JPH107957A - Erasable colorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an erasable colorant compsn. which does not dye clothes even when attached thereto by mistake and can easily be erased by washing with water or with a detergent by using the reaction product of a reactive dye with a specific resin as the colorant. SOLUTION: This compsn. contains, as the colorant, a reaction product of a reactive dye and a water-soluble resin pref. having at least one functional group selected from among hydroxyl, carboxyl, sulfo, amino, and their salt groups. Pref. at least one water-soluble resin selected from among polyethylene glycol, a polyoxyethylene-polyoxypropylene block copolymer, (modified) PVA, polysulfonic acid and its copolymer, and polyacrylic acid and its copolymer is used. Pref. the reactive dye is selected from among those based on dichlorotriazine, monochlorotriazine, vinylsulfone, chloropyrimidine, dichloroquinoxazine, and difunctional monochlorotriazine-vinylsulfone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used as ink for ink, paints, marking pens, etc., and is a water-soluble ink which can be easily erased by washing with water when adhered to a fiber aggregate such as cloth or nonwoven fabric. The present invention relates to an erasable colorant composition.

[0002]

2. Description of the Related Art Conventionally, there has been a problem that, for example, when ink and paint are adhered and fixed to a fiber assembly such as cloth such as clothes or non-woven fabric by mistake, they cannot be easily removed by washing.

On the other hand, if not only ink and paint but also ink for a marking pen or the like can be positively drawn on a fiber assembly such as clothing and easily erased, it can be used as a new coloring agent.

[0004] Conventionally, Japanese Patent Application Laid-Open No. Hei 7-3197 discloses that a pigment is reacted with a water-insoluble resin or the like to form a water-insoluble composite, and erasability is imparted by preventing dyeing to a fiber aggregate.
Alternatively, the pigment is covered with a water-insoluble resin to increase the particle size of the water-insoluble composite, thereby preventing the fiber of the pigment from being caught in the eyes and providing erasability.

[0005]

However, these techniques only increase the molecular diameter of the pigment and prevent its diffusion in the fiber, and the resulting colorant composition is a pigment dispersion. Furthermore, in the latter technique, the fixation to the writing surface is deteriorated, so that it was necessary to add a separate fixing agent to the ink component in order to prevent this.

[0006] An object of the present invention is to provide a dye with a reaction product with a water-insoluble resin without realizing erasability, without dyeing even if a coloring agent is accidentally attached to clothes, etc. An object of the present invention is to provide an erasable colorant composition that can be easily erased by washing or the like.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a colorant composition containing a reaction product of a reactive dye and a water-soluble resin has erasability. The invention according to claim 1 is an erasable colorant composition comprising a reaction product of a reactive dye and a water-soluble resin.

[0008] The water-soluble resin to be added to the dye is not particularly limited as long as it is a water-soluble resin.
A water-soluble resin having one or more functional groups selected from an H group, a COOH group, a SO ₃ H group or an NH ₃ group, or a salt thereof is preferable. The invention according to claim 2 is characterized in that the water-soluble resin is
OH group, COOH group, SO ₃ H group or NH ₃ groups, a or erased colorant composition of claim 1, wherein a functional group selected from those salts which are water-soluble resin having one or more. That is, synthetic polyhydric alcohol-based, carboxylic acid (salt) -based, and sulfonic acid (salt) -based water-soluble resins are preferred. Specifically, polyethylene glycol, polyoxyethylene polyoxypropylene block polymer compound, polyvinyl alcohol, modified polyvinyl alcohol, polysulfonic acid, polysulfonic acid copolymer, polyacrylic acid, polyacrylic acid copolymer are preferable, among which Polyethylene glycol is optimal. The invention according to claim 3 is characterized in that the water-soluble resin is polyethylene glycol, polyoxyethylene polyoxypropylene block polymer, polyvinyl alcohol, modified polyvinyl alcohol, polysulfonic acid, polysulfonic acid copolymer, polyacrylic acid, polyacrylic acid copolymer. At least one of the polymers
The erasable colorant composition according to claim 1, wherein A fourth aspect of the present invention is the erasable colorant composition according to the first, second or third aspect, wherein the water-soluble resin is polyethylene glycol.

When the average molecular weight of the water-soluble resin to be added to the colorant is low, the colorant tends to bleed, and the molecular diameter of the reacted dye also becomes small, so that it is likely that the dye easily enters the fiber. Adversely affect. Also, as the average molecular weight increases, the aqueous solution becomes more viscous,
It is not preferable from the viewpoint of handling. From this point,
It is important to control the molecular weight and molecular length of the water-soluble resin, and a water-soluble resin that makes it difficult for the dye to diffuse through the surface of the fiber and has a low viscosity is preferable. Specifically, the average molecular weight of the water-soluble resin, particularly polyethylene glycol, is preferably from 600 to 7,500. In the invention according to claim 5, the water-soluble resin has an average molecular weight of 600 to 75.
4. The erasable colorant composition according to claim 1, wherein the colorant composition is 00. The average molecular weight in the present invention indicates a weight average molecular weight.

There are two methods for controlling the molecular weight and molecular length of the dye. For example, there is a method in which a material having a large molecular weight is used as a raw material at the time of dye synthesis, and a reaction product with a dye polymer is obtained as a final product form. For example, it can be obtained by the following synthesis method.

[0011]

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Another method is to dye the resin with a dye to control the molecular weight. For example, it can be obtained by the following synthesis method.

[0013]

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The latter method is preferred in that the number of colors can be dyed in accordance with the type of the reactive dye, and thus an erasable colorant composition of many colors can be provided. Also, workability is good. In the present invention, the latter reactant is particularly adopted as a preferable coloring agent.

The reactive dye is not particularly limited, but as a result of studying particularly effective dyes, dichlorotriazine type, monochlorotriazine type, vinylsulfone type, chlorpyrimidine type, dichloroquinoxazine type, monochlorotriazine and vinylsulfone Has been found to be preferred. Among them, reactive dyes of the monochlorotriazine type and vinylsulfone type, particularly the monochlorotriazine type, are most suitable. In the invention according to claim 6, the reactive dye is:
6. The reactive dye of any one of dichlorotriazine type, monochlorotriazine type, vinylsulfone type, chlorpyrimidine type, dichloroquinoxazine type, and bifunctional group type of monochlorotriazine and vinylsulfone. A colorant composition.

In the present invention, by using a water-soluble resin as the resin to be reacted with the dye, fixing to the fiber is easily ensured, and there is no need to add a fixing agent as in the case of using a water-insoluble resin. That is, the water-soluble resin containing the dye has a hydroxyl group and the like, and is bonded to only the surface of the fiber, particularly a fiber having a large number of hydroxyl groups such as cotton, by a hydrogen bond, or a van der Waals force. Has a favorable effect. Further, such a hydrogen bond has a relatively weak bond, and the bond with the fiber can be easily broken by washing with water or the like. In addition, a fixing agent can be added as needed.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The reactive dyes include, but are not limited to, for example, Cibacron Black P-SG
(Manufactured by Ciba-Geigy), Cibacron Black P-2PD (manufactured by Ciba-Geigy), Cibacron Black F-2B (manufactured by Ciba-Geigy), Cibacron Gray GR-01 (manufactured by Ciba-Geigy), Ci
bacron Blue PB (manufactured by Ciba Geigy), Cibacron Nav
y GR-E-01 (Ciba-Geigy), Cibacron Blue FR
(Made by Ciba Geigy), Cibacron Red PB (made by Ciba Geigy), Cibacron Red 4G-EN (made by Ciba Geigy), Cibacron Red FB (made by Ciba Geigy), Cibacr
on Yellow P-6GS (Ciba Geigy), Cibacron Yell
ow 2G-E (Ciba-Geigy), Cibacron Yellow F-3R
Monochlorotriazine type reactive dyes such as Cibacron Black CN (Ciba-Geigy), Cibacron Blue CR (Ciba-Geigy), Cibac
ron Red CR (Ciba Geigy), Cibacron Yellow C
Monochlorotriazine such as -R-1 (manufactured by Ciba Geigy)-
Vinyl sulfone bifunctional reactive dye, Remazol Black
DEN Hi-Gran (manufactured by Dystar), Remazol Blue RU-N
Vinyl sulfone type reactive dyes such as Remazol Red RU-N (Dystar), Remazol Yellow RU-N (Dyster), trade name Levafix Navy Blue
E-BNA GRAN (by Dystar), Levafix BR.Red E-RN
A dichloroquinoxazine-type reactive dye such as (Dystar) and Levafix G Yellow EG (Dystar) can be used.

The water-soluble resin is not particularly limited, but may be polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene oleate, polyoxyethylene nonyl phenyl ether, carboxylic acid-modified polyvinyl alcohol, polyacrylic acid, polystyrene sulfonic acid. In addition to soda, polyvinyl alcohol, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene alkyl ether,
Polyoxyethylene nonyl phenyl ether, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan monooleate,
One or two of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, pullulan, polyacrylic acid itaconic acid copolymer and the like
Although a mixture of more than one kind can be used, polyethylene glycol is most suitable in consideration of erasability, price, handling, and the like.

The colorant composition includes a fixing agent, a bulking agent, a preservative, a fungicide, a fragrance, a surfactant, a pH adjuster, a viscosity adjuster, a dispersant, a water retention agent, a wetting agent, a defoaming agent, Leveling agent,
Viscoelasticity adjusting agents, anti-smearing agents, water, alcohol, and the like that are generally included in ink, paints, and marking pens can be included.

The coloring agent of the present invention can be used as ink, paint, ink and the like. Even if these are accidentally attached to clothes, etc., they do not enter the fiber through the surface of the fiber. Can be easily erased.

The erasable colorant composition of the present invention can be used without particular limitation as long as it is a fiber.
Nylon, vinylon, acetate, wool, rayon,
Effectively works on fibers such as acrylic, silk and polyester. In particular, in the case of a reactive dye, only the dye, a cellulose skeleton such as cotton or rayon, a fiber having an OH group such as a PVA skeleton such as vinylon, wool,
It tends to be dyed by fibers with amines such as silk, and it is thought that some interaction (bonding) occurs between the dyes and OH groups or amines. However, erasure by washing with a water-soluble resin, particularly polyethylene glycol, is considered. The properties are improved in almost all fibers.

[0022]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 12.5 g of sodium sulfate (Na ₂ SO ₄ ) was dissolved in 125 g of distilled water, and 15 g of polyethylene glycol (average molecular weight: 600) was stirred while stirring.
And 1.5 g of reactive dye Cibacron Black P-SG (manufactured by Ciba Geigy) is added and stirred for 30 minutes. Then 9
Heat to 0 ° C and add alkali (Na ₂ CO ₃ aqueous solution 20g /
1.25 ml) and stirred at 90 ° C. for 1 hour. After natural cooling, two layers were separated, so only the colored part (upper layer) was collected,
A black colorant composition was obtained. (Example 2) Sodium sulfate (Na ₂ ) was added to 125 g of distilled water.
After dissolving 12.5 g of SO ₄ , 15 g of polyethylene glycol (average molecular weight 3000) and 1.5 g of reactive dye Cibacron Gray GE-01 (manufactured by Ciba Geigy) are added with stirring, and the mixture is stirred for 30 minutes. Thereafter, the mixture is heated to 90 ° C. and alkali (Na ₂ CO ₃ aqueous solution 20 g / 1.25)
ml) and stirred at 90 ° C. for 1 hour. After natural cooling,
Since the two layers were separated, only the colored portion (upper layer) was recovered to obtain a gray colorant composition. (Example 3) Sodium sulfate (Na ₂ ) was added to 125 g of distilled water.
12.5 g of SO ₄ ) was dissolved, and while stirring, 15 g of polyethylene glycol (average molecular weight 7500) and the reactive dye Cibacron Black P-SG (manufactured by Ciba Geigy) were added.
Add 5 g and stir for 30 minutes. Thereafter, the mixture is heated to 90 ° C. and alkali (Na ₂ CO ₃ aqueous solution 20 g / 1.25 m)
l) was added and the mixture was stirred at 90 ° C for 1 hour. After natural cooling, two layers were separated, so only the colored portion (upper layer) was collected to obtain a black colorant composition. (Example 4) Sodium sulfate (Na ₂ ) was added to 125 g of distilled water.
12.5 g of SO ₄ ) was dissolved and, with stirring, 15 g of polyvinyl alcohol (degree of saponification, degree of polymerization 250) and a reactive dye Cibacron Black P-SG (manufactured by Ciba Geigy)
Is added and stirred for 30 minutes. Then 90 ° C
And heated to an alkali (Na ₂ CO ₃ aqueous solution 20 g / 1.
25 ml) and stirred at 90 ° C. for 1 hour. After natural cooling, it was recovered to obtain a black colorant composition. The product gelled.

Comparative Example 1 A colorant composition was obtained under the same conditions as in Example 1 except for polyethylene glycol. Comparative Example 2 A colorant composition was obtained under the same conditions as in Example 2 except for polyethylene glycol. Comparative Example 3 A colorant composition was obtained under the same conditions as in Example 3 except for polyethylene glycol. (Comparative Example 4) Example 4 except for polyvinyl alcohol
Under the same conditions as above, a colorant composition was obtained. (Comparative Example 5) A colorant composition was obtained under the same conditions as in Example 1 except that polyethylene glycol having an average molecular weight of 600 was changed to an average molecular weight of 500. (Comparative Example 6) A colorant composition was obtained under the same conditions as in Example 3 except that polyethylene glycol having an average molecular weight of 7,500 was changed to an average molecular weight of 8,000.

(Erasability Test) Next, the colorant compositions of Examples 1 to 4 and Comparative Examples 1 to 6 were applied to a cotton-broad test cloth using a water-free brush (No. 4). And left to dry to the touch at room temperature. After drying, use a synthetic detergent in a washing machine (adjusted to 0.2%) at 25 ° C for 1 hour.
Washing was carried out for 5 minutes and then with water for 15 minutes. After drying, it was visually evaluated according to the following criteria. 4 or more passed as the erasable colorant composition. 5. . . Completely erased. 4. . . Almost erased. (It remains faint when seen through the light.) . . Although it is thinner than before washing and has an effect,
You can see the coating marks. 2. . . Although it is thinner than before washing, there is not much effect of washing. 1. . . Same as before washing.

[0026]

[Table 1]

From Table 1, it can be seen that Examples 1 to 4 using reactive dyes were used.
All of the colorant compositions of No. 4 were completely or almost completely erased by washing. Further, it is recognized that the erasability is increased by mixing polyethylene glycol.

Further, the handwriting after leaving all the colorant compositions at room temperature until touch-drying was sufficiently fixed on the cotton broad test cloth. Further, in Comparative Example 5 in which polyethylene glycol having an average molecular weight of 500 was mixed, the coloring agent was easily bleeding, and the molecular diameter of the reacted dye was also small, so that it was considered that the dye could easily enter the fiber, and the erasability was low. Not preferred. The average molecular weight is 75
In Comparative Example 6 exceeding 00, the aqueous solution had a high viscosity, which was not preferable from the viewpoint of handling.

Examples 5 to 14 The water-soluble resins were polyoxyethylene polyoxypropylene block polymer (average molecular weight 8,000), polyoxyethylene alkyl ether (average molecular weight 1000), polyglycerin fatty acid ester (average molecular weight 900), Polyoxyethylene sorbitan monooleate (average molecular weight 31
60), polyoxyethylene sorbitan monolaurate (average molecular weight 3078), polyoxyethylene sorbitan monostearate (average molecular weight 3162), polyoxyethylene sorbitan monopalmitate (average molecular weight 3134), polyacrylic acid (average molecular weight 1000)
0), sodium polystyrene sulfonate (average molecular weight 2
0000), carboxylic acid-modified PVA (average degree of polymerization about 2)
000, saponification degree 93-95%), and a colorant composition was obtained under the same conditions as in Example 1. As a result of performing the above-mentioned erasability test on these colorant compositions, all the evaluations were in the range of 4 to 5.

[0030]

As described above, the erasable colorant of the present invention comprises:
As before, the reactive dye and the water-soluble resin are reacted without realizing the erasability with the complex of the dye and the water-insoluble resin. It can be easily erased by washing or the like by washing with water or using a detergent. Therefore, it can be used as black ink, paint, marking pen ink, etc., which can be washed out with a simple composition, and greatly contributes to this field.

Claims (9)

[Claims] 1. An erasable colorant composition comprising a reactive product of a reactive dye and a water-soluble resin as a colorant. 2. The method according to claim 1, wherein the water-soluble resin is an OH group, a COOH group,
2. A water-soluble resin having one or more functional groups selected from O ₃ H groups or NH ₃ groups or salts thereof.
The erasable colorant composition as described in the above. 3. The water-soluble resin is polyethylene glycol, polyoxyethylene polyoxypropylene block polymer, polyvinyl alcohol, modified polyvinyl alcohol, polysulfonic acid, polysulfonic acid copolymer, polyacrylic acid, polyacrylic acid copolymer. 3. The erasable colorant composition according to claim 1, which is at least one of the following. 4. The erasable colorant composition according to claim 1, wherein the water-soluble resin is polyethylene glycol. 5. The water-soluble resin has an average molecular weight of 600 to 75.
The erasable colorant composition according to claim 1, wherein 6. The reactive dye is a dichlorotriazine type,
The erasable colorant composition according to any one of claims 1 to 5, which is a reactive dye of any one of a monochlorotriazine type, a vinyl sulfone type, a chlorpyrimidine type, a dichloroquinoxazine type, and a bifunctional type of monochlorotriazine and vinyl sulfone. . 7. Black ink containing the erasable colorant composition according to claim 1. Description: 8. A paint containing the erasable colorant composition according to claim 1. 9. An ink for a marking pen, comprising the erasable colorant composition according to claim 1.