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 PDF

Info

Publication number
JP2017186489A
JP2017186489A JP2016083208A JP2016083208A JP2017186489A JP 2017186489 A JP2017186489 A JP 2017186489A JP 2016083208 A JP2016083208 A JP 2016083208A JP 2016083208 A JP2016083208 A JP 2016083208A JP 2017186489 A JP2017186489 A JP 2017186489A
Authority
JP
Japan
Prior art keywords
chitosan
gel particles
colored
coating composition
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2016083208A
Other languages
Japanese (ja)
Other versions
JP6638534B2 (en
Inventor
雄太 四ツ▲柳▼
Yuta Yotsuyanagi
雄太 四ツ▲柳▼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujikura Kasei Co Ltd
Original Assignee
Fujikura Kasei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujikura Kasei Co Ltd filed Critical Fujikura Kasei Co Ltd
Priority to JP2016083208A priority Critical patent/JP6638534B2/en
Publication of JP2017186489A publication Critical patent/JP2017186489A/en
Application granted granted Critical
Publication of JP6638534B2 publication Critical patent/JP6638534B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Paints Or Removers (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a chitosan-containing pigmented coating capable of obtaining chitosan-containing pigmented gel particles excellent in stability; chitosan-containing pigmented gel particles excellent in stability; and a coating composition using the same.SOLUTION: There are provided a chitosan-containing pigmented coating which contains cationized polysaccharides having chitosan, acid, water and quaternary ammonium base, and a coloring agent; chitosan-containing pigmented gel particles using the chitosan-containing pigmented coating; and a coating composition containing the chitosan-containing pigmented gel particles.SELECTED DRAWING: None

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.

特開2003−306646号公報JP 2003-306646 A

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・X・・・(1)
式中、R〜R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。
〜R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。
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.

Figure 2017186489
Figure 2017186489

Figure 2017186489
Figure 2017186489

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.

Claims (4)

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。  A chitosan-containing colored paint comprising chitosan, an acid, water, a cationized polysaccharide having a quaternary ammonium base, and a colorant. 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質量部である請求項1に記載のキトサン含有着色塗料。  The chitosan-containing colored paint according to claim 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. 請求項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。  A chitosan-containing colored gel particle using the chitosan-containing colored paint according to claim 1. 請求項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。  A coating composition comprising the chitosan-containing colored gel particles according to claim 3.
JP2016083208A 2016-03-31 2016-03-31 Chitosan-containing colored paint, chitosan-containing colored gel particles and coating composition Active JP6638534B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016083208A JP6638534B2 (en) 2016-03-31 2016-03-31 Chitosan-containing colored paint, chitosan-containing colored gel particles and coating composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2016083208A JP6638534B2 (en) 2016-03-31 2016-03-31 Chitosan-containing colored paint, chitosan-containing colored gel particles and coating composition

Publications (2)

Publication Number Publication Date
JP2017186489A true JP2017186489A (en) 2017-10-12
JP6638534B2 JP6638534B2 (en) 2020-01-29

Family

ID=60043868

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2016083208A Active JP6638534B2 (en) 2016-03-31 2016-03-31 Chitosan-containing colored paint, chitosan-containing colored gel particles and coating composition

Country Status (1)

Country Link
JP (1) JP6638534B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024096016A1 (en) * 2022-10-31 2024-05-10 綜研化学株式会社 Polysaccharide-containing particle production method, precursor polysaccharide-containing particles, and polysaccharide-containing particles

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130021A (en) * 1996-08-13 1998-05-19 Tioxide Specialties Ltd Zinc oxide dispersion system
JP2003306646A (en) * 2002-04-16 2003-10-31 Kowa Chem Ind Co Ltd Chitosan-containing water-based multi-color pattern coating composition
JP2007070601A (en) * 2005-08-08 2007-03-22 Sk Kaken Co Ltd Paint composition for multi-color design
JP2015071733A (en) * 2013-10-04 2015-04-16 藤倉化成株式会社 Method of producing pattern coating composition
JP2015081283A (en) * 2013-10-22 2015-04-27 藤倉化成株式会社 Method for producing pattern coating composition
JP2015081337A (en) * 2013-10-24 2015-04-27 藤倉化成株式会社 Method for producing pattern coating composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130021A (en) * 1996-08-13 1998-05-19 Tioxide Specialties Ltd Zinc oxide dispersion system
JP2003306646A (en) * 2002-04-16 2003-10-31 Kowa Chem Ind Co Ltd Chitosan-containing water-based multi-color pattern coating composition
JP2007070601A (en) * 2005-08-08 2007-03-22 Sk Kaken Co Ltd Paint composition for multi-color design
JP2015071733A (en) * 2013-10-04 2015-04-16 藤倉化成株式会社 Method of producing pattern coating composition
JP2015081283A (en) * 2013-10-22 2015-04-27 藤倉化成株式会社 Method for producing pattern coating composition
JP2015081337A (en) * 2013-10-24 2015-04-27 藤倉化成株式会社 Method for producing pattern coating composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024096016A1 (en) * 2022-10-31 2024-05-10 綜研化学株式会社 Polysaccharide-containing particle production method, precursor polysaccharide-containing particles, and polysaccharide-containing particles
WO2024095351A1 (en) * 2022-10-31 2024-05-10 綜研化学株式会社 Precursor polysaccharide-containing particles, polysaccharide-containing particles, and method for producing polysaccharide-containing particles

Also Published As

Publication number Publication date
JP6638534B2 (en) 2020-01-29

Similar Documents

Publication Publication Date Title
JP5705481B2 (en) Aqueous drawing material composition
JP5552694B2 (en) Water-based paint composition and coating film formed therefrom
JP2006199726A (en) Multi-color pattern coating material, method for producing the same and pigment dispersion
CN103849278A (en) Preparation method of water-in-water multicolor paint
CN106833081B (en) A kind of phosphorous flame-retardant agent dispersing liquid and preparation method thereof
JP2018203908A (en) Aqueous multicolor pattern coating composition and multicolor pattern coated film
JP6638534B2 (en) Chitosan-containing colored paint, chitosan-containing colored gel particles and coating composition
JP5827582B2 (en) Aqueous drawing material composition
KR100874574B1 (en) Manufacturing method of water resistant molding material and water resistant molding material
WO2021111537A1 (en) Water-soluble sheet-like coloring material, water-soluble sheet-like coloring material set, and paint set
JP7091148B2 (en) Water-soluble sheet-like coloring material
JP2013139585A (en) Water-based coating composition and coated film formed from the same
JP2525197B2 (en) Colored paint composition
JP6167845B2 (en) Method for producing pattern coating composition
JP6183128B2 (en) Method for producing pattern coating composition
WO2024146035A1 (en) Water-based flashing paint for exterior wall and preparation method therefor
CN104693878A (en) Coating thickener
EP0624181B1 (en) A single- or multicoloured water paint
JP6740681B2 (en) Method for producing patterned coating composition
JP2021130764A (en) Aqueous multicolor coating composition and multicolor coated film
JP6201624B2 (en) Method for producing pattern coating composition
JP7406969B2 (en) Water-soluble sheet color materials, water-soluble sheet sets, and paint sets
CN105419506B (en) A kind of dumb light emulsion paint and preparation method thereof
JP7329661B2 (en) Water-soluble sheet-like coloring material
JP2022077645A (en) Coating film and photoluminescent coating composition

Legal Events

Date Code Title Description
RD03 Notification of appointment of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7423

Effective date: 20181116

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20181212

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20191113

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20191126

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20191209

R150 Certificate of patent or registration of utility model

Ref document number: 6638534

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250