JPH02110116A - Epoxyacrylate resin composition - Google Patents
Epoxyacrylate resin compositionInfo
- Publication number
- JPH02110116A JPH02110116A JP26134888A JP26134888A JPH02110116A JP H02110116 A JPH02110116 A JP H02110116A JP 26134888 A JP26134888 A JP 26134888A JP 26134888 A JP26134888 A JP 26134888A JP H02110116 A JPH02110116 A JP H02110116A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- meth
- resin
- epoxy
- epoxyacrylate
- 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
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011342 resin composition Substances 0.000 title claims abstract 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical group CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine salts Chemical class 0.000 claims description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 150000003018 phosphorus compounds Chemical group 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000003365 glass fiber 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
- 238000009787 hand lay-up Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は、エポキシアクリレート樹脂組成物に関する。[Detailed description of the invention] The present invention relates to epoxy acrylate resin compositions.
１分子中に少なくとも２個のエポキシ基を有するエポキ
シ化合物と（メタ）アクリル酸から得られるエポキシア
クリレートをスチレン等の重合性ビニル単量体に溶解し
たエポキシアクリレート樹脂は、耐食性、機械的特性、
硬化性、作業性でエポキシ樹脂や不飽和ポリエステル樹
脂よりも優れているので、ハンドレイアップ成形、レジ
ントランスファー成形、フィラメントワインディング成
形、ｓｕＣやＢＭＣ等の加圧成形法により、耐食を目的
としたヘルメット、スポーツ用品等の用途に用いられて
いる。また、（メタ）アクリル酸エステル類で希釈した
ものは、紫外線、電子線硬化用樹脂として印刷インキ、
塗料の分野で用いられている。Epoxy acrylate resin, which is obtained by dissolving epoxy acrylate obtained from an epoxy compound having at least two epoxy groups in one molecule and (meth)acrylic acid in a polymerizable vinyl monomer such as styrene, has excellent corrosion resistance, mechanical properties,
It has better curing properties and workability than epoxy resins and unsaturated polyester resins, so it can be used as a helmet for corrosion resistance by hand lay-up molding, resin transfer molding, filament winding molding, and pressure molding methods such as suC and BMC. , used in sports equipment, etc. In addition, those diluted with (meth)acrylic acid esters can be used as printing inks and as ultraviolet and electron beam curing resins.
Used in the paint field.
従来、エポキシアクリレート樹脂は耐食性、機械的特性
、接着性に優れている反面、貯蔵安定性が悪いという欠
点を有していた。一般にエポキシアクリレート樹脂は、
特公昭４５−４００６９号に示される方法で、空気又は
酸素の存在下でエポキシ樹脂と（メタ）アクリル酸を反
応させることにより得られる。 しかし、このエポキ
シアクリレート樹脂は室温で４〜６ケ月を経過すると粘
度の上昇、ゲル化時間の短縮等が著しくなり使用できな
くなる。この貯蔵安定性を延長させる目的で重合禁止剤
を添加する方法がある。しかし、この方法では貯蔵安定
性は改良されるものの、触媒を添加したときのゲル化時
間が長くなり、作業性が低下するばかりでなく、低温時
の硬化性を著しく悪化させる。また、コバルト塩等の促
進剤を添加した樹脂は、無添加のものに比較して一層、
貯蔵安定性が悪くなる。コバルト塩は通常、成形直前に
添加されるが、特にガラスフレークコンパウンド等、あ
らかじめ混合したものを使用する場合は貯蔵安定性が問
題となっていた。Conventionally, epoxy acrylate resins have excellent corrosion resistance, mechanical properties, and adhesive properties, but have had the disadvantage of poor storage stability. Generally, epoxy acrylate resin is
It can be obtained by reacting an epoxy resin with (meth)acrylic acid in the presence of air or oxygen according to the method disclosed in Japanese Patent Publication No. 45-40069. However, when this epoxy acrylate resin is left at room temperature for 4 to 6 months, the viscosity increases and the gelation time becomes noticeably shortened, making it unusable. There is a method of adding a polymerization inhibitor for the purpose of extending this storage stability. However, although this method improves storage stability, it prolongs gelation time when a catalyst is added, which not only reduces workability but also significantly deteriorates curability at low temperatures. In addition, resins to which accelerators such as cobalt salts have been added are even more effective than those without additives.
Storage stability deteriorates. Cobalt salts are usually added just before molding, but storage stability has been a problem, especially when premixed products such as glass flake compounds are used.
これらの問題点を解決するために特開昭６０−９４４１
５、特開昭６０−１６１４１４では、マレイン酸モノア
ルキルエステルをエポキシアクリレート樹脂に添加する
ことにより貯蔵安定性を改良しているが、常法により合
成した樹脂にそれらを添加してもその貯蔵安定化効果は
小さい。また、マレイン酸モノアルキルエステルが硬化
に関与せずにエポキシアクリレート樹脂硬化物に残存す
るため本来の特徴である耐食性能が低下し、熱水に浸漬
するとブリスターの発生や剥離の原因となる。In order to solve these problems, Japanese Patent Application Laid-Open No. 60-9441
5. In JP-A No. 60-161414, storage stability is improved by adding maleic acid monoalkyl ester to epoxy acrylate resin, but even if they are added to resin synthesized by a conventional method, the storage stability is not improved. effect is small. In addition, since the maleic acid monoalkyl ester remains in the cured epoxy acrylate resin without participating in curing, the original characteristic of corrosion resistance deteriorates, and when immersed in hot water, it causes blistering and peeling.
また、エポキシアクリレート樹脂は、製造後、硬化時間
が短くなる傾向にあるため作業に支障をきたす場合があ
る。Furthermore, since epoxy acrylate resins tend to take a short curing time after being manufactured, this may hinder work.
そこで鋭意検討した結果、コバルト塩等の促進剤が存在
しても又はしなくても良好な貯蔵安定性を有し、耐食性
、機械的特性は従来と変わらず、しかも低温時の硬化性
が著しく良好なエポキシアクリレート樹脂を見出し、本
発明を完成した。As a result of extensive research, we found that it has good storage stability with or without accelerators such as cobalt salts, has the same corrosion resistance and mechanical properties as conventional products, and has remarkable hardening properties at low temperatures. A good epoxy acrylate resin was discovered and the present invention was completed.
本発明は、１分子中に少なくとも２個のエポキシ基を有
するエポキシ化合物と（メタ）アクリル酸（Ｂ）とを不
活性ガス気流中で反応させて得られるエポキシアクリレ
ート （１）を液状の重合性ビニル単量体（ｎ）に溶解
してなるエポキシアクリレート樹脂（１１１１）に、１
分子中に少なくとも１個の重合性ビニル基を有するマレ
イン酸モノエステル（ＩＶ）を添加してなる、貯蔵性が
良好で低温硬化性に優れたエポキシアクリレート樹脂組
成物及びさらにコバルト塩（Ｖ）を添加してなるエポキ
シアクリレート樹脂組成物である。The present invention provides liquid polymerizable epoxy acrylate (1) obtained by reacting an epoxy compound having at least two epoxy groups in one molecule with (meth)acrylic acid (B) in an inert gas stream. In epoxy acrylate resin (1111) dissolved in vinyl monomer (n), 1
An epoxy acrylate resin composition with good storage stability and excellent low temperature curability, which is prepared by adding maleic acid monoester (IV) having at least one polymerizable vinyl group in the molecule, and further comprising a cobalt salt (V). It is an epoxy acrylate resin composition formed by adding.
本発明で用いられるエポキシアクリレート（Ｉ）は、エ
ポキシ樹脂と（メタ）アクリル酸を不活性ガス中でエス
テル化触媒と重合禁止剤の存在下に反応させることによ
り得られる。反応温度は通常、１００〜１８０℃である
。 エポキシ樹脂成分としては例えば、エピクロルヒド
リン又はメチルエピクロルヒドリンとビスフェノールＡ
、ビスフェノールＦ又はブロム化ビスフェノールＡとの
反応により合成されるグリシジルエーテル；フェノール
ノボラック、ブロム化ノボラックで代表される多核フェ
ノール樹脂とエピクロルヒドリン又はメチルエピクロル
ヒドリンとの反応により得られるポリグリシジルエーテ
ル；ビスフェノールＡ又はビスフェノールＦのエチレン
オキサイド又はプロピレンオキサイド付加グリコール又
は水添ビスフェノールＡとエピクロルヒドリン又はメチ
ルエピクロルヒドリンとの反応により得られるグリシジ
ルエーテル；等であり、これ等は単独または併用して使
用することができる。Epoxy acrylate (I) used in the present invention is obtained by reacting an epoxy resin and (meth)acrylic acid in an inert gas in the presence of an esterification catalyst and a polymerization inhibitor. The reaction temperature is usually 100 to 180°C. Examples of epoxy resin components include epichlorohydrin or methylepichlorohydrin and bisphenol A.
, glycidyl ether synthesized by reaction with bisphenol F or brominated bisphenol A; polyglycidyl ether obtained by reaction of polynuclear phenol resin represented by phenol novolak or brominated novolak with epichlorohydrin or methylepichlorohydrin; bisphenol A or bisphenol Glycidyl ether obtained by reacting F with ethylene oxide or propylene oxide-adducted glycol or hydrogenated bisphenol A with epichlorohydrin or methylepichlorohydrin; etc., and these can be used alone or in combination.
本発明で使用される不活性ガスとしては、窒素ヘリウム
、アルゴン、二酸化炭素等があげられる。これらは単独
または併用して使用することができる。これらの中では
入手が容易な点で窒素ガスが好ましい。Examples of the inert gas used in the present invention include nitrogen helium, argon, carbon dioxide, and the like. These can be used alone or in combination. Among these, nitrogen gas is preferred because it is easily available.
エステル化触媒としては、トリエチルアミン、ピリジン
誘導体、イミダゾール誘導体等の三級窒素を含有する化
合物；トリメチルホスフィン、トリフェニルホスフィン
、等のリン化合物；又はテトラメチルアンモニウムクロ
ライド、トリエチルアミン等のアミン塩；等が用いられ
る。 添加量は、０．０００００１〜２０重量％、好ま
しくは０．００１〜１重量％である。As the esterification catalyst, compounds containing tertiary nitrogen such as triethylamine, pyridine derivatives and imidazole derivatives; phosphorus compounds such as trimethylphosphine and triphenylphosphine; or amine salts such as tetramethylammonium chloride and triethylamine; etc. are used. It will be done. The amount added is 0.000001 to 20% by weight, preferably 0.001 to 1% by weight.
重合禁止剤としては、ハイドロキノン、ターシャリ−ブ
チルハイドロキノン、等のそれ自体公知の重合禁止剤が
用いられる。使用量は、０．０００００１〜０．１重量
部の範囲から選択される。As the polymerization inhibitor, a known polymerization inhibitor such as hydroquinone, tertiary-butylhydroquinone, etc. is used. The amount used is selected from the range of 0.000001 to 0.1 parts by weight.
このようにして得られたエポキシアクリレート（Ｉ）を
重合性ビニル単量体（ＩＩ）に溶解してエポキシアクリ
レート樹脂とし、１分子中に少なくとも１個の重合性ビ
ニルを含有するマレイン酸モノエステル（ＩＶ）を添加
することにより、硬化性に優れ、貯蔵安定性に優れたエ
ポキシアクリレート樹脂が得られる。The epoxy acrylate (I) thus obtained is dissolved in the polymerizable vinyl monomer (II) to obtain an epoxy acrylate resin, and a maleic acid monoester containing at least one polymerizable vinyl in one molecule ( By adding IV), an epoxy acrylate resin with excellent curability and storage stability can be obtained.
重合性ビニル単量体（ＩＩ）としては、スチレン、クロ
ロスチレン、ジビニルペンゼン、又は（メタ）アクリル
酸メチル等の（メタ）アクリル酸エステル類、エチレン
グリコールジ（メタ）アクリレート等の多官能（メタ）
アクリル酸エステル類等が用いられる。Examples of the polymerizable vinyl monomer (II) include styrene, chlorostyrene, divinylpenzene, (meth)acrylic acid esters such as methyl (meth)acrylate, and polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate. Meta)
Acrylic acid esters and the like are used.
重合性ビニル基を含有するマレイン酸モノエステル（Ｉ
Ｖ）は、重合性ビニル基を持つ２−ヒドロキシエチル（
メタ）アクリル酸エステル等の重合性ビニル基とアルコ
ール性水酸基を有する化合物と、無水マレイン酸の反応
により常法により得られる。添加量は、通常、０．１〜
５重量部の範囲である。Maleic acid monoester (I) containing a polymerizable vinyl group
V) is 2-hydroxyethyl (
It can be obtained by a conventional method by reacting a compound having a polymerizable vinyl group and an alcoholic hydroxyl group, such as meth)acrylic acid ester, with maleic anhydride. The amount added is usually 0.1~
The range is 5 parts by weight.
このようにして得られたエポキシアクリレート樹脂は、
繊維強化剤としてガラス繊維、炭素繊維、アラミド繊維
、等に樹脂を含浸させ、従来の工ホキシアクリレート樹
脂と同様、有機過酸化物あるいは有機過酸化物と金属塩
を添加することにより常温または加熱することにより硬
化することができる。The epoxy acrylate resin obtained in this way is
Glass fibers, carbon fibers, aramid fibers, etc. are impregnated with resin as a fiber reinforcing agent, and organic peroxide or organic peroxide and metal salts are added in the same way as conventional engineered oxyacrylate resins, which can be used at room temperature or heated. It can be cured by doing this.
また必要に応じて、炭酸カルシウム、水酸化アルミニウ
ム、ガラスフレーク、ガラスバブルス等の充填剤を添加
することができる。Further, fillers such as calcium carbonate, aluminum hydroxide, glass flakes, and glass bubbles can be added as necessary.
また、このようにして得られたエポキシアクリレート樹
脂（ＩＩＩ）は、従来、貯蔵性が悪いため添加すること
ができなかったコバルト塩（ＩＶ）を添加することがで
きる。コバルト塩としては例えばナフテン酸コバルト、
オクテン酸コバルト等の有機酸塩があげられる。添加量
としては０．０１〜２重蛍部の範囲で使用される。Moreover, the epoxy acrylate resin (III) thus obtained can contain cobalt salt (IV), which could not be added conventionally due to poor storage stability. Cobalt salts include cobalt naphthenate,
Examples include organic acid salts such as cobalt octenoate. The amount added is in the range of 0.01 to 2 double fluorescent parts.
以下に実施例をあげて説明するが、本発明はこの実施例
により制限をうけるものではない。Examples will be described below, but the present invention is not limited by these examples.
実施例１
撹拌機、温度計、還流冷却器、ガス導入管を備えた容器
にエポキシ樹脂（油化シェル■製エピコート８２８）
１０００ｇ、メタクリル酸４６０ｇ 、ハイドロキノン
０．３ｇを仕込み、触媒としてイミダゾール２．９ｇを
入れ、窒素ガスを導入しながら、１５０℃で１時間反応
させ、酸価５の粘稠樹脂（ａ）を得た。Example 1 Epoxy resin (Epicoat 828 manufactured by Yuka Shell ■) was placed in a container equipped with a stirrer, thermometer, reflux condenser, and gas introduction pipe.
1,000 g of methacrylic acid, 460 g of methacrylic acid, and 0.3 g of hydroquinone were charged, and 2.9 g of imidazole was added as a catalyst, and the reaction was carried out at 150° C. for 1 hour while introducing nitrogen gas to obtain a viscous resin (a) with an acid value of 5. .
また、２−ヒドロキシエチルメタクリレ−） １３０ｇ
と、無水マレイン酸９８ｇとを１００℃で２時間反応さ
せた粘稠液（ｂ）を得た。Also, 130 g of 2-hydroxyethyl methacrylate
and 98 g of maleic anhydride were reacted at 100° C. for 2 hours to obtain a viscous liquid (b).
（ａ） ６００ｇにスチレン４００ｇ 、ら）を５ｇ添
加し、エポキシアクリレート樹脂（実施例１）を得た。(a) 400 g of styrene (5 g) was added to 600 g to obtain an epoxy acrylate resin (Example 1).
実施例２
撹拌機、温度計、還流冷却器、ガス導入管を備えた容器
にエポキシ樹脂（油化シェル側製エピコート８２８）
３４２ｇ 、エポキシ樹脂（油化シェル側製エピコート
１００１） １１４９ｇ、メタクリル酸３６６ｇ 、ハ
イドロキノン０．４ｇを仕込み、触媒としてトリメチル
アミン塩酸塩３．７ｇを入れ、窒素ガスを導入しながら
、１５０℃で１時間反応させ、酸価５の樹脂（Ｃ）を得
た。 （Ｃ） ６００ｇにスチレン４００ｇ 、 （ｂ
）５ｇを添加し、エポキシアクリレート樹脂（実施例２
）を得た。Example 2 Epoxy resin (Epicoat 828 manufactured by Yuka Shell) was placed in a container equipped with a stirrer, thermometer, reflux condenser, and gas introduction pipe.
342 g, 1149 g of epoxy resin (Epicoat 1001 manufactured by Yuka Shell), 366 g of methacrylic acid, and 0.4 g of hydroquinone were added, and 3.7 g of trimethylamine hydrochloride was added as a catalyst, and reacted at 150°C for 1 hour while introducing nitrogen gas. A resin (C) having an acid value of 5 was obtained. (C) 600g and 400g of styrene, (b
) 5g of epoxy acrylate resin (Example 2
) was obtained.
比較例１
撹拌機、温度計、還流冷却器、ガス導入管を備えた容器
にエポキシ樹脂（日本チバガイギーＱ１製アラルダイト
２６０） １０００ｇ、メタクリル酸４６０ｇ 。Comparative Example 1 In a container equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube, 1000 g of epoxy resin (Araldite 260 manufactured by Ciba Geigy Q1 Japan) and 460 g of methacrylic acid were placed.
スチレン６２６ｇ、ハイドロキノン０．３ｇ、イミダゾ
ール２，９ｇ、６％ナフテン酸銅０．５ｇを添加し、乾
繰空気を吹き込みながら、１２０℃で２．５時間反応さ
せ、酸価１５のエポキシアクリレート樹脂を得た。Add 626 g of styrene, 0.3 g of hydroquinone, 2.9 g of imidazole, and 0.5 g of 6% copper naphthenate, and react at 120°C for 2.5 hours while blowing dry air to form an epoxy acrylate resin with an acid value of 15. Obtained.
これにスチレンを添加してＮＶＭ （不揮発分）６０％
とし、エポキシアクリレート樹脂（比較例１）とした。Add styrene to this to make NVM (non-volatile content) 60%
This was used as an epoxy acrylate resin (Comparative Example 1).
比較例２
脱水したエタノール２００ｇ、無水マレイン酸９８ｇを
エタノールの沸点で２時間反応させた後、エタノールを
減圧で除去し、粘稠液（ｅ）を得た。比較例１で得たエ
ポキシアクリレート樹脂１０００ｇに（ｅ）を５ｇ添加
してエポキシアクリレート樹脂（比較例２）とした。Comparative Example 2 After reacting 200 g of dehydrated ethanol and 98 g of maleic anhydride at the boiling point of ethanol for 2 hours, the ethanol was removed under reduced pressure to obtain a viscous liquid (e). 5 g of (e) was added to 1000 g of the epoxy acrylate resin obtained in Comparative Example 1 to prepare an epoxy acrylate resin (Comparative Example 2).
樹脂を直径１８ｍｍのパイレックス性試験管に底から樹
脂を入れ、２５℃、４０℃の恒温機中に保存して、ゲル
化までの時間を測定した。その結果を第１表に示す。The resin was put into a Pyrex test tube with a diameter of 18 mm from the bottom, and the resin was stored in a thermostat at 25° C. and 40° C., and the time until gelation was measured. The results are shown in Table 1.
また、それぞれの樹脂に６％ナフテン酸コバルト０、５
ｐＨＲ添加したものについても同様な方法で４０℃にお
ける貯蔵安定性を調べた。その結果を第２表に示す。In addition, each resin contains 6% cobalt naphthenate 0, 5
The storage stability at 40°C was also examined in the same manner for those to which PHR was added. The results are shown in Table 2.
実施例１．２、比較例１〜２の液状樹脂に５５％メチル
エチルケトンパーオキサイド１．０ＰＨＲ、６％ナフテ
ン酸コバルト０．５ＰｌｉＲを添加し、片面サンドブラ
スト処理した鉄板にそれらを塗布した。２４時間室温で
硬化させ、熱水に樹脂塗布面を２００時間浸漬した。２
００時間浸漬後の塗膜の表面状態を観察した。結果を第
１表に併記する。1.0 PHR of 55% methyl ethyl ketone peroxide and 0.5 PliR of 6% cobalt naphthenate were added to the liquid resins of Example 1.2 and Comparative Examples 1 and 2, and the mixture was applied to an iron plate that had been sandblasted on one side. It was cured at room temperature for 24 hours, and the resin-coated surface was immersed in hot water for 200 hours. 2
The surface condition of the coating film after immersion for 00 hours was observed. The results are also listed in Table 1.
実施例１．２、比較例１〜２の液状樹脂に５５％メチル
エチルケトンパーオキシド１，０ＰＩＩＲ、６％ナフテ
ン酸コバルト０．１．０．３．０．５ＰＨＲを添加し、
ＪＩＳ Ｋ ６９０１に準拠してゲル化時間を求めた。55% methyl ethyl ketone peroxide 1.0 PIIR and 6% cobalt naphthenate 0.1.0.3.0.5 PHR were added to the liquid resins of Example 1.2 and Comparative Examples 1 and 2,
The gelation time was determined according to JIS K 6901.
測定温度は、１５℃と２５℃であった。測定結果を第３
表に示す。The measurement temperatures were 15°C and 25°C. The measurement results are shown in the third
Shown in the table.
第１表 貯蔵安定性試験結果と耐熱水性試験結果第
３表
ゲル化時間の測定結果
〔効果〕
本発明のエポキシアクリレート樹脂組成物は、従来のエ
ポキシアクリレート樹脂よりも貯蔵安定性に優れ、しか
も耐食性が従来のエポキシアクリレート樹脂と同等であ
り、低温領域でも硬化性が良く、経時による硬化時間の
ドリフトもないという利点がある。Table 1 Storage stability test results and hot water resistance test results Table 3 Measurement results of gelation time [Effects] The epoxy acrylate resin composition of the present invention has superior storage stability and corrosion resistance than conventional epoxy acrylate resins. It has the advantage that it is equivalent to conventional epoxy acrylate resin, has good curability even in low temperature range, and has no curing time drift over time.
Claims (1)
ポキシ化合物と（メタ）アクリル酸（Ｂ）とを不活性ガ
ス気流中で反応させて得られるエポキシアクリレート（
I ）を液状の重合性ビニル単量体（II）に溶解してな
るエポキシアクリレート樹脂（III）に、１分子中に少
なくとも１個の重合性ビニル基を有するマレイン酸モノ
エステル（IV）を添加してなる、貯蔵性が良好で低温硬
化性に優れたエポキシアクリレート樹脂組成物 ２、さらにコバルト塩（Ｖ）を添加してなる請求項第１
項記載の樹脂組成物 ３、エポキシ化合物が、エピクロルヒドリン又はメチル
エピクロルヒドリンとビスフェノールＡ、ビスフェノー
ルＦ又はブロム化ビスフェノールＡとの反応により合成
されるグリシジルエーテル；フェノールノボラック、ブ
ロム化ノボラックで代表される多核フェノール樹脂とエ
ピクロルヒドリン又はメチルエピクロルヒドリンとの反
応により得られるポリグリシジルエーテル；及びビスフ
ェノールＡ又はビスフェノールＦのエチレンオキサイド
又はプロピレンオキサイド付加グリコール又は水添ビス
フェノールＡとエピクロルヒドリン又はメチルエピクロ
ルヒドリンとの反応により得られるグリシジルエーテル
からなる群から選ばれる少なくとも一種のエポキシ樹脂
である請求項第１項記載の樹脂組成物 ４、不活性ガスが、窒素、ヘリウム、アルゴン及び二酸
化炭素からなる群から選ばれる少なくとも一種のガスで
ある請求項第１項記載の樹脂組成物 ５、エポキシ化合物と（メタ）アクリル酸（Ｂ）との反
応をエステル化触媒の存在下で行う請求項第１項記載の
樹脂組成物 ６、エステル化触媒が、トリエチルアミン、ピリジン誘
導体、イミダゾール誘導体等の三級窒素を含有する化合
物；トリメチルホスフィン、トリフェニルホスフィン等
のリン化合物；及びテトラメチルアンモニウムクロライ
ド、トリエチルアミン等のアミン塩からなる群から選ば
れる少なくとも一種の化合物である請求項第５項記載の
樹脂組成物 ７、エポキシ化合物と（メタ）アクリル酸（Ｂ）との反
応を重合禁止剤の存在下で行う請求項第１項記載の樹脂
組成物 ８、重合禁止剤が、ハイドロキノン及びターシャリーブ
チルハイドロキノンからなる群から選ばれる少なくとも
一種の化合物である請求項第７項記載の樹脂組成物 ９、重合性ビニル単量体（II）が、スチレン、クロロス
チレン、ジビニルペンゼン、（メタ）アクリル酸メチル
等の（メタ）アクリル酸エステル類、及びエチレングリ
コールジ（メタ）アクリレート等の多官能（メタ）アク
リル酸エステル類からなる群から選ばれる少なくとも一
種の化合物である請求項第１項記載の樹脂組成物 １０、重合性ビニル基を含有するマレイン酸モノエステ
ル（IV）が、重合性ビニル基を持つ２−ヒドロキシエチ
ル（メタ）アクリル酸エステル等の重合性ビニル基とア
ルコール性水酸基を有する化合物と、無水マレイン酸の
反応により得られるものである請求項第１項記載の樹脂
組成物 １１、さらに繊維強化剤を含有してなる請求項第１項記
載の樹脂組成物 １２、さらに有機過酸化物を含有してなる請求項第１項
記載の樹脂組成物 １３、さらに有機過酸化物及び金属塩を含有してなる請
求項第１項記載の樹脂組成物 １４、さらに充填剤を含有してなる請求項第１項記載の
樹脂組成物[Claims] 1. An epoxy acrylate (obtained by reacting an epoxy compound having at least two epoxy groups in one molecule with (meth)acrylic acid (B) in an inert gas stream)
A maleic acid monoester (IV) having at least one polymerizable vinyl group in one molecule is added to an epoxy acrylate resin (III) obtained by dissolving I) in a liquid polymerizable vinyl monomer (II). Claim 1: Epoxy acrylate resin composition 2 having good storage stability and excellent low temperature curability, further comprising a cobalt salt (V).
Resin composition 3 described in Section 3, a glycidyl ether in which the epoxy compound is synthesized by the reaction of epichlorohydrin or methylepichlorohydrin with bisphenol A, bisphenol F or brominated bisphenol A; polynuclear phenol resin represented by phenol novolac and brominated novolac A group consisting of polyglycidyl ethers obtained by the reaction of bisphenol A or bisphenol F with ethylene oxide or propylene oxide, or glycidyl ethers obtained by the reaction of hydrogenated bisphenol A with epichlorohydrin or methylepichlorohydrin. The resin composition 4 according to claim 1, wherein the inert gas is at least one type of epoxy resin selected from the group consisting of nitrogen, helium, argon, and carbon dioxide. Resin composition 5 according to Item 1, wherein the reaction between the epoxy compound and (meth)acrylic acid (B) is carried out in the presence of an esterification catalyst.Resin composition 6 according to Item 1, wherein the esterification catalyst is triethylamine. , pyridine derivatives, imidazole derivatives, and other tertiary nitrogen-containing compounds; trimethylphosphine, triphenylphosphine, and other phosphorus compounds; and tetramethylammonium chloride, triethylamine, and other amine salts. Resin composition 7 according to claim 5, resin composition 8 according to claim 1, wherein the reaction between the epoxy compound and (meth)acrylic acid (B) is carried out in the presence of a polymerization inhibitor. The resin composition 9 according to claim 7, wherein is at least one compound selected from the group consisting of hydroquinone and tert-butylhydroquinone, and the polymerizable vinyl monomer (II) is styrene, chlorostyrene, divinyl pen. The claim is at least one compound selected from the group consisting of (meth)acrylic esters such as zene, methyl (meth)acrylate, and polyfunctional (meth)acrylic esters such as ethylene glycol di(meth)acrylate. In the resin composition 10 described in item 1, the maleic acid monoester (IV) containing a polymerizable vinyl group is combined with a polymerizable vinyl group such as 2-hydroxyethyl (meth)acrylate having a polymerizable vinyl group. The resin composition 11 according to claim 1, which is obtained by the reaction of a compound having an alcoholic hydroxyl group and maleic anhydride, and the resin composition according to claim 1, which further contains a fiber reinforcing agent. 12. The resin composition 13 of claim 1 further comprising an organic peroxide; the resin composition 14 of claim 1 further comprising an organic peroxide and a metal salt; The resin composition according to claim 1, which contains a filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261348A JP2740527B2 (en) | 1988-10-19 | 1988-10-19 | Epoxy acrylate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261348A JP2740527B2 (en) | 1988-10-19 | 1988-10-19 | Epoxy acrylate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02110116A true JPH02110116A (en) | 1990-04-23 |
| JP2740527B2 JP2740527B2 (en) | 1998-04-15 |
Family
ID=17360590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63261348A Expired - Lifetime JP2740527B2 (en) | 1988-10-19 | 1988-10-19 | Epoxy acrylate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2740527B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068134A1 (en) * | 2004-12-24 | 2006-06-29 | Dainippon Ink And Chemicals, Inc. | Method for producing branched polyether resin composition and method for producing acid-pendant branched polyether resin composition |
| JP2012528223A (en) * | 2009-05-27 | 2012-11-12 | サントル ナシオナル ドゥ ラ ルシェルシェサイアンティフィク（セエヌエールエス） | Novel production method of thermosetting epoxy resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6094415A (en) * | 1983-10-28 | 1985-05-27 | Dainippon Ink & Chem Inc | Unsaturated epoxy resin composition of improved storage stability |
| JPS60120715A (en) * | 1983-12-05 | 1985-06-28 | Mitsubishi Gas Chem Co Inc | Production of epoxyacrylate resin |
| JPS60161414A (en) * | 1984-01-31 | 1985-08-23 | Dainippon Ink & Chem Inc | Preparation of unsaturated epoxy resin composition having improved shelf stability |
-
1988
- 1988-10-19 JP JP63261348A patent/JP2740527B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6094415A (en) * | 1983-10-28 | 1985-05-27 | Dainippon Ink & Chem Inc | Unsaturated epoxy resin composition of improved storage stability |
| JPS60120715A (en) * | 1983-12-05 | 1985-06-28 | Mitsubishi Gas Chem Co Inc | Production of epoxyacrylate resin |
| JPS60161414A (en) * | 1984-01-31 | 1985-08-23 | Dainippon Ink & Chem Inc | Preparation of unsaturated epoxy resin composition having improved shelf stability |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068134A1 (en) * | 2004-12-24 | 2006-06-29 | Dainippon Ink And Chemicals, Inc. | Method for producing branched polyether resin composition and method for producing acid-pendant branched polyether resin composition |
| US7666955B2 (en) | 2004-12-24 | 2010-02-23 | Dainippon Ink And Chemicals, Inc. | Methods for producing branched-polyether resin composition and acid pendant branched-polyether resin composition |
| JP2012528223A (en) * | 2009-05-27 | 2012-11-12 | サントル ナシオナル ドゥ ラ ルシェルシェサイアンティフィク（セエヌエールエス） | Novel production method of thermosetting epoxy resin |
| JP2015078383A (en) * | 2009-05-27 | 2015-04-23 | サントル ナシオナル ドゥ ラ ルシェルシェサイアンティフィク（セエヌエールエス） | New production method of thermosetting epoxide resin |
| US9416218B2 (en) | 2009-05-27 | 2016-08-16 | Centre National De La Recherche Scientifique (C.N.R.S.) | Methods for producing thermosetting epoxy resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2740527B2 (en) | 1998-04-15 |
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