JP2012201775A - Water-based coating material composition and coated floor - Google Patents
Water-based coating material composition and coated floor Download PDFInfo
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- JP2012201775A JP2012201775A JP2011066979A JP2011066979A JP2012201775A JP 2012201775 A JP2012201775 A JP 2012201775A JP 2011066979 A JP2011066979 A JP 2011066979A JP 2011066979 A JP2011066979 A JP 2011066979A JP 2012201775 A JP2012201775 A JP 2012201775A
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- epoxy resin
- material composition
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000768 polyamine Polymers 0.000 claims abstract description 30
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 239000008199 coating composition Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 23
- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 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 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004027 organic amino compounds Chemical class 0.000 description 2
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- -1 polyol compound Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000011850 water-based material Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical class NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、水系エポキシ樹脂による水系塗材組成物に関するものである。 The present invention relates to an aqueous coating material composition using an aqueous epoxy resin.
塗床材料としては用途によりエポキシ、ウレタン、アクリル等さまざまな樹脂が用いられ、数〜数十ｍｍに及ぶ厚塗り工法がある一方、ペンキのようにローラーやスプレー等で数十〜数百μｍの厚みで塗装する薄塗工法もある。簡易的な化粧や下地コンクリートの発塵を抑える目的で塗工される場合は薄塗工法が行われる場合が多い。ただし、この薄塗工法に用いられる材料は溶剤を含むものが多く、また、水性アクリル塗料など水性のものも開発されているが概して耐溶剤性や強度等が劣り、工場床、倉庫床、バックヤードなどある程度の耐久性が要求される部位では物性不足になりがちである。 Various materials such as epoxy, urethane, and acrylic are used as the coating material, and there are thick coating methods ranging from several to several tens of millimeters, while several tens to several hundreds of micrometers with rollers and sprays like paint. There is also a thin coating method that paints with thickness. In the case of coating for the purpose of suppressing the dust generation of simple makeup or foundation concrete, the thin coating method is often performed. However, many of the materials used in this thin coating method include solvents, and water-based materials such as water-based acrylic paints have been developed. However, they are generally inferior in solvent resistance and strength. In areas where a certain level of durability is required, such as yards, physical properties tend to be insufficient.
施工時の臭気の問題や環境への配慮などから水性材料の要求が高まる中、硬度が高く、工場床に適するエポキシ樹脂系塗材の水系化が検討されてきた。これらの多くは、液状や固形エポキシ樹脂を水に分散させてなるエマルションを主剤とし、水溶性アミンの水溶液を硬化剤とするものであり、硬化剤が水中にてエマルション粒子を架橋するバインダーとして働き、水の蒸散とともに乾燥、硬化する。そのため、従来の溶剤系のものと比較すると依然として物性に乏しく、また、低温での成膜性を確保するために成膜助剤として溶剤を含むものもある。 Amidst increasing demand for water-based materials due to odor problems during construction and environmental considerations, water-based epoxy resin coating materials that have high hardness and are suitable for factory floors have been studied. Many of these are based on an emulsion in which a liquid or solid epoxy resin is dispersed in water, and an aqueous solution of a water-soluble amine as a curing agent. The curing agent acts as a binder for crosslinking emulsion particles in water. Dry and harden with transpiration of water. For this reason, the physical properties are still poor as compared with conventional solvent-based ones, and some contain a solvent as a film-forming auxiliary in order to ensure film-forming properties at low temperatures.
これに対し、無溶剤エポキシを主剤とし、乳化力を持ったアミンを硬化剤とする自己乳化型水系エポキシ樹脂があり、これは塗工時にアミンの乳化力により塗材を強制的に水に分散させる、あるいは塗材中に水を分散させるというもので、水の蒸散を伴う以外は無溶剤型塗材と同様の硬化過程をとる。乾燥性は概してエマルション型のものに劣るが、得られる塗膜の物性が高くまた、有機揮発分を含まなくとも良好な低温成膜性が得られるというメリットがある。 On the other hand, there is a self-emulsifying water-based epoxy resin that uses solvent-free epoxy as the main agent and amine that has emulsifying power as a curing agent. Or water is dispersed in the coating material, and the curing process is the same as that of the solventless coating material except that water is evaporated. Although the drying property is generally inferior to that of an emulsion type, there are advantages that the obtained coating film has high physical properties and that good low-temperature film-forming properties can be obtained without containing organic volatiles.
（Ｉ）分子内に平均１個より多くの隣接エポキシ基を有するエポキシ樹脂、（II）平均分子量が 250〜10000 又はエチレンオキサイド含量が45重量％以上のポリアルキレンポリエーテルポリオールのポリグリシジルエーテルと分子内に平均１個より多くの隣接エポキシ基を有する疎水性エポキシ化合物との混合物であるエポキシ基含有化合物と、脂環式ポリアミン、芳香族ポリアミン及びヘテロ環族ポリアミンからなる群から選ばれる１種以上のポリアミン類とを、ポリアミン過剰で反応させて得られる自己乳化型活性有機アミン硬化剤、及び(III) 水を含有する水性エポキシ樹脂硬化性組成物が塗膜のレベリング性、造膜性に優れ、硬化フィルムが透明で、表面光沢、硬度、密着性、耐水性、耐薬品性に優れることが開示されている。（特許文献１） (I) an epoxy resin having an average of more than one adjacent epoxy group in the molecule, (II) a polyglycidyl ether and a molecule of a polyalkylene polyether polyol having an average molecular weight of 2500 to 10,000 or an ethylene oxide content of 45% by weight or more One or more selected from the group consisting of an epoxy group-containing compound which is a mixture of a hydrophobic epoxy compound having an average of more than one adjacent epoxy group and an alicyclic polyamine, aromatic polyamine and heterocyclic polyamine Self-emulsifying type active organic amine curing agent obtained by reacting polyamines in excess with polyamine, and (III) water-based epoxy resin curable composition containing water is excellent in coating leveling and film-forming properties It is disclosed that the cured film is transparent and has excellent surface gloss, hardness, adhesion, water resistance, and chemical resistance. (Patent Document 1)
エポキシ樹脂、平均分子量 200〜12000 でエチレンオキサイド含有量80重量％以上のポリアルキレンポリエーテルポリオール化合物と過剰のポリイソシアネート化合物とを反応させて得られるウレタン結合含有化合物と、エポキシ化合物と、平均分子量 300〜5000のアルキルフェノールエトキシレートとを、特定割合で反応させて得られるエポキシ基含有乳化性化合物、及び水 を含む乳化性エポキシ樹脂組成物、並びにこれと活性有機アミノ化合物 とを混合し、硬化させて得られる硬化性組成物が乳化性、貯蔵安定性に優れ、また活性有機アミノ化合物で硬化した場合、硬化速度、硬化物の皮膜強度、耐水性等に優れることが開示されている。 （特許文献３） Epoxy resin, urethane bond-containing compound obtained by reacting a polyalkylene polyether polyol compound having an average molecular weight of 200 to 12000 and an ethylene oxide content of 80% by weight or more with an excess polyisocyanate compound, an epoxy compound, and an average molecular weight of 300 An epoxy group-containing emulsifying compound obtained by reacting ˜5000 alkylphenol ethoxylates in a specific ratio, an emulsifying epoxy resin composition containing water, and an active organic amino compound are mixed and cured. It is disclosed that the resulting curable composition is excellent in emulsifiability and storage stability, and when cured with an active organic amino compound, it is excellent in curing speed, film strength of the cured product, water resistance, and the like. (Patent Document 3)
平均１個より多いエポキシ基を持つポリエポキシドと、水性エマルションタイプのポリアミン誘導体とを含み、後者は、ポリオキシエチレングリコールのジグリシジルエーテル１当量に対し、分子内に２個の活性水素を持つアミンを１．０１〜２当量反応させ、疎水性ジエポキシドをエポキシ基過剰量で反応させて得られるエポキシ基含有化合物、第一又は／及び第二アミノ基を２個以上持つポリアミン類、平均１個より多いエポキシ基を持つ疎水性ポリエポキシド、モノエポキシド及びアクリロニトリルから選択される単独又は混合物IVを反応させて作られる組成物が、水希釈可能な水性ポリエポキシド組成物となることが開示されている。（特許文献４） Including polyepoxide having an average of more than one epoxy group and an aqueous emulsion type polyamine derivative, the latter comprising an amine having two active hydrogens in the molecule for one equivalent of diglycidyl ether of polyoxyethylene glycol. An epoxy group-containing compound obtained by reacting 1.01 to 2 equivalents and reacting a hydrophobic diepoxide with an excess of epoxy groups, polyamines having two or more primary or / and secondary amino groups, an average of more than one It is disclosed that a composition made by reacting a single or mixture IV selected from hydrophobic polyepoxides having epoxy groups, monoepoxides and acrylonitrile is an aqueous polyepoxide composition which can be diluted with water. (Patent Document 4)
（A)ビスフェノールＡ型液状エポキシ樹脂および／またはビスフェノールＦ型液状エポキシ樹脂、 (B)無溶剤型ポリアミンおよび／または無溶剤型ポリアミドアミン、(C) 溶解性パラメーター10以上で、沸点130 ℃以下のアルコール系溶剤、を主成分とする塗り床用下塗塗料組成物は旧塗膜を溶解、膨潤軟化させることなしに簡便かつ円滑に塗装補修ができることが開示されている。（特許文献５） (A) Bisphenol A type liquid epoxy resin and / or bisphenol F type liquid epoxy resin, (B) Solvent-free polyamine and / or solvent-free polyamidoamine, (C) Solubility parameter of 10 or more and boiling point of 130 ° C or less It has been disclosed that an undercoating composition for an undercoat containing an alcohol solvent as a main component can be easily and smoothly applied and repaired without dissolving and swelling and softening the old paint film. (Patent Document 5)
主剤が無溶剤エポキシ樹脂であり、硬化剤が自己乳化型アミンと非自己乳化エマルジョン型アミンからなることを特徴とする水系エポキシ樹脂組成物とすること、また無溶剤であり、成膜助剤を含まない水系エポキシ樹脂組成物とすることで、低温での成膜性が良く、硬度が高く、耐摩耗性が高く、顔料の色別れがない塗材となり、成膜助剤、溶剤を含まないことから作業環境が改善でき、環境負荷が少ない、また住環境のシックハウスを防げることが開示されている。（特許文献６） A water-based epoxy resin composition characterized in that the main agent is a solvent-free epoxy resin, and the curing agent is composed of a self-emulsifying amine and a non-self-emulsifying emulsion type amine. By using a water-based epoxy resin composition that does not contain, the film forming property at low temperature is good, the hardness is high, the wear resistance is high, and there is no color separation of the pigment, and it does not contain film forming aids and solvents. Therefore, it is disclosed that the working environment can be improved, the environmental load is small, and the sick house in the living environment can be prevented. (Patent Document 6)
しかし、自己乳化型水系エポキシ樹脂は水性でありながら優れた塗膜が得られるが、水を含んだまま無溶剤型の硬化が起こるため、混合してから塗装するまでの時間により発色、特に明度が安定し難いという欠点があった。 However, self-emulsifying water-based epoxy resins can provide excellent coatings while being water-based, but solvent-free curing occurs while containing water, so color development, especially brightness, depending on the time from mixing to coating However, it was difficult to stabilize.
解決しようとする課題は、色安定性が良いエポキシ樹脂水系塗材組成物及び塗床を提供することである。 The problem to be solved is to provide an epoxy resin water-based coating composition and a coating floor having good color stability.
請求項１の発明は、エポキシ樹脂とポリアミンおよび水を成分とする水系塗材組成物であって、前記ポリアミンがシアノエチル化ポリアミンを含む水系塗材組成物で塗工時経時色安定性が良く、物性の優れた塗り床となる。 The invention of claim 1 is an aqueous coating composition comprising an epoxy resin, a polyamine and water as components, wherein the polyamine is an aqueous coating composition containing a cyanoethylated polyamine and has good color stability over time when applied, The coated floor has excellent physical properties.
請求項２の発明は、前記塗材組成物が、エポキシ樹脂１０〜４０重量％、顔料１０〜３０重量％、ポリアミン１０〜４０重量％、水２０〜６０重量％を含有する請求項１に記載の水系塗材組成物で薄塗り用途で安定した作業性と発色性が得られる。 According to a second aspect of the present invention, the coating material composition contains 10 to 40% by weight of an epoxy resin, 10 to 30% by weight of a pigment, 10 to 40% by weight of a polyamine, and 20 to 60% by weight of water. With this water-based coating material composition, stable workability and color developability can be obtained for thin coating applications.
請求項３の発明は、前記エポキシ樹脂が無溶剤であることを特徴とする請求項１乃至２いずれかに記載の水系塗材組成物で簡便で、塗装時の作業環境が良く、硬化物性も高い水系塗材組成物となる。 Invention of Claim 3 is simple with the water-based coating material composition in any one of Claims 1 thru | or 2 characterized by the above-mentioned, and the epoxy resin is solvent-free, the working environment at the time of coating is good, and hardened | cured material property also A high aqueous coating material composition is obtained.
請求項４の発明は、前記水系塗材組成物がコーンプレート粘度計によりずり速度３８．３ｓｅｃ−１の条件で、温度２５℃の測定される混合初期の粘度が２００〜１０００ｍＰａ・ｓである請求項１乃至３のいずれかに記載の水系塗材組成物で薄塗り塗材として安定した発色性と仕上がりが得られる。 According to a fourth aspect of the present invention, the water-based coating composition has a viscosity of 200 to 1000 mPa · s measured at a temperature of 25 ° C. under a shear rate of 38.3 sec −1 by a cone plate viscometer. The water-based coating material composition according to any one of Items 1 to 3 can provide stable color development and finish as a thin coating material.
請求項５の発明は、請求項３及び４のいずれかに記載の水系塗材組成物が塗布された塗床で塗膜物性が高く、塗り継ぎが目立たず、安定した発色の仕上がりの塗床が得られる。 The invention of claim 5 is a coating floor coated with the water-based coating composition according to any one of claims 3 and 4, having high coating film properties, inconspicuous coating, and a stable colored finish. Is obtained.
本発明の水系塗材組成物は、熱硬化性エポキシ樹脂で、成膜助剤等の有機溶剤を全く含まずに強靭で、また、特に塗装時間に起因する色むらが出にくく、仕上がりに優れ、得られる塗床は塗り継ぎ面が目立たず、発色が安定した仕上がりとなる特徴を有する。 The water-based coating material composition of the present invention is a thermosetting epoxy resin, is tough without containing any organic solvent such as a film forming aid, and is particularly resistant to color unevenness due to the coating time and excellent in finish. The obtained coated floor has a feature that the joint surface is not noticeable and the finished color is stable.
本発明は、エポキシ樹脂水系塗材組成物がシアノエチル化ポリアミンを含み、塗材粘度を調整することにより主剤、硬化剤の混合から塗装までの時間による発色の安定性を向上できることで発明に到った。 The present invention has led to the invention that the epoxy resin water-based coating composition contains cyanoethylated polyamine, and by adjusting the viscosity of the coating material, the stability of color development can be improved over time from mixing of the main agent and curing agent to coating. It was.
本発明に用いるエポキシ樹脂はビスフェノールＡ型、ビスフェノールＦ型、ノボラック型、脂環型、グリシジルアミン型、水添ビスフェノールＡ型などのエポキシ樹脂を上げることができ、ポリエチレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、１，６ヘキサンジオール、トリメチロールプロパンのグリシジルエーテルやネオデカン酸グリシジルエステルなどの反応性希釈剤を混合して用いることもできる。 Epoxy resins used in the present invention can be bisphenol A type, bisphenol F type, novolac type, alicyclic type, glycidylamine type, hydrogenated bisphenol A type, etc., such as polyethylene glycol, polypropylene glycol, neopentyl glycol. A reactive diluent such as glycidyl ether of 1,6-hexanediol or trimethylolpropane or glycidyl ester of neodecanoic acid can be mixed and used.
水系塗材組成物の主剤のエポキシ樹脂は液状で、無溶剤であれば良く、エポキシ樹脂と希釈剤を適宜選択して、硬化剤と混合した状態で乳化でき、必要に応じて水で希釈できるものとする。
The epoxy resin as the main component of the water-based coating composition may be liquid and solvent-free, and can be emulsified in a state where the epoxy resin and diluent are appropriately selected and mixed with a curing agent, and can be diluted with water as necessary. Shall.
塗材組成物の硬化剤は、混合時に乳化して水系塗材となれば良く、自己乳化型アミンを含み、シアノエチル化ポリアミンが含まれていれば良い。
自己乳化型アミンはエポキシ樹脂の硬化剤に用いられるポリアミンにポリアルキレングリコールのグリシジルエーテルをアダクト変性するなどして得られる親水基を有し、乳化する能力を付与したもので、市販品にアデカＥＨ４２２７（（株）ＡＤＥＫＡ、商品名）、フジキュアーＦＸＩ−９１９（富士化成工業（株）、商品名）、ダイトクラールＩ６０２０、ダイトクラールＩ５９９５（大都産業（株）、商品名）等があげられる。
シアノエチル化ポリアミンはエポキシ硬化剤として用いられる各種ポリアミンをアクリロニトリルに付加させることにより得られる物である。
ポリアミンは、メタキシリレンジアミン、イソホロンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンジアミン、アミノメチルピペラジン、ポリオキシアルキレンジアミンやこれらのエポキシアダクト生成物、マンニッヒ反応生成物、カルボン酸との反応により生成するポリアミドなどが代表的なものとして挙げることがてきる。
自己乳化型アミンとシアノエチル化ポリアミンの混合した市販品にダイトクラールＩ６０２０がある。
The curing agent of the coating material composition only needs to be emulsified during mixing to form a water-based coating material, and may contain a self-emulsifying amine and a cyanoethylated polyamine.
A self-emulsifying amine has a hydrophilic group obtained by adduct-modifying glycidyl ether of polyalkylene glycol in a polyamine used as a curing agent for an epoxy resin, and has the ability to emulsify. Adeka EH4227 is a commercially available product. (Adeka Co., Ltd., trade name), Fuji Cure FXI-919 (Fuji Kasei Kogyo Co., Ltd., trade name), Daito Krall I 6020, Daito Krall I 5995 (Daito Sangyo Co., Ltd., trade name) and the like.
The cyanoethylated polyamine is obtained by adding various polyamines used as an epoxy curing agent to acrylonitrile.
Polyamines are metaxylylenediamine, isophoronediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, aminomethylpiperazine, polyoxyalkylenediamine and their epoxy adduct products, Mannich reaction products, and reactions with carboxylic acids. As a typical example, the polyamide produced by the above process can be mentioned.
There is Daitokural I6020 as a commercial product in which a self-emulsifying amine and a cyanoethylated polyamine are mixed.
この他、希釈剤や消泡剤等の添加剤を配合することができる。
硬化剤にはシリカ、セルロース、ポリアクリル酸、変性ポリウレア、アマイドワックスなどの粘度調整剤や、三級アミンやアルキルフェノール類などの硬化促進剤を添加することができる。
In addition, additives such as a diluent and an antifoaming agent can be blended.
Viscosity modifiers such as silica, cellulose, polyacrylic acid, modified polyurea and amide wax, and curing accelerators such as tertiary amines and alkylphenols can be added to the curing agent.
本発明で使用する顔料は普く知られた顔料、体質顔料、トーナーをいい、チタン白、カーボンブラック、炭酸カルシウム粉、硫酸バリウム、タルク、シリカ粉、アルミナ、酸化マグネシウム、水酸化マグネシウム、窒化ホウ素、酸化亜鉛、酸化鉄、フタロシアニン銅等を使うことができる。 The pigments used in the present invention are well-known pigments, extenders, and toners, such as titanium white, carbon black, calcium carbonate powder, barium sulfate, talc, silica powder, alumina, magnesium oxide, magnesium hydroxide, boron nitride. Zinc oxide, iron oxide, copper phthalocyanine, etc. can be used.
本発明の水系塗材組成物はエポキシ樹脂と硬化剤とは、エポキシ当量と硬化剤のアミン価等との関係は概ね普く知られた手法で配合され、重量比のみでは表せないが、エポキシ樹脂１０〜４０重量％、顔料１０〜３０重量％、ポリアミン１０〜４０重量％、水２０〜６０重量％を配合することが好ましい。このうちポリアミンに含まれるシアノエチル化ポリアミンの含有量はベースとなるアミンの構造、種類により異なり、効果が得られる配合量と硬化性、硬化物性の均衡を採り適宜選択する。
In the water-based coating composition of the present invention, the relationship between the epoxy resin and the curing agent, the epoxy equivalent and the amine value of the curing agent is generally blended by a generally known method, and it cannot be expressed only by the weight ratio. It is preferable to blend 10 to 40% by weight of resin, 10 to 30% by weight of pigment, 10 to 40% by weight of polyamine, and 20 to 60% by weight of water. Among these, the content of the cyanoethylated polyamine contained in the polyamine varies depending on the structure and type of the base amine, and is appropriately selected taking into account the balance between the blending amount for obtaining the effect, curability, and cured physical properties.
本発明の水系塗材組成は、コーンプレート粘度計で温度２５℃、ずり速度３８．３ｓｅｃ−１の条件で測定される混合初期の粘度が２００〜１０００ｍＰａ・ｓである時、着色顔料の分離や系中に分散している水分の揮発が抑制されると考えられ、混合後長い時間安定した発色が得られ、好ましい。 The water-based coating material composition of the present invention has a viscosity of 200 to 1000 mPa · s at the initial stage of mixing measured by a cone plate viscometer at a temperature of 25 ° C. and a shear rate of 38.3 sec −1. It is considered that the volatilization of water dispersed in the system is suppressed, and stable color development is obtained for a long time after mixing, which is preferable.
使用混合初期の粘度が１０００ｍＰａ・ｓを超えると薄塗り用途としては塗装作業性が著しく低下し、適さない。薄塗り塗り床塗材用途としては、実用上問題ない色差は、ＪＩＳ Ｋ５６００−４−５及びＪＩＳ Ｋ５６００−４−６に基づく測定で、ΔＥが１．００以下であり、本発明の水系塗材組成物は良好な仕上がりを得ることができる。 If the viscosity at the initial stage of use exceeds 1000 mPa · s, the coating workability is remarkably lowered as a thin coating application, which is not suitable. For use as a thin coating floor coating material, the practically no color difference is a measurement based on JIS K5600-4-5 and JIS K5600-4-6, ΔE is 1.00 or less, and the aqueous coating material of the present invention The composition can obtain a good finish.
以下 実施例・比較例・参考例で詳細に説明する。結果は表１に記す。 Examples, comparative examples, and reference examples will be described in detail below. The results are shown in Table 1.
ｊＥＲ８２８（三菱化学(株)、商品名、ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量１９０）を５０重量部、ネオデカン酸グリシジルエステルを９重量部、沈降性硫酸バリウムを１０重量部、タイピュアＲ−９６０（デュポン（株）、商品名、チタン白）２９重量部、カーボンＭＡ−１００（三菱化学（株）、カーボンブラック）１重量部を混合し、三本ロールミルにて分散・混錬させた後、添加剤としてＢＹＫ−３３３（ビックケミー（株）、商品名、シリコン系ハジキ防止剤）０．５重量部、及びＢＹＫ−０７７（ビックケミー（株）、商品名、シリコン系消泡剤）０．５重量部を配合して水系塗材組成物主剤とし、硬化剤として、ダイトクラールＩ６０２０（大都産業（株）、商品名、エポキシ変性イソホロンジアミンと水およびシアノエチル化キシリレンジアミンの混合物）を５０重量部と水を５０重量部を混合・撹拌したものとし、主剤と硬化剤を混合し、撹拌したものを実施例１の水系塗材組成物とした。 50 parts by weight of jER828 (Mitsubishi Chemical Corporation, trade name, bisphenol A type liquid epoxy resin, epoxy equivalent 190), 9 parts by weight of glycidyl neodecanoate, 10 parts by weight of precipitated barium sulfate, Taipure R-960 ( DuPont Co., Ltd., trade name, titanium white 29 parts by weight, carbon MA-100 (Mitsubishi Chemical Co., Ltd., carbon black) 1 part by weight are mixed, dispersed and kneaded in a three-roll mill, then added BYK-333 (BIC Chemie Co., Ltd., trade name, silicon-based repellency inhibitor) 0.5 parts by weight, and BYK-077 (Bic Chemie Co., Ltd., trade name, silicone-based antifoaming agent) 0.5 parts by weight To form a water-based coating material composition main ingredient, and as a curing agent, Daitokural I6020 (Daito Sangyo Co., Ltd., trade name, epoxy-modified isophoronediamine and water Mixture of cyanoethylated xylylenediamine) and 50 parts by weight of water were mixed and stirred, and the base agent and the curing agent were mixed and stirred to obtain the aqueous coating material composition of Example 1. .
実施例１の硬化剤にＳＮシックナー６５１（サンノプコ（株）、商品名、アクリル系増粘剤）２重量部を添加し、水を４８重量部に変えた以外は実施例１と同じに行い、さらに希釈水とし、水６０重量部を加えて撹拌し、実施例２の水系塗材組成物とした。 The same procedure as in Example 1 was conducted except that 2 parts by weight of SN thickener 651 (San Nopco, trade name, acrylic thickener) was added to the curing agent of Example 1 and water was changed to 48 parts by weight. Further, diluted water was added, and 60 parts by weight of water was added and stirred to obtain an aqueous coating material composition of Example 2.
比較例１
実施例２のダイトクラールＩ６０２０に変えて、ダイトクラールＩ５９９５（大都産業（株）、商品名、エポキシ変性イソホロンジアミンと水の混合物）に変えた以外同じに行い、比較例１の水系塗材組成物とした。
Comparative Example 1
The same procedure as in Example 2 was repeated except that Daitokural I5920 (Daito Sangyo Co., Ltd., trade name, epoxy-modified isophoronediamine and water mixture) was used. It was.
参考例１
実施例１の水系塗材組成物２００重量部に希釈水として水３０重量部を加えて撹拌し、参考例１の水系塗材組成物とした。
Reference example 1
30 parts by weight of water as dilution water was added to 200 parts by weight of the aqueous coating composition of Example 1 and stirred to obtain an aqueous coating composition of Reference Example 1.
実施例、比較例、参考例の水系塗材組成物（主剤、硬化剤及び希釈水を混合直後）をＥ型粘度計ＴＶ−２０（東機産業（株））でＪＩＳ Ｋ５６００−２−３の方法に準じて測定した。使用したコーンプレートは角度が１°３４′、半径が２４ｍｍであり、測定時のずり速度は３８．３ｓｅｃ−１（１０回転／分）、温度は２５℃で実施した。
色差ΔＥ
ＪＩＳ Ａ５４３０に規定されるフレキシブルボードにエポキシ樹脂プライマーを塗布し、吸い込みを無くした状態のものに、実施例、比較例、参考例の水系塗材組成物を、刷毛で１５０ｇ／ｍ２の塗布量にて塗布し、撹拌直後に塗布したものと１０分、２０分及び３０分静置後塗布したもの（いずれも２３℃２４時間静置にて硬化させたもの）との色差ΔＥを測定した。なお、測定は色彩色差計ＣＲ−４１０（ミノルタ（株））を用い、ＪＩＳ Ｋ５６００−４−５に準拠して行い、色差の計算はＪＩＳ Ｋ５６００−４−６に従い計算した。
Color difference ΔE
Applying the epoxy resin primer to the flexible board specified in JIS A5430 and eliminating the suction, the aqueous coating material compositions of Examples, Comparative Examples, and Reference Examples are applied in a brush amount of 150 g / m 2 . The color difference ΔE was measured between what was applied immediately after stirring and what was applied after standing for 10 minutes, 20 minutes and 30 minutes (all cured at 23 ° C. for 24 hours). The measurement was performed using a color difference meter CR-410 (Minolta Co., Ltd.) according to JIS K5600-4-5, and the color difference was calculated according to JIS K5600-4-6.
本発明の水系塗材組成物は、薄塗りであり、簡便な作業で、仕上がりと物性に優れる床防塵が水系で実現でき、大きな面積でも、塗り継ぎが目立たず、経時により発色性が同じであり、綺麗な床が得られ、たとえば食品工場の床などの、作業環境中の臭気が問題となる場合でも容易に適用することができる。 The water-based coating material composition of the present invention is thinly coated, and floor dust can be realized in water based on simple work and excellent in finish and physical properties.Even in a large area, the coating is not conspicuous, and the color developability is the same over time. Yes, a beautiful floor can be obtained and can be easily applied even when the odor in the work environment becomes a problem, such as a floor of a food factory.
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|---|---|---|---|---|
| JPS5456700A (en) * | 1977-07-18 | 1979-05-07 | Hoechst Ag | Hardening agent for aqueous epoxide resin dispersion* method and application thereof |
| JPH0987361A (en) * | 1995-09-27 | 1997-03-31 | Asahi Denka Kogyo Kk | Aqueous epoxy resin curable composition |
| JP2007002250A (en) * | 2005-06-23 | 2007-01-11 | Cognis Ip Management Gmbh | Curing agent for coating composition |
-
2011
- 2011-03-25 JP JP2011066979A patent/JP5639938B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5456700A (en) * | 1977-07-18 | 1979-05-07 | Hoechst Ag | Hardening agent for aqueous epoxide resin dispersion* method and application thereof |
| JPH0987361A (en) * | 1995-09-27 | 1997-03-31 | Asahi Denka Kogyo Kk | Aqueous epoxy resin curable composition |
| JP2007002250A (en) * | 2005-06-23 | 2007-01-11 | Cognis Ip Management Gmbh | Curing agent for coating composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096866A (en) * | 2018-06-13 | 2018-12-28 | 河北晨阳工贸集团有限公司 | A kind of water-base epoxy dumb light floor coatings and preparation method thereof |
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