JPH0794597B2 - Two-component epoxy resin composition - Google Patents
Two-component epoxy resin compositionInfo
- Publication number
- JPH0794597B2 JPH0794597B2 JP1138534A JP13853489A JPH0794597B2 JP H0794597 B2 JPH0794597 B2 JP H0794597B2 JP 1138534 A JP1138534 A JP 1138534A JP 13853489 A JP13853489 A JP 13853489A JP H0794597 B2 JPH0794597 B2 JP H0794597B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing agent
- resin composition
- rubber
- group
- 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 - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 title claims description 21
- 229920000647 polyepoxide Polymers 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 6
- -1 silane compound Chemical class 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 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 description 5
- 238000001879 gelation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000962 poly(amidoamine) Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は二液型エポキシ樹脂組成物、更に詳しくは、親
水性硬化剤の水分吸収によるゲル化時間や可使時間の短
縮化を抑えた二液型エポキシ樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a two-pack type epoxy resin composition, and more particularly to a two-pack type epoxy resin composition which suppresses shortening of gelation time and pot life due to water absorption of a hydrophilic curing agent. Type epoxy resin composition.
従来技術と発明が解決しようとする課題 接着剤やシーリング材等に用いられている二液型エポキ
シ樹脂組成物は、一般にエポキシ樹脂主剤と硬化剤とで
構成されている。ところで、硬化剤として、アミン系、
アミド系、ポリサルファイド系、チオ尿素系など各種の
ものがあり、これらの中から用途分野に応じて取捨選択
されている。しかしながら、これらの脂肪族ポリアミン
やポリアミドアミン系の硬化剤は一般に親水性を有して
おり、貯蔵期間中に外気の水分を吸収し易い。この水分
は、エポキシ樹脂と硬化剤を混合した場合、硬化促進作
用を有し、経日でゲル化時間や可使時間が短縮すること
になり、また経日粘度上昇、主剤／硬化剤混合粘度、硬
化性の低下（硬さの低下）など初期性能に影響をもたら
す。2. Related Art and Problems to be Solved by the Invention A two-pack type epoxy resin composition used as an adhesive or a sealing material is generally composed of an epoxy resin base and a curing agent. By the way, as a curing agent, amine-based,
There are various types such as amide type, polysulfide type, and thiourea type, and these are selected according to the field of application. However, these aliphatic polyamine and polyamidoamine-based curing agents generally have hydrophilicity and easily absorb moisture in the outside air during the storage period. This water has a curing-accelerating effect when the epoxy resin and the curing agent are mixed, which shortens the gelling time and pot life with the passage of time. In addition, the initial performance is affected such as a decrease in curability (a decrease in hardness).
そこで、本発明者らは、かかる親水性硬化剤に特定量の
吸湿性物質を添加しておけば、親水性硬化剤への水分吸
収、ひいてはゲル化時間や可使時間の短縮化を抑えるこ
とができ、かつ親水性硬化剤の機能に支障を来さないこ
とを見出し、本発明を完成させるに至った。Therefore, the inventors of the present invention suppress the absorption of water into the hydrophilic curing agent and thus the shortening of gelation time and pot life by adding a specific amount of a hygroscopic substance to the hydrophilic curing agent. The present invention has been completed, and it was found that the function of the hydrophilic curing agent is not hindered and the present invention has been completed.
発明の構成と効果 すなわち、本発明は、エポキシ樹脂主剤と親水性硬化剤
から成る二液型エポキシ樹脂組成物（但し、エポキシ樹
脂主剤あるいは親水性硬化剤の少なくとも一方に、カル
ボキシル基もしくはアミノ基含有のブタジエンゴムまた
はブタジエン−アクリロニトリル共重合ゴム、あるいは
シロキサン結合を介して架橋しうる反応性ケイ素基含有
のゴム系有機重合体を配合したものを除く）において、
親水性硬化剤に対して0.5〜５％（重量％、以下同様）
の、エポキシ基と反応する官能基を有さない加水分解性
シラン化合物を添加したことを特徴とする二液型エポキ
シ樹脂組成物を提供するものである。Structure and Effect of the Invention That is, the present invention is a two-pack type epoxy resin composition comprising an epoxy resin main agent and a hydrophilic curing agent (provided that at least one of the epoxy resin main agent and the hydrophilic curing agent contains a carboxyl group or an amino group). A butadiene rubber or a butadiene-acrylonitrile copolymer rubber, or a compound containing a rubber-based organic polymer containing a reactive silicon group capable of crosslinking via a siloxane bond)
0.5 to 5% of hydrophilic curing agent (% by weight, the same below)
And a hydrolyzable silane compound having no functional group that reacts with an epoxy group is added.
本発明における主剤成分のエポキシ樹脂としては、通常
のビスフェノール型、ウレタン変性ビスフェノール型、
臭素化ビスフェノール型、ノボラック型、脂肪族型、脂
環族型のエポキシ樹脂が使用されてよく、常温液状が好
ましい。固形のものについては液状のものと併用すれば
よい。The epoxy resin as the main component in the present invention, a normal bisphenol type, urethane-modified bisphenol type,
Brominated bisphenol type, novolak type, aliphatic type and alicyclic type epoxy resins may be used, and liquid at room temperature is preferable. The solid one may be used in combination with the liquid one.
本発明における硬化剤としては、用途分野に応じて通常
のダイマー酸に脂肪族アミンを反応させたポリアミド樹
脂、ポリアミドアミン、脂肪族ポリアミン、変性脂肪族
ポリアミン、チオ尿素変性ポリアミン、脂環式ポリアミ
ン、アミンアダクト等の親水性を有するものが挙げら
れ、これらの１種または２種以上の混合物を用いる。As the curing agent in the present invention, a polyamide resin obtained by reacting an aliphatic amine with a normal dimer acid depending on the field of use, a polyamide amine, an aliphatic polyamine, a modified aliphatic polyamine, a thiourea modified polyamine, an alicyclic polyamine, Examples thereof include those having hydrophilicity such as amine adduct, and one or a mixture of two or more thereof is used.
本発明における加水分解性シラン化合物としては、エポ
キシ基と反応する官能基を有さないものであって、たと
えばテトラメトキシシラン、テトラエトキシシラン、メ
チルトリメトキシシラン、メチルトリエトキシシラン、
フェニルトリメトキシシラン、フェニルトリエトキシシ
ランなどのアルコキシシラン化合物；ビニルトリクロル
シラン、ビニルトリメトキシシラン、ビニルトリエトキ
シシラン、ビニルトリス（β−メトキシエトキシ）シラ
ン、ビニルトリアセトキシシランなどのビニルシラン化
合物；等が挙げられ、これらの１種又は２種以上の混合
物を用いる。特に、加水分解性アルコキシシラン化合物
が吸水性が大であり、本発明により有効に用いることが
できる。使用量は、上記親水性硬化剤に対して0.5〜５
％、好ましくは0.8〜３％の範囲で選定する。0.5％未満
であると、親水性硬化剤への水分吸収防止効果が得られ
ず、また５％を越えると、反対に硬化の遅延化作用を有
し、初期のゲル化、可使時間が延長される傾向となる。
さらに、加水分解性シラン化合物は親水性硬化剤に添加
する充填材の経日による沈降を防止する効果を有し、ま
た使用するまでの貯蔵後にも、硬化性（硬さ）、接着性
などの物性を変化させないといった付加効果もある。The hydrolyzable silane compound in the present invention does not have a functional group that reacts with an epoxy group, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
Alkoxysilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane; vinylsilane compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane and vinyltriacetoxysilane; and the like. And a mixture of one or more of these is used. In particular, the hydrolyzable alkoxysilane compound has a large water absorption and can be effectively used in the present invention. The amount used is 0.5 to 5 with respect to the hydrophilic curing agent.
%, Preferably 0.8 to 3%. If it is less than 0.5%, the effect of preventing water absorption by the hydrophilic curing agent cannot be obtained, and if it exceeds 5%, on the contrary, it has a retarding effect on curing, and the initial gelation and pot life are extended. Tends to be done.
Furthermore, the hydrolyzable silane compound has an effect of preventing sedimentation of the filler to be added to the hydrophilic curing agent due to the passage of time, and even after storage until use, the curability (hardness), adhesiveness, etc. It also has the additional effect of not changing the physical properties.
本発明に係る二液型エポキシ樹脂組成物は、上述のエポ
キシ樹脂主剤と、加水分解性シラン化合物を添加した親
水性硬化剤とで構成され、必要に応じて主剤と硬化剤の
一方または両方に、通常の充填材（炭酸カルシウム、ク
レー、タルク、硫酸バリウム、マイカ、コロイダルシリ
カなど）、可塑剤、希釈剤等を適量加えてもよい。The two-pack type epoxy resin composition according to the present invention is composed of the above-mentioned epoxy resin main agent and a hydrophilic curing agent to which a hydrolyzable silane compound is added, and as necessary, one or both of the main agent and the curing agent. Ordinary fillers (calcium carbonate, clay, talc, barium sulfate, mica, colloidal silica, etc.), plasticizers, diluents and the like may be added in appropriate amounts.
なお、本発明の二液型エポキシ樹脂組成物において、エ
ポキシ樹脂主剤あるいは親水性硬化剤の少なくとも一方
に、たとえば特開昭57-108124号公報に記載されるよう
なカルボキシル基もしくはアミノ基含有のブタジエンゴ
ムまたはブタジエン−アクリロニトリル共重合ゴム、あ
るいは特願平１-49088号明細書（特開平２-228365号公
報参照）に記載されるようなシロキサン結合を介して架
橋しうる反応性ケイ素基含有のゴム系有機重合体を配合
したものは、本発明の対象外である。Incidentally, in the two-pack type epoxy resin composition of the present invention, at least one of the epoxy resin main component and the hydrophilic curing agent is a butadiene containing a carboxyl group or an amino group as described in JP-A-57-108124. Rubber or butadiene-acrylonitrile copolymer rubber, or a rubber containing a reactive silicon group capable of being cross-linked through a siloxane bond as described in Japanese Patent Application No. 1-49088 (see JP-A-2-228365). Those containing a system organic polymer are outside the scope of the present invention.
次に実施例および比較例を挙げて、本発明をより具体的
に説明する。Next, the present invention will be described more specifically with reference to Examples and Comparative Examples.
実施例１〜８および比較例1,2 下記表１に示す重量部数の各成分を混合して、主剤成分
と硬化剤成分を調製する。Examples 1 to 8 and Comparative Examples 1 and 2 The components in the weight parts shown in Table 1 below are mixed to prepare a main component and a curing agent component.
次に、主剤成分と硬化剤成分を二液混合（接着剤調製）
し、その直後と、35℃,90％RHで30日間貯蔵後の接着剤
について、可使時間またはゲル化時間を測定する。さら
に、上記貯蔵後の接着剤の硬化性および接着性を評価す
る。これらの結果を表１に併記する。Next, the main component and hardener component are mixed in two liquids (adhesive preparation)
Then, the pot life or gelation time of the adhesive is measured immediately after that and after storage for 30 days at 35 ° C. and 90% RH. Furthermore, the curability and adhesiveness of the adhesive after storage are evaluated. The results are also shown in Table 1.
注 エピコート828:シェル化学社製のビスフェノール
Ａ型エポキシ樹脂 充填材：炭酸カルシウム、クレー、タルク、硫酸バリウ
ム、マイカなど EA631:大日本インキ化学工業社製のポリアミドアミ
ン EA140:大日本インキ化学工業社製のポリアミドアミン マイカマイド506:エー・シー・アイ・ジャパン社製のポ
リアミドアミン EH231:旭電化工業社製の変性脂肪族ポリアミン エチルシリケート28:コルコート社製のテトラエトキシ
シラン Ａ−162:日本ユニカー社製のメチルトリエトキシシラン Ａ−163:日本ユニカー社製のメチルトリメトキシシラン Ｓ−210:チッソ社製のビニルトリエトキシシラン 充填材：主剤に用いたものと同じ 実施例１〜６および比較例１の接着剤について、接
着剤200gの20℃における、粘度が10万cpsに達するまで
の時間（分）を測定する。 Note Epicoat 828: Shell Chemical Co., Ltd. bisphenol A type epoxy resin Filler: Calcium carbonate, clay, talc, barium sulfate, mica, etc. EA631: Polyamine amine manufactured by Dainippon Ink and Chemicals, Inc. EA140: Dainippon Ink and Chemicals Polyamidoamine Mica Mide 506: Polyamidoamine manufactured by ACI Japan EH231: Modified aliphatic polyamine ethyl silicate manufactured by Asahi Denka Co., Ltd. 28: Tetraethoxysilane manufactured by Colcoat Co., A-162: manufactured by Unicar Japan Methyltriethoxysilane A-163: Methyltrimethoxysilane manufactured by Nippon Unicar S-210: Vinyltriethoxysilane manufactured by Chisso Corporation Filler: same as that used as the main agent Adhesion of Examples 1 to 6 and Comparative Example 1 For the agent, the time (minutes) until the viscosity of 200 g of the adhesive reaches 100,000 cps at 20 ° C. is measured.
実施例7,8および比較例２の接着剤について、接着
剤100gが20℃においてゲル化するまでの時間（分）を測
定する。For the adhesives of Examples 7 and 8 and Comparative Example 2, the time (minutes) until 100 g of the adhesive gels at 20 ° C. is measured.
接着剤を熱硬化（実施例１〜６および比較例1:60℃
×180分、実施例7,8および比較例2:50℃×90分）させ、
冷却したときのショアーＤ硬度を測定する。Thermosetting the adhesive (Examples 1 to 6 and Comparative Example 1: 60 ° C.
× 180 minutes, Examples 7 and 8 and Comparative Example 2: 50 ° C. × 90 minutes),
The Shore D hardness when cooled is measured.
生布に接着剤を塗布し、これをJIS G3141鋼板に貼
り合せ、上記と同様に熱硬化した後、手剥離で評価す
る。CF:材料破壊。表１の結果から、比較例の貯蔵後の
可使時間（比較例１）、ゲル化時間（比較例２）が大き
く短縮するのに対して、実施例ではほとんど変化がなく
優れることがわかる。また本発明の加水分解性シラン化
合物を添加することにより、硬化性、接着性に悪影響を
及ぼさないことがわかる。An adhesive is applied to a raw cloth, which is attached to a JIS G3141 steel plate, which is heat-cured in the same manner as above, and then evaluated by manual peeling. CF: Material destruction. From the results in Table 1, it can be seen that the pot life after storage (Comparative Example 1) and the gelation time (Comparative Example 2) of the Comparative Example are greatly shortened, while the Examples are excellent with almost no change. Further, it is understood that the addition of the hydrolyzable silane compound of the present invention does not adversely affect the curability and adhesiveness.
Claims (1)
二液型エポキシ樹脂組成物（但し、エポキシ樹脂主剤あ
るいは親水性硬化剤の少なくとも一方に、カルボキシル
基もしくはアミノ基含有のブタジエンゴムまたはブタジ
エン−アクリロニトリル共重合ゴム、あるいはシロキサ
ン結合を介して架橋しうる反応性ケイ素基含有のゴム系
有機重合体を配合したものを除く）において親水性硬化
剤に対して0.5〜５重量％の、エポキシ基と反応する官
能基を有さない加水分解性シラン化合物を添加したこと
を特徴とする二液型エポキシ樹脂組成物。1. A two-pack type epoxy resin composition comprising an epoxy resin main agent and a hydrophilic curing agent (provided that at least one of the epoxy resin main agent and the hydrophilic curing agent has a carboxyl group- or amino group-containing butadiene rubber or butadiene-containing rubber). Acrylonitrile copolymer rubber or a rubber-based organic polymer containing a reactive silicon group that can be cross-linked through a siloxane bond) except 0.5 to 5% by weight of an epoxy group relative to the hydrophilic curing agent. A two-pack type epoxy resin composition, wherein a hydrolyzable silane compound having no reactive functional group is added.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1138534A JPH0794597B2 (en) | 1989-05-31 | 1989-05-31 | Two-component epoxy resin composition |
| GB9011980A GB2232158B (en) | 1989-05-31 | 1990-05-30 | Two-pack epoxy resin compositions |
| DE19904017592 DE4017592C2 (en) | 1989-05-31 | 1990-05-31 | Two-pack epoxy resin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1138534A JPH0794597B2 (en) | 1989-05-31 | 1989-05-31 | Two-component epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH036255A JPH036255A (en) | 1991-01-11 |
| JPH0794597B2 true JPH0794597B2 (en) | 1995-10-11 |
Family
ID=15224403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1138534A Expired - Fee Related JPH0794597B2 (en) | 1989-05-31 | 1989-05-31 | Two-component epoxy resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0794597B2 (en) |
| DE (1) | DE4017592C2 (en) |
| GB (1) | GB2232158B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5160298A (en) * | 1974-11-25 | 1976-05-26 | Sumitomo Bakelite Co | EHOKISHIJUSHOKOKAZAISOSEIBUTSU |
| JPS603407B2 (en) * | 1980-12-24 | 1985-01-28 | 日東電工株式会社 | Two-part epoxy resin composition |
| JP2694995B2 (en) * | 1989-03-01 | 1997-12-24 | 鐘淵化学工業株式会社 | Two-part curable composition with improved storage stability |
| JPH06178822A (en) * | 1992-12-15 | 1994-06-28 | Matsushita Electric Ind Co Ltd | Laser therapy equipment |
-
1989
- 1989-05-31 JP JP1138534A patent/JPH0794597B2/en not_active Expired - Fee Related
-
1990
- 1990-05-30 GB GB9011980A patent/GB2232158B/en not_active Expired - Lifetime
- 1990-05-31 DE DE19904017592 patent/DE4017592C2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH036255A (en) | 1991-01-11 |
| GB2232158B (en) | 1992-04-15 |
| DE4017592A1 (en) | 1990-12-06 |
| GB9011980D0 (en) | 1990-07-18 |
| DE4017592C2 (en) | 1996-05-30 |
| GB2232158A (en) | 1990-12-05 |
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