JPH0841407A - Oily ball point pen and ink composition therefor - Google Patents

Abstract

PURPOSE:To provide an ink composition for oily ball point pen, composed of a colorant, a resin, an organic solvent and a fluorine-based phosphonic acid compound, capable of providing a holograph free from unevenness of darkness or split and excellent in feeling in writing and smoothness. CONSTITUTION:This ink composition for oily ball point pen is composed of (A) preferably 5.0 to 40.0wt.% colorant such as an acid dye, (B) preferably 2.0 to 30.0wt.% resin such as a ketone resin, (C) preferably 20.0 to 70.0wt.% organic solvent such as phenyl cellosolve and (D) preferably 0.1 to 10.0wt.% fluorine-based phosphonic acid compound represented by formula I and/or II (R is a 2 to 10C alkyl or an alkylphenyl; Rf is a 6 to 13C perfluorocarbon; M is H, an alkaline metal, etc.), e.g. a compound of formula III. In addition, the viscosity of this composition is preferably 500 to 10000mPa.S at 20 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink for an oil-based ballpoint pen which is excellent in writability and particularly needs lubricity.

[0002]

2. Description of the Related Art Unlike other types of writing instruments, a ballpoint pen has friction between the ball and the tip during writing, which causes abrasion of the tip during writing, resulting in light and shade on the handwriting. There is a problem that defects such as line breakage may occur, and the writing feel may be poor, and it has been desired to develop an ink for a ballpoint pen having good lubricity. The conventional oil-based ink for ballpoint pens has a viscosity of 10,000 mPa · S.
The lubricating effect by keeping it higher than the above and a certain degree of lubricity were maintained by blending an oily agent such as oleic acid.However, during long-distance writing, especially during long-distance writing under high writing pressure. There is a problem that the lubricating effect is insufficient and the writing performance is deteriorated. In addition, JP-A-52-12
3722, 55-84376, and Japanese Patent Publication No. 1-39467 propose inks using a fatty acid, a non-alkali metal salt of naphthenic acid, a lanolin derivative, a fluorine-based surfactant, and / or a silicone-based surfactant. The desired lubricity has not been achieved. Therefore, the present invention is excellent in lubricity at the time of writing, particularly while maintaining the lubricity even at the time of long-distance writing under high writing pressure, has good writing performance with no shading or line cracks in handwriting, and also has writing quality. It is intended to provide a good oil-based ink composition for ballpoint pens.

[0003]

Means for Solving the Problems The present invention provides "1. An oil-based ink composition for ballpoint pens comprising at least a colorant, a resin, an organic solvent, and a fluorinated phosphonic acid compound. A compound represented by the following general formula (a) and / or (b):
The ink composition for oil-based ballpoint pens as described in 1.

[Chemical 3]

[Chemical 4] R: C2-C10 alkyl group or alkylphenyl group Rf: Perfluorocarbon group having a carbon number of C6-C13 M: hydrogen atom or alkali metal, NH4, amine salt,
An alkyl group having a carbon number of C1 to C3. The oil-based ink composition for a ballpoint pen according to any one of claims 1 and 2, which contains 0.1 to 10.0% by weight of a fluorine-based phosphonic acid compound. 4. The viscosity of the ink composition at 20 ° C is 500 to 1
The ink composition for an oil-based ballpoint pen according to any one of claims 1 to 3, which has a viscosity of 30,000 mPa · S. 5. The ink composition for oil-based ballpoint pens according to claim 1, wherein a dye is used as a colorant. 6. Use stainless steel for the tip of the ballpoint pen,
An oil-based ballpoint pen filled with the ink composition for an oil-based ballpoint pen according to any one of claims 1 to 7. ".

As a result of various studies on the lubricity of oil-based ballpoint pen inks, the present inventor has found that the desired lubricity can be obtained by incorporating a fluorine-based phosphonic acid compound.

The mechanism of lubrication of the fluorinated phosphonic acid compound with respect to the ballpoint pen is that the interaction between the perfluorocarbon group and the phosphonic acid group in the compound causes the tip of the ballpoint pen made of stainless steel or the like to firmly adhere to the surface of the ball. By adsorbing, a lubricating layer is formed to maintain high viscosity and excellent lubricity even during long-distance writing under high writing pressure, which could not be obtained only by adding an oily agent such as oleic acid. Is what you can get. Therefore, when it is used for a material having a low ink viscosity, for example, a viscosity of 500 to 10,000 mPa · S at 20 ° C., and further a viscosity of 500 to 7,000 mPa · S, the writing feeling is improved, and particularly excellent lubrication is obtained. The effect can be obtained.

When a pigment is used as the colorant, the wear rate of the chip increases, but when a fluorinated phosphonic acid compound is used, good lubricating performance can be obtained. When a dye is used as the colorant, the effect of the colorant on the wear of the chip is small, so that it is possible to obtain a better lubricating performance.

The present invention will be described in detail below.
Specific examples of the fluorine-based phosphonic acid compound include compounds having the structural formulas shown below.

Embedded image And the like, and the blending amount is 0.1 to 10.0% by weight.
Is particularly preferable, and 0.5 to 5.0% by weight is particularly preferable. If it is less than this range, the desired lubrication effect cannot be obtained, and if it is more than this range, ink dripping, crying, and show-through on paper are observed, which is not preferable.

The colorant used in the present invention can be used without limitation with dyes and pigments conventionally used in ballpoint pen inks. Specific examples of the dyes include acid dyes, basic dyes, and Examples thereof include metal complex dyes, salt-forming dyes, azine dyes, anthraquinone dyes, phthalocyanine dyes, and triphenylmethane dyes.

Examples of the pigment include inorganic pigments such as carbon black, titanium oxide, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, cobalt blue, chrome green, and chromium oxide, azo pigments, condensed polyazo pigments, and phthalocyanines. Examples thereof include organic pigments such as pigments, quinacridone pigments, indigo pigments, and thioindigo pigments, metal pigments such as bronze powder and aluminum powder, and various fluorescent pigments.

These colorants can be used alone or in combination with others, and the blending amount thereof is preferably 5.0 to 40.0% by weight.

The resin used in the present invention is blended for the purpose of adjusting viscosity and fixing the handwriting. Specific examples thereof include ketone resins, phenol resins, rosin resins, polyvinylpyrrolidone and polyvinyl butyral. ,
Examples thereof include polyvinyl acetate, polyamide resin, cellulose resin, maleic acid resin, and modified products thereof. These resins can be used alone or in combination with others. Further, the compounding amount of the resin largely depends on the kind, the degree of polymerization, etc., but 0.1 to 50.0 wt% is preferable, and 2.0 to 30.0 wt% is particularly preferable.
When the amount is less than this range, the viscosity of the entire ink is lowered, and when the tip end is left downward, a phenomenon of ink dripping from the tip end occurs, and writing fastness is deteriorated. If it is too large, the viscosity is too high, and the writing feel tends to be heavy, which is not preferable.

As the organic solvent used in the present invention, an organic solvent which can satisfactorily dissolve the resin used in the present invention as described above can be used. Specific examples thereof include phenyl cellosolve, phenyl carbitol, benzyl alcohol, propylene glycol, triethylene glycol, polyethylene glycol, 1,3-butanediol, α-ethylhexanol, etc., but the resin and dye to be mixed are dissolved. Any solvent will do. These solvents can be used alone or in combination with others. In addition, the compounding amount of the solvent is 20.0 to
70.0% by weight is preferred.

The ink composition for oil-based ballpoint pens of the present invention comprises at least the above-mentioned colorant, resin, organic solvent, and fluorine-based phosphonic acid compound,
In addition, you may mix | blend a dispersing agent, a coloring aid, an oiliness agent, an activator etc. as needed.

As a material for the tip of the ball-point pen used in the present invention, a stainless steel material is more preferable because it is less worn, the adsorption of the fluorinated phosphonic acid compound is stronger, and the lubricity is increased.

[0015]

EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples.

Example 1 The black ink for an oil-based ballpoint pen was prepared by mixing and stirring the components of Formulation Example 1. The viscosity of this ink at 20 ° C. is measured by a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.),
The ink was 4,000 mPa · S, and the ink was filled in a ballpoint pen having a stainless steel tip and a φ0.7 mm carbide ball, and as a result of writing, it showed a good color tone and good writability. Angle 70 °, writing speed 4 m / min. In the high writing pressure performance test written in the above, there was little wear of the tip until the writing distance exceeded 5,000 m, and good writing performance was maintained, which was satisfactory.

Example 2 The respective components of Formulation Example 2 were mixed and stirred to prepare a blue ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 3,800 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of filling with a ball-point pen having a super hard ball of No. 3 and writing, it showed good color tone and good writability. Even in the same high writing pressure performance test as in Example 1, the writing distance was 5,000 m.
The wear of the tip was small and good writing performance was maintained until it exceeded, and it was satisfactory.

Example 3 The respective components of Formulation Example 3 were mixed and stirred to prepare a red ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 4,000 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of filling with a ball-point pen having a super hard ball of No. 3 and writing, it showed good color tone and good writability. Even in the same high writing pressure performance test as in Example 1, the writing distance was 5,000 m.
The wear of the tip was small and good writing performance was maintained until it exceeded, and it was satisfactory.

Example 4 The respective components of Formulation Example 4 were mixed and stirred to prepare a green ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 8,500 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of filling with a ball-point pen having a super hard ball of No. 3 and writing, it showed good color tone and good writability. Even in the same high writing pressure performance test as in Example 1, the writing distance was 5,000 m.
The wear of the tip was small and good writing performance was maintained until it exceeded, and it was satisfactory.

Example 5 The respective components of Formulation Example 5 were mixed and stirred to prepare a black ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 4,500 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of filling with a ball-point pen having a super hard ball of No. 3 and writing, it showed good color tone and good writability. Even in the same high writing pressure performance test as in Example 1, the writing distance was 5,000 m.
The wear of the tip was small and good writing performance was maintained until it exceeded, and it was satisfactory.

Example 6 The respective components of Formulation Example 6 were mixed and stirred to prepare a green ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 4,000 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of writing in a ball-point pen having a super hard ball of No. 3, a good color tone was obtained and the writing performance was good, and the writing distance was 4,000 m in the same high writing pressure performance test as in Example 1.
The wear of the tip was small and good writing performance was maintained until it exceeded, and it was satisfactory.

Example 7 The black ink for oil-based ballpoint pens of Example 1 was filled in a ballpoint pen having nickel-white chips and φ 0.7 mm super hard balls and the result was writing. Even in the same high writing pressure performance test as in Example 1, the tip was less worn and good writing performance was maintained until the writing distance exceeded 4,000 m, which was satisfactory.

Comparative Example 1 The respective components of Formulation Example 7 were mixed and stirred to prepare a black ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 5,200 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of writing in a ball-point pen having a super hard ball of No. 3, a good color tone was initially shown and the writability was good, but in the same high writing pressure performance test as in Example 1, the writing distance was about 1,000 m. However, the abrasion of the tip caused shading and line breaks in the handwriting, which was not satisfactory.

Comparative Example 2 The black ink for oil-based ballpoint pens was prepared by mixing and stirring the components of Formulation Example 8. The viscosity of this ink at 20 ° C. is 5,000 mPa · S as measured by a B-type viscometer, and the ink is used with a stainless steel tip and φ0.7 mm.
As a result of writing in a ball-point pen having a super hard ball of No. 3, a good color tone was initially shown and the writability was good, but in a high writing pressure performance test similar to that of Example 1, a tip at a writing distance of about 500 m was used. It was not satisfactory because the handwriting caused light and shade on the handwriting.

Comparative Example 3 A black ink for oil-based ballpoint pens was prepared by mixing the components of Formulation Example 9 and stirring. The viscosity of this ink at 20 ° C. was 3,200 mPa · S as measured by a B-type viscometer, and the ink was used with a stainless steel tip and φ0.7 mm.
As a result of writing in a ball-point pen having a super hard ball of No. 3, a good color tone was initially shown and the writability was good, but in a high writing pressure performance test similar to that of Example 1, a tip at a writing distance of about 500 m was used. It was not satisfactory because the handwriting caused light and shade on the handwriting.

Comparative Example 4 The components of Formulation Example 10 were mixed and stirred to prepare a black ink for oil-based ballpoint pens. The viscosity of this ink at 20 ° C. is 20,000 mPa · S as measured by a B-type viscometer.
The ink is stainless steel tip and φ0.7m
As a result of filling in a ball-point pen having a super-hard ball of m and writing, it was found that the color tone was good and the writing quality was not good, and it was not satisfactory. After that, the same high writing pressure performance test as in Example 1 was performed, but no progress of wear of the tip was observed until the writing distance exceeded 5,000 m.

[Table 1]

Table 2 shows the evaluation results of the writing feel and the high writing pressure test of the above Examples and Comparative Examples.

[Table 2]

【The invention's effect】

As is apparent from the above-mentioned embodiments, the present invention has excellent lubricity at the time of writing due to its specific structure, and particularly maintains the lubricity at the time of long-distance writing under high writing pressure.
Has good writing performance with no shading or line breaks in handwriting,
It is intended to provide an ink composition for an oil-based ballpoint pen which has a good writing quality.

Claims (6)

[Claims] 1. An ink composition for an oil-based ballpoint pen comprising at least a colorant, a resin, an organic solvent, and a fluorinated phosphonic acid compound. 2. The ink composition for an oil-based ballpoint pen according to claim 1, wherein the fluorine-based phosphonic acid compound comprises a compound represented by the following general formula (a) and / or (b). Embedded image Embedded image R: C2-C10 alkyl group or alkylphenyl group Rf: Perfluorocarbon group having a carbon number of C6-C13 M: hydrogen atom or alkali metal, NH4, amine salt,
Alkyl group having C1 to C3 carbon number 3. A fluorine-containing phosphonic acid compound in an amount of 0.1 to 1
The oil-based ink composition for a ballpoint pen according to claim 1, which is blended with 0.0% by weight. 4. The viscosity of the ink composition at 20 ° C. is 50.
The ink composition for an oil-based ballpoint pen according to any one of claims 1 to 3, which has a viscosity of 0 to 10,000 mPa · S. 5. A dye used as a coloring agent according to claim 1.
The ink composition for an oil-based ballpoint pen according to any one of 1. 6. An oil-based ballpoint pen filled with the ink composition for an oil-based ballpoint pen according to claim 1, wherein a stainless steel material is used as the material of the tip of the ballpoint pen.