JP4881629B2 - Erasable colorant composition - Google Patents
Erasable colorant composition Download PDFInfo
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- JP4881629B2 JP4881629B2 JP2006050280A JP2006050280A JP4881629B2 JP 4881629 B2 JP4881629 B2 JP 4881629B2 JP 2006050280 A JP2006050280 A JP 2006050280A JP 2006050280 A JP2006050280 A JP 2006050280A JP 4881629 B2 JP4881629 B2 JP 4881629B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は、墨汁、水性インキ等に用いることができる着色材組成物に関する。さらに詳しくは、紙に塗布した場合に、滲みなどの問題がなく、また誤って衣服などに付着した場合でも家庭で一般に行われている簡単な洗濯により完全に消去することができる着色材組成物に関する。 The present invention relates to a colorant composition that can be used in ink, water-based ink, and the like. More specifically, when applied to paper, there is no problem such as bleeding, and even if it accidentally adheres to clothes etc., it can be completely erased by simple washing that is generally done at home. About.
従来の墨汁は、衣服などの繊維に誤って付着した場合、乾燥してしまうと洗濯で消去することが困難であった。そこで、洗濯で消去できる着色材組成物を墨汁等に用いることが提案されている。
しかし、これらの着色材組成物は色材として染料を使用したものであり、そのため紙に塗布した場合に、高湿度下での滲みの問題があった。 However, these colorant compositions use dyes as colorants, and therefore have a problem of bleeding under high humidity when applied to paper.
一方、色材として顔料との複合物や樹脂粒子を使用した着色材組成物も提案されており、染料を使用したものに比べて滲みの問題が生じにくいと考えられる。また着色材組成物自体の洗濯消去性も改善されている。
しかし、これらの着色材組成物は着色材粒子が大きいため、比較的低粘度の墨汁やインキに用いた場合、経時で沈殿等の問題が生じる恐れがある。 However, since these colorant compositions have large colorant particles, problems such as precipitation may occur over time when used in relatively low-viscosity ink or ink.
本発明の課題は、紙に塗布した場合、滲みなどの問題がなく、また布、不織布などの繊維集合体に付着した場合に、簡単な洗濯により消去することができ、低粘度にしても安定な着色材組成物を提供するところにある。 The problem of the present invention is that when applied to paper, there is no problem such as bleeding, and when it adheres to a fiber assembly such as cloth or nonwoven fabric, it can be erased by simple washing, and is stable even at low viscosity. A colorant composition is provided.
本発明者らは、上記課題を解決するために色材に微粒な顔料を用い、また消去性を向上させる要因として顔料の再分散性に着目した。すなわち衣類に付着して乾燥してしまった墨汁等を水洗により消去することは、繊維に付着している顔料を水に再分散することであると考えた。
そこで、顔料を容易に水に再分散させる手段として、顔料に対して水溶性樹脂の比率を高くした。また顔料特性として、顔料に分散樹脂（水溶性樹脂）を十分に吸着させるために吸油量の小さいものを選択し、さらに墨汁等に用いた場合の着色力を担保するために比表面積は一定の値以上とすることで、期待される着色材組成物が得られることを見出した。
In order to solve the above-mentioned problems, the present inventors have used fine pigment as a coloring material, and paid attention to redispersibility of the pigment as a factor for improving erasability. That is, it was thought that erasing the ink ink and the like that had adhered to the clothes and dried by washing with water was to redisperse the pigment adhering to the fibers in water.
Therefore, as a means for easily redispersing the pigment in water, the ratio of the water-soluble resin to the pigment was increased. In addition, as a pigment characteristic, a material having a small oil absorption amount is selected in order to sufficiently adsorb the dispersion resin (water-soluble resin) on the pigment, and the specific surface area is constant in order to secure the coloring power when used in ink. It has been found that an expected colorant composition can be obtained when the value is not less than the above value.
すなわち本請求項１の発明は、少なくとも着色顔料、水溶性樹脂及び水を含む着色材組成物であって、前記水溶性樹脂Ｒは水溶性樹脂Ａと水溶性樹脂Ｂから構成されており、前記着色顔料Ｐが水溶性樹脂Ａにより分散されており、前記着色顔料Ｐと前記水溶性樹脂Ｒの重量比（Ｐ／Ｒ比）が１／１〜１／３０であり、前記着色顔料Ｐの比表面積が２００ｍ２／ｇ以上であり、かつ吸油量が７０ｍｌ／１００ｇ以下であることを特徴とする洗濯により消去可能な着色材組成物である。本請求項２の発明は、前記着色顔料Ｐが、カーボンブラックである請求項１記載の洗濯により消去可能な着色材組成物である。本請求項３の発明は、前記水溶性樹脂Ａが、スチレンアクリル酸共重合体、スチレンマレイン酸共重合体の群から選ばれる１又は２の水溶性樹脂である請求項１又は２記載の洗濯により消去可能な着色材組成物である。本請求項４の発明は、前記水溶性樹脂Ｂが、スチレンアクリル酸共重合体、スチレンマレイン酸共重合体の群から選ばれる１又は２の水溶性樹脂である請求項１乃至３のいずれかの項に記載の洗濯により消去可能な着色材組成物である。本請求項５の発明は、前記着色顔料P、前記水溶性樹脂Ａと水を少なくとも配合し分散して顔料分散体を得た後、この顔料分散体に前記水溶性樹脂Ｂの水溶液を添加することを特徴とする請求項１乃至４のいずれかの項に記載の洗濯により消去可能な着色材組成物を製造する方法である。本請求項６の発明は、請求項１乃至４のいずれかの項に記載の着色材組成物で構成された墨汁である。本請求項７の発明は、請求項１乃至４のいずれかの項に記載の着色材組成物で構成された水性インキである。 That is, the invention of claim 1 is a colorant composition containing at least a color pigment, a water-soluble resin and water, wherein the water-soluble resin R is composed of a water-soluble resin A and a water-soluble resin B, The color pigment P is dispersed by the water-soluble resin A, the weight ratio (P / R ratio) between the color pigment P and the water-soluble resin R is 1/1 to 1/30, and the ratio of the color pigment P A colorant composition erasable by washing, having a surface area of 200 m 2 / g or more and an oil absorption of 70 ml / 100 g or less. The invention of claim 2 is the colorant composition erasable by washing according to claim 1, wherein the color pigment P is carbon black. The invention according to claim 3 is characterized in that the water-soluble resin A is one or two water-soluble resins selected from the group of styrene acrylic acid copolymers and styrene maleic acid copolymers. It is a coloring material composition which can be erased by. The invention of claim 4 is characterized in that the water-soluble resin B is one or two water-soluble resins selected from the group of styrene acrylic acid copolymer and styrene maleic acid copolymer. It is a coloring material composition erasable by the washing | cleaning of description to term. In the invention of claim 5, after the color pigment P, the water-soluble resin A and water are blended and dispersed to obtain a pigment dispersion, an aqueous solution of the water-soluble resin B is added to the pigment dispersion. The method for producing a colorant composition erasable by washing according to any one of claims 1 to 4. The invention of claim 6 is a black ink composed of the colorant composition according to any one of claims 1 to 4. The invention of claim 7 is a water-based ink comprising the colorant composition according to any one of claims 1 to 4.
本発明により、紙に塗布した場合には滲みなどの問題が生じず、また誤って衣服などに付着した場合でも家庭で一般に行われている簡単な洗濯により完全に消去することができる着色材組成物を得ることができる。これらの着色材組成物は、墨汁、水性インキ等に用いることができる。 According to the present invention, a colorant composition that does not cause bleeding or other problems when applied to paper, and can be completely erased by simple washing that is generally performed at home even when it accidentally adheres to clothes, etc. You can get things. These colorant compositions can be used for ink, water-based inks and the like.
＜着色顔料＞
本発明で用いられる着色顔料は、粒径が細かく、着色効果のあることが求められる。具体的には粒径０．０１〜０．１μｍのカーボンブラックが好ましいが、特に限定されるものではない。また最適な着色力と再分散性のバランスを担保するために、比表面積が２００ｍ２／ｇ以上、好ましくは２００〜４００ｍ２／ｇであり、かつ吸油量が７０ｍｌ／１００ｇ以下、好ましくは４０〜７０ｍｌ／１００ｇの物性を有することが必要である。
<Coloring pigment>
The color pigment used in the present invention is required to have a fine particle size and a coloring effect. Specifically, carbon black having a particle size of 0.01 to 0.1 μm is preferable, but not particularly limited. In order to ensure an optimal balance of color strength and re-dispersibility, a specific surface area of 200 meters 2 / g or more, preferably 200 to 400 m 2 / g, and an oil absorption of 70 ml / 100 g or less, preferably 40 It is necessary to have a physical property of 70 ml / 100 g.
着色顔料の配合量は、着色材組成物全量に対して１〜１０重量％、好ましくは２〜７重量％である。着色顔料が着色材組成物全量に対して１重量％未満の場合は、発色が低下する。着色顔料が着色材組成物全量に対して１０重量％を超える場合は、粘度が上がって筆記や描画し難くなるほか、繊維に付着した後落ちにくくなる。 The blending amount of the color pigment is 1 to 10% by weight, preferably 2 to 7% by weight, based on the total amount of the colorant composition. When the color pigment is less than 1% by weight based on the total amount of the colorant composition, the color development is lowered. When the color pigment exceeds 10% by weight with respect to the total amount of the colorant composition, the viscosity increases and it becomes difficult to write or draw, and it is difficult to drop after adhering to the fiber.
＜水溶性樹脂Ｒ＞
本発明では水溶性樹脂を用いる。この水溶性樹脂（以下、水溶性樹脂Ｒと称する）は、着色顔料を分散させ、かつ得られた顔料分散体の分散安定性に優れる水溶性樹脂Ａ、及び顔料分散体に後添加する水溶性樹脂Ｂから構成される。
<Water-soluble resin R>
In the present invention, a water-soluble resin is used. This water-soluble resin (hereinafter referred to as “water-soluble resin R”) is a water-soluble resin A in which a colored pigment is dispersed and the resulting pigment dispersion is excellent in dispersion stability, and a water-soluble resin that is added later to the pigment dispersion. It is composed of resin B.
＜水溶性樹脂Ａ＞
水溶性樹脂Ａは、顔料分散能力、分散安定性に優れることに加え、水への再分散性（溶解性）が求められることから、比較的、分子量が低い（分子量：1００００以下）スチレンアクリル酸共重合体、スチレンマレイン酸共重合体が特に好ましい。その他アラビヤガム、グアーガム、キサンタンガム、デキストリン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、メチルヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルヒドロキシプロピルセルロース、ポリエチレンオキサイド、ポリアクリル酸、ポリビニルピロリドン、ポリエチレングリコール、ポリビニルアルコールなどを用いることができる。樹脂Ａは、着色材組成物全量に対して０．１〜７．０重量％、特に０．２〜３．５重量％が好ましい。０．１重量％未満の場合には、経時による顔料の凝集が起こり、７．０重量％を超える場合には、分散時にゲル化が生じるからである。
また、かかる樹脂Ａを含む水溶性樹脂Ｒは、前記着色顔料Ｐと前記水溶性樹脂Ｒとの重量比（Ｐ／Ｒ）を１／１〜１／３０とすることにより、良好な洗濯消去性着色材組成物を得ることができる。
<Water-soluble resin A>
The water-soluble resin A has a relatively low molecular weight (molecular weight: 10000 or less) styrene acrylic acid because it is required to have redispersibility (solubility) in water in addition to excellent pigment dispersion ability and dispersion stability. A copolymer and a styrene maleic acid copolymer are particularly preferred. Other Arabia gum, guar gum, xanthan gum, dextrin, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, etc. Can be used. Resin A is preferably 0.1 to 7.0% by weight, particularly preferably 0.2 to 3.5% by weight, based on the total amount of the colorant composition. This is because when the amount is less than 0.1% by weight, the pigment aggregates with time, and when it exceeds 7.0% by weight, gelation occurs during dispersion.
In addition, the water-soluble resin R containing the resin A has good laundry erasability by setting the weight ratio (P / R) of the color pigment P and the water-soluble resin R to 1/1 to 1/30. A colorant composition can be obtained.
なお、前記着色顔料Ｐと前記水溶性樹脂Ｒの重量比（Ｐ／Ｒ比）が１／１を超える場合は、洗濯による消去性が低下する。一方、前記着色顔料と前記水溶性樹脂の重量比（Ｐ／Ｒ比）が１／３０未満となる場合は、粘度が高くなり、使用感が低下する。 In addition, when the weight ratio (P / R ratio) of the said color pigment P and the said water-soluble resin R exceeds 1/1, the erasability by washing falls. On the other hand, when the weight ratio (P / R ratio) between the color pigment and the water-soluble resin is less than 1/30, the viscosity increases and the feeling in use decreases.
前記着色顔料Ｐと前記樹脂Ａの重量比（Ｐ／Ａ比）は１０／１〜１．５／１、好ましくは５／１〜２／１である。前記着色顔料と前記樹脂Ａの重量比（Ｐ／Ａ比）が１０／１を超える場合、顔料の分散性が低下し、経時的に凝集し、洗濯による消去性が低下する。前記着色顔料と前記樹脂Ａの重量比（Ｐ／Ｒ比）が１．５／１未満の場合は、粘度が高くなり、使用感が低下し、分散時にゲル化し易くなる。 The weight ratio (P / A ratio) between the color pigment P and the resin A is 10/1 to 1.5 / 1, preferably 5/1 to 2/1. When the weight ratio (P / A ratio) between the colored pigment and the resin A exceeds 10/1, the dispersibility of the pigment is lowered, and it aggregates with time, and the erasability by washing is lowered. When the weight ratio (P / R ratio) between the color pigment and the resin A is less than 1.5 / 1, the viscosity increases, the feeling of use decreases, and gelation tends to occur during dispersion.
＜水溶性樹脂Ｂ＞
本発明の水溶性樹脂Ｂは、乾燥後の水に対する再溶解性が高いこと、粘度がある程度低いことが求められる。特に好ましいのは、アルカリで中和されることにより水に可溶となるアニオン性樹脂であるスチレンアクリル酸共重合体、スチレンマレイン酸共重合体である。その他アラビヤガム、グアーガム、キサンタンガム、デキストリン、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、メチルヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルヒドロキシプロピルセルロース、ポリエチレンオキサイド、ポリアクリル酸、ポリビニルピロリドン、ポリエチレングリコール、ポリビニルアルコールなどを用いることができる。また水溶性樹脂Bの配合量は、着色材組成物全量に対して、１．０〜３０．０重量％であり、好ましくは、１０．０〜２５．０重量％である。１．０重量％未満の場合、洗濯消去性が低下し、３０．０重量％を超える場合、粘度が高くなり、使用感が低下する。
<Water-soluble resin B>
The water-soluble resin B of the present invention is required to have high re-solubility in water after drying and a certain low viscosity. Particularly preferred are styrene acrylic acid copolymers and styrene maleic acid copolymers which are anionic resins that are soluble in water when neutralized with an alkali. Other Arabia gum, guar gum, xanthan gum, dextrin, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, polyethylene oxide, polyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, etc. Can be used. Moreover, the compounding quantity of the water-soluble resin B is 1.0-30.0 weight% with respect to the coloring material composition whole quantity, Preferably, it is 10.0-25.0 weight%. When it is less than 1.0% by weight, the washing erasability is lowered, and when it exceeds 30.0% by weight, the viscosity is increased and the feeling of use is lowered.
また、上記アニオン性樹脂の樹脂中和剤は、水に溶解し、アルカリ性を示すことが必要であり、アルキルアミン類のモノエチルアミン、インプロピルアミンジメチルアミン、ジエチルアミンや、無機塩類である水酸化ナトリウム、水酸化カリウム、水酸化リチウムが好適に用いられ、その他アルカノールアミン類のモノエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、またジアミン類のエチレンジアミン、プロピレンジアミンなどが用いられる。 In addition, the resin neutralizing agent of the anionic resin must be dissolved in water and exhibit alkalinity, such as alkylamine monoethylamine, inpropylamine dimethylamine, diethylamine, and sodium hydroxide which is an inorganic salt. , Potassium hydroxide and lithium hydroxide are preferably used, and other alkanolamines such as monoethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and diamines such as ethylenediamine and propylenediamine are used. It is done.
＜水＞
本発明で用いられる水は、慣用的に用いられる水、例えばイオン交換水や蒸留水、超純水など不純物を含まないものが好ましいが特に限定されるものではない。水の量は、広い範囲、例えば着色材組成物全量に対して５０〜９０重量％の範囲から選択できる。好ましい水の量は６０〜８０重量％である。
<Water>
The water used in the present invention is not particularly limited, although water that does not contain impurities such as conventionally used water, such as ion-exchanged water, distilled water, and ultrapure water is preferable. The amount of water can be selected from a wide range, for example, from 50 to 90% by weight based on the total amount of the colorant composition. A preferable amount of water is 60 to 80% by weight.
＜その他の添加剤＞
その他必要に応じて、グリセリン、プロピレングリコール、エチレングリコール等の多価アルコールや、防錆剤（例えば、ベンゾトリアゾール、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトレートなど）、防腐防黴剤（例えば、ベンゾイソチアゾリン系防腐防黴剤、ペンタクロロフェノール系防腐防黴剤、クレゾール系防腐防黴剤など）、界面活性剤、湿潤剤、消泡剤、レベリング剤、凝集防止剤、ｐＨ調整剤、擬塑性付与剤等の慣用の添加剤を添加することができる。
<Other additives>
Other polyhydric alcohols such as glycerin, propylene glycol and ethylene glycol, rust preventives (for example, benzotriazole, tolyltriazole, dicyclohexylammonium nitrate), antiseptic / antifungal agents (for example, benzoisothiazoline-based antiseptics) Antifungal agents, pentachlorophenol antiseptic / antifungal agents, cresol antiseptic / antifungal agents, etc.), surfactants, wetting agents, antifoaming agents, leveling agents, anti-aggregation agents, pH adjusters, pseudoplastic imparting agents, etc. Conventional additives can be added.
なお、本発明の着色材組成物は、着色顔料、水性樹脂Ａと水を少なくとも配合し分散してまず顔料分散体を得た後、この顔料分散体に水性樹脂Ｂの水溶液を添加することによって得ることができる。 In addition, the coloring material composition of the present invention is obtained by adding and dispersing an aqueous resin B to the pigment dispersion after first obtaining a pigment dispersion by blending and dispersing at least the color pigment, the aqueous resin A and water. Obtainable.
＜製造方法＞
本発明の着色材組成物の製造方法においては、まず着色顔料及び前記水性樹脂Ａ、水、必要に応じて顔料濡れ剤を配合したものを分散し、顔料分散体を作製する。次に当該水性顔料分散体に水性樹脂Ｂを添加し、さらに各種の添加剤を添加し、均一になるまで攪拌することにより、水性インキ組成物を得る。得られたインキ組成物は公知の脱泡工程、濾過工程を経ることが好ましい。濾過は、通常の濾紙による濾過、減圧濾過等、公知の濾過方法を挙げることができるが、工業生産的には加圧濾過が効率がよいと考えられる。
<Manufacturing method>
In the method for producing a colorant composition of the present invention, a pigment dispersion is first prepared by dispersing a colored pigment, the aqueous resin A, water, and a pigment wetting agent as necessary. Next, an aqueous ink composition is obtained by adding the aqueous resin B to the aqueous pigment dispersion, adding various additives, and stirring until uniform. The obtained ink composition is preferably subjected to a known defoaming step and filtration step. The filtration may be a known filtration method such as filtration with ordinary filter paper, vacuum filtration, etc., but pressure filtration is considered efficient for industrial production.
上記水性顔料分散体製造時の分散工程においては公知の分散機や攪拌機を用いることができる。具体的にはビーズミル、ボールミル、サンドミル、ロールミル、ニーダー等の分散機、またターボミキサーなどの攪拌機などが挙げられる。 A known disperser or stirrer can be used in the dispersion step when the aqueous pigment dispersion is produced. Specific examples include a disperser such as a bead mill, a ball mill, a sand mill, a roll mill, and a kneader, and a stirrer such as a turbo mixer.
以下に実施例を示し、本発明をさらに詳細に説明する。 The following examples illustrate the present invention in more detail.
＜顔料分散体の製造＞
まず、以下の組成成分をビーズミル（商品名「ダイノーミル」、シンマルエンタープライゼス社製）にて分散を1時間行うことにより、実施例に使用する黒色顔料分散体（１）乃至（５）を各々調製した。
<Manufacture of pigment dispersion>
First, the black pigment dispersions (1) to (5) used in the examples were dispersed by dispersing the following composition components in a bead mill (trade name “Dynomill”, manufactured by Shinmaru Enterprises) for 1 hour. Prepared.
〔顔料分散体（１）〕
カーボンブラック ２０重量部
（キャボット社製、商品名「モナーク８００」）
ポリビニルアルコール ２０重量％水溶液 ２０重量部
（クラレ社製、商品名「ポバール４０３」）
水 ６０重量部
[Pigment dispersion (1)]
20 parts by weight of carbon black (trade name “Monarch 800” manufactured by Cabot Corporation)
Polyvinyl alcohol 20% by weight aqueous solution 20 parts by weight (Kuraray Co., Ltd., trade name “Poval 403”)
60 parts by weight of water
〔顔料分散体（２）〕
カーボンブラック ２０重量部
（キャボット社製、商品名「モナーク１１００」）
スチレンアクリル酸共重合体 ２０重量％水溶液 ２０重量部
（ジョンソンポリマー社製、商品名「ジョンクリルＪ−６７８」〔水酸化ナトリウム中和〕）
水 ６０重量部
[Pigment dispersion (2)]
20 parts by weight of carbon black (trade name “Monarch 1100” manufactured by Cabot Corporation)
Styrene acrylic acid copolymer 20% by weight aqueous solution 20 parts by weight (manufactured by Johnson Polymer Co., Ltd., trade name “Johncrill J-678” [neutralized with sodium hydroxide])
60 parts by weight of water
〔顔料分散体（３）〕
カーボンブラック ２０重量部
（三菱化学社製、「＃２３００」）
スチレンアクリル酸共重合体 ２０重量％水溶液 ２０重量部
（ジョンソンポリマー社製、商品名「ジョンクリルＪ−６７８」〔水酸化ナトリウム中和〕）
水 ６０重量部
[Pigment dispersion (3)]
20 parts by weight of carbon black (Mitsubishi Chemical Corporation, “# 2300”)
Styrene acrylic acid copolymer 20% by weight aqueous solution 20 parts by weight (manufactured by Johnson Polymer Co., Ltd., trade name “Johncrill J-678” [neutralized with sodium hydroxide])
60 parts by weight of water
〔顔料分散体（４）〕
カーボンブラック ２０重量部
（デグサ社製、商品名「リーガル９９Ｒ」）
スチレンアクリル酸共重合体 ２０重量％水溶液 ２０重量部
（ジョンソンポリマー社製、商品名「ジョンクリルＪ−６７８」〔水酸化ナトリウム中和〕）
水 ６０重量部
[Pigment dispersion (4)]
Carbon black 20 parts by weight (made by Degussa, trade name “Regal 99R”)
Styrene acrylic acid copolymer 20% by weight aqueous solution 20 parts by weight (manufactured by Johnson Polymer Co., Ltd., trade name “Johncrill J-678” [neutralized with sodium hydroxide])
60 parts by weight of water
〔顔料分散体（５）〕
カーボンブラック ２０重量部
（キャボット社製、商品名「モナーク８８０」）
スチレンアクリル酸共重合体 ２０重量％水溶液 ２０重量部
（ジョンソンポリマー社製、商品名「ジョンクリルＪ−６７８」〔水酸化ナトリウム中和〕）
水 ６０重量部
[Pigment dispersion (5)]
20 parts by weight of carbon black (trade name “Monarch 880” manufactured by Cabot)
Styrene acrylic acid copolymer 20% by weight aqueous solution 20 parts by weight (manufactured by Johnson Polymer Co., Ltd., trade name “Johncrill J-678” [neutralized with sodium hydroxide])
60 parts by weight of water
＜墨汁又はインキの作製＞
前記水顔料分散体（１）〜（５）を用いて表１記載の配合比（単位：重量部）により配合し、これをディスパーにて３０分攪拌し、実施例１〜４及び比較例１〜３の墨汁又はインキを製造した。なお表中の樹脂液（１）〜（４）は以下のものを示す。
樹脂液（１）：スチレンマレイン酸共重合体（星光化学社製、商品名「Ｘ−１」）３０重量％、水酸化ナトリウム（和光純薬社製）５．１重量％の水溶液。
樹脂液（２）：スチレンアクリル酸共重合体（ジョンソンポリマー社製、商品名「Ｊｏｈｎｃｒｙｌ６９０」）３０重量％、トリエタノールアミン（和光純薬社製）１９．１重量％の水溶液。
樹脂液（３）：ポリビニルアルコール（クラレ社製、商品名「ポバール４０３」）３０重量％の水溶液。
樹脂液（４）：カルボキシメチルセルロース（第一工業製薬社製、商品名「セロゲン５Ａ」）２０重量％の水溶液。
<Preparation of ink or ink>
Using the water pigment dispersions (1) to (5), they were blended at a blending ratio (unit: parts by weight) shown in Table 1, and stirred for 30 minutes with a disper. Examples 1-4 and Comparative Example 1 -3 inks or inks were produced. In addition, resin liquid (1)-(4) in a table | surface shows the following.
Resin liquid (1): An aqueous solution of 30% by weight of a styrene maleic acid copolymer (trade name “X-1” manufactured by Seiko Chemical Co., Ltd.) and 5.1% by weight of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.).
Resin liquid (2): Styrene acrylic acid copolymer (manufactured by Johnson Polymer Co., Ltd., trade name “Johncryl 690”) 30% by weight, triethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) 19.1% by weight aqueous solution.
Resin liquid (3): An aqueous solution of 30% by weight of polyvinyl alcohol (manufactured by Kuraray, trade name “Poval 403”).
Resin liquid (4): An aqueous solution of 20% by weight of carboxymethyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Serogen 5A”).
＜評価＞
１．消去性試験
〔試験サンプルの作製〕
綿ブロード（晒）の試験布に水を含まない画筆（平筆４号）を用いて、作製した墨汁又はインキを塗布し、室温で指触乾燥するまで放置した。
〔洗濯〕
乾燥後の試験サンプルを洗濯機で弱アルカリ性合成洗剤を使用して（０．２重量％量）２０℃で１５分間洗濯し、５分間手でもみ洗いした。その後、１５分間水洗し、乾燥後に試験サンプルを目視で観察し、以下の基準により評価した。評価結果を表１に示す。
〔消去性評価基準〕
○ ：汚れが除去されている。
△ ：色、筆跡がはっきりわかる。
× ：全く落ちない。
<Evaluation>
1. Erasability test (preparation of test sample)
The prepared ink or ink was applied to a cotton broad (bleached) test cloth using no paint brush (flat brush No. 4) and left to dry at the room temperature.
〔Washing〕
The dried test sample was washed with a weak alkaline synthetic detergent in a washing machine (0.2% by weight) at 20 ° C. for 15 minutes and hand-washed for 5 minutes. Thereafter, the sample was washed with water for 15 minutes, and after drying, the test sample was visually observed and evaluated according to the following criteria. The evaluation results are shown in Table 1.
[Eraseability Evaluation Criteria]
○: Dirt is removed.
Δ: Color and handwriting clearly understood.
X: It does not fall at all.
本発明の着色材組成物は、墨汁（墨液）、水性インキ等の着色材組成物として用いることができる。
The coloring material composition of the present invention can be used as a coloring material composition such as ink (ink ink) and water-based ink.
Claims (7)
前記水溶性樹脂Ｒは水溶性樹脂Ａと水溶性樹脂Ｂから構成されており、
前記着色顔料Ｐが水溶性樹脂Ａにより分散されており、
前記着色顔料Ｐと前記水溶性樹脂Ｒの重量比（Ｐ／Ｒ比）が１／１〜１／３０であり、
前記着色顔料Ｐの比表面積が２１０〜３２０ｍ ２ ／ｇであり、かつ吸油量が７０ｍｌ／１００ｇ以下であることを特徴とする洗濯により消去可能な着色材組成物。 A colorant composition comprising at least a color pigment, a water-soluble resin and water,
The water-soluble resin R is composed of a water-soluble resin A and a water-soluble resin B,
The color pigment P is dispersed by the water-soluble resin A,
The weight ratio (P / R ratio) between the color pigment P and the water-soluble resin R is 1/1 to 1/30,
A colorant composition erasable by washing, wherein the color pigment P has a specific surface area of 210 to 320 m 2 / g and an oil absorption of 70 ml / 100 g or less.
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| JP2006050280A JP4881629B2 (en) | 2006-02-27 | 2006-02-27 | Erasable colorant composition |
| PCT/JP2007/053527 WO2007097448A1 (en) | 2006-02-27 | 2007-02-26 | Eliminable colorant composition |
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| JP6713376B2 (en) * | 2016-08-04 | 2020-06-24 | 株式会社サクラクレパス | Erasable colorant composition |
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| JPH0816206B2 (en) * | 1987-12-28 | 1996-02-21 | 株式会社サクラクレパス | Aqueous erasable marking pen ink composition |
| JPH03157467A (en) * | 1989-11-16 | 1991-07-05 | Dainichiseika Color & Chem Mfg Co Ltd | Pastel ink composition for writing utensil |
| JPH04239070A (en) * | 1991-01-11 | 1992-08-26 | Taiyo Ink Seizo Kk | Thermosetting ink composition for printed circuit board |
| JPH073197A (en) * | 1991-07-30 | 1995-01-06 | Pentel Kk | Erasable water-soluble ink composition |
| JP3158309B2 (en) * | 1992-07-01 | 2001-04-23 | 株式会社トンボ鉛筆 | Aqueous marking ink composition for writing board |
| FR2733505B1 (en) * | 1995-04-26 | 1997-07-18 | Imaje Sa | WATER-BASED INK COMPOSITION FOR MARKING OF ALL MEDIA |
| JPH09157576A (en) * | 1995-12-04 | 1997-06-17 | Pilot Ink Co Ltd | Marking ink for warning against the presence of glass |
| JP3824180B2 (en) * | 1996-05-31 | 2006-09-20 | 株式会社サクラクレパス | Erasable colorant composition |
| JP3824181B2 (en) * | 1996-06-24 | 2006-09-20 | 株式会社サクラクレパス | Erasable colorant composition |
| JP3512564B2 (en) * | 1996-07-12 | 2004-03-29 | 株式会社サクラクレパス | Water-based erasable marking pen ink composition |
| JP3824184B2 (en) * | 1996-11-28 | 2006-09-20 | 株式会社サクラクレパス | Indian ink composition |
| JP2001040264A (en) * | 1999-07-29 | 2001-02-13 | Nippon Color Kogyo Kk | Marking ink composition for white board |
| JP3917404B2 (en) * | 2001-10-29 | 2007-05-23 | パイロットインキ株式会社 | Aromatic water-based ink composition and writing or applicator using the same |
| JP3934431B2 (en) * | 2002-02-13 | 2007-06-20 | 株式会社サクラクレパス | How to write on fabric |
| JP4198704B2 (en) * | 2004-07-21 | 2008-12-17 | 株式会社サクラクレパス | Coloring composition erasable by washing |
| JP5030400B2 (en) * | 2005-07-20 | 2012-09-19 | 株式会社サクラクレパス | Coloring composition erasable by washing |
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