JPH02292325A - Epoxy resin composition prepared by using microencapsulated amine curing agent - Google Patents
Epoxy resin composition prepared by using microencapsulated amine curing agentInfo
- Publication number
- JPH02292325A JPH02292325A JP11296389A JP11296389A JPH02292325A JP H02292325 A JPH02292325 A JP H02292325A JP 11296389 A JP11296389 A JP 11296389A JP 11296389 A JP11296389 A JP 11296389A JP H02292325 A JPH02292325 A JP H02292325A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing agent
- amine curing
- core material
- resin composition
- 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 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 40
- 150000001412 amines Chemical class 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000011162 core material Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- 239000003094 microcapsule Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000935 solvent evaporation Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000002775 capsule Substances 0.000 description 7
- 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 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- -1 polymethylene Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- BZUILZIKDIMXBK-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1OC1 BZUILZIKDIMXBK-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101100173586 Schizosaccharomyces pombe (strain 972 / ATCC 24843) fft2 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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、常温（通常４０℃以下）で機械的に安定で、
加熱によりカプセルが破壊し硬化剤が放出するマイクロ
カプセル型アミン系硬化剤を用いることで、貯蔵安定性
に優れ、かつ接着性、耐水性、耐熱性、耐薬品性などに
優れたエポキシ樹脂組成物に関するもので、接着剤、シ
ール材、塗料などに用いられる．
〔従来の技術〕
エポキシ系、ウレタン系、ポリスルファイド系等の樹脂
が接着剤、シール材等に使用されており、その用途の多
様化により、一液型で貯蔵安定性の良い接着剤が求めら
れ、硬化剤のマイクロカプセル化が試みられている（例
えば特開昭４８ − ７６９３５号公報）。[Detailed Description of the Invention] [Industrial Application Field] The present invention is mechanically stable at room temperature (usually 40°C or lower),
By using a microcapsule-type amine curing agent whose capsules are destroyed by heating and the curing agent is released, this epoxy resin composition has excellent storage stability and excellent adhesion, water resistance, heat resistance, chemical resistance, etc. It is used in adhesives, sealants, paints, etc. [Prior technology] Epoxy, urethane, and polysulfide resins are used for adhesives, sealants, etc., and as their applications diversify, one-component adhesives with good storage stability are being developed. In response to this demand, attempts have been made to microencapsulate curing agents (for example, Japanese Patent Application Laid-open No. 76935/1983).
このようなマイクロカプセルは、壁材がかた《外圧で容
易に破壊して硬化剤を放出するため、接着剤としたとき
の貯蔵安定性が悪く、さらに界面重合法によりカプセル
化しているので製造時の作業性に劣るという問題があっ
た。Such microcapsules have poor storage stability when used as an adhesive because the wall material is easily destroyed by external pressure and releases the curing agent. Furthermore, they are encapsulated using an interfacial polymerization method, which makes them difficult to manufacture. There was a problem that the workability was poor.
また特に反応性の高いアミン系硬化剤は、壁材の選択や
、そのカプセル化が困難なため、いまだ実用的なものは
ないのが現状である。In addition, particularly highly reactive amine curing agents are difficult to select for wall materials and to encapsulate, so there are currently no practical ones.
本発明はかかる問題点を解決するためになされたもので
あって、機械的に安定なマイクロカプセル型アミン系硬
化剤を用いたエポキシ樹脂組成物を提供する。The present invention was made to solve these problems, and provides an epoxy resin composition using a mechanically stable microcapsule type amine curing agent.
即ち本発明は、（ａ）エポキシ樹脂、及び（ｂ）融点が
４０〜１５０℃のアミン系硬化剤を核材とし、該核材を
包合する壁材が、その軟化点が４０〜２００℃の熱可塑
性樹脂であるマイクロカプセル型アミン系硬化剤を主成
分とするエポキシ樹脂組成物に関する。That is, the present invention uses (a) an epoxy resin and (b) an amine curing agent with a melting point of 40 to 150°C as a core material, and a wall material enclosing the core material has a softening point of 40 to 200°C. The present invention relates to an epoxy resin composition whose main component is a microcapsule type amine curing agent which is a thermoplastic resin.
本発明の核材としてのアミン系硬化剤は、常温（通常２
０〜４０℃）で固形で、融点が４０〜１５０℃、好まし
くは６０〜１００℃が望ましい。 ４０℃未満では、核
材がつぶれて得られたカプセルの機械的強度が低下し、
１５０℃を越えるとカプセルが破壊した時に硬化剤が放
出されに《い。The amine curing agent as the core material of the present invention is used at room temperature (usually 2
It is solid at a temperature of 0 to 40°C) and has a melting point of 40 to 150°C, preferably 60 to 100°C. If the temperature is lower than 40°C, the core material will collapse and the mechanical strength of the resulting capsule will decrease.
If the temperature exceeds 150°C, the curing agent will not be released when the capsule is destroyed.
かかるアミン系硬化剤の具体例としては、例えばヘキサ
メチレンジアミン、オクタメチレンジアミン、デカンメ
チレンジアミン等のポリメチレンジアミン、メタフェニ
レンジアミン、ジアミノジフェニルメタン、ジアミノジ
フエニルスルフォンなどの芳香族アミン、ビス（４−ア
ミノシクロー、二トシル）メタン、ポリアミドボリアミ
ンなどが挙げられる。Specific examples of such amine-based curing agents include polymethylene diamines such as hexamethylene diamine, octamethylene diamine, and decane methylene diamine, aromatic amines such as metaphenylene diamine, diaminodiphenylmethane, and diaminodiphenylsulfone, and bis(4- Examples include aminocyclo, ditosyl)methane, and polyamidebolyamine.
本発明で用いられる壁材は、軟化点が４０〜２００℃、
好ましくは６０〜１５０℃の熱可塑性樹脂である。The wall material used in the present invention has a softening point of 40 to 200°C,
Preferably it is a thermoplastic resin having a temperature of 60 to 150°C.
ここで軟化点とは、Ｖ Ｉ ＣＡＴ法により測定したも
のである。 軟化点が４０℃未満の場合は、保存時のカ
プセルの機械的強度に欠け、２００℃を越えるとカプセ
ルの破壊が困難となるため好ましくない。Here, the softening point is measured by the VI CAT method. If the softening point is less than 40°C, the capsule will lack mechanical strength during storage, and if it exceeds 200°C, it will be difficult to break the capsule, which is not preferred.
熱可塑性樹脂の具体例として、例えばポリビニルブチラ
ール、ボリアミド樹脂、ボリスルフォン樹脂、ポリカー
ボネート樹脂、酢酸セルロース樹脂、ポリ塩化ビニル、
ポリエチレン、ヒドロキシプロビルメチルセルロースフ
タレート、エチルセルロース、ブロビオン酸セルロース
、ブチル酸セルロース、ポリビニルホルマール、ポリメ
チルメタアクリレート、ボリスチレン、ポリエステル、
ポリブタジエン、ポリエーテルスルフォン、フエノキシ
樹脂、エチレンー酢酸ビニル共重合体、塩化ビニループ
ロビレンー酢酸ビニル共重合体、プチルメタクリレート
、スチレンープチルメククリレート共重合体等が挙げら
れる。Specific examples of thermoplastic resins include polyvinyl butyral, polyamide resin, polysulfone resin, polycarbonate resin, cellulose acetate resin, polyvinyl chloride,
Polyethylene, hydroxyprobyl methyl cellulose phthalate, ethyl cellulose, cellulose brobionate, cellulose butyrate, polyvinyl formal, polymethyl methacrylate, polystyrene, polyester,
Examples include polybutadiene, polyethersulfone, phenoxy resin, ethylene-vinyl acetate copolymer, vinyl chloride-propylene-vinyl acetate copolymer, butyl methacrylate, styrene-butyl meccrylate copolymer, and the like.
なお、これらの熱可塑性樹脂はエポキシ樹脂と反応せず
、倣粒子状態で硬化物に分散するため、硬化時の内部ヒ
ズミを抑え、接着力の低下を防ぐという効果も与える。Note that these thermoplastic resins do not react with the epoxy resin and are dispersed in the cured product in the form of imitation particles, so they also have the effect of suppressing internal distortion during curing and preventing a decrease in adhesive strength.
本発明において用いるマイクロカプセル型硬化剤は、上
記壁材が前記アミン系硬化剤を包合しており、その核材
と壁材の容量比はｔ：Ｏ．Ｓ〜１：１０で、好ましくは
１：２〜１：５である。In the microcapsule type curing agent used in the present invention, the wall material encapsulates the amine curing agent, and the volume ratio of the core material to the wall material is t:O. S~1:10, preferably 1:2 to 1:5.
これより壁材が少なすぎると核材を覆いきれない場合が
あり、また多すぎると加熱しても壁材が壊れず核材の流
出が望めない恐れがある。If the wall material is too small, it may not be able to cover the core material, and if it is too large, the wall material may not break even if heated, and the core material may not flow out.
またマイクロカプセルの平均粒子径は１００μｍ以下、
好ましくは１０〜７０μｍであり、１００μｍを越える
粗粒になると、硬化物の特性が低下する恐れがある。
ここで平均粒子径は、顕微鏡（光学顕微鏡及び電子顕微
鏡）を用い、乾式にてサンプルを観察し、Ｆｅｒｅｔ径
にて粒度分布を測定することにより得た。
゜
かかるマイクロカプセル型硬化剤は、通常の雰囲気温度
下、例えば４０℃以下で機械的に安定で、熱可塑性樹脂
の軟化点以上に加熱すると、カプセルが破壊して内蔵さ
れた硬化剤が放出される。In addition, the average particle diameter of microcapsules is 100 μm or less,
The particle size is preferably 10 to 70 μm, and if the particle size exceeds 100 μm, the properties of the cured product may deteriorate.
Here, the average particle diameter was obtained by dryly observing a sample using a microscope (optical microscope and electron microscope) and measuring the particle size distribution using Feret diameter.
Such microcapsule-type curing agents are mechanically stable under normal atmospheric temperatures, for example, below 40°C, and when heated above the softening point of the thermoplastic resin, the capsules break and the built-in curing agent is released. Ru.
このようなマイクロカプセル型硬化剤は、通常の方法（
例えば、溶剤蒸発法、スプレードライ法など）でカプセ
ル化することにより得られる。Such microcapsule-type curing agents can be prepared using the usual method (
For example, it can be obtained by encapsulation using a solvent evaporation method, a spray drying method, etc.
本発明のエポキシ樹脂組成物は、前記マ・イクロカプセ
ル型アミン系硬化剤をエポキシ樹脂に室温にて、例えば
３本ロール、ミキサー、ディスパー等で均一に分散させ
ることによって得られる。The epoxy resin composition of the present invention can be obtained by uniformly dispersing the microcapsule type amine curing agent in an epoxy resin at room temperature using, for example, a three-roller, mixer, or disper.
マイクロカプセル型アミン系硬化剤の添加量は、用いる
硬化剤やエポキシ樹脂の種類によって異なるが、エポキ
シ樹脂１００重量部に対して通常０．１−１００重量部
、好ましくは１〜５０重量部とする。 添加量が上記範
囲より少なすぎるとエポキシ樹脂を十分硬化できず、ま
た多すぎると硬化剤の一部が未反応状態で残り、硬化物
の特性、特に耐水性が低下する恐れがある。The amount of the microcapsule type amine curing agent added varies depending on the type of curing agent and epoxy resin used, but it is usually 0.1-100 parts by weight, preferably 1-50 parts by weight per 100 parts by weight of the epoxy resin. . If the amount added is too small than the above range, the epoxy resin cannot be cured sufficiently, and if it is too large, a portion of the curing agent remains unreacted, which may reduce the properties of the cured product, especially the water resistance.
本発明に用いるエポキシ樹脂としては、ビスフェノール
Ａ型エポキシ樹脂が好適であるが、ビスフェノールＦ型
エポキシ樹脂、環状脂肪族エポキシ樹脂、トリス（２，
３エポキシプ口ピル）イソシアヌレート、ヒダントイン
型エポキシ樹脂、フェノールまたはタレゾールノボラソ
ク型エポキシ樹脂、フタル酸グリシジルエステル型エポ
キシ樹脂、β−メチルエビクロルヒドリン型エポキシ樹
脂などを単独で、もしくは２種以上混合して使用するこ
ともできる。As the epoxy resin used in the present invention, bisphenol A type epoxy resin is suitable, but bisphenol F type epoxy resin, cycloaliphatic epoxy resin, tris(2,
3) Isocyanurate, hydantoin type epoxy resin, phenol or Talezol novorasoc type epoxy resin, phthalate glycidyl ester type epoxy resin, β-methylevichlorohydrin type epoxy resin, etc. alone or in combination It is also possible to use a mixture of the above.
またこのようなエポキシ樹脂に、粘度調整等の目的でフ
ェニノレグリシジノレエーテノレ、アリノレグリシジル
エーテル等の反応性希釈剤や、平均分子量５０００〜ｔ
ｏｏｏｏｏのフェノキシ樹脂を、エポキシ樹脂１００重
量部に対して通常５０重量部以下、好ましくは３０重量
部以下添加することもできる。In addition, reactive diluents such as pheninoleglycidinoleate, alinoleglycidyl ether, etc., and an average molecular weight of 5,000 to t are added to such epoxy resins for the purpose of viscosity adjustment, etc.
It is also possible to add oooooo phenoxy resin to 100 parts by weight of the epoxy resin, usually at most 50 parts by weight, preferably at most 30 parts by weight.
多くいれすぎるとエポキシ樹脂特有の前記特性を損なう
恐れがあるので好ましくない。If too much is added, it is not preferable because there is a risk of impairing the characteristics peculiar to the epoxy resin.
また、硬化時の残留応力を緩和する目的で上記エポキシ
樹脂を一部ゴム変性して用いることもできる。 この場
合のゴム成分としては、通常平均分子量が１０００〜５
０００で１分子当りに含有するカルボキシル基数が平均
１．５〜２．５、好ましくは１．８〜２．４であり、分
子両末端にカルボキシル基を有する直鎖状のものが好ま
しい。 特にエポキシ樹脂との相溶性の点から、アクリ
ロニトリルを１０〜３０重量部、好ましくは１５〜２５
重量部含有する液状ブタジエンーアクリ口ニトリル共重
合ゴムが好ましい。 ゴム変性する場合のゴム質ボリマ
ーの含有率は、エポキシ樹脂の特性を維持しつつゴム特
性を引き出すため、樹脂成分全体の５〜３０重量％が好
ましい。Further, the above epoxy resin may be partially modified with rubber and used for the purpose of alleviating residual stress during curing. In this case, the rubber component usually has an average molecular weight of 1000 to 5.
000 and the number of carboxyl groups contained per molecule is 1.5 to 2.5 on average, preferably 1.8 to 2.4, and a linear one having carboxyl groups at both ends of the molecule is preferable. In particular, from the viewpoint of compatibility with the epoxy resin, 10 to 30 parts by weight of acrylonitrile, preferably 15 to 25 parts by weight,
Liquid butadiene-acrylic nitrile copolymer rubber containing parts by weight is preferred. In the case of rubber modification, the content of the rubbery polymer is preferably 5 to 30% by weight of the entire resin component in order to bring out the rubber properties while maintaining the properties of the epoxy resin.
本発明においては、前記マイクロカプセル型硬化剤以外
に、ジシアンジアミド系、ヒドラジド系、アミンイミド
系等のカプセル化されていない潜在性の硬化剤を併用す
ることができる。 その量は硬化剤の種類によって適宜
設定できるが、例えばエポキシ樹脂１００重量部に対し
てジシアンジアミドを通常１〜２０重量部添加すればよ
い。In the present invention, in addition to the microcapsule type curing agent, a non-encapsulated latent curing agent such as a dicyandiamide type, hydrazide type, or amine imide type can be used in combination. The amount can be set appropriately depending on the type of curing agent, but for example, 1 to 20 parts by weight of dicyandiamide may be added to 100 parts by weight of the epoxy resin.
さらに硬化促進剤を併用して硬化時間を短くすることも
できる。 かかる硬化促進剤としては、アルキル置換グ
アニジン系、３一置換フエニル１．１−ジメチル尿素系
、イミダゾール系、イミダゾリン系、３級アミン系、モ
ノアミノピリジン系、アミンイミド系等を挙げることが
できる。Furthermore, a curing accelerator can be used in combination to shorten the curing time. Examples of such curing accelerators include alkyl-substituted guanidine-based, 3-substituted phenyl-1,1-dimethylurea-based, imidazole-based, imidazoline-based, tertiary amine-based, monoaminopyridine-based, and amineimide-based.
本発明においては、耐水性、耐薬品性、密着性等を向上
させる目的で、シラン系カップリング剤をさらに添加す
ることもできる。 かかるシラン系カップリング剤とし
ては、例えばＸＳ五Ｙｓ（Ｘはビニル基、メタアクリ口
キシプ口ピル基、アミノアルキル基、メルカブトアルキ
ル基、エポキシアルキル基等の非加水分解型の有機基、
Ｙはハロゲン、アルコキシ基等の加水分解型基）で表さ
れるシラン化合物が好適で、Ｔ−アミノプロピルトリエ
トキシシラン、ビニルトリアセトキシシランなどを挙げ
ることができる。In the present invention, a silane coupling agent may be further added for the purpose of improving water resistance, chemical resistance, adhesion, etc. Such silane coupling agents include, for example,
Y is preferably a silane compound represented by a halogen, a hydrolyzable group such as an alkoxy group, and examples thereof include T-aminopropyltriethoxysilane and vinyltriacetoxysilane.
またシリカ、クレー、石膏、炭酸カルシウム、硫酸バリ
ウム、石英粉、ガラス繊維、カオリン、マイ力、アルミ
ナ、永和アルミナ、水酸化アルミ、タルク、ドロマイト
、ジルコン、チタン化合物等の充填剤、顔料、老化防止
剤等を目的に応じて適宜配合することもできる。In addition, fillers such as silica, clay, gypsum, calcium carbonate, barium sulfate, quartz powder, glass fiber, kaolin, miryoku, alumina, Eiwa alumina, aluminum hydroxide, talc, dolomite, zircon, titanium compounds, pigments, and anti-aging Agents and the like may be added as appropriate depending on the purpose.
さらに溶接性を付与する目的で、アルミ、亜鉛、ステン
レス、銅などの粒状粉末や針状粉末を導電性粉末として
添加することもできる。Further, for the purpose of imparting weldability, granular powder or acicular powder of aluminum, zinc, stainless steel, copper, etc. can be added as conductive powder.
またシール性を向上させる目的で、通常１００〜２００
℃で分解する発泡剤を０．１〜５重量部添加してもよく
、かかる発泡剤として例えばジアゾカルボンアミド、ジ
ニトロソペンタメチレンテトラミン、４，４−ジオキシ
ビスベンゼンスルフォニルヒドラジド等が挙げられる。In addition, for the purpose of improving sealing performance, it is usually 100 to 200
0.1 to 5 parts by weight of a blowing agent that decomposes at <0>C may be added, such as diazocarbonamide, dinitrosopentamethylenetetramine, 4,4-dioxybisbenzenesulfonyl hydrazide, and the like.
本発明のエポキシ樹脂組成物は、使用するマイクロカプ
セル型アミン系硬化剤が機械的に安定であるため、エポ
キシ樹脂に配合して組成物とした場合の常温（通常４０
゜Ｃ以下）での貯蔵安定性に優れる。 また、加熱によ
りカプセルが破壊し、硬化剤が放出されエポキシ樹脂と
反応して、接着性、耐水性等に優れた硬化物を得ること
ができる。The epoxy resin composition of the present invention uses a microcapsule type amine curing agent that is mechanically stable.
Excellent storage stability at temperatures below ℃. In addition, the capsule is destroyed by heating, and the curing agent is released and reacts with the epoxy resin, making it possible to obtain a cured product with excellent adhesiveness, water resistance, and the like.
実施例及び比較例の樹脂組成物の配合を表に示す。 こ
こで各成分は下記の通りで、部は重量部を示す。The formulations of the resin compositions of Examples and Comparative Examples are shown in the table. Here, each component is as follows, and parts indicate parts by weight.
（イ）ビスフェノールＡ型エポキシ樹脂（常温で液状、
エポキシ当量約１９０）
（口）ゴム変性エポキシ樹脂（ブタジエンーアクリ口ニ
トリル共重合体１０部と、ビスフェノールＡ型エポキシ
樹脂（エポキシ当量約１９０）９０部を、溶解混合釜で
１６０℃で１時間反応させて得た。）
（ハ）フェノキシ樹脂（平均分子ｆｆｔ２ ０ ０ ０
０）（二）重合度５００〜１０００のポリビニルブチ
ラール（ＶＩＣＡＴ法による軟化点６０〜７０℃、アセ
チル基３〜５ｍｏｌχ、ブチラール．２Ｊ７０ｍｏｌχ
以上、残りは水酸基）を壁材とし、ドデカンメチレンジ
アミン（融点７２℃）を核材とするマイクロカプセル型
硬化剤。（核材と壁材の容量比は１：２、平均粒子径５
０μｍ）
（ホ）ポリスルフォン（ＶＩＣＡ’ｌ’法による軟化点
１６０℃）を壁材とし、ｍ−フェニレンジアミン（融点
６２℃）を核材とするマイクロカプセル型硬化剤。（核
材と壁材の容量比はｌ：１、平均粒子径３３μｍ）
（へ）エチレンー酢酸ビニル共重合体樹脂（ＶｔＣＡＴ
法による軟化点４０℃未満）を壁材とし、ｍフエニレン
ジアミン（融点６２℃）を核材とするマイクロカプセル
型硬化剤。（核材と壁材の容量比は１：３、平均粒子径
４５μｍ）
（ト）ボリスチレン（ＶＩＣＡＴ法による軟化点２２０
℃）を壁材とし、ドデカンメチレンジアミン（融点７２
℃）を核材とするマイクロカプセル型硬化剤。（核材と
壁材の容量比は１：２、平均粒子径２５μｍ）
（チ）重合度５００〜１０００のポリビニルブチラール
（ＶＩＣＡＴ法による軟化点６０〜７０℃、アセチル基
３〜５１ＩＩＯｌχ、ブチラール基７０ｍｏｌＸ以上、
残りは水酸基）を壁材とし、ドデカンメチレンジアミン
（融点７２’ｃ）を核材とするマイクロカプセル型硬化
剤。（核材と壁材の容量比はｌ：２０、平均粒子径２５
μｍ）
（り）ジシアンジアミド
（ヌ） ３−（３．４−ジクロルフエニル）−Ｌｌ−ジ
メチル尿素
（ル）アルミニウム粉末
上記実施例及び比較例で得られたエポキシ樹脂組成物の
特性を下記の方法で評価し、その結果を表に合わせて示
した。(a) Bisphenol A type epoxy resin (liquid at room temperature,
(Epoxy equivalent: approx. 190) (10 parts of rubber-modified epoxy resin (butadiene-acrylic nitrile copolymer) and 90 parts of bisphenol A type epoxy resin (epoxy equivalent: approx. 190) were dissolved and reacted at 160°C for 1 hour in a mixing pot. ) (c) Phenoxy resin (average molecular fft2 0 0 0
0) (2) Polyvinyl butyral with a degree of polymerization of 500-1000 (softening point 60-70°C by VICAT method, acetyl group 3-5 molχ, butyral.2J70 molχ)
A microcapsule-type curing agent that uses dodecane methylene diamine (melting point 72°C) as a core material and uses a wall material (remaining hydroxyl groups) as a core material. (Capacity ratio of core material and wall material is 1:2, average particle size is 5
0 μm) (e) A microcapsule-type curing agent that uses polysulfone (softening point 160°C by VICA'l' method) as a wall material and m-phenylenediamine (melting point 62°C) as a core material. (Capacity ratio of core material and wall material is 1:1, average particle size 33 μm) (f) Ethylene-vinyl acetate copolymer resin (VtCAT
A microcapsule-type curing agent that uses m-phenylenediamine (melting point: 62°C) as a core material and uses m-phenylenediamine (melting point: 62°C) as a wall material. (Capacity ratio of core material and wall material is 1:3, average particle diameter 45 μm) (g) Borystyrene (softening point 220 by VICAT method)
℃) was used as the wall material, and dodecane methylene diamine (melting point 72
A microcapsule type curing agent whose core material is ℃). (Capacity ratio of core material and wall material is 1:2, average particle diameter 25 μm) (h) Polyvinyl butyral with a degree of polymerization of 500 to 1000 (softening point by VICAT method: 60 to 70°C, acetyl group 3 to 51 IIOlχ, butyral group 70 mol that's all,
A microcapsule-type curing agent that uses dodecane methylene diamine (melting point 72'c) as a core material and uses a wall material (the rest is hydroxyl groups) as a core material. (Capacity ratio of core material and wall material is 1:20, average particle size is 25
μm) (ri)dicyandiamide(nu)3-(3.4-dichlorophenyl)-Ll-dimethylurea(ru)aluminum powder The characteristics of the epoxy resin compositions obtained in the above examples and comparative examples were evaluated by the following method. The results are shown in the table.
（１）貯蔵安定性
４０℃で保存し、３週間後の粘度が初期よりどれだけ増
粘したかを下記の基準で評価した。(1) Storage stability After storage at 40° C., the viscosity after 3 weeks was evaluated based on the following criteria to see how much it had increased in viscosity from the initial level.
○：変化なし
×：２倍以上増粘した
なお粘度は、高化式フローテスターを用い２０℃、荷重
１ ｋｇ、ダイ径１ｍｌで測定した。○: No change ×: The viscosity increased by more than 2 times. The viscosity was measured using a Koka type flow tester at 20°C, a load of 1 kg, and a die diameter of 1 ml.
（２）剪断接着力
ＪＴＳ．Ｋ−６８５０に従い、２枚のｓｐｃｃ−ｓｒ鋼
板（１００ Ｘ２５Ｘ １．６ｔ ａｍ）を、上記接着
剤組成物で接着して試験片を作成した。 これ実施例ｌ
、２、比較例１、３、４では１００℃で１時間加熱硬化
させた後、また実施例３、４、比較例２では１６０℃で
１時間加熱硬化させた後、室温で測定した。(2) Shear adhesive strength JTS. A test piece was prepared by bonding two spcc-sr steel plates (100 x 25 x 1.6 t am) with the above adhesive composition in accordance with K-6850. This is an example l
, 2. Comparative Examples 1, 3, and 4 were heat-cured at 100°C for 1 hour, and Examples 3, 4, and Comparative Example 2 were heat-cured at 160°C for 1 hour, and then measured at room temperature.
（３）耐水性
４０℃の温水に上記（２）で作成したサンプルを、ＩＯ
日間漫消した後室温で（２）と同様にして接着力を測定
し、初期値に対しての保持率により下記のｇＨａで評価
した。(3) Water resistance: Place the sample prepared in (2) above in 40°C warm water using IO
After being cured for a few days, the adhesive strength was measured at room temperature in the same manner as in (2), and the retention rate with respect to the initial value was evaluated using the following gHa.
○：８０％以上 Δ：６０へ８０％ ×：６０％以下○: 80% or more Δ: 60 to 80% ×: 60% or less
Claims (4)
し、該核材を包合する壁材が、その軟化点が４０〜２０
０℃の熱可塑性樹脂であるマイクロカプセル型アミン系
硬化剤、 を主成分としてなるエポキシ樹脂組成物。(1) (a) An epoxy resin and (b) an amine curing agent with a melting point of 40 to 150°C as a core material, and a wall material that encloses the core material has a softening point of 40 to 20°C.
An epoxy resin composition comprising as a main component a microcapsule type amine curing agent which is a thermoplastic resin at 0°C.
ポキシ樹脂１００重量部に対して０．１〜１００重量部
である請求項１記載のエポキシ樹脂組成物。(2) The epoxy resin composition according to claim 1, wherein the amount of the microcapsule type amine curing agent added is 0.1 to 100 parts by weight per 100 parts by weight of the epoxy resin.
の容量比が１：０．５〜１：１０である請求項１又は２
記載のエポキシ樹脂組成物。(3) Claim 1 or 2, wherein the volume ratio of the core material and wall material of the microcapsule type amine curing agent is 1:0.5 to 1:10.
The epoxy resin composition described.
び／又は硬化促進剤をさらに含有してなる請求項１ない
し３記載のエポキシ樹脂組成物。(4) The epoxy resin composition according to any one of claims 1 to 3, further comprising a latent curing agent and/or a curing accelerator that are not microencapsulated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11296389A JPH02292325A (en) | 1989-05-02 | 1989-05-02 | Epoxy resin composition prepared by using microencapsulated amine curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11296389A JPH02292325A (en) | 1989-05-02 | 1989-05-02 | Epoxy resin composition prepared by using microencapsulated amine curing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02292325A true JPH02292325A (en) | 1990-12-03 |
Family
ID=14599922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11296389A Pending JPH02292325A (en) | 1989-05-02 | 1989-05-02 | Epoxy resin composition prepared by using microencapsulated amine curing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02292325A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03182520A (en) * | 1989-12-13 | 1991-08-08 | Matsumoto Yushi Seiyaku Co Ltd | Microcapsule of amine curing agent |
| JPH04249544A (en) * | 1990-12-28 | 1992-09-04 | Toho Rayon Co Ltd | Resin composition, prepreg and production of prepreg |
| EP0590975A1 (en) * | 1992-10-02 | 1994-04-06 | W.R. Grace & Co.-Conn. | Low viscosity and solvent-free one-component type epoxy resin adhesive composition |
| JPH0753673A (en) * | 1993-06-08 | 1995-02-28 | Mitsubishi Rayon Co Ltd | Epoxy resin composition and prepreg |
| EP0672707A2 (en) * | 1994-03-15 | 1995-09-20 | Toray Industries, Inc. | Microencapsulated curing agent for thermosetting resin compositions |
| US5811497A (en) * | 1994-09-16 | 1998-09-22 | Kabushiki Kaisha Toshiba | Aromatic curing catalyst for epoxy resins |
| US7253131B2 (en) | 2001-05-16 | 2007-08-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP2019199511A (en) * | 2018-05-15 | 2019-11-21 | 旭化成株式会社 | Method for producing epoxy resin composition |
-
1989
- 1989-05-02 JP JP11296389A patent/JPH02292325A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03182520A (en) * | 1989-12-13 | 1991-08-08 | Matsumoto Yushi Seiyaku Co Ltd | Microcapsule of amine curing agent |
| JPH04249544A (en) * | 1990-12-28 | 1992-09-04 | Toho Rayon Co Ltd | Resin composition, prepreg and production of prepreg |
| EP0590975A1 (en) * | 1992-10-02 | 1994-04-06 | W.R. Grace & Co.-Conn. | Low viscosity and solvent-free one-component type epoxy resin adhesive composition |
| JPH0753673A (en) * | 1993-06-08 | 1995-02-28 | Mitsubishi Rayon Co Ltd | Epoxy resin composition and prepreg |
| EP0672707A2 (en) * | 1994-03-15 | 1995-09-20 | Toray Industries, Inc. | Microencapsulated curing agent for thermosetting resin compositions |
| EP0672707A3 (en) * | 1994-03-15 | 1996-07-03 | Toray Industries | Microencapsulated curing agent for thermosetting resin compositions. |
| US5589523A (en) * | 1994-03-15 | 1996-12-31 | Toray Industries, Inc. | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US5726222A (en) * | 1994-03-15 | 1998-03-10 | Toray Industries, Inc. | Microcapsule-type curing agent, method for producing the same, thermosetting resin composition, prepreg and fiber reinforced composite material |
| US5811497A (en) * | 1994-09-16 | 1998-09-22 | Kabushiki Kaisha Toshiba | Aromatic curing catalyst for epoxy resins |
| US7253131B2 (en) | 2001-05-16 | 2007-08-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP2019199511A (en) * | 2018-05-15 | 2019-11-21 | 旭化成株式会社 | Method for producing epoxy resin composition |
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