JPH10279876A - Water-base ball-point pen pigment ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base ball-point pen pigment ink composition which has excellent lubricating properties, can provide a uniformly dense drawn line and a long distance of writing without the wear of the ball socket of a metal tip and has good touch in writing by using a dipolyoxyethylene alkyl ether phosphoric acid and/or a specified tripolyoxyethylene alkyl ether phosphoric acid. SOLUTION: This ink comprises a pigment, a water-soluble resin, a water-soluble organic solvent and a dipolyoxyethylene alkyl ether phosphoric acid represented by formula I (R is a 4C or higher saturated or unsaturated hydrocarbon group; and n is a number of 6 or greater) and/or a tripolyoxyethylene alkyl ether phosphoric acid represented by formula II (R is a 4C or higher saturated or unsaturated hydrocarbon group; and n is a number of 6 or greater). The compounds of formulas I and/or II may be used alone or together and are used in an amount of about 0.5-3.0 wt.%, desirably 0.8-2.0 wt.% based on the total weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ballpoint pen ink using a pigment as a colorant, and more particularly, to a method in which the tip of the ballpoint pen is a metal, and the ink to be filled is a pigment, a water-soluble resin, and a water-soluble ink. The present invention relates to an aqueous pigment ink composition for a ballpoint pen containing a solvent.

[0002]

2. Description of the Related Art A conventional ballpoint pen using a metal tip is an oil-based ink for a ballpoint pen using benzyl alcohol, phenyl glycol, oleic acid or the like as a dye, a resin, or a solvent, or an aqueous ink using a dye and an aqueous ink containing an aqueous medium. Although inks for ballpoint pens have been used, they have the disadvantage that light resistance and water resistance are inferior due to the use of dyes. In order to solve these drawbacks, aqueous pigment inks for ballpoint pens using pigments have been proposed. However, the water-based pigment ink is a coloring agent used because the pigment is insoluble in water and a solvent.However, the pigment is finely dispersed and stably dispersed to provide excellent long-term stability and lubricity. There is a problem that the ink must be a pigment ink for an aqueous ballpoint. In order to solve the above-mentioned problems, for example, an ink containing a metal salt and / or an amine salt of N-acylsarcosine (Japanese Patent Application Laid-Open No. Sho 62-27)
479), an ink containing a polyether polyol having a primary or secondary alcohol group at a molecular terminal (JP-A-62-227372), an ink containing a polyglycerin fatty acid ester (JP-A-2-38474), Those containing an organic phosphate as an alkali metal, ammonium or alkanol salt (Japanese Patent Publication No. 1-4943)
2) an ink containing an alkali metal salt and / or an amine salt of N-acylmethyltauric acid
Although 4977) and the like have been proposed, problems such as increased bleeding of the writing line and aggregation of the pigment occur, so that an amount sufficient to obtain a sufficient lubricating effect cannot be added. As writing progresses, the ball seat wears out and the writing feel worsens,
The writing condition is extremely poor, such as in Braille, and the drawback that the writing distance is short cannot be solved.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to improve the disadvantages of the conventional pigment inks for water-based ballpoint pens, to provide excellent lubricity, to prevent wear of the ball seat of the metal chip, and to ensure uniformity during writing. An object of the present invention is to provide a water-based pigment ink composition for a ballpoint pen, which maintains ink outflow, has a uniform writing line density, has a long writing distance, has an effect of suppressing corrosion of metal chips, and has an extremely good writing feel.

[0004]

As a result of various studies to solve the above-mentioned problems, the present invention provides a water-based pigment ink composition for a ballpoint pen containing a pigment, a water-soluble resin and a water-soluble solvent. Dipolyoxyethylene alkyl ether phosphoric acid represented by the formula (1) and / or
The present inventors have found that the present invention is effective by containing the tripolyoxyethylene alkyl ether phosphoric acid represented by the general formula (2), and completed the present invention.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention provides a pigment ink composition for an aqueous ballpoint pen, which contains dipolyoxyethylene alkyl ether phosphoric acid and / or tripolyoxyethylene alkyl ether phosphoric acid.
Excellent lubricity, no friction of ball seat of metal tip, keeps uniform ink outflow during writing, has uniform writing line density, long writing distance, has the effect of suppressing metal chip corrosion, An extremely good aqueous pigment ink composition for a ballpoint pen is obtained.

[0006] By incorporating dipolyoxyethylene alkyl ether phosphoric acid and / or tripolyoxyethylene alkyl ether phosphoric acid used in the present invention, the inner surface of a metal chip in a pigment water-based ballpoint pen ink having a metal tip at the tip, That is, the writing feel is improved because a layer is formed between the ball and the ball seat. Those represented by R of the dipolyoxyethylene alkyl ether phosphoric acid represented by the general formula (1) and the tripolyoxyethylene alkyl ether phosphoric acid represented by the general formula (2) are saturated or unsaturated having 4 or more carbon atoms. Hydrocarbons, specifically butyl, amyl, hexyl,
Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, butenyl, hexenyl, oleyl and the like. Also, the number n of polyoxyethylene added needs to be 6 or more. If it is less than 6, the dissolving and dispersing power with water is poor, and the ink aggregates in a short period of time, resulting in lack of stability. The dipolyoxyethylene alkyl ether phosphoric acid represented by the general formula (1) and / or the tripolyoxyethylene alkyl ether phosphoric acid represented by the general formula (2) can be used alone or in combination. The addition amount can be 0.5 to 3.0% by weight based on the total amount of the composition. 0.5
Addition of less than 10% by weight leads to insufficient formation of the layer or insufficient improvement of the writing feel. Addition of 2.0% by weight or more improves the writing feeling, but the ink leaks naturally from the tip of the metal tip. The pre-leakage phenomenon began to occur, and the more preferable addition amount was in the range of 0.8 to 2.0% by weight based on the total amount of the composition. It is not clear why the aqueous pigment ink composition for ballpoint pens of the present invention gives a good writing feel, but the anion generated by the dissociation of ionic dipolyoxyethylene alkyl ether phosphate or tripolyoxyethylene alkyl ether phosphate is By adsorbing on the inner surface of the metal chip, the surface of the ball and the pigment particles, a layer is formed between the ball and the ball seat, and the effect of the extreme pressure additive and the effect of lubrication are exhibited. Conceivable. The pigment used in the pigment ink composition for aqueous ballpoint pen of the present invention is not particularly limited, and any one of inorganic and organic pigments used in ordinary pigment aqueous ballpoint pen ink compositions can be used. The amount used is selected in the range of 5 to 30% by weight, preferably 8 to 20% by weight based on the composition.

Examples of the water-soluble resin include a water-soluble acrylic resin, a cross-linked acrylic acid resin, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxycellulose, hydroxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate, and acetic acid. Copolymers of vinyl and polyvinylpyrrolidone are exemplified. These water-soluble resins can be used alone or as a mixture of two or more, and are contained in the range of 0.1 to 0.4% by weight based on the composition. If the content is less than 0.1% by weight, the viscosity suitable for the ink composition cannot be obtained, and if it exceeds 0.4% by weight, the viscosity of the ink composition becomes too high, so that the outflow of the ink during use is small. Scratches and Braille occur, the writing feel is heavy, and the writing properties are poor.

Examples of the water-soluble organic solvent include propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether, triethylene glycol, tetraethylene glycol, glycerin, polyethylene glycol, triethylene glycol monomethyl ether, and triethylene glycol monoethyl. One or a mixture of two or more ethers can be used, and usually used in a range of 10 to 40% by weight.

Further, in addition to the above main components, commonly used pigment dispersants, rust preventives, preservatives, moisturizers, defoamers and the like can be added and used. Examples of the pigment dispersant include an acrylic / styrene copolymer, a maleic acid / styrene copolymer, and a neutralized salt thereof.Examples of the rust inhibitor include benzotriazole, tolyltriazole, and dicyclohexylammonium nitrate. Can be illustrated. Examples of the preservative include sodium benzoate, potassium sorbate, sodium pentachlorophenol, and the like. As the humectant, a hygroscopic substance such as urea or a urea derivative can be used.

[0010]

Next, the present invention will be described in detail with reference to examples and comparative examples.

[0011]

[Table 1]

In Examples 1 to 4 and Comparative Examples 1 to 3, as shown in Table 1, water-soluble solvents such as ethylene glycol and glycerin and water were measured and stirred, and a water-soluble resin, a crosslinked acrylic resin, was stirred. An acid resin, hydroxypropylcellulose and the like are added and completely dissolved, and a pigment and an acryl-styrene copolymer as a pigment dispersant are added thereto.After uniformly dispersing the pigment, dioxyethylene alkyl ether phosphoric acid and Alternatively, an anionic surfactant of trioxyethylene alkyl phosphate is added, and further, additives of urea, benzotriazole, and potassium sorbate are added, and stirring is continued so that the pH value finally becomes 7.5 to 9.0. Add triethylamine or triethanolamine to
A ballpoint pen ink composition was obtained.

The physical properties of the inks obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 2.

[0014]

[Table 2]

Approximately 0.8 g of the inks obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were charged into a polyethylene pipe having a diameter of 3.5 mm, and a metal (nickel white) chip for an aqueous ballpoint pen was attached thereto. After filling the ink end with grease for preventing ink drying and outflow, the air inside the pipe was removed using centrifugal force, and the results of the test for writing feel, lubricity, and the presence or absence of chip corrosion were examined. It is shown in Table 3.

[0016]

[Table 3]

[0017]

As described in detail above, the effect is obtained in a pigment ink composition for an aqueous ballpoint pen containing a pigment, a water-soluble resin and a water-soluble solvent, by using dipolyoxyethylene alkyl ether phosphate and / or tripolyoxyethylene alkyl. By containing ether phosphoric acid,
Excellent lubricity, no wear of the ball seat of the metal tip, keeps uniform ink outflow during writing, has uniform writing line density, long writing distance, has the effect of suppressing metal chip corrosion, An extremely good aqueous pigment ink composition for a ballpoint pen is obtained.

Claims (1)

[Claims] 1. An aqueous pigment ink composition for a ballpoint pen containing a pigment, a water-soluble resin and a water-soluble organic solvent,
The following general formula (1) And / or a dipolyoxyethylene alkyl ether phosphoric acid represented by the general formula (2): A water-based pigment ink composition for ballpoint pens, comprising a tripolyoxyethylene alkyl ether phosphoric acid represented by the formula: