JP2013170226A - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
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- JP2013170226A JP2013170226A JP2012035172A JP2012035172A JP2013170226A JP 2013170226 A JP2013170226 A JP 2013170226A JP 2012035172 A JP2012035172 A JP 2012035172A JP 2012035172 A JP2012035172 A JP 2012035172A JP 2013170226 A JP2013170226 A JP 2013170226A
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- resin composition
- meth
- curable resin
- acrylate
- hydroxyl group
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- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 150000007514 bases Chemical class 0.000 claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 20
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 20
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 9
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007877 V-601 Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、硬化性樹脂組成物に関する。本発明の硬化性樹脂組成物は、各種塗料を始め、インキ、接着剤並びにシーリング剤、ゲルなどとして、広範な用途に利用し得るものである。 The present invention relates to a curable resin composition. The curable resin composition of the present invention can be used in a wide variety of applications including various paints, inks, adhesives, sealing agents, gels, and the like.
従来、プラスチックフィルムなどの耐熱性に乏しい基材に対して使用される塗料やインキは、１００〜１４０℃程度で硬化させる必要がある。そのため、これらの塗料やインキには、水酸基とイソシアネート基の反応や、エポキシ基とアミノ基の反応などを用いた、比較的低温で硬化する樹脂組成物が使用されている。 Conventionally, paints and inks used for substrates having poor heat resistance, such as plastic films, need to be cured at about 100 to 140 ° C. Therefore, a resin composition that cures at a relatively low temperature using a reaction between a hydroxyl group and an isocyanate group, a reaction between an epoxy group and an amino group, or the like is used for these paints and inks.
これらの塗料やインキは、反応性の材料が混合された状態では、室温でも反応が徐々に進行し保存安定性が得られない。そのために、水酸基を有する樹脂やエポキシ基を有する樹脂を主剤とし、イソシアネート基を有する化合物やアミノ基を有する化合物を硬化剤として、主剤と硬化剤を塗装する際に混合して使用する２液型として使用されるものである。しかし、これらの主剤もしくは硬化剤の成分が溶剤と反応して反応性を失ってしまうと、主剤と硬化剤を混合した後の硬化反応が得られなくなるため、イソシアネート基やエポキシ基は水やアルコールを溶剤とする場合には使用することができなかった。一方、環境対応という側面からは、水系もしくはアルコール系の溶剤でも使用できる低温硬化性樹脂組成物が求められている。 In these paints and inks, when reactive materials are mixed, the reaction proceeds gradually even at room temperature, and storage stability cannot be obtained. For this purpose, a two-pack type that uses a resin having a hydroxyl group or a resin having an epoxy group as a main component, a compound having an isocyanate group or a compound having an amino group as a curing agent, and a mixture used when coating the main agent and the curing agent. It is used as However, if these main agents or curing agent components react with the solvent and lose reactivity, the curing reaction after mixing the main agent and the curing agent cannot be obtained, so the isocyanate group or epoxy group is water or alcohol. It was not possible to use it as a solvent. On the other hand, from the viewpoint of environmental friendliness, a low-temperature curable resin composition that can be used even in an aqueous or alcoholic solvent is required.
本発明は、耐熱性に乏しい基材に使用することができる硬化性樹脂組成物であって、かつ溶剤選択性のない硬化性樹脂組成物を提供することを目的とする。 An object of this invention is to provide the curable resin composition which is a curable resin composition which can be used for a base material with poor heat resistance, and does not have solvent selectivity.
本発明は、水酸基を有するアクリル酸エステル（ａ）を構成成分として３０％以上重合してなるアクリル重合体（Ａ）と、窒素を含む複素環を有する塩基性化合物（Ｂ）を含有する硬化性樹脂組成物に関する。 The present invention is a curable composition comprising an acrylic polymer (A) obtained by polymerizing 30% or more of an acrylic ester (a) having a hydroxyl group as a constituent component and a basic compound (B) having a nitrogen-containing heterocyclic ring. The present invention relates to a resin composition.
また、本発明は窒素を含む複素環を有する塩基性化合物（Ｂ）が、アクリル重合体（Ａ）の固形分１００重量部に対し０．５重量部以上含まれることを特徴とする硬化性樹脂組成物に関する。 In the present invention, the basic compound (B) having a nitrogen-containing heterocyclic ring is contained in an amount of 0.5 part by weight or more based on 100 parts by weight of the solid content of the acrylic polymer (A). Relates to the composition.
また、水酸基を有するアクリル酸エステル（ａ）が２−ヒドロキシエチルアクリレートであることを特徴とする硬化性樹脂組成物に関する。 The present invention also relates to a curable resin composition, wherein the acrylic ester (a) having a hydroxyl group is 2-hydroxyethyl acrylate.
また、窒素を含む複素環を有する塩基性化合物（Ｂ）が１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エンであることを特徴とする硬化性樹脂組成物に関する。 The present invention also relates to a curable resin composition wherein the basic compound (B) having a nitrogen-containing heterocyclic ring is 1,8-diazabicyclo [5,4,0] undec-7-ene.
本発明の硬化性樹脂組成物は、１００〜１４０℃程度の比較的低温で硬化するため、耐熱性に乏しい基材に使用することができる。また、従来では難しかった水系やアルコール系を溶剤とした場合にも使用することができる。 Since the curable resin composition of the present invention is cured at a relatively low temperature of about 100 to 140 ° C., it can be used for a substrate having poor heat resistance. Moreover, it can be used also when the water system and alcohol system which were difficult conventionally are used as a solvent.
本発明の硬化性樹脂組成物は、水酸基を有するアクリル酸エステル（ａ）を構成成分として３０％以上重合してなるアクリル重合体（Ａ）と、窒素を含む複素環を有する塩基性化合物（Ｂ）を含有するものである。前記アクリル重合体（Ａ）中の水酸基による自己架橋反応を、前記塩基性化合物（Ｂ）の存在により促進することができるため、従来必要であった硬化剤を必要としない自己架橋型の硬化性樹脂組成物である。 The curable resin composition of the present invention comprises an acrylic polymer (A) obtained by polymerizing 30% or more of an acrylic ester (a) having a hydroxyl group as a constituent component, and a basic compound (B) having a nitrogen-containing heterocyclic ring. ). Since the self-crosslinking reaction by the hydroxyl group in the acrylic polymer (A) can be promoted by the presence of the basic compound (B), a self-crosslinking curable property that does not require a conventionally required curing agent. It is a resin composition.
まず、アクリル重合体（Ａ）から説明する。アクリル重合体（Ａ）は、その構成成分の合計１００重量％中に水酸基を有するアクリル酸エステル（ａ）を３０重量％以上の割合で含む。水酸基を有するアクリル酸エステル（ａ）の水酸基が架橋部位として硬化反応に寄与するため、必須である。メカニズムは定かではないが、アクリル重合体（Ａ）において、水酸基を有するアクリル酸エステル（ａ）中の水酸基が、同じく水酸基を有するアクリル酸エステル（ａ）もしくは他の（メタ）アクリル酸エステルとエステル交換反応をすることで、硬化が進むと考えられる。また、他の成分としてアクリル酸、もしくはメタクリル酸を含む場合は、これらとエステル化反応することでも、硬化が進むと考えられる。 First, the acrylic polymer (A) will be described. The acrylic polymer (A) contains the acrylic ester (a) having a hydroxyl group in a proportion of 30% by weight or more in a total of 100% by weight of the constituent components. Since the hydroxyl group of the acrylic ester (a) having a hydroxyl group contributes to the curing reaction as a crosslinking site, it is essential. Although the mechanism is not clear, in the acrylic polymer (A), the hydroxyl group in the acrylic ester (a) having a hydroxyl group is the same as the acrylic ester (a) or other (meth) acrylic ester having a hydroxyl group. It is thought that curing proceeds by performing an exchange reaction. Moreover, when acrylic acid or methacrylic acid is included as another component, it is thought that hardening progresses also by esterifying with these.
また、水酸基を有するアクリル酸エステル（ａ）が構成成分の３０重量％以上の割合でないと、１００〜１４０℃程度では硬化反応が進まない。水酸基を有するアクリル酸エステル（ａ）を３０重量％以上含むことが、低温での架橋反応に重要であると考えられる。好ましくは４０重量％以上であり、より好ましくは５０重量％以上である。
また、水酸基を有するアクリル酸エステル（ａ）の代わりに、水酸基を有するメタクリル酸エステルを用いた場合も、１００〜１４０℃程度では硬化反応が進まない。
Moreover, if the acrylic ester (a) having a hydroxyl group is not a proportion of 30% by weight or more of the constituent components, the curing reaction does not proceed at about 100 to 140 ° C. It is considered that containing 30% by weight or more of the acrylic acid ester (a) having a hydroxyl group is important for the crosslinking reaction at a low temperature. Preferably it is 40 weight% or more, More preferably, it is 50 weight% or more.
Moreover, also when the methacrylic acid ester which has a hydroxyl group is used instead of the acrylic acid ester (a) which has a hydroxyl group, hardening reaction does not advance at about 100-140 degreeC.
水酸基を有するアクリル酸エステル（ａ）は特に限定されないが、好適な例として、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレート、３−ヒドロキシプロピルアクリレートなどが挙げられる。 The acrylic acid ester (a) having a hydroxyl group is not particularly limited, and suitable examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxypropyl acrylate and the like.
また、水酸基を有するアクリル酸エステル（ａ）が、２−ヒドロキシエチルアクリレートであることがより好ましい。この場合、理由は定かでないが、１００〜１４０℃程度でより硬化反応が進みやすい。 The acrylic acid ester (a) having a hydroxyl group is more preferably 2-hydroxyethyl acrylate. In this case, the reason is not clear, but the curing reaction is more likely to proceed at about 100 to 140 ° C.
アクリル重合体（Ａ）の構成成分として使用できるその他の単量体としては特に限定されないが、好適な例として、（メタ）アクリル酸エステルが挙げられる。
（メタ）アクリル酸エステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、テトラヒドロフルフリール（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、オキセタン(メタ)アクリレート等のアルキル（メタ）アクリレート類、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート等のアルコキシポリアルキレングリコール（メタ）アクリレート類が挙げられる。好ましくはアルキル（メタ）アクリレートである。
Although it does not specifically limit as another monomer which can be used as a structural component of an acrylic polymer (A), (meth) acrylic acid ester is mentioned as a suitable example.
As (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl ( Alkyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Data) acrylates, methoxy polypropylene glycol (meth) acrylate, alkoxy polyalkylene glycols such as ethoxy polyethylene glycol (meth) acrylate (meth) acrylates. Alkyl (meth) acrylate is preferable.
また、上記（メタ）アクリル酸エステルと併用できる単量体として、（メタ）アクリルアミド、及びＮ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド、アクリロイルモルホリン等のＮ置換型（メタ）アクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリレート類、（メタ）アクリロニトリル等のニトリル類、スチレン、α−メチルスチレン等のスチレン類、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル類、酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビニル類などがあげられる。 Moreover, as a monomer which can be used together with the (meth) acrylic acid ester, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide , N-substituted (meth) acrylamides such as diacetone (meth) acrylamide and acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and other amino group-containing (meta ) Nitriles such as acrylates, (meth) acrylonitrile, styrenes such as styrene and α-methylstyrene, vinyls such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether Ether, vinyl acetate, fatty acid vinyl such as vinyl propionate and the like.
また、カルボキシル基を有する単量体も好適に使用することができる。カルボキシル基を有する単量体としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマール酸、クロトン酸などから１種又は２種以上を選択して使用することができる。 Moreover, the monomer which has a carboxyl group can also be used conveniently. As the monomer having a carboxyl group, one or more kinds selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like can be used.
さらに、本発明の硬化性樹脂組成物は、窒素を含む複素環を有する塩基性化合物（Ｂ）を必須成分として含む。この塩基性化合物（Ｂ）は一般的にはエステル化反応やマイケル付加反応の触媒として使用されることがあるが、窒素を含む複素環構造の電子的配置により、塩基性触媒としての求核性が高く、その効果が大きいものと考えられる。本発明は、この塩基性化合物（Ｂ）が、アクリル重合体中（Ａ）に水酸基を有するアクリル酸エステル（ａ）が３０％以上含む場合において、水酸基を有するアクリル酸エステル（ａ）のエステル交換反応もしくはエステル化反応を促進する効果が非常に高いことを見出したものである。
窒素を含む複素環を有する塩基性化合物（Ｂ）を含まない場合、１００〜１４０℃程度では硬化反応が進まないため、窒素を含む複素環を有する塩基性化合物（Ｂ）は本発明の硬化性樹脂組成物に必要不可欠である。
Furthermore, the curable resin composition of this invention contains the basic compound (B) which has a heterocyclic ring containing nitrogen as an essential component. This basic compound (B) is generally used as a catalyst for esterification reaction or Michael addition reaction, but nucleophilicity as a basic catalyst due to the electronic arrangement of the heterocyclic structure containing nitrogen. The effect is considered high. In the present invention, when the basic compound (B) contains 30% or more of the acrylic ester (a) having a hydroxyl group in the acrylic polymer (A), the ester exchange of the acrylic ester (a) having a hydroxyl group is carried out. It has been found that the effect of promoting the reaction or esterification reaction is very high.
When the basic compound (B) having a nitrogen-containing heterocyclic ring is not included, since the curing reaction does not proceed at about 100 to 140 ° C., the basic compound (B) having a nitrogen-containing heterocyclic ring is curable according to the present invention. It is essential for the resin composition.
また、窒素を含む複素環を有する塩基性化合物（Ｂ）は、硬化性樹脂組成物の固形分１００重量％中に０．５重量％以上含まれることがより好ましい。
０．５重量％より少ない場合、１００〜１４０℃程度では硬化反応が進みにくい。窒素を含む複素環を有する塩基性化合物（Ｂ）の含有量は、０．５重量％〜１０重量％が好ましく、１重量％〜５重量％がより好ましい。１０重量％を超えると、１００〜１４０℃程度では硬化反応は進むが、塩基性化合物（Ｂ）の樹脂との相溶性が悪くなり、塗膜の白化の現象が起き、好ましくない場合がある。
In addition, the basic compound (B) having a nitrogen-containing heterocyclic ring is more preferably contained in an amount of 0.5% by weight or more in 100% by weight of the solid content of the curable resin composition.
When the content is less than 0.5% by weight, the curing reaction hardly proceeds at about 100 to 140 ° C. The content of the basic compound (B) having a nitrogen-containing heterocyclic ring is preferably 0.5% by weight to 10% by weight, and more preferably 1% by weight to 5% by weight. When it exceeds 10% by weight, the curing reaction proceeds at about 100 to 140 ° C., but the compatibility of the basic compound (B) with the resin is deteriorated, and the phenomenon of whitening of the coating film occurs, which is not preferable.
窒素を含む複素環を有する塩基性化合物（Ｂ）は特に限定されないが、好適な例として、１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エン、１，５−ジアザビシクロ［４，３，０］ノネン−５、１，４−ジアザビシクロ［２，２，２］オクタンなどが挙げられる。 The basic compound (B) having a heterocyclic ring containing nitrogen is not particularly limited, and preferred examples include 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,5-diazabicyclo [4, 3,0] nonene-5, 1,4-diazabicyclo [2,2,2] octane and the like.
また、窒素を含む複素環を有する塩基性化合物（Ｂ）が１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エンであることがより好ましい。この場合、１００〜１４０℃程度でより硬化反応が進みやすい。 The basic compound (B) having a nitrogen-containing heterocyclic ring is more preferably 1,8-diazabicyclo [5,4,0] undec-7-ene. In this case, the curing reaction is more likely to proceed at about 100 to 140 ° C.
なお、本発明の硬化性樹脂組成物を加熱、乾燥して得られた硬化塗膜は、水や溶媒を含んでゲルになることができる。
特に、アクリル重合体（Ａ）の構成成分として、水酸基を有するアクリル酸エステル（ａ）の比率が高い場合や、他に親水性のモノマーが含まれる場合は、水を含むゲルとして好適に使用することができる。
水を含むゲルは、おむつや生理用品などの吸水性ポリマーのほか、電池に使用される水系電解質を固化させることにも使用され、さらに人工関節や植物工場の培地などにも使用される。
In addition, the cured coating film obtained by heating and drying the curable resin composition of this invention can turn into a gel containing water and a solvent.
In particular, as a constituent component of the acrylic polymer (A), when the ratio of the acrylic acid ester (a) having a hydroxyl group is high or other hydrophilic monomers are included, it is preferably used as a gel containing water. be able to.
Gels containing water are used to solidify water-based electrolytes used in batteries, as well as water-absorbing polymers such as diapers and sanitary products, and are also used in artificial joints and plant factory media.
以下、実施例によって本発明を具体的に説明するが、本発明は実施例に特に限定されるものではない。なお、実施例における「部」は、「重量部」を表す。
重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定したポリスチレン換算の値である。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “part” represents “part by weight”.
The weight average molecular weight of the polymer is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
（合成例１）
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、２−ヒドロキシエチルアクリレートを４０部、ベンジルメタクリレートを５０部、ブチルアクリレートを１０部、チオグリセロールを５部、及びイソプロピルアルコールを１０５部仕込み、窒素ガスで置換した。反応容器内を８０℃に加熱して、Ｖ−６０１（和光純薬製）０．５０部を添加した後７時間反応した。固形分測定により９５％が反応したことを確認後、室温まで冷却して、重量平均分子量４，５００のアクリル重合体Ａ−１の固形分５０％溶液を得た。
(Synthesis Example 1)
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 40 parts 2-hydroxyethyl acrylate, 50 parts benzyl methacrylate, 10 parts butyl acrylate, 5 parts thioglycerol, and 105 isopropyl alcohol. Charged part and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 0.50 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it cooled to room temperature and obtained the solid content 50% solution of acrylic polymer A-1 of the weight average molecular weight 4,500.
合成例および比較合成例で使用する材料を以下に列挙する。
［水酸基を有するアクリル酸エステル（ａ）］
・ＨＥＡ：２−ヒドロキシエチルアクリレート
・４ＨＢＡ：４−ヒドロキシブチルアクリレート
・ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
・
［その他の（メタ）アクリル酸エステル、（メタ）アクリル酸］
・ＭＡＡ：メタクリル酸
・ＢｚＭＡ：ベンジルメタクリレート
・ＢＡ：ブチルアクリレート
The materials used in the synthesis examples and comparative synthesis examples are listed below.
[Acrylic acid ester having a hydroxyl group (a)]
-HEA: 2-hydroxyethyl acrylate-4HBA: 4-hydroxybutyl acrylate-HEMA: 2-hydroxyethyl methacrylate-
[Other (meth) acrylic acid esters, (meth) acrylic acid]
MAA: methacrylic acid BzMA: benzyl methacrylate BA: butyl acrylate
（合成例２〜７、９、比較合成例１、２）
表１に記載した原料と仕込み量を用いた以外は合成例１と同様にして合成を行い、アクリル重合体Ａ−２〜Ａ−７、Ａ−９、Ｈ−１、Ｈ−２の固形分５０％の溶液を得た。
(Synthesis Examples 2 to 7, 9 and Comparative Synthesis Examples 1 and 2)
The synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and preparation amounts described in Table 1 were used, and the solid content of acrylic polymers A-2 to A-7, A-9, H-1, and H-2 A 50% solution was obtained.
（合成例８）
ガス導入管、温度計、コンデンサー、及び攪拌機を備えた反応容器に、２−ヒドロキシエチルアクリレートを４０部、ベンジルメタクリレートを５０部、ブチルアクリレートを１０部、及びイソプロピルアルコールを１００部仕込み、窒素ガスで置換した。反応容器内を８０℃に加熱して、Ｖ−６０１（和光純薬製）１．５部を添加した後５時間反応した。固形分測定により９５％が反応したことを確認後、室温まで冷却して、重量平均分子量３０，０００のアクリル重合体Ａ−８の固形分５０％溶液を得た。
(Synthesis Example 8)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 40 parts of 2-hydroxyethyl acrylate, 50 parts of benzyl methacrylate, 10 parts of butyl acrylate, and 100 parts of isopropyl alcohol are charged with nitrogen gas. Replaced. The inside of the reaction vessel was heated to 80 ° C., and 1.5 parts of V-601 (manufactured by Wako Pure Chemical Industries) was added, followed by reaction for 5 hours. After confirming that 95% had reacted by solid content measurement, it cooled to room temperature and obtained the solid content 50% solution of acrylic polymer A-8 with a weight average molecular weight 30,000.
（実施例１）
下記の組成の混合物を均一に撹拌混合した後、エタノールで固形分３０％まで希釈した。
以下に固形分の量を示す。
・アクリル重合体：Ａ−１ １０．０部
・塩基性化合物：ＤＢＵ（１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エン） ０．２部
この樹脂組成物をブリキ板に＃１６のバーコーターで塗工し、硬化条件として１００℃１０分加熱乾燥させた。
（ＩＰＡラビング）
３ポンドハンマーにガーゼを巻きＩＰＡ（イソプロピルアルコール）を含浸させ、得られた塗膜上を往復させ、塗膜が溶解するまでの回数を求めた。
（塗膜外観）
さらに、塗膜の外観を目視で評価した。
○：問題なし
△：少し白化
×：大いに白化
Example 1
A mixture having the following composition was stirred and mixed uniformly, and then diluted with ethanol to a solid content of 30%.
The amount of solid content is shown below.
Acrylic polymer: 10.0 parts of A-1 Basic compound: DBU (1,8-diazabicyclo [5,4,0] undec-7-ene) 0.2 part
This resin composition was applied to a tin plate with a # 16 bar coater, and dried by heating at 100 ° C. for 10 minutes as curing conditions.
(IPA rubbing)
A gauze was wound around a 3-lb hammer and impregnated with IPA (isopropyl alcohol), and the resulting coating film was reciprocated to determine the number of times until the coating film was dissolved.
(Appearance of coating film)
Furthermore, the appearance of the coating film was visually evaluated.
○: No problem △: Slightly whitened ×: Highly whitened
ここで、実施例および比較例で使用する材料を以下に列挙する。
［塩基性化合物］
・ＤＢＵ：１，８−ジアザビシクロ［５，４，０］ウンデカ−７−エン
・ＤＢＮ：１，５−ジアザビシクロ［４，３，０］ノネン−５
・DABCO：１，４−ジアザビシクロ［２，２，２］オクタン
・ＤＭＢＡ：ジメチルベンジルアミン
・
［硬化剤］
・ＩＰＤＩ：イソホロンジイソシアネート
・
［中和剤］
・ＤＭＡＥ：ジメチルアミノエタノール
Here, materials used in Examples and Comparative Examples are listed below.
[Basic compounds]
DBU: 1,8-diazabicyclo [5,4,0] undec-7-ene DBN: 1,5-diazabicyclo [4,3,0] nonene-5
DABCO: 1,4-diazabicyclo [2,2,2] octane DMBA: dimethylbenzylamine
[Curing agent]
IPDI: isophorone diisocyanate
[Neutralizer]
DMAE: dimethylaminoethanol
（実施例２〜１５、比較例１〜１１）
表２に記載した原料と仕込み量、硬化条件、希釈溶媒を用いた以外は実施例１と同様にして配合を行い樹脂組成物を得た後、同様に評価した。
(Examples 2-15, Comparative Examples 1-11)
A resin composition was obtained by mixing in the same manner as in Example 1 except that the raw materials, preparation amounts, curing conditions, and diluting solvent described in Table 2 were used.
表２に評価結果を示す。
（実施例１６）
下記の組成の混合物を均一に撹拌混合した後、水で固形分３０％まで希釈した。
以下に固形分の量を示す。
・アクリル重合体：Ａ−２ １０．０部
・塩基性化合物：ＤＢＵ ０．２部
・中和剤：ＤＭＡＥ １．０部
この樹脂組成物を実施例１と同様に評価した。
(Example 16)
A mixture having the following composition was stirred and mixed uniformly, and then diluted with water to a solid content of 30%.
The amount of solid content is shown below.
Acrylic polymer: 10.0 parts of A-2 Basic compound: 0.2 parts of DBU Neutralizing agent: 1.0 part of DMAE
This resin composition was evaluated in the same manner as in Example 1.
（比較例１２）
下記の組成の混合物を均一に撹拌混合した後、水で固形分３０％まで希釈した。
以下に固形分の量を示す。
・アクリル重合体：Ａ−２ １０．０部
・硬化剤：ＩＰＤＩ ２．０部
・中和剤：ＤＭＡＥ １．０部
この樹脂組成物を実施例１と同様に評価した。
(Comparative Example 12)
A mixture having the following composition was stirred and mixed uniformly, and then diluted with water to a solid content of 30%.
The amount of solid content is shown below.
-Acrylic polymer: 10.0 parts of A-2-Curing agent: 2.0 parts of IPDI-Neutralizing agent: 1.0 part of DMAE
This resin composition was evaluated in the same manner as in Example 1.
表３に評価結果を示す。
比較例１１、１２は、硬化剤としてＩＰＤＩを用いている。ＩＰＤＩはイソシアネート基を有し、水酸基含有のアクリル重合体とは低温で架橋する硬化剤である。
しかしながら、比較例１１では溶媒がアルコール系、比較例１２では溶媒が水系であるため、ＩＰＤＩのイソシアネート基が溶媒と反応して活性を失ってしまい、硬化反応が進まない。
一方、本発明の硬化性樹脂組成物は、溶媒がアルコール系、水系の場合でも活性を失うことなく、硬化反応を進めることができる。
Comparative Examples 11 and 12 use IPDI as a curing agent. IPDI is a curing agent that has an isocyanate group and crosslinks with a hydroxyl group-containing acrylic polymer at a low temperature.
However, in Comparative Example 11, the solvent is alcohol-based, and in Comparative Example 12, the solvent is water-based. Therefore, the isocyanate group of IPDI reacts with the solvent to lose its activity, and the curing reaction does not proceed.
On the other hand, the curable resin composition of the present invention can advance the curing reaction without losing the activity even when the solvent is alcohol or water.
Claims (4)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020152812A (en) * | 2019-03-20 | 2020-09-24 | 日本ポリエチレン株式会社 | Resin composition and method for producing thermal reversible crosslinkable molding using resin composition |
| WO2022270460A1 (en) * | 2021-06-21 | 2022-12-29 | 積水化学工業株式会社 | (meth)acrylic resin composition, inorganic fine particle-dispersed slurry composition, and inorganic fine particle-dispersed molded product |
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| JPH07118547A (en) * | 1993-10-20 | 1995-05-09 | Dainippon Ink & Chem Inc | Curing composition |
| JPH10109034A (en) * | 1996-05-22 | 1998-04-28 | Nippon Paint Co Ltd | Acrylic monomer bonded with malonate group and its production |
| JP2003119401A (en) * | 2001-10-10 | 2003-04-23 | Dainippon Ink & Chem Inc | Curable resin composition |
| JP2009132909A (en) * | 2007-11-07 | 2009-06-18 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive for optical member and optical member |
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|---|---|---|---|---|
| JPH07118547A (en) * | 1993-10-20 | 1995-05-09 | Dainippon Ink & Chem Inc | Curing composition |
| JPH10109034A (en) * | 1996-05-22 | 1998-04-28 | Nippon Paint Co Ltd | Acrylic monomer bonded with malonate group and its production |
| JP2003119401A (en) * | 2001-10-10 | 2003-04-23 | Dainippon Ink & Chem Inc | Curable resin composition |
| JP2009132909A (en) * | 2007-11-07 | 2009-06-18 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive for optical member and optical member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020152812A (en) * | 2019-03-20 | 2020-09-24 | 日本ポリエチレン株式会社 | Resin composition and method for producing thermal reversible crosslinkable molding using resin composition |
| JP7218636B2 (en) | 2019-03-20 | 2023-02-07 | 日本ポリエチレン株式会社 | RESIN COMPOSITION AND METHOD FOR MANUFACTURING THERMALLY VERY CROSSLINKABLE MOLDED PRODUCT USING SAME RESIN COMPOSITION |
| WO2022270460A1 (en) * | 2021-06-21 | 2022-12-29 | 積水化学工業株式会社 | (meth)acrylic resin composition, inorganic fine particle-dispersed slurry composition, and inorganic fine particle-dispersed molded product |
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