JP6811562B2 - Stationery with a clip - Google Patents

Description

The present invention relates to a writing instrument provided with a clip.

A writing tool having a clip, particularly a heat-changing writing tool having a clip and accommodating a heat-changing ink is known (for example, Patent Document 1). The thermochromic writing tool described in Patent Document 1 has a friction body separately provided at the tip end portion of the clip, and the clip itself is detachably attached to the writing tool main body via an attachment portion. The handwriting with the heat-discoloring ink is abraded by a friction body to raise the temperature of the heat-discoloring ink, thereby erasing or discoloring.

Japanese Unexamined Patent Publication No. 2012-96388

When removing the clip from the writing instrument body for use with the friction body, the clip must be slid along the axial direction of the thermochromic writing instrument. However, due to the strong locking between the clip and the mounting portion, it may be difficult to slide the clip and it may not be easy to perform. Further, in this case, if the clip is forcibly slid, the clip may be bent or broken. Alternatively, there is a risk of damaging the mounting portion, in which case the clip can no longer be mounted.

Therefore, an object of the present invention is to provide a writing tool provided with a clip having a simple structure and easy to attach / detach.

According to one aspect of the present invention, a writing instrument provided with a clip, a mounting surface is formed on the outer surface of the writing instrument, and the clip is detachably attached to the mounting surface by a magnetic force, and Provided is a writing instrument characterized by being an erasing member capable of erasing the handwriting by the writing instrument.

Further, according to another aspect, one of the clip or the mounting surface has at least two first magnetic portions made of a magnetic material arranged apart from each other in the axial direction. Here, the magnetic material includes a soft magnetic material such as iron and a hard magnetic material such as a permanent magnet.

According to another aspect, the clip or the other side of the mounting surface has at least two second magnetic parts made of a magnetic material, and each of the second magnetic parts has the first magnetic part. It is arranged so as to face each of the portions.

Further, according to another aspect, the magnetic portion is characterized in that the magnetic force on the rear side is larger than the magnetic force on the front side. In the axial direction of the writing instrument, the writing part side is defined as the "front" side, and the side opposite to the writing part is defined as the "rear" side.

Further, according to another aspect, an inclined surface is formed at an end portion of the clip on the side facing the mounting surface.

Further, according to another aspect, the writing instrument is a heat-discoloring writing instrument, and the handwriting of the writing instrument can be thermally discolored by the frictional heat generated when the writing instrument is scraped by the erasing member.

According to the aspect of the present invention, it is common to provide a writing tool having a clip having a simple structure and easy to attach / detach.

It is a side view which shows the writing state of the writing instrument by embodiment of this invention. It is a perspective view of the clip of the writing instrument of FIG. It is a partial cross-sectional view of the rear end portion of the writing instrument of FIG. It is a side view of the rear end portion of the writing instrument of FIG. It is another side view of the rear end part of the writing instrument of FIG. It is a partial cross-sectional view of the rear end portion of the writing instrument of FIG. 1 in the state of holding an article. It is a partial cross-sectional view of the rear end portion of the writing instrument according to another embodiment of the present invention. It is a partial sectional view of the rear end portion of the writing instrument according to still another embodiment of the present invention. It is a vertical cross-sectional view which shows the writing state of the writing instrument of FIG. It is a vertical cross-sectional view which shows the non-writing state of the writing instrument of FIG. It is a perspective view of the inner cylinder of the writing instrument of FIG. It is a vertical sectional view of the inner cylinder of FIG. It is a perspective view of the outer sliding member of the writing instrument of FIG. It is a vertical sectional view of the outer sliding member of FIG. It is a perspective view of the inner sliding member of the writing instrument of FIG. It is a vertical sectional view of the inner sliding member of FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. A common reference code is attached to the corresponding components throughout the drawings.

FIG. 1 is a side view showing a writing state of the writing instrument 1 according to the embodiment of the present invention. The writing tool 1 has a barrel 2 and a clip 3. The axle cylinder 2 has a tubular front shaft 4 and a tubular rear shaft 5 whose front end is screwed onto the rear end of the front shaft 4. At the tip of the front shaft 4, a hole is formed for projecting the writing portion 6a of the refill 6 which is a cursive house housed in the shaft cylinder 2. The front shaft 4 and the rear shaft 5 are formed of a resin material such as a polycarbonate resin.

In the present specification, in the axial direction of the writing instrument 1, the writing portion 6a side is defined as the "front" side, and the side opposite to the writing portion 6a is defined as the "rear" side. Further, the "axis line" means the central axis line of the writing tool 1. Further, in the writing tool 1, the refill 6 slides in the front-rear direction in the barrel 2 by the infestation mechanism described later. At this time, the state in which the writing portion 6a protrudes from the shaft cylinder 2, that is, the hole in the front shaft 4 is referred to as a writing state (FIG. 9), and the state in which the writing portion 6a is immersed in the shaft cylinder 2 is a non-writing state (FIG. 10). ).

FIG. 2 is a perspective view of the clip 3 of the writing instrument 1 of FIG. 1, and FIG. 3 is a partial cross-sectional view of the rear end portion of the writing instrument of FIG. The clip 3 is attached to the outer surface of the writing tool 1, that is, the outer surface of the rear shaft 5. That is, the first mounting surface 3a is formed on the side of the clip 3 facing the rear shaft 5, and the outer surface of the rear shaft 5 facing the first mounting surface 3a has a shape complementary to the first mounting surface 3a. The second mounting surface 5a of the above is formed. In the present embodiment, the first mounting surface 3a and the second mounting surface 5a are formed on a flat surface, but may be a curved surface or the like.

A flat first inclined surface 3b inclined in a direction away from the outer surface of the rear shaft 5 is formed behind the first mounting surface 3a, and separated from the outer surface of the rear shaft 5 in front of the first mounting surface 3a. A flat second inclined surface 3c that inclines in the direction of the sloping surface is formed. The outer surface 3d on the opposite side of the first mounting surface 3a of the clip 3 is formed in a cylindrical surface shape. In the present embodiment, the first inclined surface 3b is a gentler inclined surface than the second inclined surface 3c, but may have the same inclination. Further, the second inclined surface 3c may not be provided and may be flush with the first mounting surface 3a.

The clip 3 may be configured as a whole, or a part of the front end portion, the rear end portion, or the like as an erasing member. That is, by rubbing the handwriting by the writing instrument 1 with the clip 3 as the erasing member, the handwriting can be erased.

The first mounting surface 3a of the clip 3 is provided with two first magnetic portions 7 made of a magnetic material, which are arranged apart from each other in the axial direction. The second mounting surface 5a of the rear shaft 5 is provided with two second magnetic portions 8 made of a magnetic material, which are arranged so as to face each of the first magnetic portions 7. The clip 3 is detachably attached to the second attachment surface 5a of the rear shaft 5 by a magnetic force. That is, the magnetic material constituting the first magnetic portion 7 and the second magnetic portion 8 is attached to the axle cylinder 2 so that the clip 3 can be detachably attached to the second mounting surface 5a of the rear shaft 5. It is set so that the magnetic force of is generated. Therefore, one of the first magnetic part 7 or the second magnetic part 8 may be made of a hard magnetic material such as a permanent magnet and the other may be made of a soft magnetic material such as iron, and the first magnetic part 7 and the second magnetic part 7 may be made of a soft magnetic material. Both of the magnetic parts 8 may be made of a hard magnetic material.

4 is a side view of the rear end portion of the writing tool 1 of FIG. 1, FIG. 5 is another side view of the rear end portion of the writing tool 1 of FIG. 1, and FIG. 6 is a state in which the article 9 is sandwiched. It is a partial cross-sectional view of the rear end portion of the writing tool 1 of FIG. By pressing the rear end of the clip 3 toward the axle tube 2, the front end of the clip 3 is lifted (FIG. 4). Even in this state, the magnetic force acts in the direction in which the barrel 2 and the clip 3 are attracted. In other words, the arrangement and magnetic force of the first magnetic portion 7 and the second magnetic portion 8 are set so that the magnetic force acts even in this state at least. Therefore, by releasing the pressure on the rear end portion of the clip 3 from the state of FIG. 4, the clip 3 returns to the original position by the magnetic force, and an article such as a shirt pocket or paper can be sandwiched.

The clip 3 is rotated with respect to the barrel 2 with the suction portions of the first magnetic portion 7 and the second magnetic portion 8 on the rear side as axes, that is, with the axis orthogonal to the axis of the writing tool 1 as the rotation axis. It may be (Fig. 5). With such an arrangement, the suction force between the barrel 2 and the clip 3 is weakened, and the clip 3 can be easily removed. The first magnetic portion 7 on the rear side is provided so as to protrude from the first mounting surface 3a so that the clip 3 can be easily rotated with respect to the axle cylinder 2 and for the alignment of the clip 3, and the corresponding rear The second magnetic portion 8 on the side may be provided in a concave shape with respect to the second mounting surface 5a so as to receive the first magnetic portion 7. On the contrary, the second magnetic portion 8 on the rear side is provided so as to project with respect to the second mounting surface 5a, and the corresponding first magnetic portion 7 on the rear side is concave with respect to the first mounting surface 3a. It may be provided so as to receive the second magnetic part 8.

When sandwiching a thin article 9 such as paper, the article 9 is sandwiched by inserting it from the second inclined surface 3c side in front of the clip 3 so as to slide between the clip 3 and the barrel 2. Can be done (Fig. 6).

In the present embodiment, the first magnetic portion 7 and the second magnetic portion 8 are formed in a columnar shape having a radius of 3 mm and a height of 3 mm, but may have different shapes. For example, FIG. 7 is a partial cross-sectional view of the rear end portion of the writing tool 1 according to another embodiment of the present invention, and FIG. 8 is a partial cross-sectional view of the rear end portion of the writing tool 1 according to still another embodiment of the present invention. However, as shown in FIGS. 7 and 8, one of the first magnetic portion 7 and the second magnetic portion 8 may be formed in a single plate shape.

The first magnetic part 7 and the second magnetic part 8 may be one each, but at least one of the first magnetic part 7 and the second magnetic part 8 is at least two, and these are separated in the axial direction. It is preferably arranged. Further, the first magnetic portion 7 and the second magnetic portion 8 may be exposed from the first mounting surface 3a and the second mounting surface 5a, respectively, but one of the first mounting surface 3a and the second mounting surface 5a or Both may be covered with a metal plate or the like. By covering with a metal plate, the first mounting surface 3a and the second mounting surface 5a become flush with each other, and it becomes easy to remove the adhering dust and the like.

In order to take the form shown in FIG. 4, it is preferable that the magnetic force on the rear side of the first magnetic portion 7 and the second magnetic portion 8 serving as a fulcrum is larger than the magnetic force on the front side. Specifically, the magnetic force on the rear side is preferably 1.5 times or more the magnetic force on the front side because it easily functions as a fulcrum. Specifically, the magnetic force is obtained by measuring the maximum magnetic flux density on the surface of each magnetic part using a magnetic flux densitometer (FUSO MG-3003SD Co., Ltd.), and the rear side serving as a fulcrum is a magnetic force of 350 mT or more. Is preferable. The fulcrum may be the first magnetic part on the front side.

9 is a vertical cross-sectional view showing the writing state of the writing instrument 1 of FIG. 1, and FIG. 10 is a vertical cross-sectional view showing the non-writing state of the writing instrument 1 of FIG. A rear wall portion 5b is formed at the rear end portion of the rear shaft 5. The inner wall in front of the inner wall in the vicinity of the rear wall portion 5b of the rear shaft 5 has a larger inner diameter, and therefore, a step portion 5c is formed at the boundary portion thereof. An infestation mechanism is arranged in the axle cylinder 2, particularly in the rear axle 5. The infestation mechanism includes an inner cylinder 10, an outer sliding member 11, an inner sliding member 12, a ball 13, a coil spring 14, and a heavy body 15.

11 is a perspective view of the inner cylinder 10 of the writing tool 1 of FIG. 1, and FIG. 12 is a vertical cross-sectional view of the inner cylinder 10 of FIG. The inner cylinder 10 has a cylindrical inner cylinder main body 10a, a large-diameter flange portion 10b, a medium-diameter flange portion 10c, and a small-diameter flange portion 10d. The large-diameter flange portion 10b is an annular protrusion formed at the front end portion of the inner cylinder main body 10a and having a diameter larger than that of the inner cylinder main body 10a. The medium-diameter flange portion 10c is an annular protrusion formed behind the large-diameter flange portion 10b and having a diameter smaller than the diameter of the large-diameter flange portion 10b. The small-diameter flange portion 10d is an annular protrusion formed behind the medium-diameter flange portion 10c and having a diameter larger than the diameter of the inner cylinder main body 10a and smaller than the diameter of the medium-diameter flange portion 10c. On the side surface of the inner cylinder body 10a, through holes 10e into which the ball 13 can be inserted are formed evenly at three locations in the radial direction. A large diameter portion 10f is formed on the inner surface of the front end portion of the inner cylinder 10, and a small diameter portion 10g having an inner diameter smaller than that of the large diameter portion 10f is formed behind the large diameter portion 10f. The inner cylinder 10 is formed of a resin material such as a polycarbonate resin.

13 is a perspective view of the outer sliding member 11 of the writing tool 1 of FIG. 1, and FIG. 14 is a vertical cross-sectional view of the outer sliding member 11 of FIG. The outer sliding member 11 is a cylindrical member as a whole, and the outer diameter of the outer sliding member 11 is smaller than the inner diameter of the rear shaft 5. A thick portion 11a, which is a holding portion, is formed on the inner surface of the rear end portion of the outer sliding member 11. The front portion of the thick portion 11a, that is, the inner surface of the front end portion, has a tapered surface 11b, which is a slope whose inner diameter decreases from the front end to the rear and is continuously connected to the front end of the thick portion 11a, formed in an annular shape. Has been done. The tapered surface 11b is a release portion. The inner diameter of the thick portion 11a of the outer sliding member 11 is larger than the outer diameter of the inner cylinder main body 10a of the inner cylinder 10 and smaller than the outer diameter of the small diameter flange portion 10d of the inner cylinder 10. The outer sliding member 11 is preferably formed of a metal material such as stainless steel, but may be formed of a resin material or a resin material mixed with metal powder.

15 is a perspective view of the inner sliding member 12 of the writing tool 1 of FIG. 1, and FIG. 16 is a vertical cross-sectional view of the inner sliding member 12 of FIG. The inner sliding member 12 has an inner sliding member main body 12a which is a cylindrical member as a whole. A first flange portion 12b, which is an annular protrusion, is formed at the rear end portion of the inner sliding member main body 12a, and an annular protrusion is formed between the rear end and the front end of the inner sliding member main body 12a. 2 Flange portion 12c is formed. The outer diameter of the inner sliding member main body 12a of the inner sliding member 12 is smaller than the inner diameter of the small diameter portion 10g of the inner cylinder 10. The outer diameters of the first flange portion 12b and the second flange portion 12c are larger than the inner diameter of the small diameter portion 10g of the inner cylinder 10. An annular recess 12d is formed on the outer peripheral surface of the inner sliding member main body 12a between the first flange portion 12b and the second flange portion 12c.

A plurality of ribs 12e extending in the axial direction are formed at the front end portion of the inner sliding member main body 12a. When the front end of the inner sliding member main body 12a is inserted into the rear end of the refill 6, press-fitting is performed by the plurality of ribs 12e. In this state, the rear end surface of the refill 6 comes into contact with the front end surface of the second flange portion 12c, but due to the ventilation holes 12f being formed in the second flange portion 12c, the inside of the refill 6 and the inside of the shaft cylinder 2 Communicate. The inner sliding member 12 is preferably formed of a metal material such as stainless steel having a specific gravity, but may be formed of a resin material, a resin material mixed with metal powder, or a rubber elastic material such as an elastomer. good.

With reference to FIG. 9 or 10, the inner cylinder 10, the coil spring 14, and the outer sliding member 11 are attached to the outside of the inner sliding member main body 12a of the inner sliding member 12 in this order. Further, the heavy body 15 is attached to the rear end portion of the inner sliding member 12. In this state, when the retracting mechanism is inserted into the rear shaft 5 from the front, the large-diameter flange portion 10b of the inner cylinder 10 and the inner surface of the rear shaft 5 are fixed by press fitting. The ball 13 is always arranged between the outer sliding member 11 and the inner sliding member 12 in a state of being housed in the through hole 10e of the inner cylinder 10.

Therefore, the ball 13 and the outer sliding member 11 are slidably arranged between the inner peripheral surface of the rear shaft 5 and the outer peripheral surface of the inner cylinder 10, and the inner sliding member 12 is placed in the inner cylinder 10. Arranged to be slidable. The sliding of the inner sliding member 12 is regulated by the elastic force of the coil spring 14, and the sliding of the inner sliding member 12 is regulated by the rear wall portion 5b of the rear shaft 5 via the heavy body 15. To. The front end of the coil spring 14 is supported by the rear end surface of the inner cylinder 10, and the rear end of the coil spring 14 is supported by the front end surface of the first flange portion 12b. Regarding the sliding of the outer sliding member 11, the rear end surface of the small diameter flange portion 10d of the inner cylinder 10 regulates the sliding forward, and the step portion 5c of the rear shaft 5 regulates the sliding backward.

Next, the operation of the haunting mechanism of the writing tool 1 will be described. When the user shakes the writing tool 1 in the axial direction, the haunting mechanism holds or releases the refill 6, thereby switching between the writing state and the non-writing state.

Switching from the written state (FIG. 10) to the non-written state (FIG. 9) will be described. In the writing instrument 1 in the writing state, the outer sliding member 11 and the inner sliding member 12 are locked together with the ball 13. In this state, when the user shakes the writing tool 1 in the axial direction while holding the writing tool 1 and the retracting mechanism receives an inertial force in the rear direction, the outer sliding member 11 slides rearward, and the rear end face thereof is formed. It collides with the step portion 5c of the rear shaft 5. At this time, the locking of the inner sliding member 12 and the ball 13 by the thick portion 11a of the outer sliding member 11 is released. That is, the tapered surface 11b of the outer sliding member 11 and the ball 13 are aligned in the radial direction, the ball 13 is disengaged from the recess 12d of the inner sliding member 12, and the refill 6 is released from being held by the retracting mechanism. As a result, the urging force of the coil spring 14 arranged on the outer diameter of the inner sliding member 12 causes the inner sliding member 12 integrated with the refill 6 by press-fitting to slide rearward. As a result, the writing portion 6a at the tip of the refill 6 is immersed in the shaft cylinder 2 through the hole at the tip of the front shaft 4, and the writing instrument 1 is in a non-writing state.

Next, switching from the non-writing state (FIG. 9) to the writing state (FIG. 10) will be described. The ball 13 is arranged between the thick portion 11a of the outer sliding member 11 and the outer peripheral surface of the inner sliding member 12 other than the recess 12d. In this state, when the user shakes the writing tool 1 in the axial direction while holding the writing tool 1 and the retracting mechanism receives an inertial force in the forward direction, the inner sliding member 12 moves forward in the inner cylinder 10 together with the refill 6. Sliding. As a result, the ball 13 fits into the recess 12d of the inner sliding member 12. Next, the outer sliding member 11 slides forward between the rear shaft 5 and the inner cylinder 10, and the tapered surface 11b comes into contact with the ball 13.

Next, the outer sliding member 11 continues to slide as it is by the inertial force, gets over the ball 13 by being guided by the tapered surface 11b, and locks the inner sliding member 12 together with the ball 13 by the thick portion 11a. That is, the thick portion 11a of the outer sliding member 11 and the ball 13 are aligned in the radial direction to lock the inner sliding member 12 together with the ball 13. At this time, since the refill 6 is held by the infestation mechanism in a state where the writing portion 6a at the tip of the refill 6 protrudes from the hole at the tip of the front shaft 4, the writing tool 1 is in the writing state. When writing is performed in this state, the writing pressure causes the inner sliding member 12 to slide backward, that is, the thick portion 8a of the outer sliding member 11 is locked to the ball 13 and the inner sliding member 12. Since the force acts in the direction, the writing state is not released.

According to the present invention, as described above, since magnetic force is used for the attachment structure of the clip, there is no need for a complicated structure that may cause breakage, and the simple structure of close contact between the surfaces makes it easy to attach and detach. It is possible to provide a writing tool with a simple clip. Further, since the attachment portion does not have a protruding member such as the attachment portion of the clip described in Patent Document 1, it can be firmly sandwiched over the entire surface without damaging the end portion of the article. Further, since there is no protruding member, there is no deterioration of the member, and it is possible to provide a long-term mounting function.

Further, after the clip 3 is completely removed from the barrel 2, the article may be sandwiched by returning the clip 3 to the original position while sandwiching the article. By doing so, the clip can be sandwiched not only at the end of the article but also at the center thereof, and can be attached to the writing tool 1 at various articles and at various places.

In the present embodiment, the second mounting surface to which the clip is mounted is provided on the axle tube, but it may be provided on the cap. The present invention can be applied to any writing instrument having a clip, such as a mechanical pencil or a marking pen.

The refill 6 in the above-described embodiment may contain a heat-changing ink containing a heat-coloring material. In this case, the writing tool 1 is a heat-discoloring writing tool, and the clip 3 is a friction body. The handwriting of the writing instrument 1 can be thermally discolored by the frictional heat generated when the clip 3 as a friction body is rubbed.

Here, the thermochromic ink maintains a predetermined color (first color) at room temperature (for example, 25 ° C.), and when the temperature is raised to a predetermined temperature (for example, 60 ° C.), it changes to another color (second color). The ink has the property of returning to the original color (first color) when cooled to a predetermined temperature (for example, −5 ° C.). In the writing instrument 1, making the second color colorless and raising the temperature of the drawn line written in the first color (for example, red) to make it colorless is referred to as "erasing" here. Therefore, the drawn lines are rubbed against the written surface or the like on which the drawn lines are written by a friction body to generate frictional heat, whereby the drawn lines are changed to colorless, that is, erased. As a matter of course, the second color may be a color other than colorless.

As the thermochromic microcapsule pigment to be a thermochromic coloring material, any pigment that changes color due to heat such as frictional heat, for example, one having a function of being colored to colorless, colored to colored, colorless to colored, etc. The present invention is not particularly limited, and various substances can be used, and examples thereof include microencapsulated thermochromic compositions containing at least a leuco dye, a color developer, and a color change temperature adjuster.

The leuco dye that can be used is not particularly limited as long as it is an electron-donating dye and functions as a color former. Specifically, conventionally known inks such as triphenylmethane, spiropirane, fluorane, diphenylmethane, rhodamine lactam, indrillphthalide, and leucochloridium are available from the viewpoint of obtaining ink having excellent color development characteristics. It can be used alone (1 type) or in combination of 2 or more types (hereinafter, simply referred to as "at least 1 type").

Specifically, 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone, 3,3-bis (p-dimethylaminophenyl) -6. -Dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1) -Ethyl-2-methylindol-3-yl) -4-azaphthalide, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6 -Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 2- (2-chloroanilino) -6- Dibutylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 1,2-benz-6-diethylaminofluorane, 1,2-benz-6-dibutylaminofluorane, 1,2-Benz-6-ethylisoamylaminofluorane, 2-methyl-6- (N-p-tolyl-N-ethylamino) fluorane, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethylamino) fluorane, 2- (3'-trifluoromethylanilino) -6-diethylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl-6- Cyclohexylaminofluorane, 3-di (n-butyl) amino-6-methoxy-7-anilinofluorane, 3,6-bis (diphenylamino) fluorane, methyl-3', 6'-bisdiphenylaminofluorane , Chloro-3', 6'-bisdiphenylaminofluorane, 3-methoxy-4-dodecoxystylinoquinolin, and the like.

These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, and the like, and develop color development when these skeletons (rings) are opened.

The color developer that can be used is a component having the ability to develop the color of the leuco dye, and is, for example, a phenol resin compound, a salicylic acid metal chloride, a salicylic acid resin metal salt compound, a solid acid compound, or the like. Can be mentioned.

Specifically, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, hexafluorobisphenol, p. N-butyl-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, dodecyl phosphite, 2,2-bis (4'-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4'-Hydroxyphenyl) ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4'-hydroxy) Phenyl) ethane, 1,1-bis (4'-hydroxyphenyl) -3-methylbutane, 1,1-bis (4'-hydroxyphenyl) -2-methylpropane, 1,1-bis (4'-hydroxyphenyl) ) N-hexane, 1,1-bis (4'-hydroxyphenyl) n-heptane, 1,1-bis (4'-hydroxyphenyl) n-octane, 1,1-bis (4'-hydroxyphenyl) n -Nonan, 1,1-bis (4'-hydroxyphenyl) n-decane, 1,1-bis (4'-hydroxyphenyl) n-dodecane, 2,2-bis (4'-hydroxyphenyl) butane, 2 , 2-Bis (4'-Hydroxyphenyl) ethylpropionate, 2,2-Bis (4'-Hydroxyphenyl) -4-methylpentane, 2,2-Bis (4'-Hydroxyphenyl) hexafluoropropane, At least one of 2,2-bis (4'-hydroxyphenyl) n-heptane, 2,2-bis (4'-hydroxyphenyl) n-nonane and the like can be mentioned.

The amount of the developer to be used may be arbitrarily selected according to the desired color density and is not particularly limited, but is usually 0.1 to 1 part by mass with respect to 1 part by mass of the leuco dye described above. It is preferable to select within the range of about 100 parts by mass.

The discoloration temperature adjusting agent that can be used is a substance that controls the discoloration temperature in the coloration of the leuco dye and the color developer. As the discoloration temperature adjusting agent that can be used, conventionally known ones can be used. Specific examples thereof include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons and the like.

More specifically, bis (4-hydroxyphenyl) phenylmethane dicaprylate (C ₇ H ₁₅ ), bis (4-hydroxyphenyl) phenylmethane dilaurate (C ₁₁ H ₂₃ ), bis (4-hydroxyphenyl) phenyl. Methanedimilistate (C ₁₃ H ₂₇ ), bis (4-hydroxyphenyl) phenyl ethane dimilistate (C ₁₃ H ₂₇ ), bis (4-hydroxyphenyl) phenylmethane dipalmitate (C ₁₅ H ₃₀ ), bis At least one such as (4-hydroxyphenyl) phenylmethane dibehenate (C ₂₁ H ₄₃ ), bis (4-hydroxyphenyl) phenylethylhexylidene dimystate (C ₁₃ H ₂₇ ) and the like can be mentioned.

The amount of the discoloration temperature adjusting agent used may be appropriately selected according to the desired hysteresis width, the color density at the time of color development, and the like, and is not particularly limited, but is usually based on 1 part by mass of the leuco dye. , It is preferable to use within the range of about 1 to 100 parts by mass.

The thermochromic microcapsule pigment is obtained by microencapsulating a thermochromic composition containing at least the leuco dye, a color developer, and a color change temperature adjusting agent so that the average particle size is 0.2 to 3 μm. Can be manufactured. Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, insitu polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, and air. Examples thereof include a suspension coating method and a spray drying method, which can be appropriately selected depending on the intended use.

For example, in the phase separation method from an aqueous solution, a leuco dye, a color developer, and a discoloration temperature adjuster are heated and melted, then put into an emulsifier solution, heated and stirred to disperse them in the form of oil droplets, and then as a capsule film agent. Using a resin raw material, for example, an amino resin solution, an isocyanate-based resin solution, etc. are gradually added, and the reaction is continued to prepare the mixture, and then the dispersion is filtered to produce the desired thermochromic microcapsule pigment. be able to.

The contents of these leuco dyes, color developing agents, and discoloration temperature adjusting agents vary depending on the type of leuco dye, coloring agent, discoloring temperature adjusting agent, microencapsulation method, etc. used. The color developer 0.1 to 100 and the discoloration temperature adjusting agent 1 to 100 by mass ratio. The mass ratio of the capsule membrane agent to the capsule contents is 0.1 to 1.

The thermochromic microcapsule pigment can be obtained by appropriately combining the types and amounts of the leuco pigment, the color developer, and the color change temperature adjusting agent to obtain the color development temperature (for example, color development at 0 ° C. or higher) and the decolorization temperature (for example, 0 ° C. or higher). For example, (decoloring at 50 ° C. or higher) can be set to a suitable temperature, and it is preferable that the color changes from colored to colorless due to heat such as frictional heat.

In the thermochromic microcapsule pigment, the wall film is preferably formed of a urethane resin, a urea / urethane resin, an epoxy resin, or an amino resin from the viewpoint of further improving the drawing density, storage stability, and writability. Examples of the urethane resin include compounds of isocyanate and polyol. Examples of the epoxy resin include a compound of an epoxy resin and an amine. Examples of the amino resin include melamine resin, urea resin, benzoguanamine resin and the like. The thickness of the wall film of the microcapsule coloring material is appropriately determined according to the required strength of the wall film and the drawing density.

The average particle size of the heat-discoloring microcapsule pigment suppresses adverse effects on colorability, color development, easy decolorization, stability, fluidity in ink, and writeability, and photocolor change described later. From the viewpoint of compatibility with the microcapsule pigment, the thickness is preferably 0.2 to 5 μm, more preferably 0.3 to 3 μm. The "average particle size" specified here is a value obtained by measuring the average particle size (50% diameter) (refractive index 1.8) with a particle size analyzer [Microtrack HRA9320-X100 (manufactured by Nikkiso Co., Ltd.)]. Is.

If the average particle size is less than 0.2 μm, a sufficient drawing density cannot be obtained, while if it exceeds 5 μm, the writing property is deteriorated, the dispersion stability of the heat-discoloring microcapsule pigment is lowered, and the ink is caused by vibration. It is not preferable because backing is likely to occur. (Ink back means that the ink recedes due to the impact when switching from the writing state to the non-writing state, and air is mixed in the refill from the writing part, and bubbles are generated in the ink, causing writing defects. (There is a risk.) Further, the 90% diameter is 8 μm or less, preferably 6 μm or less. When particles having a large diameter are present in a certain proportion or more, the above-mentioned influence tends to become more remarkable. The microcapsule pigment in the above-mentioned average particle size range (0.2 to 5 μm) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution or the like, stirring is performed when producing the microcapsule pigment. It can be prepared by a suitable combination of conditions.

The specific gravity of the thermochromic microcapsule pigment is in the range of 0.9 to 1.3, preferably 1.0 to 1.2. If the specific gravity is out of this range, the dispersion stability of the microcapsule pigment tends to decrease. Further, the microcapsule pigment having a specific gravity of more than 1.3 is liable to cause ink back due to vibration.

In the water-based ink composition for writing instruments, in addition to the above-mentioned heat-discoloring microcapsule pigment, water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as a solvent as a balance, and for each writing instrument (ballpoint pen). Depending on the application (for marking pens, etc.), a water-soluble organic solvent, thickener, lubricant, rust preventive, preservative or antibacterial agent, etc. may be appropriately contained as long as the effect is not impaired. it can.

Examples of the water-soluble organic solvent that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, and glycerin, ethylene glycol monomethyl ether, and diethylene glycol monomethyl. Ether can be used alone or in combination.

Of these, glycerin is preferably used for the purpose of suppressing ink solidification in the writing portion due to ink back, and the amount of glycerin added is preferably 1 to 10% by mass with respect to the total amount of ink. The mechanism of action by glycerin is unknown, but it is presumed that it has the effect of reducing the cohesive force of pigments and ink components in a dry state.

As the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose and polysaccharides is preferable. Specifically, Arabic gum, tragacant gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, dieutan gum, dextran, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, starch glycolic acid and The salt, propylene glycol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyacrylic acid and its salt, carboxyvinyl polymer, polyethyresioxide, copolymer of vinyl acetate and polyvinylpyrrolidone, crosslinked acrylic acid polymer and Examples thereof include the salt, the non-crosslinked acrylic acid polymer and its salt, the styrene acrylic acid copolymer and its salt, and the like.

Of these, it is preferable to use polysaccharides. Due to its rheological properties, polysaccharides tend to be less susceptible to fluidity due to vibration, and are less likely to cause problems such as writing defects due to ink back. In particular, xanthan gum is preferable because it has an excellent balance with other properties required for writing instrument ink.

As the lubricant, fatty acid ester of polyhydric alcohol, which is also used as a surface treatment agent for pigments, higher fatty acid ester of sugar, polyoxyalkylene higher fatty acid ester, alkyl phosphate ester, alkyl sulfonate of higher fatty acid amide, alkyl allyl sulfone Examples thereof include esters, derivatives of polyalkylene glycols, fluorine-based surfactants, and polyether-modified silicones. Examples of the rust preventive include benzotriazole, tolyltriazole, dicyclohexylammonium nitrate, saponins and the like. Examples of the preservative or antibacterial agent include phenol, sodium omadin, sodium benzoate, and benzimidazole compounds.

In order to produce this water-based ink composition for writing instruments, a conventionally known method can be adopted. For example, in addition to the above-mentioned heat-discoloring and photo-discoloring microcapsule pigments, a predetermined amount of each component in the above-mentioned water-based is used. It is obtained by blending and stirring and mixing with a stirrer such as a homomixer or a disper. Further, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.

The viscosity value of the water-based ink composition for writing instruments is preferably 500 to 2000 mPa · s at 25 ° C. and a shear rate of 3.83 / s, and 20 to 100 mPa · s at a shear rate of 383 / s. By setting the viscosity in the above range, it is possible to obtain an ink having excellent writability and stability over time. Further, S = αD ⁿ (where 1>n> 0) (S is shear stress (dyn / cm ² ), D is shear rate (s ^-1 ), α is non-Newtonian viscosity coefficient). The required non-Newtonian viscosity index n is preferably 0.2 to 0.6. By setting the non-Newtonian viscosity index n in the above range in addition to the above viscosity range, it is possible to appropriately set the fluidity of the ink with respect to vibration, and it is possible to prevent the occurrence of ink back.

The surface tension of the water-based ink composition for writing instruments is preferably 25 to 45 mN / m, more preferably 30 to 40 mN / m. Within this range, the balance between the inside of the pen tip and the wettability of the ink becomes appropriate, and it is possible to prevent the occurrence of ink back.

In the refill, the ink follower may be arranged immediately behind the ink. The material constituting the follower can be at least composed of a non-volatile or refractory organic solvent and a thickener. The non-volatile or refractory organic solvent used for the ink follower is used as a base oil for the ink follower, and for example, liquid paraffin is used. Mineral oil and chemically synthesized oil are used as the liquid paraffin, and polybutene, polyα-olefin, ethylene α-olefin oligomer and the like can be used as the chemically synthesized oil.

Specific examples of the mineral oil that can be used include commercially available Diana process oils NS-100, PW-32, PW-90, NR-68, and AH-58 (manufactured by Idemitsu Kosan Co., Ltd.).

Specific examples of the polybutene that can be used include commercially available Nissan polybutene 200N, polybutene 30N, polybutene 10N, polybutene 5N, polybutene 3N, polybutene 015N, polybutene 06N, polybutene 0N (all manufactured by Nippon Petrochemicals Co., Ltd.), and polybutene. Examples include HV-15 (manufactured by Nippon Petrochemicals Co., Ltd.) and 35R (manufactured by Idemitsu Kosan Co., Ltd.).

Specific poly-α-olefins that can be used include, for example, commercially available barrel process oils P-26, P-46, P-56, P-150, P-350, P-1500, P-2200, and the like. (P-10000, P-37500) (manufactured by Matsumura Petroleum Co., Ltd.) and the like.

Specific ethylene α-olefin oligomers that can be used include, for example, commercially available Lucant HC-10, HC-20, HC-100, HC-150, (HC-600, HC-2000) (above, Mitsui). (Made by Chemicals), etc.

These non-volatile or non-volatile organic solvents can be used alone or in combination of two or more.

Examples of the thickener used for the ink follower include calcium salt of phosphate ester, fine particle silica, polystyrene-polyethylene / butylene rubber-polystyrene block copolymer, polystyrene-polyethylene / propylene rubber-polystyrene block copolymer, and hydrogenated styrene. -Butadiene rubber, block copolymers of styrene-ethylenebutylene-olefin crystals, block copolymers of olefin crystals-ethylenebutylene-olefin crystals, acetalkoxyaluminum dialchelates and the like can be mentioned, and one or more of these can be used.

Preferred commercially available products of the calcium salt of the phosphoric acid ester that can be used include Crodax DP-301LA (manufactured by Croda Japan Co., Ltd.) and the like. The fine particle silica that can be used includes hydrophilic fine particle silica and hydrophobic fine particle silica, and preferred commercially available products of hydrophilic silica include AEROSIL-300 and AEROSIL-380 (manufactured by Nippon Aerosil Co., Ltd.). Preferred commercially available products of hydrophobic silica include AEROSIL-974D and AEROSIL-972 (manufactured by Nippon Aerosil Co., Ltd.).

Preferred commercially available polystyrene-polyethylene / butylene rubber-polystyrene block copolymers include Clayton GFG-1901X, Clayton GG-1650 (above, Shell Japan), Septon 8007, Septon 8004 (above, Kuraray) and the like. Can be mentioned. Further, preferred commercially available polystyrene-polyethylene / propylene rubber-polystyrene block copolymers include Clayton GG-1730 (manufactured by Shell Japan), Septon 2006, Septon 2063 (all manufactured by Kuraray) and the like.

Preferred commercially available products of hydrogenated styrene-butadiene rubber include DYNARON1320P, DYNARON1321P (above, manufactured by JSR Corporation), Toughtech Hl041, Toughtech Hl141 (above, manufactured by Asahi Kasei Kogyo Co., Ltd.) and the like.

Preferred commercial products of the block copolymer of styrene-ethylenebutylene-olefin crystal include DYNARON4600P (manufactured by JSR Corporation), and preferred commercial products of the block copolymer of olefin crystal-ethylenebutylene-olefin crystal include DYNARON6200P and DYNARON6201B (manufactured by JSR Corporation). (Made by JSR) and the like.

Preferable commercially available products of acetalkoxyaluminum dialchelates include Plenact AL-M (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like.

Among these thickeners, from the viewpoint of further exerting the effects of the present invention, thermoplastic olefin-based elastomers such as styrene-ethylenebutylene-olefin crystal block copolymers and olefin crystals-ethylenebutylene-olefin crystal block copolymers. Preferable to use.

Further, from the viewpoint of obtaining an ink follower that prevents the occurrence of ink back, the average value of the tan δ values measured for each frequency while increasing exponentially in the frequency domain 1 to 63 rad / s should be 1.0 or more. Is preferable, and 1.7 to 3.4 is more preferable.

Here, tan δ is a value meaning a loss elastic modulus / storage elastic modulus, and conventionally, it is an average value of tan δ values measured for each frequency while increasing exponentially in the frequency domain “1-63 rad / s”. It has been known that a value of 1.0 or less is preferable. In the present invention, by setting the average value of the tan δ values measured for each frequency at 1 to 63 rad / s to 1.0 or more, it is possible to absorb vibration and prevent the occurrence of ink back.

As a material for forming the friction body, a thermosetting rubber such as silicone rubber, nitrile rubber, ethylene propylene rubber, ethylene propylene diene rubber, and a rubber elastic material such as a thermoplastic elastomer such as a styrene elastomer, an olefin elastomer, and a polyester elastomer, A mixture of two or more kinds of elastic rubber materials and a mixture of elastic rubber materials and synthetic resin can be used, and this is subjected to a wear test (ASTM D1044) specified in JIS K7204 under a load of 9.8 N and a 1000 rpm environment. Below, the amount of taber wear on the wear wheel CS-17 of the taber wear tester is configured to be less than 25 mg, and a friction body is formed.

Further, an alkyl sulphonic acid phenyl ester or a cyclohexanedicarboxylic acid ester may be added to the material of the friction body. By containing the alkyl sulphonic acid phenyl ester and the cyclohexanedicarboxylic acid ester in the friction body, it is possible to erase the handwriting without damaging the paper surface and blurring the printed characters and the like. Further, the friction body preferably has a durometer A hardness of 70 or more specified in JIS K6203. As a result, a predetermined hardness can be secured, and a more stable scraping operation becomes possible. The friction body can also be applied as a touch pen or a stylus pen, and may be provided with conductivity.

Further, the friction body is preferably colored with a color having a brightness value lower than that of the heat-discoloring ink contained in the writing instrument 1. That is, when the heat-discoloring ink of the writing instrument 1 is transferred to the surface of the friction body without discoloration when the friction body is used, the transfer of the heat-discoloring ink can be made inconspicuous. In particular, by making the color of the friction body black, it is possible to make the surface stains due to the use of the friction body inconspicuous.

The brightness value uses the Mansell color system using a measuring device such as a general-purpose color difference meter (TC-8600A, manufactured by Tokyo Denshoku Co., Ltd.), and the brightness value of the friction body measures the surface of the heat-discoloring ink. The brightness value is a writing speed of 4.5 m / min on a paper surface (former JIS P3201; high-quality paper made from 100% chemical pulp, basis weight range 40 to 157 g / m2, whiteness 75.0% or more). It is obtained by measuring the ink on the drawn line written with a pitch interval of 0.1 mm.

1 Writing tool 2 Axle cylinder 3 Clip 3a 1st mounting surface 4 Front shaft 5 Rear shaft 5a 2nd mounting surface 6 Refill 7 1st magnetic part 8 2nd magnetic part

Claims (3)

A writing instrument provided with a clip, wherein a mounting surface is formed on the outer surface of the writing instrument, the clip is detachably attached to the mounting surface by a magnetic force, and the handwriting by the writing instrument can be erased. member der is,
A writing tool characterized in that one of the clip or the mounting surface has at least two first magnetic portions made of a magnetic material arranged apart from each other in the axial direction . The other of the clip or the mounting surface has at least two second magnetic parts made of a magnetic material, and each of the second magnetic parts is arranged to face each of the first magnetic parts. The writing tool according to claim 1 , wherein the writing tool is characterized by being magnetized. The writing tool according to claim 1 or 2 , wherein the magnetic portion on the rear side has a larger magnetic force on the rear side than the magnetic force on the front side.

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