JP2017186489A - Chitosan-containing pigmented coating, chitosan-containing pigmented gel particle, and coating composition - Google Patents
Chitosan-containing pigmented coating, chitosan-containing pigmented gel particle, and coating composition Download PDFInfo
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- 239000007863 gel particle Substances 0.000 title claims abstract description 77
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 76
- 239000008199 coating composition Substances 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title abstract description 17
- 238000000576 coating method Methods 0.000 title abstract description 17
- 150000004676 glycans Chemical class 0.000 claims abstract description 29
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 29
- 239000005017 polysaccharide Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000003086 colorant Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 12
- 239000003973 paint Substances 0.000 claims description 63
- 239000002612 dispersion medium Substances 0.000 description 31
- 239000000839 emulsion Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000000049 pigment Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004606 Fillers/Extenders Substances 0.000 description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003349 gelling agent Substances 0.000 description 6
- -1 halide ions Chemical class 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 235000010981 methylcellulose Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000006196 deacetylation Effects 0.000 description 3
- 238000003381 deacetylation reaction Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000161 Locust bean gum Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000711 locust bean gum Substances 0.000 description 2
- 235000010420 locust bean gum Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OYINQIKIQCNQOX-UHFFFAOYSA-M 2-hydroxybutyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCC(O)C[N+](C)(C)C OYINQIKIQCNQOX-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000008886 Ceratonia siliqua Species 0.000 description 1
- 235000013912 Ceratonia siliqua Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000698776 Duma Species 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- DJXRIQMCROIRCZ-XOEOCAAJSA-N vibegron Chemical compound C1([C@H]([C@@H]2N[C@H](CC=3C=CC(NC(=O)[C@H]4N5C(=O)C=CN=C5CC4)=CC=3)CC2)O)=CC=CC=C1 DJXRIQMCROIRCZ-XOEOCAAJSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、キトサン含有着色塗料、キトサン含有着色ゲル粒子および塗料組成物に関する。 The present invention relates to a chitosan-containing colored paint, a chitosan-containing colored gel particle, and a paint composition.
液状またはゲル状の2色以上の着色粒子が懸濁した多彩模様塗料は、1回の塗装で散らし模様ができることから、壁材等の装飾に利用されている。
多彩模様塗料等に用いられるゲル状の着色粒子(着色ゲル粒子)として、キトサンと酸水溶液と着色剤とを含む着色塗料を用いたものが知られている。このような着色塗料においては、キトサンと酸とがイオン錯体を形成しており、塩化カルシウム水溶液等の分散媒と接触させると、着色塗料の表面がゲル化してキトサン膜が形成される(例えば特許文献1)。
しかし、特許文献1に記載の着色ゲル粒子は安定が低い問題がある。例えば、該着色ゲル粒子を含有する塗料の保管時に、着色ゲル粒子同士が付着して再分散できなくなったり、着色ゲル粒子から漏れ出した着色剤によって塗料が濁ったりする。その結果、鮮明な多彩模様が得られない問題があった。A multicolored paint in which colored particles of two or more colors in a liquid or gel form are suspended is used for decoration of wall materials and the like because it can be scattered by one application.
As gel-like colored particles (colored gel particles) used for multicolored paints and the like, those using a colored paint containing chitosan, an acid aqueous solution and a colorant are known. In such a colored paint, chitosan and an acid form an ionic complex, and when contacted with a dispersion medium such as an aqueous calcium chloride solution, the surface of the colored paint gels to form a chitosan film (for example, a patent) Reference 1).
However, the colored gel particles described in Patent Document 1 have a problem of low stability. For example, when the paint containing the colored gel particles is stored, the colored gel particles adhere to each other and cannot be redispersed, or the paint becomes cloudy due to the colorant leaking from the colored gel particles. As a result, there was a problem that a clear and colorful pattern could not be obtained.
本発明は、上記事情に鑑みてなされたものであって、安定性に優れたキトサン含有着色ゲル粒子が得られるキトサン含有着色塗料、安定性に優れたキトサン含有着色ゲル粒子およびこれを用いた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 the above circumstances, and provides chitosan-containing colored paint particles capable of obtaining chitosan-containing colored gel particles excellent in stability, chitosan-containing colored gel particles excellent in stability, and a paint using the same An object is to provide a composition.
本発明は、以下の態様を有する。
[1]キトサンと、酸と、水と、四級アンモニウム塩基を有するカチオン化多糖類と、着色剤とを含むことを特徴とするキトサン含有着色塗料。
[2]前記カチオン化多糖類の含有量が、前記キトサン100質量部に対して6.0〜200質量部である[1]に記載のキトサン含有着色塗料。
[3]前記[1]または[2]に記載のキトサン含有着色塗料を用いたキトサン含有着色ゲル粒子。
[4]前記[3]に記載のキトサン含有着色ゲル粒子を含む塗料組成物。The present invention has the following aspects.
[1] A chitosan-containing colored paint comprising chitosan, an acid, water, a cationized polysaccharide having a quaternary ammonium base, and a colorant.
[2] The chitosan-containing colored paint according to [1], wherein the content of the cationized polysaccharide is 6.0 to 200 parts by mass with respect to 100 parts by mass of the chitosan.
[3] Chitosan-containing colored gel particles using the chitosan-containing colored paint described in [1] or [2].
[4] A coating composition containing the chitosan-containing colored gel particles according to [3].
本発明のキトサン含有着色塗料によれば、安定性に優れたキトサン含有着色ゲル粒子が得られる。
本発明のキトサン含有着色ゲル粒子は、安定性に優れる。
本発明の塗料組成物に含まれるキトサン含有着色ゲル粒子は、安定性に優れる。According to the colored paint containing chitosan of the present invention, colored gel particles containing chitosan excellent in stability can be obtained.
The chitosan-containing colored gel particles of the present invention are excellent in stability.
The chitosan-containing colored gel particles contained in the coating composition of the present invention are excellent in stability.
<キトサン含有着色塗料>
本発明のキトサン含有着色塗料(以下、単に「着色塗料」とも記す。)は、キトサンと、酸と、水と、四級アンモニウム塩基を有するカチオン化多糖類と、着色剤とを含む。<Colored paint containing chitosan>
The chitosan-containing colored paint of the present invention (hereinafter also simply referred to as “colored paint”) contains chitosan, an acid, water, a cationized polysaccharide having a quaternary ammonium base, and a colorant.
キトサンとしては、特に限定されず、市販品を用いることができる。
キトサンの脱アセチル化度は、希酸への溶解性の点から、75%以上が好ましい。キトサンの脱アセチル化度は、コロイド滴定法により測定される。
キトサンの分子量は、100万以上が好ましい。分子量が前記範囲の下限値以上であれば得られる着色ゲル粒子の強度が優れる。キトサンの分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定される標準プルラン(例えば昭和電工株式会社製)換算の重量平均分子量である。It does not specifically limit as chitosan, A commercial item can be used.
The degree of deacetylation of chitosan is preferably 75% or more from the viewpoint of solubility in dilute acid. The degree of deacetylation of chitosan is measured by a colloid titration method.
The molecular weight of chitosan is preferably 1 million or more. If the molecular weight is at least the lower limit of the above range, the strength of the colored gel particles obtained is excellent. The molecular weight of chitosan is a weight average molecular weight in terms of standard pullulan (for example, manufactured by Showa Denko KK) measured by gel permeation chromatography (GPC).
酸は、キトサンと酸とのイオン錯体を形成し、キトサンを水に溶解させるために用いられる。着色塗料を後述する分散媒に接触させたときに、着色塗料の表面でイオン錯体がゲル化し、キトサンを含む皮膜が形成される。
酸としては、水に溶解し、キトサンとイオン錯体を形成するものであれば特に限定されず、例えば塩酸、硝酸等の無機酸;酢酸、ギ酸、アクリル酸、乳酸、リンゴ酸、グルタミン酸等の有機酸等が挙げられる。これらの酸は1種単独で用いてもよく2種以上を併用してもよい。これらの中では、臭気とコストの点で、乳酸、リンゴ酸、塩酸が好ましい。The acid forms an ionic complex of chitosan and acid, and is used to dissolve chitosan in water. When the colored paint is brought into contact with a dispersion medium described later, the ion complex gels on the surface of the colored paint, and a film containing chitosan is formed.
The acid is not particularly limited as long as it dissolves in water and forms an ionic complex with chitosan. For example, inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid, formic acid, acrylic acid, lactic acid, malic acid, and glutamic acid An acid etc. are mentioned. These acids may be used alone or in combination of two or more. Among these, lactic acid, malic acid, and hydrochloric acid are preferable in terms of odor and cost.
カチオン化多糖類は、カチオン性基を有する多糖類である。本発明においてはカチオン性基として少なくとも四級アンモニウム塩基を有する多糖類が用いられる。四級アンモニウム塩基を有するカチオン化多糖類が着色塗料に含まれることで、得られるキトサン含有着色ゲル粒子の安定性が優れる。
カチオン化多糖類としては、例えば、カチオン化ヒドロキシエチルセルロース、カチオン化グアルゴム、カチオン化ローカストビーンガム等が挙げられる。The cationized polysaccharide is a polysaccharide having a cationic group. In the present invention, a polysaccharide having at least a quaternary ammonium base as a cationic group is used. When the cationized polysaccharide having a quaternary ammonium base is contained in the colored paint, the stability of the resulting chitosan-containing colored gel particles is excellent.
Examples of the cationized polysaccharide include cationized hydroxyethyl cellulose, cationized guar gum, and cationized locust bean gum.
四級アンモニウム塩基としては、例えば下記式(1)で表される基が挙げられる。
−N+R1R2R3・X−・・・(1)
式中、R1〜R3はそれぞれ独立にアルキル基を示し、X−は対イオンを示す。
R1〜R3におけるアルキル基としては、例えばメチル基、エチル基等が挙げられる。
X−としては、四級アンモニウムイオンと塩を形成可能なものであればよく、例えばCl−、F−、Br−、I−等のハロゲン化物イオン等が挙げられる。Examples of the quaternary ammonium base include a group represented by the following formula (1).
-N + R 1 R 2 R 3 · X − (1)
In the formula, R 1 to R 3 each independently represents an alkyl group, and X − represents a counter ion.
Examples of the alkyl group in R 1 to R 3 include a methyl group and an ethyl group.
X − is not particularly limited as long as it can form a salt with a quaternary ammonium ion, and examples thereof include halide ions such as Cl − , F − , Br − and I − .
カチオン化多糖類における四級アンモニウム塩基の含有量は、デュマ法により測定される窒素の値として、0.4〜3.0重量%が好ましく、1.0〜2.0重量%がより好ましい。 The content of the quaternary ammonium base in the cationized polysaccharide is preferably 0.4 to 3.0% by weight, more preferably 1.0 to 2.0% by weight as the value of nitrogen measured by the Dumas method.
カチオン化多糖類は、市販のものを用いることができる。公知の方法により製造したものを用いてもよい。例えばグリシジルトリメチルアンモニウムクロライド等のカチオン化剤と多糖類とを反応させることでカチオン化多糖類が得られる。 Commercially available cationized polysaccharides can be used. You may use what was manufactured by the well-known method. For example, a cationized polysaccharide can be obtained by reacting a cationizing agent such as glycidyltrimethylammonium chloride with a polysaccharide.
着色剤としては、例えばカーボンブラック、酸化チタン、酸化鉄、クロム酸鉛、カドミウムイエロー、カドミウムレッド等の無機顔料;パール顔料、マイカ顔料、マイカコーティングパール顔料、アルミニウム粉、ステンレス粉等の光輝性顔料;フタロシアニンブルー、フタロシアニングリーン、キナクリドンレッド等の有機顔料等が挙げられる。これら着色剤は1種単独で用いてもよく2種以上を併用してもよい。 Examples of the colorant include inorganic pigments such as carbon black, titanium oxide, iron oxide, lead chromate, cadmium yellow, and cadmium red; bright pigments such as pearl pigments, mica pigments, mica-coated pearl pigments, aluminum powder, and stainless steel powder. Organic pigments such as phthalocyanine blue, phthalocyanine green, and quinacridone red; These colorants may be used alone or in combination of two or more.
本発明の着色塗料は、必要に応じて、本発明の効果を損なわない範囲で、キトサン、酸、前記カチオン化多糖類および着色剤以外の他の成分をさらに含んでいてもよい。他の成分としては、例えば樹脂エマルション、体質顔料、公知の添加剤等が挙げられる。
樹脂エマルションとしては、一般に市販されている樹脂エマルションを使用することができ、例えばポリ酢酸ビニル、アクリル樹脂、ポリスチレン、アクリロニトリル、ベオバ(分岐脂肪酸ビニルエステル)、天然又は合成ゴムや、それらの共重合体のエマルション等が挙げられる。これらの樹脂エマルションは1種単独で用いてもよく2種以上を併用してもよい。中でも、アクリル樹脂のエマルションが好ましい。
体質顔料としては、例えばカオリン、硫酸バリウム、含水ケイ酸マグネシウム、炭酸カルシウム等が挙げられる。これらの体質顔料は1種単独で用いてもよく2種以上を併用してもよい。
添加剤としては、例えば増粘剤、分散剤、消泡剤、防腐剤、レベリング剤等が挙げられる。The colored paint of the present invention may further contain other components other than chitosan, acid, the cationized polysaccharide and the colorant, as necessary, as long as the effects of the present invention are not impaired. Examples of other components include resin emulsions, extender pigments, and known additives.
As the resin emulsion, commercially available resin emulsions can be used. For example, polyvinyl acetate, acrylic resin, polystyrene, acrylonitrile, beova (branched fatty acid vinyl ester), natural or synthetic rubber, and copolymers thereof And the like. These resin emulsions may be used alone or in combination of two or more. Among them, an acrylic resin emulsion is preferable.
Examples of extender pigments include kaolin, barium sulfate, hydrous magnesium silicate, and calcium carbonate. These extender pigments may be used alone or in combination of two or more.
Examples of the additive include a thickener, a dispersant, an antifoaming agent, a preservative, and a leveling agent.
本発明の着色塗料中、酸の含有量は、キトサン100質量部に対して20〜150質量部が好ましく、60〜90質量部がより好ましい。酸の含有量が前記範囲の下限値以上であれば、キトサンの溶解性が良好で、前記範囲の上限値以下であれば、着色ゲル粒子の強度が良好である。 In the colored paint of the present invention, the acid content is preferably 20 to 150 parts by mass, more preferably 60 to 90 parts by mass with respect to 100 parts by mass of chitosan. If the acid content is at least the lower limit of the above range, the chitosan solubility is good, and if it is below the upper limit of the above range, the strength of the colored gel particles is good.
本発明の着色塗料中、水の含有量は、着色塗料の全質量(100質量%)に対して40〜97質量%が好ましい。 In the colored paint of the present invention, the content of water is preferably 40 to 97% by mass with respect to the total mass (100% by mass) of the colored paint.
本発明の着色塗料中、前記カチオン化多糖類の含有量は、キトサン100質量部に対して6.0〜200質量部が好ましく、6.0〜100質量部がより好ましく、6.0〜50質量部がさらに好ましい。前記カチオン化多糖類の含有量が前記範囲の下限値以上であれば、キトサン含有着色ゲル粒子の安定性がより優れる。前記カチオン化多糖類の含有量が前記範囲の上限値以下であれば、キトサン含有着色ゲル粒子の強度が高く、この着色ゲル粒子を含む塗料組成物の塗装時に、スプレー法で塗装した場合でも、キトサン含有着色ゲル粒子の形状が崩れにくい。そのため、形成される塗膜におけるキトサン含有着色ゲル粒子由来の模様が鮮明になる。 In the colored paint of the present invention, the content of the cationized polysaccharide is preferably 6.0 to 200 parts by mass, more preferably 6.0 to 100 parts by mass, and more preferably 6.0 to 50 parts by mass with respect to 100 parts by mass of chitosan. Part by mass is more preferable. If content of the said cationized polysaccharide is more than the lower limit of the said range, stability of chitosan containing colored gel particle will be more excellent. If the content of the cationized polysaccharide is less than or equal to the upper limit of the range, the strength of the colored gel particles containing chitosan is high, even when the coating composition containing the colored gel particles is applied, even when applied by a spray method, The shape of chitosan-containing colored gel particles is difficult to collapse. Therefore, a pattern derived from chitosan-containing colored gel particles in the formed coating film becomes clear.
本発明の着色塗料中、着色剤の含有量は、キトサンと酸と水と前記カチオン化多糖類との合計100質量部に対して、0.01〜50質量部が好ましく、0.1〜30質量部がより好ましい。 In the colored paint of the present invention, the content of the colorant is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts per 100 parts by mass in total of chitosan, acid, water and the cationized polysaccharide. Part by mass is more preferable.
本発明の着色塗料は、キトサンと、酸と、水と、前記カチオン化多糖類と、着色剤と、必要に応じて他の成分とを混合することにより調製できる。各成分の混合順序は特に限定されない。例えば、酸の水溶液にキトサンおよび前記カチオン化多糖類を加えて撹拌混合し、得られた混合物に着色顔料を加えて撹拌混合することで本発明の着色塗料を得ることができる。 The colored paint of the present invention can be prepared by mixing chitosan, acid, water, the cationized polysaccharide, a colorant, and other components as necessary. The mixing order of each component is not particularly limited. For example, the colored paint of the present invention can be obtained by adding chitosan and the cationized polysaccharide to an aqueous acid solution and stirring and mixing, adding a color pigment to the resulting mixture and stirring and mixing.
(作用効果)
以上説明した着色塗料にあっては、キトサンと、酸と、水と、着色剤とを含むため、後述するように分散媒と接触させることで、キトサン含有着色ゲル粒子が得られる。また、四級アンモニウム塩基を有するカチオン化多糖類を含むため、得られるキトサン含有着色ゲル粒子の安定性が優れる。
例えば、本発明の着色塗料を用いて得られるキトサン含有着色ゲル粒子は、塗料組成物中で長期間保管されたときに、着色ゲル粒子同士の凝集が生じにくい。保管中に着色ゲル粒子が沈降しても、塗料組成物を振とうさせる等の簡単な操作で、着色ゲル粒子を分散媒に再分散させることができる。また、保管中に着色ゲル粒子から着色剤が漏れ出して塗料組成物が濁る等の不具合が生じにくい。
また、本発明の着色塗料を用いて得られるキトサン含有着色ゲル粒子は、強度に優れる。特に、カチオン化多糖類の含有量がキトサン100質量部に対して6.0〜100質量部の範囲内である場合には、スプレー塗装のような、キトサン含有着色ゲル粒子にかかる負荷が大きい塗装方法で塗料組成物を塗布した場合でも、キトサン含有着色ゲル粒子の形状が崩れにくい。そのため、キトサン含有着色ゲル粒子に由来して塗膜に形成される模様が鮮明になる。したがって、キトサン含有着色ゲル粒子は、塗料中だけでなく単独で保管したときの安定性にも優れる。(Function and effect)
Since the above-described colored paint contains chitosan, acid, water, and a colorant, chitosan-containing colored gel particles can be obtained by contacting with a dispersion medium as described later. Moreover, since the cationized polysaccharide which has a quaternary ammonium base is included, the stability of the obtained chitosan containing colored gel particle is excellent.
For example, chitosan-containing colored gel particles obtained using the colored paint of the present invention are less likely to aggregate between the colored gel particles when stored for a long time in the coating composition. Even if the colored gel particles settle during storage, the colored gel particles can be re-dispersed in the dispersion medium by a simple operation such as shaking the coating composition. In addition, problems such as the colorant leaking from the colored gel particles during storage and the coating composition becoming cloudy are unlikely to occur.
The chitosan-containing colored gel particles obtained using the colored paint of the present invention are excellent in strength. In particular, when the content of the cationized polysaccharide is in the range of 6.0 to 100 parts by mass with respect to 100 parts by mass of chitosan, coating with a large load on the chitosan-containing colored gel particles, such as spray coating. Even when the coating composition is applied by the method, the shape of the chitosan-containing colored gel particles is difficult to collapse. Therefore, the pattern formed in the coating film derived from the chitosan-containing colored gel particles becomes clear. Accordingly, the chitosan-containing colored gel particles are excellent in stability not only in the paint but also when stored alone.
<キトサン含有着色ゲル粒子>
本発明のキトサン含有着色ゲル粒子(以下、単に「着色ゲル粒子」とも記す。)は、前述の本発明の着色塗料を用いたものである。
本発明の着色塗料に分散媒を接触させると、着色塗料の表面がゲル化して皮膜が形成される。これにより、皮膜と該皮膜に内包された着色塗料とから構成される着色ゲル粒子が得られる。この皮膜には少なくともキトサンおよびカチオン化多糖類が含まれる。
着色ゲル粒子の形状としては、特に限定されない。<Colored gel particles containing chitosan>
The chitosan-containing colored gel particles of the present invention (hereinafter also simply referred to as “colored gel particles”) are those using the above-described colored paint of the present invention.
When the dispersion medium is brought into contact with the colored paint of the present invention, the surface of the colored paint is gelled to form a film. Thereby, the colored gel particle comprised from the membrane | film | coat and the colored coating material included in this membrane | film | coat is obtained. This film contains at least chitosan and a cationized polysaccharide.
The shape of the colored gel particles is not particularly limited.
(分散媒)
分散媒は、ゲル化剤を含む水溶液である。
ゲル化剤としては、水酸化ナトリウム等のアルカリ金属塩、塩化カルシウム等のアルカリ土類金属塩、アンモニア水等が挙げられる。これらゲル化剤は、1種単独で用いてもよく、2種以上を併用してもよい。これらの中でも塩化カルシウムが好ましい。(Dispersion medium)
The dispersion medium is an aqueous solution containing a gelling agent.
Examples of the gelling agent include alkali metal salts such as sodium hydroxide, alkaline earth metal salts such as calcium chloride, and aqueous ammonia. These gelling agents may be used alone or in combination of two or more. Of these, calcium chloride is preferred.
分散媒は、必要に応じて、ゲル化剤以外の他の成分を含んでいてもよい。
他の成分としては、例えば水溶性高分子化合物、体質顔料、公知の添加剤等が挙げられる。
水溶性高分子化合物としては、例えばヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ポリビニルアルコール等が挙げられる。中でもカルボキシメチルセルロースまたはメチルセルロースが好ましい。
体質顔料としては、着色塗料の説明において先に例示した体質顔料が挙げられる。
添加剤としては、着色塗料の説明において先に例示した添加剤が挙げられる。The dispersion medium may contain components other than the gelling agent as required.
Examples of other components include water-soluble polymer compounds, extender pigments, and known additives.
Examples of the water-soluble polymer compound include hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol and the like. Of these, carboxymethylcellulose or methylcellulose is preferred.
The extender includes the extender exemplified above in the description of the colored paint.
As an additive, the additive illustrated previously in description of a colored coating material is mentioned.
分散媒中、ゲル化剤の含有量は、分散媒の全質量(100質量%)に対し、0.1〜5質量%が好ましく、0.5〜3質量%がより好ましい。ゲル化剤の含有量が上記範囲内であれば、安定した皮膜が得られやすくなる。 0.1-5 mass% is preferable with respect to the total mass (100 mass%) of a dispersion medium, and, as for content of a gelatinizer in a dispersion medium, 0.5-3 mass% is more preferable. When the content of the gelling agent is within the above range, a stable film is easily obtained.
分散媒中、水溶性高分子化合物の含有量は、分散媒の全質量(100質量%)に対し、0.05〜3質量%が好ましい。 In the dispersion medium, the content of the water-soluble polymer compound is preferably 0.05 to 3% by mass with respect to the total mass (100% by mass) of the dispersion medium.
分散媒は、例えば、ゲル化剤を含む水溶液を用意し、必要に応じて水溶性高分子化合物を含む水溶液、体質顔料を含む分散液等とを撹拌混合し、水を加えて希釈することにより得られる。 The dispersion medium is prepared by, for example, preparing an aqueous solution containing a gelling agent, stirring and mixing an aqueous solution containing a water-soluble polymer compound, a dispersion containing an extender pigment, and the like, if necessary, and adding water to dilute. can get.
(着色ゲル粒子の製造方法)
本発明の着色ゲル粒子は、本発明の着色塗料と分散媒とを接触させる工程を経て製造される。本発明の着色ゲル粒子の製造方法としては、例えば以下の(1)〜(3)の方法が挙げられる。
(1)本発明の着色塗料の乾燥膜を形成し、該乾燥膜を分散媒に浸漬してゲル化させ、ゲル化した膜を分散媒から引き上げて任意の大きさに切断する方法。
(2)本発明の着色塗料を分散媒に投入し、ディソルバ等の分散機で撹拌しながら細分化する方法。
(3)本発明の着色塗料を、製造する着色ゲル粒子の形状に成形し、成形した着色塗料を乾燥させることなく分散媒に移動させる方法。(Method for producing colored gel particles)
The colored gel particles of the present invention are produced through a step of bringing the colored paint of the present invention into contact with a dispersion medium. Examples of the method for producing the colored gel particles of the present invention include the following methods (1) to (3).
(1) A method of forming a dried film of the colored paint of the present invention, immersing the dried film in a dispersion medium to cause gelation, and lifting the gelled film from the dispersion medium to cut it into an arbitrary size.
(2) A method in which the colored paint of the present invention is charged into a dispersion medium and subdivided while stirring with a disperser such as a dissolver.
(3) A method in which the colored paint of the present invention is formed into the shape of the colored gel particles to be produced, and the formed colored paint is transferred to a dispersion medium without drying.
上記(3)の方法において、着色塗料を所定の形状に成形する方法としては、例えば、印刷等により着色塗料を担体上に塗布し、該着色塗料を担体ごと、または担体から分離させて分散媒へ移動させるする方法(特開2015−71733号公報)、所定の形状の網の目を有する網状体を着色塗料に浸漬し、引き上げて網の目に着色塗料の膜を張り、該網状体を分散媒に浸漬して着色塗料の膜を分散媒に移動させる方法(特開2015−813337号公報)、着色塗料をノズルで分散媒へ直接滴下し移動させる方法等が挙げられる。
担体上または網状体の網の目に形成する着色塗料の膜の厚さは、特に制限されないが、通常、10〜300μm程度である。In the above method (3), as a method for forming the colored paint into a predetermined shape, for example, the colored paint is applied on a carrier by printing or the like, and the colored paint is separated from the carrier or from the carrier. (Japanese Patent Laid-Open No. 2015-71733), a net having a mesh of a predetermined shape is dipped in a colored paint, pulled up to apply a film of the colored paint to the mesh, and the net Examples thereof include a method of immersing in a dispersion medium to move the colored paint film to the dispersion medium (Japanese Patent Laid-Open No. 2015-81337), a method of directly dropping the colored paint onto the dispersion medium with a nozzle, and the like.
The thickness of the colored paint film formed on the carrier or the mesh of the mesh is not particularly limited, but is usually about 10 to 300 μm.
上記(2)、(3)の方法では、着色ゲル粒子が分散媒に分散した分散液が得られる。この分散液をそのまま塗料組成物の調製に用いてもよいし、分散液から着色ゲル粒子を回収し、回収した着色ゲル粒子を塗料組成物の調製に用いてもよい。 In the methods (2) and (3), a dispersion liquid in which colored gel particles are dispersed in a dispersion medium is obtained. This dispersion may be used as it is for the preparation of the coating composition, or the colored gel particles may be recovered from the dispersion and the recovered colored gel particles may be used for the preparation of the coating composition.
≪塗料組成物≫
本発明の塗料組成物は、前述の本発明の着色ゲル粒子を含む。
塗料組成物に含まれる着色ゲル粒子は1種でもよく2種以上でもよい。塗料組成物が色調の異なる2種以上の着色ゲル粒子を含む場合、該塗料組成物を多彩模様塗料として用いることができる。≪Paint composition≫
The coating composition of the present invention contains the aforementioned colored gel particles of the present invention.
The colored gel particles contained in the coating composition may be one type or two or more types. When the coating composition contains two or more kinds of colored gel particles having different color tones, the coating composition can be used as a multicolor paint.
塗料組成物には、着色ゲル粒子を分散する分散媒が含まれる。塗料組成物の分散媒としては、水、着色ゲル粒子の説明において挙げた分散媒等が挙げられる。
塗料組成物には、必要に応じて、樹脂エマルション、公知の添加剤等が含まれてもよい。塗料組成物が樹脂エマルションを含む場合、樹脂エマルションに含まれる水が塗料組成物の分散媒を兼ねてもよい。
樹脂エマルションは、バインダの役割を果たす。樹脂エマルションとしては、着色塗料の説明において先に例示した樹脂エマルションが挙げられ、アクリル樹脂エマルションが好ましい。
添加剤としては、着色塗料の説明において先に例示した添加剤が挙げられる。The coating composition contains a dispersion medium for dispersing the colored gel particles. Examples of the dispersion medium of the coating composition include water and the dispersion medium mentioned in the description of the colored gel particles.
The coating composition may contain a resin emulsion, a known additive, and the like as necessary. When the coating composition contains a resin emulsion, water contained in the resin emulsion may also serve as a dispersion medium for the coating composition.
The resin emulsion serves as a binder. Examples of the resin emulsion include the resin emulsions exemplified above in the description of the colored paint, and an acrylic resin emulsion is preferable.
As an additive, the additive illustrated previously in description of a colored coating material is mentioned.
塗料組成物中、着色ゲル粒子の含有量は、特に限定されないが、塗料組成物の全質量(100質量%)に対し、5〜80質量%が好ましい。 Although content of a coloring gel particle is not specifically limited in a coating composition, 5-80 mass% is preferable with respect to the total mass (100 mass%) of a coating composition.
塗料組成物中、樹脂エマルションの含有量は、固形分換算量として、塗料組成物の全質量(100質量%)に対し、10〜50質量%が好ましい。樹脂エマルションの含有量が上記範囲内であれば、塗料組成物の塗装作業性がよく、耐久性のよい塗膜が得られる。 In the coating composition, the content of the resin emulsion is preferably 10 to 50% by mass with respect to the total mass (100% by mass) of the coating composition as a solid content conversion amount. When the content of the resin emulsion is within the above range, a coating film with good coating workability and durability can be obtained.
以下、実施例により本発明をさらに詳しく説明する。ただし本発明は、以下の実施例に限定されるものではない。
なお、以下の各例中、「部」は「質量部」を示し、「%」は「質量%」を示す。
各例で使用した材料を以下に示す。Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In the following examples, “part” indicates “part by mass” and “%” indicates “% by mass”.
The materials used in each example are shown below.
<使用材料>
キトサン:甲陽ケミカル株式会社製「コーヨーキトサンSK−200」、脱アセチル化度90%、分子量200万。
カチオン化HEC:塩化O−[2−ヒドロキシ−3−(トリメチルアンモニオ)プロピル]ヒドロキシエチルセルロース、ライオン・スペシャリティ・ケミカルズ社製「レオガード(登録商標)MLP」。
カチオン化ローカストビーンガム:ローカストビーンヒドロキシプロピルトリモニウムクロリド、東邦化学工業株式会社製「カチナール(登録商標)CLB−100」。
HEC:ヒドロキシエチルセルロース、ダイセルファインケム社製「HECダイセルSP600」。
カチオン化PVA:四級アンモニウム塩基含有変性ポリビニルアルコール、日本合成化学社製「ゴーセネックス(登録商標)K−434」。
PVA:ポリビニルアルコール、日本合成化学社製「ゴーセノール(登録商標)GM−14」。
CMC:カルボキシメチルセルロース、ダイセルファインケム社製「CMCダイセル2260」。
メチルセルロース水溶液:信越化学工業株式会社製「メトローズ(登録商標)SM−25」。
アクリル樹脂エマルション:DIC株式会社製「ボンコート(登録商標)CF−6140」。<Materials used>
Chitosan: “Koyo Chitosan SK-200” manufactured by Koyo Chemical Co., Ltd., deacetylation degree 90%, molecular weight 2 million.
Cationized HEC: O- [2-Hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose chloride, “Leogard® MLP” manufactured by Lion Specialty Chemicals.
Cationized locust bean gum: locust bean hydroxypropyltrimonium chloride, “Kachinal (registered trademark) CLB-100” manufactured by Toho Chemical Industries, Ltd.
HEC: Hydroxyethyl cellulose, “HEC Daicel SP600” manufactured by Daicel Finechem.
Cationized PVA: Modified polyvinyl alcohol containing quaternary ammonium base, “GOHSEX (registered trademark) K-434” manufactured by Nippon Synthetic Chemical Co., Ltd.
PVA: polyvinyl alcohol, “GOHSENOL (registered trademark) GM-14” manufactured by Nippon Synthetic Chemical Co., Ltd.
CMC: Carboxymethylcellulose, “CMC Daicel 2260” manufactured by Daicel Finechem.
Methylcellulose aqueous solution: “Metroses (registered trademark) SM-25” manufactured by Shin-Etsu Chemical Co., Ltd.
Acrylic resin emulsion: “Boncoat (registered trademark) CF-6140” manufactured by DIC Corporation.
<実施例1〜7、比較例1〜4>
(着色塗料の製造)
表1〜2に示す組成に従い、以下の手順で各材料を混合して着色塗料を製造した。
5%乳酸水溶液を入れたステンレス容器に、表1〜2中の乳酸水溶液および着色剤以外の材料を添加し、室温にて90分間攪拌し、透明な液体を得た。その後、着色剤を添加し、着色塗料を得た。<Examples 1-7, Comparative Examples 1-4>
(Manufacture of colored paint)
According to the composition shown in Tables 1-2, each material was mixed in the following procedures to produce a colored paint.
Materials other than the lactic acid aqueous solution and the colorant shown in Tables 1 and 2 were added to a stainless steel container containing a 5% aqueous lactic acid solution, and stirred at room temperature for 90 minutes to obtain a transparent liquid. Thereafter, a colorant was added to obtain a colored paint.
(着色ゲル粒子の製造)
塩化カルシウム水溶液とメチルセルロース水溶液とを混合して、塩化カルシウム濃度1%、メチルセルロース濃度0.8%の分散媒200gを調製した。
上記着色塗料100gを上記分散媒200gと接触させて、着色ゲル粒子の水分散液を得た。着色塗料と分散媒との接触は、着色塗料を0.2mmのスペーサーを両端に貼り付けたアクリル板しごき塗りを行い、アクリル板ごと分散媒に浸漬し、分散媒中でアクリル板から着色ゲル粒子を剥離することによって行った。
上記着色ゲル粒子の水分散液から、濾過にて着色ゲル粒子を回収した。
幅2mm長さ10mm厚み0.2mmの着色ゲル粒子が多数得られた。(Production of colored gel particles)
A calcium chloride aqueous solution and a methylcellulose aqueous solution were mixed to prepare 200 g of a dispersion medium having a calcium chloride concentration of 1% and a methylcellulose concentration of 0.8%.
100 g of the colored paint was brought into contact with 200 g of the dispersion medium to obtain an aqueous dispersion of colored gel particles. The contact between the colored paint and the dispersion medium is performed by ironing the acrylic paint with a 0.2 mm spacer pasted on both ends, dipping the acrylic board together with the dispersion medium, and coloring gel particles from the acrylic board in the dispersion medium. It was performed by peeling off.
The colored gel particles were collected from the aqueous dispersion of the colored gel particles by filtration.
Many colored gel particles having a width of 2 mm, a length of 10 mm, and a thickness of 0.2 mm were obtained.
(塗料組成物の製造および評価)
上記着色ゲル粒子100部に対してアクリル樹脂エマルション80部を添加し、塗料組成物を得た。
得られた塗料組成物について、以下の評価を行った。ただし、安定性評価の結果が×であった比較例1〜4については、スプレー評価は行わなかった。結果を表1〜2に示す。(Manufacture and evaluation of coating compositions)
80 parts of an acrylic resin emulsion was added to 100 parts of the colored gel particles to obtain a coating composition.
The following evaluation was performed about the obtained coating composition. However, no spray evaluation was performed on Comparative Examples 1 to 4 in which the result of the stability evaluation was x. The results are shown in Tables 1-2.
「安定性評価」
塗料組成物を、50℃にて1ヶ月間保管した。保管後の塗料組成物中の着色ゲル粒子の安定状態(着色ゲル粒子同士の凝集のない均一な状態であるかどうか、着色ゲル粒子の膜の破れに伴う塗料組成物の濁りがないかどうか)を目視にて確認し、以下の基準で安定性を評価した。
○:着色ゲル粒子が均一な状態であり、再分散できる。
×:着色ゲル粒子が不均一な状態であり、塗料組成物に濁りがある。"Stability evaluation"
The coating composition was stored at 50 ° C. for 1 month. The stable state of the colored gel particles in the coating composition after storage (whether the colored gel particles are in a uniform state without aggregation between the colored gel particles, or whether the coating composition is not turbid due to the tearing of the colored gel particle film) Was visually confirmed, and the stability was evaluated according to the following criteria.
○: Colored gel particles are in a uniform state and can be redispersed.
X: The colored gel particles are in a non-uniform state, and the coating composition is turbid.
「スプレー評価」
基材(アクリル板)の表面に、上記安定性評価で50℃、1ヶ月間保管した後の塗料組成物をスプレーにより塗布し、常温で乾燥して塗膜を形成した。得られた塗膜の状態(着色ゲル粒子による模様の鮮明さ)を目視にて確認し、以下の基準で評価した。塗膜の模様が鮮明であることは、着色ゲル粒子の強度が高く、スプレー塗装時に着色ゲル粒子の形状が崩れなかったことを示す。
○:塗膜の模様が鮮明であった。
×:塗膜の模様に不鮮明な部分があった。"Spray evaluation"
On the surface of the substrate (acrylic plate), the coating composition after being stored at 50 ° C. for 1 month in the above-described stability evaluation was applied by spraying, and dried at room temperature to form a coating film. The state of the obtained coating film (the clearness of the pattern by the colored gel particles) was visually confirmed and evaluated according to the following criteria. A clear coating pattern indicates that the strength of the colored gel particles is high, and the shape of the colored gel particles did not collapse during spray coating.
○: The pattern of the coating film was clear.
X: The pattern of the coating film had an unclear part.
上記結果に示すように、実施例1〜7で得られた着色ゲル粒子は、塗料中での安定性に優れていた。特に、カチオン化多糖類の含有量がキトサン100質量部に対して6.0〜100質量部である実施例1〜5、7の着色ゲル粒子は強度が高く、スプレー塗装時に形状が崩れなかった。
一方、四級アンモニウム塩基を有するカチオン化多糖類の代わりにカチオン化されていない多糖類を用いた比較例1、多糖類ではないカチオン化高分子化合物を用いた比較例2、アニオン化多糖類を用いた比較例3の着色ゲル粒子は、それらを用いていない比較例4と同様、安定性が悪かった。As shown in the above results, the colored gel particles obtained in Examples 1 to 7 were excellent in stability in the paint. In particular, the colored gel particles of Examples 1 to 5 and 7 in which the content of the cationized polysaccharide is 6.0 to 100 parts by mass with respect to 100 parts by mass of chitosan has high strength, and the shape did not collapse during spray coating. .
On the other hand, Comparative Example 1 using a non-cationized polysaccharide instead of a cationized polysaccharide having a quaternary ammonium base, Comparative Example 2 using a cationized polymer compound that is not a polysaccharide, The colored gel particles of Comparative Example 3 used were poor in stability as in Comparative Example 4 not using them.
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