JP2011137107A - Ink composition for oily ball point pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for an oily ball point pen good in writing feeling and capable of suppressing wearing of a ball seat in the ink composition for the oily ball point pen. <P>SOLUTION: The ink composition for the oily ball point pen includes at least a coloring agent, an organic solvent and a salt-formation object of an anionic surfactant and/or a cationic surfactant having an aromatic ring. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink composition for oil-based ballpoint pens, and more particularly to an ink composition for oil-based ballpoint pens containing an anionic surfactant and / or a cationic surfactant in the ink composition.

  Conventionally, many oil-based ballpoint pen ink compositions using various surfactants have been proposed for the purpose of excellent lubricity and smooth writing in oil-based ballpoint pen ink compositions.

  As such oil-based ballpoint pen ink compositions, those using fluorine-based surfactants and silicon-based surfactants are disclosed in JP-A-6-248217, “Ballpoint pen ink composition”, JP-A-9-151354. It is disclosed in “oil-based ink composition for ballpoint pens” and the like.

"Japanese Patent Laid-Open No. 6-248217" "Japanese Patent Laid-Open No. 9-151354"

  However, when various surfactants such as Patent Documents 1 and 2 are used, the wear of the ball seat can be suppressed while improving the writing quality to some extent, but it is not fully satisfactory.

  An object of the present invention is to provide an oil-based ballpoint pen ink composition that has good writing quality and can suppress wear of a ball seat.

In order to solve the above problems, the present invention
“1. An oil-based ballpoint pen ink composition comprising at least a colorant, an organic solvent, and an anionic surfactant having an aromatic ring and / or a salt-formation body of a cationic surfactant. object.
2. Content of the said salt-form body is 0.1-20.0 mass%, The ink composition for oil-based ball-point pens of Claim 1 or 2 characterized by the above-mentioned.
3. 2. The ink composition for oil-based ballpoint pens according to item 1, wherein the cationic surfactant is an ammonium salt.
4). 4. The oil-based ballpoint pen ink composition according to any one of Items 1 to 3, wherein the anionic surfactant is alkylbenzene sulfonic acid and / or a salt thereof.
5. The ink composition for oil-based ballpoint pens according to any one of Items 2 to 4, wherein the ammonium salt is a quaternary ammonium salt having an aromatic ring.
6). 6. The ink composition for oil-based ballpoint pens according to item 5, wherein the quaternary ammonium salt is at least one selected from benzoxonium compounds, alkyldimethylbenzylammonium compounds, and alkyldiethylbenzylammonium compounds. .
7). The oil-based ballpoint pen according to any one of claims 1 to 6, wherein the oil-based ballpoint pen ink composition contains at least one of oxyethylene alkylamine and polyoxyethylene alkylamine. Ink composition.
8. The ink composition for oil-based ballpoint pens according to any one of Items 1 to 7, wherein the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ is 10 to 5000 mPa · s. "

  The present invention has provided an ink composition for an oil-based ballpoint pen that has good writing quality and can suppress wear of a ball seat.

  A feature of the present invention is that the oil-based ballpoint pen ink composition contains an anionic surfactant having an aromatic ring and / or a salted product of a cationic surfactant.

  Anionic surfactants and cationic surfactants can improve the lubricity between the ball and the chip body, obtain a smooth writing feeling, and improve writing quality. However, since an anionic surfactant and a cationic surfactant are highly water-soluble, they are difficult to use alone in an oil-based ink composition because they are difficult to dissolve in an organic solvent. Therefore, it is important that the anionic surfactant and the cationic surfactant are each contained in the ink composition for oil-based ballpoint pens as a salt-forming body.

  There are various methods for neutralizing with an anionic surfactant, but a more stable salt-forming body can be prepared by carrying out a neutralization reaction using a cationic surfactant. Therefore, it is preferable to use a salt-forming body of an anionic surfactant and a cationic surfactant. Similarly, there are various methods for neutralizing with a cationic surfactant, but a more stable salt-forming body can be created using an anionic surfactant. preferable.

  However, not all anionic surfactants and / or cationic surfactant salt formations have good writing quality and do not suppress wear of the ball seat. As a result of diligent research, the inventor of the present invention has good writing quality when an anionic surfactant and / or a salt form of a cationic surfactant has an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring. In addition, it has been found that wear of the ball seat can be suppressed. This has the effect of suppressing metal contact between the ball and the chip body by forming a lubricating film that is easily adsorbed to metal, improving lubricity, good writing, and wear of the ball seat. It is assumed that it suppresses.

  As described above, the present invention requires the use of an anionic surfactant having an aromatic ring and / or a salt-formation body of a cationic surfactant.

Anionic surfactants include dialkyl sulfosuccinic acid, alkylbenzene sulfonic acid, naphthalene sulfonic acid, naphthalene sulfonic acid
-Formaldehyde condensate, alkane sulfonic acid, olefin sulfonic acid, N-methyl-N-acyl taurine, alkyl sulfate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl Examples include ether phosphoric acid, fatty acid and / or a salt thereof. These anionic surfactants may be used alone or in combination of two or more.

In addition, anionic surfactants having an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring are specifically alkylbenzenesulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid-formaldehyde condensate, polyoxyethylene alkylphenyl Examples include ether phosphoric acid and / or a salt thereof. In consideration of writing taste, alkylbenzene sulfonic acid and / or its salt are preferable, and sodium benzene alkyl benzene (RC ₆ H) is particularly preferable in view of the temporal stability of the salt formed by reacting with ammonium salt. _4- SO ₃ Na, R; alkyl group) is preferable, and sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxidesulfonate, and the like can be given.

  Specific examples of the alkylbenzene sulfonic acid and / or a salt thereof include Neopelex GS, Neopelex G-15, Neopelex G-25, Neopelex G-65, Neopelex No. 6F powder (manufactured by Kao Corporation), Adeka Hope HAN-40, Adeka Hope SAN-40PD (Asahi Denka Kogyo Co., Ltd.), Raipon LS-250, Raipon LS-625, (Lion Corporation), etc. Is mentioned.

  Examples of the cationic surfactant include primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Among these, for cationic surfactants, quaternary ammonium salts are effective for preparing a salt-form having better stability over time.

  Examples of quaternary ammonium salts include benzoxonium compounds (Benzoxonium), alkylbenzyldimethylammonium compounds, lauryltrimethylammonium compounds, stearyltrimethylammonium compounds, cetyltrimethylammonium compounds, and distearyldimethylammonium compounds. These quaternary ammonium salts may be used alone or in combination of two or more.

  Among them, quaternary ammonium salts having an aromatic ring include benzoxonium compounds (Benzoxonium), alkyldimethylbenzylammonium compounds, tetradecyldimethylbenzylammonium compounds, hexadecyldimethylbenzylammonium compounds, octadecyldimethylbenzylammonium compounds, octadecyls. Examples of dimethylbenzylammonium compounds, cocoalkyldimethylbenzylammonium compounds, and alkyldiethylbenzylammonium compounds include dodecyldiethylbenzylammonium compounds, and benzoxonium compounds (Benzoxonium) are the most important in terms of writing quality and stability over time. preferable.

Quaternary ammonium salts having an aromatic ring, specifically, cationic _M 2 -100, cationic _F 2 -35R, the -40E, the -50, the -50E, cationic _S 2 -100 (NOF Corporation Etc.).

  In addition, when the content of the anionic surfactant having an aromatic ring and / or the salt formation of the cationic surfactant is less than 0.1% by mass with respect to the total amount of the ink composition, desired lubricity is obtained. May not be obtained, and if it exceeds 20.0% by mass, the ink aging may become unstable. Therefore, the content is preferably 0.1 to 20.0% by mass with respect to the total amount of the ink composition. More preferably, it is 0.5-10.0 mass% with respect to the ink composition whole quantity, Most preferably, it is 2.0-8.0 mass%.

Further, when an organic amine having ethylene oxide (CH ₂ CH ₂ O) is used in combination with the salt structure, a lubricating effect is more easily obtained. Therefore, as the organic amine, ethylene oxide
It is preferable to use oxyethylene alkylamine or polyoxyethylene alkylamine having (CH ₂ CH ₂ O). You may use these individually or in mixture of 2 or more types.

Specific examples of the oxyethylene alkylamine and polyoxyethylene alkylamine include Naimine L-201, Naimine L-202, L-207, S-202, S-204, S-210, and T. ₂ -206, the S-210, the DT-203, the DT-208, Nymeen L-207, the T ₂ -206, etc. the DT-208 (NOF Corporation) and the like.

  In addition, the content of the organic amine is preferably 0.1 to 10.0% by mass, more preferably 1.0 to 5.0% by mass with respect to the total amount of the ink composition, considering lubricity and stability over time. %.

The ink viscosity of the oil-based ballpoint pen ink composition of the present invention is not particularly limited. However, when the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ is less than 10 mPa · s, bleeding or ink sag occurs in the handwriting. In addition, if the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ exceeds 5,000 mPa · s, the ball rotation resistance during writing tends to increase, and the writing taste tends to become heavy. Therefore, the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ is preferably 10 to 5,000 mPa · s. More preferably, it is 50-3,000 mPa * s, Most preferably, it is 100-1,500 mPa * s which has the effect which suppresses abrasion of a ball seat.

    As for the colorant used in the present invention, there are dyes and pigments. As for the dyes, oil-soluble dyes, acid dyes, basic dyes, metal-containing dyes, and various salt-forming dyes can be used. is there.

  Regarding the dye, specifically, Bali First Black 1802, Bali First Black 1805, Bali First Black 1807, Bali First Violet 1701, Bali First Blue 1601, Bali First Blue 1605, Bali First Blue 1621, Bali First Red 1320, Bali First Red 1355, Bali First Red 1360, Bali First Yellow 1101, Bali First Yellow 1151, Nigrosine Base EXBP, Nigrosine Base EX, BASE OF BASIC DYES ROB-B, BASE OF BASIC DYES RO6G-B, BASE OF BASIC DYES VPB-B, BASE OF BASIC DYES VB-B, BASEOF BASIC D ES MVB-3 (above, manufactured by Orient Chemical Co., Ltd.), Eisenspiron Black GMH-Special, Eisenspiron Violet C-RH, Eisenspiron Blue GNH, Eisenspiron Blue 2BNH, Eisenspiron Blue C-RH, Eisen Spiron Red C-GH, Eisen Spiron Red C-BH, Eisen Spiro Yellow C-GNH, Eisen Spiro Yellow C-2GH, S. P. T.A. Blue 111, S.I. P. T.A. Blue GLSH-special P. T.A. Red 533, S.D. P. T.A. Orange 6, S. B. N. Violet 510, S.I. B. N. Yellow 510, S.I. B. N. Yellow 530, S.I. R. C-BH (above, manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Examples of pigments include inorganic, organic, and processed pigments. Specifically, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, and quinophthalone Selenium-based, triphenylmethane-based, perinone-based, perylene-based, goxazine-based, metallic pigment, pearl pigment, fluorescent pigment, phosphorescent pigment, and the like. These dyes and pigments may be used alone or in combination of two or more. As for content of a coloring agent, 1.0-50.0 mass% is preferable with respect to the ink composition whole quantity.

  Examples of the organic solvent used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, 3- Glycol ethers such as methoxybutanol and 3-methoxy-3-methylbutanol, glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol and ethylene glycol, benzyl alcohol, methanol, ethanol, 1 -Propanol, 2-propa Alcohol, isopropanol, isobutanol, t-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate and other higher alcohols, phenyl The organic solvent generally used as ink for oil-based ballpoint pens, such as cellosolves, such as cellosolve, can be illustrated, and these can be used 1 type or 2 or more types. The content of the organic solvent is preferably 5.0 to 50.0% by mass with respect to the total amount of the ink composition in consideration of solubility of the colorant, handwriting drying property, blurring, and the like.

  In addition, oleic acid, linoleic acid, stearic acid, ricinoleic acid, lauric acid, phosphate ester surfactants are used as organic acids and surfactants to improve the colorant stability over time and lubricity. Fluorine-based surfactants, silicon-based surfactants, acetylene-based surfactants, etc. as pigment dispersants, polyvinyl butyral resins, polyvinyl alcohol resins, acrylic resins, etc., as viscosity modifiers, ketone resins, terpene resins, Add resin such as alkyd resin, phenoxy resin, polyvinyl acetate, polyvinylpyrrolidone, pseudo plasticity imparting agent such as organic acid amide, cross-linked acrylic acid polymer, etc. Also add color stabilizer, plasticizer, chelating agent, water, etc. You may use suitably. These may be used alone or in combination of two or more.

Next, a method for producing a salt-form of an anionic surfactant and / or a cationic surfactant having an aromatic ring will be described.
Formulation Example 1
First, 100 g of water and 30 g of alkylbenzene sulfonate were weighed and heated in a beaker and dissolved using a disper stirrer. Then, 19.5 g of a benzoxonium compound was weighed, stirred, and filtered using a filter paper. To obtain a salt structure.

Next, an Example is shown and this invention is demonstrated.
The oil-based ballpoint pen ink composition of Example 1 is a salt-formation of an anionic surfactant having an aromatic ring and a cationic surfactant as a colorant, a dye, an organic solvent, benzyl alcohol, and a lubricant. Body (prepared with Formulation 1), oleic acid as stabilizer, polyoxyethylene alkylamine (Nymine L207: NOF Corporation), polyvinyl pyrrolidone as resin (PVP K-90: made by ASP Japan) And a ketone resin (Hilac 110H: manufactured by Hitachi Chemical Co., Ltd.), weighed a predetermined amount, heated to 60 ° C., and completely dissolved using a disper stirrer to prepare an ink composition for an oil-based ballpoint pen. Obtained. Specific blending amounts are as follows. The ink viscosity was measured at a shear rate of 500 s ^{-1 in} an environment of 20 ° C. using an AR-G2 (stainless steel 40 mm 2 ° rotor) manufactured by TA Instruments, Inc. and found to be 160 mPa · s. It was.

Example 1
Dye (Spiron Black-GMH-S) 15.0% by mass
Dye (Barry First Violet 1701) 15.0% by mass
Organic solvent (benzyl alcohol) 60.7 mass%
Salt-formed body (produced in Formulation Example 1) 5.0% by mass
Stabilizer (oleic acid) 1.0% by mass
Stabilizer (polyoxyethylene alkylamine) 1.0% by mass
Resin (Polyvinylpyrrolidone) 0.3% by mass
Resin (ketone resin) 2.0% by mass

Formulation Examples 2-7
As shown in Table 1, except that each component was changed, salt-formed bodies of Formulation Examples 2 to 7 were prepared in the same manner as Formulation Example 1, and the salt-formed bodies were used in Examples and Comparative Examples.

Examples 2-6 and 8-9
As shown in Table 2, oil-based ballpoint pen ink compositions of Examples 2 to 6 and 8 were obtained in the same procedure as Example 1 except that each component was changed. Table 2 shows the measurement and evaluation results.
Example 7
As shown in Table 2, except that each component was changed, each component other than water was carried out in the same procedure as in Example 1, and after cooling at room temperature, water was added and an ink composition for an oil-based ballpoint pen was obtained by disper stirring. It was.

Comparative Examples 1-7
As shown in Table 3, the components were mixed in the same procedure as in Example 1 except that the respective components were changed, and ink compositions for oil-based ballpoint pens of Comparative Examples 1 to 7 were obtained. Table 3 shows the measurement and evaluation results.

Test and Evaluation A ballpoint pen tip in which the ink composition for oil-based ballpoint pens prepared in Examples 1 to 9 and Comparative Examples 1 to 7 is rotatably held in an ink containing cylinder (polypropylene) with a ball diameter of φ0.7 mm. The ball pen refill equipped with (stainless steel wire) was filled, and the following tests and evaluations were performed using writing paper JIS P3201 as writing test paper.

Written taste: A hand-written sensory test was performed and evaluated.
Very smooth ・ ・ ・ ◎
Smooth thing ○○
Somewhat heavy ・ ・ ・ △
Heavy thing

Abrasion resistance test: The wear of the ball seat after the writing test was measured with a running test machine with a load of 200 gf, a writing angle of 70 °, and 4 m / min.
Ball seat wear is less than 2μm and can be written.
Ball seat wear is 2 μm or more and less than 5 μm, and can be written on.
The wear of the ball seat is 5 μm or more and less than 10 μm, resulting in poor writing.
Wear of ball seat is 10μm or more, and writing becomes impossible ... ×

Dissolution stability: The dissolution stability after adding the salt-forming body and the surfactant was evaluated by microscopic observation.
Undissolved and free of precipitates ... ◎
Some undissolved and precipitates were confirmed, but there was no problem in writing performance.
Some undissolved and precipitates are confirmed and writing performance is poor.

  In Examples 1 to 9, good performance was obtained in terms of writing taste, abrasion resistance test, and dissolution stability.

  In Comparative Examples 1-4, since the salt-formation body without the aromatic ring produced by the ink composition 6-7 is used, the writing is heavy, or the wear of the ball seat is severe in the wear resistance test, and the writing failure or I was unable to write.

  In Comparative Example 5, since a silicon-based surfactant was used, the writing was heavy. Further, in the wear resistance test, the ball seat was so worn that writing was poor or writing was impossible.

  In Comparative Example 6, since an anionic surfactant was used alone, dissolution was not stable, and precipitates were confirmed. Furthermore, in the wear resistance test, which is heavy in writing, the ball seat was severely worn, and writing was poor or impossible to write.

In Comparative Example 7, since a cationic surfactant was used alone, dissolution was not stabilized and precipitates were confirmed. In addition, the writing taste was heavy.

  In order to prevent the ink from drooping, the ball held rotatably at the tip of the ball-point pen tip is pressed against the inner wall of the tip end edge directly by a coil spring or via a pressing body, and the tip is pressed by the pressing force at the time of writing. It is preferable to provide a valve mechanism for allowing the ink to flow out by providing a gap between the inner wall of the tip edge and the ball, and closing the minute gap at the tip of the tip when not in use.

  The present invention relates to an ink composition for oil-based ballpoint pens, and more specifically, at least a colorant, an organic solvent, an anionic surfactant having an aromatic ring and / or a salted product of a cationic surfactant, By using an oil-based ballpoint pen ink composition characterized by containing an oil-based ballpoint pen ink composition, it is possible to provide an oil-based ballpoint pen ink composition with good writing quality and capable of suppressing wear of the ball seat. Therefore, it can be widely used as a ballpoint pen, such as a cap type and a knock type.

Claims (8)

An ink composition for oil-based ballpoint pens, comprising at least a colorant, an organic solvent, and an anionic surfactant having an aromatic ring and / or a salt form of a cationic surfactant. 2. The oil-based ballpoint pen ink composition according to claim 1, wherein a content of the salt-forming body is 0.1 to 20.0 mass%. The ink composition for oil-based ballpoint pens according to claim 1 or 2, wherein the cationic surfactant is an ammonium salt. The oil-based ballpoint pen ink composition according to any one of claims 1 to 3, wherein the anionic surfactant is alkylbenzenesulfonic acid and / or a salt thereof. The oil composition for ballpoint pens according to any one of claims 2 to 4, wherein the ammonium salt is a quaternary ammonium salt having an aromatic ring. 6. The oil-based ballpoint pen ink composition according to claim 5, wherein the quaternary ammonium salt is at least one selected from a benzoxonium compound, an alkyldimethylbenzylammonium compound, and an alkyldiethylbenzylammonium compound. . The oil-based ballpoint pen ink according to any one of claims 1 to 6, wherein the oil-based ballpoint pen ink composition contains at least one of oxyethylene alkylamine and polyoxyethylene alkylamine. Composition. 8. The oil ballpoint ink composition according to claim ^1, wherein the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ is 10 to 5000 mPa · s.