JPH06313142A - Metallic gloss color water-base ink composition - Google Patents

Abstract

PURPOSE:To obtain the subject ink which can give writing with a metallic gloss even after a long-term storage by mixing an aluminum powder with a water-soluble dye and water and lowering the content of inorganic salts to a specified value. CONSTITUTION:This ink composition essentially consists of an aluminum powder as a metallic powder pigment, a water-soluble dye, a resin, a water-soluble organic solvent and water, and has a content of inorganic salts of 0.5wt.% or below. When the ink composition has a content of inorganic salts of above 0.5wt.% and it is stored for a long time, the aluminum powder is deteriorated, and therefore, the metallic gloss of writing is lost or the writing is discolored. Agglomeration among aluminum powder particles occurs, and the aluminum powder is settled. An effective means for lowering the content of inorganic salts to 0.5wt.% or below is to lower the content of inorganic salts in the water- soluble dye which is the main source of contamination with inorganic salts.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink composition in which aluminum powder and a water-soluble dye are used in combination as a coloring material, and more specifically, it is possible to obtain a handwriting having a metallic luster even after long-term storage. The present invention relates to a metallic luster color water-based ink composition.

[0002]

2. Description of the Related Art Various ink compositions are known in which an aluminum powder and a dye are used together as a coloring material to obtain a handwriting of a metallic luster color. For example, in a metallic luster color ink for a marking pen in which a fine metal powder selected from aluminum, copper, zinc, and a copper alloy surface-treated with a fatty acid or a fatty acid salt is dispersed in a resin-dissolved organic solvent, (a) the resin Is at least one solvent selected from a phenol resin, a hydrocarbon resin having a hydroxyl group, and a polyvinyl butyral resin, (b) the organic solvent is a lower aliphatic alcohol,
In Japanese Unexamined Patent Publication (Kokai) No. 4-126782 in which a metallic gloss color ink for marking pens, which is at least one solvent selected from glycol ethers, is the gist of the invention,
As the dye, C.I. I solvent dyes are disclosed.

On the other hand, various inks using water as the main solvent have been proposed in order to improve the strong odor and toxicity of the ink using the organic solvent as the main solvent. For example, Japanese Patent Laid-Open No. 63-95277 discloses a water-based metallic color ink containing an aluminum powder pigment, an amphoteric compound, a resin emulsion, and water as essential components, and a water-soluble dye as a colorant. It is disclosed. In addition, Japanese Patent Laid-Open No. 1-210478 in which an aqueous metallic ink characterized in that an acetylene alcohol derivative is added as an additive to an ink main component composed of a resin, an aluminum paste and water is also colored. Dyes are disclosed as materials.

[0004]

[Problems to be Solved by the Invention] When stored for a long time,
The points are that the aluminum powder in the ink deteriorates and the metallic luster does not appear in the handwriting, or the handwriting discolors, and that the aluminum powder agglomerates and the aluminum powder settles. . With regard to this aluminum powder settling out, when the writing instrument that fills the ink has a stirring member such as a metal ball for redispersing the pigment that has aggregated and settled in the ink containing chamber, Although this is not a big problem, for example, in the case of a writing instrument of a type such that a stirring member is not normally arranged in the ink containing chamber such as a ballpoint pen, a big problem that writing is impossible occurs.

[0005]

The present invention contains at least aluminum powder, which is a metal powder pigment, a water-soluble dye, a resin, a water-soluble organic solvent, and water, and has an inorganic salt content of 0. The gist of the invention is a metallic luster color water-based ink composition of 5% by weight or less.

The details will be described below. Aluminum powder, which is a metal powder pigment, imparts a metallic luster to the handwriting, and is an aluminum powder obtained by a stamping method in which aluminum pieces are crushed with a polishing agent such as stearic acid in a stamping mill, or by a spraying method. And a lubricant and a suitable liquid are placed in a drum together with steel balls, and the product is obtained by a ball mill method in which the aluminum drum is crushed by rotating the drum and is preferably in the form of flakes.

As the commercially available aluminum powder, Super Fine No. 22000, the same No. 18
000, Fine No. 900, the same No. 800, Super Fine No. 22000 WN (all manufactured by Daiwa Metal Powder Co., Ltd.), AA12, AA8, No. 900, N
o. 18000 (Fukuda Metal Foil & Powder Co., Ltd.),
Aluminum powder 1000 and aluminum powder 2700 (above, manufactured by Nakatsuka Metal Foil Powder Co., Ltd.) and the like can be mentioned. The amount used is preferably 5 to 20% by weight with respect to the total amount of the ink composition.

The water-soluble dye is used in combination with the above-mentioned aluminum powder for producing a colored metallic luster, that is, a metallic luster color. Conventionally known water-soluble dyes such as acid dyes, basic dyes and direct dyes can be used. Acid dyes include C.I. I. Acid Yellow 23, C.I. I. Acid Red 52, C.I. I. Food Yellow 3, C.I. I. Acid Blue 1 and the like, and as the basic dye,
C. I. Basic Blue 7, C.I. I. Basic Red 1 and the like can be mentioned. As the direct dye, C.I. I. Direct Blue 86, C.I. I. Direct green 6,
C. I. Direct Orange 8 and the like can be mentioned. The amount used is preferably 5 to 20% by weight with respect to the total amount of the ink composition.

The resin is used as a dispersant or a fixing agent for aluminum powder, or is used for adjusting the viscosity to a desired one according to the application. Specific examples of the resin for dispersion and fixing include resin emulsions such as styrene-acrylic acid ester copolymer, acrylic acid ester-vinyl acetate copolymer, and acrylic acid ester copolymer. Examples of the resin include guar gum of seed polysaccharide, locust bean gum and its derivative, zansan gum of microbial type, color agin of seaweed polysaccharide, alginsan and its derivative, taragant gum of resin polysaccharide, cellulose derivative and the like. The amount to be used can be appropriately adjusted according to the conditions such as the relationship with the aluminum powder and other components, the purpose of use and the structure of the writing instrument to be filled.

The water-soluble organic solvent is used for various qualities as an aqueous ink composition, that is, for the purpose of, for example, preventing ink from drying with a pen tip and preventing ink from freezing at low temperatures. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol and glycerin, ethylene glycol monomethyl ether,
Diethylene glycol monomethyl ether, 2-pyrrolidone, triethanolamine and the like can be used alone or in combination. The amount used is preferably 5 to 40% by weight with respect to the total amount of the ink composition.

Water is used as the main solvent.

In the metallic luster color water-based ink composition according to the present invention, the amount of the inorganic salt in the ink composition must be 0.5% by weight or less. This is because when the amount of the inorganic salt in the ink composition is more than 0.5% by weight, when the ink composition is stored for a long period of time, the aluminum powder in the ink is altered and the metallic luster does not appear in the handwriting, or the handwriting This is because the aluminum powder is discolored or the aluminum powders are agglomerated with each other and the aluminum powder settles.

In order to reduce the amount of the inorganic salt in the ink composition to 0.5% by weight or less, the content of the inorganic salt in the water-soluble dye, which is the main factor of the mixing of the inorganic salt into the ink composition, is set. Reduction is an effective means. To reduce the content of inorganic salts in water-soluble dyes, a commercially available dye is washed in an aqueous solution of hydrochloric acid, or a commercially available dye is dissolved in water, and hydrochloric acid is added to the dye to precipitate the dye. And a method of using a dye obtained by dissolving a commercially available dye in an organic solvent, filtering and then drying the filtrate.

In addition to the above components, various additives such as a wetting agent, a lubricant, an antifreezing agent, an antiseptic agent and an anticorrosive agent can be used in the metallic luster color aqueous ink composition.

In producing the metallic luster color water-based ink composition of the present invention, various conventionally known methods can be adopted. For example, it can be easily obtained by stirring and mixing with a stirrer such as a turbo mixer, or by mixing and grinding with a disperser such as a ball mill.

[0016]

[Function] Using aluminum as the main solvent, aluminum powder,
In the ink composition using the water-soluble dye in combination, the aluminum powder undergoes a chemical change to generate hydrogen and discoloration occurs. It is considered that this is because chlorine ions and sulfate ions of the inorganic salt in the ink composition accelerate the chemical change of the aluminum powder. The metallic luster color water-based ink composition of the present invention has a content of the inorganic salt in the ink of, for example, 0.5 weight% by a method of using a commercially available water-soluble dye with a reduced content of the inorganic salt. %, The aluminum does not deteriorate, so that even if the ink composition is stored for a long period of time,
It does not occur that the aluminum powder in the ink is deteriorated, the metallic luster does not appear in the handwriting, the handwriting is discolored, and the aluminum powders agglomerate to cause the aluminum powder to settle.

[0017]

【Example】

Preparation of purified water-soluble dye C. I. 10 parts by weight of Acid Yellow 23 10% by weight
It was added to 100 parts of hydrochloric acid aqueous solution with stirring, stirred for 30 minutes and then filtered, and the solid content was dried at 80 ° C. to obtain a purified dye 1. The inorganic salt content of this product was 1.7% by weight.

Example 1 Aluminum powder (Super Fine No. 22000, manufactured by Daiwa Metal Powder Industry Co., Ltd.) 10.0 parts by weight Purified dye 1 5.0 parts by weight Styrene-acrylic acid ester copolymer emulsion 15.0 Parts by weight ethylene glycol 15.0 parts by weight glycerin 10.0 parts by weight water 44.9 parts by weight Proxel XL-2 (preservative, manufactured by ICI Japan Co., Ltd.) 0.1 parts by weight Each of the above components is mixed in a lab mixer 1 Stir and mix for hours,
A gold metallic luster color water-based ink composition was obtained. The content of the inorganic salt in this ink composition was 0.09% by weight.

Preparation of Purified Water-Soluble Dye C. I. 10 parts of Food Yellow 3 with 10 parts of methanol
It was added to 0 part with stirring and stirred for 30 minutes, and then the insoluble matter was filtered. Methanol was distilled off from this filtrate and the solid content was dried to obtain a purified dye 2. The inorganic salt content of this product was 0.15% by weight.

Example 2 Aluminum powder (AA12, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) 10.0 parts by weight Purified dye 2 6.0 parts by weight Guar gum derivative (Jaguar HP60, manufactured by Sansho Co., Ltd.) 2.0 Parts by weight propylene glycol 20.0 parts by weight ethylene glycol 10.0 parts by weight water 51.9 parts by weight Proxel GXL (previously described) 0.1 parts by weight The above components are mixed and stirred for 2 hours with a stirrer to produce a copper-colored metal A glossy aqueous ink composition was obtained. The viscosity of this ink composition is 35,000 cps (E type viscometer 1 rpm at
25 ° C.), and the viscosity ratio at 1/10 rpm was 3.1. Further, the content of the inorganic salt in this ink composition was 0.01% by weight.

Preparation of Purified Water-Soluble Dye C. I. 10 parts by weight of 10 parts of Direct Green 6
The mixture was added to 100 parts of hydrochloric acid aqueous solution with stirring, stirred for 30 minutes and then filtered, and the solid content was dried at 80 ° C. to obtain a purified dye 3. The inorganic salt content of this product was 3.0% by weight.

Example 3 Aluminum powder (Super Fine No. 22000, manufactured by Daiwa Metal Powder Industry Co., Ltd.) 10.0 parts by weight Purified Dye 3 9.0 parts by weight Styrene-acrylic acid ester copolymer emulsion 15.0 Parts by weight ethylene glycol 10.0 parts by weight glycerin 10.0 parts by weight water 58.9 parts by weight Proxel XL-2 (previously described) 0.1 parts by weight The above components are mixed and stirred for 2 hours with a stirrer to produce a green metal. A glossy aqueous ink composition was obtained. The viscosity of this ink composition is 34000 cps (E type viscometer 1 rpm at
25 ° C.) and the viscosity ratio at 1/10 rpm was 3.3. The content of the inorganic salt in this ink composition was 0.25% by weight.

Comparative Example 1 Instead of the purified dye 1 of Example 1, C.I. I. A gold metallic luster color water-based ink composition was obtained in the same manner as in Example 1 except that Acid Yellow 23 (before purification, inorganic salt content 25%) was used. The content of the inorganic salt in this ink composition was 1.25% by weight.

Comparative Example 2 Instead of the purified dye 2 of Example 2, C.I. I. A copper-colored metallic gloss aqueous ink composition was obtained in the same manner as in Example 2 except that Food Yellow 3 (before purification, inorganic salt content 20%) was used. The content of the inorganic salt in this ink composition was 1.20% by weight.

Comparative Example 3 Aluminum powder (Super Fine No. 22000, manufactured by Daiwa Metal Powder Industry Co., Ltd.) 10.0 parts by weight Purified Dye 3 6.0 parts by weight C.I. I. Direct Green 6 (before purification, inorganic salt content 20% by weight) 3.0 parts by weight Locust bean gum (manufactured by Sansho Co., Ltd.) 2.0 parts by weight Ethylene glycol 10.0 parts by weight Glycerin 10.0 parts by weight Parts water 58.9 parts by weight Proxel XL-2 (previously described) 0.1 parts by weight The above components were treated in the same manner as in Example 3 to obtain a green metallic luster color aqueous ink composition. The viscosity of this ink composition is
34000cps (E type viscometer 1 rpm at 25
C.) and the viscosity ratio at 1/10 rpm was 3.3. Further, the content of the inorganic salt in this ink composition,
It was 0.78% by weight.

As described above, the metallic luster color water-based ink compositions obtained in Example 1 and Comparative Example 1 were mixed with a commercially available valve-type fiber-made pen nib type marker (in the ink storage chamber, stirring for redispersion of the precipitated pigment). What was filled with the member) was used as a test sample, and the examples 2 and 3 and the comparative examples 2 and 3 were used.
The metallic luster color water-based ink composition obtained in step 1 was filled in the ink containing portion of a ballpoint pen consisting of a polypropylene hollow shaft cylinder in which a nickel-white ballpoint pen tip (ball material: cemented carbide) was connected at one end. A test sample was prepared by removing the air bubbles therein by centrifugation, and a time-course test was performed. The results are shown in Table 1. Incidentally, Examples 1 to 3 and Comparative Example 1
Writing paper filled with ink composition No. 3 to No. 3 fine paper (JIS
When written on P3201 Writing Paper A), all were well written, and it was possible to obtain a handwriting having a metallic luster.

Aging test: The above marker and ballpoint pen are left in a thermostatic chamber at 50 ° C. for one month with the pen tip facing upward and the pen tip facing downward. After that, the markers filled with the ink compositions of Example 1 and Comparative Example 1 are shaken 10 times and written on high-quality paper (described above). Examples 2, 3 and Comparative Examples 2, 3
The appearance of the ballpoint pen filled with the ink composition (1) is observed and further written on a fine paper (described above).

[0028]

[Table 1]

[0029]

As described in detail above, the metallic luster color water-based ink composition according to the present invention gives a clear metallic luster color handwriting even after being stored for a long period of time and has no sedimentation separation. It is useful because it can achieve the desired purpose.

Claims (1)

[Claims] 1. An aluminum powder which is a metal powder pigment,
A metallic luster color water-based ink composition containing at least a water-soluble dye, a resin, a water-soluble organic solvent, and water, and having an inorganic salt content of 0.5% by weight or less.