WO2007080914A1

WO2007080914A1 - Colorant composition

Info

Publication number: WO2007080914A1
Application number: PCT/JP2007/050219
Authority: WO
Inventors: Toshiki Misawa
Original assignee: Sakura Color Products Corporation
Priority date: 2006-01-12
Filing date: 2007-01-11
Publication date: 2007-07-19
Also published as: JP4861014B2; JP2007186581A

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 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, an anionic resin (A), and an anionic resin (B), that the colorant is dispersed with the dispersing resin, that the anionic resin (A) is in a state neutralized with an amine having a boiling point of 7°C or below and the anionic resin (B) is in a state neutralized with an amine having a boiling point of 17°C or above, and that the A/B weight ratio is 0.7 to 1.5.

Description

Specification

Colorant composition

Technical field

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.

Background art

[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.

Patent Document 1: JP-A-9-316379

Patent Document 2: JP-A-10-7957

[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.

Disclosure of the invention

Problems to be solved by the invention

[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.

Means for solving the problem

[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,

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

The water-soluble resin includes dispersed resin, ionic resin A and ionic resin B,

The colored pigment is dispersed by the dispersed resin.

The anionic resin A is neutralized with an amine having a boiling point of 7 ° C or lower, and the anionic resin B is neutralized with an amine having a boiling point of 17 ° C or higher. The most important means is to provide a colorant composition having a weight ratio of the anionic resin A to the anionic resin B of 0.7 to 1.5.

The invention's effect

[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.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] <Coloring pigment>

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] 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] <Water-soluble fat and oil>

In the present invention, the colorant composition seems to be easily removed by washing (washing). In order to make it, water-soluble rosin is used. In the coloring material composition of the present invention, three types of water-soluble resins, namely a dispersed resin, a charcoal resin A, and a charcoal resin B, are essential components.

[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 setting it within this range, it becomes possible to improve the washing erasability in the colorant composition containing the color pigment. 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] <Dispersed resin>

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] 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] <Vanion-based rosin>

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 erasability is decreased. It is not preferable.

[0014] <A-on rosin A>

Of the anionic resin, the anionic resin A is neutralized with an amine having a boiling point of 7 ° C or lower. Examples of the amines having a boiling point of 7 ° C. or less used for neutralizing the anionic resin A include ammonia, methylamine, dimethylamine and trimethylamine. Of these, alkylamines such as methylamine, dimethylamine, and trimethylamine are preferable. These amines can be used alone or in combination of two or more.

[0015] A suitable blending ratio of the amines having a boiling point of 7 ° C or less is 0.1 to 20% by weight, more preferably 1.0 to 15% by weight, based on the total amount of the colorant composition. 0. If less than 1% by weight, the wash erasability also decreases due to a decrease in the solubility of the resin. On the other hand, if it exceeds 20% by weight, the penetration of the ink is promoted and the wash erasability is reduced. .

[0016] <Vanion-based rosin B>

Of the above-mentioned eron-based resins, eron-based resin B is neutralized with amines having a boiling point of 17 ° C or higher. Examples of amines having a boiling point of 17 ° C or higher used for neutralizing anionic resin B include alkylamines such as monoethylamine, impropylamine, dimethylamine, and jetylamine; monoethanolamine, diethanolamine, triethanolamine, and the like. Examples include alkanolamines such as ethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine; and diamines such as ethylenediamine and propylenediamine. Of these, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine are preferable. These amines can be used alone or in combination of two or more.

[0017] A suitable blending ratio of amines having a boiling point of 17 ° C or higher is 0.1 to 20% by weight, more preferably 1.0 to 15% by weight, based on the total amount of the colorant composition. When the amount is less than 1% by weight, the washing erasability is also reduced due to a decrease in the solubility of the resin. On the other hand, when it exceeds 20% by weight, the water resistance after drying is lowered and the surface appearance is lowered. Therefore, it is not preferable.

[0018] <Other accessories>

Others such as glycerin, propylene glycol, ethylene glycol, etc. A monohydric alcohol or an antiseptic / antifungal agent may be added.

[0019] <Production method>

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.

[0020] (First step; production of colored pigment dispersion)

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.

[0021] (Second step; preparation of ergonomic resin A and B)

The ionic resin is dissolved in two aqueous solutions and neutralized by adding an amine having a boiling point of 7 ° C or lower and an amine having a boiling point of 17 ° C or higher, respectively. And anionic resin B aqueous solution.

[0022] (Third step; production of coloring material composition)

To the colored pigment dispersion prepared in the first step above, add the aqueous resin A and the aqueous resin B in the second step, and stir with a disperser for about 30 minutes. As a result, the colorant composition of the present invention can be obtained.

Example

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.

[0024] <Manufacturing>

(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, neutralize by adding ammonia (boiling point 33.0 ° C) or methylamine (boiling point 7.0 ° C) to one of the two ergonal resins. did. The other char-on resin was neutralized by adding triethanolamine (boiling point 360.0 ° C) to obtain a char-on resin B aqueous solution. Finally, the anionic resin A aqueous solution and the aqueous anion resin B aqueous solution are added to the colored pigment dispersion. The mixture was added and stirred for 30 minutes to obtain the coloring material compositions (inkbrush) of Examples 1 to 4.

[0025] (Comparative Example 1)

A coloring material composition having the composition shown in Table 1 and different from that of the example in that the charcoal resin A had a strong force was prepared as Comparative Example 1. The preparation method is the same as the method described in Examples 1 to 4.

[Comparative Example 2]

As a comparative example 2, the composition shown in Table 1 was different from the example in that the charon resin A and the charonous resin B were not added, but a poval aqueous solution was added afterwards. Prepared. The preparation method is the same as the method described in Examples 1 to 4.

[0027] (Comparative Example 3)

A colorant composition different from the examples in the composition shown in Table 1 except that the weight ratio of the char-on resin A to the char-on resin B is not within the range of 0.7 to 1.5. Was prepared as Comparative Example 3. The preparation method is the same as the method described in Examples 1 to 4.

[0028] (Comparative Example 4)

Comparative composition of the colorant composition shown in Table 1 which is different from the examples in that the arn resin A and the ar resin B are not added, but instead an aqueous carboxymethyl cellulose solution is added instead. Prepared as 4. The preparation method is the same as the method described in Examples 1 to 4.

[0029] [Table 1]

(Unit:% by weight)

In addition, each raw material in Examples 1-4 and Comparative Examples 1-4 used the following.

(1) Monarch800 (carbon black manufactured by ZCABOT Co.): 20 wt ^_0/0, PVA403 (manufactured by Kurarene soil): 4% by weight of colored pigment dispersion

(2) Monarch800 (carbon black manufactured by ZCABOT Co.): 20 wt ^_0/0, Joncryl678 (Johnson Nporima Co.): 4 wt% of the colored pigment dispersion

(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 colored pigment dispersion

(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 colored pigment dispersion

(5) 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

(6) X-1 (manufactured by styrene-maleic acid copolymer Z Review Photochemical Co.): 30 wt ^_0/0, Mechiruamin (榭fat neutralizer Z manufactured by Wako Pure Chemical Industries, Ltd.): 1.8% by weight aqueous solution (7) 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

(8) PVA403 (Poval Z Kurarene made earth): 30 weight ^_0/0 solution of

(9) Serogen 5A (Carboxymethyl Cellulose Z Daiichi Kogyo Seiyaku Co., Ltd.): 20% by weight aqueous solution

[0031] <Evaluation>

(1) Erasure evaluation

Apply the colorant composition of Examples 1 to 4 and Comparative Examples 1 to 4 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.

The results are shown in Table 1. The evaluation contents in Table 1 are as follows.

○: Dirt is removed.

Δ: Color and handwriting clearly understood.

X: Not falling at all.

[0033] (2) Appearance evaluation

The coloring material compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were copied onto a calligraphy paper using a brush and left at room temperature for 1 week. Then, it was turned over 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 4 was evaluated.

○: It does not flow.

Slightly flows out.

X: Runs out without knowing the handwriting.

Industrial applicability

[0035] 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

The scope of the claims

[1] A coloring material composition containing at least a coloring pigment, a water-soluble rosin and water and having erasability by washing,

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,

The colored pigment is dispersed by the dispersed resin.

The anionic resin A is neutralized with an amine having a boiling point of 7 ° C or lower, and the anionic resin B is neutralized with an amine having a boiling point of 17 ° C or higher. A colorant composition, wherein the weight ratio of the anionic resin A to the anionic resin B is 0.7 to 1.5.

[2] The amine having a boiling point of 7 ° C or lower is one or two or more amines selected from the group power of ammonia, methylamine, dimethylamine, and trimethylamine,

And the amine having a boiling point of 17 ° C or higher is monoethylamine, impropylamine, dimethylamine, jetylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine. 2. The colorant composition according to claim 1, wherein the colorant composition is one or two or more amines selected from the group strength of min, ethylenediamine and propylenediamine.

[3] A sumi ink comprising the colorant composition according to claim 1.

[4] A water-based ink composition comprising the colorant composition according to claim 1.