JPH11209647A - Water-base color chip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain water-base color chips having high gloss and high tinting power by using, as the principal component, a component comprising a pigment and a nitric ester of a carboxyalkylcellulose having a specified or higher degree of substitution with nitric ester groups and a specified or higher degree of substitution with carboxyalkylcellulose in a specified ratio. SOLUTION: These chips mainly consist of a component comprising (A) 15-80 wt. % pigment and (B) 20-85 wt.% nitric ester of a carboxyalkylcellulose having a degree of substitution with nitric ester groups per anhydride glucose of 0.2 or above and a degree of substitution with carboxyalkylcellulose of 0.05 or above. In further detail, component A, component B, water, an organic solvent and a neutralizing agent are milled, and the mixture is reduced into chips. Component B used is one in which all or part of the hydrogen ions of the carboxyl groups have been neutralized with alkali metal, ammonium or monobasic organic amine ions. The color ships are useful for use in a water-base ink or coating material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous color chip, and more particularly, to an aqueous color chip used in aqueous printing inks, paints and the like having excellent clarity, coloring power and gloss. The water-based color chip of the present invention is used as a functional coating material used for water-based paints, printing inks, plastic paints, paper coatings, film processing, leather paints, textile processing, magnetic paints, conductive pastes, and the like. .

[0002]

2. Description of the Related Art Conventionally, a color chip obtained by mixing a pigment with a thermoplastic resin, a plasticizer, and a solvent and then heating and kneading the mixture on two rolls (hereinafter, abbreviated as chipping) is It is known that the dispersion (state) is extremely excellent, the gloss and coloring power are large, and the hue becomes clear. In addition, there are many advantages such as the fact that it can be easily formed into an ink or a pigment simply by dissolving in a varnish, a solvent or the like.

Further, it is known that a pigment having a strong cohesive strength, which cannot be dispersed by a dispersing machine such as a sand mill or a bead mill, can be dispersed. Therefore, particularly in the case of pigments that are strongly agglomerated, poorly dispersed portions called chica are likely to occur, and the dispersibility is improved by adding a solvent and a plasticizer, but this is not an effective means. Further, when nitrocellulose is used as a resin, there is a risk of ignition in the ground meat, so that the ground meat at high temperature and high viscosity is dangerous, and efficient dispersion is desired.

[0004] Further, when a chip of a thermoplastic resin or a cellulose ester such as nitrocellulose is used as a chip, a large amount of an organic solvent is used, so that there is a danger of ignition, air pollution by a volatile solvent, deterioration of a working environment, and the like. In order to prevent this, collection facilities and recycling facilities are installed to protect the environment, but there is a problem that capital investment is large.

[0005] Further, for reasons such as environmental preservation and improvement of work safety, water-based paints and inks are being developed. Examples of resins used for these applications include aqueous cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose. However, these cellulose derivatives have a problem that a desired pigment dispersibility cannot be obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous color chip having high gloss and high coloring power, which is useful for aqueous inks and paints.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, according to the present invention, the pigment is 15 to 80% by weight and the degree of nitrate ester substitution per anhydrous glucose unit is 0.1%.
2 or more, carboxyalkyl ether group substitution degree is 0.0
An aqueous color chip comprising, as a main component, 20 to 85% by weight of a nitric acid ester of carboxyalkyl cellulose of 5 or more.

The aqueous color chip of the present invention can be produced, for example, by kneading a nitric acid ester of carboxyalkylcellulose, water, an organic solvent, a neutralizing agent, and a pigment with a roll mill or the like to form chips. Work safety and environmental protection can be improved. Hereinafter, the present invention will be described in detail.

In the present invention, if the content of the pigment exceeds 80% by weight, it is difficult to form a chip and the workability is poor. On the other hand, if the content of the pigment is less than 15% by weight, the coloring power becomes poor at the time of preparing the paint. Preferably, pigment 30
７０70% by weight. The carboxyalkylcellulose nitrate used in the present invention is a carboxyalkylcellulose such as carboxymethylcellulose or carboxyethylcellulose, which is treated with a known nitric acid esterified mixed acid, for example, a nitric acid esterified mixed acid composed of sulfuric acid / nitric acid and water. The carboxyalkyl cellulose nitrate contained in the nitrate ester group substitution degree is 0.2
As described above, the degree of carboxyalkyl ether group substitution is 0.05
The details are described in detail in JP-A-5-3930.
1 and an aqueous cellulose derivative disclosed in JP-A-5-39302.

If the nitrate ester substitution degree is less than 0.2,
If the pigment dispersibility becomes insufficient and the degree of carboxyalkyl ether group substitution is less than 0.05, the solubility in water becomes insufficient, and a large amount of organic solvent is required. Preferably, the degree of nitrate ester substitution is 0.5 or more and 2.5 or less, and the degree of carboxyalkyl ether group substitution is 0.3
Not less than 2.0. More preferably, the substitution degree of the nitrate ester group is 0.6 or more and 2.1 or less, and the substitution degree of the carboxyalkyl ether group is 0.4 or more and 1.6 or less.

The carboxylalkyl cellulose nitrate used in the present invention has a carboxyl group contained therein which is neutralized. Neutralized means that all or part of the hydrogen ions of the carboxyl group is replaced with one or a combination of two or more ions of an alkali metal ion, an ammonium ion or a monobasic organic amine to form a salt. Say that

Examples of the alkali metal ion used for neutralizing the carboxyl group contained in the nitric acid ester of carboxyalkylcellulose include ions of elements of the first group of the periodic table such as lithium, sodium, potassium and rubidium. Preferred examples of the monobasic organic amine include ions of an organic compound containing one amino group in a molecule such as ethylamine, propylamine, butylamine, triethylamine, and diethylethanolamine. For other metal element ions and dibasic or higher polybasic organic amine ions, the interaction between molecules becomes excessive, and the solubility in water or a mixed solvent with an organic solvent is insufficient. Tend to be.

As the organic solvent, alcohols,
Solvents composed of one or a combination of two or more of polyhydric alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, carbonates and the like can be used. Examples of alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-heptanol.
Octanol, n-nonyl alcohol, n-decanol, n-undecanol or isomers thereof, cyclopentanol, cyclohexanol and the like can be mentioned.
Preferred are alcohols having 1 to 6 alkyl carbon atoms.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-cyclohexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
Examples include 9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.

Derivatives of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, cellosolve acetate, etc., or a solvent pocket book edited by the Society of Synthetic Organic Chemistry, Japan (Ohm, September 20, 1990).
Polyhydric alcohols and their derivatives described on pages 79 to 574;

Examples of ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone and cyclohexanone. Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate, butyrate, diisopropyl succinate, diisopropyl glutarate, diisopropyl adipate, dibutyl phthalate, dioctyl phthalate, And ε-
And cyclic esters such as caprolactone and ε-caprolactam.

As ethers, diethyl ether,
Examples include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like. Examples of the carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and the like.

Examples of pigments include titanium dioxide, iron oxide, zinc oxide, carbon black, phthalocyanine pigment, insoluble azo pigment, azo lake pigment, anthraquinone pigment, quinacridone pigment, ultramarine, navy blue, cobalt oxide, strontium chromate, titanium yellow, and titanium black. And known color pigments such as molybdenum red, molybdenum white, lithopone and emenald green.

In addition, if necessary, a dispersant, a thickener,
Antifoaming agents, epoxy stabilizers, thioether stabilizers, urea stabilizers, and the like can be added in conventional amounts. An example of the method for producing the aqueous color chip of the present invention will be described. Examples of the mixing ratio of the pigment, the carboxyalkyl cellulose nitrate, water and the solvent, and the neutralizing agent used in the present invention are 5 to 32% by weight of the pigment, 8 to 34% by weight of the carboxyalkyl cellulose nitrate, 20 to 20% of water. 36% by weight, 15 to 25% by weight of a solvent, and 1 to 3% by weight of a neutralizing agent. These are uniformly kneaded with a kneader, heated and kneaded with two rolls to disperse the pigment, and then rolled to evaporate water and solvent to form a film, which is then coarsely crushed into a color chip.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. In addition, the evaluation method in an Example is as follows. <Measurement of Gloss> A color chip, an acrylic / styrene-based emulsion F2430 (manufactured by Asahi Kasei Kogyo Co., Ltd.), and a film-forming aid were stirred and mixed by a three-one motor to obtain a paint.

The paint was applied to a glass plate and dried, and the gloss at 60 ° to 60 ° was measured with a digital variable-angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd.

[0022]

Production Example 1 100 g of carboxymethylcellulose (degree of carboxymethylether group substitution = 0.7) and sulfuric acid /
3 liters of a mixed acid composed of nitric acid / water = 64.7 / 24.4 / 10.9 (% by weight) is placed in a 5 liter reaction vessel, and a nitrification reaction is performed while stirring at 5 ° C. for 1 hour. The product is deacidified in a centrifuge and immediately washed with copious amounts of water.
0 g of carboxymethylcellulose nitrate was obtained.

The obtained carboxymethyl cellulose nitrate has a carboxymethyl ether group substitution degree of 0.1.
In 7, the degree of nitrate ester substitution is determined from the nitrogen content,
It was 1.8.

[0024]

Example 1 600 parts by weight of carboxymethyl cellulose nitrate (50% wet cotton) obtained in Production Example 1 and carbon black MA-100 (Mitsubishi Chemical Corporation) as a pigment
300 parts by weight), 126 parts by weight of water, 360 parts by weight of isopropyl alcohol, and 145 parts by weight of aqueous ammonia (10%), and kneaded with a kneader until uniform.
The mixture was kneaded for 10 minutes in a two-roll heated to 0 ° C., rolled into a film, and crushed to obtain an aqueous color chip.

The obtained color chip was mixed with an acrylic / styrene emulsion F2430 to prepare a paint having a pigment concentration of 9%, and the gloss of the coating film was measured. As a result, the gloss value was 86%, indicating a satisfactory high gloss value.

[0026]

Example 2 The pigment was phthalocyanine blue LIONOL
Except for changing to BLUE KLH (manufactured by Toyo Ink Mfg. Co., Ltd.), a color chip was prepared in the same manner as in Example 1, a similar coating material was prepared, and the gloss of the coating film was measured. As a result, the gloss value was 82%, showing a satisfactory high gloss value.

[0027]

[Comparative Example 1] Carbon black MA-100 and acrylic / styrene emulsion F without using color chips
2430 was stirred and mixed with a three-one motor to prepare a paint having a pigment concentration of 9%, and the gloss of the coating film was measured. As a result, the gloss value was 40%, which was a low gloss value.

[0028]

The present invention is an aqueous color chip obtained by kneading a composition comprising a carboxyalkylcellulose nitrate ester, a pigment, water, a solvent and a neutralizing agent with a roll mill or the like to form chips. Improved safety,
Improve environmental conservation.

The color chip of the present invention is useful as a high gloss and high coloring power color chip for aqueous inks and coatings.

Claims (1)

[Claims] 1. A nitric acid ester of carboxyalkylcellulose having a pigment content of 15 to 80% by weight, a degree of substitution of a nitrate ester group per anhydroglucose unit of 0.2 or more, and a degree of substitution of a carboxyalkyl ether group of 0.05 or more. A water-based color chip comprising 20 to 85% by weight as a main component.