JPS63118321A - Curing of epoxy resin - Google Patents
Curing of epoxy resinInfo
- Publication number
- JPS63118321A JPS63118321A JP26175687A JP26175687A JPS63118321A JP S63118321 A JPS63118321 A JP S63118321A JP 26175687 A JP26175687 A JP 26175687A JP 26175687 A JP26175687 A JP 26175687A JP S63118321 A JPS63118321 A JP S63118321A
- Authority
- JP
- Japan
- Prior art keywords
- component
- compound
- epoxy resin
- curing
- epoxy 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 15
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 14
- 239000004382 Amylase Substances 0.000 claims abstract description 6
- 102000013142 Amylases Human genes 0.000 claims abstract description 6
- 108010065511 Amylases Proteins 0.000 claims abstract description 6
- 235000019418 amylase Nutrition 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract 7
- 229920000642 polymer Polymers 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- -1 allols Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 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 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- WEZHJSFDIFQAFL-UHFFFAOYSA-N 2-[2-(methylamino)propan-2-yl]phenol Chemical compound CNC(C)(C)C1=CC=CC=C1O WEZHJSFDIFQAFL-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- BDLVNNJRAIUIMO-UHFFFAOYSA-N amino(hydroxy)silicon Chemical compound N[Si]O BDLVNNJRAIUIMO-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane 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
- 239000012254 powdered material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- XNYADZUHUHIGRZ-UHFFFAOYSA-N propane-1,1,3-triamine Chemical compound NCCC(N)N XNYADZUHUHIGRZ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明はエポキシ基と反応性を有する化合物をサイク
ロデキストリン包接化合物とすることにより、常温で化
学的に安定化したエポキシ樹脂用硬化剤を使用したエポ
キシ樹脂の硬化方法に関するものである。[Detailed Description of the Invention] <Industrial Application Field> This invention provides a curing agent for epoxy resin that is chemically stabilized at room temperature by using a cyclodextrin clathrate compound as a compound that is reactive with epoxy groups. This relates to a method of curing the epoxy resin used.
く従来の技術と発明が解決しようとする問題点〉エポキ
シ樹脂は常温で液状または熱ｗ５性の状態のものを、エ
ポキシ基と反応性を有する化合物（エポキシ樹脂用硬化
剤）と反応させることにより熱硬化性の固体に変化させ
ることができる。従ってエポキシ樹脂を硬化させて使用
するときは、硬化前のエポキシ樹脂と硬化剤を別々に保
存しておき、使用時に両名を混合する方法がとられてい
る。Prior Art and Problems to be Solved by the Invention> Epoxy resins can be made by reacting liquid or thermally stable epoxy resins at room temperature with compounds that are reactive with epoxy groups (curing agents for epoxy resins). It can be converted into a thermosetting solid. Therefore, when an epoxy resin is cured and used, the epoxy resin before curing and the curing agent are stored separately, and the two are mixed together before use.
エポキシ樹脂用硬化剤としては従来から第１アミン、第
２アミン、アミン錯化合物、有機酸及びその無水物、ア
ルロール類、フェノール類等が用いられてきたが、これ
らは化学的に不安定であったり、揮発性があったり、人
体にきわめて右Ｊ）である物が多く、またエポキシ樹脂
と均一にＪシ合分散できないものが多いので取扱や作業
性等に難点があった。Traditionally, primary amines, secondary amines, amine complex compounds, organic acids and their anhydrides, allols, phenols, etc. have been used as curing agents for epoxy resins, but these are chemically unstable. Many of them are volatile, volatile, or extremely harmful to the human body, and many of them cannot be mixed and dispersed uniformly with epoxy resins, making them difficult to handle and work with.
そこで、この発明はエポキシ基と反応性を有する化合物
をサイクロデキストリン包接化合物とした。常温で化学
的に安定なエポキシ樹脂用硬化剤をエポキシ樹脂へ混合
分散した後９０℃以上に加熱することにより前記サイク
ロデキストリン包接化合物を分解してエポキシ樹脂の硬
化反応を開始させるようにしたエポキシ樹脂の硬化方法
（第１発明）、及び前記エポキシ樹脂用硬化剤に更に微
量のアミラーゼを添加したエポキシ樹脂用硬化剤を３０
℃以上に加熱することにより前記アミラーゼによりサイ
クロデキストリンを分解してエポキシ樹脂の硬化反応を
開始させるようにしたエポキシ樹脂の硬化方法（第２発
明）を提供することを目的として開発したものである。Therefore, in this invention, a cyclodextrin clathrate compound is used as a compound having reactivity with an epoxy group. An epoxy resin in which a curing agent for epoxy resin that is chemically stable at room temperature is mixed and dispersed in an epoxy resin and then heated to 90°C or higher to decompose the cyclodextrin inclusion compound and initiate a curing reaction of the epoxy resin. A method for curing resin (first invention), and a curing agent for epoxy resin in which a trace amount of amylase is further added to the curing agent for epoxy resin.
This invention was developed for the purpose of providing an epoxy resin curing method (second invention) in which cyclodextrin is decomposed by the amylase and the epoxy resin curing reaction is started by heating to a temperature above .degree.
この発明に用いられるエポキシ樹脂と反応性を有する物
質の例をあげると次のとおりである。Examples of substances that are reactive with the epoxy resin used in the present invention are as follows.
［１］有機ポリアミン
（イ）エチレンジアミン（ＥＤＡ）
Ｈ，Ｎ −ＣＨ２−ＣＨｚ −ＮＨｚ
（ロ）ジエチレントリアミン（ＤＴＡ）Ｈ２Ｎ ＣＨ
ｚ ＣＨ２ＮＨＣＨｚＣＨ２ＮＨ２（ハ）ジエチルア
ミノプロビルアミン（ＤＥＰ（ニ）Ｎ−アミノエチルピ
ペラジン（Ｎ−ＡＥ［２］内在アミンアダクト、分離ア
ダクト（ロ）アミネチレノキシドアダクト
ＣＨ，−ＣＨスーＮ ＲＮ ＣＨ２ＣＨ２（
ハ）シアノエチル化合物
［３］ポリアミド樹脂
［４］芳香族アミン
（ロ）４４′メチレンジアニリンジフエニルメタン（Ｄ
ＤＭ）
（ハ）ジアミノジフェニルスルフォン（ＤＤ［５］アミ
ン予予備金物
（イ）ジシアンジアミド（Ｄｉｃｙ）
）、１．Ｎ −Ｃ−Ｎ）−１−ＣＮ
ＮＨ
（ロ）複素環アミン
（ハ）キシリレンジアミン
（ニ）ピベレジン
（ホ）ピリジン
（へ）イミダゾール
（ト）アミノエチルピペレジン
（チ）メンタンジアミン
（す）トリメチルアミン
ＨＩ
ＣＨ３−Ｎ −ＣＨｉ
（ヌ）ベンジルジメチルアミン（ＢＤＭＡ）（ル）αメ
チルベンジルジメチルアミン（ヲ）ジメチルアミノメチ
ルフェノール（ＤＭＰ（ワ）トリメチルアミノメチルフ
ェノール（ＤＭＰ−３０）
ＨＩＣＨｉ
［７］アミン塩アミン錯化合物
（イ）トリジメチルアミノメチルフェノール（ＤＭＰ−
３０・トリ２エチルヘキソエート）（ロ）ＢＦ３・モノ
エチルアミン（ＢＦ３ＭＥＡ）
（ハ）ＢＦ３・アミン錯化合物
［８］有機酸、酸無水物
（イ）無水フタル酸（ＰＡ）
（ロ）無水へキサヒドロフタル酸（ＨＨＰＡ）（ハ）無
水マレイン酸（ＭＡ）
（ニ）無水ピロメリット酸（ＰＭＤＡ）（ホ）ベンゾフ
ェノンテトラカルボン酸無水物（ＢＴＤＡ）
（へ）メチルナジック酸無水物（ＭＮＡ）（ト）ドデシ
ル無水コハク酸（ＤＤＳＡ）（チ）無水クロレンディッ
ク酸（ＨＥＴ）Ｉ
（す）ジクロル無水マレイン酸（ＤＣＭＡ）［９］ ’
１．ｒ機酸無水物予備縮合物［１０コ尿素樹脂
［１１］メラミン樹脂
［１２］アニリンホルムアルデヒド樹脂［１３］多価フ
ェノール
（イ）ビスフェノールＡ
Ｈ３
（ロ）トリメチロ、−ルアリルオキシフェノール［１５
コエポキシブチル化フエノール樹脂［１６」エポキシ樹
脂エステル
［１７］ロジン変性エステル
［１８］スチレン化エポキシ樹脂エステル［１９］エポ
キシ樹脂変性アルキツド樹脂「２０］イソシアネ一ト化
合物
［２１］フラン樹脂
［２２］ポリエステル樹脂
［２３］シリコン樹脂
［２４］ポリスルフイド樹脂
Ｈ５（Ｃ２Ｈ４０ＣＨ−ＯＣ−Ｈ４’ｙＳ）ｎ Ｃｚ
ＫＳＨ−Ｃ２Ｈ＋−〇−ＣＨ，−０
［２５］エポキシ樹脂コールタール変性物［２６］特殊
硬化剤ケトイミン
この発明に用いられるサイクロデキストリン（以下ＣＤ
という）は、α、β、γのいずれも使用できるが、特に
βが適している。[1] Organic polyamine (a) Ethylenediamine (EDA) H,N -CH2-CHz -NHz (b) Diethylenetriamine (DTA) H2N CH
z CH2NHCHzCH2NH2 (c) Diethylaminoprobylamine (DEP (d) N-aminoethylpiperazine (N-AE [2] Intrinsic amine adduct, separation adduct (b) Aminethylenoxide adduct CH, -CH-N RN CH2CH2 (
c) Cyanoethyl compound [3] Polyamide resin [4] Aromatic amine (b) 44' methylene dianiline diphenylmethane (D
DM) (c) Diaminodiphenylsulfone (DD[5] amine pre-metallic material (a) dicyandiamide (Dicy)), 1. N -C-N)-1-CN NH (b) Heterocyclic amine (c) Xylylenediamine (d) Piverezine (e) Pyridine (h) Imidazole (t) Aminoethylpiperezine (th) Menthanediamine (s) Trimethylamine HI CH3-N -CHi (N) Benzyldimethylamine (BDMA) (L) α-methylbenzyldimethylamine (W) Dimethylaminomethylphenol (DMP (W) Trimethylaminomethylphenol (DMP-30) HICHi [7] Amine Salt amine complex compound (a) tridimethylaminomethylphenol (DMP-
30.tri2ethylhexoate) (b) BF3.monoethylamine (BF3MEA) (c) BF3.amine complex compound [8] Organic acid, acid anhydride (a) Phthalic anhydride (PA) (b) To anhydride Xahydrophthalic acid (HHPA) (c) Maleic anhydride (MA) (d) Pyromellitic anhydride (PMDA) (e) Benzophenonetetracarboxylic anhydride (BTDA) (f) Methylnadic anhydride (MNA) ( h) Dodecylsuccinic anhydride (DDSA) (h) Chlorendic anhydride (HET) I (l) Dichloromaleic anhydride (DCMA) [9] '
1. rMorganic acid anhydride precondensate [10 Kourea resin [11] Melamine resin [12] Aniline formaldehyde resin [13] Polyhydric phenol (a) Bisphenol A H3 (b) Trimethylo, -ruallyloxyphenol [15]
Coepoxybutylated phenolic resin [16] Epoxy resin ester [17] Rosin modified ester [18] Styrenated epoxy resin ester [19] Epoxy resin modified alkyd resin [20] Isocyanate compound [21] Furan resin [22] Polyester Resin [23] Silicone resin [24] Polysulfide resin H5 (C2H40CH-OC-H4'yS)n Cz
KSH-C2H+-〇-CH,-0 [25] Epoxy resin coal tar modified product [26] Special curing agent ketimine Cyclodextrin (hereinafter referred to as CD
), any of α, β, and γ can be used, but β is especially suitable.
この発明に係るエポキシ基と反応性を有する化合物のサ
イクロデキストリン包接化合物（エポキシ樹脂用硬化剤
）は、ＣＤの水溶液とエポキシ基と反応性を有する化合
物を混合し包接化合物とした後、通常は乾燥して粉末化
したものを用いる。The cyclodextrin clathrate compound (curing agent for epoxy resin) of a compound having reactivity with an epoxy group according to the present invention is prepared by mixing an aqueous solution of CD and a compound having reactivity with an epoxy group to form an clathrate compound. Use dried and powdered material.
この発明に係るエポキシ樹脂用硬化剤をエポキシ樹脂に
混合分散し、包接化合物からＣＤをはずしてエポキシ基
と反応性を有する化合物を再生するには９０℃以上に加
熱してやればよい。The curing agent for epoxy resin according to the present invention may be mixed and dispersed in an epoxy resin and heated to 90° C. or higher in order to remove the CD from the clathrate compound and regenerate the compound that is reactive with the epoxy group.
また、本発明に用いるＣＤはグルコースがα−１，４結
合により環化したものであるから、予めアミラーゼ（澱
粉分解酵素）を、包接化合物に添加しておけば、アミラ
ーゼが作用する温度（たとエバ４０℃）に保持すること
により、ＣＤが分解してエポキシ基と反応性を有する化
合物を遊離させることができる。Furthermore, since the CD used in the present invention is glucose cyclized through an α-1,4 bond, if amylase (starch degrading enzyme) is added to the clathrate compound in advance, the temperature at which amylase acts ( By holding the evaporator at a temperature of 40° C.), the CD can be decomposed and a compound having reactivity with an epoxy group can be liberated.
実施例１
純分２５％のジエチレントリアミンのサイクロデキスト
リンによる包接化合物１６部、３−ビスフェノールＡＡ
グリシジールエーテルジェポキサ（エピコート１００１
５ｈｅｌｌ （：ｈｅｍｉｃａｌ Ｃｏ、、ＬＬｄ。Example 1 16 parts of inclusion compound of 25% pure diethylenetriamine with cyclodextrin, 3-bisphenol AA
Glycidyl ether jepoxa (Epicote 1001
5hell (:chemical Co,, LLd.
の製品）４９部、メチルエチルケトン３０部、メチルイ
ソブチルケトン３０部、トルエン５０部を混合した塗装
液にてボンド鋼板に塗装した後１３０℃５分間加熱した
後、常温で３日間奉仕して硬化せしめた。A bonded steel plate was coated with a coating solution containing 49 parts of the product), 30 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone, and 50 parts of toluene, heated at 130°C for 5 minutes, and then left to harden at room temperature for 3 days. .
この塗装液はジエチレントリアミンのガス化によって毒
性を非常に少なくすることが可能であり、揮散を少なく
したので作業上安全である。This coating liquid can be made extremely less toxic by gasifying diethylenetriamine, and is safe for work because volatilization is reduced.
従来エポキシ樹脂は殆どエポキシ樹脂と硬化剤の二液タ
イプとなっており混合した場合直ちに硬化本能を開始す
るため使用時、経時的に粘度が上昇し作業がしにくいこ
とや使用ロス（硬化してしまい使えなくなる）が多いこ
とが問題であった。Conventional epoxy resins are mostly two-component types, consisting of epoxy resin and curing agent, and when mixed, they immediately start their curing instinct, so the viscosity increases over time during use, making it difficult to work and causing loss of use (hardening). The problem was that there were a lot of cases where it became unusable.
本発明ではこの問題が一掃されることになる。即ち加熱
処理によりＣＤの膜が破れて反応を開始することになる
ため、−液状で保管や使用ができる。The present invention eliminates this problem. That is, since the heat treatment causes the CD film to break and a reaction to begin, it can be stored and used in a liquid state.
実施例２
純分３０％の無水フタル酸のサイクロデキストリンによ
る包接化合物８０部、２−ビスフェノ−（エピコート８
３４ ５ｈｅｌｌ （：ｈｅｍｉｃａｌ Ｃｏ、、１．
ｔｄ、の製品）８０部、エピコート１００１を１０部、
二酸化ケイ素（サイロイド２４４富士デビイソン■の製
品）８部から成る注型液を電気回路用プリント板に塗布
して１３０℃３０分間加熱しついで常温により２日間放
置せしめて塗布液を硬化せしめた。Example 2 80 parts of cyclodextrin inclusion compound of 30% pure phthalic anhydride, 2-bispheno-(Epicote 8
34 5hell (:chemical Co,, 1.
td, product) 80 parts, 10 parts of Epicote 1001,
A casting solution consisting of 8 parts of silicon dioxide (a product of Thyroid 244 Fuji Davison ■) was applied to a printed circuit board for electrical circuits, heated at 130° C. for 30 minutes, and then allowed to stand at room temperature for 2 days to harden the coating solution.
この塗布液は蒸発する無水フタル酸の５１を少なくする
ことが出来たので、従来のように硬化が不均−になるこ
となく安定に硬化せしめることが可能であった。Since this coating solution was able to reduce the amount of evaporated phthalic anhydride, it was possible to stably cure the coating without causing uneven curing unlike conventional methods.
実施例３
ポリアクリル酸エステルエマルジョン（ディクナル＃１
５７１大 日本インキ■の製品）１００部、４−グリシ
ジールエーテルジエボキサイド（エボシ８１２ ５ｈｅ
ｌｌ Ｃｈｅｍｉｃａｌ Ｃｏ、、Ｌｔｄ、の製品）５
部、サイクロデキストリンにより包接化合物としたジア
ミノプロピルアミン（純分２５％）５部添加せしめ、更
にアンモニア１〜２部を添加し攪拌せしめて植毛用接着
剤とした。Example 3 Polyacrylic acid ester emulsion (Dicnal #1
571 Dai Nippon Ink■ product) 100 parts, 4-glycidyl ether dieboxide (Eboshi 812 5he
ll Chemical Co., Ltd.) 5
5 parts of diaminopropylamine (purity 25%) made into an clathrate compound with cyclodextrin were added thereto, and 1 to 2 parts of ammonia was further added and stirred to obtain an adhesive for hair transplantation.
この接着剤をウレタンフオームの６ｍｍ厚さのシートに
１５０ｇ／ｍ″塗布し、ナイロン１．ＯｄＯ，７ｍｍの
パイルを静電植毛せしめついで１０５℃で乾燥セしめ包
接化合物を分解せしめ、ついで１１０℃５分間加熱架橋
せしめて化粧用パフ製造用植毛シートとした。This adhesive was applied at 150 g/m'' to a 6 mm thick sheet of urethane foam, electrostatically flocked with a 7 mm pile of nylon 1.OdO, dried at 105°C to decompose the clathrate, and then heated to 110°C. It was heat-crosslinked for 5 minutes to obtain a flocked sheet for producing cosmetic puffs.
この接着剤は常温で安定であり、包接化合物を用いない
接着剤のよ°うに常温で３日間放置しても凝固すること
はなかった。又耐油性、耐水性を良好とするために比較
的低温で接着剤を硬化することができた。This adhesive was stable at room temperature and did not solidify even when left at room temperature for 3 days unlike adhesives that do not use clathrate compounds. Furthermore, the adhesive could be cured at a relatively low temperature to improve oil resistance and water resistance.
実施例４
ビスフェノールＡジエボキサイド
（エピコート８２８ ５ｈｅｌｌ Ｃｈｅｍｉｃａｌ
Ｃｏ、、Ｌｔｄ、の製品）１００部にサイクロデキスト
リンにより包接されたメタフェニレンジアミンを５０部
（純分３０％）チタンホワイトｌＯ部を混合した塗布液
を予め離型剤を塗布した防護ヘルメット凸型成型体に塗
布し、ついでガラス繊維織物を重ねついで更に２回塗布
液を塗布し、ついで内部離型処理した凹型防護ヘルメッ
ト成型体をかぶらせて加圧し１２０℃２時間加熱せしめ
て硬化せしめた後成型体を取り去り防護ヘルメットとし
た。Example 4 Bisphenol A dieboxide (Epicote 828 5hell Chemical
A protective helmet convex coated with a coating solution containing 100 parts of metaphenylenediamine clathrated with cyclodextrin and 10 parts of titanium white (purity 30%) was pre-applied with a release agent. The coating liquid was applied to the molded body, and then the glass fiber fabric was layered and the coating solution was applied twice more.Then, the concave protective helmet molded body, which had been internally released, was placed on top of the molded body, pressurized, and heated at 120°C for 2 hours to harden it. After removing the molded body, it was made into a protective helmet.
この塗布液はメタフェニレンジアミンの上記な殆ど無く
し毒性を消すことが出来たことにより作業環境を良好に
することが出来た。This coating liquid was able to eliminate most of the above-mentioned toxicity of meta-phenylenediamine, thereby improving the working environment.
実施例５
エピコート１００１ （Ｓｈｅｌｌ Ｃｈｅｍｉｃａｌ
Ｃｏ、、Ｌｔ、ｄ。Example 5 Epicote 1001 (Shell Chemical
Co,,Lt,d.
の製品）１００部、サイクロデキストリンにより包接化
合物とした無水クロレンデック酸く純分３０％）１４０
部、メチルエチルケトン１１０部からなる塗布液を予め
アミノシラノール（東しシリコン５Ｈ−６０２０）０．
５％水溶液に含浸し４０％絞りとし乾燥し１４０℃１０
分間加熱処理したガラス織布を両面に塗布し１００℃以
下で乾燥せしめついで３枚重ねて離型処理をした熱板に
て１６０℃１０分間加熱加圧して印刷回路用ガラス繊維
積層板とした。product) 100 parts, anhydrous chlorendic acid clathrate compounded with cyclodextrin (purity 30%) 140
A coating solution consisting of 110 parts of methyl ethyl ketone and 0.0 parts of aminosilanol (Toshi Silicone 5H-6020) was preliminarily applied.
Impregnated with 5% aqueous solution, squeezed 40% and dried at 140℃10
A glass woven fabric heated for 1 minute was coated on both sides, dried at 100° C. or lower, and three sheets were stacked and heated and pressed at 160° C. for 10 minutes using a hot plate that had been subjected to mold release treatment to obtain a glass fiber laminate for printed circuits.
この塗布液は包接化合物を使用しない場合に比べて１０
倍以上可使時間を延長することが可能であった。This coating solution is 10% higher than when no clathrate is used.
It was possible to extend the pot life by more than double.
Claims (2)
れる混合物を９０℃以上に加熱することを特徴とするエ
ポキシ樹脂の硬化方法。 （Ａ）成分：エポキシ基を有する高分子化合物。 （Ｂ）成分：エポキシ基と反応性を有する化合物のサイ
クロデキストリン包接化合物。(1) A method for curing an epoxy resin, which comprises heating a mixture obtained by mixing and dispersing component (B) in component (A) to 90° C. or higher. Component (A): a polymer compound having an epoxy group. Component (B): a cyclodextrin clathrate compound of a compound that is reactive with an epoxy group.
れる混合物を３０℃以上に加熱することを特徴とするエ
ポキシ樹脂の硬化方法。 （Ａ）成分：エポキシ基を有する高分子化合物。 （Ｂ）成分：エポキシ基と反応性を有する化合物のサイ
クロデキストリン包接化合物と微量のアミラーゼとの混
合物。(2) A method for curing an epoxy resin, which comprises heating a mixture obtained by mixing and dispersing component (B) in component (A) to 30° C. or higher. Component (A): a polymer compound having an epoxy group. Component (B): A mixture of a cyclodextrin clathrate compound of a compound reactive with an epoxy group and a trace amount of amylase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26175687A JPS63118321A (en) | 1987-10-19 | 1987-10-19 | Curing of epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26175687A JPS63118321A (en) | 1987-10-19 | 1987-10-19 | Curing of epoxy resin |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59057462A Division JPS60202115A (en) | 1984-03-27 | 1984-03-27 | Curing agent for epoxy resin, and curing of said epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63118321A true JPS63118321A (en) | 1988-05-23 |
Family
ID=17366266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26175687A Pending JPS63118321A (en) | 1987-10-19 | 1987-10-19 | Curing of epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63118321A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009114221A (en) * | 2007-11-01 | 2009-05-28 | Tokuyama Dental Corp | Curable composition |
-
1987
- 1987-10-19 JP JP26175687A patent/JPS63118321A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009114221A (en) * | 2007-11-01 | 2009-05-28 | Tokuyama Dental Corp | Curable composition |
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