Writing instrument

Abstract

To provide a writing instrument which has a visible portion on a pen tip that allows a direction of writing to be visually recognized, and can draw a written line without any difference in density without causing uneven supply of ink to a pen core.SOLUTION: Provided is a writing instrument that supplies an ink composition for a writing instrument housed in a writing instrument body to a pen core of a pen tip, the writing instrument including a visible portion that allows the writing direction to be visually recognized on the pen tip. A porosity of the pen core is 30 to 70%. The ink composition for the writing instrument contains colored resin particles with an average particle diameter of 1 to 10 μm, and has an ink viscosity of 8 to 20 mPa.s. The colored resin particles have a particle size distribution (Mv / Mn) of 1 to 3 and contain at least one association agent selected from group X below; Group X: Methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylethylmethylcellulose, hydroxypropylmethylcellulose.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a writing instrument having a visible portion at the pen tip that allows the writing direction to be visually confirmed, and more specifically, to a writing instrument that can draw written lines without unevenness in the supply of ink to the pen core and without differences in density. [Background technology]

[0002] Conventionally, the pen tips of writing instruments known as paint markers, underline markers, etc. have been equipped with wide pen cores that enable drawing wide lines, and are widely used due to their excellent marking visibility and ease of use. The pen tip of a writing instrument such as a line marker is generally made by imparting capillary action to a porous material such as synthetic resin fibers bundled into a rod shape or a sintered polymer, which allows ink supplied from the shaft, which is the main body of the writing instrument, to be guided to the pen tip, making it possible to write with the ink.

[0003] In addition, with the spread of writing instruments that contain fluorescent ink inside the barrel, which is the main body of the writing instrument, writing instruments with pen tips of many different structures and shapes that enable wide lines to be drawn have become available on the market, allowing users to choose from a wide range of writing instruments to suit their needs and making them more comfortable to use.

[0004] The applicant has disclosed 1) a writing instrument having a writing lead that can guide and retain ink supplied from a shaft body that is the main body of the writing instrument, in which the tip has a visible portion (window portion) that allows the writing direction to be visually confirmed (see, for example, Patent Document 1), and 2) a writing instrument in which the tip has a holder having a writing portion and an ink guide portion for supplying ink to the writing portion, and has a relay porous body for supplying ink contained in the writing instrument body to the ink guide portion provided in the holder, and in which the holder is the visible portion that allows the writing direction to be visually confirmed (see, for example, Patent Document 2). With this type of writing instrument, the characters you write are visible from each visible part of the pen tip, so you can draw lines exactly where you want to check, without going beyond the mark.

[0005] However, in the writing instrument of Patent Document 1, the ink is supplied to the pen core from the ink guide parts on both sides to the writing part, and because the ink flow path is restricted, there are cases where the ink supply is uneven between the outside and center of the writing part of the pen core, causing slight differences in density in the written lines (non-uniformity of density).Also, in the writing instrument of Patent Document 2, the ink is supplied from the ink guide parts to the writing part of the pen core from the center to the outside of the writing part, causing slight differences in density in the written lines (non-uniformity of density). In particular, when the average particle diameter of the coloring material, such as colored resin particles, contained in the ink composition exceeds 1 μm, this tendency is likely to become evident. Furthermore, when an association agent, which is a component that loosely aggregates the coloring material, is contained in the ink composition, this tendency becomes even more pronounced, which is another problem. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2000-52682 A (claims, FIG. 7, etc.) [Patent Document 2] JP 2012-20575 A (Claims, FIG. 3, etc.) Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of the above-mentioned problems with the conventional technology and aims to solve them, and to provide a writing instrument that has a visible part at the pen tip that allows the writing direction to be visually confirmed, and that can draw written lines without unevenness in the supply of ink to the pen tip and without differences in density. [Means for solving the problem]

[0008] As a result of intensive studies to solve the problems of the above-mentioned conventional technologies, etc., the inventors of the present invention supply the ink composition accommodated in the writing instrument body to the pen core at the pen tip, and have a visible part capable of visually recognizing the writing direction at the pen tip. The porosity of the pen core is 30 to 70%, the ink composition for the writing instrument contains colored resin particles having an average particle diameter of 1 to 10 μm, and the ink viscosity is 8 to 20 mPa·s. By setting the particle size distribution of the colored resin particles within a specific range, etc., it has been found that a writing instrument having the above object can be obtained, and the present invention has been completed.

[0009] That is, the writing instrument of the present invention supplies the ink composition for the writing instrument accommodated in the writing instrument body to the pen core at the pen tip, and has a visible part capable of visually recognizing the writing direction at the pen tip. The porosity of the pen core is 30 to 70%, the ink composition for the writing instrument contains colored resin particles having an average particle diameter of 1 to 10 μm, and the ink viscosity is 8 to 20 mPa·s. It is a writing instrument characterized in that the particle size distribution (Mv / Mn) of the colored resin particles is 1 to 3 and contains at least one associating agent selected from the following Group X. <Group X> Methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl ethyl methyl cellulose, hydroxypropyl methyl cellulose It is preferable that the ink pH of the ink composition for the writing instrument is 7 or less. It is preferable that the surface tension of the ink composition for the writing instrument is 30 to 60 mN / m.

Effect of the Invention

[0010] According to the present invention, there is provided a writing instrument capable of drawing lines without density differences without causing unevenness in the supply of ink to the pen core in a writing instrument having a visible portion at the pen tip that allows the writing direction to be visually confirmed. In particular, there is provided a writing instrument capable of drawing lines without density differences even when the size of the colored resin particles blended in the ink composition used exceeds 1 μm in average particle diameter or when the ink composition contains an association agent that is a component that loosely aggregates color materials. [Brief description of the drawings]

[0011] [Figure 1] 1A, 1B, and 1C show an example of an embodiment of a writing implement of the present invention, in which FIG. 1A is a plan view, FIG. [Diagram 2] FIG. 2 is a perspective view of the writing instrument of FIG. 1 with the cap removed. [Diagram 3] 1A, 1B, and 1C show another embodiment of the writing implement of the present invention, where FIG. 1A is a plan view, FIG. [Figure 4] 1A, 1B, and 1C show another embodiment of the writing implement of the present invention, where FIG. 1A is a plan view, FIG. [Diagram 5] 1A and 1B show another embodiment of the writing implement of the present invention, where (a) is a front view and (b) is a longitudinal sectional view. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. 1(a) to (c) are a plan view, a front view, and a vertical sectional view showing an example of an embodiment of a writing implement of the present invention. The writing instrument A of this embodiment is a marking pen type writing instrument, and as shown in Figures 1(a) to (c), it is equipped with a barrel (barrel tube) 10 which forms the main body of the writing instrument, an ink absorbing body 20, a pen tip 30, a pen core 35, a holder 40 having a visible part, a cap 50, and a friction body 60.

[0013] The barrel 10 is formed, for example, from a thermoplastic resin, a thermosetting resin, etc., and as shown in Figure 1(c), has a bottomed, cylindrical rear barrel 11 that houses an ink occlusion body 20 impregnated with an ink composition for a writing instrument, and a front barrel 15 to which is fixed a holder 40 having a visible part to which the pen core 35 of the pen tip 30 is attached. Rear barrel 11 is molded into a bottomed cylindrical shape using a resin such as PP, and functions as the main body (shaft body) of the writing implement. As shown in FIG. 1(c), rear barrel 11 is provided with a retaining member 13 made of retaining pieces 12, 12... that retain the rear end of ink occluder 20 inside the rear end side, and the entire rear barrel and the front barrel described below are molded to be opaque or transparent (and translucent), although either may be adopted from the viewpoint of appearance and practicality. In addition, front barrel 15 is fixed to the front side of rear barrel 11 by fitting or the like. Tip barrel 15 is provided with a fitting portion 16 for fastening holder 40 having a visible portion for fixing pen core 35 of pen tip 30, which will be described later. Tip barrel 15 having this structure is molded from a resin such as PP.

[0014] The ink occlusion body 20 is impregnated with a writing instrument ink composition containing colored resin particles having an average particle diameter of 1 to 10 μm, which will be described later, and includes, for example, fiber bundles made of one or a combination of two or more of natural fibers, animal hair fibers, polyacetal resins, acrylic resins, polyester resins, polyamide resins, polyurethane resins, polyolefin resins, polyvinyl resins, polycarbonate resins, polyether resins, polyphenylene resins, etc., processed fiber bundles such as felt, and porous bodies such as sponges, resin particles, and sintered bodies. This ink occlusion body 20 is contained and held within the writing instrument body 10.

[0015] The pen tip 30 is equipped with a holder 40 having a visible part that holds the pen core 35. As shown in Figures 1 and 2, the holder 40 that holds the pen core 35 fixes the pen core 35 that serves as the writing core and is fixed to the tip opening of the tip barrel 15 of the writing instrument body 10, and has a visible part 41 that allows the writing direction to be visually confirmed, and a holder (not shown) on the tip side of the visible part 41 that holds the tip side (end face) of the pen core 35. A holding groove (not shown) into which the U-shaped pen core 35 is fitted and held is formed on the entire outer circumferential surface of the holder 40 in the longitudinal direction. Furthermore, an air circulation groove 42 is formed in the outer circumferential surface groove of the holder 40 in the longitudinal direction.

[0016] The entire holder 40 thus constructed is made of a hard material, for example, a hard material having visibility, such as a resin having no rubber elasticity. Examples of resins having no rubber elasticity that are visible include PP, PE, PET, PEN, nylon (including amorphous nylon in addition to general nylons such as nylon 6 and nylon 12), acrylic, polymethylpentene, polystyrene, ABS, and other materials having a visible light transmittance of 50% or more, so that characters written in the writing direction can be effectively seen in the visible portion 41. Note that only the visible portion 41 may be made of a material having visibility. Note that the visible light transmittance can be obtained by measuring the reflectance with a multi-light source spectrophotometer (MSC-5N, manufactured by Suga Test Instruments Co., Ltd.). In addition, the holder 40 may be made of one of the above materials, or two or more of them may be used to further improve durability and visibility, and may be molded by various molding methods such as injection molding and blow molding.

[0017] As shown in Figures 1 and 2, the pen core 35 has a generally U-shaped overall configuration and is equipped with ink guide portions 36, 36 and a writing portion 37 that guides ink from the ink guide portions 36, 36. The pen core 35 is made of a porous material because it has good ink outflow properties. For example, the pen core may be made of parallel fiber bundles made of one or a combination of two or more of natural fibers, animal hair fibers, polyacetal resin, polyethylene resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, polyolefin resin, polyvinyl resin, polycarbonate resin, polyether resin, polyphenylene resin, etc., fiber cores made by processing fiber bundles such as felt or resin-processing these fiber bundles, or porous bodies (sintered cores) made by sintering plastic powders of thermoplastic resins such as polyolefin resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, etc. Preferred pen cores 35 are fiber bundle cores, fiber cores, sintered cores, felt cores, sponge cores, and inorganic porous cores, and sintered cores are particularly preferred from the standpoints of deformation moldability and productivity.

[0018] In order to further exert the effects of the present invention, the pen core 35 used in the present invention preferably has a pore size of 30 to 60 μm and a porosity of 30 to 70%. By achieving this predetermined pore size and / or porosity, in combination with the ink properties described below, the effects of the present invention are achieved, that is, the occurrence of less density variation in drawn lines and the occurrence of no liquid leakage. The pen core 20 of this embodiment is a pore size sintered polyethylene powder with an average particle size of 200 μm. It is composed of a sintered core (sintered body) with a diameter of 50 μm and a porosity of 60%. The "average particle size" as defined in the present invention is a D50 value calculated on a volume basis with a refractive index of 1.81 using a particle size distribution analyzer HRA9320-X100 (manufactured by Nikkiso Co., Ltd.). The "porosity" is calculated as follows. First, a pen core with a known mass and apparent volume is immersed in water until it is fully saturated with water, and then the weight is measured after it is removed from the water. The volume of water that has soaked into the pen core is derived from the measured mass. The porosity is calculated from the following formula (A) by assuming that this volume of water is the same as the pore volume of the pen core. Porosity (unit: %) = (volume of water) / (apparent volume of pen core) x 100 ……(A) The "pore size" was determined by measuring the pore size distribution using a mercury porosimeter (Pore Master GT model, manufactured by QUANTACHROM), and the average value was taken as the pore size.

[0019] The pen core 35 having the above characteristics is preferably subjected to a hydrophilic treatment using a surfactant. For example, the hydrophilic treatment may be a method of treating the pen core with a solution containing a surfactant. The surfactant may be at least one of anionic surfactants such as alkyl carboxylates, alkyl sulfates, and alkyl phosphates, cationic surfactants such as aliphatic ammonium salts, and nonionic surfactants such as (polyoxyethylene) alkyl ethers, (polyoxyethylene) fatty acid ester ethers, and (polyoxyethylene) sorbitan fatty acid esters.

[0020] Moreover, in order to ensure a sufficient writing flow rate, the length of the pen core 35 in the width direction of the present embodiment is preferably 0.50 mm or more, and particularly preferably 1.00 to 3.00 mm. Writing portion 37 is inclined (knife cut) so as to provide an inclination that makes writing easy, and this inclination, etc. is appropriately set according to ease of use for writing, etc. Furthermore, writing portion 37 is desirably a writing portion that draws thick lines, preferably a line width of 1 mm or more, and more preferably a line width of 2 mm or more. In this pen tip 30, the pen core 35 is fixed (attached) to the holder 40 by fitting the pen core 35 into a holder or the like (not shown). Furthermore, to ensure the fixation (prevention of the pen core 35 from falling out), adhesion with an adhesive, welding, or the like may be further used.

[0021] When holder 40 having pen core 35 of the above-described configuration fixed thereto is inserted into front barrel 15, fitting portion 40a of holder 40 fits into fitting portion 16 of front barrel 15, whereby pen core 35 is attached (fixed) to writing instrument barrel body 10 via holder 40, and the rear end portions 36a, 36b of ink guide portions 36, 36 of pen core 35 are configured to fit inside the tip side of ink occlusion body 20. In this embodiment, the rear ends of the ink guide parts 36, 36 have different lengths, with one being a short rear end 36a and the other being a long rear end 36b, and the insertion lengths are different. This is because the pen core 35 has a generally U-shaped overall shape before being attached to the holder 40, but since the writing part 37 is inclined when attached to the holder 40, the lower (or upper) rear end 36b (or 36a) is longer and enters the inside of the tip side of the ink occluder 20 after attachment. In addition, since the insertion lengths are different, ink is taken in from the ink occluder 20 at different locations, and therefore ink is taken in by the pen core 35 more efficiently than when the insertion lengths are the same. Note that recesses may be formed inside the tip side of the ink occlusion body 20, into which the rear end portions 36a, 36b of the ink guide portions 36, 36 are inserted. When the pressure inside the barrel 10 increases, ink drips from the pen tip, but in the writing instrument A of this embodiment, as shown in Figure 2, the air circulation groove 42 regulates the air flow between the inside of the barrel 10 and the outside air.

[0022] Cap 50 is removably attached to the outer peripheral surface of the tip end of front barrel 15 by fitting or the like. The friction body 60 is fixed to the rear end of the rear barrel 11, and when thermochromic colored resin particles are used as the colored resin particles of the ink composition for a writing instrument described later, the thermochromic drawn line (handwriting or image) can be reliably thermochromed (discolored or changed to another color) only in the area that is desired to be thermochromed. The elastic material constituting the friction body 60 includes synthetic resins (rubber, elastomer) having elasticity, such as silicone resin, SBS resin (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene copolymer), fluorine-based resin, chloroprene resin, nitrile resin, polyester-based resin, olefin-based resin, ethylene propylene diene rubber (EPDM), silicone rubber, nitrile rubber, styrene-based elastomer, olefin-based elastomer, polyester-based elastomer, or a mixture of two or more of these. This friction body 60 is preferably formed from the above-mentioned synthetic resin (rubber, elastomer) having a pencil line erasability (erasability rate) of less than 70% as specified in JIS S 6050-2002, thereby making it possible to provide a friction body that easily generates frictional heat through rubbing action and has low wear.

[0023] In the writing instrument A of the present invention, ink occlusion body 20 which occludes an ink composition for a writing instrument, as described below, is inserted and held in rear barrel 11 which constitutes barrel body 10 of the writing instrument, and then front barrel 15 and holder 40 having visible part 41 to which pen core 35 is fixed by fitting or the like are sequentially fixed by fitting or the like, whereby writing instrument A can be easily produced. The ink composition for a writing instrument occluded in ink occlusion body 20 is efficiently supplied to writing part 37 of pen core 35 by capillary force, and is used for writing.

[0024] The ink composition for a writing instrument occluded in the ink occluder 20 contains at least colored resin particles having an average particle size of 1 to 10 μm. The colored resin particles that can be used are not particularly limited as long as they are composed of colored resin particles, and examples thereof include: 1) colored resin particles in which a colorant consisting of a pigment such as an inorganic pigment such as carbon black or titanium oxide, or an organic pigment such as a phthalocyanine pigment or an azo pigment is dispersed in the resin particles; 2) colored resin particles in which the surfaces of the resin particles are coated with a colorant consisting of the above-mentioned pigment; 3) colored resin particles in which a colorant consisting of a dye such as a direct dye, an acid dye, a basic dye, a food dye, or a fluorescent dye is dyed onto the resin particles; 4) colored resin particles that have been made thermochromic using a leuco dye or the like; and 5) colored resin particles that have been made photochromic using a photochromic dye (compound), a fluorescent dye, or the like that serves as a photochromic dye. The resin component of the colored resin particles 1) to 3) above may be, for example, at least one selected from polymers or copolymers of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, styrene, acrylonitrile, butadiene, etc., benzoguanamine, phenolic resins, epoxy resins, urethane resins, etc., which may be subjected to crosslinking or other treatments as necessary. As a method for coloring these resins, conventionally known techniques such as suspension polymerization and dispersion polymerization are used.

[0025] Examples of the thermochromic colored resin particles of 4) above include thermochromic colored resin particles produced by microencapsulating a thermochromic composition containing at least a leuco dye which is an electron-donating dye and functions as a color former, a color developer which is a component capable of causing the leuco dye to develop color, and a color change temperature regulator which can control the color change temperature in the color development of the leuco dye and the color developer, so as to have a predetermined average particle size. Examples of the microencapsulation method include, for example, interfacial polymerization, interfacial polycondensation, insitu polymerization, liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melting dispersion cooling, air suspension coating, spray drying, etc., and can be appropriately selected according to the application. For example, in the phase separation method from an aqueous solution, the leuco dye, developer, and discoloration temperature regulator are heated and melted, then put into an emulsifier solution, heated and stirred to disperse in oil droplets, and then, as the capsule membrane agent, a resin raw material whose wall membrane is a urethane resin, epoxy resin, amino resin, etc. is used, for example, an amino resin solution, specifically, each liquid such as a methylolmelamine aqueous solution, a urea solution, and a benzoguanamine solution is gradually put in, and then reacted to prepare, and then the dispersion is filtered to produce a thermochromic colored resin particle made of a thermochromic microcapsule pigment. In this thermochromic colored resin particle, the type and amount of the leuco dye, developer, and discoloration temperature regulator can be suitably combined to set the color development temperature and decolorization temperature of each color to a suitable temperature. The thermochromic colored resin particles are preferably ones that exhibit reversible thermochromicity. The ones that exhibit reversible thermochromicity may be of various types, such as a thermal decolorization type that is decolorized by heating from a colored state, a color memory retention type that alternately retains a colored state or a decolored state in a specific temperature range, or a thermal color development type that develops color from a decolored state by heating and returns to the decolored state by cooling from the colored state, either alone or in combination.

[0026] Examples of the photochromic colored resin particles of 5) above include photochromic colored resin particles composed of at least one selected from photochromic dyes (compounds), fluorescent dyes, etc., and resins such as terpene phenol resins, and photochromic colored resin particles produced by microencapsulating a photochromic composition containing at least one selected from photochromic dyes (compounds), fluorescent dyes, etc., an organic solvent, and additives such as antioxidants, light stabilizers, and sensitizers, so as to have a predetermined average particle size. The microencapsulation method can be similar to the preparation of the above-mentioned thermochromic resin particles. By suitably using photochromic dyes (compounds), fluorescent dyes, etc., the photochromic colored resin particles can be made to have the property of being colorless in indoor lighting environments (indoor lighting fixtures selected from incandescent lamps, fluorescent lamps, lamps, white LEDs, etc.) and coloring in ultraviolet irradiation environments (irradiation with light of 200 to 400 nm wavelength, or irradiation with sunlight containing ultraviolet rays). Among the above colored resin particles, hollow resin particles having voids inside the particles can be used as white pigments, and the above colored resin particles 1) to 5) can be used as fluorescent pigments, microencapsulated pigments of thermochromic pigments and photochromic pigments (coloring materials), etc. In addition, the above resin particles 1) to 5) can be resin particles manufactured by known manufacturing methods, and if commercially available products are available, they may be used.

[0027] These colored resin particles have an average particle size of 1 to 10 μm, preferably 1 to 5 μm, in order to obtain sufficient coloring power and to exert the effects of the present invention. If the average particle size of the colored resin particles is less than 1 μm, the coloring power will be insufficient, while if it exceeds 10 μm, the flowability from the pen core will be poor and the dispersion stability will decrease, which is undesirable.

[0028] In the present invention, it is important that the colored resin particles used have a certain size (within the above-mentioned range of average particle size) as described above. In the present invention, it is preferable to use colored resin particles having the above average particle size and having a certain degree of flexibility, since this prevents flow from being impeded even inside the pen core, where the voids are prone to change (the porosity is high), and also makes it less likely that concentration differences will occur. The colored resin particles having the above average particle size preferably have a 10% strength of 30 MPa or less as measured by a microcompression test. This allows the colored resin particles to be soft particles, which do not impede flow inside the pen core with the above characteristics and are less likely to cause concentration differences. Furthermore, if the 10% strength is 5 MPa or more, the ink can flow out more stably. That is, by setting the 10% strength to be 5 to 30 MPa, it is possible to highly achieve both good ink outflow stability and drawn lines without density differences. In the present invention, the "microcompression test" can be carried out using, for example, MCT-510 manufactured by Shimadzu Corporation. In this case, the average value of five particles can be used. This 10% strength can be calculated using the following formula. C(x) = (2.48 × P) / (π × d2) C(x): 10% strength (MPa) P: Test force at 10% displacement of particle diameter (N) d: Particle diameter (mm)

[0029] The content of these colored resin particles is preferably 3 to 30% and more preferably 10 to 30% of the total amount of the ink composition. If the content of these colored resin particles is less than 3%, a preferable line density cannot be obtained, and if it exceeds 30%, the writing feel becomes heavy and the drawn lines are prone to smearing, which are undesirable.

[0030] The ink composition for writing instruments used preferably contains an association agent. When the colored resin particles having a large average particle size are used, color separation due to color material settling over time is likely to occur. When an association agent is used, this is suppressed, but the problem of concentration difference is likely to occur. In the present invention, even if an association agent is contained, the ink viscosity, etc. described below is adjusted, and further, a pen core having the above characteristics is used, so that the effects of the present invention can be achieved to a high degree. Examples of the association agent that can be used include at least one of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl ethyl methyl cellulose, and hydroxypropyl methyl cellulose. Hydroxyethyl cellulose is particularly preferred because of its good particle association properties. Of these, it is preferable that the viscosity of a 2% by weight aqueous solution is 7 mPa·s or more and 1000 mPa·s or less. If the viscosity of the 2% by weight aqueous solution exceeds 1000 mPa·s, the ink flowability decreases. On the other hand, if the viscosity of the 2% by weight aqueous solution is too low, the effect cannot be obtained. The content of these association agents is preferably 0.1 to 1% based on the total amount of the ink composition, depending on the above aqueous solution viscosity.

[0031] The ink composition for a writing instrument used contains, in addition to the colored resin particles and association agent having the above-mentioned characteristics, water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as the solvent as the remainder, and further may contain, as appropriate, optional components such as a water-soluble organic solvent, a thickener, a preservative or antibacterial agent, a water-soluble resin, a resin emulsion, etc., within a range that does not impair the effects of the present invention. 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, as well as ethylene glycol monomethyl ether and diethylene glycol monomethyl ether, which can be used alone or in combination.

[0032] The usable thickener is preferably at least one selected from the group consisting of synthetic polymers and polysaccharides, specifically, gum arabic, tragacanth gum, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, diutan gum, dextran, starch glycolic acid and its salts, propylene glycol alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyacrylic acid and its salts, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinylpyrrolidone, crosslinked acrylic acid polymer and its salts, non-crosslinked acrylic acid polymer and its salts, styrene acrylic acid copolymer and its salts, etc. Examples of preservatives or antibacterial agents include phenol, sodium omadine, sodium benzoate, and benzimidazole compounds. Examples of water-soluble resins include polyacrylic acid, water-soluble styrene-acrylic resin, water-soluble styrene-maleic acid resin, water-soluble maleic acid resin, water-soluble styrene resin, polyvinylpyrrolidone, polyvinyl alcohol, water-soluble ester-acrylic resin, ethylene-maleic acid copolymer, polyethylene oxide, water-soluble urethane resin, and the like. Examples of the resin emulsion include acrylic emulsion, vinyl acetate emulsion, urethane emulsion, styrene-butadiene emulsion, and styrene-acrylonitrile emulsion. These water-soluble resins and resin emulsions can be used alone or in combination of two or more.

[0033] To produce this ink composition for writing instruments, a conventionally known method can be adopted, and for example, the ink composition can be obtained by blending predetermined amounts of the above-mentioned components in addition to the colored resin particles having the above average particle size, and stirring and mixing them with a stirrer such as a homomixer or a disperser. Furthermore, if necessary, coarse particles in the ink composition may be removed by filtration or centrifugation.

[0034] In the present invention, the pH of the ink composition for a writing instrument used is preferably 5.0 to 8.0, more preferably 7.0 or less, from the viewpoint of ink stability and, when an association agent is blended, from the viewpoint of more effectively exerting the effect of the inclusion of an association agent by adjusting the pH to a specific value. The pH can be adjusted, if necessary, by using a pH adjuster, such as an alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, an amine compound, such as triethanolamine, diethanolamine, monoethanolamine, dimethylethanolamine, morpholine, or triethylamine, or ammonia.

[0035] The viscosity of the ink composition for a writing instrument used is preferably 8 to 20 mPa·s at 25° C. and a shear rate of 192 / s using a Complate type viscometer, in order to further stabilize the colored resin particles having the above average particle size. This viscosity range can be adjusted by adjusting the amounts of each of the ink components, thickeners, and the like. In order to more effectively achieve a line drawn without density difference and to prevent strike-through, the ink composition for a writing instrument used preferably has a surface tension of 30 to 60 mN / m, more preferably 30 to 45 mN / m at 25° C. The surface tension can be adjusted by adjusting the amounts of the components constituting the ink, the inclusion of a thickener, etc.

[0036] The particle size distribution (Mv / Mn) of the colored resin particles in the ink composition for a writing instrument used must be 1 to 3, and preferably 1 to 2, in order to uniformize the particle fluidity inside the pen core and thereby prevent concentration differences. The volume average particle diameter (Mv) and number average particle diameter (Mn) of the colored resin particles can be measured using a particle size distribution measuring device HRA9320-X100 (manufactured by Nikkiso Co., Ltd.) In addition, the particle size distribution (Mv / Mn) can be calculated from the measured values ​​of Mv and Mn.

[0037] In addition, the contact angle between the ink composition and the polyethylene terephthalate film is preferably 10 to 70°, and more preferably 20 to 40°, from the viewpoint of wettability between the ink and the pen core and prevention of ink dripping. In order to achieve this contact angle, the amounts of the various components constituting the ink, the inclusion of a thickener, etc. can be adjusted.

[0038] The ink composition for a writing instrument thus constituted is prepared into, for example, a colored resin particle pigment ink, a fluorescent ink, a thermochromic ink, or the like, depending on the above-mentioned colored resin particle species. In this embodiment, the ink occlusion body 20 is impregnated in such a manner that both end faces (front side, rear side) of the ink occlusion body 20 are not impregnated, as shown in FIG. 1(c) (the impregnated portion is indicated by the reference symbol I in the figure). In this embodiment, the impregnated volume of the ink occluder 20 is 80% of the total volume. This is to prevent ink scattering due to impact such as dropping. The impregnated volume of the ink occluder 20 may be in a form (illustrated symbol I) in which both end faces (front side, rear side) of the ink occluder 20 are not impregnated, and if the impregnated volume is 60 to 95% of the total volume, it is possible to highly simultaneously prevent ink scattering due to impact such as dropping and efficiently supply ink to the ink guide core 45. The ink composition for impregnation in this embodiment has a compounding composition using the above-mentioned colored resin particles.

[0039] The writing instrument A of the present invention comprises an ink absorbing body 20 which absorbs the writing instrument ink composition having the above-mentioned physical properties and is inserted and held within the barrel 10 of the writing instrument, and the tip side of the writing instrument A can be easily produced by sequentially fixing, by fitting or the like, a holder 40 having a visible part 41 to which a pen core 35 of the above-mentioned configuration is fixed via a tip barrel 15, and the ink absorbed in the ink absorbing body 20 is efficiently supplied by capillary force to the writing part 37 of the pen core 35 of the pen tip 30, and is used for writing (making marks, etc.).

[0040] As described above, the writing instrument A of the present invention supplies the writing instrument ink composition contained in the writing instrument body 10 to the pen core 35 of the pen tip 30, and has a visible part 41 on the pen tip 30 through which the writing direction can be visually confirmed, and the porosity of the pen core 35 is 30 to 70%, the ink composition contains colored resin particles with an average particle diameter of 1 to 10 μm, the ink viscosity is 8 to 20 mPa·s, and the particle size distribution (Mv / Mn) of the colored resin particles is 1 to 3. This makes it possible to obtain a writing instrument that can draw written lines without density differences without causing uneven ink supply between the outside and center of the writing part 37 of the pen core 35. In particular, even if the colored resin particles contained in the ink composition used are large, exceeding 1 μm in average particle diameter, or contain an association agent that is a component that loosely aggregates color materials, it is possible to draw written lines without density differences. Furthermore, the colored resin particles having the above average particle size preferably have a 10% strength of 5 to 30 MPa as measured by a microcompression test, and the ink composition has properties such that the viscosity, surface tension, and pH fall within the above-mentioned respective ranges, thereby making it possible to further enhance the effects of the present invention. In addition, this type of writing implement A has a maximized area of ​​the visible part 41, and the written characters can be seen from the visible part 41 of the pen tip 30, so that lines can be drawn exactly on the parts you want to check without going beyond the line. Furthermore, in this writing instrument A, a friction body 60 is fixed to the rear end of the rear barrel 11 of the writing instrument body 10, and the ink composition is a compounded formulation using thermochromic colored resin particles, so that a thermochromic line (handwriting or image) drawn with the writing part 37 can be reliably thermochromed (discolored or changed to another color) by the friction body 60 (by generating frictional heat through a rubbing action) in only the parts that are desired to be thermochromic.

[0041] The writing instrument of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the technical concept of the present invention. Figures 3 to 5 are drawings showing other embodiments of the writing instrument of the present invention. The same components as those in Figures 1 and 2 are indicated by the same reference numerals and their explanations are omitted. The ink composition used in each of the writing instruments in Figures 3 to 5 is the same as that used in the writing instrument A of the above embodiment. Writing instrument B of the embodiment in Fig. 3 differs only in that a friction body 60 is fixed to the top of a cap 60, and is used in the same manner as writing instrument A, and exerts the same effects and the like as writing instrument A. In this writing instrument B, a thermochromic drawn line (handwriting or image) drawn with the writing part 37 of the pen core 35 can be reliably thermochromed (discolored or changed to another color) by the friction body 60 fixed to the top of the cap 50 (by generating frictional heat by a rubbing action) in only the part to be thermochromic. The writing instrument C of the embodiment in FIG. 4 has a friction body 60 fixed to the rear end of the rear barrel 11 and a friction body 60 fixed to the top of the cap 60 (the friction body 60 is fixed at two points), and is used in the same manner as the above-mentioned embodiments, and exerts the same effects as those of the above-mentioned writing instruments A and B.

[0042] Figure 5 shows a writing instrument D that differs from the writing instruments A to C in Figures 1 to 4 in terms of the ink supply mechanism to the writing part and the shape of the visible part. Below, the configuration and other aspects that differ from the writing instrument A of the above embodiment will be mainly described. This writing instrument D is an embodiment of a writing instrument in which the pen tip 30 is provided with a porous body 38 which serves as the writing part, an ink guide wick 45 which holds the porous body 38 and supplies the writing instrument ink composition to the writing part 38, and the ink guide wick 45 is provided inside a holder 70, and the holder 70 is a visible part which allows the writing direction to be visually confirmed. The writing instrument D of this embodiment is a marking pen type writing instrument, and as shown in Figures 5(a) and (b), it comprises a flat barrel tube 10 with an elliptical cross-section which forms the main body (barrel) of the writing instrument, an ink absorbing body 20, a pen tip 30, and an ink guide core 45. The barrel 10, which is the main body of the writing instrument, and the ink occlusion body 20 are configured in the same manner as in the above-mentioned writing instrument A, so the same reference numerals are used and their explanations are omitted. Furthermore, the ink composition for a writing instrument occluded in the ink occlusion body 20 is also the same as the ink composition for a writing instrument described in detail in the above-mentioned embodiment, so its explanation is omitted.

[0043] The ink guide core 45 serves as an intermediate core that directly supplies ink from the ink occluder 20 to the porous body 38 that serves as the writing part fixed to the holder 70 of the pen tip 30, which will be described later, and is structured to be fitted into the insertion part 21 on the front side of the ink occluder 20. This ink guide core 45 has continuous pores (flow paths) such as a fiber bundle core obtained by processing a fiber bundle such as a fiber bundle or a fiber bundle such as felt, a hard sponge, a resin particle porous body made of a resin particle sintered body, or a sliver core, as in the ink occluder 20. There are no particular limitations on the shape, structure, etc., of the ink guide core 45, so long as the ink impregnated in the ink occluder 20 can be supplied via the ink guide core 45 to the porous body 38 that serves as the writing part fixed to the holder 70, which will be described later. The cross-sectional shape of this ink guide core 45 can be, for example, a circle, an ellipse, a square, a rectangle, a trapezoid, a parallelogram, a diamond, other square shapes, a semi-cylindrical shape, a half-moon shape, etc., and preferably the shape of the ink guide core 45 is such that the visible side, where the writing direction can be seen, is the same as or smaller than the side surfaces, and more preferably the shape is a rectangular parallelepiped or elliptical, which can ensure the flow rate of ink without impeding the visibility of the ink guide section 75.

[0044] As shown in Figures 5(a) and (b), the pen tip 30 comprises a porous body 38 which constitutes the writing portion (pen core), and a holder 70 which holds the porous body 38 and has a cylindrical ink guide portion 75 in which the ink guide core 45 is disposed for supplying ink to the writing portion, and a main body portion 71 which has a cylindrical portion into which the ink guide core 45 is inserted is connected to the holder 70 at the rear side. A flange portion 72 is provided on the outer peripheral surface of this main body portion 71, and the rear side of the main body portion 71 is fixed by fitting into the tip opening of the front barrel 15, thereby providing a structure that further prevents the ink guide core 45 from shifting or falling off due to being dropped, etc. The porous body 38 that forms the writing part is fixed to the tip of the holder 70, and is similar to the pen core 30 described in detail in the embodiment of the writing instrument A above (porosity of 30 to 70%), so its description is omitted. The shape of the porous body 38 that becomes the writing part may be, for example, a chisel shape, a bullet shape, a cylinder, an elliptical cylinder, a cube, a rectangular parallelepiped, or the like in appearance, or a trapezoid, a parallelogram, a diamond, a semi-cylindrical, a half-moon, or the like in cross section. In this embodiment, the porous body 38 is chisel-shaped. The chisel shape is a shape in which the tip forms an inclined surface with respect to the center line of the pen shaft, and the inclined surface is flat. In addition, the porous body 38 that becomes the writing part is preferably inclined at an angle of 40 to 90 degrees with respect to the long axis direction of the main body shaft so that writing is easy, and in this embodiment, it is inclined at 75 degrees. The shape, inclination, etc. of the porous body 45 that becomes the writing part are appropriately set according to the ease of use for writing, etc. In addition, the porous body 45 that becomes the writing part is a writing part that has a thick line width, preferably a line width of 2 mm or more, more preferably a line width of 3 mm or more.

[0045] The holder 70 has at least one ink guide section 75 inside for supplying ink to the writing section, and in this embodiment, one ink guide section 75 is arranged penetrating approximately the center in the longitudinal direction in order to maximize the area ratio of the visible section and to efficiently supply ink to the porous body that forms the writing section. The shape, size, number, etc. of this ink guide portion 75 can be appropriately selected as long as the ink composition impregnated in the ink absorbing body 20 contained in the writing instrument body can be efficiently supplied with ink by capillary action to the porous body 38 which constitutes the writing portion via the main body portion 71 having the above-mentioned cylindrical portion and the ink guide wick 45 arranged within the ink guide portion 75. In particular, in order to ensure a sufficient writing flow rate for the ink guide core 45 and visibility through the ink guide portion 75, it is desirable that the length in the axial direction of the ink guide portion 75 be 3 mm or more. Also, it is desirable that the total cross-sectional area of ​​the ink guide portion 75 inside the holder 70 be 3 mm2 or more. The shape of this ink guide portion 75 is preferably straight toward the writing portion 38, which is the long axis direction, but may be tapered. Also, it may be oriented at an angle of 0 to 30° relative to the long axis of the main body shaft, and may be two or more lines, but it is preferable that only one line is provided.

[0046] In this embodiment, there is a gap 73 between the ink guide core 45 and the ink guide portion 75, and with the gap 73 formed, the ink guide core 45 is connected to the porous body 38 that serves as the writing portion. This allows the ink to be filled from the gap 73, and by combining the ink supply from the ink guide core 45 and the ink supply from the capillary action (direct liquid action) of the gap 73, the remaining ink amount can be visually confirmed, and writing can be continued for a while even if the ink runs out, resulting in a configuration that allows the pen to have a clean appearance, ensures stable quality, and also ensures an escape route for air. Furthermore, the ink guide core 45 may be in a tightly sealed state (sealed) within the ink guide portion 70 without forming a gap between the ink guide core 45 and the ink guide portion 75. Even in this case, the appearance can be made clean, and the ink in the ink occlusion body 20 can be efficiently supplied in an appropriate amount to the porous body 38, which is the writing portion fixed to the holder 70 of the pen tip 30.

[0047] The entire structure of the holder 70, other than the ink guide section 75 in which the ink guide core 45 is arranged, forms the visible section, and its four outer surfaces (front, back, and each side) are approximately parallel to enable effective visual confirmation of the writing direction. Furthermore, ribs 76, 76 (one side not shown) which hold the porous body 38 serving as the writing part are provided on both side surfaces of the upper side of the holder 70, and a bottom surface portion 77 which abuts against the bottom surface of the porous body 38 is provided between the ribs. An outlet of the ink guide portion 75 is formed in the center of this bottom surface portion 77. Furthermore, an abutment portion 78 which the front end surface of the porous body 38 abuts against is provided on one end surface of the rib body, and the other end surface serves as an entrance for inserting the porous body 38.

[0048] The holder 70 including the main body 71 is made of a material having visibility, such as polypropylene, polyethylene, PET, PEN, nylon (including amorphous nylon in addition to general nylons such as nylon 6 and nylon 12), acrylic, polymethylpentene, polystyrene, ABS, etc., and is preferably made of a material having a visible light transmittance of 50% or more. In order to achieve even better visibility, a visible light transmittance of 80% or more will provide even better visibility. The holder 70 can be made of one of the above materials, or two or more materials from the viewpoint of further improving durability and visibility. When made of two or more materials, it is preferable that at least one of them is made of a material having a visible light transmittance of 50% or more, and it can be molded by various molding methods such as injection molding and blow molding.

[0049] In the writing instrument D of this embodiment, which is configured in this manner, the ink guide section 75 is located approximately in the center of the holder 70, and an ink guide wick 45 impregnated with ink is disposed within the ink guide section 70. This allows the ink composition impregnated in the ink occluder 20 to be efficiently supplied by capillary action to the porous body 38, which constitutes the writing section, via the ink guide wick 45. Furthermore, by disposing the ink guide wick 45 in the ink guide section 70, assembly is made easier, and even if a particularly strong impact is applied, such as when the writing instrument is dropped, the ink guide wick 45 can be prevented from shifting or falling off due to the fixation caused by the engagement of the holder 70, and ink smears can be prevented. As described above, the writing instrument D supplies the ink composition for the writing instrument contained in the writing instrument body 10 to the porous body 38 that serves as the pen core of the pen tip 30, and has a holder that allows the writing direction to be visually confirmed at the pen tip 30, and the porosity of the porous body that serves as the pen core is 30 to 70%, the ink composition contains colored resin particles with an average particle diameter of 1 to 10 μm, the ink viscosity is 8 to 20 mPa·s, and the particle size distribution (Mv / Mn) of the colored resin particles is 1 to 3. This makes it possible to obtain a writing instrument that can draw written lines without density differences without causing uneven ink supply between the center and the outside of the porous body 38, as with the writing instruments A to C. In particular, even if the colored resin particles contained in the ink composition used are large, with an average particle diameter exceeding 1 μm, or contain an association agent that is a component that loosely aggregates color materials, it is possible to draw written lines without density differences. Furthermore, the colored resin particles having the above average particle size preferably have a 10% strength of 5 to 30 MPa as measured by a microcompression test, and the ink composition has properties such that the viscosity, surface tension, and pH fall within the above-mentioned respective ranges, thereby making it possible to further enhance the effects of the present invention in the writing instrument D.

[0050] In addition, with this type of writing instrument D, the entire holding body 70 except for the ink guide core 45 is a visible part, and the written characters can be seen from the holding body 70 of the pen tip 30, so that lines can be drawn exactly in the areas you want to check without going beyond the line. Furthermore, in this writing instrument D as well, the friction body 60 is fixed to the rear end of the rear barrel 11 of the writing instrument body 10, and the ink composition is formulated using thermochromic colored resin particles, so that the thermochromic lines (handwriting or images) drawn with the writing part 38 can be reliably thermochromed (discolored or changed to another color) by the friction body 60 (by generating frictional heat through a rubbing action) in only the areas that are desired to be thermochromic. In particular, by forming the ink guide portion 75 in the approximate center of the length of the holder 70, ink can be supplied to the porous body 38, which is the writing part, efficiently and without bias, and a writing instrument that can be used until the end is provided. Also, by forming the ink guide portion 75 in the approximate center of the length of the holder 70, it is easy to determine the writing direction, and a shape that is very easy to write with is obtained. Furthermore, by providing the ribs 76, 76 on the upper part of the holder 70, when writing with a ruler, it is possible to draw straight lines without soiling the ruler.

[0051] The writing instrument of the present invention is not limited to the above-described embodiments, and can be modified in various forms without departing from the gist of the present invention. In the writing instruments A to D of the above embodiments, the barrel of the writing instrument body is formed into a circular or elliptical shape, but it may be formed into an irregular shape such as a triangular shape or a square shape with more than four sides. In the above embodiments, the pen cores 35, 38 have been described in detail as being of the sintered core type. However, other than the sintered body, as mentioned above, the pen cores may be fiber bundles, fiber cores, foams, sponge bodies, felt bodies, and the like. Furthermore, in each of the above embodiments, a writing instrument is shown that uses capillary force to efficiently supply ink absorbed in the ink absorbing body 20 to the writing portions of the pen cores 35, 38 (filled type), but the writing instrument may also be equipped with a valve mechanism, for example, an ink chamber containing ink directly inside the barrel body that forms the main body of the writing instrument, a valve mechanism is provided between the ink chamber and the writing core, and the valve rod is retracted against the spring force of the valve mechanism by pressing toward the pen tip, releasing the valve portion and allowing the ink to be drawn out, thereby supplying ink to each pen core having the above-mentioned physical properties. In addition, in the writing instrument D of the above embodiment, ink is supplied from the ink absorbing body 20 to the porous body 38 that forms the writing part using a single component, the ink guide core 45. However, ink may also be supplied from the ink absorbing body 20 to the porous body 38 that forms the writing part using two components, for example, an intermediate porous body from the ink absorbing body 20 to the tubular part 73a, and an ink supply core similar to the ink guide core inside the ink guide part 75. EXAMPLES

[0052] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0053] [Examples 1 to 6 and Comparative Examples 1 to 3] An ink composition for a writing instrument containing colored resin particles having the composition shown in Table 1 below was prepared by a conventional method. The colored resin particles used were thermochromic and photochromic, and were those obtained in the following Production Examples. The average particle size, 10% strength, pH, viscosity (mPa·s), particle size distribution (Mv / Mn), surface tension (mN / m), and contact angle (°) of the obtained colored resin particles were measured by the following methods.

[0054] (Method of measuring average particle size) This is the D50 value measured using HRA9320-X100 (manufactured by Nikkiso Co., Ltd.). (Method of measuring 10% strength) The calculation was performed using MCT-510 (manufactured by Shimadzu Corporation) according to the above formula. (Method of measuring pH of ink composition) The pH (25° C.) was measured using a glass electrode (HORIBA). (Method of measuring ink viscosity) The viscosity (25°C) was measured using a compact type viscometer TV-2 (manufactured by TOKIMEC). (Method for measuring particle size distribution (Mn / Mv) of colored resin particles) The distribution was calculated using the above-mentioned distribution measuring device and the above-mentioned formula. (Method of measuring surface tension) The surface tension (25° C.) was measured using an automatic surface tensiometer, DY-300 (manufactured by Kyowa Interface Science Co., Ltd.). (Method of measuring contact angle) The contact angle (°) was measured using a contact angle meter, DM-500 (manufactured by Kyowa Interface Science Co., Ltd.).

[0055] (Manufacture of thermochromic pigment A) 1 part by mass (hereinafter simply referred to as "part") of ETAC (manufactured by Yamada Chemical Industry Co., Ltd.) as a leuco dye, 2 parts of bisphenol A as a color developer, and 24 parts of myristyl myristate as a color-changing temperature regulator were heated and melted at 100°C to obtain 27 parts of a homogeneous composition. 10 parts of isocyanate and 10 parts of polyol were added as encapsulating agents to the homogeneous hot solution of 27 parts of the composition obtained above, and the mixture was stirred and mixed. Next, 60 parts of a 12% aqueous polyvinyl alcohol solution was used as a protective colloid, and emulsified at 25°C to prepare a dispersion. Next, 5 parts of a 5% polyamine was used, and the mixture was treated at 80°C for 60 minutes to obtain a core-shell type thermochromic pigment A (colored: black, decolored: colorless). After cooling the dispersion to room temperature, acid was added, filtered, washed with water, and dried using a spray dryer to obtain a powdered thermochromic pigment that becomes colored resin particles. The hue was a deep blue in the colored state, and decolorized by heat such as frictional heat (for example, 60°C or higher). The average particle size of this thermochromic pigment was 2.1 μm, the particle size distribution (Mv / Mn) was 1.8, and the 10% strength was 7.2 MPa.

[0056] (Manufacture of thermochromic pigment B) By changing the stirring conditions during the polymerization of the above particles, a thermochromic pigment B having a different average particle size was obtained. The average particle size of this thermochromic pigment was 3.1 μm, the particle size distribution (Mv / Mn) was 3.9, and the 10% strength was 6.4 MPa.

[0057] (Manufacture of thermochromic pigment C) By changing the stirring conditions during the polymerization of the above particles, a thermochromic pigment C having a different average particle size was obtained. The average particle size of this thermochromic pigment was 4.2 μm, the particle size distribution (Mv / Mn) was 2.2, and the 10% strength was 6.8 MPa.

[0058] (Manufacture of photochromic pigment A) As a photochromic dye, 3 parts of 1,3,3-trimethylindolino-6'-(1-piperidinyl)spironaphsozazine, 10 parts of diethylene glycol dibenzoate, and 10 parts of methyl ethyl ketone were heated and melted at 80°C to obtain 23 parts of a homogeneous composition. To the homogeneous hot solution of 23 parts of the composition obtained above, 10 parts of isocyanate and 10 parts of polyol were added as capsule membrane agents and mixed by stirring. Next, 60 parts of a 12% aqueous polyvinyl alcohol solution was used as a protective colloid to emulsify at 25°C to prepare a dispersion. Next, 5 parts of a 5% polyamine was used and treated at 80°C for 60 minutes to obtain microcapsules. The microencapsulated aqueous dispersion obtained by the above procedure was spray-dried to obtain a powdered photochromic pigment. This photochromic pigment has the property of being colorless in an indoor lighting environment and developing a red color in an ultraviolet ray irradiation environment [sunlight and black light (315-400 nm)]. The average particle size of this photochromic pigment was 2.8 μm, the particle size distribution (Mv / Mn) was 1.7, and the 10% strength was 8.9 MPa.

[0059] (Manufacture of photochromic pigment B) The stirring conditions during the polymerization of the above particles were changed to obtain a photochromic pigment B having a different average particle size. The average particle size of this photochromic pigment was 3.4 μm, the particle size distribution (Mv / Mn) was 3.5, and the 10% strength was 8.1 MPa.

[0060] (Production of Colored Urethane Particles A) 2.8 parts by mass of a water-insoluble dye (Valifast Red 1355, manufactured by Orient Chemical Industry Co., Ltd.) and 11.5 parts by mass of ethylene glycol monobenzyl ether as an organic solvent were heated to 60°C, and 7.2 parts by mass of a diphenylmethane diisocyanate (3 moles) trimethylolpropane (1 mole) adduct (D-109, manufactured by Mitsui Chemicals, Inc.) as a prepolymer was added thereto to prepare an oil phase solution. Meanwhile, 200 parts by mass of distilled water were heated to 60°C, and 15 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant was dissolved therein to prepare an aqueous phase solution. The oil phase solution was added to the aqueous phase solution at 60°C, and the mixture was emulsified and mixed by stirring with a homogenizer for 6 hours to complete the polymerization. The obtained dispersion was centrifuged to obtain colored urethane particles (red particles). The colored urethane particles had an average particle size of 2.1 μm, a particle size distribution (Mv / Mn) of 1.6, and a 10% strength of 18.4 MPa.

[0061] (Production of Colored Urethane Particles B) The stirring conditions during the polymerization of the above particles were changed to obtain colored urethane particles B having a different average particle size. The average particle size of the colored urethane particles was 2.8 μm, the particle size distribution (Mv / Mn) was 3.2, and the 10% strength was 14.7 MPa.

[0062] As the writing instruments using each of the ink compositions obtained above, writing instrument A conforming to Figs. 1 and 2 and writing instrument D conforming to Fig. 5 were used. [Structure of writing implement A: Based on Figures 1 and 2] (Configuration of pen core 35) Sintered polyethylene (PE) core with average particle size of 200 μm, pore size of 50 μm, porosity of 60%, writing part 37: width = 4 mm, knife cut, ink guide part: φ(t) 1.6 mm, difference in insertion length of ink guide part end: 3 mm, writing core width = 1.75 mm This pen core 35 was immersed in an aqueous solution of a surfactant BT-9 (polyoxyethylene alkyl ether, manufactured by Nikko Chemicals Co., Ltd.) and then dried for treatment. (Configuration of the holder 40) Made of acrylic resin, visible light transmittance 85% (Reflectance was measured using a multi-light source spectrophotometer (MSC-5N) manufactured by Suga Test Instruments Co., Ltd., and this was used as the visible light transmittance.) Size of visible part 41 (square) after pen core is attached: 5mm x 6mm x 3mm x 4mm

[0063] (Configuration of Writing Instrument Components Other than Pen Core 35 and Holder 40) Ink occlusion body 20: PET fiber bundle, porosity 85%, φ6×77mm Writing instrument body, cap: Made of polypropylene (PP) (Method of occluding ink composition into ink occluder 20) The ink was forcibly filled using a syringe, and the ink was not occluded at both end faces of the ink occluding body 20 in the state shown in FIG. 1(c) (volume fraction: 80%). (Configuration of friction body 60) The friction body used was made of an olefin-based elastomer.

[0064] [Structure of writing implement D: Based on Figure 5] (Pen tip configuration) Writing part (porous body 38): PE sintered core with average particle diameter of 200 μm, pore size of 50 μm, porosity of 60%, upper side length of 5 mm, lower side length of 6 mm, height of 3 mm, chamfered on both sides of the front end This porous body 38 was immersed in an aqueous solution of a surfactant: BT-9 (polyoxyethylene alkyl ether, manufactured by Nikko Chemicals Co., Ltd.) and then dried for treatment. Holder 70 (including main body): Made of ABS resin, visible light transmittance 85% Ink guide part 70: Cylindrical shape, inner diameter: φ1.7mm (Configuration of writing implement components other than the pen tip) Ink guide core 45: PET fiber bundle, porosity 65%, φ1.5mm x 35mm Ink occlusion body 20: PET fiber bundle, porosity 85%, φ15×55mm The porous body 38 and the holder 70 were bonded together by soaking the porous body 38 in an organic solvent (ethyl acetate) and drying it while the porous body 38 was attached to the holder 70 from the chamfered side. (Method of occluding ink composition into ink occluder 20) The ink was forcibly filled using a syringe, and the ink was not occluded at both end faces of the ink occluding body 20 in the state shown in FIG. 1(c) (volume fraction: 80%). (Configuration of friction body 60) The friction body used was made of an olefin-based elastomer.

[0065] Each of the ink compositions shown in Table 1 below was absorbed into the resulting writing implements A and D, and the difference in density of the drawn lines was evaluated by the following evaluation method. (Method of evaluating line density difference) A straight line of about 20 cm was written on commercially available PPC paper, and the density of the center and outside of the line 20 cm from the beginning was evaluated according to the following criteria. The results are shown in Table 1 below. Evaluation criteria: A: No difference in concentration was observed. B: A slight difference in concentration is observed. C: A clear difference in concentration is observed.

[0066] Each of the ink compositions shown in Table 1 below was occluded in the resulting writing implement A, and color separation was evaluated by the following evaluation method. (Evaluation method for color separation) The writing implement was stored in a landscape position at 50° C. and 65% RH for one month, after which writing was performed and the difference in the density of the drawn lines before and after storage was evaluated according to the following criteria. Evaluation criteria: A: No difference in concentration was observed. B: A slight difference in concentration is observed. C: Some concentration difference is observed. D: A clear difference in concentration is observed.

[0067] [Table 1]

[0068] As is clear from the results in Table 1 above, the writing instruments of Examples 1 to 6, which fall within the scope of the present invention, were found to be able to draw written lines without density differences without causing unevenness in the supply of ink to the pen core, compared to the writing instruments of Comparative Examples 1 to 3, which fall outside the scope of the present invention. In particular, it was confirmed that written lines without density differences could be drawn even when the colored resin particles blended in the ink composition used in Example 4 had a large average particle diameter of 4.2 μm, and even when the ink composition contained an association agent that acts as a component that loosely aggregates the coloring materials of Examples 1 to 5. [Industrial Applicability]

[0069] The pen tip of the present invention can be suitably applied to a so-called marking pen type writing instrument, known as an underline pen. [Explanation of symbols]

[0070] A writing instrument 10 Axial body 20 Ink occluder 30 Pen Tips 35 Pen core 40 Holder 41 Visible part 50 Cap 60 Friction body

Claims

1. A writing instrument in which an ink composition for a writing instrument contained in a main body of the writing instrument is supplied to a pen core at the tip of the pen, and the pen tip has a visible portion through which the writing direction can be visually confirmed, the pen core has a porosity of 30 to 70%, the ink composition for a writing instrument contains colored resin particles having an average particle diameter of 1 to 10 μm, the ink viscosity is 8 to 20 mPa·s, and the particle size distribution (Mv / Mn) of the colored resin particles is 1 to 3, wherein the pen core at the tip of the writing instrument is hydrophilically treated with at least one surfactant selected from Group A below, and the total amount of the ink composition for a writing instrument contains at least one association agent selected from Group X below at 0.1 to 1%. <Group A> Alkyl carboxylates, alkyl sulfates, alkyl phosphates, fatty acid ammonium salts, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid ester ethers, polyoxyethylene sorbitan fatty acid esters <Group X> Methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl ethyl methyl cellulose Hydroxypropyl methylcellulose

2. 2. The writing instrument according to claim 1, wherein the ink composition for a writing instrument has an ink pH of 7 or less.

3. 3. The writing instrument according to claim 1, wherein the ink composition for a writing instrument has a surface tension of 30 to 60 mN / m.

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