WO2007094357A1

WO2007094357A1 - Erasable colorant composition

Info

Publication number: WO2007094357A1
Application number: PCT/JP2007/052606
Authority: WO
Inventors: Toshiki Misawa
Original assignee: Sakura Color Products Corporation
Priority date: 2006-02-16
Filing date: 2007-02-14
Publication date: 2007-08-23
Also published as: JP2007217538A; JP4841966B2

Abstract

A colorant composition that when applied to paper, is free from the problem of exudation, etc., and that even when water spraying is conducted after drying, is free from pigment outflow, ensuring excellent surface decorating capability, and that when stuck to a fiber assembly, such as cloth or nonwoven fabric, can be erased by simple washing using a weakly alkaline synthetic detergent. There is provided a colorant composition containing at least a coloring pigment, a water-soluble resin and water, characterized in that the water-soluble resin (R) consists of water-soluble resin (A) and anionic resin (B), and that the coloring pigment (P) is dispersed by the water-soluble resin (A) and the anionic resin (B) has an acid value of 110 or below, and that the weight ratio of coloring pigment (P) to water-soluble resin (R), ratio P/R, is in the range of 1/1 to 1/30, the weight ratio of coloring pigment (P) to resin (A), ratio P/A, in the range of 10/1 to 1.5/1, and the weight ratio of resin (A) to resin (B), ratio A/B, in the range of 0.02 to 1.2.

Description

Specification

Erasable colorant composition

Technical field

The present invention relates to a colorant composition that can be used for ink, paints, marking pen inks, and the like. More specifically, when applied to paper, there is no problem of bleeding, etc., and it is excellent in surface appearance, and even if it accidentally adheres to clothes etc., it is easy to use a weak alkaline synthetic detergent commonly used at home. The present invention relates to a colorant composition that can be completely erased by washing.

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] 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] On the other hand, a coloring material composition using a pigment as a coloring material has also been proposed, and bleeding problems are less likely to occur than those using a dye. In addition, the washability of the colorant composition itself is improved. Therefore, it is also conceivable to use these colorant compositions in ink.

[0005] However, when a calligraphy work is mounted on a hanging shaft or the like, generally water is sprayed by spraying to restore the shrinkage of the calligraphic paper that occurs when the ink dries. Even when the colorant composition is used, there is a practical problem that the pigment flows out due to its erasability.

Disclosure of the invention

Problems to be solved by the invention

[0006] The problem of the present invention is that, when applied to paper, there are no problems such as bleeding, and even when sprayed with water after drying, the pigment does not flow out and is excellent in surface appearance. It is an object of the present invention to provide a colorant composition that can be erased by simple washing with a weak alkaline synthetic detergent when adhering to a coalescence.

Means for solving the problem

[0007] In the colorant composition used for ink and the like, the present inventors set the acid value of the post-added resin to 110 or less in order to prevent the pigment from flowing out due to water spray performed at the time of covering. on the other hand

The balance of performance required by increasing the acid value of the dispersion resin in order to compensate for the erasability that decreases with improvement in surface appearance, i.e., to increase the erasability during washing using weak alkaline synthetic detergent. It came to achieve.

That is, the invention of claim 1 is a coloring material composition containing at least a color pigment, a water-soluble resin and water, and the water-soluble resin R is composed of a water-soluble resin A and an anionic resin B. The color pigment P is dispersed in a water-soluble resin A, the acid value of the anionic resin B is 110 or less, and the weight ratio of the color pigment P to the water-soluble resin R (P / R Ratio) is 1/1 to: 1/30, and the weight ratio (P / A ratio) of the colored pigment P to the resin A is S10 / 1 to: 1.5 / 1, and the resin A and the resin A colorant composition erasable by washing, wherein the weight ratio (A / B) of the resin B is from 0.02 to 1.2. The invention of claim 2 is characterized in that the anionic resin B is one or more anionic resins selected from the group consisting of a styrene acrylic acid copolymer, a styrene maleic acid copolymer, and an ethylene maleic acid copolymer force. The colorant composition according to claim 1, wherein The invention of claim 3 is characterized in that the anionic resin B is neutralized with a neutralizing agent selected from the group consisting of inorganic salts, alkanolamines, alkylamines and diamines and dissolved in water. 1. A coloring material composition which can be erased by washing according to 1. The invention of claim 4 is one or more water-soluble resins selected from the group consisting of the water-soluble resin A force polybulal alcohol, styrene acrylic acid copolymer and styrene maleic acid copolymer. This colorant composition can be erased by washing. The invention of claim 5 is the colorant composition erasable by washing according to claim 1, wherein the water-soluble resin A has an acid value S110 exceeding. In the invention of claim 6, the color pigment, the water-soluble resin A and water are at least blended and dispersed to obtain a pigment dispersion, and then an aqueous solution of the water-soluble resin B is added to the pigment dispersion. The colorant composition erasable by washing according to claim 1, This is a method for manufacturing a product. The invention of claim 7 is a black ink comprising the colorant composition of claim 1. The invention of claim 8 is a paint composed of the colorant composition of claim 1. The invention of claim 9 is an ink for a marking pen comprising the colorant composition of claim 1.

The invention's effect

[0009] According to the present invention, when applied to paper, problems such as bleeding do not occur, and it is excellent in appearance, and even when it is accidentally attached to clothes, etc., weakly alkaline synthesis commonly used at home It is possible to obtain a colorant composition that can be completely erased by simple washing with a detergent. These colorant compositions can be used in inks, paints, marking pen inks, etc.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] <Coloring pigment>

The color pigment used in the present invention is required to have a coloring effect with a fine particle size. Specifically, pigments with a particle size of 0.05 to 0.5 zm are preferred. For example, carbon black, aniline black, iron black, monoazo, anthraquinone, quinacridone, phthalocyanine, ultramarine, bitumen, and anthraquinone can be used.

[0011] The blending amount of the color pigment is:! To 10% by weight, preferably 2 to 7% by weight, 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 be difficult to drop after adhering to the fiber.

[0012] <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 composed of a water-soluble resin A and an anionic resin B in which a colored pigment is dispersed and the resulting pigment dispersion is excellent in dispersion stability.

[0013] <Water-soluble resin A>

As the resin A, PVA, styrene acrylic acid copolymer, styrene maleic acid copolymer, and other carboxymethyl cellulose, arabic gum, dextrin, polyacrylic acid and the like can be used. Anion resin such as styrene acrylic acid copolymer Is preferably used as an aqueous solution neutralized with an alkali, and the acid value of the anion resin exceeds 110. Resin A is preferably 0.1 to 10.0 wt%, particularly 0.5 to 1.5 wt%, based on the total amount of the colorant composition. When the content is less than 0.1%, the aggregation of the pigment occurs with time, and when the content exceeds 10.0%, gelling occurs during dispersion.

In addition, the water-soluble resin R containing the resin A, which has strength, has a good laundry erasable colorant composition by setting the weight ratio (PZR) of the color pigment P and the water-soluble resin to lZl to lZ30. You can get power S.

[0014] When the weight ratio (P / R ratio) between the color pigment P and the water-soluble resin R exceeds 1/1, the erasability by washing decreases. On the other hand, when the weight ratio (P / R ratio) between the color pigment and the water-soluble resin is less than 1Z30, the viscosity increases and the feeling in use decreases.

[0015] The weight ratio (PZA ratio) of the color pigment P to the resin A is 10Z1 to: 1.5 / 1, preferably 5 / :! to 2/1. When the weight ratio (PZA ratio) between the colored pigment and the resin A exceeds 10Z1, the dispersibility of the pigment is reduced, and it aggregates with time, and the erasability by washing is reduced. When the weight ratio (P / R ratio) between the color pigment and the resin A is less than 1.5 / 1, the viscosity becomes high and gelation tends to occur during dispersion.

[0016] <Vanion resin B>

As the anionic resin B of the present invention, an anionic resin that becomes soluble in water when neutralized with an alkali is used. As the anionic resin, styrene acrylic acid copolymer, styrene maleic acid copolymer, and ethylene maleic acid copolymer are preferred. These resins have a certain degree of viscosity and an acid value of 110 or less. is necessary. The amount of the anionic resin is 10.0 to 30.0% by weight, preferably 10.0 to 15.0% by weight, based on the total amount of the colorant composition. If it is less than 10.0% by weight, the washing erasability decreases, and if it exceeds 30.0% by weight, the viscosity increases and the feeling of use decreases.

[0017] Further, the resin neutralizing agent of the anionic resin must be dissolved in water and exhibit alkalinity, and alkylamines such as monoethylamine, inpropylamine dimethylamine, and jetylamine are preferably used. Other alkanolamines such as monoethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and diamines such as ethylenediamine and propylenediamine are used. It is done. Alkylamines are preferably used. The amount of the resin neutralizing agent is 0.1 to 20% by weight, preferably 1.0 to 15% by weight. If it is less than 0.1% by weight, the washing erasability is also lowered due to a decrease in the solubility of the resin, and if it exceeds 20% by weight, the penetration of the ink is promoted and the washing erasability is lowered.

[0018] The weight ratio (A / B) between the resin A and the resin B is preferably 0.02-1-2. By setting the amount within such a range, a synergistic effect between the resin A in which the color pigment is dispersed and the resin B that exhibits wash erasability with water can be exhibited.

[0019] Other additives>

Other polyhydric alcohols such as glycerin, propylene glycol and ethylene glycol, antifungal agents (for example, benzotriazole, tolyltriazole, dicyclohexylammonium nitrate), antiseptic / antifungal agents (as required) For example, benzoisothiazoline antiseptic / antifungal agent, pentachlorophenol antiseptic / antifungal agent, talesol antiseptic / antifungal agent), surfactant, wetting agent, antifoaming agent, leveling agent, anti-aggregation agent, pH Conventional additives such as adjusting agents and pseudoplasticity imparting agents can be added.

[0020] The colorant composition of the present invention is obtained by first mixing and dispersing a color pigment, resin A and water to obtain a pigment dispersion, and then adding an aqueous solution of resin B to the pigment dispersion. Can be obtained by

[0021] <Production method>

In the method for producing a colorant composition of the present invention, a pigment dispersion is first prepared by dispersing a color pigment, the resin A, water, and, if necessary, a pigment wetting agent. Next, resin B is added to the aqueous pigment dispersion, various additives are further added, and the mixture is stirred until uniform to obtain an aqueous ink composition. The obtained ink composition is preferably subjected to a known defoaming step and filtration step.

[0022] 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 Bonore mill, a sand mill, a roll mill, a kneader, and a stirrer such as a turbo mixer.

Example

[0023] Hereinafter, the present invention will be described in more detail with reference to examples. <Manufacture of pigment dispersion>

First, the following composition components were dispersed in a bead mill (trade name “Dynomill”, manufactured by Shinmaru Enterprises) for 1 hour, whereby black pigment dispersions (1), (2), A red pigment dispersion (3) and a blue pigment dispersion (4) were respectively prepared.

[Black pigment dispersion (1)]

Carbon black

(Product name "Monarch 800" manufactured by Cabot Corporation)

Polybulal alcohol 20% by weight aqueous solution

(Kuraray's product name "Poval 403")

water

[Black pigment dispersion (2)]

Carbon black

(Product name "Monarch 800" manufactured by Cabot Corporation)

Styrene acrylic acid copolymer 20% by weight aqueous solution 20 parts by weight

(Johnson Polymer Co., Ltd., trade name "John Talillo 678" [sodium hydroxide neutralized]) Water 60 parts by weight

[Red pigment dispersion (3)]

(Dainippon Ink & Chemicals, P.R.267)

(Johnson Polymer Co., Ltd., trade name "John Talillo 678" [NaOH neutralization]) Water

[0028] [Blue pigment dispersion (4)]

Fast Gen Blue TRG

(Dainippon Ink & Chemicals, p. B. 15: 3)

Styrene acrylic acid copolymer 20% by weight aqueous solution

(Johnson Polymer Co., Ltd., trade name "John Clinole 678" [neutralized with sodium hydroxide]) Water [0029] <Preparation of ink or ink>

Using the water pigment dispersions (1) to (4), they were mixed at the mixing ratio shown in Table 1 (unit: parts by weight) and stirred for 30 minutes with a disperser. Examples:! To 4 and comparison For example:! ~ 4 inks or inks were produced. In addition, the resin liquid in a table | surface shows the following.

Resin liquid (1): Acrylic acid polymer (trade name ¾_310, manufactured by Seiko Polymer Co., Ltd.) 30% by weight, ethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 1. 4% by weight aqueous solution

Resin liquid (2): Styrene maleic acid copolymer (trade name “H — 1712”, manufactured by Seiko Polymer Co., Ltd.) 30% by weight, etylamine (manufactured by Wako Pure Chemical Industries) 1. 9% by weight aqueous solution.

Resin liquid (3): Styrene acrylic acid copolymer (trade name “John Tall 690” manufactured by Johnson Polymer Co., Ltd.) 30% by weight, sodium hydroxide (manufactured by Wako Pure Chemical Industries) 5.1% by weight aqueous solution.

Resin liquid (4): Styrene acrylic acid copolymer (manufactured by Johnson Polymer Co., Ltd., trade name “Johntalyl 690”) 30% by weight, triethanolamine (manufactured by Wako Pure Chemical Industries) 19.1% by weight aqueous solution. Resin solution (5): Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name "Poval 403") 30 weight ^_0/0 aqueous solution.

Resin liquid (6): Carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Serogen 5A”) 20% by weight aqueous solution.

[0030] <Evaluation>

1. Erasability test

[Preparation of test sample]

The prepared ink or ink was applied to a cotton broad (bleach) test cloth using water and a paintbrush (flat brush No. 4), and left to dry at the room temperature.

m)

The test sample after drying was washed with a weak alkaline synthetic detergent (0.2% by weight) in a washing machine at 20 ° C. for 15 minutes, and then hand-washed for 5 minutes. Thereafter, it was washed with water for 15 minutes, and after drying, the test sample was visually observed and evaluated according to the following criteria. Table 1 shows the evaluation results. [Eraseability Evaluation Criteria]

○: Dirt is removed.

Δ: Color and handwriting clearly understood. X: Not fall at all.

2.Appearance test

The calligraphy paper was copied using a brush and left at room temperature for a week. Then, it was turned over on a plywood board, sprayed with water by spraying, and the flow of the pigment was evaluated according to the following criteria. [Evaluation criteria for surface appearance]

○: It does not flow.

Δ: Slightly flows out.

X: Flows out without knowing the handwriting.

[table 1]

Industrial applicability

The coloring material composition of the present invention can be used as a coloring material composition for ink (marking ink), paint, and ink for marking pens. In particular, it is difficult to use the coloring material composition of the present invention to display a scroll, which has been difficult to achieve with conventional erasable coloring material compositions. I can.

Claims

The scope of the claims

[1] 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 an anionic resin B, and the color pigment P is dispersed in the water-soluble resin A.

The acid value of the anionic resin B is 110 or less,

The weight ratio (P / R ratio) between the color pigment P and the water-soluble resin R is lZl˜: 1Z30, and the weight ratio (P / A ratio) between the color pigment P and the resin A is 10 / 1˜: 1. A colorant composition erasable by washing, wherein the colorant composition is 5/1, and the weight ratio (A / B) of the resin A to the resin B is 0.02 to 1.2.

[2] The anionic resin B is one or more anionic resins selected from the group consisting of a styrene acrylic acid copolymer, a styrene maleic acid copolymer, and an ethylene maleic acid copolymer. Colorant composition.

[3] The anionic resin B is neutralized with any neutralizing agent selected from the group consisting of inorganic salts, alkanolamines, alkylamines and diamines, and dissolved in water. Coloring composition that can be erased by washing.

[4] The water-soluble resin A is one or more water-soluble resins selected from the group consisting of polybutyl alcohol, styrene acrylic acid copolymer, and styrene maleic acid copolymer. Possible colorant composition.

[5] The colorant composition erasable by washing according to claim 1, wherein the acid value of the water-soluble resin A exceeds 110.

[6] The coloring pigment P, the water-soluble resin A and water are at least blended and dispersed to obtain a pigment dispersion, and then an aqueous solution of the water-soluble resin B is added to the pigment dispersion. A method for producing a colorant composition erasable by washing according to claim 1.

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

[8] A paint composed of the colorant composition according to claim 1.

[9] An ink for a marking pen comprising the colorant composition according to claim 1.