JP3939717B2 - Water-soluble paint composition - Google Patents
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- JP3939717B2 JP3939717B2 JP2004255319A JP2004255319A JP3939717B2 JP 3939717 B2 JP3939717 B2 JP 3939717B2 JP 2004255319 A JP2004255319 A JP 2004255319A JP 2004255319 A JP2004255319 A JP 2004255319A JP 3939717 B2 JP3939717 B2 JP 3939717B2
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- 239000000203 mixture Substances 0.000 title claims description 11
- 239000003973 paint Substances 0.000 title description 13
- 239000008199 coating composition Substances 0.000 claims description 73
- 238000000576 coating method Methods 0.000 claims description 62
- 239000011248 coating agent Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 16
- 239000001023 inorganic pigment Substances 0.000 claims description 16
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 8
- 230000002335 preservative effect Effects 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007793 ph indicator Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- CJUOSBUQOWKEKJ-UHFFFAOYSA-N Mebhydrolin napadisilate Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O.C1N(C)CCC2=C1C1=CC=CC=C1N2CC1=CC=CC=C1.C1N(C)CCC2=C1C1=CC=CC=C1N2CC1=CC=CC=C1 CJUOSBUQOWKEKJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- -1 barita Substances 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
本発明は、水性塗料組成物に関し、より詳しくは、マーキング等の一時的な使用の後、塗膜を除去することが可能な水性塗料組成物に関する。 The present invention relates to an aqueous coating composition, and more particularly to an aqueous coating composition capable of removing a coating film after temporary use such as marking.
対象物に目視可能な塗料を一時的に付着させるマーキング手法が、玩具、文具、広告、アスファルト若しくはコンクリート舗装道路、または壁若しくは橋梁などの屋外建築物等、様々な対象に施されている。 Marking techniques for temporarily attaching a visible paint to an object are applied to various objects such as toys, stationery, advertisements, asphalt or concrete paved roads, or outdoor buildings such as walls or bridges.
一時的なマーキングは、情報を一定期間保持する目的で行われるものであり、その目的を達成した後には、本来、被塗物やその周辺環境を元どおりに復元して被塗物の美観やその周辺環境を保持することが求められる。他方、野外で行なわれるマーキングにあっては、マーキングに供した塗膜が、強い雨や、雑踏及び自動車の通過等に耐え、マーキング機能を目的とする期間保持することが求められる。 Temporary marking is performed for the purpose of retaining information for a certain period of time, and after achieving that purpose, the object and its surrounding environment must be restored to the original condition, It is required to maintain the surrounding environment. On the other hand, in the case of marking performed outdoors, it is required that the coating film used for the marking withstands heavy rain, hustle and traffic, and keeps it for a period for the purpose of marking function.
従来、屋内における一時的なマーキング目的のための手法としては、チョークと黒板と黒板ふきとをセットとするもの、あるいはマーカーペンと白板と拭き取り具とをセットとするものが広く知られている。 Conventionally, as a technique for temporary marking purposes indoors, a method using a set of chalk, a blackboard, and a blackboard wipe, or a method using a marker pen, a white plate, and a wiping tool as a set is widely known.
一方、屋外における一時的なマーキングのための手法としては、例えば、チョーク、白墨、刷毛塗りペンキ、エアゾールスプレー、ロールコート等用いて、任意の対象物に対しマーキング材料を付着することが行なわれている。 On the other hand, as a technique for temporary marking outdoors, for example, a marking material is attached to an arbitrary object using, for example, chalk, white ink, brush paint, aerosol spray, roll coat, etc. Yes.
しかし、これら従来の手法では、対象物に付着させたマーキング材料が、目的とする期間情報を保持してその目的を達した後も除去されることなく放置され、被塗物の美観や被塗物周辺の環境を損ねていたのが現状であった。 However, in these conventional methods, the marking material adhered to the object is left without being removed even after reaching the purpose while retaining the target period information, and the aesthetics of the object or the object to be coated The current situation was that the environment around things was damaged.
これに対して、本発明者は、揮発性のアルカリ物質であるアンモニアとｐＨ指示薬とを組成物中に含ませて、ｐＨ指示薬の発する色を経時的に変化させることを可能としながら、バインダーとして、水溶性且つ生分解性の水溶性セルロースを用いて、形成した塗膜を水洗で除去でき、且つ自然分解させることを可能とした、環境適応性に優れる水性塗料組成物を提案している（特許文献１）。
しかしながら、特許文献１に記載の水性塗料組成物は、バインダーとして、水溶性セルロースを用いた結果、形成される乾燥塗膜が、被塗物に付着した状態で時間の経過と共に分解されることを可能とする一方、当該乾燥塗膜が、剥離強度、耐衝撃性及び耐摩擦性の点で必ずしも充分な特性を有するものではなかった。即ち、屋外において使用される場合には、当該乾燥塗膜が、雨や雑踏及び自動車の通過等による衝撃に曝されるが、雨に曝されると水により膨潤して塗膜が破壊し易く、また雑踏及び自動車の通過等の機械的衝撃を受けると当該塗膜が比較的柔らかい塗膜であることから剥離若しくは損傷し易く、目的とする期間、所望のマーキングを保持できない場合があった。なお、セルロース系化合物は、線状で、通常高分子であり、分子が絡み易いことから、この系のバインダーに加水分解性を付与するには低分子化に寄らざるを得ず、剥離強度、耐衝撃性及び耐摩擦性を同時に付与する設計とすることは困難であった。 However, the water-based paint composition described in Patent Document 1 uses water-soluble cellulose as a binder, and as a result, the dried coating film formed is decomposed over time in a state of being attached to the object to be coated. On the other hand, the dry coating film does not necessarily have sufficient properties in terms of peel strength, impact resistance and friction resistance. That is, when used outdoors, the dried coating film is exposed to impacts such as rain, crowds, and passing cars, but when exposed to rain, the coating film is easily swelled and easily destroyed. In addition, when subjected to mechanical impacts such as crowds and passing of automobiles, the coating film is a relatively soft coating film, so that it is easily peeled off or damaged, and a desired marking may not be maintained for a target period. In addition, since the cellulose compound is linear, usually a polymer, and molecules are easily entangled, in order to impart hydrolyzability to the binder of this system, it must be reduced in molecular weight, peel strength, It has been difficult to design to impart impact resistance and friction resistance at the same time.
本発明は、このような従来技術の問題に鑑みなされたものであり、使用目的を達した後、無公害の手段で形成された乾燥塗膜を瞬時に取り除くことができるとともに除去後の塗膜をそのまま放置することで自然消滅させることができ、且つ剥離強度、耐衝撃性及び耐摩擦性が大きく、外部環境においても目的とする期間塗膜を保持することができる、塗料組成物を提供することを目的とする。 The present invention has been made in view of such problems of the prior art, and after reaching the intended purpose, the dried coating film formed by non-polluting means can be instantaneously removed and the coating film after removal A coating composition that can be naturally extinguished by leaving it as it is, has high peel strength, impact resistance, and friction resistance, and can maintain a coating film for a target period even in an external environment. For the purpose.
本発明らは、上記課題を解決するため、基本的に相反する、剥離強度、耐衝撃性及び耐摩擦性という、マーキング機能を保持するために要求される特性と、無公害の手段で任意に取り除くことができ、且つその後は自然消滅させることができるという、環境適応性のために要求される特性とを、如何にして同時に充足させるかという点について鋭意検討を重ねた結果、
顔料として、環境への還元が可能で硬度の大きな「無機」の顔料を用い、バインダーとして、ガラス転移温度−２０〜４０℃の水溶性若しくは水分散性の非セルロース系アニオン性樹脂を用い、これらを水溶性増粘剤と共に水中に分散または溶解して、水性塗料組成物を調製したところ、これにより得られる乾燥塗膜が、ジェット水流で瞬時に除去でき且つ除去した塗膜をそのまま放置することで自然分解できるばかりか、野外の環境においても１月以上所望のマーキング機能を保持できることを見出し、本発明を完成するに至った。
In order to solve the above-mentioned problems, the present inventors basically have contradictory characteristics such as peel strength, impact resistance and friction resistance, which are required to maintain the marking function, and can be arbitrarily selected by pollution-free means. As a result of earnestly examining how to satisfy simultaneously the characteristics required for environmental adaptability that can be removed and then disappeared naturally,
As a pigment, an “inorganic” pigment that can be reduced to the environment and has high hardness is used, and as a binder, a water-soluble or water-dispersible non-cellulosic anionic resin having a glass transition temperature of −20 to 40 ° C. is used. Was dispersed or dissolved in water together with a water-soluble thickener to prepare an aqueous coating composition. The resulting dried coating film could be removed instantaneously with a jet of water and the removed coating film was left as it was. It was found that the desired marking function can be maintained for one month or more in the outdoor environment, and the present invention has been completed.
すなわち、本発明は、炭酸カルシウムを主成分とする少なくとも１種の無機顔料成分（Ａ）と、少なくとも１種のガラス転移温度−２５〜４０℃の非セルロース系アニオン性樹脂からなるバインダー（Ｂ）と、少なくとも１種の水溶性増粘剤（Ｃ）と、水（Ｄ）とを含むことを特徴とする水性塗料組成物を提供するものである。ここで、本願明細書中で記載する「ガラス転移温度」は、ＤＳＣ測定器（マックサイエンス社製：３１００Ｓ型）により測定したものである。 That is, the present invention provides a binder (B) comprising at least one inorganic pigment component (A) mainly composed of calcium carbonate and at least one non-cellulosic anionic resin having a glass transition temperature of from 25 to 40 ° C. And an at least one water-soluble thickener (C) and water (D). Here, the “glass transition temperature” described in the present specification is measured with a DSC measuring instrument (manufactured by Mac Science: Model 3100S).
本発明の水性塗料組成物においては、バインダー（Ｂ）が、ガラス転移温度−２５〜３５℃の非セルロース系アニオン性樹脂であることがより好ましく、具体的には、例えば、酢酸ビニル、エチレン酢酸ビニル、水分散性アクリル樹脂、ウレタン樹脂、またはシリコンアクリル酸エステルハイブリッド樹脂等の水分散の非セルロース系アニオン性樹脂、或いは水溶性アクリル樹脂等の水溶性の非セルロース系アニオン性樹脂を挙げることができる。 In the aqueous coating composition of the present invention, the binder (B) is more preferably a non-cellulosic anionic resin having a glass transition temperature of −25 to 35 ° C. Specifically, for example, vinyl acetate, ethylene acetate Examples include water-dispersed non-cellulosic anionic resins such as vinyl, water-dispersible acrylic resins, urethane resins, or silicon acrylate hybrid resins, or water-soluble non-cellulosic anionic resins such as water-soluble acrylic resins. it can.
また、本発明の水性塗料組成物における水溶性増粘剤（Ｃ）としては、アルカリ活性型の増粘剤が好ましく、例えば、カルボキシル系コポリマー等を挙げることができる。またアルカリ活性型の増粘剤を含む場合には、更にアルカリ成分を含むものが好ましく、アルカリ成分としてはアンモニアが好ましい。 The water-soluble thickener (C) in the aqueous coating composition of the present invention is preferably an alkali-active thickener, and examples thereof include a carboxyl copolymer. Further, when an alkali-active thickener is included, one further containing an alkali component is preferable, and ammonia is preferable as the alkali component.
本発明の水性塗料組成物は、水性塗料組成物の総重量に対して、それぞれ、無機顔料（Ａ）を２０〜６５重量％、バインダー（Ｂ）を２〜６重量％（固形分換算値）、水溶性増粘剤（Ｃ）を０．５〜１．４重量％（固形分換算値）含むものが好ましい。また、アルカリ成分としてアンモニアを含む場合には水性塗料組成物の総重量に対してアンモニアを０．１〜０．６重量％含むものが好ましい。 The aqueous coating composition of the present invention is 20 to 65% by weight of the inorganic pigment (A) and 2 to 6% by weight of the binder (B) based on the total weight of the aqueous coating composition (in terms of solid content). What contains 0.5 to 1.4 weight% (solid content conversion value) of water-soluble thickener (C) is preferable. Moreover, when ammonia is included as an alkali component, what contains 0.1 to 0.6 weight% of ammonia with respect to the total weight of an aqueous coating composition is preferable.
本発明の水性塗料組成物は、更に、少なくとも１種の消泡剤及び／または少なくとも１種の防腐剤を含むものが好ましい。消泡剤を含む場合、当該消泡剤を水性塗料組成物の総重量に対して０．０５〜１．０重量％含むものが好ましく、水性塗料組成物の総重量に対して０．０５〜０．５重量％含むものがより好ましい。同様に、防腐剤を含む場合、当該防腐剤を水性塗料組成物の総重量に対して０．０２〜０．１０重量％含むものが好ましい。 The aqueous coating composition of the present invention preferably further contains at least one antifoaming agent and / or at least one preservative. When the antifoaming agent is included, the antifoaming agent preferably contains 0.05 to 1.0% by weight based on the total weight of the aqueous coating composition, and 0.05 to 1.0% based on the total weight of the aqueous coating composition. Those containing 0.5% by weight are more preferred. Similarly, when a preservative is included, the preservative preferably contains 0.02 to 0.10% by weight based on the total weight of the aqueous coating composition.
本発明は更に、上記水性塗料組成物を塗布することで得られる一時的なマーキング塗膜を提供する。 The present invention further provides a temporary marking coating film obtained by applying the aqueous coating composition.
本発明のマーキング塗膜は、圧力５〜２０Mpaで、毎分５〜２０L噴出できるノズルからの高圧ジェット水流で除去することができ、且つ除去後、自然環境で自然消滅可能なものである。 The marking coating film of the present invention can be removed with a high-pressure jet water stream from a nozzle capable of ejecting 5 to 20 L / min at a pressure of 5 to 20 MPa, and can be naturally extinguished in the natural environment after the removal.
本発明は更に、上記の水性塗料組成物を被塗物に塗布する工程を含む、一時的なマーキング方法を提供する。本発明のマーキング方法は、更に、形成された塗膜を、高圧水流で除去する工程と、除去された塗膜を自然環境に放置して自然消滅させる工程とを含むものが好ましい。 The present invention further provides a temporary marking method including the step of applying the above-mentioned aqueous coating composition to an object to be coated. The marking method of the present invention preferably further includes a step of removing the formed coating film with a high-pressure water stream and a step of allowing the removed coating film to stand in a natural environment and naturally disappear.
本発明によれば、通常の塗装手段で一時的なマーキングが可能である。加えて、本発明によれば、マーキングの目的を達した後は、マーキングに供した塗膜を高圧水流で除去できるとともに、除去した塗膜をそのまま放置すれば、跡形もなく自然消滅させることができ、無公害な手段で、被塗物及びその周辺環境を元の状態に戻すことができる。更に本発明によれば、屋外におけるマーキングであっても、マーキング機能を１月以上の期間保持することができる。 According to the present invention, it is possible to perform temporary marking with ordinary coating means. In addition, according to the present invention, after reaching the purpose of marking, the coating film used for marking can be removed with a high-pressure water flow, and if the removed coating film is left as it is, it can be naturally extinguished without a trace. The object to be coated and its surrounding environment can be returned to the original state by non-polluting means. Furthermore, according to the present invention, the marking function can be maintained for a period of one month or more even when marking is performed outdoors.
Ｉ．水性塗料組成物
本発明の水性塗料組成物は、溶媒として水（Ｄ）を用い、これに炭酸カルシウムを主成分とする少なくとも１種の無機顔料（Ａ）と、少なくとも１種のガラス転移温度−２５〜４０℃の水溶性若しくは水分散性の非セルロース系アニオン性樹脂からなるバインダー（Ｂ）と、少なくとも１種の水溶性増粘剤（Ｃ）とを必須成分として分散または溶解したものである。以下、本発明の水性塗料組成物を、各成分毎に具体的に説明する。
I. Water-based paint composition The water-based paint composition of the present invention uses water (D) as a solvent, and contains at least one inorganic pigment (A) mainly composed of calcium carbonate, and at least one glass transition temperature. A binder (B) composed of a water-soluble or water-dispersible non-cellulose anionic resin at 25 to 40 ° C. and at least one water-soluble thickener (C) are dispersed or dissolved as essential components. . Hereinafter, the water-based coating composition of the present invention will be specifically described for each component.
（Ａ）無機顔料
本発明の水性塗料組成物における無機顔料は、炭酸カルシウムを主成分とするものである。
(A) Inorganic pigment The inorganic pigment in the aqueous coating composition of the present invention is mainly composed of calcium carbonate.
（イ）炭酸カルシウムは、自然界に存在する石灰石、貝殻の主成分であるばかりか炭酸ガス存在下で水に可溶となるため、目的のマーキングを達成した後塗膜を除去してそのまま放置することで自然界に還元することができる。
（ロ）また、炭酸カルシウムは水性塗料中で白色顔料として機能するとともに、他の有色顔料と組み合わせる場合には、塗料の色彩ベースとなる体質顔料としても機能し得るので、様々なマーキング機能を付与することができる。
（ハ）更に、マーキングに供される塗膜の耐衝撃性及び耐摩擦性を増大させ、野外環境での雑踏や車の通過等の機械的衝撃に対して耐性を付与することができる。
(B) Calcium carbonate is not only the main component of natural limestone and shells but also soluble in water in the presence of carbon dioxide, so after achieving the desired marking, the coating film is removed and left as it is. It can be reduced to nature.
(B) In addition, calcium carbonate functions as a white pigment in water-based paints, and when combined with other colored pigments, it can also function as an extender pigment that serves as a color base for paints. can do.
(C) Furthermore, the impact resistance and friction resistance of the coating film used for marking can be increased, and resistance can be imparted to mechanical impacts such as crowds in the outdoor environment and passing of cars.
本発明で用いられる無機顔料は、上記（イ）〜（ハ）の点で、無機顔料の総重量に対して炭酸カルシウムを、９０重量％以上含有するものが好ましく、９４重量％以上含有するものがより好ましい。勿論、白色のマーキングを目的とする場合には、無機顔料の総重量に対して炭酸カルシウムを１００重量％含有するものが好ましい。 The inorganic pigment used in the present invention preferably contains 90% by weight or more, more preferably 94% by weight or more of calcium carbonate with respect to the total weight of the inorganic pigment in terms of (a) to (c) above. Is more preferable. Of course, when white marking is intended, it is preferable to contain 100% by weight of calcium carbonate with respect to the total weight of the inorganic pigment.
また、２種以上の無機顔料を用いる場合には、目的とするマーキング機能に応じて好適な無機顔料を炭酸カルシウムと組合せればよいが、上記（イ）乃至（ハ）の点で、組み合せる無機顔料も、天然に存在する無色顔料を選択することが好ましい。具体的には、例えば、炭酸カルシウム、シリカ、タルク、バライタ、クレイ、マイカ、ベントナイト等を挙げることができる。 In addition, when two or more kinds of inorganic pigments are used, a suitable inorganic pigment may be combined with calcium carbonate in accordance with the target marking function. However, the inorganic pigments are combined in the above points (a) to (c). As the inorganic pigment, it is preferable to select a naturally occurring colorless pigment. Specific examples include calcium carbonate, silica, talc, barita, clay, mica, bentonite and the like.
また、塗膜の基調となる色を白色以外の有色にしたい場合には、所望の色彩となるように着色顔料を炭酸カルシウムと組合せればよい。また、着色顔料としては、例えばパーマネントレッド、酸化鉄、パーマネントイエロー等を挙げることができる。 In addition, when it is desired to change the color of the coating film to a color other than white, a color pigment may be combined with calcium carbonate so as to obtain a desired color. Examples of the color pigment include permanent red, iron oxide, and permanent yellow.
無機顔料の含有量は、所望のマーキング機能を付与する上で重要であるが、その一方で塗料組成物の塗工性に大きく影響する。このため、無機顔料の量は、水性塗料組成物の総重量に対して２０〜６５重量％とすることが好ましく、３０〜６０重量％とすることがより好ましく、４０〜５０重量％とすることが最も好ましい。２０重量％未満では、塗膜の隠蔽力が小さくなりマーキングの確認が難くなり易い。またこの濃度では、塗膜の乾燥が遅くなり易い。一方、６５重量％より多くなると、平滑な塗装面を得にくく、マーキングにおける作業性や、被塗物の美観性の点で問題を生じることがある。 The content of the inorganic pigment is important for providing a desired marking function, but greatly affects the coatability of the coating composition. For this reason, the amount of the inorganic pigment is preferably 20 to 65% by weight, more preferably 30 to 60% by weight, and more preferably 40 to 50% by weight based on the total weight of the aqueous coating composition. Is most preferred. If it is less than 20% by weight, the hiding power of the coating film becomes small and it is difficult to confirm the marking. At this concentration, drying of the coating film tends to be slow. On the other hand, when it exceeds 65% by weight, it is difficult to obtain a smooth painted surface, which may cause problems in terms of workability in marking and aesthetics of the object to be coated.
（Ｂ）バインダー
本発明の塗料組成物は、バインダーとして、ガラス転移温度が−２５から４０℃、より好ましくはガラス転移温度が−２０から１０℃の水溶性若しくは水分散性の非セルロース系アニオン性樹脂を含むものである。
(B) Binder The coating composition of the present invention has a water-soluble or water-dispersible non-cellulosic anionic property having a glass transition temperature of −25 to 40 ° C., more preferably a glass transition temperature of −20 to 10 ° C., as a binder. It contains resin.
バインダーが、水溶性若しくは水分散性であることに加え、そのガラス転移温度が−２５から４０℃の非セルロース系アニオン性樹脂であるため、マーキングに供した塗膜を環境に対する影響が全くない水流で除去すること、更には除去した塗膜をそのまま放置することで自然消滅させることを可能とし、その一方で、被塗物に対する塗膜に、所望の期間のマーキングを達成する上で充分な剥離強度を付与することができる。 In addition to being water-soluble or water-dispersible, the binder is a non-cellulosic anionic resin having a glass transition temperature of −25 to 40 ° C. In addition, it is possible to allow the film to be removed spontaneously by leaving it as it is, and to remove the film sufficiently to achieve the desired period of marking on the film to be coated. Strength can be imparted.
このようなバインダーとしては、例えば、酢酸ビニル、エチレン酢酸ビニル、水分散性アクリル樹脂、ウレタン樹脂、またはシリコンアクリル酸エステルハイブリッド樹脂等の水分散性の非セルロース系アニオン性樹脂、或いは水溶性アクリル樹脂等の水溶性の非セルロース系アニオン性樹脂等を挙げることができ、これらの１種または２種以上を塗料組成物中に含有させることができる。本発明においては、これらバインダーの中でも、塗膜を剥離した後、塗膜が自然環境中の水分により迅速に分解して自然に戻り易い点で、酢酸ビニル樹脂またはエチレン酢酸ビニル樹脂系共重合体が好ましい。 Examples of such a binder include water-dispersible non-cellulosic anionic resins such as vinyl acetate, ethylene vinyl acetate, water-dispersible acrylic resins, urethane resins, and silicon acrylate hybrid resins, or water-soluble acrylic resins. Water-soluble non-cellulosic anionic resins and the like, and one or more of these can be contained in the coating composition. In the present invention, among these binders, a vinyl acetate resin or an ethylene vinyl acetate resin-based copolymer is used in that the coating film is rapidly decomposed by moisture in the natural environment and easily returns to the natural state after peeling the coating film. Is preferred.
もっとも、より長期間のマーキング機能を保持することを要求される場合には、アクリル樹脂を使用することも好ましい。但し、アクリル樹脂を含有する場合には、アクリル樹脂のガラス転移温度が４０℃を超えると、特に高圧水流による後処理において塗膜を除去し難くなるので、ガラス転移温度を４０℃以内にすることに特に注意すべきである。 However, when it is required to maintain a marking function for a longer period, it is also preferable to use an acrylic resin. However, when the acrylic resin is contained, if the glass transition temperature of the acrylic resin exceeds 40 ° C., it becomes difficult to remove the coating film particularly in the post-treatment with a high-pressure water flow, so the glass transition temperature should be within 40 ° C. Special attention should be paid to.
バインダーの量は、塗料組成物の粘度（塗工性、塗膜の美観性に関わる）及び除去後における乾燥塗膜の分解性（多量の樹脂を含有すると、完全に分解することが困難に成り易い）の点から、水性塗料組成物の総重量に対して樹脂固形換算値で２〜６重量％とすることが好ましく、２〜５重量％とすることがより好ましく、１〜４重量％とすることが最も好ましい。 The amount of the binder is such that the viscosity of the coating composition (related to coating properties and coating aesthetics) and the decomposability of the dried coating after removal (including a large amount of resin makes it difficult to completely decompose). From the point of easy), it is preferably 2 to 6% by weight, more preferably 2 to 5% by weight, more preferably 1 to 4% by weight based on the total weight of the aqueous coating composition. Most preferably.
（Ｃ）増粘剤
本発明の水性塗料組成物は、所望の塗工性を付与する一方、マーキング終了後の塗膜の除去及び分解を確保するため、水溶性の増粘剤を含有する。
(C) Thickener The water-based coating composition of the present invention contains a water-soluble thickener in order to provide desired coating properties while ensuring removal and decomposition of the coating film after completion of marking.
本発明の水性塗料組成物における増粘剤は、水溶性のものであればよく、例えば、ベンナイト、メチルセルロース若しくはその誘導体、カゼイン若しくはその塩、カルボキシル系コポリマー、ヒドロキシル系コポリマー等、一般的な水溶性の増粘剤を使用することができる。本発明においては、経時的な沈降に対する安定性が高い点で、アルカリ活性タイプのカルボキシル系コポリマーが好ましく、この場合には、水性塗料組成物中に更にアルカリ成分を含有するものが好ましい。 The thickener in the water-based coating composition of the present invention may be water-soluble, for example, general water-soluble such as bennite, methylcellulose or a derivative thereof, casein or a salt thereof, a carboxyl copolymer, a hydroxyl copolymer, and the like. Thickeners can be used. In the present invention, an alkali-active type carboxyl copolymer is preferable in terms of high stability against sedimentation over time, and in this case, an aqueous coating composition further containing an alkali component is preferable.
アルカリ活性タイプの水系増粘剤と共にアルカリ成分を含有する場合、当該アルカリ成分は、本発明の水性塗料組成物のｐＨを６．５〜１１．０の範囲に調節できるものであればよく、例えば苛性ソーダ、アンモニア等の一般的なアルカリ成分を含有することができる。中でも、乾燥塗膜の耐水性を上げることができ、延いては外部環境でのマーキング機能保持期間を延長できる点で、アンモニア等の揮発性のアルカリが好ましい。 In the case of containing an alkali component together with an alkaline active type water-based thickener, the alkali component only needs to be capable of adjusting the pH of the aqueous coating composition of the present invention to a range of 6.5 to 11.0. Common alkali components such as caustic soda and ammonia can be contained. Among these, volatile alkalis such as ammonia are preferable in that the water resistance of the dried coating film can be increased and the marking function retention period in the external environment can be extended.
また、水溶性増粘剤（Ｃ）の含有量は、バインダーの含有量について述べた点と同様の点で水性塗料組成物の総重量に対して固形換算値で０．５〜１．４重量％とすることが好ましく、０．８〜１．２重量％とすることがより好ましい。 Further, the content of the water-soluble thickener (C) is 0.5 to 1.4% in terms of solids with respect to the total weight of the aqueous coating composition in the same manner as described for the content of the binder. %, And more preferably 0.8 to 1.2% by weight.
また、アルカリ活性タイプの増粘剤と共にアルカリ成分を含有する場合、アルカリ成分の含有量は、アルカリ中和による増粘剤の増粘力を発揮させるため、水性塗料組成物のｐＨが６．５〜１１．０の範囲になる量にすることが好ましい。例えば、アルカリ活性タイプのカルボキシル系コポリマーエマルジョンを含有することでｐＨが３〜５となっている水性塗料組成物の場合には、水性塗料組成物におけるアンモニアNH３濃度を０．０５６〜０．１１２重量％の範囲とすることが好ましい。この場合、例えば、２８重量％のアンモニア水を用い、当該アンモニア水を水性塗料組成物の総重量に対して０．２〜０．４重量％の範囲で添加すればよい。 Further, when an alkali component is contained together with the alkali active type thickener, the pH of the aqueous coating composition is 6.5 because the content of the alkali component exerts the thickening power of the thickener by alkali neutralization. The amount is preferably in the range of ˜11.0. For example, in the case of an aqueous coating composition having a pH of 3 to 5 by containing an alkali active type carboxyl copolymer emulsion, the ammonia NH 3 concentration in the aqueous coating composition is 0.056 to 0.112. It is preferable to set it as the range of weight%. In this case, for example, 28% by weight of ammonia water is used, and the ammonia water may be added in a range of 0.2 to 0.4% by weight with respect to the total weight of the aqueous coating composition.
もっとも、水性塗料組成物に対して要求される粘度は、はけ塗り、印刷等、それを塗工する手段によって異なる。従って、目的に応じて、アンモニアの含有量を適宜増減して組成物の粘度を調節することが好ましい。また、インキ・塗料における通常の調整法に準じて、塗料組成物の変更、希釈などを行って、目的とする粘度に調整することもできる。例えば、刷毛塗りで所望のマーク（文字など）を塗装する場合には、アルカリ成分の含有量や増粘剤の濃度を調整して水性塗料組成物を２００〜６００ｍPa・secの粘度に調整することが好ましい。なお、本発明の塗料組成物は、塗布するまで初期の粘度を保持するため、アンモニア等の揮発成分や水の揮発、飛散などを防ぐことが好ましく、本発明の塗料組成物を保存する際には、密閉容器で保存することが望ましい。もっとも、使用直前に溶媒で希釈して所望の粘度とすることも可能である。 However, the viscosity required for the water-based coating composition varies depending on the means for applying it, such as brushing or printing. Therefore, it is preferable to adjust the viscosity of the composition by appropriately increasing or decreasing the ammonia content according to the purpose. In addition, the viscosity can be adjusted to the target viscosity by changing or diluting the coating composition according to the usual adjustment method for inks and coatings. For example, when applying a desired mark (letters, etc.) by brushing, adjust the content of the alkali component and the concentration of the thickener to adjust the aqueous coating composition to a viscosity of 200 to 600 mPa · sec. Is preferred. In addition, since the coating composition of the present invention maintains the initial viscosity until it is applied, it is preferable to prevent volatilization components such as ammonia, water volatilization and scattering, and the like, when storing the coating composition of the present invention. Is preferably stored in a sealed container. However, it is also possible to dilute with a solvent immediately before use to obtain a desired viscosity.
（Ｄ）水
本発明の水性塗料組成物は、上記した各有効成分をバランス量の水に配合することにより水性塗料組成物としている。
含有させる水は、脱イオン水や蒸留水の他、水道水であってもよい。もっとも、使用する水が比較的多くの電解質を含んでいる場合には、水性塗料組成物の安定性が損なわれることがあるため、脱イオン水が好ましく、水道水を使用する際には、電解質の量が４０μＳ/ｃｍ以下のものが好ましい。また、水の含有量は、水性塗料組成物の総重量に対して４０〜７０重量％とすることが好ましく、４５〜６５重量％とすることがより好ましい。
(D) Water The water-based coating composition of the present invention is made into a water-based coating composition by blending each of the above-mentioned active ingredients in a balanced amount of water.
The water to be contained may be tap water in addition to deionized water or distilled water. However, when the water to be used contains a relatively large amount of electrolyte, the stability of the aqueous coating composition may be impaired. Therefore, deionized water is preferable. Is preferably 40 μS / cm or less. The water content is preferably 40 to 70% by weight and more preferably 45 to 65% by weight with respect to the total weight of the aqueous coating composition.
（Ｅ）付加的成分
本発明の水性塗料組成物は、以上の成分を必須成分とするが、更に種々の付加的成分を添加することができる。
(E) Additional component Although the aqueous coating composition of this invention makes the above component an essential component, a various additional component can be further added.
例えば、上記各必須成分を攪拌し塗料組成物とする際に発生する泡を抑えるため、少なくとも１種の消泡剤を含ませることができ、微生物やバクテリアの発生による腐敗を防止するために、少なくとも１種の防腐剤を含ませることができる。これら消泡剤及び防腐剤の種類に関し特に制限はないが、消泡剤としてはシリコン系のものが好ましく、防腐剤としては、ジアゾリン系のものが好ましい。 For example, at least one antifoaming agent can be included in order to suppress foam generated when the essential components are stirred to form a coating composition, and in order to prevent spoilage due to generation of microorganisms and bacteria, At least one preservative can be included. Although there is no restriction | limiting in particular regarding the kind of these antifoamer and antiseptic | preservative, A silicon type thing is preferable as an antifoamer, and a diazoline type thing is preferable as an antiseptic | preservative.
また、これら付加的成分を添加する場合、消泡剤の量は、水性塗料組成物の総重量に対して０．０５〜１．００重量％とすることが好ましく、０．１〜０．２がより好ましい。また、防腐剤の量は、水性塗料組成物の総重量に対して０．０２〜０．１０重量％とすることが好ましい。もっとも、これら付加的成分の最適な含有量は、水性塗料組成物の各必須成分との相性に支配されるので、含有する各必須成分の種類に応じて好適な量を含有させることが好ましい。 Moreover, when adding these additional components, it is preferable that the quantity of an antifoamer shall be 0.05-1.00 weight% with respect to the total weight of an aqueous coating composition, 0.1-0.2 Is more preferable. The amount of the preservative is preferably 0.02 to 0.10% by weight based on the total weight of the aqueous coating composition. However, since the optimum content of these additional components is governed by the compatibility with each essential component of the aqueous coating composition, it is preferable to contain a suitable amount depending on the type of each essential component contained.
次に、本発明の水性塗料組成物を製造する方法について説明する。なお、以下に示す方法は、本発明の水性塗料生成物を製造するための一具体例に過ぎず、この方法以外の方法及び成分を用いて製造することも可能である。 Next, the method for producing the aqueous coating composition of the present invention will be described. In addition, the method shown below is only one specific example for producing the water-based paint product of the present invention, and can be produced using methods and components other than this method.
まず、溶媒として電解質を含有しない水を用い、これにアルカリ活性型の水溶性増粘剤を加え１〜１０分攪拌溶解させる。次いで、アルカリ中和による増粘効果を出すためにアンモニア水を加え、撹拌時の発泡を抑制するために消泡剤を加え５〜１５分攪拌し溶解する。更に溶解液に炭酸カルシウムを加え２０〜４０分攪拌した後、メディア型分散機で粒度２０〜５０μmまで分散させる。最後に、分散液に、水、水溶性若しくは水分散性の非セルロース系アニオン性樹脂のエマルジョン、防腐剤の順で添加した後１０〜３０分攪拌し、水性塗料組成物とする。 First, water that does not contain an electrolyte is used as a solvent, and an alkali-active water-soluble thickener is added thereto and stirred and dissolved for 1 to 10 minutes. Next, ammonia water is added to obtain a thickening effect by alkali neutralization, and an antifoaming agent is added to suppress foaming during stirring, and the mixture is stirred and dissolved for 5 to 15 minutes. Further, calcium carbonate is added to the solution and stirred for 20 to 40 minutes, and then dispersed to a particle size of 20 to 50 μm with a media type dispersing machine. Finally, water, a water-soluble or water-dispersible non-cellulosic anionic resin emulsion, and an antiseptic are added in this order, followed by stirring for 10 to 30 minutes to obtain an aqueous coating composition.
ＩＩ．マーキング方法
次に本発明の水性塗料組成物を用いたマーキング方法について説明する。
本発明のマーキング方法は、本発明の水性塗料組成物を被塗物へ塗布する他は特に制限はなく、従来インキや塗料等に適用されている公知の塗布方法により被塗物へ本発明の水性塗料組成物を塗布すればよい。
II. Marking method Next, a marking method using the aqueous coating composition of the present invention will be described.
The marking method of the present invention is not particularly limited except that the aqueous coating composition of the present invention is applied to the object to be coated, and the coating method of the present invention can be applied to the object by a known coating method applied to conventional inks and paints. An aqueous coating composition may be applied.
もっとも、本発明の水性塗料組成物は、前述したように、乾燥後に得られる塗膜が、高圧水流で除去することができ、且つ除去された塗膜が自然環境で自然消滅可能なものである。よって、本発明のマーキング方法にあっても、更に、形成された塗膜を、高圧水流で除去する工程を含むことが好ましく、更に除去された塗膜を自然環境に放置して自然消滅させる工程を含むことがより好ましい。 However, as described above, in the aqueous coating composition of the present invention, the coating film obtained after drying can be removed with a high-pressure water stream, and the removed coating film can naturally disappear in the natural environment. . Therefore, even in the marking method of the present invention, it is preferable that the method further includes a step of removing the formed coating film with a high-pressure water stream, and a step of allowing the removed coating film to stand in the natural environment and naturally disappear. It is more preferable to contain.
本発明のマーキング方法においては、被塗物の種類についても特に制限はない。本発明の塗料組成物を塗布することによって被塗物が著しく損傷を受けるような材質のものでなければ、形状・表面状態の如何にかかわらず塗布できる。
また、本発明のマーキング方法においては、塗膜の厚さに関しても特に制限はなく、インキ・塗料分野における通常の手法にしたがって、重ね塗りを行うことも可能である。
In the marking method of the present invention, there is no particular limitation on the type of the object to be coated. If the material to be coated is not significantly damaged by applying the coating composition of the present invention, it can be applied regardless of the shape and surface state.
In the marking method of the present invention, the thickness of the coating film is not particularly limited, and it is possible to perform overcoating according to a usual method in the ink / paint field.
ＩＩＩ．乾燥塗膜
以上のような本発明の水性塗料組成物及びそれを用いるマーキング方法により形成される乾燥塗膜は、外部環境でマーキングに供された場合でも、所望の期間、より具体的には１月以上、マーキング機能を保持し得るものである。そして、目的とするマーキングを達成した後には、高圧の水流、より具体的には、例えば、圧力５〜２０Mpaで、毎分５〜２０L噴出できるノズルからの高圧ジェット水流で除去でき、更に除去後の塗膜は、自然分解によって一定期間経過後に消滅し環境に還元できるものである。従って、本発明の乾燥塗膜によれば、充分なマーキング期間を確保できるとともに、マーキング終了後には、被塗物及びその周辺環境を簡易且つ無公害の手段で復元することができる。
III. Dry coating film The above-described water-based coating composition of the present invention and the dry coating film formed by the marking method using the same, even when subjected to marking in an external environment, more specifically 1 The marking function can be maintained for more than a month. And after achieving the target marking, it can be removed with a high-pressure water stream, more specifically, a high-pressure jet water stream from a nozzle that can eject 5 to 20 L / min. The coating film disappears after a certain period by natural decomposition and can be reduced to the environment. Therefore, according to the dried coating film of the present invention, a sufficient marking period can be ensured, and the object to be coated and its surrounding environment can be restored by simple and non-polluting means after completion of marking.
このような本発明の特徴は、主に、炭酸ガス存在化で水に可溶であり、且つ硬度の大きな炭酸カルシウムを主成分とし、更に当該主成分のバインダーとして、水溶性若しくは水分散性で、所定のガラス転移温度を有する非セルロース系アニオン性樹脂を含むことに基づく。 Such a feature of the present invention is mainly soluble in water in the presence of carbon dioxide gas, and has a high hardness as calcium carbonate as a main component, and further as a binder of the main component as water-soluble or water-dispersible. Based on containing a non-cellulosic anionic resin having a predetermined glass transition temperature.
以下、本発明を実施例に基づき更に説明するが、本発明はこれら実施例に何等限定されるものではない。 EXAMPLES Hereinafter, although this invention is further demonstrated based on an Example, this invention is not limited to these Examples at all.
（実施例１）
２０００mlのビーカーに水道水３５０重量％を入れ、これにアルカリ活性型の水溶性増粘剤（カルボキシルコポリマー、チバスペシャリティケミカル（株）、ビスカレックスHV30）０．９重量％を加え、１〜２分間攪拌をした。次に、攪拌しながらアルカリ中和による増粘効果を出すためにアンモニア水（アンモニア濃度２８重量％）０．３重量％（アンモニア換算値０．０８４重量％）を少量づつ加え、消泡剤（ビニルポリマー等、楠本化成（株）、ディスパロンAQ-500）を０．０５重量％加え均一に混合した。続けて炭酸カルシウム（白石工業（株）、ホワイトンH）４５重量％を加え、３０分間攪拌を続け、炭酸カルシウムを分散させた。この白色分散液をメディア型分散機で粒度２０〜５０μmになるまで分散させた。得られた分散液を攪拌しながら水道水１６重量％と、バインダーとしてガラス転移温度−２０℃のエチレン酢酸ビニル樹脂のエマルジョン（昭和高分子（株）、ポリゾールＰ−７）３重量％（固形分換算では１．５重量％）と、防腐剤（化合物名：ベンゾイソジアゾリン、アビシア（株）、Proxel BD２０）０．２重量％とを添加し、２０分間攪拌して、水性塗料組成物（１）を得た。得られた塗料組成物の粘度を、B型粘度計により測定したところ、５６０ｍPa・secであった。
Example 1
Place 350% by weight of tap water in a 2000 ml beaker, and add 0.9% by weight of alkali-active water-soluble thickener (carboxyl copolymer, Ciba Specialty Chemicals Co., Ltd., Biscarex HV30) for 1-2 minutes. Stir. Next, in order to produce a thickening effect by alkali neutralization while stirring, 0.3% by weight of ammonia water (ammonia concentration: 28% by weight) (ammonia conversion value: 0.084% by weight) is added little by little. 0.05% by weight of vinyl polymer, etc. (Enomoto Kasei Co., Ltd., Disparon AQ-500) was added and mixed uniformly. Subsequently, 45% by weight of calcium carbonate (Shiraishi Kogyo Co., Ltd., Whiten H) was added, and stirring was continued for 30 minutes to disperse the calcium carbonate. This white dispersion was dispersed with a media-type disperser until the particle size became 20 to 50 μm. While stirring the obtained dispersion, 16% by weight of tap water and 3% by weight (solid content) of an ethylene vinyl acetate resin emulsion (Showa High Polymer Co., Ltd., Polysol P-7) having a glass transition temperature of -20 ° C as a binder. 1.5 wt% in terms of conversion) and 0.2 wt% of an antiseptic (compound name: benzoisodiazoline, Avicia Co., Ltd., Proxel BD20) are added and stirred for 20 minutes to form an aqueous coating composition ( 1) was obtained. It was 560 mPa * sec when the viscosity of the obtained coating composition was measured with the B-type viscometer.
この塗料組成物（１）を用いて、当工場内の原料及び製品のトラックが毎日１００台程度の頻度で出入りするアスファルト道路及びコンクリート道路、並びに実験中１１日間雨に曝されたコンクリート壁、木材、および鉄板に、それぞれ、屋外において、降雨時を避けて塗料用刷毛で文字をマーキングし、マーキング後の塗膜（文字）の経時変化を観察した。その結果、何れの被塗物でも、塗膜を高圧洗浄機で除去するまでの１ヶ月間、マーキング機能を保持した。また、高圧洗浄機を用い、この塗膜に向けて圧力７Mpaで毎分７Lの高圧ジェット水流を噴出したところ、当該塗膜を除去することができた。更に除去した塗膜のスラッジを地面に放置したところ、約１年で跡形もなく消失することが確認された。 Using this coating composition (1), asphalt roads and concrete roads where trucks of raw materials and products in this factory come in and out at a frequency of about 100 every day, and concrete walls and wood exposed to rain for 11 days during the experiment Each of the iron plate and the iron plate was marked outdoors with a paint brush while avoiding rain, and the change with time of the coating film (characters) after the marking was observed. As a result, in any object, the marking function was maintained for one month until the coating film was removed with a high-pressure washing machine. Moreover, when a high pressure jet water flow of 7 L / min was ejected toward the coating film at a pressure of 7 Mpa using a high pressure washer, the coating film could be removed. Furthermore, when the sludge of the removed coating film was left on the ground, it was confirmed that it disappeared without a trace in about one year.
（比較例１）
実施例１において、バインダーとしてガラス転移温度−２０℃のエチレン酢酸ビニル樹脂に代え、水溶性セルロースエーテル（ガラス転移温度１４０℃、信越化学工業（株）、メトローズ６５ＳＨ−４０００）を添加したこと以外は実施例１と同様にして水性塗料組成物（２）を得た。
(Comparative Example 1)
In Example 1, instead of ethylene vinyl acetate resin having a glass transition temperature of −20 ° C. as a binder, water-soluble cellulose ether (glass transition temperature 140 ° C., Shin-Etsu Chemical Co., Ltd., Metrolose 65SH-4000) was added. In the same manner as in Example 1, an aqueous coating composition (2) was obtained.
この塗料組成物（２）を用いて、実施例１と同様にマーキングを行なったところ、約１週間程で何れの被塗物でも乾燥塗膜に剥離若しくは損傷が認められマーキング機能を保持できなかった。 Using this coating composition (2), marking was carried out in the same manner as in Example 1. As a result, peeling or damage was observed on the dried coating film and the marking function could not be maintained in about one week. It was.
（比較例２）
実施例１において、バインダーとしてガラス転移温度−２０℃のエチレン酢酸ビニル樹脂に代え、ガラス転移温度７７℃のアクリル樹脂のエマルジョン（大成ファインケミカル（株）社製、アクリットＷＥＭ０３０Ｕ）を添加したこと以外は実施例１と同様にして水性塗料組成物（３）を得た。
(Comparative Example 2)
In Example 1, instead of ethylene vinyl acetate resin having a glass transition temperature of −20 ° C. as a binder, an emulsion of acrylic resin having a glass transition temperature of 77 ° C. (Acrit WEM030U, manufactured by Taisei Fine Chemical Co., Ltd.) was added. In the same manner as in Example 1, an aqueous coating composition (3) was obtained.
この塗料組成物（３）を用いて、実施例１と同様にマーキングを行なったところ、何れの被塗物でも、塗膜を高圧洗浄機で除去するまでの１ヶ月間、マーキング機能を保持した。しかし、この塗膜を高圧洗浄機で除去することはできず、被塗物を元の状態に復元する事ができなかった。 Using this coating composition (3), marking was performed in the same manner as in Example 1. As a result, the marking function was maintained for one month until the coating film was removed with a high-pressure washing machine. . However, this coating film could not be removed with a high-pressure washing machine, and the object to be coated could not be restored to its original state.
以上述べたように、本発明の水性塗料組成物及びそれを用いるマーキング法で得られる塗膜は、野外で用いられた場合でも充分な期間マーキング機能を保持することができ、且つマーキングの目的を達した後、直ちに高圧水流で除去することができる。加えて高圧水流で除去した塗膜は、そのまま放置するだけで一定期間経過後に消失し環境に還元する。このため、本発明の水性塗料組成物及びそれを用いるマーキング法は、アスファルトまたはコンクリート舗装上になされる一時的な標識、壁や橋梁などの屋外構築物の修理位置を表示するためのマーキングなどに好適に用いられる。 As described above, the water-based paint composition of the present invention and the coating film obtained by the marking method using the same can maintain a marking function for a sufficient period even when used outdoors, and the purpose of marking is as follows. Once reached, it can be removed immediately with a high pressure water stream. In addition, the coating film removed by the high-pressure water flow disappears after a certain period of time and is reduced to the environment simply by leaving it as it is. For this reason, the water-based paint composition of the present invention and the marking method using the same are suitable for temporary marking on asphalt or concrete pavement, marking for indicating the repair position of outdoor structures such as walls and bridges, etc. Used for.
Claims (11)
該組成物の総重量に対して、それぞれ、該無機顔料（Ａ）を２０〜６５重量％、該バインダー（Ｂ）を１〜４重量％（固形分換算値）、前記水溶性増粘剤（Ｃ）を０．５〜１．４重量％（固形分換算値）含む、マーキング用水性塗料組成物。 A binder comprising at least one inorganic pigment component (A) mainly composed of calcium carbonate and at least one water-soluble or water-dispersible non-cellulosic anionic resin having a glass transition temperature of −25 to 40 ° C. An aqueous coating composition for marking comprising (B), at least one water-soluble thickener (C), and water (D),
The inorganic pigment (A) is 20 to 65% by weight, the binder (B) is 1 to 4 % by weight (in terms of solid content), and the water-soluble thickener (based on the total weight of the composition). A water-based coating composition for marking containing 0.5 to 1.4% by weight (in terms of solid content) of C).
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