JPH05295291A - Water-dispersed pigment composition - Google Patents

Abstract

(57) [Summary] [Purpose] It has excellent build-up properties, has little change in hue even when a paper-strengthening agent is added, has a good texture, has a small difference in color between the front and back, and has good fixability on cellulose fibers. To provide an excellent aqueous dispersion pigment composition. An aqueous dispersion pigment composition comprising a pigment, a dispersant and an aqueous medium, wherein the dispersant contains an amphoteric surfactant as a main component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to aqueous dispersion pigment compositions. More specifically, it relates to an aqueous dispersion pigment composition that can be suitably used as a coloring agent for paper and pulp.

[0002]

2. Description of the Related Art Conventionally, pigments such as organic pigments, inorganic pigments and extender pigments have been dispersed in water with a resin varnish, an anionic surfactant, a nonionic surfactant, etc. as a coloring agent for papermaking, and an aqueous dispersion has been obtained. A pigment composition is used.

However, these aqueous dispersion pigment compositions generally have a low affinity for pulp, and Al
The surface charges of pigment particles are neutralized by ³⁺ , Fe ³⁺ , cationic polymers, etc., and soft flocs, which are weak against mechanical external force, are formed on paper (cellulose fiber) for dyeing. When soft floc was used, the build-up property was deteriorated, so dyes had to be used for deep color dyeing.

On the other hand, in recent years, it has been strictly required to improve the quality of paper, reduce costs, and rationalize the production process. In order to cope with the accompanying changes in paper making conditions, emulsion sizing agents and papers are used. Dependence on strength enhancers is increasing.

However, coagulant-based retention improvers are generally used as retention aids including paper strength enhancers.
When such flocculant type is used, hard flocs are formed, so the dyeing rate (fixing rate) is reduced depending on the amount added, and in some cases, hue change is caused, and the texture There was a problem such as damage to.

[0006]

Therefore, the present inventors have found that
As a result of intensive studies in view of the above aqueous dispersion pigment composition, when an amphoteric surfactant was added as a dispersant to the aqueous dispersion pigment composition, surprisingly, the build-up property was excellent, and the emulsion The present invention has been completed for the first time by discovering a completely new fact that excellent color developability, build-up property and texture are maintained even when a sizing agent or an retention aid is used.

[0007]

That is, the present invention is an aqueous dispersion pigment composition comprising a pigment, a dispersant and an aqueous medium, wherein the dispersant contains an amphoteric surfactant as a main component. And an aqueous dispersion pigment composition.

[0008]

ACTION AND EXAMPLE The aqueous dispersion pigment composition of the present invention comprises
As described above, it is composed of a pigment, a dispersant and an aqueous medium, and has an amphoteric surfactant as a main component as a dispersant.

Examples of the pigment used in the aqueous dispersion pigment composition of the present invention include various organic pigments and inorganic pigments. The type of the pigment is not particularly limited, but it has excellent color sharpness and colorability. Organic pigments are preferred in that respect.

Examples of the organic pigments include monoazo pigments derived from acetoacetic acid arylide derivatives and β-naphthol derivatives, lake pigments obtained by lakeifying monoazo dyes such as β-oxynaphthoic acid dyes, disazo pigments and condensed disazo pigments. Isoindoline derivatives, naphthalene or perylene tetracarboxylic acid derivatives, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridone, dioxazine, pyrazoloquinazolone, phthalocyanine pigments, lake pigments laked from basic dyes such as triarylmethane dyes, etc. Specific examples of such organic pigments include Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Yellow 42 (CI
77492), Pigment Yellow 74 (CI 11741),
Pigment Yellow 83 (CI 21108), Pigment Yellow 106, Pigment Yellow 108 (CI
68240), Pigment Yellow 117, Pigment
Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI
12075), Pigment Orange 67, Pigment Red 3 (CI 12120), Pigment Red 48: 1
(CI 15865: 1), Pigment Red 48: 4 (C.
I. 15865: 4), Pigment Red 101 (CI 774)
91), Pigment Red 112 (CI 12370), Pigment Red 123 (CI 71145), Pigment Red 169 (CI 45160: 2), Pigment Violet 23 (CI 51319), Pigment Violet 2
7 (CI 42555: 3), Pigment Blue 1 (CI 4
2595: 2), Pigment Blue 15: 1 (CI 7416
0), Pigment Blue 15: 3 (CI 74160), Pigment Blue 61 (CI 42765: 1), Pigment Green 7 (CI 74260), Pigment Green 3
6 (CI 74265). Among these organic pigments, Pigment Red 112, Pigment
Violet 23, Pigment Blue 15: 1, Pigment Blue 15: 3, and Pigment Green 7 are preferable.

Typical examples of the inorganic pigment include iron oxide, iron ferricyanide, sulfur-containing sodium aluminum silicate, titanium dioxide and carbon black. Specific examples of the inorganic pigment include pigment yellow. 42 (CI 77492), pigment
White 6 (CI 77891), Pigment Blue 27
(CI 77510), Pigment Blue 29 (CI 7700
7) and Pigment Black 7 (CI 77266).

The above-mentioned pigments are usually used alone or in combination of two or more, and the amount of such pigments is 10 to 70% (% by weight, the same applies hereinafter) in the aqueous dispersion pigment composition. It is preferably adjusted so as to contain 20 to 50%. When the amount of such pigments is less than 10%, the coloring power tends to be weakened, and the practicality of the resulting aqueous dispersion pigment composition tends to be low, and when it exceeds 70%. However, it tends to cause thickening and gelation, and the resulting aqueous dispersion pigment composition tends to have low stability and low practicality. The average particle size of the pigment is usually 0.1-
The average particle size is about 1 μm, preferably about 0.1 to 0.3 μm. When the average particle size is about this range, there is no aggregation and the pigment is uniformly dispersed in the aqueous dispersion pigment composition.

The dispersant used in the aqueous dispersion pigment composition of the present invention contains an amphoteric surfactant as a main component.

Examples of the amphoteric surfactant include carboxylates such as alkali metal salts of higher fatty acids, sulfuric acid esters such as higher alcohols and higher alkyl ethers, sulfonates such as alkylbenzene and alkylnaphthalene, and higher alcohols. Examples thereof include those composed of an anion moiety such as a phosphate ester and a cation moiety such as an amine salt such as higher alkyl or a quaternary ammonium salt such as higher alkyl. Such amphoteric surfactants are usually used alone or in admixture of two or more.

Specific examples of the amphoteric surfactant include soybean lecithin, sodium laurylaminopropionate, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, coconut oil fatty acid amidopropyl dimethyl betaine, 2-alkyl-N-carboxymethyl- N-hydroxyethyl imidazolinium betaine, 2
-Alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, 2-alkyl-N-sodium carboxymethyl-N-carboxymethyloxyethyl imidazolinium betaine and the like can be mentioned.

In the present invention, the amphoteric surfactant can be used alone as the dispersant, and if necessary, other components can be added to the dispersant in addition to the amphoteric surfactant. However, such a component may be one that is compatible with the dispersant or can be stably and uniformly dispersed in the dispersant. Specific examples of such components include, for example, carboxylate type, sulfate type,
Anionic surfactants such as sulfonate type and phosphoric acid ester type, nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type, amine salt or ammonium salt of a copolymer composed of (meth) acrylic acid, Examples thereof include alkali-neutralized salts of maleic acid and maleic anhydride. These components can be used alone or in combination of two or more. The blending amount of such components may be appropriately adjusted within a range that does not impair the object of the present invention.

The amount of the dispersant to be blended is preferably 5 to 40 parts, more preferably 10 to 30 parts, based on 100 parts of the pigment (parts by weight; the same applies hereinafter). When the amount of such a dispersant is less than 5 parts, the dispersibility tends to be poor, and the stability of the resulting composition tends to be low, resulting in poor practicability, and more than 40 parts. In this case, foaming will occur during papermaking.

Examples of the aqueous medium used in the aqueous dispersion pigment composition of the present invention include water and mainly water. The water-based organic solvent such as ethylene glycol, diethylene glycol, glycerin, or propylene glycol, which is conventionally used in water, is a water-soluble organic solvent that has been used as an antifreezing agent or an anti-drying agent in an aqueous dispersion pigment composition. Examples include blended materials.

The amount of the above-mentioned aqueous medium may be adjusted according to the amount of the pigment contained in the usually obtained aqueous dispersion pigment composition.

As mentioned above, the aqueous dispersion pigment composition of the present invention comprises a pigment, a dispersant and an aqueous medium. In addition to these, the aqueous dispersion pigment composition also contains a preservative such as a benzotriazole type preservative. Various additives such as an inorganic or organic thickener may be blended, if necessary, within a range that does not impair the object of the present invention.

The method for producing the aqueous dispersion pigment composition of the present invention is not particularly limited, but each of the above components is prepared by using a dispersing machine such as a sand grinder, a centri mill, a dyno mill, a ball mill, a roll mill or a speed line mill. Examples include a method of mixing and milling.

The thus-obtained aqueous dispersion pigment composition of the present invention can be suitably used as a colorant for paper and pulp, but it can also be used as a colorant for water-based inks. When the aqueous dispersion pigment composition is used as a colorant for paper and pulp, the composition may be added during papermaking or may be applied on the manufactured papermaking.

Although the aqueous dispersion pigment composition of the present invention has a very low viscosity, the phenomenon in which pigment particles aggregate or settle is observed even when stored for a long time. Absent. This basically means that adsorption occurs on the surface of the finely divided pigment near the cation portion, which has a relatively small action as a hydrophilic group of the dispersant, and as a result, the anion portion repels each other. It is considered that this is because the aggregation and sedimentation of the particles are suppressed and the dispersion is stabilized.

At the time of dyeing, since the conventional aqueous dispersion pigment composition is anionic, it is easy to form an ion complex between Al ³⁺ or Fe ³⁺ and the cationic polymer, and a retention aid. When such substances are added, hard flocs are formed, and since the pigment exists in a non-uniform state on the cellulose fiber, the original color developability of the pigment is impaired and the build-up property and texture are adversely affected. Was becoming.

However, the aqueous dispersion pigment composition of the present invention exhibits an anionic property when it is alkaline, like the conventional aqueous dispersion pigment composition, but when it becomes acidic, it shows anionic property until now and dissociates into water. In addition, carboxylic acid salts, sulfuric acid esters, sulfonic acid salts, phosphoric acid esters, etc. are replaced by hydrogen and become insoluble in water. Instead, dissociation of amine salts, quaternary ammonium salts, etc. occurs and the solution becomes cationic. Present.

As a result, the aqueous dispersion pigment composition of the present invention has the same Al ³⁺ content as the conventional aqueous dispersion pigment composition.
Cellulosic fiber that does not easily form an ion complex between Fe and Fe ³⁺ and a cationic polymer, and that flocs due to addition of retention aids are soft flocs rather than hard flocs due to the coagulation action, and are anionic. On the other hand, since it also has a self-dyeing ability, it enables dyeing with excellent leveling and color development properties and excellent build-up properties.

That is, the aqueous dispersion pigment composition of the present invention is excellent in dyeability even when a small amount of the pigment is added, as compared with the conventional aqueous dispersion pigment composition in which an anionic surfactant is used. When the amount is increased, the upper limit of the amount of addition that can improve the dyeability increases accordingly, and when compared with an aqueous dispersion pigment composition using a cationic surfactant, the decrease in dyeability of the pigment is small. is there.

Next, the aqueous dispersion pigment composition of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the amounts of dispersants are all shown as the amount of active ingredient.

Example 1 Sand grinder (manufactured by Inoue Seisakusho Co., Ltd.) containing the following components
Was dispersed for 2 hours to obtain an aqueous dispersion pigment composition for papermaking.

Component (parts) Pigment Black 7 20.0 (Average particle size: 0.1 μm) Lauryldihydroxyethyl betaine 8.0 Ethylene glycol 5.0 Benzisothiazoline 0.1 Amount of water to be 100 parts Example 2 The following ingredients were applied with a sand grinder. Disperse for 1 hour,
An aqueous dispersion pigment composition for papermaking was obtained.

Component (parts) Pigment Yellow 83 20.0 (Average particle size: 0.2 μm) Coconut oil fatty acid amide propyl dimethyl betaine 3.0 Ethylene glycol 5.0 Benzisothiazoline 0.1 Amount of water to be 100 parts Example 3 Disperse for 1 hour with a grinder,
An aqueous dispersion pigment composition for papermaking was obtained.

Component (part) Pigment Red 112 15.0 (Average particle size: 0.3 μm) Soybean lecithin 4.0 Ethylene glycol 5.0 Benzisothiazoline 0.1 Amount in which the total amount of water is 100 parts Example 4 The following ingredients are put in a sand grinder for 3 hours. Distributed processing,
An aqueous dispersion pigment composition for papermaking was obtained.

Component (part) Pigment Blue 15: 3 15.0 (Average particle size: 0.2 μm) 2-Alkyl-N-carboxymethyl-1.5 N-hydroxyethylimidazolinium betaine Ethylene glycol 5.0 Benzisothiazoline 0.1 Water Amount of 100 parts Example 5 The following components were dispersed for 1 hour with a sand grinder,
An aqueous dispersion pigment composition for papermaking was obtained.

Components (parts) Pigment Yellow 42 50.0 (Average particle size: 0.7 μm) Sodium laurylaminopropionate 5.0 Ethylene glycol 5.0 Benzisothiazoline 0.1 Amount of water to be 100 parts Comparative Example 1 Used in Example 1 Lauryl dihydroxyethyl betaine
An aqueous dispersed pigment composition for papermaking was obtained in the same manner as in Example 1 except that 4.0 parts of naphthalenesulfonic acid formalin condensate was used instead of 8.0 parts.

Comparative Example 2 Aqueous papermaking solution was prepared in the same manner as in Example 2 except that 1.5 parts of a polycarboxylic acid salt type polymer compound was used in place of 3.0 parts of coconut oil fatty acid amide propyl dimethyl betaine used in Example 2. A dispersed pigment composition was obtained.

Comparative Example 3 An aqueous dispersion pigment composition for papermaking was obtained in the same manner as in Example 3 except that 3.0 parts of styrene-acrylic acid copolymer was used instead of 4.0 parts of soybean lecithin used in Example 3. ..

Comparative Example 4 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 1.5 used in Example 4
An aqueous dispersion pigment composition for papermaking was obtained in the same manner as in Example 4 except that 3.0 parts of styrene-maleic acid copolymer was used instead of the parts.

Comparative Example 5 Instead of 5.0 parts of sodium laurylaminopropionate used in Example 5, polyacrylate type polymer compound was used.
An aqueous dispersion pigment composition for papermaking was obtained in the same manner as in Example 5 except that 1.0 part was used.

Experimental Examples The aqueous dispersion pigment compositions obtained in Examples 1-5 and Comparative Examples 1-5 were subjected to various performance tests according to the following methods. The results are shown in Table 1.

(1) Build-up test Pulp slurry with a solid content of 3% (LBKP / NBKP = 50)
/ 50, csf = 400 cc), the aqueous dispersion pigment composition 1, 5, 10 or 20% in terms of pulp solid content, emulsion size (Size Pine N-700, Arakawa Chemical Industry Co., Ltd.)
1.0%) and sulfuric acid band 3.0% were added and uniformly dispersed to obtain a pulp slurry having a pH of 4.5. Using this pulp slurry, a TAPPI standard sheet machine (manufactured by Toyo Seiki Co., Ltd.) is used to make paper with a basis weight of 80 g / m ² ,
The coloring power of the papermaking paper was measured using a Macbeth densitometer RD-918. The coloring power in Table 1 is a value obtained by multiplying the value measured by the Macbeth densitometer by 100.

(2) Color difference between front and back of the paper The paper made in the same manner as the build-up test in (1) was subjected to color difference measurement using a colorimetric color difference meter (ND-1001DP, manufactured by Nippon Denshoku Co., Ltd.). Then, the difference between the front and back of coloring (color difference) was evaluated.

(3) Hue stability test by adding paper strength enhancer Pulp slurry with solid content of 3% (LBKP / NBKP = 50)
/ 50, csf = 400 cc), 5% of the aqueous dispersion pigment composition in terms of pulp solid content, emulsion sizing agent (Size Pine N-700, manufactured by Arakawa Chemical Industry Co., Ltd.) 1.0%, paper strengthening agent (polish) TRON 117, manufactured by Arakawa Chemical Industry Co., Ltd.
0.7% and sulfuric acid band 3.0% were added and uniformly dispersed to obtain a pulp slurry of pH 4.5. Using this pulp slurry, a TAPPI standard sheet machine was used to make paper having a basis weight of 80 g / m ² to obtain a papermaking paper.

The obtained papermaking paper was compared with the papermaking paper obtained in the same manner as above except that no paper strengthening agent was added, and the changes in hue and density were visually observed and evaluated.

[0044]

[Table 1]

As is clear from the results shown in Table 1, the paper-making paper using the aqueous dispersion pigment composition of the present invention obtained in Examples 1 to 5 has excellent build-up property and a paper strength enhancer. There is no change in hue due to the addition of, and the difference between the front and back of coloring is small.

Therefore, it can be seen that the aqueous dispersion pigment compositions of the present invention obtained in Examples 1 to 5 have very good fixability on cellulose fibers.

[0047]

The aqueous dispersion pigment composition of the present invention has excellent build-up properties, has no change in hue even when a paper strength enhancer or the like is added, has a good texture, and has a small difference in color between front and back sides. It has very good fixability to cellulose fibers.

Therefore, the aqueous dispersion pigment composition of the present invention can be suitably used as a coloring agent for paper and pulp.

[Procedure amendment]

[Submission date] May 25, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

Examples of the amphoteric surfactant include carboxylic acid salts such as alkali metal salts of higher fatty acids and higher salts.
Ruki ether, luxury alcohol which sulfuric acid ester,
Alkyl Ben Ze emissions, sulfonates such as alkyl naphthalene, was composed of fine and anionic moiety such as phosphate esters such as an alcohol, amine salts such as higher alkyl, a cationic moiety such as quarternary ammonium salts, such as higher alkyl Some things are listed. Such amphoteric surfactants are usually used alone or in admixture of two or more.

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Claims (1)

[Claims] 1. An aqueous dispersion pigment composition comprising a pigment, a dispersant, and an aqueous medium, wherein the dispersant contains an amphoteric surfactant as a main component.