WO2006009165A1

WO2006009165A1 - Colorant composition eliminable by washing

Info

Publication number: WO2006009165A1
Application number: PCT/JP2005/013304
Authority: WO
Inventors: Toshiki Misawa; Manabu Kamegawa
Original assignee: Sakura Color Products Corporation
Priority date: 2004-07-21
Filing date: 2005-07-20
Publication date: 2006-01-26
Also published as: CN1989211B; CN1989211A; TW200617111A

Abstract

A colorant composition which comprises a coloring pigment, a pigment-dispersing resin, a water-eliminable resin which, after having been dried at ordinary temperature (25°C), is water-soluble, and water, wherein the pigment-dispersing resin and the eliminable resin both are water-soluble resins, the pigment-dispersing resin comprises a pigment-dispersing resin (A) having an acid value of 110-220, the weight ratio of the coloring pigment (P) to the water-soluble resins (R) consisting of the pigment-dispersing resin (A) and the water-eliminable resin (B), P/R ratio, is from 1/1 to 1/30, the weight ratio of the coloring pigment (P) to the pigment-dispersing resin (A), P/A ratio, is from 10/1 to 1.5/1, and the water-eliminable resin comprises at least 10 wt.% eliminable resin comprising polyvinyl alcohol (PVA) having a degree of saponification of 75-98 mol% and a viscosity of 30.0 mPa·sec or lower (4% aqueous solution; 20°C).

Description

Specification

Coloring composition erasable by washing

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, Japanese ink that can be erased by washing has been proposed (Patent Document 1, Patent Document 2).

Patent Document 1: JP-A-9-316379

Patent Document 2: JP-A-10-7957

[0003] However, these colorant compositions use dyes, and when applied to paper from their constituent elements, there is a problem of bleeding under high humidity.

[0004] The problem of the present invention is that, when applied to paper, it does not cause bleeding under high humidity, and when it adheres to a fiber assembly such as a cloth or nonwoven fabric, it can be erased by simple washing (washing). It is in providing a colorant composition that can be produced.

Disclosure of the invention

Means for solving the problem

[0005] The present invention is a colorant composition comprising a color pigment, a pigment-dispersed resin, a water-erasable resin having water solubility after drying at room temperature (25 ° C), and water,

The above-mentioned pigment-dispersed resin and erasable resin are water-soluble resins that are erasable by washing.

[0006] A preferred embodiment of the present invention includes the pigment-dispersed resin A having an acid value of 110 to 220 as the pigment-dispersed resin, the color pigment P, the pigment-dispersed resin A, and a water-erasable resin. The weight ratio (PZR ratio) with the water-soluble rosin R composed of B is 1Z1 ~ 1Z30, The colorant composition according to claim 1, wherein a weight ratio (PZA ratio) between the color pigment P and the pigment-dispersed resin A is 10Z1 to: L.5 / 1.

[0007] Further, in a preferred embodiment of the present invention, the water-soluble resin R is composed of the pigment-dispersed resin A and a water-erasable resin B having an acid value of 200 to 260,

The water-erasable resin B has a larger acid value than the pigment-dispersed resin A and

The colorant composition according to claim 1, wherein a weight ratio (BZA) of the water-erasable resin B and the pigment-dispersed resin A is 0.9 to 30.

[0008] It is preferable that the pigment-dispersed resin A and the water-erasable resin B are selected from the group forces of styrene / acrylic acid copolymer, styrene / maleic acid copolymer and polyacrylic acid, respectively. Further, it is preferable that the water-erasable resin B is neutralized and dissolved in water by any neutralizing agent selected from inorganic salts, alkanolamines, alkylamines and diamines.

[0009] Further, in a preferred embodiment of the present invention, as the erasable resin, a polybulu alcohol having an acidity of 75 to 98 mol% and a viscosity of 30.0 mPa'sec (4% aqueous solution, 20 ° C) or less ( The colorant composition comprising 10% by weight or more of an erasable resin made of PVA).

[0010] As a preferred method for producing the colorant composition containing the pigment-dispersed resin A having an acid value in the specific range, a coloring pigment, the pigment-dispersed resin A and water are blended and dispersed. After the pigment dispersion is obtained, an aqueous solution of water-erasable rosin B having an acid value higher than that of the pigment-dispersed rosin A is added to the pigment dispersion. It is a manufacturing method of a color material composition. The acid value of the pigment-dispersed resin A is preferably 110 to 220, and the acid value of the water-erasable resin B is preferably 200 to 260. In addition, as a preferable method for producing the colorant composition containing polybulal alcohol having a specific range of hatchability and viscosity, a pigment dispersion is obtained by blending and dispersing at least a color pigment, a pigment dispersion resin, and water. After that, an erasable rosin aqueous solution containing 10% by weight or more of polybutyl alcohol having a degree of hatching of 75 to 98 mol% and a viscosity of 30.0 mPa'sec (4% aqueous solution, 20 ° C) or less was added to the pigment dispersion. A method for producing a colorant composition erasable by washing, characterized by post-attaching. The invention's effect

[0011] This prevents problems such as bleeding under high humidity because no dye is used. Even if the colorant composition adheres to fibers such as clothes, the erasability by washing is improved.

Therefore, it can be applied to colorant compositions such as ink, ink for sign pens, ink for marking pens, etc. with a viscosity of 200 mPa • s or less, and colorant compositions such as high-viscosity paints, and can be erased by washing. A material composition can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] <Coloring pigment>

The color pigment used in the present invention is required to have a coloring effect with a fine particle size. Specifically, a pigment having a particle size of 0.05 to 0.5 m is preferable. For example, carbon black, ar phosphorus black, iron black, monoazo, anthraquinone, quinacridone, phthalocyanine, ultramarine, bitumen, and anthraquinone can be used.

[0013] The blending amount of the color pigment is 1 to: LO wt%, preferably 2 to 7 wt%, based on the total amount of the colorant composition. If the color pigment is less than 1% by weight with respect to the total amount of the colorant composition, the coloration will decrease. 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 fall off after adhering to the fiber.

[0014] <Water-soluble fat and oil>

The present invention uses a water-soluble resin as a pigment-dispersed resin and a water-erasable resin. The pigment dispersion resin A is a resin that disperses the color pigment, and includes that it is used as a resin for preparing a pigment dispersion in the production process. In addition, the water-erasable resin B is used as a resin that is blended as a post-added resin for the pigment dispersion dispersed by the pigment-dispersed resin in the manufacturing method.

[0015] It is preferable that the pigment-dispersed resin A is soluble in water, disperses a colored pigment as a pigment dispersion, and is excellent in dispersion stability. Particularly, as the pigment-dispersed resin A used in the present invention, an oil having an acid value of 110 to 220, preferably an oil having an acid value of 210 to 220 can be suitably used. For example, a styrene acrylic copolymer, a styrene maleic acid copolymer, a polyacrylic acid, an ethylene maleic acid copolymer and the like having an acid value of 110 to 220, preferably an acid value of 210 to 220 can be exemplified.

And the water-soluble resin R which is composed of the powerful pigment-dispersed resin A and the water-erasable resin B force (Hereinafter sometimes referred to as water-soluble rosin R) is a coloring pigment-containing coloring by setting the weight ratio (PZR) of the colored pigment P and the water-soluble rosin R to 1Z1 to LZ30. It becomes possible to improve the washing erasability in the material composition.

[0016] When the weight ratio (PZR ratio) between the color pigment P and the water-soluble rosin R exceeds 1Z1, the erasability by washing decreases. On the other hand, when the weight ratio (PZR ratio) between the colored pigment and the water-soluble rosin is less than 1Z30, the viscosity increases and the feeling in use decreases.

[0017] Further, the pigment-dispersed resin A is preferably 0.1 to 7.0% by weight, more preferably 0.2 to 3.5% by weight, based on the total amount of the colorant composition. When the pigment-dispersed resin A is less than 0.1% by weight with respect to the total amount of the colorant composition, the dispersibility of the pigment decreases, and aggregates with time, and the erasability by washing decreases. When the pigment-dispersed resin A exceeds 7.0% by weight based on the total amount of the colorant composition, the dispersibility of the pigment is improved, but the viscosity is increased, the feeling of use is lowered, and the gel is easily gelled with time. Become.

[0018] The weight ratio (PZA ratio) between the colored pigment P and the pigment-dispersed resin A is 10Z1 to: L. 5/1, preferably 5Zl to 2Zl. When the weight ratio (PZ A ratio) between the colored pigment and the pigment-dispersed resin A is more than 10Z1, the dispersibility of the pigment is reduced, and is aggregated with time, and the erasability by washing is reduced. When the weight ratio (PZR ratio) between the colored pigment and the pigment-dispersed resin A is less than 1.5Z1, the viscosity increases, the feeling of use decreases, and gelation is likely to occur over time.

[0019] Thus, a colorant composition comprising a color pigment, a pigment-dispersed resin, a water-erasable resin having water-dissolving performance after drying at room temperature (25 ° C), and water,

The pigment-dispersed resin contains a pigment-dispersed resin A having an acid value of 110 to 220, and the water-soluble resin R is composed of the colored pigment P, the pigment-dispersed resin A, and the water-erasable resin B. Weight ratio (PZR ratio) is 1Z1 ~: LZ30,

By using a colorant composition in which the weight ratio (PZA ratio) of the colored pigment P and the pigment-dispersed resin A is 10Z1 to: L. 5/1, since no dye is used, high humidity is maintained. Even if the above colorant composition adheres to fibers such as clothes without causing problems such as bleeding, the erasability by washing is improved. Therefore, coloring material composition that can be erased by washing by applying it to coloring material composition such as ink, ink for pen, ink for marking pen, etc. Providing things Can do.

[0020] In the present invention, the acid value of 200 to 260 is particularly preferred as a water-soluble rosin which further improves the washing erasability by neutral water in the pigment dispersion of the dispersed colored pigment. Alternatively, 200 to 240 water erasable rosin B can be suitably used. Examples thereof include styrene acrylic copolymers, styrene maleic acid copolymers, polyacrylic acid, and ethylene maleic acid copolymers having an acid value of 200 to 260, preferably 200 to 240.

[0021] The water-erasable rosin B is contained in an amount of 1 to 30% by weight, preferably 10 to 25% by weight, based on the total amount of the colorant composition. When the water-soluble rosin is less than 1% by weight with respect to the total amount of the colorant composition, the erasability by washing decreases. On the other hand, when the water-soluble rosin exceeds 30% by weight with respect to the total amount of the colorant composition, the viscosity increases and the feeling of use decreases.

[0022] In this way, a coloring material containing a coloring pigment is obtained by dispersing a coloring pigment with a resin having an acid value of 110 to 220 and increasing water solubility with a water-erasable resin B having an acid value of 200 to 260. In the composition, the washing erasability can be improved.

[0023] The weight ratio (BZA) of the water-erasable resin B and the pigment-dispersed resin A is preferably 0.9 to 30. By setting the amount within such a range, a synergistic effect of the pigment-dispersed resin A in which the color pigment is dispersed and the water-erasable resin B that exhibits wash-erase by water can be exhibited.

[0024] Further, in order to increase the washing erasability with water, the water-soluble rosin, particularly the water-erasable rosin B having a carboxylic acid, dissolves in water, exhibits alkalinity, and is neutralized. It is preferable to include a neutralizing agent that dissolves in water even after these rosins are coated or written and dried. Specifically, when the water-soluble resin selected from the group strength of styrene acrylic copolymer, styrene maleic acid copolymer, polyacrylic acid and ethylene-maleic acid copolymer is water erasable resin B, It is preferable to include a neutralizing agent. The neutralizing agent is selected from the group of inorganic salts, alkanolamines, alkylamines and diamines. Examples of inorganic salts include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, and diisopananol. And diisopananolamine. Examples of diamines include ethylenediamine, propylenediamine, N, N, Ν ', N'-tetramethylethylenediamine. In particular, even after the resin neutralized with the alkylamines and inorganic salts is dried, the erasability with water is high, which is preferable. If ammonia is used as the neutralizing agent, the ammonia is volatilized when the coating film or handwriting is dried, so that the washing erasability tends to deteriorate.

[0025] The neutralizing agent contains the water-soluble rosin in an amount of 0.1 to 20% by weight, preferably 1.0 to 15% by weight, based on the total amount of the colorant composition. When the neutralizing agent is less than 0.1% by weight with respect to the total amount of the colorant composition, the resin is hardly dissolved in water. On the other hand, if the water-soluble rosin exceeds 20% by weight with respect to the total amount of the colorant composition, the washing erasability is lowered, and bleeding occurs under high humidity after drying.

[0026] The colorant composition of the present invention is obtained by first blending and dispersing a colored pigment, pigment-dispersed resin A and water to obtain a pigment dispersion, and then water erasable resin in the pigment dispersion. It can be obtained by later adding an aqueous solution of B. The acid value of the pigment-dispersed resin A is preferably 110 to 220, and the acid value of the water-erasable resin B is preferably 200 to 260 as described above.

[0027] In the present invention, as described above, a water-erasable rosin that is a water-soluble rosin is used. In particular, as described above, it is preferable to use water-erasable rosin as the supplemented calcareous rosin. It is important to use a water-soluble resin having a water-erasing ability that is highly soluble in water after drying at room temperature (25 ° C) and has a low viscosity to some extent. As a powerful water-soluble rosin, it is also possible to use a urinary resin C such as polybulal alcohol, polybululpyrrolidone, polyethylene oxide. For example, a product name “PVA403” manufactured by Kurarene Co., Ltd. may be mentioned. It is also possible to mix the water erasable resin B and the resin C.

[0028] Other polyhydric alcohols such as glycerin, propylene glycol, and ethylene glycol, and antiseptic / antifungal agents may be added as necessary.

[0029] Further, as the water erasable resin, the water erasable resin B in the specific range is used without using the water erasable resin B in the specific range or as the water C with the water erasable resin B or in the specific acid value range. As B, it is preferable to use a polybutyl alcohol having a hatching degree of 75 mol% or more and less than 98 mol% and a viscosity of 30.0 mPa ′ sec (4% aqueous solution, 20 ° C.) or less. For example, a product name “P VA403” manufactured by Kurarene is available. Degree of hatching 75 mol% or more and less than 98 mol%, preferably 78 mol% or more and less than 82 mol%, viscosity is 30.0 mPa 'sec (4% aqueous solution, 20 ° C) or less, preferably 10 mPa' sec (4% aqueous solution, 20 ° C) or less, and 2 mPa 'sec (4 By using a polybulal alcohol having a% aqueous solution of 20 ° C. or more, it is possible to provide a colorant composition having good water erasability by washing while maintaining an appropriate viscosity and good usability. If the acidity is less than 75 mol%, the viscosity becomes too high and the feeling in use is lowered. When the acidity exceeds 98 mol%, the water erasability by washing is insufficient for the coating film dried at room temperature (25 ° C). Even if the viscosity exceeds 30.0 mPa 'sec (4% aqueous solution, 20 ° C), the viscosity becomes too high and the feeling of use decreases.

[0030] On the other hand, it is preferable to use the polybulal alcohol used in the present invention having a polymerization degree of 100 to 600, preferably 350 to 450. This polybulal alcohol is contained in an amount exceeding 10% by weight to less than 27% by weight, preferably 12% by weight or more and 26% by weight or less, based on the total amount of the colorant composition. If the polyvinyl alcohol is 10% by weight or less, the water erasability by washing decreases, and if it is 27% by weight or more, the viscosity increases and the feeling of use decreases.

[0031] A coloring material composition comprising a coloring pigment, a pigment-dispersed resin, a water-erasable resin having water-dissolving performance after drying at room temperature (25 ° C) and water, and the specific range as the erasable resin By using the polybulal alcohol having the acidity and viscosity of the dye, the above colorant composition can be applied to fibers such as clothes without causing problems such as bleeding under high humidity. Even if it adheres, the erasability by washing improves. Therefore, it can be applied to colorant compositions such as ink, ink for signboards, and ink for marking pens with a viscosity of 200 mPa · s or less, and colorant compositions such as high-viscosity paints, and can be erased by washing. A colorant composition can be provided.

[0032] In the present invention, as described above, together with the polyvinyl alcohol having the above-mentioned specific range of degree of hatching and viscosity, the water-erasable resin B has an acid value of 200 to 260, preferably 200 to 240. Water-soluble rosin can be suitably used. Examples thereof include styrene acrylic copolymers, styrene maleic acid copolymers and ethylene maleic acid copolymers having an acid value of 00 to 260, preferably 200 to 240.

[0033] The water-erasable rosin B is preferably contained in an amount of 1 to 30% by weight, more preferably 10 to 25% by weight, based on the total amount of the colorant composition. [0034] Thus, in addition to the specific polyvinyl alcohol, the color pigment is dispersed with a resin having an acid value of 110 to 220, and the water solubility is increased with a water-erasable resin B having an acid value of 200 to 260. As a result, it is possible to further improve the washing erasability in the colorant composition containing the color pigment.

[0035] The weight ratio (BZA) of the water erasable resin B and the pigment dispersion resin A is preferably 0.9 to 30 as described above. By setting the content in such a range, the synergistic effect between the resin A in which the color pigment is dispersed and the water erasable resin B that exhibits wash erasability with water can be further exhibited.

[0036] As in the case of the water-erasable resin B, when a polyvinyl alcohol having a specific range of hatching and viscosity is used, it dissolves in water, exhibits alkalinity, and is neutralized. It is preferable to include a neutralizing agent that dissolves in water even after the resin is applied or written and dried. Specifically, as described above, when the water-erasable resin B is selected from the group strength of styrene acrylic copolymer, styrene maleic acid copolymer, and ethylene maleic acid copolymer, the neutralizing agent is included. Preferably. The neutralizing agent is selected from the group consisting of inorganic salts, alkanolamines, alkylamines and diamines. Examples of inorganic salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., and examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and monoisoprono V—. Luamine, diisopananolamine, triisopananolamine and the like can be mentioned. Examples of the diamine include ethylenediamine, propylenediamine, N, N, Ν ', Ν, and monotetramethylethylenediamine. In particular, even after the coconut oil neutralized with the alkylamines and inorganic salts is dried, the erasability with water is high, which is preferable. When ammonia is used as a neutralizing agent, ammonia is volatilized when the coating film or handwriting is dried, and thus the washing erasability tends to be lowered.

[0037] As described above, the neutralizing agent is contained in an amount of 0.1 to 20% by weight, preferably 1.0 to 15% by weight, based on the total amount of the colorant composition.

As described above, polyhydric alcohols such as glycerin, propylene glycol, and ethylene glycol, and antiseptic / antifungal agents may be added as necessary.

[0038] The colorant composition of the present invention includes at least a color pigment, a pigment dispersion resin and water. First, a pigment dispersion is obtained by combining and dispersing, and then the aqueous solution of the specific polybutyl alcohol can be added to the pigment dispersion by post-addition. In addition, when the other water-soluble rosin is further added, it can be obtained after addition with the aqueous solution of the specific polyvinyl alcohol.

Example

[0039] In the composition shown in Table 1, a coloring pigment, rosin A, water, and a pigment wetting agent are blended if necessary, and dispersed for 1 hour in a bead mill (Dynomill: manufactured by Shinmaru Enterprises). Next, an aqueous solution of resin B is added to this pigment dispersion and stirred for 30 minutes to obtain a ink coloring material composition.

[0040] [Table 1]

mm ^ 、％晷軍 z I (ifT oav έ: Be ^ —) oosip uow: ¾. (I

[00]

l70CCl0 / S00Zdf / X3d 01S9T600 / 900Z OAV Fat (styrene acrylic copolymer, manufactured by Johnson Polymer Co., Ltd., trade name: Johncryl 683) 3.4 wt%, rosin neutralizer (sodium hydroxide) 0.4 wt%, the balance being water pigment dispersion

2) trade name: Shimura Fast Red 4127 17 weight ^_0/0, water-soluble榭脂(styrene-acrylic copolymer, Johnson Polymer Co., Ltd., trade name: Johncryl 683) 3. 4% by weight,榭脂neutralizer (water Sodium oxide) 0.4% by weight, the balance being water pigment dispersion

3) trade name: Fastogen Blue TGR 17 weight ^_0/0, water-soluble榭脂(styrene-acrylic copolymer, Johnson Polymer Co., Ltd., trade name: Johncryl 683) 3. 4% by weight,榭脂neutralizer (water Sodium oxide) 0.4% by weight, the balance being water pigment dispersion

4) Product name: 30% aqueous solution of Johncryl 690 (styrene acrylic copolymer Z Johnson Polymer Co., Ltd.)

5) Product Name: 30 weight ^_0/0 aqueous solution of PVA403 (PVA Z Kurarene made of earth)

6) Product name: Johncryl 611 (styrene acrylic copolymer Z Johnson Polymer) 20% aqueous solution

7) Product name: 20% by weight aqueous solution of PVA102 (made of Bhopal Z Kralene)

8) Product name: Monarch800 (carbon black, manufactured by ZCAB0T) 17% by weight, water-soluble resin (styrene acrylic copolymer, manufactured by Johnson Polymer, product name: Johncryl 678), 3.4% by weight, resin neutralizer (Sodium hydroxide) 0.5% by weight, the balance being water pigment dispersion

9) Product name: Monarch800 (carbon black, ZCAB0T) 17% by weight, water-soluble resin (styrene acrylic copolymer, manufactured by Seiko Chemical Industry Co., Ltd., product name: X-1), 3.4% by weight, resin Neutralizer (sodium hydroxide) 0.6% by weight, the balance being water pigment dispersion

10) Product name: X—1202S (styrene-maleic acid copolymer, manufactured by Seiko Chemical Industry Co., Ltd.), 30% by weight aqueous solution (neutralized with sodium hydroxide)

[0042] The acid values of the resins shown in the table are values based on product information or values measured by a conventional method.

[0043] Next, this ink composition was applied to a cotton broad (bleached) test cloth using a paint brush that does not contain water (Flat Brush No. 4), and was allowed to stand at room temperature until it was dry to the touch. After that, the test sample after drying was washed in a washing machine using a weakly alkaline synthetic detergent having a weak pH (0.2% by weight based on the amount of water in the washing tub) at 20 ° C for 15 minutes and then washed with water for 15 minutes. . Visual inspection of test samples after drying Observed and evaluated.

[0044] <Evaluation of erasability>

○ is pass and ΔX is fail.

○: Dirt is removed.

Δ: Color and handwriting clearly understood.

X: Not fall at all.

[0045] <Evaluation of writing quality>

○ is pass and ΔX is fail.

〇: Very smooth.

Δ: Stickiness and strength.

X: I can hardly write.

[0046] From Table 1, in the case of the colorant composition of this example, the above-mentioned colorant was accidentally applied to fibers such as clothes without using a dye, so that problems such as bleeding under high humidity did not occur. Even if the composition adheres, the erasability by washing is improved. Moreover, the writing quality is also good.

[0047] Next, in the composition shown in Table 2, a color pigment, a pigment dispersion containing pigment-dispersed resin and water, a resin solution containing PVA and water, water, and a pigment wetting agent as necessary. Disperse for 1 hour in a bead mill (Dai No Mill: manufactured by Shinmaru Enterprises). Next, an aqueous solution of polybulal alcohol is added to the pigment dispersion and stirred for 30 minutes to obtain a ink coloring material composition. About these, the hatching degree and the viscosity were measured. The number of test samples is n = 3.

[0048] [Table 2]

Content (* a%) Ke ^ ftl¾ Viscosity / 4%, 2 T.

Ito

(mol%) (nPa ■ s) 1 2 3 4 5 6 1 2 Black star ¾ ^ body "―-10.0 15.0 15.0 20.0 Black 觸² '1-10.0

--20.0 10.0 Body ⁴ >--20.0

Resin solution ^5> 78.5 to 81.5 2.8 to 3.3 85.0 85.0

Resin liquid ^w 87.0-89.0 21.0-25.0 60.0 60.0

Boiling liquid "95.0 ~ 97.0 23.0 ~ 29.0 70.0

Resin liquid ^s〗 98.0 to 99.0 5.2 to 6.0 70.0 Resin solution ^9> 87.0-89.0 98.0 to 122.0 60.0 resin solution ¹⁰⁾ 76.7 to 79.3 11.7-14.3 60.0

Ion--5.0 5.0 20.0 10.0 25.0 25.0 10.0 30.0 Total-One 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Thigh ¹⁰ )--2.0 2.0 4.0 4.0 3.0 3.0 4.0 2.0 Tree-One 25.9 25.5 12.8 14.8 12.6 12.6 0.8 12.4

--0.0 0.0 0.0 0.0 0.0 0.0 21.0 0.0 Reverse male-1 O O O O O O X O Writing quality 1-O O O O O O O O X

[0049] (table note)

1) Product Name: Monarch800 (made of carbon black ZCABOT Co., Ltd.) 20 weight ^_0/0, PVA403 (manufactured by Kuraray Co., Ltd.) 4% by weight, the balance of water pigment dispersion

2) trade name: Monarch800 (carbon black manufactured by ZCABOT Co.): 20 wt ^_0/0, Joncryl6 78 (Johnson Ltd. Polymer Co.) 4% by weight, the resin neutralizer (Mizusani匕sodium) 0.5 wt%, the balance Water pigment dispersion

3) Product Name: Shimura First Red 4127 (manufactured by PR267 / Dainippon Ink and Chemicals, Inc.), 20 weight ^_0/0, manufactured by PVA403 (Kurarene soil) 4% by weight, the balance of water pigment dispersion

4) Product Name: Fast Gen Blue TGR (PB15: 3Z manufactured by Dainippon Ink and Chemicals, Inc.), 20 weight ^_0/0, PVA403 (manufactured by Kurarene soil) 4% by weight, the balance of water pigment dispersion

30 weight 5) PVA403 (manufactured by PVAZ Kurarene earth) ^_0/0 solution

6) 20% aqueous solution of B-17 (manufactured by PVAZ Denka)

7) 20% aqueous solution of C-500 (PVAZ Nippon Gosei Co., Ltd.)

30 weight of 8) PVA105 (manufactured by PVAZ Kurarene soil) ^_0/0 aqueous solution

9) 20% by weight aqueous solution of B-33 (manufactured by PVAZ Denka)

10) Content of pigment in the pigment dispersion of 1) to 4) above

11) The amount of PVA with a degree of hatching of less than 98 mol% in the PVA oil solution of 5) to 9) above

12) Amount of PVA having an acidity of 98 mol% or more in the PVA oil solution of 5) to 9) above [0050] <Method for measuring degree of oxidation>

Including the above Examples and Comparative Examples, the measurement was performed according to the degree of hatching according to the present invention and IS K 6726.

[0051] <Measurement method of viscosity>

Including the above Examples and Comparative Examples, the viscosity in the present invention was measured according to JIS K 6726.

[0052] Next, the ink composition of each test sample was applied to a cotton broad (bleached) test cloth with no water paint (flat brush No. 4) until it was dry to the touch at room temperature. Each was left alone. After that, dry each test sample in a washing machine using a weakly alkaline synthetic detergent. (0.2% by weight with respect to the amount of water in the washing tub) Washed at 20 ° C for 15 minutes and then washed with water for 15 minutes. After drying, each test sample was visually observed and evaluated.

[0053] <Erasability evaluation>

○ is pass and ΔX is fail.

○: Dirt is removed.

Δ: Color and handwriting clearly understood.

X: Not fall at all.

[0054] <Writing evaluation>

○ is pass and ΔX is fail.

〇: Very smooth.

(Triangle | delta): There is shakiness.

X: I can hardly write.

[0055] From Table 2, the colorant composition of this example uses a dye, and thus the above colorant is accidentally applied to fibers such as clothes without causing problems such as bleeding under high humidity. Even if the composition adheres, the erasability by washing is improved. Moreover, the writing quality is also good.

Industrial applicability

[0056] 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 (ink ink) and paint.

Claims

The scope of the claims

[1] A coloring material composition comprising a coloring pigment, a pigment-dispersing resin, a water-erasable resin having water-dissolving performance after drying at room temperature (25 ° C), and water.

A colorant composition that can be erased by washing, wherein the pigment-dispersed resin and the erasable resin are water-soluble resins.

[2] The pigment-dispersed resin contains a pigment-dispersed resin A having an acid value of 110 to 220,

The weight ratio (PZR ratio) of the color pigment P to the water-soluble resin R composed of the pigment-dispersed resin A and the water-erasable resin B is 1Z1 to: LZ30.

The colorant composition erasable by washing according to claim 1, wherein a weight ratio (PZA ratio) between the color pigment P and the pigment-dispersed resin A is 10Z1 to: L. 5/1.

[3] The water-soluble resin R is composed of the pigment-dispersed resin A and a water-erasable resin B having an acid value of 200 to 260,

The colorant composition capable of being erased by washing according to claim 2, wherein a weight ratio (BZA) of the water-erasable resin B and the pigment-dispersed resin A is 0.9 to 30.

[4] The laundry according to claim 2, wherein the pigment-dispersed resin A and the water-erasable resin B are selected from the group forces of styrene-acrylic acid copolymer, styrene-maleic acid copolymer, and polyacrylic acid, respectively. Colorant composition erasable by

[5] The water-erasable resin B is selected from the group strength of inorganic salts, alkanolamines, alkylamines and diamines, neutralized with any neutralizing agent and dissolved in water. A coloring material composition which can be erased by washing.

[6] The erasable resin comprising polybulal alcohol (PVA) having an acidity of 75 to 98 mol% and a viscosity of 30. OmPa-sec (4% aqueous solution, 20 ° C) or less. The colorant composition according to claim 1, comprising 10% by weight or more.

[7] A coloring material composition comprising a coloring pigment, a pigment-dispersing resin, a water-erasable resin having water-dissolving performance after drying at room temperature (25 ° C), and water.

Both the pigment-dispersed resin and the erasable resin are water-soluble resins.

The pigment-dispersed resin contains a pigment-dispersed resin A having an acid value of 110 to 220, The weight ratio (PZR ratio) of the color pigment P to the water-soluble resin R composed of the pigment-dispersed resin A and the water-erasable resin B is 1Z1 to: LZ30.

The weight ratio (PZA ratio) between the colored pigment P and the pigment-dispersed resin A is 10Z1 to: L. 5/1,

As the water-erasable resin, an erasable resin composed of polybulal alcohol (PVA) having an acidity of 75 to 98 mol% and a viscosity of 30.0 mPa'sec (4% aqueous solution, 20 ° C) or less is 10 A coloring material composition containing at least wt%.

[8] A sumi ink comprising the colorant composition according to claim 2.

[9] A sumi ink comprising the colorant composition according to claim 6.

[10] A water-based ink composition comprising the colorant composition according to claim 2.

[11] A water-based ink composition comprising the colorant composition according to claim 6.

[12] After coloring pigment, pigment-dispersed resin A and water are blended and dispersed to obtain a pigment dispersion, the pigment dispersion has a higher acid value than pigment-dispersed resin A. A method for producing a colorant composition erasable by washing, wherein an aqueous solution of fat B is added afterwards.

13. The method for producing a colorant composition erasable by washing according to claim 12, wherein the acid value of the pigment-dispersed resin A is 110 to 220, and the acid value of the water-erasable resin B is 200 to 260.

[14] A pigment dispersion is obtained by blending and dispersing at least a coloring pigment, a pigment dispersion resin, and water, and then the degree of hatching is 75 to 98 mol% and the viscosity is 30.0 mPa'sec (4 A method for producing a colorant composition that is erasable by washing, comprising post-implanting an erasable rosin aqueous solution containing 10% by weight or more of a polybulal alcohol of 20% or less (20 ° C).