JPH02227421A - Low-temperature curing type epoxy resin composition - Google Patents
Low-temperature curing type epoxy resin compositionInfo
- Publication number
- JPH02227421A JPH02227421A JP4955189A JP4955189A JPH02227421A JP H02227421 A JPH02227421 A JP H02227421A JP 4955189 A JP4955189 A JP 4955189A JP 4955189 A JP4955189 A JP 4955189A JP H02227421 A JPH02227421 A JP H02227421A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- hot water
- amine
- component
- water resistance
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000013035 low temperature curing Methods 0.000 title description 7
- -1 alicyclic amine Chemical class 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 229940126214 compound 3 Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 45
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 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
- 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 abstract description 2
- 238000001723 curing Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 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 6
- 238000007654 immersion Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920003319 Araldite® Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- HIVQCJOGAHNXBO-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] propanoate Chemical compound CCC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C HIVQCJOGAHNXBO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、低温硬化型エポキシ樹脂組成物に関し、さら
に詳しくは、低温で速やかに硬化し、かつ耐温水性の優
れた硬化物が得られるエポキシ樹脂組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a low-temperature curing epoxy resin composition, and more specifically, it cures quickly at low temperatures and provides a cured product with excellent hot water resistance. The present invention relates to an epoxy resin composition.
（従来の技術〕
エポキシ樹脂は、耐熱性、耐摩耗性、耐水性などに優れ
た性質を持ち、従来からも、接着剤、コーティング剤な
ど、各種の用途に用いられてきた。(Prior Art) Epoxy resins have excellent properties such as heat resistance, abrasion resistance, and water resistance, and have been used for various purposes such as adhesives and coating agents.
ところで、このエポキシ樹脂は、そのほとんどが二液硬
化型であり、硬化剤としては分子中に活性水素を持つ脂
肪族アミン、芳香族アミンあるいは酸無水物などが使用
されている。By the way, most of these epoxy resins are two-component curing type, and aliphatic amines, aromatic amines, or acid anhydrides having active hydrogen in the molecule are used as curing agents.
しかし、これらの硬化剤を用いた場合、５°Ｃ以下の低
温では、硬化剤の反応性が著しく低く、硬化物は充分な
機械的強度を示し得ない。However, when these curing agents are used, the reactivity of the curing agent is extremely low at low temperatures of 5° C. or lower, and the cured product cannot exhibit sufficient mechanical strength.
そのため、硬化剤としてメルカプタンや低分子量脂肪族
アミンを用いることによって、低温での反応性を高める
ことが行われている。Therefore, reactivity at low temperatures has been increased by using mercaptans or low molecular weight aliphatic amines as curing agents.
また、低温でもアミンと速やかに付加反応する多価アル
コールの不飽和酸エステルをエポキシ樹脂に添加して、
その反応熱を利用することにより、低温での反応性を高
めることが提案されている（例えば、特開昭５２−８０
４３号公報）。In addition, by adding unsaturated acid esters of polyhydric alcohols to epoxy resins, which quickly undergo addition reactions with amines even at low temperatures,
It has been proposed to increase the reactivity at low temperatures by utilizing the heat of reaction (for example, JP-A-52-80
Publication No. 43).
しかしながら、硬化剤としてメルカプタンを用いた場合
には、メルカプタンが著しく不快な臭気を放つので作業
性が悪く、また、得られた硬化物は非常に跪く、耐温水
性がきわめて悪いという欠点があった。However, when mercaptan is used as a curing agent, the workability is poor because mercaptan emits a very unpleasant odor, and the obtained cured product has a very poor resistance to hot water. .
また、硬化剤として低分子量脂肪族アミンを用いた場合
には、低分子量脂肪族アミンが揮発性であるため樹脂組
成が変化しやすく不安定であり、かつ硬化剤の低分子量
脂肪族アミンが皮膚刺激性を有するので作業性が悪く、
しかも硬化物の架橋密度が高くなりすぎるため硬化物が
脆くなるという欠点があった。In addition, when a low molecular weight aliphatic amine is used as a curing agent, the resin composition tends to change and is unstable because the low molecular weight aliphatic amine is volatile, and the low molecular weight aliphatic amine of the curing agent It is irritating and has poor workability.
Moreover, there was a drawback that the cured product became brittle because the crosslinking density of the cured product became too high.
また、多価アルコールの不飽和酸エステルをエポキシ樹
脂に添加した場合は、多価アルコールの不飽和酸エステ
ル１分子当たりの官能基数が少なく、そのため硬化物の
架橋密度が低くなり充分な機械的強度が得られず、しか
も多価アルコールの不飽和酸エステルの添加により硬化
物の耐温水性が大きく低下するという欠点があった。Additionally, when an unsaturated acid ester of a polyhydric alcohol is added to an epoxy resin, the number of functional groups per molecule of the unsaturated acid ester of a polyhydric alcohol is small, resulting in a low crosslinking density of the cured product and sufficient mechanical strength. However, the addition of the unsaturated acid ester of polyhydric alcohol significantly lowers the hot water resistance of the cured product.
そこで、多価アルコールの不飽和酸エステルの官能基数
が３〜６個と多官能のものを用い、硬化剤としてポリア
ミドを用いることによって、硬化物の耐温水性の向上を
図ることも提案されているが（例えば、特開昭６２−１
７９５２４号公報）、この場合も温水（７０〜１００℃
）に数週間浸漬するような厳しい条件下では充分な強度
を示さず、硬化物表面にタックが残るなどの問題があっ
た。Therefore, it has been proposed to improve the hot water resistance of the cured product by using a polyfunctional unsaturated acid ester of polyhydric alcohol with 3 to 6 functional groups and using polyamide as the curing agent. (For example, JP-A-62-1
79524), and in this case also hot water (70 to 100°C)
) did not exhibit sufficient strength under severe conditions such as immersion in water for several weeks, and there were problems such as tack remaining on the surface of the cured product.
このような事情により、作業性の低下を招くことなく、
低温でも速やかに硬化し、かつ耐温水性の優れた硬化物
が得られるエポキシ樹脂組成物の出現が望まれている。Due to these circumstances, without reducing work efficiency,
There is a desire for an epoxy resin composition that cures quickly even at low temperatures and provides a cured product with excellent hot water resistance.
したがって、本発明は、低温でも速やかに硬化し、かつ
作業性も良好で、しかも耐温水性の優れた硬化物が得ら
れるエポキシ樹脂組成物を提供することを目的とする。Therefore, an object of the present invention is to provide an epoxy resin composition that cures quickly even at low temperatures, has good workability, and can yield a cured product with excellent hot water resistance.
本発明は、エポキシ樹脂に多官能の多価アルコールの不
飽和酸エステルを特定割合で添加し、かつ硬化剤として
脂環族アミンを含んだアミン系化合物を特定割合で用い
ることによって、上記目的を達成したものである。The present invention achieves the above object by adding a specific proportion of an unsaturated acid ester of a polyfunctional polyhydric alcohol to an epoxy resin and using a specific proportion of an amine compound containing an alicyclic amine as a curing agent. This has been achieved.
すなわち、本発明は、下記の（ａ）、（ｂ）および（ｃ
）を含有することを特徴とする低温硬化型エポキシ樹脂
組成物に関する。That is, the present invention provides the following (a), (b) and (c)
).Regarding a low temperature curing epoxy resin composition.
（ａ）エポキシ樹脂 １００重量部（
ｂ） １分子中に官能基を３〜６個
有する多価アルコールの不飽
和酸エステル ５〜４０重量部（ｃ）脂
環族アミンを組成中に含む
アミン系化合物 ３０〜１００重量部本発重
全おいて、上記組成にすることにより、エポキシ樹脂組
成物が低温で速やかに硬化し、かつ耐温水性の優れた硬
化物が得られるようになるのは、下記の理由によるもの
である。(a) 100 parts by weight of epoxy resin (
b) Unsaturated acid ester of polyhydric alcohol having 3 to 6 functional groups in one molecule 5 to 40 parts by weight (c) Amine compound containing an alicyclic amine in the composition 30 to 100 parts by weight All in all, the reason why the epoxy resin composition cures rapidly at low temperatures and provides a cured product with excellent hot water resistance by using the above composition is as follows.
（ｂ）成分の１分子中に官能基を３〜６個有する多価ア
ルコールの不飽和酸エステルが、（ａ）成分のエポキシ
樹脂と硬化剤である（ｃ）成分との反応性を高め、低温
でも速やかに硬化反応が進行するようにさせる。そして
、硬化剤として用いた（ｃ）成分中の脂環族アミンが、
（ロ）成分の添加による硬化物の耐温水性の低下を防止
する。このように、脂環族アミンが、（ロ）成分の添加
による硬化物の耐温水性の低下を防止できるのは、上記
脂環族アミンが、脂肪族アミンに比べて反応性が低い反
面、疎水性が大きく、芳香族アミンに比べて反応性は高
いが疎水性は小さく、これら反応性と疎水性とのバラン
スが良（とれているという理由によるものであると考え
られる。また、上記組成物における［有］）成分は官能
基数が多いので、硬化物の架橋密度を低下させることが
なく、したがって硬化物は充分な機械的強度を有し得る
。そして、（ｂ）成分、（ｃ）成分とも、メルカプタン
のように悪臭を放つことがなく、また低分子量脂肪族ア
ミンのような皮膚刺激性がないので、作業性の低下を招
かない。The unsaturated acid ester of polyhydric alcohol having 3 to 6 functional groups in one molecule of component (b) increases the reactivity between the epoxy resin of component (a) and the component (c) which is a curing agent, Allows the curing reaction to proceed quickly even at low temperatures. The alicyclic amine in component (c) used as a curing agent is
(b) Preventing a decrease in hot water resistance of the cured product due to the addition of the component. In this way, the reason why alicyclic amines can prevent the deterioration of the hot water resistance of the cured product due to the addition of component (b) is that while the above-mentioned alicyclic amines have lower reactivity than aliphatic amines, This is thought to be due to the fact that it has a high hydrophobicity and has a high reactivity but a low hydrophobicity compared to aromatic amines, and that the reactivity and hydrophobicity are well balanced. Since the components in the product have a large number of functional groups, the crosslinking density of the cured product is not reduced, and therefore the cured product can have sufficient mechanical strength. Both components (b) and (c) do not give off a bad odor like mercaptans, and do not cause skin irritation like low molecular weight aliphatic amines, so they do not cause a decrease in workability.
上記組成物における（ａ）成分のエポキシ樹脂は、エポ
キシ樹脂（エポキサイド）として知られているものであ
ればどのようなものでもよく、例えば、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
ビスフェノールＡＤ型エポキシ樹脂、ノボラック型エポ
キシ樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂
、グリシジルアミンエポキシ樹脂、グリシジルエステル
型エポキシ樹脂、脂環族エポキシ樹脂などが挙げられる
。The epoxy resin as component (a) in the above composition may be any known epoxy resin (epoxide), such as bisphenol A epoxy resin, bisphenol F epoxy resin,
Examples include bisphenol AD type epoxy resin, novolak type epoxy resin, halogenated bisphenol A type epoxy resin, glycidylamine epoxy resin, glycidyl ester type epoxy resin, and alicyclic epoxy resin.
これらのエポキシ樹脂の市販品としては、例えば、エピ
コー′ト８２８、エピコート８３４、エピコート１００
１、エピコート８０７、エピコート１５２、エピコート
５０５０、エピコート６０４、エピコート８７１（いず
れも商品名、油化シェルエポキシ■製〕、アラルダイト
ＣＹ２５０、アラルダイトＣＹ２６０ ［いずれも商
品名、チバガイギー社製］、スミエポキシＥＬＡ１１５
、スミエポキシＥＬＡ１２７ （いずれも商品名、住
友化学工業■製）、ＡＣＲエポキシＲ１１２、ＡＣＲエ
ポキシＲ８６〔いずれも商品名、ＡＣＲ■製）、ＤＥＲ
６６１、ＤＥＲ６６７（いずれも商品名、ダウケミカル
■製〕、エピクロンＮ ６６５ （商品名、大日本イン
キ化学工業■製〕などが挙げられる。Commercial products of these epoxy resins include, for example, Epicoat 828, Epicoat 834, and Epicoat 100.
1. Epicote 807, Epicote 152, Epicote 5050, Epicote 604, Epicote 871 (all brand names, manufactured by Yuka Shell Epoxy ■), Araldite CY250, Araldite CY260 [all brand names, manufactured by Ciba Geigy], Sumiepoxy ELA115
, Sumiepoxy ELA127 (all trade names, manufactured by Sumitomo Chemical ■), ACR Epoxy R112, ACR Epoxy R86 (both trade names, manufactured by ACR ■), DER
661, DER667 (all trade names, manufactured by Dow Chemical ■), and Epiclon N 665 (trade name, manufactured by Dainippon Ink & Chemicals ■).
これらのエポキシ樹脂は単独でまたは２種以上混合して
用いられる。また、エポキシ樹脂組成物の粘度を低下さ
せ作業性を向上させるために、上記エポキシ樹脂の一部
に代えて、分子量が小さく低粘度の多官能性エポキサイ
ド、あるいは−官能性のエポキサイドなどを用いてもよ
い、ただし、これらは全エポキシ樹脂中の３５重量％以
下にとどめることが望ましい。These epoxy resins may be used alone or in combination of two or more. In addition, in order to reduce the viscosity of the epoxy resin composition and improve workability, a polyfunctional epoxide with a small molecular weight and low viscosity, or a -functional epoxide may be used in place of a part of the epoxy resin. However, it is desirable to limit the amount of these to 35% by weight or less based on the total epoxy resin.
伽）成分の１分子中に官能基を３〜６個有する多価アル
コールの不飽和酸エステルとしては、１分子中に官能基
が５個以上存在し、かつ分子量が１．０００以下のもの
が好ましく、このような（ロ）成分の市販品としては、
例えば、アロエックスＭ４０Ｇ （商品名、東亜合成
化学工業■製）、ＫＡＹＡＲＡＤ Ｄ３１０ 、ＫＡＹ
ＡＲＡＤ ＤＰＨＡ （いずれも商品名、日本化薬■製
〕などが挙げられる。佽) The unsaturated acid ester of a polyhydric alcohol having 3 to 6 functional groups in one molecule is one that has 5 or more functional groups in one molecule and has a molecular weight of 1.000 or less. Preferably, commercial products of such component (b) include:
For example, Aroex M40G (trade name, manufactured by Toagosei Chemical Industry ■), KAYARAD D310, KAY
Examples include ARAD DPHA (both trade names, manufactured by Nippon Kayaku ■).
この（ｂ）成分は、（ａ）成分のエポキシ樹脂１００重
量部に対して、５〜４０重量部、好ましくは１０〜３０
重量部の割合で配合するが、これは、（ロ）成分の配合
割合が上記範囲より少なくなると、硬化促進効果が小さ
く、したがって低温での硬化性を充分に改善することが
できず、また、この（ロ）成分の配合割合が上記範囲よ
り多くなると、硬化促進効果は増々顕著になるが、硬化
物の耐温水性が大きく低下するようになるからである。This component (b) is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the epoxy resin of component (a).
This is because if the blending ratio of component (b) is less than the above range, the curing accelerating effect will be small, and therefore the curability at low temperatures cannot be sufficiently improved. If the blending ratio of component (b) exceeds the above range, the curing accelerating effect will become more and more pronounced, but the hot water resistance of the cured product will be greatly reduced.
（ｃ）成分は、脂環族アミンを組成中に含むアミン系化
合物であるが、本発明において、この（ｃ）成分の脂環
族アミンを組成中に含むアミン系化合物とは、■脂環族
アミンだけの場合および■脂環族アミンとマンニッヒ変
成アミンとの混合物の場合を意味する。Component (c) is an amine compound containing an alicyclic amine in its composition. In the present invention, the amine compound containing an alicyclic amine as component (c) in its composition is defined as: This means the case of only a group amine and the case of a mixture of an alicyclic amine and a Mannich-modified amine.
上記脂環族アミンは、エポキシ樹脂の硬化剤として通常
用いられている脂環族アミンであればどのようなもので
もよ（、例えば、イソホロンジアミン、メンセンジアミ
ン、Ｎ−アミノエチルピペラジン、３．９−ビス（３−
アミノプロピル）−２，４，８゜１０−テトラオキシス
ピロ（５，５） ウンデカンアダクト、ビス（４−アミ
ノ−３−メチルシクロヘキシル）メタン、水添ジアミノ
ジフェニルメタンなどが挙げられ、その市販品としては
、例えば、グリップコートＨ３２６（商品名、住人ゴム
工業■製）、アラルダイｌ−Ｘ Ｂ５１４０（商品名、
チバガイギー社製）、バーサミンＣ３０（商品名、ヘン
ケル白水■製）、エビキエア３Ｇ２１（商品名、油化シ
ェルエポキシ■製）などが挙げられる。The alicyclic amine mentioned above may be any alicyclic amine commonly used as a curing agent for epoxy resins (for example, isophorone diamine, menthene diamine, N-aminoethylpiperazine, 3. 9-bis(3-
Examples include aminopropyl)-2,4,8゜10-tetraoxyspiro(5,5) undecane adduct, bis(4-amino-3-methylcyclohexyl)methane, hydrogenated diaminodiphenylmethane, and commercially available products thereof include , for example, Grip Coat H326 (trade name, manufactured by Jujumu Kogyo ■), Araldye l-X B5140 (trade name,
(manufactured by Ciba Geigy), Versamine C30 (trade name, manufactured by Henkel Hakusui ■), and Ebiquiair 3G21 (trade name, manufactured by Yuka Shell Epoxy ■).
この脂環族アミンは、単独で用いることができるが、硬
化を促進するために耐温水性を低下させない範囲で各種
マンニッヒ変成アミンを添加した２成分系として用いる
ことができる。このマンニッヒ変成アミンとしては、例
えば、メタキシレンジアミンのマンニッヒ変成化合物、
トリエチレンテトラミンのマンニッヒ変成化合物、ジエ
チレントリアミンのマンニッヒ変成化合物などが挙げら
れ、その市販品としては、例えば、グリップコートＨ３
１２（商品名、住人ゴム工業■製）、エビキュアー３０
１２（商品名、油化シヱルエボキシ■製）、バーサミン
ｌ−３６８（商品名、ヘンケル白水■製）などが挙げら
れる。このマンニッヒ変成アミンは、それ単独でばら）
成分の添加による硬化物の耐温水性の低下を防止する効
果が充分ではなく、したがって、本発明において、この
マンニッヒ変成アミンを用いる場合は、前記のように脂
環族アミンと混合した状態で使用する。そして、そのよ
うに、脂環族アミンとマンニッヒ変成アミンとを混合し
て用いる場合、マンニッヒ変成アミンは、脂環族アミン
による耐温水性低下防止効果を損なわないようにするた
め、（ｃ）成分の全反応当量の５０％以下にされる。This alicyclic amine can be used alone, but it can also be used as a two-component system in which various Mannich-modified amines are added to the extent that hot water resistance is not reduced in order to promote curing. Examples of the Mannich-modified amine include Mannich-modified compounds of metaxylene diamine,
Examples include Mannich-modified compounds of triethylenetetramine and Mannich-modified compounds of diethylenetriamine, and commercially available products thereof include Gripcoat H3.
12 (product name, manufactured by Jumu Rubber Industries ■), Ebicure 30
12 (trade name, manufactured by Yuka Siel Eboxy ■), Versamine 1-368 (trade name, manufactured by Henkel Hakusui ■), and the like. This Mannich-modified amine can be used separately)
The effect of preventing a decrease in the hot water resistance of the cured product due to the addition of the component is not sufficient. Therefore, in the present invention, when using this Mannich-modified amine, it is used in a mixed state with an alicyclic amine as described above. do. When a mixture of an alicyclic amine and a Mannich-modified amine is used in this way, the Mannich-modified amine is used as the component (c) in order not to impair the effect of preventing a drop in hot water resistance caused by the alicyclic amine. 50% or less of the total reaction equivalents.
上記（ｃ）成分の脂環族アミンを組成中に含むアミン系
化合物は、（ａ）成分のエポキシ樹脂の硬化剤として作
用するとともに、その一部が（ｂ）成分の１分子中に官
能基を３〜６個有する多価アルコールの不飽和酸エステ
ルと反応する。そして、その（ｃ）成分中の脂環族アミ
ンが、■）成分の添加による耐温水性の低下を防止する
上においても特に有効に作用する。したがって、この（
ｃ）成分の配合量は、（ａ）成分のみならず、（ｂｌ成
分の配合量によっても変動する０本発明においては、上
記のような事情を考慮して、この（ｃ）成分の配合割合
を、（ａ）成分のエポキシ樹脂１００重量部、（６）成
分の１分子中に官能基を３〜６個有する多価アルコール
の不飽和酸エステル５〜４０重量部のときに、３０〜１
００重量部の範囲、好ましくは４０〜７０重量部の範囲
にする。つまり、この（ｃ）成分の配合割合が上記範囲
より少なくなると、硬化が遅（なるとともに、得られる
硬化物の架橋密度が低くなって、充分な強度が得られな
くなり、また、（ｂ）成分の配合量によっては、耐温水
性が低下するようになる。一方、この（ｃ）成分の配合
割合が前記範囲より多くなると、反応に寄与しないアミ
ンが残留して可塑剤的作用をし、エポキシ樹脂本来の良
好な機械的物性や耐水性がｌ員なわれるようになる。The amine compound containing the alicyclic amine of component (c) in its composition acts as a curing agent for the epoxy resin of component (a), and a part of it acts as a curing agent for the epoxy resin of component (b). It reacts with an unsaturated acid ester of a polyhydric alcohol having 3 to 6 . The alicyclic amine in component (c) also acts particularly effectively in preventing a decrease in hot water resistance caused by the addition of component (2). Therefore, this (
The amount of component c) varies depending on not only component (a) but also the amount of component (bl). In the present invention, taking the above circumstances into consideration, 100 parts by weight of the epoxy resin as component (a) and 5 to 40 parts by weight of an unsaturated acid ester of polyhydric alcohol having 3 to 6 functional groups in one molecule of component (6), 30 to 1
00 parts by weight, preferably 40 to 70 parts by weight. In other words, if the blending ratio of component (c) is less than the above range, curing will be slow (as well as the crosslinking density of the resulting cured product will be low, making it impossible to obtain sufficient strength). Depending on the blending amount of component (c), hot water resistance will decrease.On the other hand, if the blending ratio of component (c) exceeds the above range, amines that do not contribute to the reaction will remain and act like a plasticizer, causing the epoxy The resin's inherent good mechanical properties and water resistance are improved.
本発明の低温硬化型エポキシ樹脂組成物は、加熱を要す
ることな（、低温で速やかに硬化し、かつ耐温水性の優
れた硬化物が得られるので、多くの産業分野への応用が
期待できる。例えば、７０〜１００℃程度の温水で洗浄
されることの多い食品工場の床材として使用することが
できるなど、建築用資材として使用することができる。The low-temperature-curing epoxy resin composition of the present invention does not require heating (it cures quickly at low temperatures, and can provide a cured product with excellent hot water resistance, so it can be expected to be applied to many industrial fields. For example, it can be used as a flooring material in food factories, which is often washed with hot water of about 70 to 100°C, and it can be used as a building material.
また、広い温度範囲で使用可能な接着剤として使用する
ことができるし、通常は加熱硬化で使用される強化樹脂
成形品の常温硬化用樹脂材として使用することもできる
。そして、それぞれの用途に応じて、例えば、珪砂、タ
ルク、炭酸カルシウム、シリカ粉末、クレー、硫酸バリ
ウム粉末、水酸化アルミニウム、プラスチック粉末、ガ
ラス粉末、金属粉末などの充填剤を所望に応して２．０
００重置部程度まで配合してもよいし、また、顔料など
を所望量配合することができる。これらの場合のように
、本発明のエポキシ樹脂組成物は、（ａｌ成分、（ロ）
成分および（ｃ）成分がそれぞれ前記の特定割合で含ま
れておればよく、これらの必須成分に加えて、さらに他
の成分が配合されてもよい。Further, it can be used as an adhesive that can be used in a wide temperature range, and can also be used as a resin material for curing at room temperature for reinforced resin molded products that are usually used for heat curing. Then, fillers such as silica sand, talc, calcium carbonate, silica powder, clay, barium sulfate powder, aluminum hydroxide, plastic powder, glass powder, and metal powder are added as desired depending on each application. .0
It may be blended up to about 0.00 parts, or pigments and the like may be blended in a desired amount. As in these cases, the epoxy resin composition of the present invention contains (al component, (b)
It is sufficient that the component and (c) component are each contained in the above-mentioned specific proportions, and other components may be further blended in addition to these essential components.
つぎに実施例をあげて本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例１〜３および比較例１〜２
第１表に示す５種類のエポキシ樹脂組成物を調製し、そ
れらの低温での薄膜硬化時間の評価および耐温水性の評
価を行った。その結果を第１表に示す、低温でのｌ！膜
膜化化時間評価基準および耐温水性の評価基準は次に示
すとおりである。Examples 1 to 3 and Comparative Examples 1 to 2 Five types of epoxy resin compositions shown in Table 1 were prepared, and their thin film curing time at low temperature and hot water resistance were evaluated. The results are shown in Table 1, l! The film forming time evaluation criteria and hot water resistance evaluation criteria are as shown below.
■耐１１はし礪劇伍基浬
各組成のエポキシ樹脂組成物により、ＪＩＳ Ｋ ７１
１３に準じて、１号ダンベルを常温で注型し、１２時間
室温で静置後、７０℃の温水に浸漬し、２８日間後の引
張強度を測定する。■Epoxy resin compositions with various compositions meet JIS K 71
According to No. 13, a No. 1 dumbbell is cast at room temperature, left to stand at room temperature for 12 hours, then immersed in 70°C warm water, and the tensile strength after 28 days is measured.
■ での の
各組成のエポキシ樹脂組成物を１００μｍの厚さに塗布
し、０℃におけるドラインダレコーダーの２次条痕消滅
時間で薄膜硬化時間を評価する。(2) An epoxy resin composition having each of the following compositions was applied to a thickness of 100 μm, and the thin film curing time was evaluated by the secondary streak disappearing time measured using a dryer recorder at 0°C.
第１表に示すように、伽）成分のアロニックスＭ４００
（商品名）を配合していない比較例１では、（ｃ）成分
のアラルダイトＸ Ｂ５１４０ （商品名）を増量して
いるにもかかわらず、０℃ではまったく硬化しなかった
。そして、実施例１〜３および比較例２に示すように、
（ｂ）成分の増量に伴って薄膜硬化時間が短くなるが、
（ロ）成分が多くなりすぎると、比較例２に示すように
、耐温水性が悪くなる。つまり、耐温水性は、７０℃温
水浸漬２８日後の引張強度が１００ｋｇ／ｃｊ以上であ
れば、実用に耐える耐温水性を有していると考えられる
が、比較例２は上記条件下での温水浸漬後の引張強度が
７５ｋｇ／ｄ Ｌかなく、充分な耐温水性を有している
とはいえなかった。これに対して、実施例１〜３は、同
条件下での温水浸漬後の引張強度が１００ ｋｇ／ｃｍ
をはるかに超えており、充分な耐温水性を有していた。As shown in Table 1, the ingredients of Aronix M400
In Comparative Example 1, which did not contain Araldite X B5140 (trade name), it did not cure at all at 0°C, despite the increased amount of component (c) Araldite X B5140 (trade name). And, as shown in Examples 1 to 3 and Comparative Example 2,
(b) The thin film curing time becomes shorter as the amount of the component increases, but
(b) If the amount of the component is too large, the hot water resistance deteriorates as shown in Comparative Example 2. In other words, as for hot water resistance, if the tensile strength after 28 days of immersion in 70°C hot water is 100 kg/cj or more, it is considered to have hot water resistance that can withstand practical use. The tensile strength after immersion in hot water was only 75 kg/dL, and it could not be said that it had sufficient hot water resistance. On the other hand, in Examples 1 to 3, the tensile strength after immersion in hot water under the same conditions was 100 kg/cm.
It had sufficient hot water resistance.
また、０℃という低温での薄膜硬化時間では、４８時間
以内であれば、実用に供し得る低温硬化性を有するもの
と評価されるが、実施例１〜３は、いずれも薄膜硬化時
間が４８時間以内であり、実用に供し得る低温硬化性を
有していた。In addition, if the thin film curing time at a low temperature of 0°C is within 48 hours, it is evaluated that it has low-temperature curing properties that can be used in practical applications, but in Examples 1 to 3, the thin film curing time was 48 hours It had low-temperature curing properties that could be used for practical purposes.
実施例４〜９および比較例３〜７
第２表に示す組成のエポキシ樹脂組成物を調製し、それ
らの低温での薄膜硬化時間および耐温水性を前記と同様
に評価した。その結果を第２表に示す。Examples 4 to 9 and Comparative Examples 3 to 7 Epoxy resin compositions having the compositions shown in Table 2 were prepared, and their thin film curing time at low temperature and hot water resistance were evaluated in the same manner as described above. The results are shown in Table 2.
第２表の実施例４〜９に示すように、脂環族アミンであ
るグリップコー）Ｈ３２６（商品名）および同様に脂環
族アミンであるアラルダイトＸＢ５１４０（商品名）と
マンニッヒ変成アミンであるグリップコートＨ３１２（
商品名）またはバーサミンｌ−３６８（商品名）との混
合物を用いた場合には、ＦＩ膜膜化化時間短く、したが
って低温で速やかに硬化し、かつ硬化物の温水浸漬後の
引張強度が大きく、耐温水性が優れていた。As shown in Examples 4 to 9 in Table 2, Gripco) H326 (trade name), which is an alicyclic amine, Araldite XB5140 (trade name), which is also an alicyclic amine, and Grip, which is a Mannich modified amine. Coat H312 (
When using a mixture with (trade name) or Versamine l-368 (trade name), the time to form the FI film is short, so it hardens quickly at low temperatures, and the cured product has a high tensile strength after immersion in hot water. , and had excellent hot water resistance.
しかし、比較例３〜７に示すように、脂環族アミンを用
いない場合は、低温での硬化性が優れたものでも、耐温
水性が実施例のものに比べて劣っていた。なお、（ロ）
成分のアロニックスＭ ４００ （商品名）を２５重量
部ずつ配合した実施例２、実施例４、および比較例４〜
７で、硬化剤の配合量が種々に変わっているのは、いず
れも反応当量比で全エポキシ当量に対して１：１に統一
していることによるものである。However, as shown in Comparative Examples 3 to 7, when no alicyclic amine was used, even those with excellent curability at low temperatures had poor hot water resistance compared to those of the Examples. Furthermore, (b)
Example 2, Example 4, and Comparative Examples 4 to 25 parts by weight of each component Aronix M 400 (trade name)
The reason why the blending amount of the curing agent in No. 7 is varied is that the reaction equivalent ratio is uniformly 1:1 with respect to the total epoxy equivalent in all cases.
実施例１０〜１１
第３表に示す組成のエポキシ樹脂組成物を調製し、それ
らの耐温水性を評価した。その結果を第３表に示す、な
お、これらの実施例では、充填剤として珪砂を多量に配
合している関係でモルタル状になり、薄膜を形成するこ
とができないため、薄膜硬化時間は測定していない、た
だし、低温での硬化性は、はぼ、充填剤を除いた成分に
よって決まるので、実施例１０は充填剤を除いた成分が
同組成の実施例７と、また、実施例１１は充填剤を除い
た成分が同組成の実施例８と、はぼ同様の硬化性を有す
るものと推定される。また、耐温水性も、充填剤を多量
に配合している関係で１号ダンヘルを成型することがで
きないので、ＪＩＳ Ｒ５２０１に準じて、テストピー
スを常温で注型し、２４時間室温で静置後、７０℃の温
水に浸漬し、２８日間後に三点曲げ強度と圧縮強度を測
定することによって評価した。Examples 10 to 11 Epoxy resin compositions having the compositions shown in Table 3 were prepared, and their hot water resistance was evaluated. The results are shown in Table 3. In these examples, the thin film curing time was not measured because the mixture contained a large amount of silica sand as a filler, making it mortar-like and unable to form a thin film. However, since the curability at low temperatures is determined by the ingredients excluding the filler, Example 10 has the same composition as Example 7 except for the filler, and Example 11 has the same composition as Example 7. It is estimated that this sample has the same curability as Example 8, which has the same composition except for the filler. In addition, regarding hot water resistance, it is not possible to mold No. 1 Danher because it contains a large amount of filler, so according to JIS R5201, a test piece was cast at room temperature and left at room temperature for 24 hours. After that, it was immersed in hot water at 70°C, and evaluated by measuring three-point bending strength and compressive strength after 28 days.
第
表
第３表に示すように、本発明の実施例１Ｏ〜１１のエポ
キシ樹脂組成物は、温水浸漬後の三点曲げ強度および圧
縮強度がそれぞれ１２０ｋｇ／ ｃｊ ６００ｋｇ／
Ｃ−と大きく、通常のコンクリートの約２倍の値を示し
、耐温水性が優れていた。As shown in Table 3, the epoxy resin compositions of Examples 1O to 11 of the present invention have a three-point bending strength and a compressive strength of 120 kg/cj 600 kg/cj, respectively, after immersion in hot water.
It had a high C- value, about twice that of ordinary concrete, and had excellent hot water resistance.
以上説明したように、本発明の低温硬化型エポキシ樹脂
組成物は、低温で速やかに硬化し、かつ耐温水性の優れ
た硬化物が得られる。したがって、本発明の低温硬化型
エポキシ樹脂組成物は、例えば、温水で洗浄される食品
工場の床材として好適に使用されるなど、その低温で速
やかに硬化し、かつ耐温水性の優れた硬化物が得られる
という特性を活用することによって、各種の用途に好適
に使用することができる。As explained above, the low temperature curable epoxy resin composition of the present invention cures quickly at low temperatures and provides a cured product with excellent hot water resistance. Therefore, the low-temperature-curing epoxy resin composition of the present invention is suitable for use as a flooring material in food factories that is washed with hot water, for example, because it cures quickly at low temperatures and has excellent hot water resistance. By taking advantage of its ability to obtain products, it can be suitably used for various purposes.
Ｆ−巴・（±F-Tomoe・(±
Claims (1)
とを特徴とする低温硬化型エポキシ樹脂組成物。 （ａ）エポキシ樹脂 １００重量部 （ｂ）１分子中に官能基を３〜６個有する多価アルコー
ルの不飽和酸エステル ５〜４０重量部 （ｃ）脂環族アミンを組成中に含むアミン系化合物 ３
０〜１００重量項(1) A low-temperature curable epoxy resin composition characterized by containing the following (a), (b) and (c). (a) Epoxy resin 100 parts by weight (b) Unsaturated acid ester of polyhydric alcohol having 3 to 6 functional groups in one molecule 5 to 40 parts by weight (c) Amine type containing alicyclic amine in the composition Compound 3
0-100 weight terms
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1049551A JPH0657743B2 (en) | 1989-02-28 | 1989-02-28 | Low temperature curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1049551A JPH0657743B2 (en) | 1989-02-28 | 1989-02-28 | Low temperature curable epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02227421A true JPH02227421A (en) | 1990-09-10 |
| JPH0657743B2 JPH0657743B2 (en) | 1994-08-03 |
Family
ID=12834330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1049551A Expired - Lifetime JPH0657743B2 (en) | 1989-02-28 | 1989-02-28 | Low temperature curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657743B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044653A (en) * | 1998-07-31 | 2000-02-15 | Mitsubishi Chemicals Corp | Resin composition for floor material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62179524A (en) * | 1986-02-03 | 1987-08-06 | チバ・ガイギ−・アクチエンゲゼルシヤフト | Epoxy resin composition |
-
1989
- 1989-02-28 JP JP1049551A patent/JPH0657743B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62179524A (en) * | 1986-02-03 | 1987-08-06 | チバ・ガイギ−・アクチエンゲゼルシヤフト | Epoxy resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000044653A (en) * | 1998-07-31 | 2000-02-15 | Mitsubishi Chemicals Corp | Resin composition for floor material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0657743B2 (en) | 1994-08-03 |
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