２３０℃、反応圧力３０〜２０
ｋｇ／ｃｚ”の条件下、生成するアンモニアガスを廃ガ
ス導管を経て放出しながら反応を行った。反応後反応混
合物を真空で蒸留することによりｌ−エチル−２−フェ
ニルイミダシリンが得られた。このものに市販の安定化
ニッケルを加え、水素ガスの雰囲気下に２００℃〜２２
０℃に加熱して脱水素反応を行った。反応終了後、反応
物中の触媒を濾別除去し、真空蒸留することによりｌ−
エチル−２−フェニルイミダゾールを得た。沸点１４０
〜１４３℃／ ２ 、５ ａｖ＋Ｈｇ。Synthesis Example I 2859 N-ethylethylenediamine, 333 g of benzonitrile, and 21 g of zinc acetate were placed in a 172 autoclave at a temperature of 220-230°C and a reaction pressure of 30-20°C.
The reaction was carried out under the condition of "kg/cz" while releasing the generated ammonia gas through the waste gas conduit. After the reaction, the reaction mixture was distilled in vacuo to obtain l-ethyl-2-phenylimidacillin. Commercially available stabilized nickel was added to this material, and the mixture was heated at 200°C to 22°C in an atmosphere of hydrogen gas.
The dehydrogenation reaction was carried out by heating to 0°C. After the reaction is completed, the catalyst in the reaction product is removed by filtration, and l-
Ethyl-2-phenylimidazole was obtained. boiling point 140
~143°C/2,5 av+Hg.
合成例２
合成例１のＮ−エチル−エチレンジアミンをＮ−ブチル
−エチレンジアミン３２３ｇに変えた以外は合成例１と
同様に反応を行い１−ブチル−２−フェニルイミダゾー
ルを得た。Synthesis Example 2 The reaction was carried out in the same manner as in Synthesis Example 1 except that N-ethyl-ethylenediamine in Synthesis Example 1 was changed to 323 g of N-butyl-ethylenediamine to obtain 1-butyl-2-phenylimidazole.
得られたｌ−ブチル−２−フェニルイミダゾール物性値
を以下に示した。The physical property values of the obtained l-butyl-2-phenylimidazole are shown below.
沸点１４３〜１４６℃／２ＩＩｌｌｌＨｇＭＲ
０，８５〜０．９５ ｄ ３ＨＣＨ，−１
，０５〜１．９５ ｔｓ ４ＨＣＨｔ−３，
８〜４．１ ｔ ２ＨＮＣＨ＊−７，７，
１ｓ ２ＨＨ罵Ｈ
７，２〜７．８ 鵬 ５ＨＨ−くζ
〉〉実施例！、２及び比較例１，２．３．４エピコート
８２８（２，２−ビス（４−オキジフェニル）プロパン
のジグリシジルエーテル）１０重量部と各種イミダゾー
ル類０．５重量を室温で３分間撹拌混合し、エポキシ樹
脂との配合の容易さを検討した。Boiling point 143-146℃/2IIllHgMR 0.85-0.95 d 3HCH, -1
,05~1.95ts 4HCHt-3,
8-4.1 t 2HNCH*-7,7,
1s 2HH curse H 7,2~7.8 Peng 5HH-kuζ
>>Example! , 2 and Comparative Example 1, 2.3.4 10 parts by weight of Epicote 828 (diglycidyl ether of 2,2-bis(4-oxydiphenyl)propane) and 0.5 parts by weight of various imidazoles were stirred and mixed at room temperature for 3 minutes. The ease of blending with epoxy resin was investigated.
イミダゾールとしてはｌ−エチル−２−フェニルイミダ
ゾール（ＩＥ２Ｐｈ１ｍＸ実施例１）、■＝ニブチル−
２−フニニルイミダゾールＩＢ２ＰｈｌＩｌ）（実施例
２）、２−フェニルイミダゾール（２ＰｈＩｍＸ比較例
１）、ｌ−メチル−２−メチルイミダゾール（ＩＭ２Ｍ
ＩｓＸ比較例２）、２−エチルー４−メチルイミダゾー
ル（２Ｅ４ＭＩｍＸ比較例３）、２−メチルイミダゾー
ル（２ＭＩＩＩＩＸ比較例４）を用いた。As imidazole, l-ethyl-2-phenylimidazole (IE2Ph1mX Example 1), ■=nibutyl-
2-phenylimidazole IB2PhlIl) (Example 2), 2-phenylimidazole (2PhImX Comparative Example 1), l-methyl-2-methylimidazole (IM2M
IsX Comparative Example 2), 2-ethyl-4-methylimidazole (2E4MImX Comparative Example 3), and 2-methylimidazole (2MIIIX Comparative Example 4) were used.
結果を表！に示した。Show your results! It was shown to.
表１から明らかなように実施例で用いた本発明のｌＢ２
Ｐｈ１ｍ１１Ｂ２Ｐｈｌ−は、比較例で用いた２Ｐｈｌ
ａ、１Ｍ２Ｍ１ｍ、２Ｅ４ＭＩｍ、２Ｍｌ−に比べて、
すみやかに溶解し配合が容易であった。As is clear from Table 1, lB2 of the present invention used in the examples
Ph1m11B2Phl- is 2Phl used in the comparative example
Compared to a, 1M2M1m, 2E4MIm, 2Ml-,
It dissolved quickly and was easy to blend.
実施例３．４および比較例５．６
エポキシ樹脂としてエピコート８２８の１００重量部、
イミダゾール類の４重量部を室温で３０分間撹拌混合し
て得られたエポキシ樹脂組成物の可使時間を評価し、さ
らに該組成物を６０℃で６時間、１５０℃で４時間硬化
して得られた硬化物のガラス転移温度、体積抵抗、吸収
率、耐薬品性を評価した。Example 3.4 and Comparative Example 5.6 100 parts by weight of Epicote 828 as epoxy resin,
The pot life of an epoxy resin composition obtained by stirring and mixing 4 parts by weight of imidazoles at room temperature for 30 minutes was evaluated, and the composition was further cured at 60°C for 6 hours and at 150°C for 4 hours. The glass transition temperature, volume resistance, absorption rate, and chemical resistance of the cured product were evaluated.
イミダゾールとしてはＩＥ２ＰｈＩｓ（実施例３）、ｌ
Ｂ２Ｐｈ１ｍ（実施例４）、１Ｍ２Ｍｌ５（比較例５）
および２ Ｅ ４ Ｍ Ｉ ｍ（比較例６）を使用した
。Imidazole includes IE2PhIs (Example 3), l
B2Ph1m (Example 4), 1M2Ml5 (Comparative Example 5)
and 2 E 4 M I m (Comparative Example 6).
結果を表２に示した。The results are shown in Table 2.
表２中、可使時間は２５℃において初期粘度が２倍とな
るに要した時間を表す。In Table 2, pot life represents the time required for the initial viscosity to double at 25°C.
吸収率は２４℃の水中に２４時間浸漬した後の重量増加
割合（％）を表す。Absorption rate represents the weight increase rate (%) after immersion in water at 24° C. for 24 hours.
耐薬品性は２４℃の５％硫酸、５％水酸化ナトリウム、
あるいはメタノール溶液中に２４時間浸漬した後の重量
増加割合（％）として表した。Chemical resistance: 5% sulfuric acid, 5% sodium hydroxide at 24℃
Alternatively, it was expressed as a weight increase rate (%) after being immersed in a methanol solution for 24 hours.
表２から明らかなように本発明のＩＥ２Ｐｈ１ｍ１１Ｂ
２Ｐｈ１ｍを用いたエポキシ樹脂組成物は可使時間が長
く、硬化物は耐水性、耐薬品性に優れていた。As is clear from Table 2, IE2Ph1m11B of the present invention
The epoxy resin composition using 2Ph1m had a long pot life, and the cured product had excellent water resistance and chemical resistance.
実施例５．６および比較例７．８
エポキシ樹脂としてエピコート８２８の１００重量部、
４−メチルへキサヒドロフタル酸無水物（４ＭＨＨＰＡ
）の８６重量部、イミダゾール類の１重量部を室温で３
０分間撹拌混合して得られたエポキシ樹脂組成物を８０
℃で３時間、１５０℃で４時間硬化して得られた硬化物
の体積抵抗、熱変形温度、煮沸吸収率を評価した。Example 5.6 and Comparative Example 7.8 100 parts by weight of Epicote 828 as epoxy resin,
4-Methylhexahydrophthalic anhydride (4MHHPA
) and 1 part by weight of imidazoles at room temperature.
The epoxy resin composition obtained by stirring and mixing for 0 minutes was
The volume resistance, heat distortion temperature, and boiling absorption rate of the cured product obtained by curing at 150° C. for 3 hours and 4 hours at 150° C. were evaluated.
イミダゾールとしてはＩＥ２Ｐｈ１ｍ（実施例５）、Ｉ
Ｂ２Ｐｈ１ｍ（実施例６）、１Ｍ２ＭＩｍ（比較例７）
および２Ｅ４Ｍ１１（比較例８）を使用した。As imidazole, IE2Ph1m (Example 5), I
B2Ph1m (Example 6), 1M2MIm (Comparative Example 7)
and 2E4M11 (Comparative Example 8) were used.
結果を表３中に示した。The results are shown in Table 3.
表３中、煮沸吸収率は１００℃の水中に２４時間浸漬し
た後の重量増加割合（％）を表す。In Table 3, the boiling absorption rate represents the weight increase rate (%) after being immersed in water at 100° C. for 24 hours.
表３から明らかなように本発明のＩＥ２Ｐｈｌｅ。As is clear from Table 3, IE2Phle of the present invention.
ｌＢ２Ｐｈ１＋＋＋を用いて得られる硬化物は耐水性に
優れていた。The cured product obtained using lB2Ph1+++ had excellent water resistance.
発明の効果
本発明の１−アルキル−２−フェニルイミダゾールはエ
ポキシ樹脂との相溶性が良く、かつ低温で低粘度の液性
を示すためエポキシ樹脂との配合が非常に容易である。Effects of the Invention The 1-alkyl-2-phenylimidazole of the present invention has good compatibility with epoxy resins and exhibits low viscosity liquid properties at low temperatures, so it is very easy to blend with epoxy resins.
本発明の１−アルキル−２−フェニルイミダゾールを含
有するエポキシ樹脂組成物は可使時間が長く、硬化物は
耐水性、耐薬品性に優れている。The 1-alkyl-2-phenylimidazole-containing epoxy resin composition of the present invention has a long pot life, and the cured product has excellent water resistance and chemical resistance.
Claims (1)
を含有することを特徴とするエポキシ樹脂用硬化剤。[Claims] 1. General formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (In the formula, R^1 represents an alkyl group having 1 to 6 carbon atoms. R^2 is hydrogen or represents an alkyl group having 1 to 4 carbon atoms.) A curing agent for epoxy resin, characterized by containing 1-alkyl-2-phenylimidazole represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14450987A JPS63308030A (en) | 1987-06-09 | 1987-06-09 | Curing agent for epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14450987A JPS63308030A (en) | 1987-06-09 | 1987-06-09 | Curing agent for epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63308030A true JPS63308030A (en) | 1988-12-15 |
Family
ID=15364012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14450987A Pending JPS63308030A (en) | 1987-06-09 | 1987-06-09 | Curing agent for epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63308030A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086155A (en) * | 1990-09-27 | 1992-02-04 | Texaco Chemical Company | 1-isopropyl-2-tolylimidazole as an epoxy resin curative |
| US5189118A (en) * | 1991-02-28 | 1993-02-23 | Texaco Chemical Company | Mixtures of 1-isopropyl-2-aryl imidazole and 1-isopropyl-2-aryl imidazoline as epoxy resin curatives |
-
1987
- 1987-06-09 JP JP14450987A patent/JPS63308030A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5086155A (en) * | 1990-09-27 | 1992-02-04 | Texaco Chemical Company | 1-isopropyl-2-tolylimidazole as an epoxy resin curative |
| US5189118A (en) * | 1991-02-28 | 1993-02-23 | Texaco Chemical Company | Mixtures of 1-isopropyl-2-aryl imidazole and 1-isopropyl-2-aryl imidazoline as epoxy resin curatives |
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