WO2007080913A1 - Colorant composition - Google Patents

Colorant composition Download PDF

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Publication number
WO2007080913A1
WO2007080913A1 PCT/JP2007/050218 JP2007050218W WO2007080913A1 WO 2007080913 A1 WO2007080913 A1 WO 2007080913A1 JP 2007050218 W JP2007050218 W JP 2007050218W WO 2007080913 A1 WO2007080913 A1 WO 2007080913A1
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Prior art keywords
water
resin
weight
colorant composition
colorant
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PCT/JP2007/050218
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French (fr)
Japanese (ja)
Inventor
Toshiki Misawa
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Sakura Color Products Corporation
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Publication of WO2007080913A1 publication Critical patent/WO2007080913A1/en

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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

Definitions

  • the present invention relates to a colorant composition that can be used as ink for ink, paint, marking pen ink, and the like. More specifically, a colorant composition that does not cause bleeding under high humidity when applied to paper, and can be erased by simple water washing (washing) when adhering to a fiber assembly such as cloth or nonwoven fabric. Related to things.
  • Patent Document 1 JP-A-9-316379
  • Patent Document 2 JP-A-10-7957
  • the present invention is a colorant composition having at least a color pigment, a water-soluble resin, and water and having erasability by washing,
  • the water-soluble resin As the water-soluble resin, a dispersed resin and a charcoal resin are included, and the colored pigment is dispersed by the dispersed resin,
  • the most important means is to use a colorant composition that is neutralized with an amine having a boiling point of 10 to 10 ° C.
  • the erasable colorant composition of the present invention can be removed by washing even if it is accidentally attached to clothes, and the drawn characters and paintings bleed even in a cover work in which water is sprayed. That thing. Also, problems such as bleeding under high humidity will not occur.
  • the coloring pigment used in the present invention can be used without limitation as long as it has a coloring effect with a fine particle size.
  • black pigments include carbon black, aniline black, iron black, Z red pigments, monoazo, anthraquinone, quinacridone, and blue pigments such as phthalocyanine, ultramarine blue, bitumen, and anthraquinone. it can.
  • the amount of the color pigment is not particularly limited as long as the ratio to the water-soluble rosin is satisfied, but preferably 1.0 to 0.00 with respect to the total amount of the colorant composition. % By weight, more preferably 2.0 to 7.0% by weight. When the color pigment is less than 1% by weight with respect to the total amount of the colorant composition, the color development decreases. If the color pigment exceeds 10% by weight with respect to the total amount of the colorant composition, the viscosity will increase and it will be difficult to write or draw, and it will be difficult to fall off after adhering to the fiber.
  • a water-soluble coagulant is used so that the colorant composition can be easily removed by washing (washing).
  • two types of water-soluble resins namely a dispersion resin and a carbonic resin, are essential components.
  • the dispersed resin used in the present invention preferably contains a resin that is soluble in water, disperses the colored pigment as a colored pigment dispersion, and is excellent in dispersion stability.
  • a resin that is soluble in water disperses the colored pigment as a colored pigment dispersion, and is excellent in dispersion stability.
  • Specific examples include ruboxymethyl cellulose, arabic gum, dextrin, styrene acrylic acid copolymer, styrene maleic acid copolymer, polyacrylic acid, and PVA (polybulal alcohol). Of these, PVA, styrene acrylic copolymer, and styrene maleic acid copolymer are preferable.
  • the blending amount of the dispersion resin is not particularly limited as long as the ratio of the color pigment to the water-soluble rosin is satisfied, but is preferably 0.1 to the total colorant composition. ⁇ : LO. 0 wt%, more preferably 0.5 to 1.5 wt%.
  • the amount is less than 1% by weight, agglomeration of the colored pigment occurs with time. On the other hand, when it exceeds 10.0% by weight, gelation tends to occur during dispersion, which is preferable.
  • the eron resin used in the present invention is an eron resin that is neutralized with an alkali and dissolved in water, and can be used without particular limitation as long as it has a certain low viscosity.
  • suitable compounds include styrene acrylic acid copolymers, styrene maleic acid copolymers, and ethylene maleic acid copolymers.
  • the amount of the char-on resin is not particularly limited as long as the ratio of the color pigment to the water-soluble resin is satisfied, but preferably 10% of the total amount of the colorant composition. It is 0 to 30.0% by weight, and more preferably 10.0 to 15.0% by weight. If it is less than 10.0% by weight, the washing erasability deteriorates, and if it exceeds 30.0% by weight, the viscosity increases and the feeling in use decreases, which is not preferable.
  • the char-on resin used in the present invention is in the form of an aqueous solution neutralized with amines having a boiling point of 10 to 10 ° C, and this is added to the pigment dispersion later.
  • Boiling point-10-10 ° C amins include methylamine, dimethylamine, Tylamine can be exemplified. These amines can be used alone or in combination of two or more.
  • a suitable blending ratio of the amine having a boiling point of 10 to 10 ° C is 0.1 to 20% by weight, more preferably 1.0 to 15% by weight, based on the total amount of the colorant composition. It is. When less than 1% by weight, the wash erasability is also lowered due to a decrease in the solubility of the resin. On the other hand, when it exceeds 20% by weight, the penetration of ink is promoted and the wash erasability is lowered. Absent.
  • polyhydric alcohols such as glycerin, propylene glycol, and ethylene glycol, and antiseptic / antifungal agents may be added as necessary.
  • the colorant composition of the present invention can be efficiently produced through the following steps.
  • the colorant composition of the present invention is not limited to those produced by the following production method.
  • Color pigment, dispersed resin, water, and if necessary, a color pigment wetting agent are mixed and dispersed for about 1 hour with a disperser such as a bead mill.
  • Dissolve an ionic resin in an aqueous solution add an amine of an amine having a boiling point of 10 to 10 ° C., and neutralize to prepare an aqueous ionic resin.
  • the colorant composition of the present invention is obtained. Can do.
  • Examples 1 to 4 The colorant compositions of Examples 1 to 4 were prepared with the compositions shown in Table 1.
  • a preparation method first, a color pigment, a dispersion resin, and ion-exchanged water were blended, and dispersion was performed for 1 hour with a bead mill (Dynomill: manufactured by Shinmaru Enterprises). Next, it is neutralized by adding either methylamine (boiling point 7 ° C) or trimethylamine (boiling point 3 ° C) to the aion-based resin, which is a post-added resin. . Finally, an aqueous solution of pre-on resin (added resin after) was added to the colored pigment dispersion and stirred for 30 minutes to obtain the coloring material compositions (inkbrush) of Examples 1 to 4.
  • a colorant composition having the composition shown in Table 1 and different from the examples in that the post-added rosin was changed to polybulal alcohol (Poval) was prepared as Comparative Example 1.
  • the preparation method is the same as the method described in Examples 1 to 3.
  • a colorant composition having the composition shown in Table 1 and different from the examples in that the anion resin was neutralized with sodium hydroxide was prepared as Comparative Example 2.
  • the preparation method is the same as the method described in Examples 1 to 4.
  • a coloring material composition as shown in Table 1 was prepared as Comparative Example 3, which was different from the Example in that neutralization of the charcoal resin was carried out with triethanolamine having a boiling point of 360 ° C. .
  • the preparation method is the same as the method described in Examples 1 to 4.
  • the preparation method is the same as the method described in Examples 1 to 4.
  • a colorant composition having the composition shown in Table 1 and different from that of Example in that neutralization of anionic resin was carried out with ammonia having a boiling point of 33 ° C. was prepared as Comparative Example 5.
  • the preparation method is the same as the method described in Examples 1 to 4.
  • Johncryl690 manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.: 30 wt 0/0, Hydroxyl sodium salt (Cobalt Neutralizer Z Wako Pure Chemical Industries): 5.1 wt% aqueous solution
  • Johncryl690 manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.: 30 wt 0/0, triethanolamine ⁇ Min (resin neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 19.1% by weight aqueous solution
  • the coloring material compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were copied on a calligraphy paper using a brush and left at room temperature for 1 week. Then, it was turned upside down on a plywood board, sprayed with water by spraying, and the run-out of the coloring material yarns and the compositions of Examples 1 to 4 and Comparative Examples 1 to 5 was evaluated.
  • the colorant composition of the present invention can be used as a water-based ink composition such as ink for marking pens in addition to ink and paint.

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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)

Abstract

The invention aims at providing a colorant composition which does not cause bleeding in mounting or under high-humidity conditions and which can be obliterated by simple water washing even when adheres to clothes accidentally. A colorant composition which comprises a colorant, a water-soluble resin component, and water as the essential components and which can be obliterated by washing, characterized in that the P/R ratio is 1:1 to 1:30 wherein P is the weight of the colorant and R is the weight of the water-soluble resin component, that the water-soluble resin component comprises a dispersing resin and an anionic resin, that the colorant is dispersed with the dispersing resin, and that the anionic resin is in a state neutralized with an amine having a boiling point of -10 to 10°C.

Description

明 細 書  Specification
着色材組成物  Colorant composition
技術分野  Technical field
[0001] 本発明は、墨汁、絵具、マーキングペン用インキ等として用いることができる着色材 組成物に関する。さらに詳細には、紙に塗布した場合、高湿度下で滲みを生じること なぐまた布、不織布などの繊維集合体に付着した場合に、簡単な水洗 (洗濯）により 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 as ink for ink, paint, marking pen ink, and the like. More specifically, a colorant composition that does not cause bleeding under high humidity when applied to paper, and can be erased by simple water washing (washing) when adhering to a fiber assembly such as cloth or nonwoven fabric. Related to things.
背景技術  Background art
[0002] 従来の墨汁は、衣服などの繊維に付着した場合、乾燥すると洗濯で消去することは 困難であった。一方、現在洗濯で消去できる墨汁が提案されている。  [0002] Conventional ink is difficult to erase by washing when it adheres to fibers such as clothes. On the other hand, ink ink that can be erased by washing has been proposed.
特許文献 1 :特開平 9— 316379  Patent Document 1: JP-A-9-316379
特許文献 2 :特開平 10— 7957  Patent Document 2: JP-A-10-7957
[0003] ところで、和紙や半紙に文字や絵画を描き、表装する場合、一般的に、皺伸ばしの ため、文字や絵画が描かれた和紙や半紙の上力も水を吹きかける作業が行われる。 ところが、着色剤を適宜選択した上で、上記技術を応用した墨汁やインキでは、かか る表装の作業において、文字や絵画が滲んでしまうという問題があった。また表装作 業を行わない場合であっても、描いた書画や絵画を高湿度の状態で放置すると、上 記同様に滲みが生じるという問題があった。  [0003] By the way, when characters and paintings are drawn and displayed on Japanese paper or half paper, generally the work of spraying water on the top of the Japanese paper or half paper on which the characters or paintings are drawn is performed for stretching. However, with the ink and ink applied with the above technique after appropriately selecting the colorant, there is a problem that characters and paintings are blurred during the covering work. In addition, even when the cover work is not performed, there is a problem that if the drawn document or painting is left in a high humidity state, bleeding occurs as described above.
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] そこで、本発明では、表装作業においても滲みが生じることがなぐまた高湿度下で も滲みを生じることなぐかつ誤って衣服に付着した場合でも、簡単な水洗 (洗濯）に より消去することができる着色材組成物を提供するところにある。 [0004] Therefore, according to the present invention, bleeding does not occur even in a cover work, and even if it adheres to clothes by mistake even when it is exposed to high humidity, it is erased by simple washing (washing). It is in providing a colorant composition that can be used.
課題を解決するための手段  Means for solving the problem
[0005] 上記課題を解決するため鋭意検討した結果、本発明では、少なくとも着色顔料、水 溶性榭脂及び水を含む、洗濯により消去性を有する着色材組成物であって、 [0005] As a result of intensive studies to solve the above problems, the present invention is a colorant composition having at least a color pigment, a water-soluble resin, and water and having erasability by washing,
前記着色顔料の重量を P、前記水溶性榭脂の重量を Rとしたとき、 P :R= 1： 1〜1 : 30であり、 When the weight of the coloring pigment is P and the weight of the water-soluble rosin is R, P: R = 1: 1 to 1 : 30
前記水溶性榭脂として、分散榭脂及びァ-オン性榭脂が含まれており、 前記着色顔料は、前記分散榭脂により分散されており、  As the water-soluble resin, a dispersed resin and a charcoal resin are included, and the colored pigment is dispersed by the dispersed resin,
前記ァニオン性榭脂は、沸点— 10〜10°Cのァミン類で中和されている 着色材組成物とすることを最も主要な手段とする。  The most important means is to use a colorant composition that is neutralized with an amine having a boiling point of 10 to 10 ° C.
発明の効果  The invention's effect
[0006] 本発明の消去性着色材組成物は、誤って衣服に付着しても洗濯で落とすことが可 能であって、かつ水を吹きかける表装作業においても、描かれた文字や絵画が滲む ことがな 、。また高湿度下での滲みなどの問題が生ずることもな 、。  [0006] The erasable colorant composition of the present invention can be removed by washing even if it is accidentally attached to clothes, and the drawn characters and paintings bleed even in a cover work in which water is sprayed. That thing. Also, problems such as bleeding under high humidity will not occur.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0007] <着色顔料 > [0007] <Coloring pigment>
本発明で用いられる着色顔料は、粒径が細かぐ着色効果を有するものであれば 制限なく用いることができる。具体的には、黒色着色顔料としてカーボンブラック、ァ 二リンブラック、鉄黒 Z赤色着色顔料として、モノァゾ、アンスラキノン、キナクリドン、 青色着色顔料として、フタロシアニン、群青、紺青、アンスラキノンなどを挙げることが できる。  The coloring pigment used in the present invention can be used without limitation as long as it has a coloring effect with a fine particle size. Specific examples of black pigments include carbon black, aniline black, iron black, Z red pigments, monoazo, anthraquinone, quinacridone, and blue pigments such as phthalocyanine, ultramarine blue, bitumen, and anthraquinone. it can.
[0008] 着色顔料の配合量は、上記水溶性榭脂との比率が満たされる限り、特に制限され るものではないが、好ましくは、着色材組成物全量に対して 1. 0〜10. 0重量％であ り、更に好ましくは 2. 0〜7. 0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％を越える場合は、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。  [0008] The amount of the color pigment is not particularly limited as long as the ratio to the water-soluble rosin is satisfied, but preferably 1.0 to 0.00 with respect to the total amount of the colorant composition. % By weight, more preferably 2.0 to 7.0% by weight. When the color pigment is less than 1% by weight with respect to the total amount of the colorant composition, the color development decreases. If the color pigment exceeds 10% by weight with respect to the total amount of the colorant composition, the viscosity will increase and it will be difficult to write or draw, and it will be difficult to fall off after adhering to the fiber.
[0009] <水溶性榭脂 >  [0009] <Water-soluble fat and oil>
本発明では、着色材組成物が、洗濯 (水洗）によって簡単に落とせるものであるよう にするため、水溶性榭脂を用いる。本発明の着色材組成物では、分散樹脂とァ-ォ ン性榭脂の 2種類の水溶性榭脂を必須成分とする。  In the present invention, a water-soluble coagulant is used so that the colorant composition can be easily removed by washing (washing). In the colorant composition of the present invention, two types of water-soluble resins, namely a dispersion resin and a carbonic resin, are essential components.
[0010] 本発明の着色材組成物では、前記着色顔料の重量を P、前記水溶性榭脂の重量 を1^としたときの重量比13 :1^を1 : 1〜1 : 30とする。この範囲にすることで、着色顔料含 有の着色材組成物において洗濯消去性を向上することが可能となる。 P= 1に対し、 R= l未満の場合、洗濯による消去性が低下するため好ましくない。一方、 P= lに対 し、 Rが 30を超える場合は、粘度が高くなり、使用感が低下するので好ましくない。 [0010] In the colorant composition of the present invention, the weight ratio 1 3 : 1 ^ is 1: 1 to 1:30, where P is the weight of the color pigment and 1 ^ is the weight of the water-soluble resin. To do. By using this range, the color pigments can be included. It becomes possible to improve the washing erasability in a colorant composition. In contrast to P = 1, when R = l is less than 1, it is not preferable because the erasability by washing decreases. On the other hand, if P is greater than 30 and R is more than 30, it is not preferable because the viscosity increases and the feeling of use decreases.
[0011] <分散樹脂 > [0011] <Dispersed resin>
本発明で用いる分散榭脂は、水に溶解可能で、着色顔料を着色顔料分散体として 分散させ、かつ分散安定性に優れる榭脂を含有することが好ましい。具体的には、力 ルボキシメチルセルローズ、ァラビヤガム、デキストリン、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、ポリアクリル酸、 PVA (ポリビュルアルコール）などを 例示できる。なかでも、 PVA、スチレアクリル共重合体、スチレンマレイン酸共重合体 が好適である。  The dispersed resin used in the present invention preferably contains a resin that is soluble in water, disperses the colored pigment as a colored pigment dispersion, and is excellent in dispersion stability. Specific examples include ruboxymethyl cellulose, arabic gum, dextrin, styrene acrylic acid copolymer, styrene maleic acid copolymer, polyacrylic acid, and PVA (polybulal alcohol). Of these, PVA, styrene acrylic copolymer, and styrene maleic acid copolymer are preferable.
[0012] 分散樹脂の配合量は、前記着色顔料と前記水溶性榭脂との比率が満たされる限り 、特に制限されるものではないが、好ましくは、着色材組成物全量に対して 0. 1〜： LO . 0重量％であり、更に好ましくは 0. 5〜1. 5重量％である。 0. 1重量％未満の場合 、経時で着色顔料の凝集が起こり、一方、 10. 0重量％を超える場合、分散時にゲル 化しやすくなるので好ましくな 、。  [0012] The blending amount of the dispersion resin is not particularly limited as long as the ratio of the color pigment to the water-soluble rosin is satisfied, but is preferably 0.1 to the total colorant composition. ~: LO. 0 wt%, more preferably 0.5 to 1.5 wt%. When the amount is less than 1% by weight, agglomeration of the colored pigment occurs with time. On the other hand, when it exceeds 10.0% by weight, gelation tends to occur during dispersion, which is preferable.
[0013] <ァ二オン性榭脂 >  [0013] <Vanion-based rosin>
本発明で用いるァ-オン性榭脂は、アルカリで中和されて水に溶解するァ-オン性 榭脂であって、粘度がある程度低いものであれば特に制限なく用いることができる。 好適な化合物の具体例としては、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、エチレンマレイン酸共重合体を挙げることができる。ァ-オン性榭脂の配 合量は、前記着色顔料と前記水溶性榭脂との比率が満たされる限り、特に制限され るものではないが、好ましくは、着色材組成物全量に対して 10. 0〜30. 0重量％で あり、更に好ましくは、 10. 0〜15. 0重量％である。 10. 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、使用感が低下するた め好ましくない。  The eron resin used in the present invention is an eron resin that is neutralized with an alkali and dissolved in water, and can be used without particular limitation as long as it has a certain low viscosity. Specific examples of suitable compounds include styrene acrylic acid copolymers, styrene maleic acid copolymers, and ethylene maleic acid copolymers. The amount of the char-on resin is not particularly limited as long as the ratio of the color pigment to the water-soluble resin is satisfied, but preferably 10% of the total amount of the colorant composition. It is 0 to 30.0% by weight, and more preferably 10.0 to 15.0% by weight. If it is less than 10.0% by weight, the washing erasability deteriorates, and if it exceeds 30.0% by weight, the viscosity increases and the feeling in use decreases, which is not preferable.
[0014] また本発明で用いるァ-オン性榭脂は、沸点— 10〜10°Cのァミン類で中和された 水溶液の形にしておき、これを後から顔料分散体に添加する添加榭脂として用いるこ とができる。沸点— 10〜10°Cのァミン類としてはメチルァミン、ジメチルァミン、トリメ チルァミンを例示することができる。これらアミン類は 1種または 2種以上で用いること ができる。 [0014] Further, the char-on resin used in the present invention is in the form of an aqueous solution neutralized with amines having a boiling point of 10 to 10 ° C, and this is added to the pigment dispersion later. Can be used as fat. Boiling point-10-10 ° C amins include methylamine, dimethylamine, Tylamine can be exemplified. These amines can be used alone or in combination of two or more.
[0015] 上記沸点— 10〜10°Cのァミン類の好適な配合割合は、着色材組成物全量に対し て 0. 1〜20重量％であり、更に好ましくは、 1. 0〜15重量％である。 0. 1重量％未 満の場合、榭脂の溶解性の低下により洗濯消去性も低下し、一方、 20重量％を超え る場合、インキの浸透を促進し、洗濯消去性が低下するので好ましくない。  [0015] A suitable blending ratio of the amine having a boiling point of 10 to 10 ° C is 0.1 to 20% by weight, more preferably 1.0 to 15% by weight, based on the total amount of the colorant composition. It is. When less than 1% by weight, the wash erasability is also lowered due to a decrease in the solubility of the resin. On the other hand, when it exceeds 20% by weight, the penetration of ink is promoted and the wash erasability is lowered. Absent.
[0016] <その他添カ卩物 > [0016] <Other accessories>
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、防腐防黴剤を添加しても良い。  In addition, polyhydric alcohols such as glycerin, propylene glycol, and ethylene glycol, and antiseptic / antifungal agents may be added as necessary.
[0017] <製造方法 > [0017] <Production method>
本発明の着色材組成物は、下記の工程を経ることで、効率的に製造することができ る。ただし、本発明の着色材組成物は下記製造方法で製造されたものに限られるも のではない。  The colorant composition of the present invention can be efficiently produced through the following steps. However, the colorant composition of the present invention is not limited to those produced by the following production method.
[0018] (第一の工程;着色顔料分散体の作製） [0018] (First step; production of colored pigment dispersion)
着色顔料、分散榭脂、水、必要に応じて着色顔料濡れ剤を配合し、ビーズミルなど の分散機にて約 1時間分散を行う。  Color pigment, dispersed resin, water, and if necessary, a color pigment wetting agent are mixed and dispersed for about 1 hour with a disperser such as a bead mill.
[0019] (第二の工程;ァ-オン性榭脂水溶液の作製） [0019] (Second step; preparation of a water-based rosin aqueous solution)
ァ-オン性榭脂を水溶液に溶解させ、沸点— 10〜10°Cのァミン類のアミン類を添 カロし中和してァニオン性榭脂水溶液を作製する。  Dissolve an ionic resin in an aqueous solution, add an amine of an amine having a boiling point of 10 to 10 ° C., and neutralize to prepare an aqueous ionic resin.
[0020] (第三の工程;着色材組成物の作製） [0020] (Third Step; Production of Colorant Composition)
上記第一の工程で作製した着色顔料分散体に、第二の工程で作製しァ-オン性 榭脂水溶液を後添加し、デイスパーで約 30分撹拌すると本発明の着色材組成物を 得ることができる。  When the colored pigment dispersion prepared in the first step is added in the second step with a charonal aqueous solution of succinic acid and stirred with a disperser for about 30 minutes, the colorant composition of the present invention is obtained. Can do.
実施例  Example
[0021] 以下、実施例により本発明を更に詳細に説明するが、本発明は下記実施例の様態 に限られるものではない。  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
[0022] <製造 > [0022] <Manufacturing>
(実施例 1〜4) 実施例 1〜4の着色材組成物は、表 1に示す組成にて調製した。調製の方法として は、まず着色顔料、分散榭脂、イオン交換水を配合し、ビーズミル (ダイノーミル:シン マルエンタープライゼス社製）にて 1時間分散を行った。次に、後添加榭脂であるァ ユオン性榭脂に、メチルァミン (沸点 7°C)、トリメチルァミン (沸点 3°C)のいずれか を加えて中和し、ァニオン性榭脂水溶液とした。最後に、前記着色顔料分散体に前 ァ-オン榭脂 (記後添加榭脂)水溶液を添加し 30分攪拌して、実施例 1〜4の着色 材組成物 (墨汁)を得た。 (Examples 1 to 4) The colorant compositions of Examples 1 to 4 were prepared with the compositions shown in Table 1. As a preparation method, first, a color pigment, a dispersion resin, and ion-exchanged water were blended, and dispersion was performed for 1 hour with a bead mill (Dynomill: manufactured by Shinmaru Enterprises). Next, it is neutralized by adding either methylamine (boiling point 7 ° C) or trimethylamine (boiling point 3 ° C) to the aion-based resin, which is a post-added resin. . Finally, an aqueous solution of pre-on resin (added resin after) was added to the colored pigment dispersion and stirred for 30 minutes to obtain the coloring material compositions (inkbrush) of Examples 1 to 4.
[0023] (比較例 1) [0023] (Comparative Example 1)
表 1に示す組成であって、後添加榭脂をポリビュルアルコール（ポバール）に変更し た点が実施例と異なる着色材組成物を比較例 1として調製した。調製方法は、実施 例 1〜 3記載の方法と同様である。  A colorant composition having the composition shown in Table 1 and different from the examples in that the post-added rosin was changed to polybulal alcohol (Poval) was prepared as Comparative Example 1. The preparation method is the same as the method described in Examples 1 to 3.
[0024] (比較例 2) [0024] (Comparative Example 2)
表 1に示す組成であって、ァニオン樹脂の中和を水酸ィ匕ナトリウムで行った点が実 施例と異なる着色材組成物を比較例 2として調製した。調製方法は、実施例 1〜4記 載の方法と同様である。  A colorant composition having the composition shown in Table 1 and different from the examples in that the anion resin was neutralized with sodium hydroxide was prepared as Comparative Example 2. The preparation method is the same as the method described in Examples 1 to 4.
[0025] (比較例 3) [0025] (Comparative Example 3)
表 1に示す糸且成であって、ァ-オン性榭脂の中和を沸点 360°Cであるトリエタノー ルァミンで行った点が、実施例と異なる着色材組成物を比較例 3として調製した。調 製方法は、実施例 1〜4記載の方法と同様である。  A coloring material composition as shown in Table 1 was prepared as Comparative Example 3, which was different from the Example in that neutralization of the charcoal resin was carried out with triethanolamine having a boiling point of 360 ° C. . The preparation method is the same as the method described in Examples 1 to 4.
[0026] (比較例 4) [Comparative Example 4]
表 1に示す組成であって、ァニオン性榭脂の中和を沸点 17°Cであるェチルァミンで 行った点が、実施例と異なる着色材組成物を比較例 4として調製した。調製方法は、 実施例 1〜4記載の方法と同様である。  A coloring material composition having a composition shown in Table 1 and having an boiling point of 17 ° C., which was different from that of the example, was prepared as Comparative Example 4 in that the anionic rosin was neutralized. The preparation method is the same as the method described in Examples 1 to 4.
[0027] (比較例 5) [0027] (Comparative Example 5)
表 1に示す組成であって、ァニオン性榭脂の中和を沸点 33°Cであるアンモニア で行った点が、実施例と異なる着色材組成物を比較例 5として調製した。調製方法は 、実施例 1〜4記載の方法と同様である。  A colorant composition having the composition shown in Table 1 and different from that of Example in that neutralization of anionic resin was carried out with ammonia having a boiling point of 33 ° C. was prepared as Comparative Example 5. The preparation method is the same as the method described in Examples 1 to 4.
[0028] [表 1] (単位：重量％) [0028] [Table 1] (Unit:% by weight)
Figure imgf000007_0001
Figure imgf000007_0001
なお、実施例 1〜4及び比較例 1〜5における各原料は次のものを使用した。  In addition, the following were used for each raw material in Examples 1-4 and Comparative Examples 1-5.
(1) Monarch800 (カーボンブラック ZCABOT社製）：20重量0 /0、 PVA403 (クラレネ土製） :4重量％の顔料分散体 (1) Monarch800 (carbon black manufactured by ZCABOT Co.): 20 wt 0/0, PVA403 (manufactured by Kurarene soil): 4% by weight of the pigment dispersion
(2) Monarch800 (カーボンブラック ZCABOT社製）：20重量0 /0、 Joncryl678 (ジョンソ ンポリマー社製）：4重量％の顔料分散体 (2) Monarch800 (carbon black manufactured by ZCABOT Co.): 20 wt 0/0, Joncryl678 (Johnson Nporima Co.): 4 wt% of the pigment dispersion
(3)シムラファーストレッド 4127 (P.R.267Z大日本インキ社製）：20重量0 /0、 Joncryl678 (ジョンソンポリマー社製）：4重量％の顔料分散体 (3) Shimura First Red 4127 (PR267Z manufactured by Dainippon Ink and Chemicals, Inc.): 20 wt 0/0, Joncryl678 (manufactured by Johnson Polymer Co., Ltd.): 4% by weight of the pigment dispersion
(4)ファーストゲンブルー TGR(P.B.15:3Z大日本インキ社製） 20重量0 /0 :Joncryl678 ( ジョンソンポリマー社製）：4重量％の顔料分散体 (4) Fast Gen Blue TGR (PB15: 3Z manufactured by Dainippon Ink and Chemicals, Inc.), 20 weight 0/0: Joncryl678 (manufactured by Johnson Polymer Co., Ltd.): 4% by weight of the pigment dispersion
(5) Johncryl690 (スチレンアクリル酸共重合体 Zジョンソンポリマー社製）：30重量0 /0、 メチルァミン (榭脂中和剤 Z和光純薬社製）： 4重量％の水溶液 (5) Johncryl690 (manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.): 30 wt 0/0, Mechiruamin (榭脂neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 4% by weight aqueous solution
(6) X-l (スチレンマレイン酸共重合体 Z星光化学社製: 30重量0 /0、トリメチルアミン（ 榭脂中和剤 Z和光純薬社製）：3.5重量％の水溶液 (6) Xl (styrene-maleic acid copolymer Z Review Photochemical Co., Ltd. 30 weight 0/0, trimethylamine (榭脂neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 3.5% by weight aqueous solution
(7) Johncryl690 (スチレンアクリル酸共重合体 Zジョンソンポリマー社製）：30重量0 /0、 水酸ィ匕ナトリウム (榭脂中和剤 Z和光純薬社製）： 5.1重量％の水溶液(7) Johncryl690 (manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.): 30 wt 0/0, Hydroxyl sodium salt (Cobalt Neutralizer Z Wako Pure Chemical Industries): 5.1 wt% aqueous solution
(8) Johncryl690 (スチレンアクリル酸共重合体 Zジョンソンポリマー社製）：30重量0 /0、 トリエタノールァミン (樹脂中和剤 Z和光純薬社製）： 19.1重量％の水溶液 (8) Johncryl690 (manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.): 30 wt 0/0, triethanolamine § Min (resin neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 19.1% by weight aqueous solution
(9) Johncryl690 (スチレンアクリル酸共重合体 Zジョンソンポリマー社製）：30重量0 /0、 ェチルァミン (榭脂中和剤 Z和光純薬社製）： 5. 8重量％の水溶液 (9) Johncryl690 (manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.): 30 wt 0/0, Echiruamin (榭脂neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 5.8% by weight aqueous solution
(10) Johncryl690 (スチレンアクリル酸共重合体 Zジョンソンポリマー社製）：30重量0 /0 、アンモニア (榭脂中和剤 Z和光純薬社製）：2.2重量％の水溶液 (10) Johncryl690 (manufactured by styrene-acrylic acid copolymer Z Johnson Polymer Co.): 30 wt 0/0, ammonia (榭脂neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 2.2% by weight aqueous solution
(11) PVA403 (ポバール Zクラレネ土製）：30重量0 /0の水溶液 (11) PVA403 (Poval Z Kurarene made earth): 30 weight 0/0 solution of
[0030] <評価 > [0030] <Evaluation>
(1)消去性評価  (1) Erasure evaluation
綿ブロード（晒）の試験布に水を含まな 、画筆（平筆 4号)を用いて、実施例 1〜4、 比較例 1〜5の着色材組成物を塗布し、室温で指触乾燥するまで放置した。その後、 乾燥後の試験サンプルを洗濯機で弱アルカリ性の合成洗剤を使用して (洗濯槽の水 量に対して 0. 2重量％) 20°Cで 15分間水洗し、 5分間手で揉み洗い後、乾燥させた 。乾燥させた試験布に着色材組成物が残っていないかを目視で観察し、評価した。  Apply the colorant composition of Examples 1 to 4 and Comparative Examples 1 to 5 using a paintbrush (Flat Brush No. 4) without water on a cotton broad (bleached) test cloth, and dry to the touch at room temperature. I left it until. After that, dry the test sample using a weakly alkaline synthetic detergent in the washing machine (0.2% by weight with respect to the amount of water in the washing tub). After that, it was dried. It was visually observed and evaluated whether or not the colorant composition remained on the dried test cloth.
[0031] その結果を表 1に示した。なお、表 1中の評価内容は次のとおりである。 The results are shown in Table 1. The evaluation contents in Table 1 are as follows.
〇：汚れが除去されている。  ○: Dirt is removed.
△:色、筆跡がはっきりわかる。  Δ: Color and handwriting clearly understood.
X：全く落ちていない。  X: Not falling at all.
[0032] (2)表装性評価 [0032] (2) Appearance evaluation
実施例 1〜4、比較例 1〜5の着色材組成物を書道用紙に毛筆を用いて書写し、室 温で 1週間放置した。その後、ベニヤ板の上に裏返して置き霧吹きで水を噴霧し、実 施例 1〜4、比較例 1〜5の着色材糸且成物の流れ出しを評価した。  The coloring material compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were copied on a calligraphy paper using a brush and left at room temperature for 1 week. Then, it was turned upside down on a plywood board, sprayed with water by spraying, and the run-out of the coloring material yarns and the compositions of Examples 1 to 4 and Comparative Examples 1 to 5 was evaluated.
[0033] その結果を表 1に示した。なお表 1中の評価内容は次のとおりである。 The results are shown in Table 1. The evaluation contents in Table 1 are as follows.
〇：流れない。  ○: It does not flow.
若干流れ出す。  Slightly flows out.
X：筆跡がわからない程流れ出す。  X: Runs out without knowing the handwriting.
産業上の利用可能性 本発明の着色材組成物は、墨汁、絵具のほか、マーキングペン用インキ等の水性 インキ組成物として用いることができる。 Industrial applicability The colorant composition of the present invention can be used as a water-based ink composition such as ink for marking pens in addition to ink and paint.

Claims

請求の範囲 The scope of the claims
[1] 少なくとも着色顔料、水溶性榭脂及び水を含む、洗濯により消去性を有する着色材 組成物であって、  [1] A coloring material composition containing at least a coloring pigment, a water-soluble rosin and water and having erasability by washing,
前記着色顔料の重量を P、前記水溶性榭脂の重量を Rとしたとき、 P :R= 1： 1〜1 : 30であり、  When the weight of the colored pigment is P and the weight of the water-soluble rosin is R, P: R = 1: 1 to 1:30,
前記水溶性榭脂として、分散榭脂及びァ-オン性榭脂が含まれており、 前記着色顔料は、前記分散榭脂により分散されており、  As the water-soluble resin, a dispersed resin and a charcoal resin are included, and the colored pigment is dispersed by the dispersed resin,
前記ァニオン性榭脂は、沸点— 10〜10°Cのァミン類で中和されているもの であることを特徴とする着色材組成物。  The colorant composition, wherein the anionic rosin is neutralized with an amine having a boiling point of 10 to 10 ° C.
[2] 前記沸点— 10〜10°Cのァミン類力 メチルァミン、ジメチルァミン及びトリメチルアミ ンの群力 選ばれる 1種または 2種以上のアミン類である請求項 1記載の着色材組成 物。 [2] The colorant composition according to claim 1, wherein the boiling point is from 10 to 10 ° C. Amines of methylamine, dimethylamine and trimethylamine are selected from one or more amines.
[3] 請求項 1記載の着色材組成物で構成された墨汁。  [3] A sumi ink comprising the colorant composition according to claim 1.
[4] 請求項 1記載の着色材組成物で構成された水性インキ組成物。  [4] A water-based ink composition comprising the colorant composition according to claim 1.
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