ballpoint pen

Abstract

A ballpoint pen, wherein the ink viscosity of the oily ballpoint pen ink composition of the ballpoint pen is 20°C and the shear rate is 500s ‑1 The pressure is in the range of 500 mPa·s to 15000 mPa·s. The ball diameter of the ball is 0.5 mm or less. The front end of the pen tip has a first caulking portion with an inclination angle of 90 degrees or more and less than 100 degrees and a second caulking portion provided on the front end side of the ballpoint pen tip and with an inclination angle of 110 degrees or more and 130 degrees or less than the first caulking portion. The angle of the bottom wall of the ball holding chamber is the same as the inclination angle of the second caulking portion.

Description

Technical Field

[0001] The invention relates to a ballpoint pen. Background Art

[0002] A ballpoint pen having a ballpoint pen tip is known. The ballpoint pen tip has, for example, an ink flow hole formed in the center of the bottom wall of a ball holding chamber and a plurality of ink flow grooves extending radially from the ink flow hole. As a ballpoint pen tip, a ball is placed on a ball seat having an approximately arc-shaped surface provided on the bottom wall of the ball holding chamber, and the front end of the pen tip is crimped inward, thereby allowing a part of the ball to protrude from the front edge of the pen tip and be held rotatably.

[0003] In addition, writing utensils are easy to affect the writing experience of ballpoint pens or markers, etc., due to the writing resistance between the ballpoint pen tip and the written surface when writing. In particular, a ballpoint pen has a ballpoint pen tip, which is provided with a metal pen tip body made of stainless steel, etc., located at the front end, and a ball made of metal such as super steel, which is held by the ball seat of the metal pen tip body. Therefore, there is the following problem in a ballpoint pen: due to the rotation of the ball when writing, the ball seat is worn, and the handwriting produces flying lines, flying white, etc., and the writing experience is deteriorated. In addition, especially when the ball diameter is reduced to less than 0.5mm, the ball sneaks into the paper surface due to the pen pressure, and the outer surface of the caulking portion is easily scraped against the written surface, which has a tendency of poor smoothness when writing.

[0004] In order to improve the smoothness of writing, which is important for ballpoint pens, the wall thickness of the caulking portion is made thinner, or the angle of the caulking portion is reduced. Specifically, the closer the angle is to the tapered surface that changes from a large diameter portion to a small diameter toward the front end of the pen tip, the less likely it is to scratch the paper. For example, the angle of the tapered surface is mostly about 30 degrees, so a technology is disclosed in which the angle of the caulking portion is set to 90 degrees or less to form a structure that is less likely to scratch the paper (see, for example, Patent Document 1). However, making the wall thickness of the caulking portion thinner or reducing the inclination angle (caulking angle) will make it easier for the ball to fall off the ball holding chamber, etc., which reduces the durability of the ballpoint pen tip.

[0005] In order to improve the durability of the ballpoint pen tip, it is considered to increase the wall thickness of the caulking portion. However, the caulking portion is easy to contact with the writing surface, etc., which reduces the smoothness when writing. That is, if the smoothness is improved, the durability is reduced, and conversely, if the durability is improved, the smoothness is reduced.

[0006] Incidentally, the following is disclosed: in a ballpoint pen tip, in order to prevent ink from leaking out from the tip end, etc., a sealing surface approximately in the shape of a circular arc is formed on the inner wall of the tip end (see, for example, Patent Document 2). However, since the wall thickness of the caulking portion becomes thinner, there is a tendency for the durability of the tip to decrease.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 6-15218

[0010] Patent Document 2: Japanese Patent Application Publication No. 2010-184495 Summary of the invention

[0011] Problems to be solved by the invention

[0012] In particular, in a ballpoint pen using a small-diameter ball with a ball diameter of 0.5 mm or less, the smaller the ball diameter, the higher the number of times the ball rotates when writing the same distance. In addition, if a small-diameter ball is used, a load is applied to the ball seat, so the ball seat is severely worn, resulting in poor writing. Therefore, if a small-diameter ball is used, new problems are likely to arise.

[0013] The object of the present invention is to obtain a ballpoint pen which uses a small-diameter ball with a ball diameter of less than 0.5 mm and can obtain stable ball rotation and stable ink outflow.

[0014] Means for solving problems

[0015] In order to solve the above problems, the ballpoint pen of the present invention comprises a ballpoint pen refill, the ballpoint pen refill comprising: an ink container filled with an oil-based ballpoint pen ink composition; and a ballpoint pen tip mounted on the front end of the ink container, the ballpoint pen is characterized in that:

[0016] The nib body of the ballpoint pen nib comprises: a ball holding chamber, which allows a part of the ball to protrude from the front end of the nib and is rotatably held; a ball seat, which is arranged on the bottom wall of the ball holding chamber, carries the ball and is in the shape of an arc surface along the outer shape of the ball; an ink flow hole, which is formed in the center of the bottom wall of the ball holding chamber; and a plurality of ink flow grooves, which extend radially from the ink flow hole.

[0017] The viscosity of the oil-based ballpoint pen ink composition is 20°C and the shear rate is 500s. -1 The lower limit is within the range of 500 mPa·s to 15000 mPa·s.

[0018] The ball diameter of the ball is less than 0.5 mm.

[0019] A sealing surface in the form of an arc is formed on the inner wall of the front end of the pen tip.

[0020] The tip of the pen has a first caulking portion with an inclination angle of 90 degrees or more and less than 100 degrees; and a second caulking portion provided at the tip of the ballpoint pen with an inclination angle of 110 degrees or more and less than 130 degrees compared to the first caulking portion.

[0021] The angle of the bottom wall of the ball holding chamber is the same as the inclination angle of the second caulking portion.

[0022] The pen tip further includes a coil spring for pressing the ball toward the front end side of the pen tip front end portion, wherein a pressing load of the coil spring is 5 gf or more and 10 gf or less.

[0023] The oil-based ballpoint pen ink composition comprises a colorant, an organic solvent, a saturated fatty acid, and a phosphoric acid ester, wherein the phosphoric acid ester has a C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O(l, m=1 or more and 30 or less).

[0024] The saturated fatty acid has 10 or more and 20 or less carbon atoms.

[0025] The carbon chain (l, m) of the terminal alkyl group of the above-mentioned phosphoric acid ester is 1 or more and 15 or less.

[0026] The oil-based ballpoint pen ink composition contains a ketone resin or a polyvinyl butyral resin.

[0027] The above colorant is a pigment or a salt-forming dye.

[0028] Effects of the Invention

[0029] The present invention can obtain a ballpoint pen which uses a small-diameter ball with a ball diameter of less than 0.5 mm and can obtain stable ball rotation and stable ink outflow. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a cross-sectional view showing an example of the ballpoint pen according to the present embodiment.

[0031] Figure 2 This is a cross-sectional view showing an example of a ballpoint pen refill according to the present embodiment.

[0032] Figure 3 This is an enlarged cross-sectional view showing an example of a ballpoint pen tip according to the present embodiment. DETAILED DESCRIPTION

[0033] In this specification, unless otherwise stated, "parts", "%", "ratios" and the like indicating the proportions are based on mass. In addition, in the present invention, "tip" refers to the ballpoint pen tip side in a ballpoint pen and the ball side in a ballpoint pen tip.

[0034] (ballpoint pen)

[0035] Figure 1 This is a cross-sectional view showing an example of the ballpoint pen 1 according to the present embodiment.

[0036] The ballpoint pen 1 of this embodiment includes a ballpoint pen refill 4 . The ballpoint pen refill 4 is a refill of the ballpoint pen 1 .

[0037] The ballpoint pen refill 4 is housed in the outer cylinder body, and the front shaft 2 and the rear shaft 3 of the ballpoint pen 1 are detachably screwed on the outer cylinder body. The ballpoint pen refill 4 is urged rearward by a coil spring 5 and is housed.

[0038] It should be noted that the rear and the rear end refer to one end side of the extension direction X of the ballpoint pen 1, and are the direction of the side where the ball 20 is not provided in the extension direction X and the end in this direction. In addition, the front, the front side, the front end and the front end refer to one end side of the extension direction X of the ballpoint pen 1, and are the direction of the side where the ball 20 is provided in the extension direction X and the end in this direction.

[0039] Figure 2 This is a cross-sectional view of an example of the ballpoint pen refill 4 according to the present embodiment. Figure 2 2 shows a main part of the ballpoint pen refill 4 with a part of the structure omitted.

[0040] The ballpoint pen refill 4 includes an ink storage cylinder 22 and a ballpoint pen tip 11 .

[0041] The ink container 22 is long and cylindrical in the extension direction X. The ink container 22 and the ballpoint pen 1 extend in the same direction X. The ink container 22 is filled with an oil-based ballpoint pen ink composition 25 and contains an ink follower 26 that follows the oil-based ballpoint pen ink composition 25. A tail plug 24 is installed at the rear end of the ink container 22 (see Figure 1 ).

[0042] The ballpoint pen tip 11 is provided at one end (front end) of the ink container 22 in the extension direction X. The extension direction X of the ink container 22 is consistent with the extension direction X of the ballpoint pen 1. Hereinafter, the extension direction X is sometimes referred to as the axial direction for explanation. That is, the extension direction X is the direction along the straight line (central axis J) passing through the cross-sectional center of the cylindrical ink container 22. In other words, the extension direction X refers to the direction along the central axis J of the cylindrical ink container 22.

[0043] The ballpoint pen tip 11 is a member that rotatably holds the ball 20. That is, the ballpoint pen tip 11 holds the ball 20 at the front end portion that is one end portion of the ink container 22 extending in the direction X. The ball 20 is a spherical member having a ball diameter of 0.5 mm or less. The ball diameter of the ball 20 only needs to be greater than 0.1 mm and less than 0.5 mm.

[0044] Specifically, the ballpoint pen tip 11 is attached to the front end of the ink container 22 via the tip holder 23 .

[0045] return Figure 1 Continue with the explanation.

[0046] In the present embodiment, the ballpoint pen 1 is described as an example of a retractable ballpoint pen 1. Specifically, the ballpoint pen 1 is configured to be able to retract the front end of the ballpoint pen tip 11, which is the tip of the ballpoint pen core 4, from the front end opening 2a of the front shaft 2 by compressing the pressing member 7 using the retractable mechanism of the rotating cam 6. The rear shaft 3 is provided with a clip 8, for example. In addition, a grip 9 made of, for example, an olefin-based thermoplastic elastomer is installed on the gripping portion of the front shaft 2.

[0047] Specifically, the ballpoint pen 1 includes a rotating cam 6 and a cam mechanism (not shown) as a retractable mechanism. The rotating cam 6 is provided on the rear shaft 3 to switch the retractability of the ballpoint pen tip 11 of the ballpoint pen refill 4. The cam mechanism includes a cam groove that engages with the rotating cam 6.

[0048] When the pressing component 7 is squeezed while the ballpoint pen tip 11 of the ballpoint pen refill 4 is immersed in the front shaft 2, the rotating cam 6 slides along the cam groove. The squeezing operation of the pressing component 7 is sometimes referred to as a pressing operation. The ballpoint pen tip 11 of the ballpoint pen refill 4 protrudes forward from the opening 2c of the front shaft 2 by the sliding of the rotating cam 6. Furthermore, the rotating cam 6 is rotated by the action of the cam mechanism, thereby limiting the relative movement of the ballpoint pen refill 4 to the axial rear. Therefore, the protruding state is maintained even after the squeezing operation is completed. In addition, if the pressing component 7 is squeezed (pressed) again in this protruding state, the ballpoint pen refill 4 is allowed to move relative to the axial rear by the action of the cam mechanism. Through this relative movement, the ballpoint pen refill 4 and the pressing component 7 are pressed back to the axial rear by the action force of the coil spring 5 and restored to the initial state.

[0049] Figure 3 This is an enlarged cross-sectional view of an example of the ballpoint pen tip 11 according to the present embodiment. Figure 3 2 shows a main part of the ballpoint pen tip 11 with a part of the structure omitted.

[0050] The ballpoint pen tip 11 includes a tip body 12. The tip body 12 is provided with a ball holding chamber 15, an ink flow hole 16, an ink flow groove 17, a ball seat 19a, and the like.

[0051] The ball holding chamber 15 holds a part of the ball 20 so that it protrudes from the front end portion 13 of the pen tip and is rotatably held. The ball holding chamber 15 is provided at the front end portion of the ink flow hole 16 in the extension direction X. A ball seat 19a having a shape along the outer shape of the ball 20 is provided on the bottom wall 19 of the ball holding chamber 15. As described above, the ball 20 is spherical. Therefore, the ball seat 19a is approximately in the shape of an arc surface. The ball 20 is placed on the ball seat 19a. The bottom wall 19 of the ball holding chamber 15 is connected to a sealing surface 14c provided on the front end portion 13 of the pen tip in the inner wall of the ball holding chamber 15, and is an area on the rear side of the ballpoint pen 1 compared to the sealing surface 14c.

[0052] The ink flow hole 16 is a hole portion that penetrates in the extension direction X and through which the ink flows. The ink is an oil-based ballpoint pen ink composition. The ink flow hole 16 is formed in the center of the bottom wall 19 of the ball holding chamber 15. The ink flow groove 17 is a groove portion that is connected to the ink flow hole 16 and extends radially from the ink flow hole 16. A plurality of ink flow grooves 17 are provided in the ballpoint pen tip 11. These plurality of ink flow grooves 17 are arranged to be connected to the ink flow hole 16 and not to be connected to the tip rear hole 18.

[0053] The tip end 13 of the ballpoint pen tip 11 is formed with a caulking portion 14 in a caulking shape toward the inside. By placing the ball 20 on the ball seat 19a of the ball holding chamber 15 and providing the caulking portion 14 to the tip end 13, the ball holding chamber 15 allows a part of the ball 20 to protrude from the tip end 13 and rotatably hold the ball 20. In addition, a sealing surface 14c having a shape similar to a circular arc surface, that is, a shape along the outer shape of the ball 20, is formed on the inner wall of the tip end 13.

[0054] As described above, the tip end portion 13 of the ballpoint pen tip 11 is formed as the swaged portion 14 in a swaged shape toward the inside. The swaged portion 14 is composed of the first swaged portion 14a and the second swaged portion 14b.

[0055] The first caulking portion 14a has an inclination angle of not less than 90 degrees and not more than 100 degrees. The second caulking portion 14b is provided at the front end side of the ballpoint pen tip 11 in comparison with the first caulking portion 14a and has an inclination angle of not less than 110 degrees and not more than 130 degrees. The inclination angle of the first caulking portion 14a is sometimes referred to as the first inclination angle α for explanation. In addition, the inclination angle of the second caulking portion 14b is sometimes referred to as the second inclination angle β for explanation. These inclination angles are sometimes referred to as caulking angles.

[0056] like Figure 3As shown, the first inclination angle α is the angle formed by two lines along the inclined surface of the first caulking portion 14a in the cross section along the extension direction X of the ballpoint pen tip 11, namely, line Lα1 and line Lα2. The second inclination angle β is the angle formed by two lines along the inclined surface of the second caulking portion 14b in the cross section along the extension direction X of the ballpoint pen tip 11, namely, line Lβ1 and line Lβ2.

[0057] The angle γ of the bottom wall 19 of the ball holding chamber 15 is the same as the inclination angle (second inclination angle β) of the second caulking portion 14b. The same angle in the present invention is defined as the same angle within ±3 degrees in consideration of measurement errors.

[0058] like Figure 3 As shown, the angle γ of the bottom wall 19 refers to the angle from one end to the other end of the bottom wall 19 along the peripheral direction of the ball 20 in the cross section along the extension direction X of the ballpoint pen tip 11. In detail, the angle γ of the bottom wall 19 is the angle formed by the line Lγ1 and the line Lγ2. In addition, the angle γ is the angle on the ball 20 side (the inside of the ball holding chamber 15) of the angle formed by the line Lγ1 and the line Lγ2. The line Lγ1 is a straight line passing through one end of the bottom wall 19 along the peripheral direction of the ball 20 and the intersection of the bottom wall 19 and the center axis J in the cross section along the extension direction X of the ballpoint pen tip 11. Lγ2 is a straight line passing through the other end of the bottom wall 19 along the peripheral direction of the ball 20 and the intersection of the bottom wall 19 and the center axis J in the cross section.

[0059] The ball 20 placed on the ball seat 19 a is held in a state of being pressed toward the front end of the ballpoint pen tip 11 by the coil spring 21 .

[0060] In order to suppress ink leakage, the following structure is preferred: the ball 20 rotatably held at the front end of the ballpoint pen tip 11 is pressed against the inner wall of the tip end portion 13 directly or through a pressing body by means of a coil spring 21. Pressing against the inner wall of the tip end portion 13 means pressing toward the front end side of the ballpoint pen tip 11. In addition, it is preferred that a valve mechanism is further provided, which forms a gap between the inner wall of the tip end portion 13 and the ball 20 by the pressing force during writing to allow ink to flow out, and the small gap at the tip end of the pen tip is also closed when not in use.

[0061] From the perspective of improving the writing feeling, the pressing load of the coil spring 21 on the ball 20 is preferably set to 30 gf or less. In particular, even when the ball diameter of the ball 20 is 0.5 mm or less and a load is locally applied between the ball 20 and the ball seat 19a, it is possible to maintain higher lubricity and easily maintain a good writing feeling. From the perspective of suppressing ink leakage and improving ink tracking, the pressing load of the coil spring 21 on the ball 20 is preferably set to 5 gf or more and 10 gf or less.

[0062] The arithmetic mean roughness (Ra) of the ball surface of the ball 20 is not limited. For example, the arithmetic mean roughness (Ra) of the ball surface is preferably 0.1nm or more and 12nm or less. If the arithmetic mean roughness (Ra) is less than 0.1nm, it is difficult for the ink to fully adhere to the ball surface, and it is difficult to obtain deep handwriting when writing, and the handwriting is prone to flying lines and flying white. If the arithmetic mean roughness (Ra) exceeds 12nm, the ball surface is too rough, and the rotational resistance of the ball 20 and the ball seat 19a is large. Therefore, the writing experience is easy to be poor, and in addition, the handwriting is prone to flying white, flying lines, uneven lines, etc., which are easy to affect the writing performance. If further considered, the arithmetic mean roughness (Ra) of the ball surface is preferably 0.1nm or more and 10nm or less, more preferably 0.5nm or more and 5nm or less. The arithmetic mean roughness (Ra) can be obtained using the model name SPI3800N manufactured by Seiko Epson.

[0063] The material used for the ball 20 is not particularly limited. Examples of the material used for the ball 20 include superhard alloy balls mainly composed of tungsten carbide, metal balls such as stainless steel, ceramic balls such as silicon carbide, silicon nitride, alumina, silicon dioxide, and zirconium oxide, and ruby ​​balls.

[0064] The material of the ballpoint pen tip 11 can include metal materials such as stainless steel, zinc white copper, brass (brass), aluminum bronze, aluminum, and resin materials such as polycarbonate, polyacetal, and ABS. Among these, stainless steel is preferably used as the material of the ballpoint pen tip 11 in consideration of the wear and stability over time of the ball seat 19a.

[0065] There is no limit to the amount of movement of the ball 20 of the ballpoint pen tip 11 in the extension direction X. For example, the amount of movement of the ball 20 in the extension direction X is preferably not less than 3 μm and not more than 30 μm. If it is less than 3 μm, it is difficult to obtain deep handwriting and a good writing experience; if it exceeds 30 μm, it is easy to affect the ink dangling performance. If further considered, the amount of movement of the ball 20 in the extension direction X is preferably not less than 10 μm and not more than 25 μm. This is because the space for storing ink through the first caulking portion 14a and the second caulking portion 14b can be increased, but if the amount of movement of the ball 20 in the extension direction X is less than 10 μm, it is difficult to obtain deep handwriting and a good writing experience.

[0066] In particular, if the ball diameter is set to a relatively small ball diameter of 0.5 mm or less, the ink consumption is easily reduced, and the writing feeling is also easily affected. Therefore, the movement amount of the ball 20 of the ballpoint pen tip 11 in the extension direction X is preferably 12 μm to 25 μm, and if further considered, it is preferably 14 μm to 25 μm. Setting the movement amount of the ball 20 in the extension direction X to this range is effective even when the ball diameter is 0.4 mm or less, so it is preferred, and further effective when the ball diameter is 0.3 mm or less, so it is preferred.

[0067] The ink consumption per 100 m of the ballpoint pen 1 is preferably 20 mg or more and 70 mg or less. This is because if the ink consumption per 100 m is less than 20 mg, it is difficult to obtain deep handwriting and a good writing feeling; if the ink consumption per 100 m exceeds 70 mg, the gap between the ball 20 and the front end 13 of the pen tip is likely to affect the suppression of ink leakage, and it is also easy to cause writing performance and ink leakage. If further consideration is taken, the ink consumption per 100 m is preferably 20 mg or more and 60 mg or less.

[0068] In particular, if the ball diameter is a relatively small ball diameter of 0.5 mm or less, the ink consumption is easily reduced, and the writing properties such as writing feeling and flying white are also easily affected. Therefore, the ink consumption per 100 m is preferably 20 mg or more and 50 mg or less, and if further considered, it is preferably 20 mg or more and 45 mg or less.

[0069] In addition, when the ball diameter is set to 0.5 mm or less, in order to achieve deeper handwriting, improve the writing experience, and suppress ink leakage, it is effective to not only set the ink consumption, but also consider the relationship with the ball diameter. Specifically, the ratio of the ball diameter (mm) of the ball pen 1 to the ink consumption (mg) per 100 m (ball diameter: ink consumption) is preferably 1:40 to 1:140. By setting this different relationship from the past, it is easy to obtain deeper handwriting, writing experience, and suppress ink leakage, so it is preferred. If further considered, the ball diameter: ink consumption is preferably 1:50 to 1:130, and more preferably 1:60 to 1:120.

[0070] It should be noted that regarding the ink consumption, a spiral writing test was conducted using five test samples at 20°C, on JIS P3201 writing paper, at a writing angle of 70°, and a writing load of 200 g, at a writing speed of 4 m / min. The average value of the ink consumption per 100 m was defined as the ink consumption per 100 m.

[0071] When writing is performed using the ballpoint pen 1 of the present embodiment configured as above, the ink as the oil-based ballpoint pen ink composition flowing out of the ink container 22 is supplied from the ink flow hole 16 to the ball 20 held in the ball holding chamber 15 via the ink flow groove 17. By supplying the ink to the ball 20, writing is performed on a paper surface or the like using the ink.

[0072] As described above, the ballpoint pen 1 of the present embodiment includes a ball seat 19a and a sealing surface 14c. In addition, the tip front end 13 of the ballpoint pen tip 11 is formed into a caulking portion 14 in the shape of a caulking inward. The caulking portion 14 is composed of a first caulking portion 14a and a second caulking portion 14b. The first caulking portion 14a has a first inclination angle α of not less than 90 degrees and less than 100 degrees. The second caulking portion 14b is provided at the front end side of the ballpoint pen tip 11 compared to the first caulking portion 14a and has a second inclination angle β of not less than 110 degrees and not more than 130 degrees. In addition, the angle γ of the bottom wall 19 of the ball holding chamber 15 is the same as the second inclination angle β of the second caulking portion 14b.

[0073] The ballpoint pen 1 of this embodiment has the ball seat 19a and the sealing surface 14c, which has the effect of making the ball 20 rotate smoothly. In addition, it is considered that the ink flowing into the ball holding chamber 15 from the ink flow hole 16 and the ink flowing into the ball holding chamber 15 from the pen tip 13 without being transferred to the paper surface (ink reflux) can stabilize the flow of ink in the ball holding chamber 15. Therefore, even if the ball seat 19a or the sealing surface 14c is worn, it is possible to obtain a stable ink outflow amount.

[0074] In addition, when forming the ball seat 19a and the sealing surface 14c, the ball 20 is transferred to the wall surfaces of the same angle of the bottom wall 19 of the ball holding chamber 15 and the inner wall of the second caulking portion 14b. Therefore, even if the curvature changes due to rebound after transfer, the curvature of the obtained transfer surface is similar, and the deviation of the ball 20 can be suppressed. As a result, uneven wear of the ball seat 19a and the sealing surface 14c of the pen tip 13 caused by the rotation of the ball 20 can also be suppressed. That is, stable rotation of the ball 20 and stable outflow of ink can be obtained.

[0075] In addition, in the ballpoint pen 1 of the present embodiment, the first inclination angle α of the first crimping portion 14a of the tip end portion 13 is an obtuse angle of 90 degrees or more and 100 degrees or less. By making the first inclination angle α an obtuse angle, the space for storing ink between the ball 20 and the tip end portion 13 can be increased compared to the case where the inclination angle (crimping angle) is less than 90 degrees. Therefore, the ink can be easily refluxed, the ink can be suppressed from climbing, the ink discharge can be suppressed, and deep handwriting, writing feeling, and wear of the ball seat can be suppressed well.

[0076] In addition, in the ballpoint pen 1 of this embodiment, the ball holding force can be improved by making the second inclination angle β of the second caulking portion 14b greater than 110 degrees and less than 130 degrees, and it is easy to make the second inclination angle β and the angle γ of the bottom wall 19 of the ball holding chamber 15 the same angle.

[0077] Therefore, the ballpoint pen 1 of the present embodiment is a ballpoint pen 1 using a small-diameter ball 20 having a ball diameter of 0.5 mm or less, and can realize stable rotation of the ball 20 and stable outflow of ink.

[0078] In addition, as described above, it is preferred that the extrusion load of the coil spring 21 on the ball 20 is between 5 gf and 10 gf. By making the extrusion load of the ball 20 between 5 gf and 10 gf, it is possible to easily maintain a good writing feel. In addition, by making the extrusion load of the ball 20 within the above range, even when the ball diameter is made less than 0.5 mm and a load is applied locally between the ball 20 and the ball seat 19a, higher lubricity can be maintained, and it is possible to easily maintain a good writing feel. Considering the writing feel, it is preferred that the extrusion load of the coil spring 21 is set to less than 10 gf. In addition, considering the ease of improving ink leakage suppression and ink tracking, it is more preferred that the extrusion load of the coil spring 21 is greater than 5 gf.

[0079] (Oil-based ballpoint pen ink composition)

[0080] Next, the oil-based ballpoint pen ink composition used in the ballpoint pen 1 of the present embodiment will be described in detail.

[0081] The ink viscosity of the oil-based ballpoint pen ink composition used in the ballpoint pen 1 of the present embodiment is 20° C. and a shear rate of 500 s. -1 (When writing) it is not less than 500mPa·s and not more than 15000mPa·s.

[0082] If the viscosity of the oil-based ballpoint pen ink composition exceeds 15000 mPa·s, the ball rotation resistance during writing becomes larger, the writing feeling tends to become heavier, and the wear suppression of the ball seat is easily affected, which in turn tends to affect the writing performance and ink following performance. Therefore, the oil-based ballpoint pen ink composition of ballpoint pen 1 is used at 20°C and a shear rate of 500 s -1 The ink viscosity of the oil-based ballpoint pen ink composition under (writing) is 15000mPa·s or less. If further consideration is given to improving the writing feel and suppressing the wear of the ball seat 19a, the ink viscosity is preferably 10000mPa·s or less. If further consideration is given to the writing feel and suppressing the wear of the ball seat, the ink viscosity is preferably 8000mPa·s or less. The ink viscosity of the oil-based ballpoint pen ink composition is further preferably 6000mPa·s or less. In addition, at 20°C and a shear rate of 500s -1 When the ink viscosity is less than 10 mPa·s, the wear of the ball seat is easily inhibited, and the handwriting may bleed or the ink may droop. Therefore, the oil-based ballpoint pen ink composition is heated to 20°C and a shear rate of 500 s. -1 The ink viscosity under (writing) is preferably 10 mPa·s or more. In addition, if further consideration is taken, the ink viscosity of the oil-based ballpoint pen ink composition is preferably 100 mPa·s or more, and further, if the wear suppression of the ball seat is taken into consideration, the ink viscosity is preferably 500 mPa·s or more, and if further consideration is taken, it is preferably 1000 mPa·s or more, and preferably 2000 mPa·s or more.

[0083] Here, in order to improve the lubricity between the ball 20 and the ball seat 19 a of the ballpoint pen tip 11 , many oil-based ballpoint pen ink compositions using various lubricants have been proposed.

[0084] For example, document A (Japanese Patent Publication No. 5-331403 "Oil-based Ballpoint Pen Ink") discloses the use of alkyl β-D-glucoside; document B (Japanese Patent Publication No. 7-196971 "Oil-based Ballpoint Pen Ink Composition") discloses the use of polyethylene glycol having an average molecular weight of 200 to 4,000,000; document C (Japanese Patent Publication No. 2007-176995 "Oil-based Ballpoint Pen Ink") discloses the use of N-acylamino acids, N-acylmethyltaurine, and N-acylmethylalanine; and document D (Japanese Patent Publication No. 3500552 "Oil-based Ballpoint Pen Ink Composition") discloses the use of phosphate esters.

[0085] However, when using various lubricants such as those in Documents A to D, although the writing feeling can be improved to a certain extent and the wear of the ball seat 19a can be suppressed, the lubricity is not satisfactory and there is room for improvement. In addition, if a small-diameter ball with a ball diameter of less than 0.5 mm is used, when writing the same distance, the smaller the diameter of the ball, the more times the ball rotates. In addition, if a small-diameter ball is used, a load will be applied to the ball seat 19a, so the wear of the ball seat 19a becomes serious, resulting in poor writing. Therefore, in the prior art, if a small-diameter ball is used, new issues are likely to arise.

[0086] In addition, an oil-based ballpoint pen ink composition is desired that can improve the writing performance of the pen tip 13 when the pen tip 13 is left in the air. This is particularly important because it is likely to affect the writing performance when using a retractable oil-based ballpoint pen such as a push-type oil-based ballpoint pen or a rotary feed-type oil-based ballpoint pen.

[0087] The present inventors have found that, as an oil-based ballpoint pen ink composition used in the ballpoint pen 1 of the present embodiment, by using an ink having an ink viscosity satisfying the above range and containing a saturated fatty acid and having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 The oil-based ballpoint pen ink composition of the phosphate ester of O (l, m=1 to 30) can improve lubricity, enhance wear suppression of the ball seat 19a and writing feel, and further improve writing performance.

[0088] By containing saturated fatty acids, l H 2l+1 OC 2 H 4 O or C m H 2m+1 The phosphate ester of saturated fatty acid and phosphate ester can improve lubricity by using the lubricating layer formed by the saturated fatty acid and the phosphate ester, and maintain lubricity between the ball 20 and the nib body 12. In addition, the wear of the ball seat 19a can be suppressed, and the whiteness of the handwriting can be suppressed and the writing feeling can be improved. Furthermore, when the nib tip 13 is placed in the atmosphere, the writing performance of the nib tip 13 when it is dry can be improved.

[0089] (Saturated fatty acids)

[0090] The saturated fatty acid contained in the oily ballpoint pen ink composition can maintain the lubricity between the ball 20 and the nib body 12, and suppress the wear of the ball seat 19a. In addition, by making the oily ballpoint pen ink composition include saturated fatty acids, the handwriting flying suppression and writing experience can be improved. Especially even in the case of a small-diameter ball with a ball diameter of less than 0.5mm, the wear of the ball seat 19a can be suppressed, and the handwriting flying suppression and writing experience can be well maintained. This is because the saturated fatty acid is adsorbed on the metal surface of the ball 20 and the nib body 12 of the ballpoint pen nib 11, and the metal contact between the ball 20 and the nib body 12 can be suppressed. Therefore, the wear of the ball seat 19a can be suppressed, and the handwriting flying suppression and writing experience can be improved. In addition, the writing performance can be improved.

[0091] As saturated fatty acids, branched saturated fatty acids and straight-chain saturated fatty acids can be cited. If the wear suppression of the ball seat 19a and the writing experience are taken into consideration, branched saturated fatty acids are preferred. By using saturated fatty acids with branches, a large structure can be provided, and the area covered on the metal surface is increased. Therefore, it is easy to adsorb on the metal surface of the ball 20 of the ballpoint pen tip 11 and the nib body 12. In this way, the metal contact between the ball 20 and the nib body 12 can be suppressed, the wear of the ball seat can be suppressed, and the whiteness of the handwriting can be suppressed and the writing experience can be improved.

[0092] Regarding saturated fatty acids, if lubricity is taken into consideration, the number of carbon atoms in the saturated fatty acid is preferably 10 or more and 20 or less. This is because if the number of carbon atoms is 10 or more, the length of the alkyl group is suitable for improving the desired lubricity, and it is easy to adsorb on the metal surface of the ballpoint pen tip. On the other hand, if the number of carbon atoms exceeds 20, since the alkyl group becomes too long, the molecules repel each other, thereby hindering adsorption on the metal surface, which easily hinders the improvement of lubricity. In addition, if lubricity is further taken into consideration, the number of carbon atoms in the saturated fatty acid is preferably 16 or more and 20 or less, and if the wear suppression of the ball seat 19a is further considered, the number of carbon atoms in the saturated fatty acid is preferably 18 or more and 20 or less.

[0093] Examples of the saturated fatty acids include branched-chain saturated fatty acids such as methyl-branched undecanoic acid, methyl-branched dodecanoic acid, methyl-branched tridecanoic acid, methyl-branched tetradecanoic acid, methyl-branched pentadecanoic acid, methyl-branched hexadecanoic acid, methyl-branched heptadecanoic acid, methyl-branched octadecanoic acid (methyl-branched stearic acid), methyl-branched nonadecanoic acid, methyl-branched eicosanoic acid, and methyl-branched behenic acid; and straight-chain saturated fatty acids such as undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid), octadecanoic acid, nonadecanoic acid, and behenic acid.

[0094] Among these, in consideration of suppressing the wear of the ball seat 19 a , suppressing the blurring of handwriting, and improving the writing feel, a methyl branched-chain saturated fatty acid having a chemical structure in which a methyl group branches from the main chain of a saturated fatty acid is preferable.

[0095] In other words, by making the oily ballpoint pen ink composition contain methyl branched saturated fatty acids, the lubricity can be improved by using the lubricating layer formed by the methyl branched saturated fatty acids, and the lubricity between the ball 20 and the nib body 12 can be maintained. In addition, the wear of the ball seat 19a can be suppressed, the handwriting can be suppressed from being shaky, and the writing feeling can be improved. Furthermore, when the ballpoint pen nib 11 (the nib tip 13) is placed in the atmosphere, the writing performance of the ballpoint pen nib 11 (the nib tip 13) when dry can be improved, so it is preferred.

[0096] By using methyl-branched saturated fatty acids, a large-volume structure can be formed, and the area of ​​the metal surface of the ball 20 of the ballpoint pen tip 11 and the nib body 12 covered is increased. That is, the methyl-branched saturated fatty acids are easily adsorbed on the metal surfaces of the ball 20 of the ballpoint pen tip 11 and the nib body 12, and can suppress the metal contact between the ball 20 of the ballpoint pen tip 11 and the nib body 12. Therefore, the friction mitigation effect is exerted, and the writing resistance of the ballpoint pen tip 11 can be suppressed. As a result, the wear of the ball seat 19a can be suppressed, the handwriting can be suppressed, and the writing experience can be improved. In addition, the writing performance can be improved, which is particularly effective.

[0097] In addition, as mentioned above, the ball diameter of the ball 20 of the ball pen 1 of the present embodiment is less than 0.5mm. If a methyl branched-chain saturated fatty acid is used, even in the case of a small-diameter ball with a ball diameter of less than 0.5mm, the wear of the ball seat 19a can be suppressed, the handwriting can be suppressed from being shaky, and the writing feeling can be well maintained. Even in the case of a load being applied locally between the ball 20 and the ball seat 19a as in a small-diameter ball, lubricity can be easily maintained, which is effective. In addition, the ball diameter is small, specifically, even if the ball diameter is less than 0.4mm, and further less than 0.3mm, the effect can be maintained, so the effect is remarkable.

[0098] Regarding the methyl branched saturated fatty acid, if lubricity is taken into consideration, the number of carbon atoms of the methyl branched saturated fatty acid is preferably 10 or more and 20 or less. This is because if the number of carbon atoms is 10 or more, the length of the alkyl group is suitable for improving the desired lubricity, and it is easy to adsorb on the metal surface of the ballpoint pen tip 11; on the other hand, if the number of carbon atoms exceeds 20, the alkyl group becomes longer, and the molecules repel each other, thereby hindering adsorption on the metal surface, which easily hinders the improvement of lubricity. In addition, if lubricity is further taken into consideration, the number of carbon atoms of the methyl branched saturated fatty acid is preferably 16 or more and 20 or less. If the wear suppression of the ball seat 19a is further considered, the number of carbon atoms of the methyl branched saturated fatty acid is preferably 18 or more and 20 or less.

[0099] It should be noted that methyl-branched unsaturated fatty acids may be used in place of methyl-branched saturated fatty acids or together with methyl-branched saturated fatty acids. In consideration of lubricity, methyl-branched saturated fatty acids are preferably used.

[0100] Specific examples of the methyl branched saturated fatty acids include methyl branched undecanoic acid, methyl branched dodecanoic acid, methyl branched tridecanoic acid, methyl branched tetradecanoic acid, methyl branched pentadecanoic acid, methyl branched hexadecanoic acid, methyl branched heptadecanoic acid, methyl branched octadecanoic acid (methyl branched stearic acid), methyl branched nonadecanoic acid, and methyl branched behenic acid.

[0101] Among these, if considering suppressing the wear of ball seat 19a, suppressing the whitening of handwriting and improving the writing experience, then preferably methyl branched hexadecanoic acid, methyl branched octadecanoic acid (methyl branched stearic acid), methyl branched eicosanoic acid. If further considered, then preferably 16-methyl octadecanoic acid (16-methyl stearic acid). In particular, when the ball diameter is below 0.5mm, even if locally in the case of applying a load between ball 20 and ball seat 19a, it is also easy to keep lubricity, so it is effective. In addition, even if it is effective in the case of making the ball diameter below 0.4mm, it is therefore preferred, and then in the case of making the ball diameter below 0.3mm, it is also effective, so it is preferred.

[0102] More specifically, preferred methyl branched-chain saturated fatty acids include 10-methylundecanoic acid, 10-methyldodecanoic acid, 12-methyltridecanoic acid, 12-methyltetradecanoic acid, 14-methylpentadecanoic acid, 14-methylhexadecanoic acid, 16-methylheptadecanoic acid, 16-methyloctadecanoic acid (16-methylstearic acid), 10-methylnonadecanoic acid, 10-methylheptadecanoic acid, 10-methylhexadecanoic acid, 10-methylpentadecanoic acid, and the like.

[0103] The content of the saturated fatty acid is preferably 0.1% by mass or more and 10% by mass or less relative to the total amount of the oil-based ballpoint pen ink composition, and is preferably 0.5% by mass or more and 10% by mass or less in consideration of lubricity, and is preferably 1% by mass or more and 5% by mass or less in consideration of the temporal stability of the ink. If the content of the saturated fatty acid is less than 0.1% by mass relative to the total amount of the oil-based ballpoint pen ink composition, the desired lubrication effect may not be obtained, and if it exceeds 10% by mass, the temporal stability of the ink may be affected.

[0104] (Phosphate)

[0105] In consideration of improving the lubricity of the ballpoint pen tip 11 and suppressing writing resistance, the oil-based ballpoint pen ink composition preferably contains a phosphoric acid ester.

[0106] In addition, if the wear suppression of the ball seat 19a and the writing feeling are further considered, it is preferable to use a ball seat having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30). This is because l H 2l+1 OC 2 H 4 O(alkoxyethyl) or C m H 2m+1 The phosphate ester of O (alkoxy) forms a lubricating layer, which can easily improve the lubricity of the ballpoint pen tip 11, easily suppress the wear of the ball seat 19a, suppress the whitening of the handwriting, and improve the writing feeling. It is particularly effective when used in an oily ballpoint pen 1.

[0107] By using a saturated fatty acid and a phosphate ester together, a lubricating effect brought about by the interaction of the two lubricating layers formed can be obtained, which is not possible in the past. It is particularly preferred to use a methyl branched saturated fatty acid and a C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30) of phosphate. In addition, when the ball diameter is 0.5 mm or less, even when a load is applied locally between the ball 20 and the ball seat 19a, higher lubricity can be maintained, so it is effective. Even when the ball diameter is 0.4 mm or less, it is effective, so it is preferred. Furthermore, when the ball diameter is 0.3 mm or less, it is also effective, so it is preferred. In addition, the writing performance can be improved.

[0108] Regarding phosphate esters, if stability in ink and easy improvement of lubricity are considered, the general formula (1) and (2) are preferred. This is because in the phosphate esters of the general formula (1) and (2), the O adjacent to P in the structure of the general formula (1) and (2) is adsorbed to the metal ballpoint pen tip body or ball, and C l H 2l+1 OC 2 H 4 O(alkoxyethyl), C m H 2m+1 O (alkoxy) forms a lubricating layer. As a result, it is easy to improve lubricity, inhibit wear of the ball seat 19a, inhibit whitening of handwriting, and improve writing feel. In particular, if the wear of the ball seat 19a is considered, it is preferred to use a C l H 2l+1 OC 2 H 4 The general formula of O(alkoxyethyl) is (Chemical 1).

[0109]

Chemistry 1

[0110]

[0111]

Chemistry 2

[0112]

[0113] In the phosphate esters of the general formula (1) and (2), regarding C l H 2l+1 OC 2 H 4 O(alkoxyethyl), C m H 2m+1 The carbon chain (l, m) of the terminal alkyl group of O (alkoxy) is preferably a specific carbon chain (l, m). The effect is estimated as follows.

[0114] C l H 2l+1 OC 2 H 4 O.C m H 2m+1 The carbon chain (l, m) of the terminal alkyl group of O is preferably 1 or more and 15 or less. l H 2l+1 OC 2 H 4 O.C m H 2m+1When the carbon chain (l, m) of the terminal alkyl of O exceeds 15, although the writing feeling and writing performance are good, the carbon chain becomes too long and it is difficult to obtain the wear suppression of the ball seat 19a. This is because the carbon chains are easily entangled with each other, and the arrangement direction of the carbon chains becomes random, and it is not arranged well, so it is impossible to obtain a lubricating layer with sufficient lubricity, and it is difficult to obtain the wear suppression of the ball seat 19a. In addition, when the carbon chain (l, m) of the terminal alkyl exceeds 15, the polarity of the terminal alkyl is close to the low polarity side, so the affinity for polar organic solvents is poor, which is easy to affect the dissolution stability. In particular, it is easy to have an impact in glycol ether solvents, and the dissolution stability in ink is prone to problems. Therefore, through long-term storage, due to the influence of metal ions in the metal pen tip, metal salt precipitates are easily generated, and the stability of the ink over time is easily deteriorated, and it is difficult to obtain the lubrication effect of the present invention. Therefore, with respect to the carbon chain (l, m) of the above-mentioned terminal alkyl, it is preferably 1 or more and 15 or less. If further considered, the carbon chain (l, m) of the above-mentioned terminal alkyl is preferably 1 or more and 10 or less. In consideration of suppressing the wear of the ball seat 19a and suppressing the blurring of handwriting, the carbon chain (l, m) of the terminal alkyl group is preferably 1 or more and 5 or less.

[0115] On the other hand, when the carbon chain (l, m) of the terminal alkyl group is set to 3 or less, although the wear of the ball seat 19a is well suppressed, the above-mentioned alkyl group cannot obtain a lubricating layer with a sufficient thickness in the ink. Therefore, a lubricating layer with insufficient cushioning properties is formed between the ball 20 and the ball seat 19a, which is likely to affect the writing feel, writing performance, and wear suppression of the ball seat 19a. Therefore, by using acid butyl phosphate (l=4), butyl acid phosphate (m=4), etc., in which the above-mentioned terminal alkyl group has a butyl group (carbon chain of the terminal alkyl group: 4), it is easy to obtain the effect of suppressing the wear of the ball seat 19a, improving the writing feel and writing performance, and is therefore preferred. Particularly preferred is an acid butyl phosphate having a butyl group (carbon chain of the terminal alkyl group: 4). 4 H 9 OCH 2 CH 2 In particular, when the ball diameter is 0.5 mm or less, lubricity is easily maintained even when a load is locally applied between the ball 20 and the ball seat 19a, so it is effective in suppressing the wear of the ball seat 19a, and is therefore preferred. Even when the ball diameter is 0.4 mm or less, it is effective, and is therefore preferred, and further when it is 0.3 mm or less, it is also effective, and is therefore preferred.

[0116] In addition, regarding the phosphoric acid esters of the general formula (1) and (2), there can be mentioned monoesters of phosphoric acid esters (n=1 in the formula 1 and 2), diesters of phosphoric acid esters (n=2 in the formula 1 and 2), triesters of phosphoric acid esters (n=3 in the formula 1 and 2), and mixtures thereof. Among them, in consideration of suppressing the wear of the ball seat 19a and the writing feeling, it is preferable to use a mixture of monoesters of phosphoric acid esters (n=1 in the formula 1 and 2) and diesters of phosphoric acid esters (n=2 in the formula 1 and 2). This is because, in the case of the triesters of phosphoric acid esters (n=3 in the formula 1 and 2), C l H 2l+1 OC 2 H 4 O(alkoxyethyl), C m H 2m+1 Too much O (alkoxy group) tends to affect the temporal stability of the ink.

[0117] In addition, in consideration of suppressing the wear of the ball seat 19a, it is preferable to mix a monoester of phosphoric acid ester and a diester of phosphoric acid ester. Regarding the mixing ratio at this time, the diester of phosphoric acid ester (n=2 in Chemical 1 and Chemical 2) has a C l H 2l+1 OC 2 H 4 O(alkoxyethyl) and C m H 2m+ 1 More O (alkoxy) groups are beneficial to lubricity. Furthermore, the stability of the ink over time can be maintained, so it is preferred that the number of diesters of phosphoric acid ester is larger. Therefore, the mixing ratio of the monoester of phosphoric acid ester to the diester of phosphoric acid ester is preferably in the range of 1:1 to 1:5. If further consideration is taken, the range of 1:1 to 1:3 is preferred.

[0118] In addition, as specific examples of phosphoric acid esters such as general formula (Chemical 1) and (Chemical 2), general formula (Chemical 1) includes butoxyethyl acid phosphate (l=4) and the like. (Chemical 2) includes methyl acid phosphate (m=1), ethyl acid phosphate (m=2), butyl acid phosphate (m=4), 2-ethylhexyl acid phosphate (m=8), isodecyl acid phosphate (m=10), lauryl acid phosphate (m=12), alkyl acid phosphate (m=12, 14, 16, 18), isotridecyl acid phosphate (m=13), oleyl acid phosphate (m=18), and tetracosyl acid phosphate (m=24).

[0119] In addition, the above has C l H 2l+1 OC 2 H 4 O or C m H 2m+1The content of the phosphate ester of O (l, m=1 to 30) is preferably 0.1% to 10% by mass relative to the total amount of the oil-based ballpoint pen ink composition. This is because if it is less than 0.1% by mass, it is difficult to obtain the desired lubricity; if it exceeds 10% by mass, the ink tends to be unstable over time. Considering these tendencies, it is preferably 0.1% to 5% by mass, and if further considered, it is preferably 0.3% to 3% by mass.

[0120] The total content of the saturated fatty acid relative to the total amount of the oil-based ballpoint pen ink composition is denoted as X, and the C l H 2l+1 OC 2 H 4 O or C m H 2m+1 The content of the phosphoric acid ester of O (l, m=1 to 30) relative to the total amount of the ink composition is Y. In this case, if the wear suppression of the ball seat 19a and the writing feeling are improved, the relationship of 0.1≤X / Y≤5 is preferably satisfied, and if further consideration is given, the relationship of 0.3≤X / Y≤3 is preferably satisfied, and the relationship of 0.5≤X / Y≤2 is more preferably satisfied.

[0121] (Organic amine)

[0122] In addition, when using the above-mentioned saturated fatty acid, the above-mentioned having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 In the case of phosphate esters of O (l, m=1 or more and 30 or less), it is preferred to use organic amines. This is because, by using organic amines to neutralize the above-mentioned saturated fatty acids and the above-mentioned phosphate esters, they can be dissolved and stably in the ink. Therefore, it is easy to obtain the effects of the above-mentioned saturated fatty acids and the above-mentioned phosphate esters, and then it is easy to improve the time stability of other ink components such as colorants. Considering the stability of the above-mentioned organic amines and the above-mentioned saturated fatty acids, the above-mentioned phosphate esters, and the colorants, it is preferred to use secondary amines or tertiary amines. This is because, with regard to the reactivity in oily inks, primary amines are the strongest, followed by secondary amines and tertiary amines, and the reactivity decreases. Primary amines easily react with the above-mentioned phosphate esters, the above-mentioned saturated fatty acids, colorants or other components, and are likely to affect the time stability of the ink. Therefore, it is preferred to use secondary amines or tertiary amines, and if further considered, it is preferred to use tertiary amines.

[0123] In addition, specific examples of organic amines include amines containing ethylene oxide such as oxyethylene alkylamines and polyoxyethylene alkylamines; alkylamines such as laurylamine and stearylamine; and aliphatic amines such as dimethylalkylamines such as distearylamine, dimethyllaurylamine, dimethylstearylamine, and dimethyloctylamine. Among these, amines containing ethylene oxide and dimethylalkylamines are preferred in consideration of stability in ink, and amines containing ethylene oxide are preferred in consideration of further consideration.

[0124] In addition, considering the stability with the above-mentioned phosphate ester, the above-mentioned saturated fatty acid, the colorant or other components, the total amine value of the above-mentioned organic amine is preferably 100 (mgKOH / g) or more and 300 (mgKOH / g or less. If it exceeds 300 (mgKOH / g), the reactivity is strong and it is easy to react with the above-mentioned components, so the stability of the ink over time is easy to deteriorate. In addition, if the total amine value is less than 100 (mgKOH / g), it is easy to react with the saturated fatty acid in the ink, the C-containing l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30) has an impact on the stability of the phosphate ester. When applied to the above-mentioned ballpoint pen 1, the adsorption of metals such as the ball 20 and the pen tip body 12 is easily deteriorated, and it is difficult to obtain lubrication performance. If the stability and lubricity of the above-mentioned components are further considered, the range of 150 (mgKOH / g) to 300 (mgKOH / g) is preferred. If the stability is further considered, the range of 200 (mgKOH / g) to 300 (mgKOH / g) is preferred. If further consideration is given, the range of 230 (mgKOH / g) to 270 (mgKOH / g) is preferred.

[0125] The total amine value indicates the total amount of primary amines, secondary amines, and tertiary amines, and is expressed as mg of potassium hydroxide equivalent to the hydrochloric acid required to neutralize 1 g of the sample.

[0126] Examples of the organic amine include oxyethylene alkylamines and polyoxyethylene alkylamines. Specific examples of the oxyethylene alkylamines and polyoxyethylene alkylamines include NYMEEN L-201 (total amine value: 232 to 246, secondary amine), NYMEEN L-202 (total amine value: 192 to 212, tertiary amine), NYMEEN L-207 (total amine value: 107 to 119, tertiary amine), NYMEEN S-202 (total amine value: 152 to 166, tertiary amine), NYMEEN S-204 (total amine value: 120 to 134, tertiary amine), NYMEEN S-210 (total amine value: 75 to 85, tertiary amine), NYMEEN DT-203 (total amine value: 227 to 247, tertiary amine), and NYMEEN DT-208 (total amine value: 146 to 180, tertiary amine) (manufactured by NOF Corporation). Specific examples of the alkylamine include FARMIN 80 (total amine value: 204 to 210, primary amine), FARMIN D86 (total amine value: 110 to 119, secondary amine), FARMIN DM2098 (total amine value: 254 to 265, tertiary amine), FARMIN DM8680 (total amine value: 186 to 197, tertiary amine) (Kao Corporation), NISSAN tertiary amine BB (total amine value: 243 to 263, tertiary amine), and NISSAN tertiary amine FB (total amine value: 230 to 250, tertiary amine) (manufactured by NOF Corporation), etc. These may be used alone or in combination of two or more.

[0127] Taking into account the stability with the above-mentioned saturated fatty acid, the above-mentioned phosphate ester, the colorant or other components, the content of the above-mentioned organic amine is preferably not less than 0.1% by mass and not more than 10% by mass relative to the total amount of the oil-based ballpoint pen ink composition. If the neutralization of the surfactant described later is further taken into account, it is preferably not less than 0.5% by mass and not more than 5% by mass.

[0128] The total content of the phosphate ester and the saturated fatty acid relative to the total amount of the ink composition is represented by A, and the content of the organic amine relative to the total amount of the ink composition is represented by B. In this case, if the temporal stability of the ink due to neutralization is taken into consideration, the relationship of 0.01≤A / B≤5 is preferably satisfied, and if further considered, the relationship of 0.1≤A / B≤3 is preferably satisfied, and 0.1≤A / B≤4 is more preferably satisfied.

[0129] (Colorant)

[0130] ​The colorant used in the oil-based ballpoint pen ink composition of the present embodiment is a dye, a pigment, etc., which is not particularly limited and can be appropriately selected for use, or can be used in combination with a dye or a pigment. As dyes, oil-soluble dyes, acid dyes, basic dyes, gold-containing dyes, etc. can be cited; as their various salt-forming dyes, etc., salt-forming dyes of acid dyes and basic dyes, salt-forming dyes of basic dyes and organic acids, and salt-forming dyes of acid dyes and organic amines can be cited. These dyes can be used alone or in combination of two or more.

[0131] Specific examples of dyes include Valifast Black 1802, Valifast Black 1805, Valifast Black 1807, Valifast Violet 1701, Valifast Violet 1704, Valifast Violet 1705, Valifast Blue 1601, Valifast Blue 1605, Valifast Blue 1613, Valifast Blue 1621, and Valifast Blue. 1631, Valifast Red 1320, Valifast Red 1355, Valifast Red1360, Valifast Yellow 1101, Valifast Yellow 1151, Nigrosine Base EXBP, NigrosineBase EX, BASE OF BASIC DYES ROB-B, BASE OF BASIC DYES RO6G-B, BASE OF BASIC DYESVPB-B, BASE OF BASIC DYES VB-B、BASE OF BASIC DYES MVB-3 (all manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Aizen Spilion Black GMH-special, Aizen Spilion Violet C-RH, Aizen Spilion Blue GNH, Aizen Spilion Blue 2BNH, Aizen Spilion Blue C-RH, Aizen Spilion Red C-GH, Aizen Spilion Red C-BH, Aizen Spilion Yellow C-GNH, Aizen Spilion Yellow C-2GH, SPTBlue 111, SPTBlue GLSH-special, SPTRed533, SPTOrange 6, SBNYellow 510, SBNYellow 530, SRC-BH (all manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.

[0132] In addition, as a colorant, considering the stability over time due to compatibility with saturated fatty acids and phosphates, it is preferred to use at least a salt-forming dye. Furthermore, if it is considered that the stability over time can be maintained by stabilizing the salt-forming bond, it is preferred to use a salt-forming dye of a basic dye and an organic acid, a salt-forming dye of an acid dye and a basic dye, or a salt-forming dye of an acid dye and an organic amine.

[0133] If further considered, then preferably use the salified dye of basic dye and organic acid, the salified dye of acid dye and organic amine.If further considered, then preferably use from the salified dye with azo skeleton dye, the salified dye with xanthene dye, the salified dye with aromatic amine.Among these, saturated fatty acid, phosphoric acid ester are produced to be difficult to influence due to bonding stability, preferably use from the salified dye of azo basic dye and organic acid, the salified dye of acid dye and aromatic amine.

[0134] As for the organic acid in the salt-forming dye of the basic dye and the organic acid, as long as it is an organic acid having a phenylsulfone group, it is easy to form a lubricating film that is easily adsorbed on the metal, which can improve the lubricity, improve the writing feeling and suppress the wear of the ball seat, so it is preferred. Furthermore, considering the long-term stability in the ink, alkylbenzene sulfonic acid is preferably used as the organic acid.

[0135] In addition, in order to improve the lubricity and light resistance of the acidic dye and the organic amine, the acidic gold-containing dye containing Cu, Cr, Fe, and Co is preferred, and the salt-forming dye of the acidic gold-containing dye and the organic amine is preferably used. In order to stabilize the acidic gold-containing dye in the oil-based ink, it is preferred to neutralize the organic amine with an amine having an aromatic ring to form a salt-forming dye.

[0136] Regarding the acidic gold-containing dye, it is preferred to use an acidic gold-containing dye containing Cu in order to improve the stability over time in the ink. There are phthalocyanine-based and azo-based acidic dyes, among which copper phthalocyanine-based acidic dyes are preferred. In addition, there are acidic gold-containing dyes having a sulfonic group (-SO 3 H) or carboxyl (-COOH) groups. If the lubricity is further improved, it is preferred to have a sulfonic acid group (-SO 3 H) of acidic gold-containing dyes. This is because if there is a sulfonic acid (-SO 3 H), it is easy to form a strong lubricating layer between the ball 20 and the ball seat 19a, so the lubricity is easily improved. In addition, it is believed that by using it in combination with an amine having an aromatic ring, a synergistic lubricating effect can also be obtained.

[0137] In addition, as for the pigment, inorganic, organic, and processed pigments can be mentioned. Specifically, carbon black, aniline black, ultramarine blue, chrome yellow, titanium oxide, iron oxide, phthalocyanine series, azo series, quinacridone series, diketopyrrolopyrrole series, quinophthalone series, threne series, triphenylmethane series, perinone series, perylene series, dioxazine series, metallic pigments, pearlescent pigments, fluorescent pigments, and light-storing pigments can be mentioned.

[0138] As a colorant, pigment is preferably used in consideration of lubricity. This is because, by using pigment particles, the pigment particles enter the gap between the ball 20 and the pen tip body 12, and thus easily play a role like a bearing. Therefore, it is possible to suppress metal contact, and it is easy to obtain the effects of improving lubricity, improving writing feeling, and suppressing wear of the ball seat 19a. In particular, by using saturated fatty acids, C l H 2l+1 OC 2 H 4 O or C m H 2m+1 The synergistic effect produced by the lubricating layer formed by the phosphate ester of O (l, m=1 to 30) and the bearing effect of the pigment particles makes it easy to maintain lubricity. Therefore, the wear of the ball seat 19a can be suppressed and the writing feel can be improved. In addition, considering the gap relationship inside the ballpoint pen tip 11, the average particle size is preferably between 1 nm and 500 nm. It is more preferably between 30 nm and 350 nm, and further preferably between 50 nm and 300 nm. The average particle size can be determined by a laser diffraction method. Specifically, a laser diffraction particle size distribution measuring machine (trade name "MicrotracHRA9320-X100", Nikkiso Co., Ltd.) is used to determine the particle size (D50) at a volume accumulation of 50% based on numerical values ​​measured using standard samples and other measurement methods calibrated.

[0139] It should be noted that the above-mentioned pigment exerts the above-mentioned effect in the dispersed state of the pigment in the oil-based ballpoint pen ink composition, so it is preferred to obtain the particle size in the dispersed state. In addition, the pigment is preferred because it is excellent in water resistance and light resistance and can obtain good color development.

[0140] As a type of pigment, if we consider saturated fatty acids, l H 2l+1 OC 2 H 4 O or C m H 2m+1 The lubricity brought by the compatibility of phosphate esters of O (l, m=1 or more and 30 or less) is preferably used from carbon black, quinacridone, threne, and diketopyrrolopyrrole pigments. Furthermore, based on the compatibility over time, if the stability of the ink over time is considered, it is preferred to use diketopyrrolopyrrole pigments.

[0141] The content of the colorant is preferably 5% by mass or more and 30% by mass or less relative to the total amount of the oil-based ballpoint pen ink composition. If it is less than 5% by mass, it tends to be difficult to obtain dark handwriting; if it exceeds 30% by mass, it tends to easily affect the solubility in the ink. If this tendency is further taken into account, it is preferably 7% by mass or more and 25% by mass or less, and if further considered, it is 10% by mass or more and 20% by mass or less.

[0142] (Organic Solvent)

[0143] Examples of the organic solvent used in the oil-based ballpoint pen ink composition of the present embodiment include glycol ether solvents such as 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-methoxybutanol, and 3-methoxy-3-methylbutanol; glycol solvents such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and ethylene glycol; and alcohol solvents such as benzyl alcohol, methanol, ethanol, 1-propanol, 2-propanol, isopropanol, isobutanol, tert-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate, or other higher alcohols, as organic solvents commonly used in inks for writing instruments.

[0144] Among these organic solvents, if we consider the above-mentioned saturated fatty acids, l H 2l+1 OC 2 H 4 O or C above m H 2m+1 O (l, m = 1 to 30) phosphate ester solubility, because it is easy to obtain the effect of improving lubricity, so it is preferred to use glycol ether solvent. This is because with saturated fatty acids, C l H 2l+1 OC 2 H 4 O or C m H 2m+1 The phosphoric acid ester of O (l, m=1 to 30) tends to have good affinity for glycol ether solvents and stably dissolves. Therefore, the ink tends to be stable over time even when stored for a long period of time.

[0145] In addition, if a glycol ether solvent is used, it is easy to absorb moisture, so the strength of the film formed when the pen tip 13 is dried is softened, and the writing performance is also easy to improve. Therefore, it is more effective if used in combination with a surfactant described later. Considering the stability in the ink, it is preferred to use an aromatic glycol ether solvent.

[0146] As for organic solvents other than glycol ether solvents, alcohol solvents are preferably used. This is because alcohol solvents are easy to volatilize and dry the tip 13 of the pen tip. As a result, the inside of the writing tip (the inside of the tip 13 of the pen tip) can be made thicker more quickly, and the ink can be suppressed from leaking out of the gap at the writing tip, thereby improving the ink leakage suppression performance, which is preferred. In addition, since it also has the effect of improving lubricity, it is preferred to use at least aromatic alcohols such as benzyl alcohol. Therefore, it is preferred to use glycol ether solvents and alcohol solvents together.

[0147] In addition, considering the improvement of solubility, handwriting drying property, bleeding, etc., the content of the organic solvent is preferably 10 mass % or more and 70 mass % or less relative to the total amount of the oil-based ballpoint pen ink composition. In addition, considering the drying property of the pen tip 13, the content of the alcohol solvent is preferably 30 mass % or more and 90 mass % or less, and more preferably 50 mass % or more and 90 mass % or less relative to the total amount of the organic solvent.

[0148] (resin)

[0149] In the present invention, resins can be used as viscosity modifiers. Specific examples of viscosity modifiers include polyvinyl butyral resins, polyacetal resins, polyvinyl alcohol resins, cellulose resins, polyvinyl pyrrolidone resins, ketone resins, terpene resins, alkyd resins, phenoxy resins, and polyvinyl acetate resins.

[0150] Among these, ketone resin is preferred because it can suppress the wear of ball seat 19a and easily suppress the whitening of handwriting. In particular, it has good compatibility with the above-mentioned saturated fatty acid and the above-mentioned phosphate ester, does not damage the lubricity that is a feature of the present invention, and synergistically improves the lubricity, making it easier to suppress the wear of ball seat 19a, so it is preferred.

[0151] Among ketone resins, it is preferred to use ketone resins having a cyclic structure such as an aromatic ring skeleton (phenyl, acetophenone, naphthyl, etc. have a benzene ring) or a cyclohexane skeleton (cyclohexyl, cyclohexanone, etc. have a cyclohexane ring). This is because a cushioning effect produced by a ketone resin having a cyclic structure can be obtained, and lubricity can be easily improved, and wear of the ball seat 19a can be suppressed, and whitening of handwriting can be suppressed. More preferably, a ketone resin having an aromatic ring has a large number of double bond structures, so it is easy to obtain a stronger cushioning effect, which is effective for lubricity and is preferred.

[0152] In addition, the ketone resin preferably has a hydroxyl value of 100 (mgKOH / g) or more because it is easy to dissolve in an organic solvent such as an alcohol solvent or a glycol solvent if it is 100 (mgKOH / g) or more. Therefore, it is easy to obtain the wear suppression effect of the ball seat 19a by the interaction with the above-mentioned methyl branched fatty acid and the above-mentioned phosphate ester. If the wear suppression of the ball seat 19a is further considered, the hydroxyl value is preferably 200 (mgKOH / g) or more, and if further considered, the hydroxyl value of the ketone resin is preferably 300 (mgKOH / g) or more. In particular, when the ball diameter is 0.5 mm or less, it is easy to maintain lubricity even when a load is locally applied between the ball 20 and the ball seat 19a, and the wear suppression of the ball seat 19a is effective, so it is preferred. In addition, it is effective even when the ball diameter is 0.4 mm or less, so it is preferred, and it is also effective when the ball diameter is 0.3 mm or less, so it is preferred.

[0153] In addition, although ketone resin can make it easy to suppress the wear of the ball seat 19a, it is difficult to fully improve the writing feeling. Therefore, it is preferably used in combination with polyvinyl butyral resin.

[0154] Regarding polyvinyl butyral resin, by using it together with the above-mentioned saturated fatty acid and the above-mentioned phosphoric acid ester, it is easy to form a lubricating layer that can obtain a higher lubricating effect. Therefore, it is possible to form an ink layer that always has elasticity between the ball 20 and the ball seat 19a, which is not easy to directly contact, and it is easy to improve the writing quality. In addition, if the above-mentioned polyvinyl butyral resin is used, it is easy to further improve the ink leakage through the formed coating, so it is preferred. In addition, when a pigment is used as a colorant, since a pigment dispersion effect can also be obtained, it is preferred to use polyvinyl butyral resin.

[0155] Here, the polyvinyl butyral resin is obtained by reacting polyvinyl alcohol (PVA) and butyraldehyde (BA), and has a structure having a butyral group, an acetyl group, and a hydroxyl group.

[0156] In addition, the polyvinyl butyral resin preferably has a hydroxyl content of 25 mol% or more. This is because, in the case of a polyvinyl butyral resin having a hydroxyl content of less than 25 mol%, the solubility in an organic solvent is insufficient, and it is difficult to obtain a sufficient effect of improving the writing feel and suppressing ink leakage. In addition, if the writing performance brought about by hygroscopicity is taken into consideration, it is preferred to use a polyvinyl butyral resin having a hydroxyl content of 25 mol% or more. In addition, the polyvinyl butyral resin having a hydroxyl content of 30 mol% or more is preferred because the writing feel is easily improved. This is because, when writing, friction heat is generated due to the rotation of the ball 20, so that the ink at the front end 13 of the pen tip is heated, and the temperature of the ink rises. The polyvinyl butyral resin described above is different from other resins and has the property that it is difficult to reduce the viscosity of the ink even if the temperature of the ink rises. Therefore, an ink layer that is always elastic is formed between the ball 20 and the ball seat 19a, which can make it difficult to make direct contact and improve the writing feel. In addition, if the polyvinyl butyral resin having a hydroxyl content exceeding 40 mol% is used, the moisture absorption is likely to increase, which is likely to affect the stability of the ink components over time. Therefore, a polyvinyl butyral resin having a hydroxyl content of 40 mol% or less is preferred. In addition, a polyvinyl butyral resin having a hydroxyl content of 30 mol% or more and 40 mol% or more is preferred, and a polyvinyl butyral resin having a hydroxyl content of 30 mol% or more and 36 mol% or less is further preferred.

[0157] The hydroxyl group amount (mol %) of the polyvinyl butyral resin refers to the content of the hydroxyl group (mol %) relative to the total molar amount of the butyral group (mol %), the acetyl group (mol %), and the hydroxyl group (mol %).

[0158] In addition, regarding the average degree of polymerization of the polyvinyl butyral resin, if the above average degree of polymerization is 200 or more, the ink leakage suppression performance is easily improved. In addition, if the above average degree of polymerization exceeds 2500, the ink viscosity becomes too high, which tends to affect the writing experience. Therefore, the above average degree of polymerization is preferably 200 to 2500. In addition, if the writing experience and ink leakage suppression are further considered, the above average degree of polymerization is preferably 1500 or less, and more preferably 1000 or less. The average degree of polymerization refers to the number of basic units constituting one molecule of the polyvinyl butyral resin, and can be a value measured by the method specified in JIS K6728 (2001 edition).

[0159] In addition, when a ketone resin and a polyvinyl butyral resin are used together, the content of the ketone resin relative to the total amount of the ink composition is set to C, and the content of the polyvinyl butyral resin relative to the total amount of the ink composition is set to D. In this case, considering the suppression of wear of the ball seat 19a, the easy balance of improving the suppression of handwriting smears and writing feeling, and the suppression of ink leakage, the relationship of 0.1≤C / D≤10 is preferred. In further consideration, the relationship of 0.5≤C / D≤7 is preferred, and 1.5≤C / D≤5 is further preferred.

[0160] When the total content of the above-mentioned resin is less than 1% by mass relative to the total amount of the oily ballpoint pen ink composition, the desired writing experience, the wear suppression of the ball seat, and the ink leakage suppression performance are prone to deterioration. If it exceeds 40% by mass, the solubility in the ink is prone to deterioration. Therefore, relative to the total amount of the oily ballpoint pen ink composition, it is preferably 1% by mass or more and 40% by mass or less. If further consideration is given, it is preferably 5% by mass or more. If it exceeds 30% by mass, the ink viscosity becomes too high, which has a tendency to affect the writing experience, so it is preferably 5% by mass or more and 30% by mass or less.

[0161] Resins other than ketone resin and polyvinyl butyral resin can appropriately use a wire drawing agent. In particular, by mixing polyvinyl pyrrolidone resin, it is easy to improve the adhesion of the ink and easily suppress the generation of residual ink at the front end of the pen tip. Therefore, it is preferably containing polyvinyl pyrrolidone resin. When the content of the above-mentioned polyvinyl pyrrolidone resin is less than 0.01% by mass relative to the total amount of the oily ballpoint pen ink composition, it has a tendency to be difficult to suppress the generation of residual ink. In addition, if it exceeds 3.0% by mass, it has a tendency to be easily deteriorated in solubility in the ink. Therefore, relative to the total amount of the oily ballpoint pen ink composition, it is preferably 0.01% by mass or more and 3.0% by mass or less. If the above reasons are further considered, it is preferably 0.1% by mass or more and 2.0% by mass or less. Specifically, the trade names manufactured by ISP Japan Co., Ltd. can be cited: PVP K-15, PVP K-30, PVP K-90, PVP K-120, etc. They can be used alone or in combination of two or more.

[0162] (Surfactant)

[0163] In the present invention, as the above-mentioned lubricity, if it is considered to suppress the wear of the ball seat 19a, suppress the whitening of the handwriting, improve the writing feeling, and the writing performance of the tip of the pen tip when the tip of the pen tip is placed in the atmosphere, it is preferred to use a surfactant. This is because if a surfactant is used, it has a tendency to soften the formed coating, which can improve the writing performance and further improve the lubricity. As the surfactant, unsaturated fatty acids, silicone surfactants, fluorine surfactants, phosphate surfactants (having Cl H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30 inclusive) excluding phosphate esters) etc.

[0164] Among these, unsaturated fatty acids, silicone surfactants, and phosphate surfactants (having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (excluding phosphoric acid esters where l, m=1 to 30)), one or more, more preferably two or more are used.

[0165] In particular, regarding the phosphate ester used in the present invention, the phosphate ester surfactant (having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30) phosphate esters) have phosphoric acid as the backbone, which makes it easy to obtain a synergistic lubricating effect. Therefore, it is preferred to use a phosphate ester surfactant. By using a phosphate ester and a phosphate ester surfactant (having C l H 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m=1 or more and 30 or less) phosphate esters are excluded), and the lubricating layer of the above phosphate ester interacts with the lubricating layer of the phosphate ester surfactant. Through this interaction, a lubricating layer with higher lubricity can be formed. Therefore, it is presumed that it has the effects of maintaining lubricity, inhibiting wear of the ball seat 19a, inhibiting whitening of handwriting, and facilitating the writing feeling.

[0166] In addition, when using a phosphate ester surfactant (having C l H 2l+1 OC 2 H 4 O or C m H 2m+1In the case of a phosphate ester (except for l, m=1 or more and 30 or less), the acid value is preferably 160 (mgKOH / g) or less. This is because the improvement in lubricity brought about by the phosphate surfactant is easily exerted. If the stability and lubricity in the ink are further considered, the acid value is preferably 30 (mgKOH / g) or more and 160 (mgKOH / g) or less. If further consideration is taken, the acid value is preferably 70 (mgKOH / g) or more and 120 (mgKOH / g) or less.

[0167] The acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the sample.

[0168] Furthermore, when the above-mentioned saturated fatty acid, ketone resin or polyvinyl butyral resin is used, lubricity can be improved more easily, which is more preferable.

[0169] Regarding the above-mentioned surfactant, if both lubricity and writing performance are further improved, the HLB value is preferably 6 or more and 14 or less. This is because if the HLB value exceeds 14, the hydrophilicity is easily enhanced, the solubility in the oily ink is easily deteriorated, it is difficult to obtain the effect of the above-mentioned surfactant, and it is difficult to obtain the lubrication effect. In addition, if the HLB value is less than 6, the lipophilicity becomes too strong, which easily affects the compatibility with the organic solvent, and the ink is difficult to stabilize over time, and then the writing performance is difficult to improve. In addition, if lubricity is considered, the HLB value is preferably 12 or less, and the HLB value is preferably 6 or more and 12 or less. If the writing performance is further considered, the HLB value is preferably 7 or more and 12 or less.

[0170] It should be noted that HLB can be obtained by the Griffin method, Kawakami method, etc., and as an example, it can be obtained by the general formula HLB=7+11.7log(Mw / Mo) (Mw: molecular weight of hydrophilic group, Mo: molecular weight of lipophilic group), etc. In particular, in a retractable writing instrument such as a push-type writing instrument or a rotary delivery writing instrument, unlike a cap-type writing instrument, the pen tip is always exposed to the outside, which easily affects the writing performance of the writing tip when it is dry, and therefore it is more preferable to use a surfactant with the above HLB value.

[0171] As the above-mentioned surfactant, specifically, as unsaturated fatty acid, oleic acid, linoleic acid, etc. can be mentioned. As silicone surfactant, dimethyl silicone, methylphenyl silicone, polyether modified silicone, higher fatty acid ester modified silicone, etc. can be mentioned. As fluorine-based surfactant, perfluorobutyl sulfonate, perfluoro group-containing carboxylate, perfluoro group-containing phosphate, perfluoro group-containing phosphate type compound, perfluoroalkyl betaine, perfluoroalkyl amine oxide compound, etc. can be mentioned.

[0172] As a phosphate ester surfactant (having C lH 2l+1 OC 2 H 4 O or C m H 2m+1 O (l, m = 1 to 30)), and examples thereof include phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, phosphoric acid diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, phosphoric acid triesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, alkyl phosphoric acid esters, alkyl ether phosphoric acid esters or their derivatives.

[0173] The content of the surfactant is preferably 0.1% by mass or more and 5.0% by mass or less relative to the total amount of the oily ballpoint pen ink composition. This is because if it is less than 0.1% by mass, it is difficult to obtain the desired lubricity; if it exceeds 5.0% by mass, the ink tends to become unstable over time. Considering these tendencies, it is preferably 0.3% by mass or more and 3.0% by mass or less relative to the total amount of the oily ballpoint pen ink composition, and if further considered, it is most preferably 0.5% by mass or more and 3.0% by mass or less.

[0174] (Fatty acid esters)

[0175] In the present invention, if the lubricity and writing performance of the tip 13 of the pen tip when the tip 13 is left in the atmosphere are to be further improved, it is preferred to use fatty acid esters. The coating strength formed when the ink of the tip 13 of the pen tip is dried is easily softened by the fatty acid esters, thereby easily improving the writing performance. In addition, since the lubricity is easily improved, the wear of the ball seat 19a is easily suppressed, and the suppression of the handwriting flying, the writing feeling, and the writing performance are easily improved, it is preferred. Therefore, by using a saturated fatty acid and a C l H 2l+1 OC 2 H 4 O or C m H 2m+1 Phosphate esters and fatty acid esters of O (l, m = 1 to 30) can easily obtain high lubricity that has not been obtained before by utilizing the lubrication effect brought about by the interaction with the formed lubricating layer. That is, it is easy to improve the overall performance of the ball seat 19a in a balanced manner, such as the wear suppression, writing feeling, and writing performance, and is therefore preferred.

[0176] Fatty acid esters are obtained by esterifying fatty acids with alcohols such as monohydric alcohols or polyhydric alcohols. Among the above-mentioned fatty acid esters, if further improving the writing performance is considered, fatty acid esters with branched alkyl groups are preferably used. This is because fatty acid esters with branched alkyl groups are bulky structures compared to straight-chain structures. Due to the large volume of the branched alkyl group, when adsorbed on the surface of a metal ball or the ball seat of the pen tip body, a thick lubricating film is formed, and the lubricity is more easily improved. In addition, because of the large volume of the branched alkyl group, the coating strength formed when the ink at the front end 13 of the pen tip dries is softened, which can improve the writing performance.

[0177] In addition, with respect to the above-mentioned fatty acid ester, it is preferred that the acid value be 0.01 (mgKOH / g) or more and 5 (mgKOH / g) or less, because it has good compatibility with the above-mentioned methyl branched fatty acid, the above-mentioned phosphate ester, and other components in the oily ballpoint pen ink composition. Since it is stable in the ink for a long time, it is possible to improve the writing performance and lubricity for a long time, and it is easy to improve the writing feeling. If further consideration is given, with respect to the acid value, it is preferably 0.01 (mgKOH / g) or more and 2.5 (mgKOH / g) or less, and more preferably 0.05 (mgKOH / g) or more and 1.0 (mgKOH / g) or less.

[0178] The acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic components (free fatty acids) contained in 1 g of the sample.

[0179] The alcohol used in the esterification reaction of the above-mentioned fatty acid ester is preferably a polyol. Regarding this point, although the reason has not yet been determined, it is speculated that when the hydroxyl group of the alcohol used in the esterification reaction of the above-mentioned fatty acid ester is large, it is easy to exert a moisturizing effect. It is speculated from this: it is possible to obtain the effect of softening the strength of the coating formed when the front end portion 13 of the pen tip is dried, and making the rotation of the ball 20 smooth, so that the handwriting does not produce white spots, and the writing performance is improved. If further consideration is given to improving the writing performance and lubricity, it is preferred that the hydroxyl group is a polyol of more than 3 yuan, and more preferably the hydroxyl group is more than 5 yuan. In addition, when there are too many hydroxyl groups, it is easy to affect the stability in the oily ink, so it is preferred that the hydroxyl group is less than 8 yuan, and more preferably the hydroxyl group is less than 6 yuan.

[0180] As a specific example of the alcohol used in the esterification reaction of the above-mentioned fatty acid ester, as a monohydric alcohol, amyl alcohol, cyclohexanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, isononanol, decanol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, etc. can be cited. As a polyhydric alcohol, ethylene glycol, propylene glycol, polyalkylene glycol, 1,3-propylene glycol, diethylene glycol, glycerol, 2-methylpropanetriol, neopentyl glycol, trimethylolethane, triethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc. can be cited. Among these, if further considering improving the writing performance and the time stability of the ink, it is preferably included using pentaerythritols such as pentaerythritol, dipentaerythritol, tripentaerythritol. The fatty acid ester esterified, if further considered, preferably includes the fatty acid ester esterified using dipentaerythritol.

[0181] In addition, the content of the fatty acid ester is more preferably 0.1% by mass or more and 10% by mass or less relative to the total amount of the oil-based ballpoint pen ink composition. This is because if it is less than 0.1% by mass, it is difficult to obtain the desired lubricity and writing performance; if it exceeds 10% by mass, the ink tends to be unstable over time. Considering this tendency, it is preferably 0.1% by mass or more and 5% by mass or less, and if further considered, it is preferably 0.1% by mass or more and 3% by mass, and most preferably 0.3% by mass or more and 2% by mass or less.

[0182] In addition, as a viscosity modifier, a pseudoplasticity imparting agent such as fatty acid amide and hydrogenated castor oil can be used appropriately, and a colorant stabilizer, a plasticizer, a chelating agent, water, etc. can also be used appropriately. These can be used alone or in combination of two or more.

[0183] As described above, the ink viscosity of the oil-based ballpoint pen ink composition of this embodiment is 20°C and the shear rate is 500s. -1 The viscosity of the ink (at the time of writing) is in the range of 500 mPa·s to 15000 mPa·s.

[0184] If the ink viscosity exceeds 15000mPa·s, the ball rotation resistance during writing becomes larger, the writing feeling tends to become heavier, and the wear suppression of the ball seat 19a is easily affected, which in turn tends to affect the writing performance and ink following performance. -1 The ink viscosity (when writing) is preferably 15000 mPa·s or less. If the writing feeling and the improvement of the wear suppression of the ball seat 19a are further considered, it is preferably 10000 mPa·s or less, if the writing feeling and the wear suppression of the ball seat 19a are further considered, it is preferably 8000 mPa·s or less, if the writing feeling is further considered, it is preferably 6000 mPa·s or less.

[0185] In addition, at 20°C and a shear rate of 500 s -1 When the ink viscosity is less than 10 mPa·s, the wear of the ball seat 19a, the bleeding of handwriting, and the dripping of ink are likely to be affected. -1 The ink viscosity (when writing) is preferably greater than 10 mPa·s. If further consideration is given, the ink viscosity is preferably greater than 100 mPa·s. If further consideration is given to the wear suppression of the ball seat 19a, the ink viscosity is preferably greater than 500 mPa·s. If further consideration is given, it is preferably greater than 1000 mPa·s, and preferably greater than 2000 mPa·s.

[0186] Example

[0187] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[0188] The oil-based ballpoint pen ink composition of Example 1 is prepared as follows. After adding a pigment and a pigment dispersant to an organic solvent and dispersing them with a disperser, a pigment dispersion, a dye, an organic solvent, a polyvinyl butyral resin, a ketone resin, a phosphate ester, an organic amine, a surfactant, a fatty acid ester, and a stringiness-imparting resin are weighed in a predetermined amount and heated to 60° C. After heating, a dispersing stirrer is used to completely dissolve them, thereby preparing an oil-based ballpoint pen ink composition. The specific mixing amounts are as follows.

[0189] Example 1

[0190]

[0191]

[0192] In Example 1, 0.3 g of the oil-based ballpoint pen ink composition prepared in the above blending amount was directly filled into Figure 1 to Figure 3 The ink containing cylinder 22 (made of polypropylene) of the ballpoint pen 1 shown is the ballpoint pen 1 of Example 1.

[0193] In addition, the specifications of the ballpoint pen refill 4 of the ballpoint pen 1 used in Example 1 are as follows.

[0194] Ball 20: Tungsten carbide ball 20

[0195] Nib body 12: The stainless steel wire having a hardness of 230 Hv to 280 Hv is cut into desired lengths.

[0196] · Extrusion load of coil spring 21: 8 gf / mm

[0197] ·Ball 20 holding force: 300gf

[0198] Movement of the ball 20 in the extension direction X: 18 μm

[0199] Arithmetic mean roughness (Ra) of the ball surface of the ball 20: 2 nm

[0200] ·1st inclination angle α: 90 degrees

[0201] · Second inclination angle β: 120 degrees

[0202] Angle γ of the bottom wall 19 of the ball holding chamber 15: 120°

[0203] The ball protrusion H protruding from the tip end portion 13 when the ball 20 is placed on the bottom wall 19: 30% of the ball diameter

[0204] Angle δ behind the tip 13 of the pen tip: 30°

[0205] Gap between balls 20 in extension direction X: 18 μm

[0206] In Example 1, the ballpoint pen refill 4 of the above specifications was placed in an oil-based ballpoint pen manufactured by Baile Co., Ltd. to produce a Figure 1 to Figure 3 Description of ballpoint pen 1.

[0207] Embodiment 2 to Embodiment 36

[0208] The components were changed as shown in the table, and the oil-based ballpoint pen ink compositions of Examples 2 to 36 were obtained by mixing in the same procedure as in Example 1. It should be noted that in Examples 2 to 36, a ballpoint pen 1 of the same specifications as in Example 1 was used except that the oil-based ballpoint pen ink compositions were different.

[0209] Comparative Examples 1-2

[0210] The oil-based ballpoint pen ink composition with the proportion shown in the table was used. Specifically, the same oil-based ballpoint pen ink composition as that of Example 1 was used in Comparative Example 1, and the same oil-based ballpoint pen ink composition as that of Example 33 was used in Comparative Example 2. In addition, a ballpoint pen 1 having the same specifications as that of the example except that the second inclination angle β was 150 degrees, the angle γ of the bottom wall 19 of the ball holding chamber 15 was 120 degrees, and the second inclination angle β and the angle γ were different angles was prepared using the oil-based ballpoint pen ink composition as a comparative ballpoint pen for Comparative Examples 1 and 2.

[0211] The viscosity of the oil-based ballpoint pen ink compositions used in Examples 1 to 33 and Comparative Example 1 was measured using a viscometer Viscometer RVDVII+ProCP-52 Spindle manufactured by Brookfield Corporation. The results were as follows: -1 The following are all in the range of 500 mPa·s to 15000 mPa·s.

[0212] Specifically, the oil-based ballpoint pen ink composition used in each example and comparative example was heated at 20° C. and a shear rate of 500 s. -1 The viscosity of the ink below is as follows.

[0213] Example 1-Example 2: Ink viscosity = 4500 mPa·s

[0214] Example 13: Ink viscosity = 3700 mPa·s

[0215] Example 19-Example 20: Ink viscosity = 2800 mPa·s

[0216] Example 21: Ink viscosity = 4300 mPa·s

[0217] Example 23: Ink viscosity = 3500 mPa·s

[0218] Example 29: Ink viscosity = 5900 mPa·s

[0219] Example 30: Ink viscosity = 7100 mPa·s

[0220] Example 31: Ink viscosity = 1500 mPa·s

[0221] Test and evaluation

[0222] The ballpoint pen 1 produced in Examples 1 to 33 and the comparative ballpoint pen produced in Comparative Example 1 were subjected to the following tests and evaluations using writing paper JIS P3201 as writing test paper.

[0223] The table shows the measurement and evaluation results.

[0224]

[0225]

[0226]

[0227]

[0228]

[0229] In the table, (1) to (15) represent the following contents respectively.

[0230] (1) Manufactured by Hodogaya Chemical Industry Co., Ltd.

[0231] (2) Manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.

[0232] (3) 16-Methylstearic acid manufactured by Nissan Chemical Industries, Ltd.

[0233] (4) Manufactured by Nissan Chemical Industries, Ltd.

[0234] (5) Oleic acid manufactured by Kao Corporation

[0235] (6) Mixing ratio of the mixture of monoester of butoxyethyl acid phosphate and diester of butoxyethyl acid phosphate = 4:6

[0236] (7) Phosphanol manufactured by Toho Chemical Industry Co., Ltd. (HLB: 8.6, acid value: 85)

[0237] (8) Phosphanol manufactured by Toho Chemical Industry Co., Ltd. (HLB: 10.5, acid value 82)

[0238] (9) NYMEEN L201 manufactured by NOF Corporation (total amine value: 232-246)

[0239] (10) Made by Sekisui Chemical Co., Ltd.

[0240] (11) Unistar HR170R manufactured by NOF Co., Ltd.

[0241] (12) Unistar H334R manufactured by NOF Corporation

[0242] (13) Manufactured by Hitachi Chemical Co., Ltd.

[0243] (14) PVP K-90 manufactured by ISP Japan Co., Ltd.

[0244] (15) FARMIN DM2098 manufactured by Kao Corporation (total amine value: 254-265)

[0245] Regarding the initial ink consumption per 100m of Example 1, Example 2, Example 13, and Example 19, a spiral writing test was conducted using an oily ballpoint pen, and the results were 30mg / 100m, 27mg / 100m, 25mg / 100m, and 40mg / 100m, respectively.

[0246] The ratio of the ball diameter (mm) of the oil-based ballpoint pens of Example 1, Example 2, Example 13, and Example 19 to the initial ink consumption (mg) per 100 m (ball diameter: ink consumption) are as follows: Example 1 is 1:100, Example 2 is 1:90, Example 13 is 1:83, and Example 19 is 1:80.

[0247] It should be noted that, when the ink consumption at the initial time of 0m to 100m in Example 1, Example 2, Example 13, and Example 19 is assumed to be Emg, and the ink consumption 100m before the ink is used up is assumed to be Fmg, E:F are as follows: Example 1 is 30:33=1:1.1, Example 2 is 27:25=1:0.93, Example 13 is 25:27=1:1.08, and Example 19 is 40:42=1:1.05.

[0248] Ink flow stability test: The handwriting after the writing test was checked using a running tester with a load of 100 gf, a writing angle of 70°, and a speed of 4 m / min.

[0249] There is no uneven wear of the sealing surface 14c of the second caulking portion 14b, the ink flow is stable, there is no ink discharge, and the handwriting is deep...

[0250] Due to the uneven wear of the sealing surface 14c of the second caulking portion 14b, the ink flow rate is unstable, and ink discharge is not smooth... ×

[0251] Scrape paper writing test: When handwriting is performed on a paper surface with a load of 100 gf and a writing angle of 70°, it is observed whether the outer surface of the second caulking portion 14 b contacts the paper surface.

[0252] The outer surface of the second caulking portion 14b will not be caught by the paper surface, and good writing can be achieved.

[0253] The outer surface of the second caulking portion 14b is caught by the paper surface, and writing cannot be done well... ×

[0254] Wear resistance test (wear test of ball seat 19a): The wear of ball seat 19a after the writing test was measured using a running tester at a load of 100 gf, a writing angle of 70°, and a speed of 4 m / min.

[0255]

[0256] Writing experience: Use handwriting to conduct sensory tests and make evaluations.

[0257]

[0258] Writing performance test: After handwriting, the pen tip is placed under an environment of 20°C and 65% RH for 30 minutes with the tip extending. Then, a running test is performed under the following writing conditions to measure the length of the written handwriting.

[0259] <Writing Conditions> Under the conditions of a writing load of 70 gf, a writing angle of 70°, and a writing speed of 4 m / min, linear writing was performed using a travel tester and evaluated.

[0260]

[0261] Ink time test: The ink in the nib body is observed under a microscope.

[0262]

[0263] In Examples 1 to 31, good performance was obtained in the wear resistance test (wear test of the ball seat 19a), writing feeling, writing performance test, and ink aging test.

[0264] In addition, compared with Comparative Examples 1 to 2, Examples 1 to 36 obtained good results in the ink flow stability test and the scraping paper writing test. In detail, in Comparative Examples 1 and 2, the uneven wear of the sealing surface 14c of the first caulking portion 14a was aggravated, the ink flow was unstable, and the ink flow was not smooth. In addition, in Comparative Examples 1 and 2, the second caulking portion 14b would catch the paper during writing, resulting in a scratchy feeling of the pen, making it impossible to write well. It is believed that this is because in Comparative Examples 1 and 2, the second inclination angle β and the angle γ are different angles, and the second inclination angle β is as large as 150 degrees.

[0265] Furthermore, when using a retractable oil-based ballpoint pen such as a push-type oil-based ballpoint pen or a twist-feed oil-based ballpoint pen, writing performance is one of the important performances, and therefore it is effective to use at least an oil-based ballpoint pen ink composition such as the present invention.

[0266] In addition, in the present embodiment, a ballpoint pen 1 is illustrated in which a ballpoint pen refill 4 containing an oil-based ballpoint pen ink composition in an ink holding cylinder is arranged in a barrel, but the ballpoint pen 1 of the present invention may also be a direct-loading oil-based ballpoint pen in which the barrel itself is an ink holding cylinder and the oil-based ballpoint pen ink composition is directly held in the barrel, or may be a structure in which an article (ballpoint pen refill 4) containing an oil-based ballpoint pen ink composition in an ink holding cylinder 22 is directly used as the ballpoint pen 1.

[0267] Industrial Applicability

[0268] The present invention can be used as a ballpoint pen, and more specifically, can be widely used as a cap-type, push-type, or other ballpoint pen.

Claims

1. A ballpoint pen, comprising a ballpoint pen refill, the ballpoint pen refill comprising: an ink container filled with an oil-based ballpoint pen ink composition; and a ballpoint pen tip mounted on the front end of the ink container, wherein: The ballpoint pen tip body comprises: a ball holding chamber, which allows a part of the ball to protrude from the front end of the pen tip and is rotatably held; a ball seat, which is arranged on the bottom wall of the ball holding chamber, carries the ball and is in the shape of an arc surface along the outer shape of the ball; an ink flow hole, which is formed in the center of the bottom wall of the ball holding chamber; and a plurality of ink flow grooves, which extend radially from the ink flow hole. The ink viscosity of the oil-based ballpoint pen ink composition is 20° C. and the shear rate is 500 s. -1 The lower limit is within the range of 500mPa·s to 15000mPa·s. The ball diameter of the ball is less than 0.5 mm, A sealing surface in the form of an arc is formed on the inner wall of the front end of the pen tip. The tip end of the pen tip has: a first caulking portion having an inclination angle of 90 degrees or more and less than 100 degrees; and a second caulking portion provided at the tip end side of the ballpoint pen tip and having an inclination angle of 110 degrees or more and less than 130 degrees compared to the first caulking portion, The angle of the bottom wall of the ball holding chamber is the same as the inclination angle of the second caulking portion.

2. The ballpoint pen according to claim 1, characterized in that It further includes a coil spring for pressing the ball toward the front end side of the front end portion of the pen tip, wherein a pressing load of the coil spring is not less than 5 gf and not more than 10 gf.

3. The ballpoint pen according to claim 1 or claim 2, characterized in that: The oil-based ballpoint pen ink composition comprises a colorant, an organic solvent, a saturated fatty acid, and a phosphoric acid ester. The phosphoric acid ester has C l H 2l+1 O-C2H4O or C m H 2m+1 O, wherein l and m=1 to 30.

4. The ballpoint pen according to claim 3, characterized in that The saturated fatty acid has 10 or more and 20 or less carbon atoms.

5. The ballpoint pen according to claim 3, characterized in that: The l and the m are 1 or more and 15 or less.

6. The ballpoint pen according to claim 3, characterized in that: The oil-based ballpoint pen ink composition includes a ketone resin or a polyvinyl butyral resin.

7. The ballpoint pen according to claim 3, characterized in that: The colorant is a pigment or a salt-forming dye.

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