JP2020006589A - Aqueous ballpoint pen - Google Patents

Abstract

To improve the writing feeling deteriorated due to the titanium component being deposited on the ball seat by writing, in an aqueous ballpoint pen using a writing ball made of a cermet material.SOLUTION: An aqueous ballpoint pen 10 comprises: a ballpoint pen tip 20 having a writing ball 30 comprising a mixture containing a hard phase component comprising at least one of groups comprising titanium carbide, titanium carbonitride and titanium nitride, a binder phase component comprising at least one of groups comprising cobalt and nickel, and chromium and molybdenum; and an aqueous ink composition 40 blended with resin particles.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an aqueous ballpoint pen provided with a writing ball having a hard phase component and a binder phase component.

  As materials forming the ball of a ballpoint pen, cemented carbides, ceramics, and the like are widely known as in Patent Documents 1 to 3 below.

Japanese Utility Model Publication No. 52-106235 JP-A-2002-19366 JP 2015-51571 A

  Ballpoint pens using balls made of cemented carbide mainly composed of tungsten carbide are widely known. The effects of these balls on the performance of ballpoint pens are also widely known.

  In addition, a ballpoint pen using a ball made of a so-called cermet material, which is a composite material obtained by mixing powder of a hard compound such as a carbide or nitride of a metal such as titanium with a binder of a metal and sintering the mixture. In such a case, when writing, a titanium component is deposited on the ball seat of the ball-point pen tip that holds the ball, which may lead to deterioration of the writing feeling such as a feeling of being caught.

  An object of the present invention is to provide an aqueous ballpoint pen using a writing ball made of a cermet as described above as a material, and to improve the writing feeling, which is deteriorated by the titanium component being deposited on the ball seat by writing.

In order to solve the above problems, an aqueous ballpoint pen according to a first aspect of the present invention includes a hard phase component consisting of at least one of titanium carbide, titanium carbonitride and titanium nitride, and a group consisting of cobalt and nickel. A ballpoint pen tip having a writing ball consisting of a mixture containing at least one of the following: a binder phase component, chromium and molybdenum;
And an aqueous ink composition containing resin particles.

  An aqueous ballpoint pen according to a second aspect of the present invention is characterized in that, in addition to the features of the first aspect, the resin particles are styrene acrylic resin.

  Further, in the water-based ballpoint pen according to the third aspect of the present invention, in addition to the features of the first or second aspect, the content of the resin particles in the aqueous ink composition is 0.5 to 10% by mass. There is a feature.

  Since it is configured as described above, the present invention provides an aqueous ballpoint pen using a writing ball made of a material called a cermet, in which the writing feeling deteriorated due to the titanium component being deposited on the ball seat by writing. It can be improved.

FIG. 1 is a front sectional view showing an aqueous ballpoint pen according to an embodiment of the present invention. FIG. 2 is an enlarged front sectional view of the vicinity of the tip of a ballpoint pen tip of the aqueous ballpoint pen according to the embodiment of the present invention. FIG. 9 is a front sectional view showing a refill incorporated in an aqueous ballpoint pen according to another embodiment of the present invention.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

(1) Aqueous ballpoint pen 10
An aqueous ball-point pen 10 according to the present embodiment is a ball-point pen as shown in FIG. 1, and has a cylindrical barrel 12 having an open front end and a closed rear end. A ball-point pen tip 20, an ink guiding portion 13 penetrating through the axial center of a collector housing portion 14 corresponding to the front half of the inner space of the barrel 12, and an ink housing portion corresponding to the latter half of the inner space of the barrel 12. The ball-point pen 20 includes a water-based ink composition 40 in a direct liquid state accommodated in the internal space 15 and a cap (not shown) that covers a portion from the front end of the ballpoint pen tip 20 to the vicinity of the rear end of the collector housing portion 14.

  A collector 17 formed by stacking ring-shaped thin plates in the axial direction is formed from the inner surface of the collector accommodating portion 14 to the outer surface of the ink guiding portion 13. The collector 17 is used to hold the aqueous ink composition 40 when the air in the ink container 15 expands due to a change in air pressure or temperature in a direct liquid type ballpoint pen, thereby preventing leakage to the outside.

  The aqueous ink composition 40 may be supplied in a batting type instead of a direct liquid type. Further, it may be accommodated in a separate refill 18 (see FIG. 3).

  FIG. 2 shows an enlarged sectional view of the vicinity of the tip of the ballpoint pen tip 20. The ball-point pen tip 20 includes a holder 21 having a cylindrical body part (not shown), a tapered part 27 formed to decrease in diameter from the tip of the body part toward the tip of the ball-point tip 20, and the inside of the holder 21. Is composed of a spherical writing ball 30 held by the user. The holder 21 includes an ink guide hole 26 penetrated from the rear end of the ballpoint pen tip 20, a ball house 22 formed by cutting and expanding an inner circumference near the tip of the holder 21, and an inner peripheral surface of the ball house 22. A portion sandwiched between the front end and the front end of the tapered portion 27, and is formed of a caulking portion 23 caulked by plastic deformation of the writing ball 30 in the center direction. Further, a ball seat 24 provided at the bottom of the ball house 22 and formed around the ink guide hole 26 is provided around the ink guide hole 26 so as to connect the ball seat 24 and the ink guide hole 26. It has ink grooves 25 equally distributed at four locations. The width and number of the ink grooves 25 may be changed according to the viscosity of the aqueous ink composition 40 and the like.

  When assembling the holder 21, the writing ball 30 is inserted into the ball house 22 from the tip. Then, by pressing the upper portion of the writing ball 30 toward the rear end, the ball seat 24 is deformed along the outer shape of the writing ball 30. After that, the tip of the tapered portion 27 is caulked using a tapered roller to provide the caulked portion 23, thereby forming the holder 21.

  The holder 21 is made of stainless steel having a Vickers hardness of about 200 to 420. The material of the holder 21 can also be formed by using a metal or resin such as nickel silver, brass, or brass, but the Vickers hardness is desirably 170 to 450.

  Further, in the present embodiment, the holder 21 is formed by cutting from a solid wire, but is not limited to cutting from a wire. For example, a hollow pipe is formed by plastic working. You may.

(2) Writing ball 30
The writing ball 30 of the present embodiment includes a hard phase component composed of at least one of a group consisting of titanium carbide (TiC), titanium carbonitride (TiCN) and titanium nitride (TiN) as main components, and cobalt (Co). And a mixture containing at least one of a binder phase component selected from the group consisting of nickel and nickel (Ni), chromium (Cr), and molybdenum (Mo). This mixture is what is called a cermet. Here, the metal element mentioned above may be either a simple substance or a compound.

  The ratio of the hard phase component to the entire writing ball 30 is desirably 70% by mass or more. When tungsten carbide (WC) is contained in the mixture as a component other than the above, the content is desirably 15% by mass or less.

  The hard phase component, the binder phase component, the material powder of chromium and molybdenum, and the mixture obtained by pulverizing and mixing the material powder of other components, if any, are formed into a substantially spherical shape, and then sintered. To form a sphere. Then, the writing ball 30 is formed by rolling the obtained sphere together with diamond powder between two whetstones held at regular intervals and finishing the ball surface 31 to a mirror surface. The Vickers hardness (Hv) of the ball surface 31 is 1600 to 2,000.

(3) Aqueous ink composition 40
The aqueous ink composition 40 of the present embodiment is an aqueous ink containing resin particles. The resin particles are particles of a synthetic resin. The type of the synthetic resin, which is a material of the resin particles, is not particularly limited as long as it has a particle diameter described below, but has a hardness suitable to play a role such as `` roller '' described later. And styrene acrylic resin are preferred.

  In addition to the resin particles, the aqueous ink composition 40 includes a solvent such as ethylene glycol, glycerin or propylene glycol, water and various additives (a pigment dispersant, a thickener, a lubricant, a rust inhibitor, a And the like, as appropriate.

  Note that the aqueous ink composition 40 may be a so-called gel ink. The aqueous ink composition 40 as such a gel ink is contained in the refill 18 as shown in FIG. The refill 18 has a structure in which a ballpoint pen tip 20 is attached via a joint 11 to the tip of a long-axis cylindrical ink storage unit 15 that stores an aqueous ink composition 40. The structure of the ballpoint pen tip 20 is as shown in FIG. A grease-like follower 41 is injected into the rear end of the water-based ink composition 40 in order to prevent the water-based ink composition 40 from flowing out of the rear end of the ink container 15. The follower 41 follows the tip of the aqueous ink composition 40 as the aqueous ink composition 40 is consumed by writing. The refill 18 is mounted on a shaft cylinder (not shown) and can be used as the aqueous ballpoint pen 10.

(4) Functions and Effects In writing, the aqueous ink composition 40 in the ink storage unit 15 is supplied to the ball house through the ink guide unit 13, the ink guide hole 26, and the ink groove 25 in the case of the water-based ballpoint pen 10 shown in FIG. 22 and is sufficiently supplied to the writing ball 30 accommodated in the ball house 22. On the other hand, in the case of the refill 18 as shown in FIG. 3, the aqueous ink composition 40 in the ink container 15 is sent to the ball house 22 through the joint 11, the ink guide hole 26 and the ink groove 25, and is stored in the ball house 22. The writing ball 30 is sufficiently supplied. In any case, the rotation of the writing ball 30 causes the aqueous ink composition 40 supplied to the ball surface 31 to be transferred or permeated to a recording medium such as paper, and the writing is completed.

  Here, the writing ball 30 is made of the cermet as described above. On the other hand, when the water-based ink composition 40 is used, the titanium particles generated by the abrasion of the writing ball 30 cause the ball seat 24. On the surface of the ball seat 24, which leads to a poor writing feeling such as a feeling of being caught.

  The resin particles contained in the aqueous ink composition 40 are blended in the aqueous ink composition in order to improve such deteriorated writing feeling. Such resin particles play a role like “roller” between the surface of the ball seat 24 having irregularities caused by the attached titanium particles and the ball surface 31, thereby contributing to an improvement in writing feeling. It is supposed to do.

  A suitable average particle diameter of the resin particles is 0.08 to 2.5 μm, more preferably 0.08 to 1.0 μm, and still more preferably 0.08 to 0.6 μm. The effect of improving the writing feeling obtained by the resin particles does not largely depend on the average particle size. However, when the average particle size exceeds 1 μm, it becomes difficult to maintain the dispersion stability of the resin particles. Is preferred.

  If the preferable content of the resin particles in the aqueous ink composition 40 is less than 0.5% by mass, it is difficult to obtain a sufficient effect for improving the writing feeling as described above. If the content exceeds 10.0% by mass, the effect on the improvement of the writing feeling as described above is not changed, but the supply of the aqueous ink composition 40 may be impaired. Therefore, in view of the function of the water-based ballpoint pen 10 including the improvement of the writing feeling, the preferable content of the resin particles in the water-based ink composition 40 is preferably 0.5 to 10.0% by mass, more preferably. Is 1.0 to 5.0% by mass. More preferably, the content is 2.0 to 4.0% by mass.

(1) Writing ball 30
Five types of writing balls 30 having the following compositions were produced by the method described above.

(1-1) Ball 1
A mixture of the following composition was formed as the writing ball 30 by the above-mentioned method to obtain a ball 1.
TiCN (hard phase component): 70% by mass
Ni: (Bound phase component) 12% by mass
Cr ₃ C ₂ : 6% by mass
Mo ₂ C: 12% by mass
The ball 1 was used in Examples 1, 2, 7 to 9 and 13 and Comparative Examples 1 and 2 below.

(1-2) Ball 2
A mixture of the following composition was formed as the writing ball 30 by the above-mentioned method to obtain a ball 2.
TiCN (hard phase component): 85% by mass
Ni (binding phase component): 8% by mass
Cr ₃ C ₂ : 3% by mass
Mo: 4% by mass
This ball 2 was used in Examples 3 and 10 below.

(1-3) Ball 3
A mixture of the following composition was formed as a writing ball 30 by the above-described method to obtain a ball 3.
TiN (hard phase component): 85% by mass
Ni (binding phase component): 8% by mass
Cr ₃ C ₂ : 3% by mass
Mo: 4% by mass
This ball 3 was used in Examples 4, 11 and 12 below.

(1-4) Example 4
A ball 4 was formed from a mixture having the following composition and formed as a writing ball 30 by the method described above.
TiCN (hard phase component): 85% by mass
Co (binding phase component): 8% by mass
Cr ₃ C ₂ : 3% by mass
Mo: 4% by mass
This ball 4 was used in Example 5 described below.

(1-5) Ball 5
A mixture of the following composition was formed as a writing ball 30 by the above-described method to obtain a ball 5.
TiCN (hard phase component): 70% by mass
Ni (binding phase component): 8% by mass
Cr ₃ C ₂ : 3% by mass
Mo: 4% by mass
WC: 15% by mass
This ball 5 was used in Example 6 described below.

(2) Examples and Comparative Examples Hereinafter, in each of Examples and Comparative Examples, the composition of the aqueous ink composition 40 used is shown.

The following products or substances were used for the components shown in each composition.
Pigment: FUJI RED 2510 (Fuji dye)
Pigment dispersant: John Krill 61J (BASF JAPAN)
Thickener: Primal TT-615 (associative thickener, Dow Chemical)
Lubricant: Plysurf A219B (Daiichi Kogyo Pharmaceutical)
Preservative: Bioden 421 (Nippon Soda)
Rust inhibitor: benzotriazole pH adjuster: triethanolamine Water-soluble organic solvent: propylene glycol Water: ion-exchanged water

The resins used as the resin particles in each composition are as follows.
MG-161E: Styrene acrylic resin, average particle size 0.1 μm, solid content 20% by mass (Nippon Paint)
FS-102E: Styrene acrylic resin, average particle size 0.08 μm, solid content 20% by mass (Nippon Paint)
OP-84J: Styrene acrylic resin hollow particles, average particle size 0.55 μm, solid content 40% by mass (Nippon Paint)
Chemipearl W900: polyethylene resin, average particle diameter 0.6 μm, solid content 40% by mass (Mitsui Chemicals)
Chemipearl W500: polyethylene resin, average particle size 2.5 μm, solid content 40% by mass (Mitsui Chemicals)
MG-155E: acrylic resin, average particle size 0.1 μm, solid content 20% by mass (Nippon Paint)

The average particle diameter of the resin particles, which particle size distribution analyzer (HRA9320-X100, manufactured by Nikkiso) was used in refractive index 1.81, it was determined as the value of _{D 50} which is calculated on a volume basis It is.

(2-1) Example 1
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (MG-161E): 15.0% by mass (net resin content: 3.0% by mass)
Water: 53.6% by mass

(2-2) Example 2
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (FS-102E): 15.0% by mass (net resin content: 3.0% by mass)
Water: 53.6% by mass

(2-3) Example 3
Same as Example 1.

(2-4) Example 4
Same as Example 2.

(2-5) Example 5
Same as Example 1.

(2-6) Example 6
Same as Example 2.

(2-7) Example 7
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (OP-84J): 7.5% by mass (net resin content: 3.0% by mass)
Water: 61.1% by mass

(2-8) Example 8
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (Chemipearl W900): 7.5% by mass (net resin content: 3.0% by mass)
Water: 61.1% by mass

(2-9) Example 9
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (Chemipearl W500): 7.5% by mass (net resin content: 3.0% by mass)
Water: 61.1% by mass

(2-10) Example 10
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (MG-155E): 15.0% by mass (net resin content: 3.0% by mass)
Water: 53.6% by mass

(2-11) Example 11
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (MG-161E): 50.0% by mass (net resin content: 10.0% by mass)
Water: 18.6% by mass

(2-12) Example 12
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (MG-161E): 2.5% by mass (net resin content: 0.5% by mass)
Water: 66.1% by mass

(2-13) Example 13
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Thickener: 1.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Resin (MG-161E): 20.0% by mass (net resin content: 4.0% by mass)
Water: 47.6% by mass

(2-14) Comparative Example 1
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Water: 68.6% by mass

(2-15) Comparative example 2
Pigment: 8.0% by mass
Pigment dispersant: 6.0% by mass
Thickener: 1.0% by mass
Lubricant: 0.5% by mass
Preservative: 0.2% by mass
Rust inhibitor: 0.3% by mass
pH adjuster: 1.4% by mass
Water-soluble organic solvent: 15.0% by mass
Water: 67.6% by mass

(3) Writing Feeling Test The water-based ballpoint pens 10 according to the respective Examples and Comparative Examples, each including the ballpoint pen tip 20 to which the above-described various writing balls 30 are mounted and the above-described various water-based ink compositions 40, are manufactured according to JIS S6054-2000. The writing feeling after 400 m of mechanical writing was evaluated based on the rules. Specifically, in an environment at a room temperature of 25 ° C. and a humidity of 60%, a tester performs test writing with a water-based ballpoint pen 10 before machine writing, and then uses an automatic writing tester to perform machine writing under the following conditions. 400 m.
Writing power: 1N
Writing angle: 60 °
Writing speed: 4.5 m / min Writing pattern: Continuous writing with a line pitch of 3 mm and a circumference of 100 mm

After the mechanical writing, the tester again made a test writing in the same manner as above, and the sensory evaluation of the difference in writing feeling from before the mechanical writing was performed according to the following criteria.
A: No change in writing feeling.
B: Slightly caught.
C: A weak feeling of catch occurred, but there was no effect on the written lines.
D: There is a case where a remarkable snagging feeling is generated and the writing line is interrupted.

  The results of the above-mentioned sensory evaluation are shown in Table 1 below together with the outlines of the respective Examples and Comparative Examples.

  First, the aqueous ballpoint pen 10 of Example 1 containing the aqueous ink composition 40 containing 3.0 mass% of styrene acrylic resin particles having an average particle diameter of 0.1 μm and using the ball 1 as the writing ball 30, The evaluation of the feeling was excellent as A. The ball 1 contains 70% by mass of TiCN as a hard phase component and 12% by mass of Ni as a binder phase component, but under the same conditions as in Example 1 except that it does not contain resin particles. Compared with the evaluation of writing sensation of the aqueous ballpoint pen of Comparative Example 1 which was extremely inferior to D, the writing sensation deteriorated by titanium particles as a hard phase component was caused by adding resin particles to the aqueous ink composition 40. The improvement was clearly observed.

  Further, the aqueous ballpoint pen 10 of Example 2 under the same conditions as Example 1 except that the same styrene acrylic resin but resin particles having an average particle diameter of 0.1 μm slightly smaller than that of Example 1 were contained in the aqueous ink composition 40. In addition, the evaluation of the writing feeling was excellent as A. Therefore, it was confirmed that the resin particles of Example 2 also improved the writing feeling deteriorated by the titanium particles as the hard phase component.

  The aqueous ballpoint pen 10 of Example 3 under the same conditions as in Example 1 was also used, except that the ball 2 having a content of TiCN as a hard phase component of 85% by mass and being larger than the ball 1 of Example 1 was used as the writing ball 30. In addition, the evaluation of the writing feeling was excellent as A. Therefore, the resin particles used in Example 1 had an effect of improving the deteriorated writing feeling even in the writing ball 30 having a higher titanium content.

  The water-based ballpoint pen 10 of Example 4 under the same conditions as in Example 2 was also excellent in the evaluation of writing feeling A, except that the ball 3 containing 85% by mass of TiN as a hard phase component was used as the writing ball 30. . Therefore, the resin particles used in Example 2 also exhibited an effect of improving the deteriorated writing feeling even in the writing ball 30 having a higher titanium content.

  The aqueous ballpoint pen 10 of Example 5 under the same conditions as Example 3 except that the ball 4 using Co instead of Ni used in the ball 2 as the binder phase component was used as the writing ball 30, The evaluation of the writing feeling was excellent as A. Therefore, the resin particles used in Example 3 (that is, Example 1) were found to have the effect of improving the deteriorated writing feeling even in the writing ball 30 using Co as the binder component.

  The aqueous solution of Example 6 under the same conditions as in Example 2 except that the ball 5 containing 15% by mass of WC was used as the writing ball 30 while containing 70% by mass of TiCN as in the case of the ball 1 as the hard phase component. The ballpoint pen 10 also had an excellent writing feeling rating of A. Therefore, it was confirmed that the resin particles used in Example 2 had an effect of improving the writing feeling, which was deteriorated even in the writing ball 30 containing Ti as a main component and containing a certain amount of WC.

  In addition, the water-based ballpoint pen 10 of Example 7 in which a styrene acrylic resin was used as the resin particles in Example 1 and Example 2 but hollow particles were used as the resin particles was also excellent in the evaluation of writing feeling as A. Therefore, it was confirmed that the hollow particles of the styrene acrylic resin used in Example 7 also had the effect of improving the deteriorated writing feeling to the same extent as the resin particles of Examples 1 and 2.

  The aqueous ballpoint pen 10 of Example 8 under the same conditions as in Example 1 except that polyethylene resin particles, which are olefin-based resins having an average particle diameter of 0.6 μm, was evaluated as having a writing feeling of B, which was lower than that of Example 1. It was somewhat inferior. However, the evaluation was superior to the evaluation D of Comparative Example 1 under the same conditions except that no resin particles were contained. Therefore, it was recognized that the olefin-based resin particles used in Example 8 had an effect of improving the writing feeling, which was deteriorated to some extent.

  In the aqueous ballpoint pen 10 of Example 9 using resin particles which are polyethylene resins which are olefinic resins as in Example 8 but have an average particle diameter as large as 2.5 μm, the evaluation of writing feeling was C, and 8 was inferior. This is presumed to be due to the increase in particle size. However, since the evaluation was somewhat superior to D in the evaluation of Comparative Example 1 under the same conditions except that the resin particles were not contained, the olefin resin particles used in Example 9 had slightly deteriorated writing. It was recognized that it had the effect of improving the feeling.

  In the water-based ballpoint pen 10 of Example 10 under the same conditions as in Example 1 except that acrylic resin particles having a different average particle diameter of 0.1 μm but a different material were used as in Example 1, the writing feeling was evaluated as B. However, it was slightly inferior to Example 1. However, the evaluation was superior to the evaluation D of Comparative Example 1 under the same conditions except that no resin particles were contained. Therefore, it was recognized that the acrylic resin particles used in Example 10 had an effect of improving the writing feeling, which was somewhat deteriorated.

  The same resin particles as in Example 1 were used, but the water-based ballpoint pen 10 of Example 11 in which the content was 10.0% by mass had a writing feeling of B, which was slightly inferior to that of Example 1. Was. Similarly, the same resin particles as in Example 1 were used, but the aqueous ballpoint pen 10 of Example 12 in which the content was 0.5% by mass also had a writing feeling of B, which was slightly inferior to Example 1. It became a thing. However, these evaluations were superior to D of the evaluation of Comparative Example 1 under the same conditions except that no resin particles were contained. Therefore, as for the content of the resin particles used in Example 1, the lower limit is 0.5% by mass and the upper limit is in the range of 10.0% by mass. It was recognized that there was.

  A gel ink containing a thickener was used as the aqueous ink composition 40, and the aqueous ballpoint pen of Example 13 in which the aqueous ink composition 40 contained 4.0% by weight of the resin particles of Example 1. In No. 10, the evaluation of writing feeling was C, which was not so excellent. However, the evaluation was superior to the evaluation D of Comparative Example 2 under the same conditions except that the resin particles were not contained. Therefore, it was recognized that the resin particles of Example 1 had an effect of improving the writing feeling, albeit slightly, even when used in gel ink.

  The present invention can be used for an aqueous ballpoint pen.

DESCRIPTION OF SYMBOLS 10 Water-based ball-point pen 11 Joint 12 Shaft cylinder 13 Ink guide part 14 Collector storage part 15 Ink storage part 17 Collector 18 Refill 20 Ball-point pen tip 21 Holder 22 Ball house 23 Caulking part 24 Ball receiver 25 Ink groove 26 Ink guide hole 27 Taper part 30 Writing ball 31 Ball surface 40 Water-based ink composition 41 Follower

Claims (3)

From a mixture containing titanium carbide, a hard phase component consisting of at least one of the group consisting of titanium carbonitride and titanium nitride, a binder phase component consisting of at least one of the group consisting of cobalt and nickel, and chromium and molybdenum A ballpoint pen tip having a writing ball,
And a water-based ink composition containing resin particles.   The water-based ballpoint pen according to claim 1, wherein the resin particles are a styrene acrylic resin.   The aqueous ballpoint pen according to claim 1, wherein the content of the resin particles in the aqueous ink composition is 0.5 to 10.0% by mass.