JP2012016866A - Writing utensil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a writing utensil such as a marker stably supplying ink to the tip of the writing utensil even when the ink contains a pigment of metal powder or the like large in particle size, and composed to prevent strength and durability of the writing utensil from being degraded.SOLUTION: This writing utensil 1 includes an ink reservoir part and a writing part 4, wherein a valve 5 connected to the writing part 4 is interposed between both of them. In the writing utensil, the writing part 4 is supported between the center part and the rear end in the axial direction of the writing part 4 by a cylindrical ink absorber 27 installed in a tip plug 3; an uneven part is formed at a part where the writing part 4 is supported; a valve element 15 is connected to the rear end of the writing part 4; a valve 5 includes the valve element 15 and a valve chest 25; the valve chest 25 is provided with a reservoir part-side opening 21 communicating with the ink reservoir part and a writing part-side opening 26 communicating with the writing part, and arranged with the valve element 15; and the ink reservoir part is filled with ink containing a scale-like pigment at concentration of 1-30 wt.%.

Description

  The present invention relates to an applicator such as a felt tip pen, a line marker, a whiteboard marker, and a corrector, and more particularly to an applicator using an ink containing a scaly pigment.

  In Patent Document 1, a metallic glossy color ink for marking containing metal powder having an average particle diameter of 1 to 25 μm is inserted into a holder so that a pen body (resin processed body of fiber bundle) can slide in the axial direction. The rear end of the pen body is inserted into a valve mechanism attached to the front part of the shaft cylinder, and an ink container is provided in the shaft cylinder at the rear part of the valve mechanism so that the pen body can be pumped (the pen tip part is intermittently connected). It is described that the amount of ink flowing out from the pen body is controlled by operating the valve mechanism connected to the rear end of the pen body and deriving ink in the direction of the writing tip). The pen body does not have a specific structure.

  Patent Document 2 describes a metal powder pigment ink composition for a writing instrument which contains a metal powder pigment surface-treated with a fatty acid or a fatty acid salt, and the writing is performed by filling the ink composition into a marking pen. However, it does not specify the structure of the pen tip used for the marking pen.

Patent Document 3 discloses a metal pigment, an amorphous silicon oxide film layer formed on the surface of the metal pigment, a metal layer formed on the surface of the amorphous silicon oxide film layer, and the metal layer. A colored metal pigment comprising at least metal particles formed on the surface,
Colored metal pigments, in which the metal particles are formed so as to directly cover a portion of the metal layer, are only described and do not suggest use in marking pens.

  In Patent Document 4, a fiber chip, a felt chip, and a plastic chip, each of which contains an ink composition for a writing instrument containing an interference color pigment coated with silicon dioxide on the surface of aluminum flakes in a solvent, are attached to the writing tip. A structure in which ink is impregnated into a fiber bundle housed in the shaft tube and ink is supplied to the writing tip, ink is stored directly in the shaft tube, and a comb groove-shaped ink flow rate adjusting member or fiber bundle A writing instrument such as a marking pen having a structure in which an ink flow rate adjusting member is interposed, a structure in which ink is directly stored in a shaft cylinder and a predetermined amount of ink is supplied to the writing tip portion by a valve mechanism is described. Again, the structure of the writing tip is not specified.

  Furthermore, when filling and writing in the writing instrument provided with the chip | tip which hardened the fiber containing the scaly pigment with the fiber, the normal chip | tip of the writing instrument as described in patent documents 1-4 is shown in FIG. Since it has such a shape and its periphery is hardened with a resin, it is difficult to impregnate the scaly pigment together with other components of the ink through the resin into the chip.

Japanese Patent Laid-Open No. 04-126782 Japanese Patent Laid-Open No. 06-299114 Japanese Patent No. 4216903 JP 2010-065086 A

The scale-like pigments such as metals used in the above prior art have a very large average particle size of about 3 to 50 μm, so that such pigments can be stably supplied to the tip of the writing instrument and written well. It is difficult to do. In addition, since the outer periphery of the writing part at the tip of the writing instrument is hardened by the resin, in order to supply the above-mentioned pigment contained in the ink to the writing part as well, between the outer periphery of the writing part and the member fixing the writing part. A gap was formed, and the pigment-containing ink could only be supplied to the writing instrument through the gap.
Furthermore, if the resin amount which hardens the applicator outer periphery in order to solve this is reduced, the intensity | strength and durability of the writing instrument will fall.
Therefore, even if the ink contains a scaly pigment having a large particle size, the ink can be stably supplied with good writing characteristics without clogging the tip of the writing instrument. It has been a problem to obtain a writing instrument such as a marker that realizes a handwriting with good adhesiveness that can exhibit a specific effect such as glitter, and has good storage stability of ink in the writing instrument.

1. In a writing instrument comprising an ink reservoir and a writing part, and a valve connected to the writing part interposed between the writing part and the writing part, the writing part is connected to the writing part by a cylindrical ink absorber installed in a tip stopper. It is supported between the central part in the axial direction and the rear end, and the supported part of the writing part is provided with a concave and convex part having a concave part whose inner surface of the concave part is not covered with resin, A valve is connected, and the valve has a valve body and a valve chamber, and the valve chamber is provided with a reservoir side opening communicating with the ink reservoir and a writing unit side opening communicating with the writing unit, and the valve body The valve body closes the writing part side opening at all times (that is, when not in use), while the reservoir side opening is opened, and the valve body moves by pressing the writing part during use. The side opening is opened, and the ink reservoir contains scaly pigment at a concentration of 1 to 30% by weight, One writing instrument ink that contains hydrogenated benzophenone type ketone resin is characterized in that it is filled.
2. 2. The writing instrument according to 1, wherein the ink contains propylene glycol monomethyl ether in addition to the scaly pigment.
3. The writing instrument according to 1 or 2, wherein the ink contains a benzophenone type ketone resin.
4). The writing instrument according to any one of 1 to 3, wherein the ink contains a thixotropic agent.

  According to the present invention, the adhesion of ink to paper is improved, there is no color change with time of handwriting, the storage stability in the writing instrument is excellent, and the scaly pigment is contained in the ink due to the structure of the writing part. However, clogging does not occur in the writing part, and the writing characteristics are excellent, and the effect of forming a good handwriting with excellent visual effects such as glitter by blending the scaly pigment is exhibited.

Sectional drawing which shows the front-end | tip part of the writing instrument of this invention, and is not supplying ink to a writing part. The expanded sectional view of the valve chamber of the writing instrument shown in FIG. Sectional drawing which shows the front-end | tip part of the writing instrument of this invention, and supplies ink to a writing part. The expanded sectional view of the valve chamber of the writing instrument shown in FIG. Sectional drawing of the writing part used with the writing instrument of this invention. Sectional drawing of the writing part used with the writing instrument of this invention. Sectional drawing of the writing part used with the conventional writing instrument.

  The present invention is specified by a combination of a writing instrument having a specific structure and an ink containing a specific pigment, and will be described in order below.

[Overview of writing instrument structure]
The writing instrument according to the present invention comprises an ink reservoir for storing the ink shown below and a writing part comprising a felt, and the writing part includes a valve connected between the writing part and the writing part, and the writing part is in a tip stopper. Is supported between the axial center of the writing part and the rear end by a cylindrical ink absorber placed on the surface, and the supported part of the writing part is formed with a surface not covered with resin. A valve body is provided at the rear end of the writing unit, the valve has a valve body and a valve chamber, and the valve chamber has a reservoir side opening communicating with the ink reservoir and a writing unit side opening communicating with the writing unit. And the valve body normally closes the writing part side opening, while the reservoir side opening is opened, and the valve body moves by pressing the writing part during use. The writing part side opening is open.
Here, the writing part coats the outer surface of the fiber bundle collected in the shape of the writing part with a resin so that the surface layer of the fiber bundle is impregnated with the resin to form a resin-impregnated layer. Become. In addition, as described above, the surface not covered with the resin in the present invention or the surface formed by removing the resin-impregnated layer means that the resin-impregnated layer of the writing part is removed by means such as grinding and the resin is impregnated. The side with no fiber bundles exposed is shown.
Such a writing instrument is a writing instrument used as a felt pen or a marker, and the ink is an ink using a specific pigment and a specific solvent described later.

  According to the structure of the writing instrument in the present invention described above, since the valve in the writing instrument is always closed, ink is not supplied from the ink reservoir to the writing part. However, when the writing part is pressed during use, the writing part and the valve body connected to the writing part are moved together in the axial direction of the writing tool to open the valve.

For this reason, since ink distribute | circulates and is supplied toward a writing part from an ink reservoir part, the user who used the writing implement of this invention can write smoothly. More specifically, the ink that has passed through the valve from the ink reservoir and moved in the direction of the writing portion contains the scaly pigment contained therein, the holes formed in the ink absorber that supports the writing portion, and the ink absorption of the writing portion. It passes through the surface formed by removing the resin-impregnated layer provided at the place supported by the body and is absorbed in the felt of the writing part. The absorbed ink is written on the paper from the tip of the writing portion, and a handwriting that exhibits a visual effect by blending the scaly pigment can be formed.
After use, the writing part and the valve body move in opposite directions, so that the valve body is closed, and no more ink in the ink reservoir is supplied to the writing part. By adopting such a structure, the storage stability and writing property of the ink can be improved.

Embodiments of the present invention will be described below with reference to the drawings.
1-4, 1 shows the writing instrument of this invention. The writing instrument 1 is mainly composed of a container 2, a tip plug 3, a writing unit (pen point) 4, a valve 5, a cap 6, and the like. Hereinafter, the configuration of each member will be described.

  The container 2 functions as one that forms an ink reservoir (liquid reservoir), and has a cylindrical shape with one end opened and the other closed. The container 2 employed in the present embodiment has a slightly small diameter on the opening side, and is further provided with a screw in the part. The container 2 is formed by deep drawing, extrusion, ironing, using aluminum, stainless steel, steel, or the like, injection molding, blow molding, or glass blow molding using a synthetic resin.

  The tip plug 3 is made by injection molding of a synthetic resin or the like. The outer shape is tapered in three stages, and the inside communicates in the longitudinal direction. The internal communication hole 10 is provided coaxially with the container 2. A screw is provided inside the thick side of the tip plug 3. The screw is combined with the screw provided in the container 2 to be integrated. The communication hole 10 has a plurality of protrusions (not shown) for making the center of the writing part 4 coincide with the center of a valve body 15 to be described later and securing a vent hole between the tip plug 3 and the writing part 4. (Omitted) is provided.

  The writing part (pen nib) 4 has a circular cross section and its tip is made of a chip having a convex spherical surface. An example of the type of tip is a tip made of a fiber bundle tip that oozes ink from the tip by capillary action. The chip is made of a fiber such as polyester of 5 to 30 denier, and the fiber bundle surface layer of the chip is impregnated with resin, and the strength is improved by being hardened by forming the resin-impregnated layer.

  The valve 5 is built in the container 2 and the tip plug 3 and includes an exterior member 11, an interior member 12, a valve body 15, and a spring 18. That is, the exterior member 11 has a cylindrical shape as a whole, a flange 20 is provided at the tip, the outer diameter of the portion closest to the flange 20 is equal to the inner diameter of the opening of the container 2, and the other portions are made slightly thinner. ing. The exterior member 11 communicates with the longitudinal direction. That is, the large diameter side of the exterior member 11 is open. An ink reservoir side opening 21 is provided on the small diameter side of the exterior member 11. The inner diameter of the exterior member 11 is small in the vicinity of the reservoir side opening, but is uniform in other parts.

The interior member 12 is configured by a flange 22 and a cylindrical portion 23, and the outer diameter of the flange 22 is equal to the outer diameter of the exterior side of the exterior member 11, and the outer diameter of the cylindrical portion 23 is on the open side of the exterior member 11. Equal to inner diameter. The length of the cylindrical portion 23 is the length from the open side of the exterior member 11 to the vicinity of the middle in the length direction of the exterior member 11.
A bulging portion 13 is formed over the entire inner surface of the end portion of the interior member 12 on the side of the reservoir opening that is not on the flange side.

The valve body 15 has a rod shape, and the vicinity of the central portion is thick to form a conical portion 24, and a substantially uniform rod-shaped portion 17 continues behind the conical portion 24. The rear end of the rod-like portion 17 is sharp. A cylindrical portion 16 is formed on the front side, that is, on the writing portion 4 side so that the reduced diameter portion 14 at the rear end of the writing portion 4 can be inserted and fixed.
In the writing instrument 1 of this embodiment, the conical part 24 and the bulging part 13 of the valve body 15 come into close contact with each other, so that the seal part of the writing part side opening 26 can be sealed.

Next, the assembly structure of the valve 5 will be described. The valve 5 is formed by inserting an interior member 12 inside an exterior member 11. Further, the valve body 15 is inside the exterior member 11 and the interior member 12, the rear end side from the conical portion 24 is in the exterior member 11, and the front end side is further in the interior member 12. That is, in the writing instrument 1 of the present embodiment, the conical portion 24 of the valve body 15 and the bulging portion 13 at the rear end of the interior member 12 are in close contact with each other inside the exterior member 11 and are closed.
The spring 18 is externally mounted on the valve body 15 and always presses the conical portion 24 of the valve body 15 toward the writing portion 4 side. Normally, the conical portion 24 is pressed toward the writing portion 4 by the spring 18, so that the conical portion 24 and the bulging portion 13 are in close contact with each other and the valve 5 is closed.
For this reason, the ink in the valve chamber 25 does not flow toward the writing unit 4.

  The overall assembly structure of the writing instrument 1 of this embodiment is as follows. That is, the valve 5 is inserted into the container from the open end of the container 2, and the flange 20 is in contact with the end surface of the container. A tip plug 3 is attached to the open end of the container 2. The writing portion 4 is slidably inserted into the communication hole 10 of the tip plug 3, the tip portion protrudes outward from the tip plug 3, and the reduced diameter portion 14 at the rear end is in the cylindrical portion 16 of the valve body 15. Has been inserted.

In addition, an ink absorber 27 made of a porous material such as sponge is provided inside the tip plug 3. The ink absorber 27 is formed in a cylindrical shape and is located in the tip plug 3 in contact with the writing portion 4 side of the flange of the interior member 12. The writing unit 4 is slidably inserted in the cylinder of the ink absorber 27.
Furthermore, the container 2 may contain ink and may contain a stirring ball.

The writing part 4 whose outer periphery is coated with resin is provided with a sliding part 28 that slides on the ink absorber 27. As shown in FIG. 5, the sliding part 28 provided in the writing part 4 covers a range of 10 to 50% of the length of the writing part 4, and the sliding part 28 is 3 to 30% of the diameter of the writing part 4. By grinding the writing part 4 to a depth of 5 mm, the resin-impregnated layer is removed and the fiber bundle not impregnated with the internal resin is exposed, or the diameter of the writing part 4 is 3 to 30 as shown in FIG. An uneven portion having a recess having a depth of% is provided, and the fiber bundle is exposed in the recess. The resin-impregnated layer, which is provided on the surface of the writing part 4 and has the role of holding it in a fixed shape, is simultaneously removed when the writing part 4 is ground, so that the concave part impedes the passage of scaly pigments in the ink. No resin layer exists.
Therefore, the ink supplied from the container 2 through the valve chamber 25 and the interior member 12 to the ink absorber 27 facing the sliding portion 28 is a portion where the fiber bundle is exposed together with the scaly pigment contained. The writing portion 4 is impregnated through the ink, and the impregnated ink is written from the tip of the writing portion 4. However, since the strength of the writing part 4 may be lowered if the writing part 4 is ground too much, it is necessary to pay attention to this point.
Here, the concavo-convex portion is provided in an arbitrary shape such as a groove shape or a lattice shape in the length direction or the circumferential direction of the writing portion 4. Further, the rear end of the writing unit 4 is cut to 3 to 30% of its diameter over 10 to 60% of its length, and the reduced diameter portion 14 is made to have a diameter of 70 to 97% before cutting.

  Next, an effect | action of the writing instrument 1 of this embodiment is demonstrated. The state of the writing instrument 1 of the present embodiment at all times, that is, when not writing is shown in FIGS. 1 and 2, the conical portion 24 of the valve body 15 is pushed by the spring 18, and the conical portion 24 is the interior member 12. Is in contact with the bulging portion 13. Therefore, the writing portion side opening 26 of the valve chamber 25 is always closed. Therefore, ink does not flow to the writing part side.

  On the other hand, at this time, the reservoir side opening 21 of the valve chamber 25, which is the rear end side of the valve body 15, is opened. Therefore, the ink reservoir 2 and the valve chamber 25 circulate, and the ink in the ink reservoir 2 can flow into the valve chamber 25.

When the valve body 15 is moved backward by pressing the writing section 4 and sliding the writing section 4 with respect to the ink absorber 27 in use, as shown in FIGS. The close contact of the member 12 with the bulging portion 13 is released. As a result, a space is formed between the conical part 24 and the bulging part 13 and the writing part side opening 26 is opened. Therefore, the ink accumulated in the valve chamber 25 flows out from the writing portion side opening 26 which is sufficiently opened, penetrates into the ink absorber 27, and the uneven portion formed by removing the resin impregnated layer formed in the writing portion 4 is removed. Through filling the exposed part of the fiber bundle such as a recess, the writing part is impregnated and penetrates the entire writing part. A path along which the ink containing the scaly pigment in the present invention flows is indicated by a line A in FIG.
In this case, the ink composition has all of the ink reservoir side opening 21, the writing part side opening 26, the hole of the ink absorber 27, the uneven part provided in the sliding part 28, and the hole of the writing part 4. A size exceeding the size of the scaly pigment is necessary for smoothly supplying the ink to the tip of the writing unit 4.
In the embodiment described above, the valve in which the conical portion 24 is brought into contact with the bulging portion 13 is illustrated as a valve that closes the writing portion side opening 26, but a valve having another structure may be employed.

[Pigment]
The pigment contained in the ink in the present invention is a scaly pigment, such as an interference pigment, a pearl pigment, a metal powder pigment, a metal-coated inorganic pigment, a pigment called a glass flake pigment, and the like. 50 μm, preferably 5 to 30 μm. When the particle diameter is in the range of 3 to 50 μm, the reflected light from the pigment is likely to interfere, and it is excellent in dispersibility as a pigment in the ink and has good writing properties.
Such a scaly pigment is contained in the ink in an amount of 1 to 30 wt%, preferably 3 to 20 wt%. If it is 1 wt% or more, the effect of containing an equiscale pigment that shows interference color in the handwriting appears, and if it is 30 wt% or less, the viscosity of the ink does not become too high, and the ink outflow from the marker, storage stability and Writability does not deteriorate. Moreover, since the scale-like pigments can be prevented from overlapping and tilting, the reflected light can sufficiently exhibit an appearance caused by the scale-like pigments such as interference colors.

As an interference pigment, a metal oxide film such as silicon oxide, titanium oxide, aluminum oxide, iron oxide, nickel oxide is formed on a base material made of at least one selected from aluminum, nickel, titanium, chromium, tin and alloys thereof. By coating two or more layers of films such as chromium oxide and tin oxide, fluorides such as magnesium fluoride, metals such as silver and copper, a pigment whose reflected light is colored by interference on the pigment surface can be used.
Chromashine (Toyo Aluminum) in which a silica layer, a silver layer, and a resin layer are laminated in order on a scaly aluminum powder, and a chroma flare in which a magnesium fluoride layer and a chromium layer are provided in order on a scaly aluminum powder ( JDS UNIPASE Corp.), and further, Chromashine BL20-R, GR20-R, GD20-R, OR20-R, BL10-R, GR10R, GD10-R, BL20-RPA, GR20-RPA, GD20-RPA, OR20-RPA, etc. can be used, and among the above, Chromashine BL20-R, GR20-R, GD20-R, OR20-R, BL20-RPA, GR20-RPA, GD20-RPA OR20-RPA is preferable.

  The pearl pigment is not particularly limited as long as it is excellent in glitter, and the surface of natural mica having a low refractive index, synthetic mica, plate-like silica, or plate-like alumina has a metal oxide or metal nitride having a high refractive index. There are those coated with a metal compound such as, fish scale foil, basic carbonate, bismuth oxychloride, but variochrome (BASF) in which a titanium oxide layer and an iron oxide layer are laminated in order on natural mica or synthetic mica, or Natural mica or synthetic mica coated with a mixed layer metal oxide of titanium oxide and iron oxide (Merck, etc.), Variochrome with a silica layer and an iron oxide layer in order on the surface of a scaly pigment made of aluminum and iron oxide ( BASF) is preferred. Pearl pigments are glossy due to regular multiple reflection on parallel surfaces having different refractive indexes. Commercially available pearl pigments include Iriodin 100 (particle size 10-60 μm, silver color), Iriodin 103 (10-50 μm, silver color), Iriodin 300 (10-60 μm, gold color), Iriodin 302 (5-20 μm, gold color). ), Iriodin 323 (5 to 20 μm, gold), Iriodin 504 (10 to 60 μm, red), Iriodin 524 (5 to 20 μm, red), Iriodin 502 (10 to 60 μm, bronze), Iriodin 520 (5 to 20 μm, (Bronze color) (manufactured by Merck Japan), ULTIMICASB-100 (5-30 μm, silver color), ULTIMICA SD-100 (10-60 μm, silver color), ULTIMARY B-100 ( 5-30 μm, gold), ULTIMICA RYD-100 (10-60 μm, gold) (Nippon Koken Kogyo Co., Ltd.), TAYCAPEARL TP-500 (10-70 μm, silver), TAYCAPEARL TPX-720 ( 7 to 45 μm, silver color) (above, manufactured by Teica). Pearl pigments can be used alone or in combination of two or more.

  As the metal powder pigment, aluminum flakes, stainless steel flakes, etc. can be used, preferably those treated with phosphate ester, phosphate and phosphide, vanadate, chromium dimer acid, dimer acid, etc., coated with resin Can be used.

  The metal-coated pigment is a pigment formed by coating a substrate such as natural mica, synthetic mica, plate-like silica, plate-like alumina or the like with a metal such as aluminum, chromium or silver.

  For example, the glass flake pigment is obtained by coating the surface of a flaky glass with a metal or a metal oxide having a higher refractive index than that of glass. The average particle diameter (longitudinal dimension) of the flaky glass is 1 to 500 μm, and the average thickness is 0.1 to 10 μm. It does not specifically limit as a chemical composition of the flake shaped glass of this embodiment, Several types, such as E glass composition, C glass composition, and A glass composition, are mentioned. The refractive index of the flaky glass is in the range of 1.4 to 1.7 regardless of its chemical composition.

  Examples of the metal coated on the surface of the flaky glass include silver, titanium, nickel, gold, platinum, palladium, cobalt, copper, and alloys thereof. Among these, silver, titanium, nickel, or alloys thereof are preferable because they are excellent in both cost and quality. When the surface of the flaky glass is coated with a metal, the thickness of the coating film is preferably 0.04 to 0.2 μm, and more preferably 0.05 to 0.15 μm. When the thickness of the coating film is less than 0.04 μm, there is a high possibility that sufficient glitter cannot be obtained. On the other hand, when the thickness of the coating film exceeds 0.2 μm, the brightness is not improved for the amount of metal used, and this is not economical.

  On the other hand, as the metal oxide coated on the surface of the flaky glass, one having a refractive index higher than that of glass is used in order to improve the glitter of the oil-based ink composition. As this kind of metal oxide, those having a refractive index of 2.0 to 3.0 are preferable. Specific examples thereof include anatase type titanium dioxide (refractive index: about 2.5), rutile type titanium dioxide (refractive index). Rate: about 2.7), iron oxide (refractive index: about 2.4-2.7), zirconium dioxide (refractive index: about 2.1), and the like. Among these, since it is particularly excellent in chemical durability and cost, either anatase type titanium dioxide or rutile type titanium dioxide is preferable, and rutile type titanium dioxide is most preferable.

  The coating film of the metal oxide is appropriately adjusted depending on the kind of the metal oxide, the required brightness, the interference color, etc., and the thickness is preferably 0.01 to 1 μm, preferably 0.03 to 0 .8 μm is more preferable. When the thickness of the metal oxide coating film is less than 0.01 μm, there is a high possibility that sufficient glitter cannot be obtained. On the other hand, when the thickness of the metal oxide coating film exceeds 1 μm, the glitter is not improved for the amount of metal oxide used, and this is not economical.

  For example, trade names “Metashine REFSX-2015PS”, “Metashine REFSX-2025PS” and “Metashine REFSX-2040PS” manufactured by Toyo Aluminum Co., Ltd. coated with silver can be exemplified.

  Moreover, the glass flake pigment by which flake shaped glass was coat | covered with the metal by sputtering method can also be used. For example, trade names “Crystal Color GF2125”, “Crystal Color GF2125-M”, “Crystal Color GF2140”, and “Crystal Color GF2140-M” manufactured by Toyo Aluminum Co., Ltd. coated with silver are available. In addition, there are trade names “Crystal Color GF2525”, “Crystal Color GF2525-M”, “Crystal Color GF2540”, and “Crystal Color GF2540-M” manufactured by the same company that are coated with nickel, chrome, and molybdenum. The company's product name “Crystal Color GF250” coated with brass, the product name “Crystal Color GF1345” manufactured by the company coated with silver alloy, and the product name “Crystal Color GF1445” manufactured by the company coated with titanium. There is.

In the ink used in the present invention, a known colorant can be blended in addition to the scaly pigment. Examples of such a colorant include dyes dissolved in the ink according to the present invention and dispersion. Possible pigments.
As dyes, various dyes such as basic dyes, direct dyes, and acid dyes can be used. Specifically, phthalocyanine series, quinacridone series, diketopyrrolopyrrole series, halogenated phthalocyanine series, isoindolinone series, azomethine metal The dyes are complex, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, condensed azo, triphenylmethane, quinophthalone, anthrapyrimidine, and the like.
As the pigment, inorganic pigments and organic pigments can be used. For example, titanium oxide, iron oxide, zinc white, cobalt blue, ultramarine, yellow lead, carbon black, phthalocyanine, anthraquinone, azo, quinacridone Etc.

[solvent]
The present invention requires the use of propylene glycol monomethyl ether as a solvent. By using this solvent, propylene glycol monomethyl ether can be present on the surface of the scaly pigment and can be dispersed in the ink in a more stable state. In particular, ester solvents such as n-propyl acetate and ethyl acetate may be used in combination.
However, it is also possible to add other solvents as long as they do not inhibit the dispersion stability. Examples of such solvents include aliphatic spirits such as mineral spirit, hexane, heptane, cyclohexane, and octane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chlorobenzene, trichlorobenzene, perchlorethylene, trichloroethylene, methanol, ethanol, n-propyl alcohol, n-butanol, etc. Alcohols, ketones such as n-propanone and 2-butanone, and glycols such as tetrahydrofuran, diethyl ether, ethylpropyl ether and ethylene glycol monobutyl ether and ethers thereof.

[resin]
The resin blended in the ink of the present invention is, for example, a hydrogenated resin represented by the following formula 2 obtained by hydrogenating a benzophenone type ketone resin represented by the following formula 1.
Formula 1
Formula 2
Specifically, the hydrogenated benzophenone type ketone resin may be VARIPLUS SK (TEGO).
The hydrogenated benzophenone type ketone resin does not cause discoloration or fading during storage over a long period of time, and is very good in color development, and also has excellent adhesion to paper and scratch resistance. In the ink of the present invention, it can be used in the range of 3 to 30 wt%, preferably 4 to 20 wt%. If it is this range, the adhesiveness to paper and water resistance can fully be obtained, preventing generation | occurrence | production of the writing defect by a viscosity rise. Moreover, since the dispersibility of the scaly pigment is excellent as compared with other resins such as a phenol resin, the scaly pigment is uniformly dispersed on the paper even during writing, and a handwriting excellent in glitter is obtained.

In the present invention, benzophenone-type ketone resin VARIPLUS AP (TEGO) can be used in combination with the above-mentioned hydrogenated benzophenone-type ketone resin as long as the effect of using the hydrogenated benzophenone-type ketone resin is not hindered. .
In addition, it is also possible to add various known ink resins. Examples of such resins include alkyd resins, ketone resins, amide resins, rosin modified resins, rosin modified phenol resins, phenol resins, xylene resins, polyvinyl butyral resins, terpene resins, coumarone-indene resins, polyvinyl pyrrolidone, polyethylene oxide, Examples thereof include polymethacrylic acid esters, α- and β-pinene / phenol polycondensation resins, maleic acid resins, acrylic resins, and polyacrylic acid polymethacrylic acid copolymers. One or two or more of these resins can be used.

[Thixotropic agent]
In the present invention, a component called a thixotropic agent or a thixotropy imparting agent can be added to the ink as a component that destroys the temporary network structure by applying a shearing force. Examples of such thixotropic agents include compounds that form a hydrogen bond by having a urea group or the like.
Examples of the thixotropic agent that can be added to the ink in the present invention include urea urethane, modified urea, polyhydroxycarboxylic acid amide, polyhydroxycarboxylic acid ester, urea-modified polyamide, oxidized polyethyleneamide, oxidized polyethylene, and fatty acid amide. . More specifically, BYK-405, BYK-410, BYK-411, BYK-420, BYK-425, BYK-430, BYK-R650, BYK-R606 (above, trade names) of BYK-Chemie Japan Co., Ltd. Yasumoto Kasei's DISPERLON series 4200-20, 4200-10, PF-911, 4401-25X, 4401-25M, NS-30, NS-5010, NS-5025, NS-5210, NS-5310 ( As mentioned above, a brand name) etc. can be illustrated. Among these, one kind can be used alone, or two or more kinds can be used in combination.

[Other ingredients]
In the coating composition and the ink composition of the present invention, a surfactant, a curing agent, or the like, which is usually blended, if necessary, to the extent that various colors of the coating film and excellent glitter are not impaired. Add various additives such as UV absorbers, static eliminating agents, thickeners, coupling agents, plasticizers, dispersants, antioxidants, polishes, synthetic preservatives, lubricants as necessary. Can do.

Example A: Two kinds of “Sakura Paint Marker Middle White” container members incorporating a writing part having a sliding part from which the resin-impregnated layer was removed and a writing part having a sliding part from which the resin-impregnated layer was not removed were prepared. These were filled with the ink composition of Example 3 shown in Table 2 below, and a writing test was conducted under the following conditions. The writing was made to a length of 100 m, and the weight of the ink that flowed out every 4 sections every 25 m was measured.
The writing part was 30 mm in length, of which the reduced diameter part at the rear end was 7 mm in length. FIG. 5 shows a writing part in which a fiber bundle is exposed by grinding and removing a resin-impregnated layer on the surface of the writing part by 0.3 mm at a position in contact with the ink absorber adjacent to the reduced diameter part. In the example shown in Table 1, the writing part of FIG. 5 was used, and in the comparative example, the writing part of FIG. 7 was used.
Writing condition: 7cm / sec
Load: 100gf
Writing angle: 85 °
Unit (g)

When the writing part having the sliding part from which the resin-impregnated layer was removed was provided, the ink weight that flowed out in each section was almost constant and the amount was large, and the ink was not clogged in the writing part. When the writing portion having a sliding portion that does not remove the resin-impregnated layer was provided, the amount of outflow of ink was small, and the amount of outflow after 25 m decreased. This tendency indicates that the ink is clogged at the writing portion.

Example B
Prepare scaly pigment-containing ink compositions having the composition shown in Table 2 below, and fill these ink compositions into "Sakura Paint Marker White" to ensure adhesion, writing properties, glitter, and storage stability. It was measured.
Adhesiveness: ◯ indicates that it does not move even when rubbed, and △ indicates that it does not move.
Writing characteristics: ○, which can be written continuously and stably
The case where blurring occurred midway was marked with x.
Brightness: The one with the same brightness after storage at 50 ° C. for 1 month is the same as the initial value.
The case where the hue and brightness were lowered was marked with Δ.
Storage stability: ○, which does not change color with ink spillage after storage at 50 ° C for 1 month
A case where a hard cake was formed or the amount of ink outflow decreased was indicated by Δ.

In Table 2,
TEGO VARIPLUS SK is a hydrogenated resin made by hydrogenating benzophenone type ketone resin.
TEGO VARIPLUS AP is a benzophenone type ketone resin Chromashine BL 20-RPA, Chromashine GR 20-RPA, Chromashine GD 20-RPA is an interference pigment
BYK-410 is a thixotropic agent. Kumanor # 510 is a phenol resin.

Examples 1 to 3 are examples using a scaly pigment-containing ink composition containing a hydrogenated resin obtained by hydrogenating a benzophenone type ketone resin and blending a thixotropic agent. Writability, glitter and storage stability are all good.
However, depending on Comparative Example 1 which does not contain a hydrogenated resin obtained by hydrogenating a benzophenone type ketone resin and contains a phenol resin, the adhesiveness and glitter are deteriorated. This reflects a decrease in the adhesive strength to the paper surface due to the absence of the hydrogenated resin and a state where Chromashine BL 20-RPA is not sufficiently dispersed.
As in the composition of Comparative Example 2, the ink composition containing a benzophenone type ketone resin without containing a hydrogenated resin obtained by hydrogenating a benzophenone type ketone resin is more adhesive than the Examples. Inferior.
Further, according to the result of Comparative Example 3, when a high concentration of an interference pigment containing a hydrogenated resin obtained by hydrogenating a benzophenone type ketone resin is blended at high concentration, the writing characteristics are deteriorated, and the glitter pigment is randomly formed on the handwriting. As a whole, the brightness is inferior. Furthermore, since the luster pigment is abundant, it is not sufficiently dispersed and storage stability is poor.

DESCRIPTION OF SYMBOLS 1 ... Writing instrument 2 ... Container 3 ... Tip stopper 4 ... Writing part 5 ... Valve 6 ... Cap 10 ... Communication hole 11 ... Exterior member 12 ... Interior member 13 ... bulging part 14 ... reduced diameter part 15 ... valve body 16 ... cylindrical part 17 ... rod-like part 18 ... spring 20 ... flange 21 ... ink reservoir side Opening 22 ... Flange 23 ... Cylindrical part 24 ... Conical part 25 ... Valve chamber 26 ... Writing part side opening 27 ... Ink absorber 28 ... Sliding part

Claims (4)

  In a writing instrument comprising an ink reservoir and a writing part, and a valve connected to the writing part interposed between the writing part and the writing part, the writing part is connected to the writing part by a cylindrical ink absorber installed in a tip stopper. It is supported between the central part in the axial direction and the rear end, and the supported part of the writing part is provided with a concave and convex part having a concave part whose inner surface of the concave part is not covered with resin, A valve body is connected. The valve has a valve body and a valve chamber. The valve chamber is provided with a reservoir-side opening communicating with the ink reservoir and a writing-unit-side opening communicating with the writing unit. The valve body normally closes the writing part side opening, while the reservoir side opening is opened, and when the writing part is pressed, the valve body moves to open the writing part side opening. The reservoir contains a scale-like pigment at a concentration of 1 to 30% by weight and is hydrogenated benzopheno Writing instrument, characterized in that also the type ketone resin ink containing is filled.   The writing instrument according to claim 1, wherein the ink comprises propylene glycol monomethyl ether.   The writing instrument according to claim 1 or 2, wherein the ink contains a benzophenone type ketone resin.   The writing instrument according to any one of claims 1 to 3, wherein the ink contains a thixotropic agent.