JP2008115202A - Ink composition for oily ballpoint pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for an oily ballpoint pen, keeping the lubricity even under high writing pressure, reducing the wear of a ball seat, providing good handwriting, and having good stability with time. <P>SOLUTION: The ink composition for the oily ballpoint pen comprising at least a coloring agent and an organic solvent contains a lubricant comprising an organic acid and phosphoric acid ester soluble in the organic solvent, an organic amine comprising one or more kinds of an alkylamine, an oxyethylenealkylamine and a poly(oxyethylene)alkylamine. <P>COPYRIGHT: (C)2008,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 to which an organic acid and a phosphate ester are added as a lubricant.

  Conventionally, unlike other types of writing instruments, the ballpoint pen has a problem in that the ball seat is worn due to the rotation of the ball during writing, and the handwriting is shaded or broken, or the writing quality is poor.

  In order to solve these problems, it has been known to add a lubricant to the ink composition for oil-based ballpoint pens for the purpose of improving the lubricity between the ball of the ballpoint pen tip and the tip body.

  Examples of inks that improve lubricity include JP-A-52-123722 “ink”, JP-A-55-84376 “ball-point pen ink”, JP-B-1-39467 “ball-point pen ink”, and JP-A-11-293174 “oil-based ink composition”. In addition, “balls and oil-based ballpoint pens” have been proposed inks for ballpoint pens to which organic acids, non-alkali metal salts of naphthenic acid, lanolin derivatives, fluorine-based and / or silicone-based surfactants, and nonylphenol-based phosphate esters are added.

JP-A-6-212111 proposes an oil-based ballpoint pen ink composition that contains oleic acid and an aliphatic amine to improve lubricity and has little deterioration over time. ing.
"Japanese Patent Laid-Open No. 52-123722" "JP 55-84376 A" Japanese Patent Publication No. 1-339467 "Japanese Patent Laid-Open No. 11-293174" "JP-A-6-212111"

  However, the use of conventional organic acids, non-alkali metal salts of naphthenic acid, lanolin derivatives, fluorine-based and / or silicone-based surfactants, and nonylphenol-based phosphates as lubricants provides lubricity under high pen pressure. In addition, the ball-point pen with good handwriting is not satisfactory, and there is a problem that stability with time is lowered.

  For this reason, conventional oil-based ballpoint pen inks increase the ink viscosity to 10,000 mPa · S or more to form a film between the ball and the ball seat to reduce the resistance of the metal contact between the ball and the ball seat, or use a lubricant or the like. By using high lubricity, the contact resistance between the ball and the ball seat was reduced and the wear of the ball seat was suppressed, but lubrication was required for long-distance writing, especially long-distance writing under high pen pressure. The effect was insufficient, the ball seat was worn out, and there was a problem that the writing performance was deteriorated, and the writing quality was lowered due to the high viscosity.

  Moreover, although it can suppress deterioration with time by containing oleic acid and an aliphatic amine as in Patent Document 5, it is not satisfactory as a ballpoint pen that maintains lubricity under high writing pressure and has good handwriting. There wasn't.

  An object of the present invention is to provide an oil-based ink composition for ballpoint pens that maintains lubricity even under high pen pressure, suppresses wear of the ball seat, has good handwriting, and has good stability over time.

In order to solve the above problems, the present invention
“1. In an oil-based ballpoint pen ink composition comprising at least a colorant and an organic solvent, a lubricant comprising an organic acid and a phosphate ester soluble in the organic solvent, an alkylamine, an oxyethylene alkylamine, and a polyoxyethylene alkyl. An oil-based ballpoint pen ink composition comprising an organic amine composed of one or more amines.
2. 2. The oil-based ballpoint pen ink composition according to item 1, wherein the organic amine is a secondary alkylamine and / or a tertiary alkylamine. The addition amount of the organic acid is 0.1% by mass or more and 10.0% by mass or less with respect to the total mass of the ink composition, and the addition amount of the phosphoric acid ester is 0 with respect to the total mass of the ink composition. 0.1 mass% or more and 3.0 mass% or less, and the total addition amount of the lubricant is 0.5 mass% or more and 12.0 mass% or less with respect to the total mass of the ink composition. The ink composition for oil-based ballpoint pens according to any one of item 1 or item 2.
4). The total amount of the organic amine is 0.1% by mass or more and 5.0% by mass or less with respect to the total mass of the ink composition, according to any one of Items 1 to 3. Ink composition for oil-based ballpoint pens.
5. When the content of the organic acid is A mass%, the phosphate ester content is B mass%, and the organic amine content is C mass% with respect to the total mass of the ink composition, A ≧ C ≧ Item 5. The ink composition for oil-based ballpoint pens according to any one of Items 1 to 4, wherein B is satisfied.
6). The ink composition for oil-based ballpoint pens according to any one of Items 1 to 5, which contains polyvinylpyrrolidone.
7. The oil-based ballpoint pen according to any one of Items 1 to 6, wherein the ink viscosity at a shear rate of 6.8 sec ⁻¹ is from 500 mPa · s to 6000 mPa · s. Ink composition. Is.

  The present invention can provide an oil-based ink composition for ballpoint pens that maintains lubricity even under high writing pressure, suppresses wear of the ball seat, has good handwriting, and has good stability over time.

  The first feature of the present invention is that a lubricant composed of an organic acid and a phosphate ester soluble in an organic solvent is used in combination.

  This is because phosphate ester significantly improves lubricity, so that the writing quality is improved, and lubricity is obtained even under high writing pressure, but the stability over time is deteriorated. Therefore, it is important to use an organic acid having good stability over time and reduce the phosphate ester content, although the improvement in lubricity is small.

  Examples of the organic acid that can be used in the present invention include oleic acid, stearic acid, ricinoleic acid, and lauric acid. Among these organic acids, it is most preferable to use other compositions in the oil-based ink composition for ballpoint pens, particularly oleic acid that exhibits an effect of improving the temporal stability of the dye.

  Examples of phosphate esters that can be used in the present invention include tridecyl alcohol phosphates, nonylphenol phosphates, styrenated phenol phosphates, Raul alcohol phosphates, and the like. By adding phosphoric acid ester, the rust prevention effect of the ballpoint pen tip is exhibited.

Specific examples of phosphate esters include the Prisurf series (Daiichi Kogyo Seiyaku Co., Ltd.) and the Phosphanol series (Toho Chemical Industry Co., Ltd.), Prisurf A212C, A210G, A207H, AL, A208B. , A208S, A208F, A212E, A219B, A206K, A217E, A215C, A213B, M208B, M208F,
Phosphanol RE-210, RE-410, RE-510, RE-610, RE-710, RE-960, RS-410, RS-610, RS-710, RS-710, RB- 410, RM-410, RM-510, RM-710, RL-210, RD-510Y, RP-710, RA-600, BH-650, ML-200, GB- 520 or the like. You may use these individually or in mixture of 2 or more types.

  If the total amount of lubricant consisting of organic acid and phosphoric acid ester is less than 0.5% by mass, the lubricity, especially lubrication at high writing pressure, will be poor. The ball seat wear tends to progress. Moreover, since ink aging stability will fall when it exceeds 12.0 mass%, it is preferable to set it as 0.5 to 12.0 mass%.

  On the other hand, when the addition amount of the organic acid is less than 0.1% by mass relative to the total amount of the ink composition, the improvement in stability with time and the improvement in lubricity are low, and when the addition amount exceeds 10.0% by mass, the ink is reversed. Since stability with time decreases, the content is preferably 0.1% by mass or more and 10.0% by mass or less.

  On the other hand, if the addition amount of the phosphate ester is less than 0.1% by mass with respect to the total amount of the ink composition, the improvement in lubricity is low, the wear of the ball seat is likely to proceed under high pen pressure, and the The rust effect is low, and if it exceeds 3.0% by mass, the ink aging stability decreases. Therefore, it is preferably 0.1% by mass or more and 3.0% by mass or less, and more preferably 1.0% by mass or less. preferable.

  Furthermore, since the stability over time decreases when the phosphoric acid ester is added in a larger amount than the organic acid, the organic acid content should be greater than the phosphoric acid ester content relative to the total amount of the ink composition. Is preferred.

  The organic solvent used in the present invention includes alcohols such as benzyl alcohol, diethylene glycol, and polyethylene glycol, and glycols, glycol ethers such as ethylene glycol monophenyl ether, and the like, which are generally used as oil-based ballpoint pen inks. These can be exemplified, and one or more of these can be used.

  The second feature of the present invention is that the ink composition contains an organic amine composed of one or more of alkylamine, oxyethylenealkylamine, and polyoxyethylenealkylamine.

  As described above, the organic acid and the phosphoric acid ester are used in combination to prevent deterioration of lubricity under high writing pressure and stability with time of the ink. It is important to improve the stability of the ester over time.

  Therefore, as the organic amine, in consideration of the temporal stability of the phosphate ester, alkylamines such as laurylamine, stearylamine, oleylamine, distearylamine, dimethyllaurylamine, dimethylstearylamine, dimethyloctylamine, and oxyethylene One or more of alkylamines or polyoxyethylene alkylamines are used.

  Also, primary amines have the strongest reactivity with other ink compositions such as phosphate esters, and then the reactivity with secondary amines and tertiary amines is low. Thus, it is preferable to use a secondary amine and / or a tertiary amine, and it is most preferable to use a tertiary amine having the lowest reactivity.

  Specifically, Farmin 20D (primary amine), Farmin 80 (primary amine), Farmin D86 (secondary amine), Farmin DM2098 (tertiary amine), Farmin DM1098 (tertiary amine) manufactured by Kao Corporation, Examples include Farmin DM 8680 (tertiary amine), Niimen L-201 (secondary amine), Naimine L-202 (tertiary amine), and Naimine L-207 (tertiary amine) manufactured by NOF Corporation.

  When the addition amount of the organic amine is less than 0.1% by mass relative to the total amount of the ink composition, the improvement in stability over time is low, and when it exceeds 5.0% by mass, the stability over time of the ink decreases. 0.1 mass% or more and 5.0 mass% or less is preferable.

  Furthermore, when the amount of organic amine added is larger than that of the organic acid, the stability over time decreases, and when the amount of phosphate ester added is higher than that of the organic amine, the temporal stability decreases, so the total amount of the ink composition is reduced. On the other hand, it is preferable that the content of the organic amine is smaller than the organic acid and larger than the content of the phosphate ester.

  Therefore, the relationship between the organic acid, phosphate ester, and organic amine is such that the content of the organic acid is A mass%, the content of the phosphate ester is B mass%, and the organic amine is based on the total mass of the ink composition. When the content of C is C mass%, it is preferable that A ≧ C ≧ B is satisfied.

The ink viscosity of the oil-based ballpoint pen ink composition of the present invention is not particularly limited, but when the ink viscosity at 20 ° C. and a shear rate of 6.8 sec ⁻¹ exceeds 6000 mPa · s, the writing quality decreases. Since it is difficult to suppress wear when it is less than 500 mPa · s, it is preferably 500 mPa · s or more and 6000 mPa · s or less, and particularly in a low viscosity ink of 3000 mPa · s or less, the surface of the ball in high writing pressure writing. Since the pressure load is more easily applied and the wear of the ball seat progresses, the effect of the present invention is remarkable.

  Moreover, it is preferable to contain polyvinyl pyrrolidone in the ink composition for oil-based ball-point pens of this invention. Since polyvinylpyrrolidone has adhesiveness, and further has viscoelasticity and film-forming properties, it can be presumed that it contributes to prevention of blurring of handwriting and suppression of lowering of handwriting density. In addition, the ink composition is also provided with an effect of imparting spinnability and preventing crying.

  Specific examples of polyvinyl pyrrolidone include trade names manufactured by IPS Japan Co., Ltd .; PVP K-15, PVP K-30, PVP K-90, PVP K-120, and the like.

  Examples of ink viscosity modifiers include phenolic resins, maleic resins, amide resins, xylene resins, hydrogenated rosin resins, ketone resins, terpene resins, organic acid amides, and pseudoplasticizers such as cross-linked acrylic acid polymers. Can be mentioned. You may use these individually or in mixture of 2 or more types. Furthermore, other organic solvents and 10% by mass or less of water can be added, and the viscosity can be adjusted.

  In addition, there are dyes and pigments for colorants, but there is no particular limitation. For dyes, oil-soluble dyes, direct dyes, acid dyes, basic dyes, metal-containing dyes, and various salt-forming dyes Etc. can be adopted. Examples of pigments include inorganic, organic, and processed pigments. Specifically, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, quinophthalone, selenium , Triphenylmethane, perinone, perylene, goxazine, 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. The addition amount is preferably 1 to 50% by mass with respect to the total amount of the ink composition.

  As other additives, pigment dispersants, dye stabilizers, plasticizers and the like can be selected and added as appropriate.

Next, an Example is shown and this invention is demonstrated.
The oil-based ballpoint pen ink composition of Example 1 is an organic solvent, a dye, a lubricant, oleic acid, a phosphate ester (Pricesurf 210B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), an organic amine (Naymin L-201), As a thickener, polyvinylpyrrolidone (PVP K-90 manufactured by IPS Japan Co., Ltd.) and a ketone resin (Hilac 110H manufactured by Hitachi Chemical Co., Ltd.) were used, and a predetermined amount was weighed and heated to 60 ° C. Then, it was completely dissolved using a disper stirrer to obtain an ink composition for oil-based ballpoint pens. Specific blending amounts are as follows. The ink viscosity was measured at 900 mPa · s using a Brookfield DV-II viscometer (No. 27 rotor) under an environment of 20 ° C. and a shear rate of 6.8 sec ⁻¹ (rotation speed: 20 rpm). there were.

Example 1
Organic solvent (benzyl alcohol) 36.5% by mass
Organic solvent (phenyl glycol) 21.0% by mass
Lubricant (oleic acid) 2.0% by mass
Lubricant (phosphate ester) 1.0% by mass
Organic amine (oxyethylene alkylamine) 1.0% by mass
Spinnability imparting resin (polyvinylpyrrolidone) 0.5% by mass
Viscosity adjusting resin (ketone resin) 0.5% by mass
Dye (Spiron Black-GMH-S) 20.0% by mass
Dye (Barry First Violet 1701) 18.0% by mass

Examples 2-7
Except having changed each component into the mixing | blending shown in Table 1 as shown in Table 1, the ink composition for oil-based ball-point pens of Examples 2-7 was obtained in the procedure similar to Example 1. FIG.

Comparative Examples 1-5
The ink was blended as shown in Table 2, and blended in the same procedure as in Example 1 to obtain oil ballpoint pen ink compositions of Comparative Examples 1-5. Table 2 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 7 and Comparative Examples 1 to 5 is held in an ink containing cylinder (polypropylene) with a ball diameter of φ0.7 mm rotatably ( Filled in a ballpoint pen refill equipped with a stainless steel wire), filled with a grease-like ink follower at the rear end of the oil-based ballpoint pen ink composition, and used copy paper (PPC paper) as writing test paper. Were tested and evaluated.

High writing pressure writing test: The wear of the ball seat after the writing test was measured with a running tester with a load of 500 gf, a writing angle of 70 °, and 4 m / min.
Ball seat wear of 5 μm or less ・ ・ ・ ◎
Ball seat wear of 10 μm or less
Ball seat wear is 20 μm or more, but can be written.
Wearing the ball seat is bad and results in poor writing ・ ・ ・ ×

Time stability test: The ink after standing at room temperature for 6 months was observed with a microscope.
Good without deposits ... ◎
Slightly generated precipitates, but no problem in practical use ... ○
Precipitates are generated and the practicality is poor.

  In Examples 1-7, since the organic acid and the phosphate ester were used in combination, the high writing pressure writing test was a good result. In addition to the combined use of an organic acid and a phosphate ester, it contains an organic amine selected from alkylamines, oxyethylene alkylamines, and polyoxyethylene alkylamines. Good results were obtained.

  In Comparative Example 1, since no organic acid was contained, a precipitate was generated in the temporal stability test. Further, in the high writing pressure writing test, there was a thing in which the handwriting deteriorated, for example, the handwriting was blurred.

  In Comparative Example 2, since a phosphate ester was not used, there was a case where wear of the ball seat progressed, resulting in poor writing.

  In Comparative Example 3, since no organic amine was used, some precipitates were generated in the temporal stability test.

  In Comparative Examples 4 and 5, since a lubricant other than phosphate ester was used, in the high writing pressure writing test, wear of the ball seat progressed, leading to poor writing.

  Since the present invention can provide an oil-based ballpoint pen ink composition that suppresses the wear of the ball seat and has good handwriting, it can be widely used as a ballpoint pen, such as a cap type, knock type, etc. A ballpoint pen using a ball having a small diameter of φ0.5 mm or less has a small contact area between the ball and the ball seat, a high load applied to the unit area, and the ball seat is easily worn, so that the effect of the present invention is remarkable.

Claims (7)

In an oil ballpoint ink composition comprising at least a colorant and an organic solvent, a lubricant comprising an organic acid and a phosphate ester soluble in the organic solvent, and one of alkylamine, oxyethylene alkylamine, and polyoxyethylene alkylamine An ink composition for oil-based ballpoint pens comprising an organic amine comprising seeds or two or more kinds. An oil composition for an oil-based ballpoint pen, wherein the organic amine is a secondary amine and / or a tertiary amine. The content of the organic acid is 0.1% by mass or more and 10.0% by mass or less with respect to the total mass of the ink composition, and the content of the phosphate ester is 0 with respect to the total mass of the ink composition. 0.1 mass% or more and 3.0 mass% or less, and the total content of the lubricant is 0.5 mass% or more and 12.0 mass% or less with respect to the total mass of the ink composition. The ink composition for oil-based ballpoint pens according to claim 1 or 2. The oiliness according to any one of claims 1 to 3, wherein the content of the organic amine is 0.1% by mass or more and 5.0% by mass or less with respect to the total mass of the ink composition. Ink composition for ballpoint pens. When the content of the organic acid is A mass%, the content of the phosphate ester is B mass%, and the content of the organic amine is C mass% with respect to the total mass of the ink composition, A ≧ C ≧ The ink composition for oil-based ballpoint pens according to any one of claims 1 to 4, wherein B is satisfied. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 5, comprising polyvinylpyrrolidone. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 6, wherein the ink viscosity at 20 ° C and a shear rate of 6.8 sec ^-1 is 500 mPa · s or more and 6000 mPa · s or less. .