JP2014019704A - Ink composition for oily ballpoint pen and oily ballpoint pen using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for oily ballpoint pen that resolves problems of the conventional art, that is, the ink composition having fine writing quality, keeping lubricity in writing at a high writing pressure (500 g), suppressing abrasion of a ball seat, and having fine handwriting.SOLUTION: An ink composition for oily ballpoint pen comprises at least a coloring agent, an organic solvent, and a benzothiazole compound.

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 a benzothiazole compound in the ink composition.

  Conventionally, unlike other types of writing instruments, a ballpoint pen is composed of a metal tip made of stainless steel or the like at the tip and a transfer ball made of metal such as super steel held in a ball receiving seat of the metal tip. Although it has a configuration in which the chip is mounted on the ink storage cylinder, there is a problem that wear of the ball seat occurs due to rotation of the ball during writing, lines are scattered on the handwriting, blurring, etc., and writing quality is deteriorated.

  In order to solve these problems, a large number of oil-based ballpoint pen ink compositions using various lubricants have been proposed for the purpose of improving the lubricity between the ball of the ballpoint pen tip and the ball seat.

  As an oil-based ballpoint pen ink composition using such a lubricant, those using fluorine-based and silicon-based surfactants are disclosed in JP-A-6-248217, “Ballpoint ink composition”, JP-A-9 JP-A-5-331354, “Ink composition for oil-based ballpoint pen”, and those using alkyl β-D-glucoside are disclosed in JP-A-5-331403 “Oil-based ballpoint pen ink”.

"Japanese Patent Laid-Open No. 6-248217" "Japanese Patent Laid-Open No. 9-151354" "Japanese Patent Laid-Open No. 5-331403"

  However, when various lubricants such as Patent Documents 1 to 3 are used, the wear of the ball seat can be suppressed while improving the writing quality to some extent, but with high writing pressure writing (500 g), the lubricity is low. It was not satisfactory, and had a problem that a line jumped on the handwriting and blurring occurred.

  An object of the present invention is to provide an oil-based ink composition for ballpoint pens that has good writing quality, maintains lubricity even in high writing pressure writing (500 g), suppresses wear of the ball seat, and has good handwriting. That is.

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 a benzothiazole compound.
2. 2. The ink composition for oil-based ballpoint pens according to item 1, wherein the benzothiazole compound has a mercapto group.
3. 3. The oil-based ballpoint pen ink composition according to item 1 or 2, wherein the benzothiazole compound is 2-mercaptobenzothiazole or a salt thereof.
4). 4. The oil-based ballpoint pen ink composition according to any one of items 1 to 3, wherein the content of the benzothiazole compound is 0.1 to 10.0% by mass.
5. 5. The oil-based ballpoint pen ink composition according to any one of items 1 to 4, wherein the colorant is a pigment.
6). The oil-based ballpoint pen according to any one of claims 1 to 5, wherein the colorant uses a pigment and a dye together, and the dye is a salt-forming dye of an alkylbenzenesulfonic acid and a basic dye. Ink composition.
7). The ink composition for oil-based ballpoint pens according to any one of claims 1 to 6, wherein the organic solvent contains an aromatic alcohol solvent.
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 5000 mPa · s or less.
9. A ball-point pen tip having a ball rotatably held in a ball holding chamber of a chip body made of a stainless steel material is provided directly or via a chip holder at the tip of the ink storage cylinder, An oil-based ballpoint pen that directly contains the ink composition for oil-based ballpoint pens according to any one of items 1 to 8.
"

  The present invention suppresses the metal contact between the ball and the chip body, so that the writing quality is good and the lubricity of the ball is maintained even in high writing pressure writing (500 g), and the wear of the ball seat is suppressed. An ink composition for an oil-based ballpoint pen that was free from blurring in the handwriting could be provided.

  The first feature of the present invention is that a benzothiazole compound is contained in the oil-based ballpoint pen ink composition.

  The benzothiazole compound used in the present invention is a kind of a heterocyclic compound and has a structure in which benzene and thiazole are condensed by sharing a side. By containing a benzothiazole compound, ball lubrication is achieved. It was found that, by improving the properties, the writing quality is good and the wear of the ball seat is suppressed, so that the handwriting does not fly or blur and the handwriting becomes good.

  This is because the benzothiazole compound has a heterocyclic structure and a benzene ring structure, it has a three-dimensional structure, works as a cushion, suppresses metal contact between the ball and the chip body, and improves lubricity Guess what to do. In particular, since the -S- of the benzothiazole compound and the benzene ring are firmly adsorbed to a metal ball or chip body, it is difficult to peel off even with the ball's shearing force. It is presumed that the wear of the ball seat can be suppressed by maintaining the property.

  Among the benzothiazole compounds, it is preferable to have a mercapto group (—SH) in consideration of lubricity in higher writing pressure writing. This is more effective because the mercapto group (—SH) is easily adsorbed to the metal, more easily adsorbs more strongly, and is less likely to be peeled off even by the shearing force of the ball.

  Specific examples of the benzothiazole compound include 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, di-2-benzothiazolyl disulfide, 2- (N, N-diethyl). Thiocarbamoylthio) benzothiazole, 2- (4′-morpholinodithio) benzothiazole, (1,3-benzothiazol-2-ylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid and its salts Can be mentioned. These benzothiazole compounds may be used alone or in combination of two or more.

  Further, in consideration of lubricity, 2-mercaptobenzothiazole or a salt thereof is most preferable. Specific examples include 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, and zinc salt of 2-mercaptobenzothiazole.

  Further, if the content of the benzothiazole compound is less than 0.1% by mass with respect to the total amount of the ink composition, there is a possibility that a lubricating effect may not be obtained. 0.1 to 10.0% by mass is preferable with respect to the total amount of the ink composition, and 1.0 to 10.0% by mass is preferable in consideration of lubricity. Considering that the solubility in the oil affects the lubricity, 1.0 to 5.0% by mass is most preferable.

  The second feature of the present invention is that it contains at least a pigment as a colorant. By using the pigment, the pigment particles enter the gap between the ball and the chip body, thereby acting like a bearing and suppressing the metal contact, thereby improving the lubricity. Furthermore, as described above, the inclusion of the benzothiazole compound improves the lubricity due to the cushioning action, but the synergistic effect due to the cushioning action by the benzothiazole compound and the bearing action of the pigment particles, By suppressing the metal contact, the lubricity can be improved even in higher pressure writing, the wear of the chip body can be easily suppressed, and the writing quality can be further improved.

  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 DPP Quinophthalone, selenium, triphenylmethane, perinone, perylene, goxazine, metallic pigment, pearl pigment, fluorescent pigment, phosphorescent pigment and the like. These pigments tend to suppress metal contact and improve lubricity by entering the gaps in the chip body. In particular, in consideration of improvement in lubricity, it is preferable to use carbon black. Further, in consideration of the gap relationship inside the chip, the average particle size is preferably 300 nm or less. More preferably, it is 150 nm or less. 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 if it is less than 0.5% by mass, the lubricating effect tends to be difficult to obtain, and if it exceeds 15.0% by mass, it tends to aggregate in the ink. 2.0-10.0 mass% is preferable, Most preferably, it is 3.0-7.0 mass%.

In addition, as dyes, oil-soluble dyes, acid dyes, basic dyes, metal-containing dyes and the like, and various salt-forming dyes thereof are adopted, but considering improvement in lubricity and stability with time of ink It is preferable to use a salt-forming dye of an organic acid and a basic dye. Among them, it is preferable to use a salt-forming dye of an alkylbenzene sulfonic acid and a basic dye. This is because it has an aromatic ring and has a sulfo group (—SO ₃ H), so that a phenyl sulfone group forms a lubricating film that is easily adsorbed to a metal, so that an effect of improving lubricity can be obtained. Because. In addition, the basic dye is a salt-forming dye that has a strong ionic bond between the alkylbenzene sulfonic acid and the basic dye, so that the ink aging stability can be maintained in various environments and for a long period of time in oil-based inks. Therefore, it is preferable.

Further, examples of the alkylbenzene sulfonic acid include dodecyl diphenyl oxide disulfonic acid, dodecyl benzene sulfonic acid, etc. In consideration of improving lubricity, dodecyl diphenyl oxide disulfonic acid having many sulfo groups (—SO ₃ H). Is preferred.

  Further, if the content of the dye is less than 0.1% by mass relative to the total amount of the ink composition, it is difficult to obtain desired lubricity, and if it exceeds 40.0% by mass, the ink aging becomes unstable. Since it is easy, 0.1-40.0 mass% is preferable with respect to the ink composition whole quantity. More preferably, it is 3.0-30.0 mass% with respect to the ink composition whole quantity, Most preferably, it is 10.0-30.0 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, polyvinyl butyral resin is preferable, because it is easy to disperse quickly and finely in an organic solvent, and the polyvinyl butyral resin is easily adsorbed to the pigment, so that it is easy to maintain long-term dispersion of the pigment. is there. In particular, among the pigments, 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 polybutyral resin is obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde (BA), and the polyvinyl butyral resin preferably has 20 to 40 mol% of hydroxyl groups in the molecule. This is because if it is less than 20 mol%, it tends to be difficult to dissolve in an alcohol-based organic solvent, and if it exceeds 40 mol%, the water resistance tends to be inferior, and more preferably 30-40 mol%. preferable. In consideration of solubility in an organic solvent, the molecular weight is preferably 100,000 or less, and more preferably 30000 or less.

  If the content of the pigment dispersant is less than 0.1% 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 increase. The total amount of the ink composition is preferably 1.0 to 20.0% by mass, and more preferably 3.0 to 10.0% by mass in consideration.

  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, 3-methoxy-3-methylbutanol, glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 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 alcohol solvent in view of the dissolution stability of the benzothiazole compound, a salt-forming dye of an alkylbenzenesulfonic acid and a basic dye, and the ink aging stability with a pigment. Furthermore, aromatic alcohol such as benzyl alcohol is most preferably used because it has an effect of improving lubricity. These organic solvents can use 1 type (s) or 2 or more types. The content of the 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 benzothiazole compound, the colorant, the handwriting drying property, the bleeding, etc. If it does, 30.0-65.0 mass% is preferable, Most preferably, it is 45.0-65.0 mass%.

  Furthermore, in order to maintain lubricity and suppress wear of the ball seat even in higher writing pressure writing (500 g), it is preferable to use a phosphate ester surfactant. The phosphoric acid group makes it easier to form a stronger lubricating layer, and the effect of making it easier to maintain lubricity even in high writing pressure writing (500 g) by suppressing metal contact through interaction with the benzothiazole compound. Is obtained.

  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 phosphate triesters, alkyl phosphate esters, alkyl ether phosphate esters or derivatives thereof. These phosphate ester surfactants may be used alone or in combination of two or more. May be used.

  Further, if the content of the phosphate ester-based surfactant is less than 0.1% by mass relative to the total amount of the ink composition, the desired lubricity tends to be difficult to obtain, and if it exceeds 5.0% by mass. In addition, since ink aging tends to be unstable, 0.1 to 5.0% by mass is more preferable with respect to the total amount of the ink composition. Most preferably, it is 0.5 to 3.0 mass% with respect to the total amount of the ink composition.

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 30000 mPa · s, the ball rotation resistance during writing tends to increase and the writing taste tends to be heavy. Therefore, the ink viscosity at 20 ° C. and a shear rate of 500 sec ⁻¹ is preferably 10 to 30000 mPa · s. Considering improvement in writing quality, 10 to 5000 mPa · s is preferable, and most preferable is 100 to 3000 mPa · s in consideration of ink sag and writing quality.

  Further, as in the present invention, fine particles may be used in order to further improve the lubricity. This is because the fine particles can improve the lubricity by suppressing the metal contact by entering the fine particles into the gaps of the chip body, like the pigment. Specific examples of the fine particles include resin fine particles such as acrylic, silicone, and polyethylene, alumina fine particles, and silica fine particles. Among these, spherical silica fine particles are preferable. The fine particles are preferably fine particles having an average particle diameter of 5 to 100 nm in consideration of lubricity, and the average particle diameter is a median diameter, and can be determined by a centrifugal sedimentation method, a laser diffraction method, a BET method, or the like.

  In addition, as surfactants, fluorine surfactants, silicone surfactants, fatty acid alkanolamides, anionic surfactants, cationic interfaces are used to improve lubricity and ink aging stability. Activators, amphoteric surfactants, oxyethylene alkylamines, polyoxyethylene alkylamines and anionic surfactants and / or cationic surfactant salt formations as viscosity modifiers, ketone resins, terpenes Resin, alkyd resin, phenoxy resin, resin such as polyvinyl acetate, pseudoplasticity imparting agent such as fatty acid amide, hydrogenated castor oil, and coloring agent, stabilizer, plasticizer, chelating agent, water, etc. Also good. 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 dissolving the pigment dispersion resin with an organic solvent and a pigment dispersant at 50 ° C. using a mixing stirrer to prepare Solution A. A pigment is added to the obtained solution A, and a dispersion base is prepared using three rolls. The remaining components were stirred on this dispersion base at 50 ° C. using a mixing stirrer to obtain an ink composition for oil-based ballpoint pens. Specific blending amounts are as follows. Ink viscosity measured at a shear rate of 500 sec ^-1 under an environment of 20 ° C using AR-G2 (stainless steel 40 mm 2 ° rotor) manufactured by TA Instruments Inc. was 1200 mPa · s. there were.

Example 1
Dyes (Salt-forming dyes of alkylbenzenesulfonic acid and xanthene basic dyes)
15.0% by mass
Dyes (Salt-forming dyes of alkylbenzenesulfonic acid and triallylmethane basic dyes)
10.0% by mass
Pigment (basic carbon black) 5.0% by mass
Pigment dispersant (polyvinyl butyral) 3.0% by mass
Organic solvent (benzyl alcohol) 54.0% by mass
Benzothiazole compound (2-mercaptobenzothiazole) 2.0% by mass
Stabilizer (oleic acid) 1.0% by mass
Resin (ketone resin) 10.0% by mass

Examples 2-9
As shown in Tables 1 and 2, oil-based ballpoint pen ink compositions of Examples 2 to 9 were obtained in the same procedure as Example 1 except that each component was changed.
Example 10
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 1-4
As shown in Table 3, the components were mixed in the same procedure as in Example 1 except that each component was changed, and ink compositions for oil-based ballpoint pens of Comparative Examples 1 to 4 were obtained. Table 3 shows the measurement and evaluation results.

Testing and evaluation
A ball having a ball diameter of φ0.7 mm is prepared by using the ink composition (0.4 g) for oil-based ballpoint pen and the grease-like ink follower prepared in Examples 1 to 10 and Comparative Examples 1 to 4 in an ink containing cylinder (polypropylene). Was filled into a ballpoint pen refill equipped with a ballpoint pen tip (stainless steel wire) that was held in a freely rotatable manner to produce an oil-based ballpoint pen. The following tests and evaluations were performed using a writing paper JIS P3201 as a writing test paper.

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

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 less than 5μm ・ ・ ・ ◎
Ball seat wear is 5 μm or more and less than 10 μm.
Ball seat wear is 10 μm or more and less than 20 μm, but can be written.
Wearing the ball seat is bad and results in poor writing ・ ・ ・ ×

  In Examples 1 to 10, good performance was obtained for both writing quality and high writing pressure writing test.

  In Comparative Examples 1 to 4, since no benzothiazole compound was contained, the ball seat was very worn in the high writing pressure writing test, and the handwriting was blurred.

  In the present invention, a lubricating coating layer (not shown) is provided on the surface of the ball and / or the abutting surface, so that the ball can be obtained by the synergistic effect of the lubricating coating layer and the fluid lubrication or mixed lubrication by the ink layer. This is preferable because the contact resistance between the contact surface and the inner wall of the chip can be remarkably reduced and the wear resistance and writing feeling of the contact surface can be remarkably improved.

  The lubricating coating layer used in the present invention includes diamond-like carbon (DLC), tungsten disulfide (WS2), molybdenum disulfide (MoS2), graphite, fluorine-containing polymers such as tetrafluoroethylene (PTFE), silicone, and the like. Conventionally known solid lubricants such as resins can be used as appropriate. The method for coating the lubricating coating layer is not particularly limited, and examples thereof include vacuum deposition, ion deposition, physical vapor deposition, chemical vapor deposition, and vacuum arc deposition. There may be. In particular, among the above-described lubricants, diamond-like carbon (DLC) is most preferably used in consideration of wear resistance and lubricity.

As in the present invention, in order to improve the writing quality, when the ink viscosity at 20 ° C. and the shear rate of 500 sec ⁻¹ is set in the range of 10 to 5000 mPa · s, a ballpoint pen is used to prevent the ink from dripping. The ball held rotatably at the tip of the tip is pressed against the inner wall of the tip end of the tip directly by a coil spring or via a pressing body, and the ink is applied to the inner wall of the tip end of the tip and the ball by the pressing force at the time of writing. It is preferable to provide a valve mechanism for allowing the chip to flow out, and to close the minute gap at the tip of the tip when not in use.

  The present invention can be used as an oil-based ballpoint pen. More specifically, the present invention can be widely used as a water-based ballpoint pen of a cap type or a knock type filled with the ink composition for oily ballpoint pens.

Claims (9)

An oil-based ballpoint pen ink composition comprising at least a colorant, an organic solvent, and a benzothiazole compound. The oil-based ballpoint pen ink composition according to claim 1, wherein the benzothiazole compound has a mercapto group. The oil-based ballpoint pen ink composition according to claim 1 or 2, wherein the benzothiazole compound is 2-mercaptobenzothiazole or a salt thereof. The oil-based ballpoint pen ink composition according to any one of claims 1 to 3, wherein the content of the benzothiazole compound is 0.1 to 10.0% by mass. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 4, wherein the colorant is a pigment. The oil-based ballpoint pen ink according to any one of claims 1 to 5, wherein the colorant is a combination of a pigment and a dye, and the dye is a salt-forming dye of an alkylbenzenesulfonic acid and a basic dye. Composition. The ink composition for oil-based ballpoint pens according to any one of claims 1 to 6, wherein the organic solvent contains an aromatic alcohol solvent. 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. The tip of the ink storage cylinder is provided with a ballpoint pen tip that is rotatably held in a ball holding chamber of a chip body made of a stainless steel material, directly or via a chip holder, Item 9. An oil-based ballpoint pen that directly contains the ink composition for oil-based ballpoint pens according to any one of Items 1 to 8.