JP2014125500A - Ink composition for an oil-based ball-point pen and ball-point pen using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for an oil-based ball-point pen exhibiting a favorable writing resumption performance in a dried-up state and an oil-based ball-point pen using the same.SOLUTION: The provided ink composition for an oil-based ball-point pen is an ink composition for an oil-based ball-point pen consisting at least of a coloring agent, an organic solvent, and 1,2-alkanediol. The 1,2-alkanediol is pasty within a 25°C environment. The content of the 1,2-alkanediol is 0.1-20.0 mass%, and a phosphoric acid ester-based surfactant is additionally included.

Description

  The present invention relates to an oil-based ballpoint pen ink composition. More specifically, the present invention relates to an oil-based ballpoint pen ink composition having good write-out performance (dry-up resistance) at the time of dry-up due to film formation at the tip of the chip, and oiliness using the same It relates to a ballpoint pen.

  Conventionally, in an oil-based ballpoint pen ink composition, if the tip of the tip is left in the air, the solvent in the ink evaporates and the colorant or resin is dried and solidified. There was a drawback that would occur.

  In order to improve the writing performance at the time of writing, it has been considered to use various solvents and additives. For example, as a main solvent containing a non-volatile organic solvent having a vapor pressure of 0.005 to 0.5 mmHg (20 ° C.), Japanese Patent Application Laid-Open No. 6-247093 “Oil Ballpoint Pen” has an average molecular weight of 200 to Japanese Patent Application Laid-Open No. 7-196971 “Ink composition for oil-based ballpoint pen” contains polyethylene glycol having a weight average molecular weight of 250,000 or more. No. 2002-3771 “Ink composition for oil-based ballpoint pen” contains at least decacademia nut oil fatty acid decaglyceryl and an alkyl group having 16 or more carbon atoms and a polyoxyethylene alkyl ether that is solid at room temperature. , JP 2008-88264 A "Oil-based ink composition for ballpoint pens" To "and the like, have been disclosed.

"Japanese Patent Laid-Open No. 6-247093" "Japanese Patent Laid-Open No. 7-196971" "JP 2002-3771 A" "Japanese Patent Laid-Open No. 2008-88264" "JP 2001-288396 A"

  However, in Patent Document 1, when a non-volatile organic solvent having a vapor pressure of 0.005 to 0.5 mmHg (20 ° C.) is contained as the organic solvent, there is an effect of preventing the ink from being completely dried. The dryness of the paper was poor, and it alone could not satisfy the writing performance.

  Moreover, in patent documents 2-3, when polyethylene glycol or polyvinylpyrrolidone having a specific molecular weight is contained as an additive, by forming a resin film on the tip of the tip, further drying of the tip of the tip is suppressed, Although it is possible to improve the dry-up resistance to some extent by suppressing the ink thickening in the chip, the resin film is hard, so writing at the time of dry-up will cause blurring and sufficient Dry-up resistance cannot be obtained. Further, in Patent Document 4, it is possible to improve the dry-up resistance to some extent by using decamacademia nut oil fatty acid decaglyceryl and polyoxyethylene alkyl ether in combination, but it is not fully satisfactory, and further, the interface Since the activator was used in combination, the ink aging stability was easily affected.

  Also, as in Patent Document 5, in the case of pigment-based inks, unlike dye-based inks, pigment particles are solidified at the tip of the tip to form a film, but the pigment particles are hard, so the dry-up performance is improved. Furthermore, in the retractable ballpoint pens such as the knock-type ballpoint pen and the rotary pay-out type ballpoint pen, the tip end portion is left out as compared with the cap-type ballpoint pen. It was desired.

  An object of the present invention is to provide an oil-based ballpoint pen ink composition having good writing performance during dry-up and an oil-based ballpoint pen using the same.

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 1,2-alkanediol.
2. 2. The ink composition for oil-based ballpoint pens according to item 1, wherein the 1,2-alkanediol is pasty in an environment of 25 ° C.
3. 3. The oil-based ballpoint pen ink composition according to item 1 or 2, wherein the content of the 1,2-alkanediol is 0.1 to 20.0% by mass.
4). 4. The oil-based ballpoint pen ink composition according to any one of items 1 to 3, wherein the oil-based ballpoint pen ink composition contains a phosphate ester-based surfactant.
5. The ink composition for oil-based ballpoint pens according to any one of Items 1 to 4, wherein the colorant contains at least a pigment.
6). The ink composition for oil-based ballpoint pens according to any one of claims 1 to 5, wherein the organic solvent contains at least an aromatic alcohol solvent.
7. The ink composition for oil-based ballpoint pens according to any one of Items 1 to 6, wherein the ink viscosity at a shear rate of 3.84 sec ⁻¹ is 1000 to 10,000 mPa · s.
8). A ball-point pen tip having a ball rotatably held in a ball holding chamber of the chip body is provided directly or via a chip holder at the tip of the ink storage cylinder, and the ink storage cylinder includes first to seventh items. An oil-based ballpoint pen comprising the ink composition for an oil-based ballpoint pen according to any one of the items.
"

  The present invention provides an oil-based ballpoint pen with excellent dry-up resistance that does not cause handwriting scumming by softening the solidification of the film formed when the tip tip is dried while the tip tip is left in the atmosphere. Ink composition for oil and oil-based ballpoint pen using the same were able to be provided.

  A feature of the present invention is that the oil-based ink composition for ballpoint pens contains 1,2-alkanediol.

The 1,2-alkanediol used in the present invention has an adjacent hydroxyl group,
General formula: R—CH (OH) —CH ₂ (OH), where R is an alkyl group
It is a compound shown by these.
Therefore, the inventor of the present application contains 1,2-alkanediol in the oil-based ink composition for ballpoint pens, so that even if the tip of the tip is dried, the handwriting is not generated and the dry-up resistance is improved. I understood that. This is because 1,2-alkanediol has particularly excellent hygroscopicity due to two adjacent hydroxyl groups, so the strength of the film formed when the tip of the tip is dried is reduced, and the ball rotates smoothly. Therefore, it is presumed that the dry-up performance is improved without causing handwriting scraping in writing during dry-up. At this time, when paste-like 1,2-alkanediol is used in an environment at 25 ° C., the strength of the film is easily relieved, and thus the dry-up resistance is easily improved.
In the present invention, the paste may be in any state as long as it is a semi-solid material having fluidity in an environment of 25 ° C.

  Specific examples of 1,2-alkanediol include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, and the like. It is done. Among these, 1,2-octanediol (melting point: 15 to 33 ° C.) is exemplified as the paste-like 1,2-alkanediol in an environment of 25 ° C. You may use these individually or in mixture of 2 or more types.

  The content of the 1,2-alkanediol is preferably 0.1 to 20.0% by mass with respect to the total amount of the ink composition. This is because if it is less than 0.1% by mass, the dry-up resistance tends to be inferior, and if it exceeds 20.0% by mass, the solubility in the ink tends to be inferior. Moreover, since it will be easy to generate | occur | produce crying in a handwriting when it exceeds 15.0 mass%, 0.1-15.0 mass% is preferable, and if it considers more, 3.0-10.0 mass% is the most preferable. .

  In the present invention, it is preferable to contain a phosphate ester surfactant. This is because the phosphate ester-based surfactant is used in combination with 1,2-alkanediol, and the reason is not clear, but the strength of the film formed when the tip end of the chip is dried is further reduced. This is because it makes it easier to rotate and improve the dry-up resistance.

  In addition, the phosphate ester surfactant used in a paste or liquid in an environment of 25 ° C., the film formed when the tip end of the chip is dried tends to be softer and more resistant to dry-up. Is preferable. In particular, in a 25 ° C. environment, a paste-form 1,2-alkanediol and a paste-form or liquid-form phosphate surfactant are used in combination, so that the film to be formed is likely to become softer. Therefore, it is preferable.

Phosphate ester surfactants include polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate diester, polyoxyethylene alkyl ether Or polyoxyethylene alkylaryl ether phosphoric acid triesters, alkyl phosphoric acid esters, alkyl ether phosphoric acid esters or derivatives thereof. These phosphoric acid ester surfactants may be used alone or in combination of two or more. May be used. Among these, phosphate ester type surfactants having an ethylene oxide group (CH ₂ CH ₂ O) are preferable. This is presumed to be because the formed film tends to be soft due to having an ethylene oxide group (CH ₂ CH ₂ O).

  Of these, it is preferable to use at least a phosphate ester surfactant having an alkyl group with 10 to 18 carbon atoms. If the alkyl group has less than 10 carbon atoms, the straight chain of the alkyl group is too short, making it difficult to form a sufficient film, and the ink at the tip of the tip tends to thicken. This is because if the carbon number of the alkyl group exceeds 18, the ink aging stability tends to be affected. If this tendency is taken into consideration, the alkyl group has 12 to 15 carbon atoms. It is most preferable to use at least a certain phosphate ester type surfactant.

  Further, the content of the phosphate ester-based surfactant is more preferably 0.1 to 5.0% by mass with respect to the total amount of the ink composition. This is because if the amount is less than 0.1% by mass, the desired film strength tends to be difficult to obtain, and if it exceeds 5.0% by mass, the ink aging tends to become unstable. Considering the tendency, 0.3 to 3.0% by mass is preferable with respect to the total amount of the ink composition, and more considering 0.5 to 2.0% by mass is more preferable.

  Specific examples of phosphate ester surfactants include Prisurf A212C, A210G, A207H, AL, A208B, and A213B from the Prisurf series (Daiichi Kogyo Seiyaku Co., Ltd.). A208S, A208F, A208M, A212E, A215C, A219B, A208N, M208F, DB-01, and the like. Also, from the Phosphanol series (manufactured by Toho Chemical Industry Co., Ltd.), Phosphanol RD-510Y, RD-720, RB-410, RA-600, ML-200, ML-220 are the same. ML-240, RS-610, GF-185, RE-410, RE610, sED-200, RP-710, SM-172, and the like. Also, from the Nikkor series (manufactured by Nikko Chemicals), NIKKOL DDP-4, DDP-6, DDP-8, TDP-2, TDP-8, TDP-10, etc. (Adeka Co., Ltd.) ADEKA COAL CS1361E, PS440E, PS810E, etc. are mentioned.

  As for the colorant used in the present invention, there are dyes and pigments. As for the dyes, there are oil-soluble dyes, acid dyes, basic dyes, metal-containing dyes, direct dyes, and various salt-forming dyes. It can be adopted. Examples of the pigment include inorganic, organic and processed pigments. These dyes and pigments can be used in combination of two or more. In particular, in the case of pigment-based inks, unlike the dye-based inks, when the tip of the tip is dried, the pigment particles solidify to form a film. It is easy to be affected. Therefore, when at least a pigment is contained, it is effective to use the 1,2-alkanediol, and it is more effective to use a phosphate ester surfactant in combination.

  As for the pigment, specifically, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, DPP, quinophthalone, selenium, triphenylmethane, Examples include perinone-based, perylene-based, gioxazine-based, metallic pigments, pearl pigments, fluorescent pigments, and phosphorescent pigments. These pigments may be used alone or in combination of two or more. The average particle diameter of the pigment is preferably 300 nm or less. This is because when the average particle size exceeds 300 nm, the particle size is large, and thus the film tends to be hard, and the dry-up performance is likely to be affected. In view of this, 250 nm or less is preferable. Here, the average particle diameter is an average particle diameter d50 measured by a particle size distribution meter. These pigments may be used alone or in combination of two or more. The content of the pigment is preferably 0.5 to 15.0% by mass with respect to the total amount of the ink composition. This is because when the amount is less than 0.5% by mass, the handwriting tends to be thinned. When the amount exceeds 15.0% by mass, the ink tends to aggregate in the ink. 0.0-10.0 mass% is preferable, Most preferably, it is 3.0-7.0 mass%.

    Examples of the pigment dispersant include polyvinyl butyral resin, polyacetal resin, polyvinyl alcohol resin, cellulose resin, polyvinyl pyrrolidone, and the like, and one or more of these can be used. Among them, the polyvinyl butyral resin is preferable, because it is easily dissolved in an organic solvent, and the polyvinyl butyral resin is easily adsorbed to the pigment, so that it is easy to maintain the dispersion of the pigment for a long period of time. As for the pigment, basic carbon black is preferable in consideration of pigment dispersibility with the polyvinyl butyral resin. Here, the basic carbon black is defined as a basic carbon black having a pH value of 7 or more obtained by dispersing carbon black particles in ion exchange water having a pH of 7 and measuring the pH at 25 ° C. with a pH meter. In consideration of pigment dispersibility, basic carbon black having a pH value of 7 to 10 is most preferable.

  The molecular weight of the polyvinyl butyral resin is preferably 100000 or less. This is because when the molecular weight exceeds 100,000, there is a tendency that the dry-up resistance performance is likely to be affected, and it is difficult to dissolve in an organic solvent. In view of this, it is more preferably 30000 or less.

  The content of the pigment dispersant is preferably 1.0 to 20.0 mass% with respect to the total amount of the ink composition. This is because if the amount is less than 1.0% by mass, the pigment dispersibility tends to be inferior, and if it exceeds 20.0% by mass, the solubility in the ink tends to be inferior and the ink viscosity tends to be high. Considering the influence on the dry-up performance, 2.0 to 10.0% by mass is preferable, and more considering 5.0 to 10.0% by mass is most preferable.

  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-pro For oil-based ballpoint pens such as alcohols such as diol, isopropanol, isobutanol, t-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate and other higher alcohols The solvent generally used as ink can be illustrated. Among these, it is preferable to use at least an aromatic alcohol solvent in view of dissolution stability with the 1,2-alkanediol and phosphate ester surfactant and ink aging stability with a pigment. Considering this, it is most preferable to use at least benzyl alcohol. These organic solvents can be used alone or in combination of two or more.

  Further, the content of the organic solvent is preferably 10.0 to 70.0% by mass with respect to the total amount of the ink composition in consideration of the solubility of the colorant, the handwriting drying property, the bleeding, and the like, and the tendency thereof is more considered. 30.0 to 60.0% by mass is preferable, and 40.0 to 60.0% by mass is most preferable.

    The ink viscosity of the oil-based ballpoint pen ink composition of the present invention is not particularly limited, but the ink viscosity at 20 ° C. and a shear rate of 3.84 sec−1 is preferably 1000 to 10,000 mPa · s. This is because when the viscosity is less than 1000 mPa · s, the ink viscosity is low, so that ink is easily produced, and ink tends to remain at the tip of the tip. This is because the dry-up performance is easily affected, and if it exceeds 10,000 mPa · s, the solid content of the resin increases, and the dry-up performance is likely to be affected. Considering further improvement in dry-up resistance, 1000 to 5000 mPa · s is preferable, and 2000 to 5000 mPa · s is most preferable.

  In addition, as surfactants, fluorine surfactants, silicone surfactants, fatty acid alkanolamides, fatty acids, anionic surfactants, cations are used as surfactants to improve lubricity and ink aging stability. Surfactants, amphoteric surfactants, anionic surfactants and / or salt-forms of cationic surfactants, etc., as viscosity modifiers, ketone resins, terpene resins, alkyd resins, phenoxy resins, Resin such as polyvinyl acetate, fatty acid amide, pseudoplasticity imparting agent such as hydrogenated castor oil, etc., as abrasion inhibitor, acrylic resin, silicone resin, polyethylene resin particles, alumina particles, silica particles, etc. Polyvinyl pyrrolidone may be used as a spinnability imparting agent, and a colorant stabilizer, a plasticizer, a chelating agent, water, or the like may be used as appropriate. These may be used alone or in combination of two or more.

Next, an Example is shown and this invention is demonstrated.
The ink composition for oil-based ballpoint pens of Example 1 was prepared by adding a pigment and a pigment dispersant to an organic solvent and dispersing with a disperser, and then adding a dye, 1,2-alkanediol, and a phosphate ester surfactant. Then, it was dissolved at 50 ° C. using a mixing stirrer to obtain an ink composition for oil-based ballpoint pens. Specific blending amounts are as follows. The ink viscosity was measured at a shear rate of 3.84 sec ⁻¹ under an environment of 20 ° C. using a Brookfield viscometer DV-2 + (CPE-42 spindle) and found to be 4400 mPa · s.

Example 1
Dye (Vari First Red 1362) 10.0% by mass
Dye (Spiron Blue C-RH) 10.0% by mass
Dye (Spiron Yellow C-GNH) 10.0% by mass
Pigment (basic carbon black) 5.0% by mass
Pigment dispersant (polyvinyl butyral) 8.0% by mass
Organic solvent (benzyl alcohol) 53.0% by mass
1,2-alkanediol (1,2-octanediol) 3.0% by mass
Phosphate ester surfactant (mixture of alkyl group having 12 and 13 carbon atoms) 1.0% by mass

Examples 2-11
As shown in Tables 1 and 2, oil-based ballpoint pen ink compositions of Examples 2 to 11 were obtained in the same procedure as Example 1 except that each component was changed.

Comparative Examples 1-2
As shown in Table 2, the oil-based ballpoint pens of Comparative Examples 1 and 2 were prepared in the same procedure as Example 1 (no addition of 1,2-alkanediol and phosphate ester surfactant) except that each component was changed. An ink composition was obtained.

Testing and evaluation
The oil-based ballpoint pen ink composition (0.4 g) and the grease-like ink follower prepared in Examples 1 to 11 and Comparative Examples 1 and 2 were placed in an ink containing cylinder (polypropylene) with a ball diameter of φ0.5 mm or φ1. Filled in a ballpoint pen refill with a ballpoint pen tip (stainless steel wire) holding a 0.0mm ball rotatably, and mounted on an oil ballpoint pen (trade name: Acroball) manufactured by Pilot Corporation, The following tests and evaluations were performed. The writing paper JIS P3201 was used as the writing test paper.

Dry-up resistance test: After writing by hand, leave it at 20 ° C and 65% RH for 30 minutes and 3 hours with the tip tip out, then write and write in the following writing conditions in the running test The length of the handwriting blur was measured.
<Writing conditions> Evaluation was performed by writing a straight line with a running test machine under the conditions of a writing load of 70 gf, a writing angle of 70 °, and a writing speed of 4 m / min.
The length of handwriting is less than 3 mm
The length of handwriting scraping is 3 mm or more and less than 20 mm ・ ・ ・ ◎
The length of the handwriting scraper is 20 mm or more and less than 40 mm ...
The length of handwriting scraping is 40 mm or more and less than 80 mm ... ×
The length of handwriting scraps is 80 mm or more. ... XX

  In Examples 1 to 11, since 1,2-alkanediol was contained, good performance was obtained in the dry-up performance test. In particular, in Examples 1 to 5 and 9 to 11, since the phosphate ester-based surfactant was used in combination, the length of the handwriting was less than 3 mm, and the dry-up resistance was greatly improved. In addition, no abnormality was observed in practical writing, and the writing performance was good.

  In Comparative Examples 1 and 2, since 1,2-alkanediol was not contained, the handwriting was severely damaged in the dry-up resistance test, and the length of the handwriting was over 40 mm. In particular, in Comparative Example 2, since the ball diameter was φ1.0 mm, the handwriting blur was particularly bad, and the length of the handwriting surpassed 80 mm, which was not able to withstand practical writing.

As in the present invention, when the ink viscosity at 20 ° C. and the shear rate of 3.84 sec ⁻¹ is set in the range of 1000 to 10000 mPa · s, the ball pen tip can be freely rotated to prevent the ink from drooping. A valve mechanism that presses the ball held on the inner wall of the tip end edge of the tip directly or via a pressing body by a coil spring, and causes the ink to flow out by giving a gap between the inner wall of the tip end edge and the ball by the pressing force at the time of writing. It is preferable that a minute gap at the tip end of the tip is also closed when not in use. Further, the above mechanism is preferable because the gap at the tip end of the chip is closed and the air entry / exit is eliminated, so that the dry-up resistance can be further improved.

  The invention can be used as an oil-based ballpoint pen. More specifically, the invention can be widely used as a cap-type, knock-type, or other oil-based ballpoint pen filled with the oil-based ballpoint ink composition.

Claims (8)

An oil-based ballpoint pen ink composition comprising at least a colorant, an organic solvent, and 1,2-alkanediol. 2. The ink composition for oil-based ballpoint pens according to claim 1, wherein the 1,2-alkanediol is pasty in an environment at 25 ° C. 3. 3. The oil-based ballpoint pen ink composition according to claim 1, wherein a content of the 1,2-alkanediol is 0.1 to 20.0 mass%. 4. The oil-based ballpoint pen ink composition according to any one of claims 1 to 3, wherein the oil-based ballpoint pen ink composition contains a phosphate ester-based surfactant. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 4, wherein the colorant contains at least a pigment. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 5, wherein the organic solvent contains at least an aromatic alcohol solvent. 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 3.84 sec ^-1 is 1000 to 10,000 mPa · s. 8. A ballpoint pen tip having a ball rotatably held in a ball holding chamber of a chip main body is provided directly or via a tip holder at a tip portion of the ink containing tube, and the ink containing tube includes An oil-based ballpoint pen characterized by directly containing the ink composition for oil-based ballpoint pens according to any one of the above items.