Multi-core writing tool

Abstract

A multi-core writing instrument (1) in which a plurality of writing bodies (2) are housed in a shaft tube (9) is provided with an expansion / contraction mechanism capable of selectively expanding / contracting one of the plurality of writing bodies (2) from a tip opening (9H) provided at one end in the longitudinal direction of the shaft tube (9), the plurality of writing bodies (2) comprise: at least one thermochromic writing body (2A) containing a reversible thermochromic ink composition; and at least one non-thermochromic writing body (2C) in which a non-thermochromic ink composition is accommodated, the non-thermochromic ink composition being an oil-based ink composition containing a pigment, and a friction member (10) being provided at the other end of the shaft tube (9) in the longitudinal direction.

Description

Technical Field

[0001] The invention relates to a multi-core writing tool. Background Art

[0002] Conventionally, a thermochromic writing instrument has been disclosed that can erase writing marks made from a reversible thermochromic ink composition by means of a friction member (see Patent Document 1).

[0003] In addition, the above-mentioned thermochromic writing tool can only produce thermochromic handwriting, so it is known that there are multi-core writing tools equipped with thermochromic writing bodies and non-thermochromic writing bodies. By using a multi-core writing tool, the user can use a multi-core writing tool to distinguish between thermochromic handwriting and non-thermochromic handwriting according to the purpose. Furthermore, by using a multi-core writing tool, after trying to write non-thermochromic handwriting with a thermochromic writing tool, the non-thermochromic writing tool set in the multi-core writing tool is used to write non-thermochromic handwriting near the thermochromic handwriting.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2003-206432 Summary of the invention

[0007] Problems to be solved by the invention

[0008] By making thermochromic handwriting and non-thermochromic handwriting a multi-core writing tool, overlapping writing is possible. However, if the thermochromic handwriting of the test writing is to be removed by a friction component, when the thermochromic handwriting is rubbed and the coloring agent contained in the non-thermochromic handwriting is adsorbed on the friction component, or the coloring agent contained in the non-thermochromic handwriting is stretched on the writing surface due to friction, stains of the handwriting are generated on the paper surface, and there is room for improvement. That is, in the prior art, it is sometimes difficult to use thermochromic handwriting and non-thermochromic handwriting closely with a writing tool.

[0009] The present invention aims to solve the above-mentioned problems and provide a multi-core writing tool with excellent practicality that allows thermochromic writing and non-thermochromic writing to be used closely with one writing tool.

[0010] Means for solving problems

[0011] In order to solve the above-mentioned problems, the present invention provides the following means.

[0012] "1. A multi-core writing tool, which contains a plurality of writing bodies in a shaft tube, and is provided with a telescopic mechanism, wherein the telescopic mechanism can selectively extend and retract one of the plurality of writing bodies from a front end opening provided at one end of the shaft tube in the longitudinal direction, wherein the multi-core writing tool is characterized in that:

[0013] The plurality of writing bodies include: at least one thermochromic writing body containing a reversible thermochromic ink composition; and at least one non-thermochromic writing body containing a non-thermochromic ink composition.

[0014] The non-thermochromic ink composition is an oil-based ink composition containing a pigment.

[0015] A friction member is provided at the other end portion of the shaft tube in the longitudinal direction.

[0016] 2. The multi-core writing implement according to item 1, wherein the content of the pigment is 50% by mass or more relative to 100% by mass of the colorant contained in the non-thermochromic ink composition.

[0017] 3. The multi-core writing implement according to item 1 or 2, wherein the oil-based ink composition contains an alkylene oxide derivative of glycerol.

[0018] 4. The multi-core writing tool according to any one of items 1 to 3, wherein the average particle size of the pigment is not less than 1 nm and not more than 500 nm.

[0019] 5. The multi-core writing instrument according to any one of items 1 to 4, wherein the oil-based ink composition contains a surfactant.

[0020] 6. The multi-core writing instrument according to any one of items 1 to 5, wherein the oil-based ink composition contains at least one selected from the group consisting of polyvinyl butyral resin, ketone resin, and terpene phenol resin.

[0021] 7. A multi-core writing tool as described in any one of items 1 to 6, characterized in that it has a sliding body, which is arranged at one end of the length direction of each of the plurality of writing bodies and has an operating part,

[0022] The above-mentioned operating portion provided on the above-mentioned thermochromic writing material and the above-mentioned operating portion provided on the above-mentioned non-thermochromic writing material have different shapes.

[0023] 8. A multi-core writing tool as described in any one of items 1 to 7, characterized in that the above-mentioned pigment is spherical.

[0024] 9. A multi-core writing tool as described in any one of items 1 to 8, characterized in that the above-mentioned pigment contains a carbon black pigment (X) and a diketopyrrolopyrrole pigment (Y), and the content ratio of the above-mentioned carbon black pigment (X) to the above-mentioned diketopyrrolopyrrole pigment (Y) in the above-mentioned pigment is 0.5≤X / Y≤5.

[0025] 10. A multi-core writing tool as described in any one of items 1 to 9, characterized in that the non-thermochromic ink composition contains polyoxypropylene glycerol ether having an average added mole number of propylene oxide of 1 to 30.

[0026] Effects of the Invention

[0027] The multi-core writing tool of the present invention can use thermochromic handwriting and non-thermochromic handwriting closely through one writing tool. In addition, even if the thermochromic handwriting of the multi-core writing tool of the present invention is decolorized (discolored) due to the friction heat generated by rubbing with the friction member, only the non-thermochromic handwriting of the oily ink composition containing the pigment can be left to produce official documents. Therefore, the multi-core writing tool of the present invention can provide a multi-core writing tool with excellent practicality. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a longitudinal cross-sectional view showing the multi-core writing tool of the present invention.

[0029] Figure 2 1 is an external view showing a multi-core writing tool of the present invention. DETAILED DESCRIPTION

[0030] The multi-core writing tool of the present invention contains a plurality of writing bodies in the shaft tube, and is provided with a telescopic mechanism, wherein the telescopic mechanism can selectively extend and retract one of the plurality of writing bodies from a front end opening provided at one end in the length direction of the shaft tube. In the multi-core writing tool 1 of the present invention, the plurality of writing bodies include: at least one thermochromic writing body containing a reversible thermochromic ink composition; and at least one non-thermochromic writing body containing a non-thermochromic ink composition. The non-thermochromic ink composition is an oily ink composition containing a pigment. A friction component is provided at the other end in the length direction of the shaft tube.

[0031] As the above-mentioned reversible thermochromic ink composition, various types can be used alone or in combination, such as a heat-erasable type that erases the color from a developed state by heating, a heat-erasable type having a color storage property of storing and maintaining a developed state or a decolorized state in a specific temperature range in a mutually variable manner, or a heat-developing type that develops color from a decolorized state by heating and returns to a decolorized state from a developed state by cooling.

[0032] As described above, in the multi-core writing tool of the present invention, the plurality of writing bodies contained in the barrel include: at least one thermochromic writing body containing a reversible thermochromic ink composition; and at least one non-thermochromic writing body containing a non-thermochromic ink composition. Therefore, according to various uses such as use for memoranda or official documents, the thermochromic writing body and the non-thermochromic writing body can be distinguished for use, and a multi-core writing tool with high convenience for users can be provided.

[0033] In addition, the user sometimes uses a non-thermochromic writing tool that uses an oily ink composition containing a pigment to write non-thermochromic handwriting near the thermochromic handwriting after pre-writing with a thermochromic writing tool. In this case, the user can make the thermochromic handwriting fade (discolor) by friction heat generated by friction with a friction member disposed at one end of the length direction of the shaft tube, and make a document that only leaves the non-thermochromic handwriting. Specifically, when the thermochromic handwriting is rubbed with a friction member to fade (discolor), the colorant contained in the non-thermochromic handwriting is not easy to be adsorbed on the friction member, and the colorant contained in the non-thermochromic handwriting is not easy to be stretched on the writing surface by friction, and it is not easy to leave stains of the handwriting, so it can be a document with good handwriting.

[0034] Furthermore, the oil-based ink composition can withstand high-load writing, and thus can also be suitably used for carbon paper, etc. Therefore, the multi-core writing instrument of the present embodiment can be suitably used for official documents.

[0035] Therefore, the present invention can provide a multi-core writing tool with excellent practicality.

[0036] The ink composition used for thermochromic writing medium and non-thermochromic writing medium may be any of aqueous ink composition and oily ink composition. For example, in order to be able to distinguish thermochromic handwriting and non-thermochromic handwriting, it is preferred that one of the non-thermochromic writing medium and the thermochromic writing medium contains an aqueous ink composition, and the other contains an oily ink composition. Specifically, it is preferred that the non-thermochromic writing medium uses an oily ink composition, and the thermochromic writing medium uses an aqueous ink composition.

[0037] It should be noted that the above-mentioned multi-core writing tool only needs to be equipped with at least a thermochromic writing body and a non-thermochromic writing body in the barrel, and the shape and structure are not particularly limited.

[0038] Examples of the shape and structure of the multi-core writing tool include telescopic writing tools having shapes and structures such as a push type, a rotation type, and a slide type.

[0039] <Reversible Thermochromic Ink Composition>

[0040] As the colorant contained in the above-mentioned reversible thermochromic ink composition, it is preferred to use a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition in a microcapsule, and the reversible thermochromic composition contains at least three essential components: (i) an electron-donating color-forming organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the temperature at which the color-forming reaction of the above two occurs.

[0041] The reversible thermochromic ink composition of the present invention contains a reversible thermochromic microcapsule pigment.

[0042] The above-mentioned reversible thermochromic microcapsule pigment (hereinafter also referred to as "microcapsule pigment") contains a reversible thermochromic composition, which at least includes (i) an electron-donating color-producing organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the occurrence temperature of the color-producing reaction of the above-mentioned two compounds.

[0043] As the above-mentioned microcapsule pigment, a microcapsule pigment containing a reversible thermochromic composition of the heat-decolorizing type described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc. can be used. The microcapsule pigment changes color before and after a predetermined temperature (color change point) as a boundary, and is in a decolorized state in a temperature range above the color change point on the high temperature side, and is in a color-developing state in a temperature range below the color change point on the low temperature side. In addition, the microcapsule pigment only exists in a specific one of the above two states in the normal temperature range, and the other state is maintained during the application of heat or cold heat required to express the state, but if the above heat or cold heat is not applied, it returns to the state presented in the normal temperature range. That is, the microcapsule pigment is a microcapsule pigment containing a reversible thermochromic composition of the heat-decolorizing type having a relatively small hysteresis width characteristic (ΔH=1°C to 7°C).

[0044] In addition, the microcapsule pigments recorded in Japanese Patent Publication No. 2006-137886, Japanese Patent Publication No. 2006-188660, Japanese Patent Publication No. 2008-45062, Japanese Patent Publication No. 2008-280523, etc. can also be used. The microcapsule pigment is a microcapsule pigment containing a reversible thermochromic composition showing a large hysteresis characteristic. That is, for the microcapsule pigment, the shape of the curve of the change in color concentration caused by temperature change is described as follows: the temperature is increased from the temperature side lower than the color change temperature region and conversely decreased from the temperature side higher than the color change temperature region along a greatly different path color change. And the microcapsule pigment contains a reversible thermochromic composition. A reversible thermochromic composition is a composition that has color storage properties in a specific temperature range [temperature range between t2 and t3 (substantially two-phase retention temperature range)] for a color development state in a low temperature range below the complete color development temperature (t1) or a color removal state in a high temperature range above the complete color removal temperature (t4).

[0045] In addition, as the above-mentioned microcapsule pigment, the microcapsule pigment described in Japanese Patent Publication No. 11-129623, Japanese Patent Publication No. 11-5973, Japanese Patent Publication No. 2001-105732, etc. can also be used. The microcapsule pigment is a microcapsule pigment containing a reversible thermochromic composition of the heat color-developing type (coloring by heating and decoloring by cooling).

[0046] The microencapsulation of the reversible thermochromic composition includes interfacial polymerization, interfacial polycondensation, in-situ polymerization, liquid solidification coating, phase separation from aqueous solution, phase separation from organic solvent, melt dispersion cooling, air suspension coating, spray drying, etc., which can be appropriately selected according to the purpose. Furthermore, a secondary resin film can be further provided on the surface of the microcapsule pigment to impart durability or modify the surface characteristics for practical use according to the purpose.

[0047] The average particle size of the microcapsule pigment is preferably in the range of 0.01 μm to 30 μm. Considering that the color development and color change of the handwriting are improved, the ink discharge stability is improved, and handwriting with excellent three-dimensional effect is easily obtained, preferably 0.05 μm to 10 μm, 0.05 μm to 7 μm, 0.1 μm to 5 μm, and more preferably 0.4 μm to 3.0 μm.

[0048] It should be noted that the average particle size of the microcapsule pigment can be measured by the following method. First, a value measured using a measuring device based on the Coulter method (inductive strip method) is obtained. Then, based on the value measured using the measuring device, a calibrated laser diffraction / scattering particle size distribution measuring device (device name: LA-300, manufactured by Horiba, Ltd.) is used to obtain the average particle size (median diameter) based on the volume basis, thereby enabling measurement.

[0049] Furthermore, the microcapsule pigment may have a non-circular cross-sectional shape in addition to a circular cross-sectional shape.

[0050] In addition, non-thermochromic dyes, pigments and other colorants may be mixed with the above-mentioned microcapsule pigments to present a color change from colored to colored. In addition, non-thermochromic dyes, pigments and other colorants may be mixed with the microcapsule pigments in the ink to present a color change from colored to colored.

[0051] As the non-thermochromic colorant in the microcapsule pigment, any dye or pigment that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof are shown below.

[0052] As the dye, acid dyes, basic dyes, direct dyes and the like can be used.

[0053] As acid dyes, new carmine (CI16255), lemon yellow (CI19140), acid blue black 10B (CI20470), guinea green (CI42085), brilliant blue FCF (CI42090), acid violet 6B (CI42640), soluble blue (CI42755), naphthalene green (CI44025), eosin (CI45380), phlox (CI45410), erythrosine (CI45430), nigrosine (CI50420), acid flavin (CI56205), etc. can be used.

[0054] As basic dyes, basic orange (CI11270), methyl violet FN (CI42535), crystal violet (CI42555), malachite green (CI42000), Victoria blue FB (CI44045), rhodamine B (CI45170), acridine orange NS (CI46005), methylene blue B (CI52015) and the like can be used.

[0055] As direct dyes, Congo Red (CI22120), Direct Sky Blue 5B (CI24400), Violet BB (CI27905), Direct Deep Black EX (CI30235), Direct Fast Black G Conc (CI35225), Direct Fast Black G (CI35255), Phthalocyanine Blue (CI74180), etc. can be used.

[0056] There is no particular limitation on the pigment. Examples include carbon black, aniline black, ultramarine blue, chrome yellow, titanium oxide, iron oxide, phthalocyanine pigments, azo pigments, quinacridone pigments, quinophthalone pigments, styrene pigments, triphenylmethane pigments, peroxycyclic pigments, perylene pigments, dioxazine pigments, and bright pigments, colored resin pigments, etc. It should be noted that the pigment may also be a water-dispersible pigment product that is preliminarily dispersed in a medium using a pigment dispersant such as a surfactant.

[0057] The microcapsule pigment may be used alone or in combination of two or more.

[0058] The content of the microcapsule pigment is 1% by mass to 50% by mass, preferably 3% by mass to 45% by mass, and more preferably 5% by mass to 30% by mass, based on the total mass of the ink composition.

[0059] When the content of the microcapsule pigment is within the above range, aggregation of the microcapsule pigment is easily suppressed, and the color development and color change properties of the obtained handwriting are good.

[0060] Examples of the reversible thermochromic ink composition include a shear-thinning ink containing a shear-thinning agent and a coagulable ink in which a microcapsule pigment is suspended in a moderately coagulated state by a water-soluble polymer coagulant.

[0061] By adding the shear-thinning agent, aggregation and sedimentation of the microcapsule pigment can be suppressed, and bleeding of handwriting can be suppressed, so that good handwriting can be formed.

[0062] Furthermore, when the writing instrument filled with the above-mentioned reversible thermochromic ink composition is in the form of a ballpoint pen, it is possible to prevent ink leakage from the gap between the ball and the pen tip when not in use, and to prevent backflow of ink when the writing tip is placed upward (in an upright state).

[0063] Examples of the shear-thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 million to 8 million) of an organic acid-modified heteropolysaccharide whose structural monosaccharides are glucose and galactose, guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 and containing methacrylic acid alkyl esters as a main component, glucomannan, thickening polysaccharides having gelling ability extracted from seaweed such as agar or carrageenan, and benzylidene hydroxyethyl cellulose. Sorbitol and benzylidene xylitol or their derivatives, cross-linked acrylic acid polymers, inorganic fine particles, polyglycerol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, fatty amides and other nonionic surfactants having an HLB value of 8 to 12, salts of dialkyl or diene sulfosuccinic acid, mixtures of N-alkyl-2-pyrrolidone and anionic surfactants, and mixtures of polyvinyl alcohol and acrylic resins.

[0064] Examples of the water-soluble polymer flocculants include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, water-soluble cellulose derivatives, etc. Specific examples of the water-soluble polysaccharides include gum tragacanth, guar gum, pullulan, and cyclodextrin, and specific examples of the water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

[0065] Water and, if necessary, a water-soluble organic solvent may be added to the ink.

[0066] Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerol, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiglycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, cyclopentane, 2-pyrrolidone, and N-methyl-2-pyrrolidone.

[0067] In addition, when the above-mentioned ink is filled in a ballpoint pen for use, it is preferred to add a lubricant such as oleic acid or other higher fatty acids, a nonionic surfactant with a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphite triester such as tris(alkoxycarbonylmethyl) thiophosphite or tris(alkoxycarbonylethyl) thiophosphite, a phosphate monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, a phosphate diester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, or a metal salt, ammonium salt, amine salt, alkanolamine salt thereof to prevent wear of the ball seat.

[0068] In addition, resins such as acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin may be added as necessary to impart adhesiveness or tackiness to the paper surface.

[0069] In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate, and sodium acetate, organic alkaline compounds such as water-soluble amine compounds, rust inhibitors such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin, preservatives or mildew inhibitors such as carbolic acid, sodium salt of 1,2-benzothiazoline-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl p-hydroxybenzoate, and 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, urea, nonionic surfactants, reduced or non-reduced starch hydrolyzates, oligosaccharides such as trehalose, wetting agents such as sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, and sodium pyrophosphate, defoaming agents, dispersants, fluorine-based surfactants or nonionic surfactants for improving ink permeability may also be added.

[0070] <Non-thermochromic ink composition>

[0071] (pigment)

[0072] The non-thermochromic ink composition used in the present invention contains a pigment. By using a pigment as a colorant, even if a friction force is applied to make the thermochromic handwriting fade (discolor) by rubbing the thermochromic handwriting with a friction member, the friction member can be easily slid. This is because the pigment particles themselves have a sliding effect. Therefore, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction member, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface, and it is not easy to leave stains of the handwriting, so that good handwriting can be formed. Furthermore, considering the sliding property, the primary particles of the pigment are preferably spherical. The spherical shape is not limited to a true sphere, and can also be approximately spherical or approximately elliptical. On the other hand, when a dye is used, it is adsorbed on the friction member by the friction force of rubbing with the friction member, so that the dye is stretched and handwriting stains are generated. The primary particle size of the pigment is, for example, more than 10nm and less than 50nm.

[0073] Furthermore, the pigment is excellent in water resistance and light resistance and can be suitably used for official documents.

[0074] Furthermore, the oil-based ink composition can withstand high-load writing and is therefore preferably used for carbon paper and official documents.

[0075] In addition, examples of the pigment include inorganic, organic, and processed pigments. Specifically, examples of the pigment include carbon black, aniline black, ultramarine blue, chrome yellow, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, diketopyrrolopyrrole, quinophthalone, threne, triphenylmethane, perinone, perylene, dioxazine, metallic pigments, pearlescent pigments, fluorescent pigments, and light-storing pigments.

[0076] The average particle size of the pigment is preferably 1 nm to 500 nm. It is more preferably 30 nm to 350 nm, and even more preferably 50 nm to 300 nm. This is because, by being in the above range, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction member, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface, so that good handwriting is easily maintained.

[0077] Furthermore, the pigment particles enter the gap between the ball and the pen tip body through the pigment particles, and easily play a role like a bearing. In addition, the pigment particles can easily improve lubricity, improve writing feeling, and inhibit the wear of the ball seat by inhibiting metal contact. Therefore, the non-thermochromic ink composition preferably contains a pigment.

[0078] The average particle size of the pigment can be measured by a laser diffraction method. Specifically, the average particle size can be determined using a laser diffraction particle size distribution measuring instrument (trade name "Microtrac HRA9320-X100", Nikkiso Co., Ltd.) based on the particle size distribution measured based on a numerical value calibrated using a standard sample or other measurement method at a volume accumulation of 50% (D50).

[0079] Note that the pigment exhibits the above-mentioned effects in a dispersed state of the pigment in the non-thermochromic ink composition, and therefore it is preferable to determine the particle size in the dispersed state.

[0080] As the type of pigment, it is preferred to use carbon black, quinacridone, threne, and diketopyrrolopyrrole pigments. Furthermore, based on the compatibility over time, if the stability of the ink over time is considered, it is preferred to use carbon black and diketopyrrolopyrrole pigments. As the pigment, carbon black is particularly preferred. When carbon black is used as a pigment, the sliding property of the surface of the pigment particles based on the friction component is improved, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction component, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface. Therefore, it is easy to maintain good handwriting, so it is preferred.

[0081] In addition, diketopyrrolopyrrole pigments can also suppress white spots in handwriting and make it easier to maintain good handwriting. Therefore, it is preferred to use carbon black and diketopyrrolopyrrole pigments in combination.

[0082] Furthermore, from the perspective of maintaining good handwriting while forming a good color tone, the content ratio of the carbon black pigment (X) and the diketopyrrolopyrrole pigment (Y) when used in combination is preferably 0.5≤X / Y≤5, and preferably 1≤X / Y≤4.

[0083] Furthermore, as described above, with respect to the pigment, from the perspective of forming good handwriting even when a friction force is applied by rubbing with a friction member, the content of the pigment is preferably high relative to the content of the colorant in the non-thermochromic ink composition, preferably 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass, and particularly preferably 100% by mass.

[0084] In general, ink compositions containing pigments tend to have insufficient writing performance and ink followability when the writing tip is dry. On the other hand, the non-thermochromic ink composition of the present invention contains polyoxyalkylene glycerol ether, and thus can maintain good writing performance and ink followability even when the content ratio of the pigment is high, thereby achieving good handwriting.

[0085] The content of the pigment is preferably 5% by mass or more and 30% by mass or less relative to the total amount of the non-thermochromic ink composition. This is because if it is less than 5% by mass, it is difficult to obtain dark handwriting, and if it exceeds 30% by mass, it tends to affect the solubility in the ink. Further considering its tendency, it is preferably 7% by mass or more and 25% by mass or less, and if further considered, it is 10% by mass or more and 20% by mass or less.

[0086] (Oxyalkylene derivatives of glycerol)

[0087] In the present invention, the oily ink composition as the non-thermochromic ink composition preferably contains an alkylene oxide derivative of glycerol. By making the oily ink composition contain an alkylene oxide derivative of glycerol, the sliding property is easily improved. Therefore, even if the friction force of the friction component is applied, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction component, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface. Therefore, it is not easy to leave stains on the handwriting, and good handwriting can be maintained. Furthermore, as mentioned above, by using it in combination with pigment particles, the sliding property can be further improved, and the friction component is easy to slide, so it is more effective.

[0088] Examples of the alkylene oxide derivatives of glycerol include polyoxyalkylene glyceryl ethers, polyoxyalkylene alkyl glucosides, polyoxypropylene alkyl ethers, and the like. In consideration of the slip properties, polyoxyalkylene glyceryl ethers are preferred.

[0089] Polyoxyalkylene glyceryl ether is obtained by addition-polymerizing alkylene oxide to glycerol or polyglycerol. Examples of the polyoxyalkylene glyceryl ether include polyoxyalkylene glyceryl ether, polyoxyalkylene diglyceryl ether, and polyoxyalkylene triglyceryl ether.

[0090] In addition, when a pigment is used as in the present invention, the viscosity of the ink usually increases over time due to the aggregation of the pigment, and the ink followability is easily reduced. However, the polar group in the structure of the alkylene oxide derivative of glycerol is adsorbed on the surface of the pigment, and the pigment is stably dispersed in the ink. Therefore, the increase in the viscosity of the ink caused by the aggregation of the pigment can be suppressed, the ink followability is improved, and good handwriting is formed. Therefore, considering the pigment dispersion stability and the ink followability, it is preferred to use polyoxyalkylene glyceryl ether, wherein, if further considered, it is preferred to use polyoxyalkylene diglyceryl ether.

[0091] In addition, polyoxyalkylene glyceryl ethers include polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, etc. Among them, since polyoxypropylene glyceryl ether has a propylene group, it has a tendency to be excellent in lipophilicity and improved in stability over time by containing it in an oily ink composition. Therefore, polyoxypropylene glyceryl ether is preferably used.

[0092] Considering that the polyoxyalkylene glyceryl ether further improves the slipping property, is less likely to leave stains of handwriting, is easy to maintain good handwriting, and further improves the dispersion stability of the pigment and the stability over time, the average value of the number of alkylene oxide added moles (the average number of alkylene oxide added moles) is preferably 1 to 50. Further considering that the average number of alkylene oxide added moles is preferably 1 to 30. Considering that the slipping property and the stability over time are further improved, the average number of alkylene oxide added moles is preferably 1 to 20, and more preferably 5 to 20.

[0093] In particular, in view of further improving the slip properties, preventing the stains of handwriting from remaining, and facilitating the maintenance of good handwriting, the average number of moles of propylene oxide added is preferably 1 to 30, more preferably 1 to 20, further preferably 5 to 20, more preferably 1 to 12, and particularly preferably 5 to 12. In addition, in view of facilitating the effect of the present invention, the structure of the polyoxyalkylene glyceryl ether is preferably a structure represented by the following formula (1) or (2).

[0094] [Chemistry 1]

[0095]

[0096] In the formula, m, n, o, p, w, x, y and z each independently represent a number indicating the number of alkylene oxide additions.

[0097] Here, m+n+o+p is the average number of moles of propylene oxide added, and w+x+y+z is the average number of moles of ethylene oxide added.

[0098] Among them, polyoxyalkylene glyceryl ether represented by formula (1) is preferred because it has a large effect of improving stability over time.

[0099] In addition, the weight average molecular weight of the alkylene oxide derivative of glycerol is preferably 5,000 or less. This is because if the weight average molecular weight is too large, it is easy to affect the stability over time, and then the viscosity of the ink composition is easy to increase, which is easy to affect the handwriting based on the ink followability. Taking into account the stability over time and the ink followability, the weight average molecular weight is preferably 3,000 or less, and then the weight average molecular weight is preferably 1500 or less, preferably 1200 or less. In addition, considering further improving the slippage, not easily leaving stains of handwriting, and maintaining good handwriting, it is preferably 900 or less. On the other hand, if the weight average molecular weight is too small, it is easy to affect the slippage and pigment dispersibility, so the weight average molecular weight is preferably 300 or more, and if further considered, the weight average molecular weight is preferably 500 or more.

[0100] The weight average molecular weight is a value obtained by converting it into polystyrene using GPC (gel permeation chromatography).

[0101] In addition, when the content of the alkylene oxide derivative of glycerol is less than 0.1% by mass relative to the total amount of the ink composition, the effects of sliding and ink following may not be obtained, and when it exceeds 40% by mass, the stability over time may be affected. Therefore, the content of the alkylene oxide derivative of glycerol is preferably 0.1% by mass to 40% by mass relative to the total amount of the ink composition, and more preferably 3% by mass to 30% by mass. Furthermore, considering the balance between the wear suppression of the ball seat and the stability over time, the content of the alkylene oxide derivative of glycerol is preferably 5% by mass to 25% by mass relative to the total amount of the ink composition, and most preferably 8% by mass to 25% by mass.

[0102] (Organic Solvent)

[0103] Examples of the organic solvent used in the non-thermochromic ink composition as the oil-based ink composition of the present invention include glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, 3-methoxybutanol, and 3-methoxy-3-methylbutanol; glycol solvents such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butanediol, and ethylene glycol; and organic solvents such as alcohol solvents such as benzyl alcohol, methanol, ethanol, 1-propanol, 2-propanol, isopropanol, isobutanol, tert-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate, and other higher alcohols.

[0104] Among these organic solvents, aromatic alcohols are preferably used as solvents because they have an aromatic ring to improve lubricity and have high compatibility with polyoxyalkylene glyceryl ethers to improve solution stability.

[0105] (Surfactant)

[0106] The non-thermochromic ink composition of the non-thermochromic writing body of the present invention preferably contains a surfactant. By making the non-thermochromic ink composition contain a surfactant, it is possible to achieve improved sliding properties, and improved writing performance and writing feel when the tip of the pen tip is dried in the state where the tip of the pen tip is placed in the atmosphere.

[0107] The surfactant is preferably at least one selected from a phosphate-based surfactant, a silicone-based surfactant, a surfactant having an acetylene bond, a fluorine-based surfactant, a fatty acid, and a fatty acid ester.

[0108] Among surfactants, phosphate ester surfactants and silicone surfactants are preferably used in view of further improving the slipping property, preventing the stain of handwriting from remaining, maintaining good handwriting, improving the writing performance and writing feeling. Furthermore, phosphate ester surfactants are preferred because they can more easily improve the slipping property.

[0109] Specific examples of the phosphate ester surfactant include alkoxyethyl (C n H 2n+1 OCH2CH2O) or alkoxy (C m H 2m+1 O), phosphoric acid esters of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphoric acid monoesters of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphoric acid diesters of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, phosphoric acid triesters of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, alkyl phosphoric acid esters, alkyl ether phosphoric acid esters or derivatives thereof.

[0110] Specific examples of phosphate ester surfactants include the Phoslex series (manufactured by SC Organic Chemicals Co., Ltd.), the JP series (manufactured by Johoku Chemical Industry Co., Ltd.), the Plysurf series (manufactured by Daiichi Kogyo Co., Ltd.), the Phosphanol series (manufactured by Toho Chemical Industry Co., Ltd.), and the NIKKOL series (manufactured by Nikkol Chemicals Co., Ltd.).

[0111] Among the phosphate ester surfactants, it is preferred to use alkoxyethyl (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 O) is selected from phosphoric acid esters, phosphoric acid monoesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers, and phosphoric acid diesters of polyoxyethylene alkyl ethers or polyoxyethylene alkyl aryl ethers.

[0112] Among the phosphate ester surfactants, it is preferred to use an alkoxyethyl group (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 O) of the phosphate ester surfactant, further considering that it is preferred to use an alkoxy group (C m H 2m+1 O) phosphate ester surfactant.

[0113] Regarding the above-mentioned phosphate ester surfactant, alkoxyethyl (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 The carbon chain (n, m) of the terminal alkyl group of the alkoxyethyl group (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 O) has an appropriate length of the carbon chain (n, m) of the terminal alkyl group, so it is easier to maintain good sliding properties, and therefore the carbon chain (n, m) of the terminal alkyl group is preferably 1 to 20. Further consideration is given to the carbon chain (n, m) being preferably 1 to 12. The carbon chain (n, m) is preferably 2 to 12, 3 to 8, or 3 to 6.

[0114] Furthermore, among the phosphate ester surfactants, it is preferred to use a phosphate ester surfactant having an alkyl group in view of further improving the slip properties, preventing the stains of handwriting from remaining, maintaining good handwriting, improving the writing performance, and the writing feeling. It is particularly preferred that the number of carbon atoms contained in the alkyl group is 8 to 18, more preferably 10 to 18, and even more preferably 12 to 18. This is because if the number of carbon atoms in the alkyl group is too small, the slip properties tend to be insufficient, and if the number of carbon atoms is too large, the stability over time tends to be affected.

[0115] By using the above-mentioned alkoxyethyl group (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 The interaction between the phosphoric acid ester surfactant of (O) and the phosphoric acid ester surfactant having an alkyl group makes it easier to improve the slip properties, so that the effects of the present invention are easily obtained, and thus it is effective and preferred.

[0116] In addition, when a phosphate ester surfactant is used, the acid value is preferably 160 (mgKOH / g) or less, more preferably 120 (mgKOH / g) or less, and further preferably 100 or less. This is because the improvement in sliding properties brought about by the phosphate ester surfactant is easily exerted. Further considering the stability and lubricity in the ink composition, the acid value is preferably 30 (mgKOH / g) or more and 160 (mgKOH / g) or less, preferably 40 (mgKOH / g) or more and 120 (mgKOH / g) or less, and more preferably 40 (mgKOH / g) or more and 100 (mgKOH / g) or less.

[0117] By using the above-mentioned alkoxyethyl group (C n H 2n+1 O-C2H4O) or alkoxy (C m H 2m+1 The interaction between the phosphate ester surfactant of (O) and the phosphate ester surfactant having a specific acid value makes it easier to improve the slip properties, so that the effects of the present invention are easily obtained, which is effective and preferred.

[0118] The acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the sample.

[0119] The content of the surfactant is preferably 0.1% by mass or more and 5.0% by mass or less relative to the total amount of the non-thermochromic ink composition. This is because, if it is less than 0.1% by mass, it is difficult to obtain the desired slippage, stains of residual handwriting, and a tendency to maintain good handwriting, writing performance, and writing experience. If it exceeds 5.0% by mass, the ink tends to become unstable over time. If these conditions are further considered, the content of the surfactant is preferably 0.3% by mass or more and 4.0% by mass or less relative to the total amount of the oily ballpoint pen ink composition, and if further considered, it is preferably 0.5% by mass or more and 3.0% by mass or less.

[0120] The non-thermochromic ink composition of the non-thermochromic writing body of the present invention preferably contains a hydroxystearic acid compound as a substance other than the above-mentioned surfactant. By containing the hydroxystearic acid compound, it is possible to achieve improved sliding properties. Therefore, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction component, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface. As a result, it is not easy to leave stains on the handwriting, so that good handwriting can be maintained.

[0121] In addition, by making the non-thermochromic ink composition contain a hydroxystearic acid compound, the lubricity of the tip of the writing body (between the ball and the ball seat of the pen tip body) can be improved. Therefore, even on the printed characters formed by printing inks such as toners, it is possible to suppress line skipping and handwriting blurring, achieve good writing properties, improve writing feel, and suppress ball seat wear by reducing friction with the ball seat.

[0122] As the hydroxystearic acid compound, hydroxystearic acid and hydroxystearic acid derivatives are preferably used in view of the sliding property, and 12-hydroxystearic acid and 12-hydroxystearic acid derivatives are particularly preferably used.

[0123] The content of the above-mentioned hydroxystearic acid is preferably 0.1% by mass or more relative to the total amount of the non-thermochromic ink composition. This is because, by being 0.1% by mass or more, the effect of the present invention is easily obtained. If further considered, it is preferably 0.2% by mass or more, preferably 0.5% by mass or more. In addition, from the aspect of being difficult to affect the time stability of the ink and easily obtaining the effect of the present invention, it is preferably 10% by mass or less, and if further considered, it is preferably 5% by mass or less, preferably 4% by mass or less.

[0124] In the case where the non-thermochromic ink composition of the present invention contains a surfactant, the mixing ratio of the alkylene oxide derivative of glycerol to the surfactant (alkylene oxide derivative of glycerol / surfactant) is preferably 1 to 30 times, more preferably 1 to 25 times, more preferably 1 to 20 times, more preferably 1 to 15 times, more preferably 2 to 15 times, preferably 3 to 15 times, and most preferably 5 to 15 times. This is because, if it is within the above range, the sliding property, writing feeling, and ink time can be improved in a balanced manner.

[0125] (Organic amine)

[0126] In order to improve the stability of the components contained in the non-thermochromic ink composition, the non-thermochromic ink composition of the present invention preferably contains an organic amine. Acid amines such as amines with ethylene oxide such as ethylene oxide alkylamines, polyoxyethylene alkylamines, alkylamines such as laurylamine, stearylamine, distearylamine, dimethyl laurylamine, dimethyl stearylamine, dimethyl octylamine, and dimethyl alkylamines can be cited. Among these, amines with ethylene oxide and dimethyl alkylamines are preferred. In addition, in order to make the sliding property and stability over time good and to easily obtain the effect of the present invention, amines with ethylene oxide are preferred.

[0127] In addition, considering the stability with the above-mentioned surfactant, pigment, and other components, the total amine value of the above-mentioned organic amine is preferably 100 (mgKOH / g) or more and 300 (mgKOH / g) or less. This is because, if it exceeds 300 (mgKOH / g), the reactivity is too strong and it is easy to react with the above-mentioned components, so there is a tendency that the stability over time is easy to deteriorate. In addition, if the total amine value is less than 100 (mgKOH / g), there is a tendency that the stability of the surfactant in the non-thermochromic ink composition is reduced, and there is a tendency that the slippage is reduced. From the aspect of stability and slippage with the above-mentioned components, it is more preferably in the range of 150 (mgKOH / g) or more and 300 (mgKOH / g) or less. In addition, from the aspect of stability, it is preferably 180 (mgKOH / g) or more and 300 (mgKOH / g) or less, and more preferably 230 (mgKOH / g) or more and 270 (mgKOH / g) or less.

[0128] In the present invention, the total amine value is a value indicating the total amount of primary amines, secondary amines, and tertiary amines, and is expressed as mg of potassium hydroxide equivalent to the hydrochloric acid required to neutralize 1 g of a sample.

[0129] In addition, regarding the reactivity of organic amines with other components in the ink composition, the reactivity with primary amines is the strongest, followed by secondary amines and tertiary amines, which have a lower reactivity. Therefore, considering the stability over time, secondary amines or tertiary amines are preferably used. They can be used alone or in combination of two or more.

[0130] (resin)

[0131] The non-thermochromic ink composition of the present invention preferably contains a resin. By containing a resin, the handwriting adhesion to the writing surface is improved, the colorant contained in the non-thermochromic handwriting is not easily adsorbed on the friction component, and the colorant contained in the non-thermochromic handwriting is not easily stretched by the friction force on the writing surface. As a result, it is not easy to leave stains on the handwriting, and good handwriting can be maintained. In addition, by containing a resin, it is possible to achieve an improvement in the suppression of ink leakage at the tip of the writing tool.

[0132] As the resin, there can be mentioned polyvinyl butyral resin, ketone resin, amide resin, rosin resin, terpene phenol resin, alkylphenol resin, polyvinyl butyral resin, styrene-maleic acid resin, ethylene-maleic acid resin, styrene-acrylic resin, acrylic resin, maleic acid resin, cellulose resin, petroleum resin, coumarone-indene resin, polyethylene oxide, polymethacrylate, ketone-formaldehyde resin, α- and β-pinene-phenol polycondensation resin, etc. These can be used alone or in combination of two or more.

[0133] Among these resins, in consideration of improving the adhesion of handwriting to the writing surface, the colorant contained in the non-thermochromic handwriting being not easily adsorbed on the friction component, the colorant contained in the non-thermochromic handwriting being not easily stretched on the writing surface due to friction, the stain of handwriting being not easily left, maintaining good handwriting, slipping property, and suppressing ink leakage at the writing tip, at least one selected from polyvinyl butyral resin, ketone resin, and terpene phenol resin is preferred. If the adhesion of handwriting to the paper surface is further considered, the resin contained in the non-thermochromic ink composition is preferably polyvinyl butyral resin, ketone resin, and terpene phenol resin, and more preferably polyvinyl butyral resin and terpene phenol resin.

[0134] The softening point of the terpene phenol resin is preferably 70° C. to 150° C. in view of further achieving the handwriting adhesion of the ink to the paper surface, the solubility stability in the ink, and the suppression of handwriting blurring by maintaining viscoelasticity. If the handwriting adhesion of the ink to the paper surface and the suppression of handwriting blurring are considered to be achieved by further maintaining viscoelasticity, the softening point is preferably 80° C. to 120° C. in view of further maintaining viscoelasticity. Here, the softening point of the resin is a value measured in accordance with JIS K2207.

[0135] In addition, the average degree of polymerization of the polyvinyl butyral resin is preferably 100 to 2,000 in consideration of improving the adhesion of handwriting to the writing surface, the colorant contained in the non-thermochromic handwriting being less likely to be adsorbed on the friction member, the colorant contained in the non-thermochromic handwriting being less likely to be stretched on the writing surface due to friction, the stain of handwriting being less likely to remain, maintaining good handwriting, slipping properties, and suppressing ink leakage at the writing tip, etc., and further considerations make the average degree of polymerization preferably 100 to 1,500, and more preferably 200 to 1,000. Here, the average degree of polymerization refers to the number of basic units constituting one molecule of the polyvinyl butyral resin, and can be a value measured by the method specified in JIS K6728 (2001 edition).

[0136] In addition, the polyvinyl butyral resin preferably has a hydroxyl content of 25 mol% or more. This is because the solubility of the polyvinyl butyral resin with a hydroxyl content of less than 25 mol% in the alkylene glycol alkyl ether solvent is insufficient, and it is difficult to obtain the effect of the present invention. If further consideration is taken, the polyvinyl butyral resin with a hydroxyl content of 30 mol% or more is preferred, which can easily improve the sliding property and the writing feeling, so it is preferred. In addition, if the polyvinyl butyral resin with a hydroxyl content exceeding 40 mol% is used, the moisture absorption is likely to increase, which is likely to affect the stability over time with the ink components, so the polyvinyl butyral resin with a hydroxyl content of 40 mol% or less is preferred. Therefore, the polyvinyl butyral resin with a hydroxyl content of 30 mol% or more and 40 mol% or less is preferred, and the hydroxyl content of 30 mol% or more and 36 mol% or less is further preferred.

[0137] The hydroxyl group amount (mol %) of the polyvinyl butyral resin refers to the content of the hydroxyl group (mol %) relative to the total molar amount of the butyral group (mol %), the acetyl group (mol %) and the hydroxyl group (mol %).

[0138] When the total content of the resin is less than 3% by mass relative to the total amount of the non-thermochromic ink composition, it is difficult to obtain sufficient effects to obtain the effects of handwriting adhesion, slippage, and ink leakage inhibition on the paper surface. In addition, when the total content of the resin exceeds 40% by mass relative to the total amount of the non-thermochromic ink composition, the solubility in the ink is easily deteriorated, the ink viscosity becomes too high, and the ink consumption is reduced, which is easy to affect the writing feeling and writing performance. Therefore, relative to the total amount of the oil-based ballpoint pen ink composition, the total content of the resin is preferably 3% by mass or more and 40% by mass or less. If further considered, it is preferably 5% by mass or more and 30% by mass or less, and preferably 10% by mass or more and 25% by mass or less.

[0139] In addition, the non-thermochromic ink composition of the present invention may also appropriately contain dyes, colorant stabilizers, plasticizers, chelating agents, defoamers, water, pseudoplasticity-imparting agents, etc. These may be used alone or in combination of two or more.

[0140] The viscosity of the non-thermochromic ink composition of the present invention is not particularly limited. -1 When the ink viscosity exceeds 15000mPa·s, the ball rotation resistance during writing becomes larger, the writing feeling tends to become heavier, and it is easy to affect the writing performance and ink following performance. In order to form good handwriting, 20℃, shear speed 5sec -1 The ink viscosity is preferably 15000mPa·s or less. In order to further improve the writing performance and ink following performance and form good handwriting, it is preferably 10000mPa·s or less. If further consideration is taken, it is preferably 8000mPa·s or less, and more preferably 6000mPa·s or less. In addition, at 20°C and a shear rate of 5sec -1 When the ink viscosity is less than 10mPa·s, it is easy to cause penetration, ink leakage, and pigment dispersion to the handwriting. Therefore, 20℃, shear speed 5sec -1 The ink viscosity at the time is preferably 10 mPa·s or more. Taking further consideration, the ink viscosity is preferably 100 mPa·s or more, and the ink viscosity is more preferably 5 mPa·s or more.

[0141] (Thermochromic writing)

[0142] Examples of the above-mentioned thermochromic writing body include ballpoint pen refills, resin-processed bodies of fiber bundles, heat-welded bodies of fiber bundles, felt-processed bodies, tubular pen bodies, fountain pen-type plate-shaped pen bodies with a slit at the tip, writing brush bodies, porous bubble bodies of synthetic resins, and marker pen refills.

[0143] A ballpoint pen refill used as a thermochromic writing body contains a reversible thermochromic ink composition directly in an ink container or impregnated in an ink absorber, and the ink container is directly or via a relay component mounted with a ballpoint pen tip that rotatably holds a ball. A marker pen refill used as a thermochromic writing body contains a reversible thermochromic ink composition directly in an ink container or impregnated in an ink absorber, and the ink container is directly or via a relay component mounted with a marker pen tip such as an extruded body of a synthetic resin having an axial ink guide path.

[0144] (Non-thermochromic writing)

[0145] Examples of the above-mentioned non-thermochromic writing body include ballpoint pen refills, or resin-processed bodies of fiber bundles, heat-welded bodies of fiber bundles, felt-processed bodies, tubular pen bodies, fountain pen-type plate-shaped pen bodies with a slit at the tip, writing brush bodies, porous bubble bodies of synthetic resins, and marker pen refills.

[0146] A ballpoint pen refill used as a non-thermochromic writing body contains a non-thermochromic ink composition directly in an ink container or impregnated in an ink absorber, and the ink container is directly or via a relay component mounted with a ballpoint pen tip that rotatably holds a ball. A marker pen refill used as a non-thermochromic writing body contains a non-thermochromic ink composition directly in an ink container or impregnated in an ink absorber, and the ink container is directly or via a relay component mounted with a marker pen tip such as an extruded body of a synthetic resin having an axial ink guide path.

[0147] (Ballpoint pen refills for use as thermochromic writing medium and non-thermochromic writing medium)

[0148] The ink consumption per 100 m of the ballpoint pen refill used as a thermochromic writing body and a non-thermochromic writing body is preferably 20 mg to 100 mg. This is because if it is within the above range, deep handwriting and good handwriting can be formed. If further consideration is taken, it is preferably 20 mg to 80 mg, and 30 mg to 70 mg.

[0149] It should be noted that regarding the ink consumption, a spiral writing test was carried out using 5 test samples at 20°C, on writing paper of JIS P3201, at a writing angle of 70°, and a writing load of 200 g, at a writing speed of 4 m / min, and the average value of the ink consumption per 100 m was defined as the ink consumption per 100 m.

[0150] In addition, the arithmetic mean roughness (Ra) of the ball surface held by the ballpoint pen tip constituting the ballpoint pen refill used as the thermochromic writing body and the non-thermochromic writing body of the present invention is preferably 0.1 nm to 12 nm. This is because good handwriting and writing feeling can be obtained by sufficiently placing ink on the surface of the ball. If further considered, the arithmetic mean roughness (Ra) is preferably 1 nm to 10 nm, and more preferably 2 nm to 8 nm. It should be noted that the measurement of surface roughness can be obtained by (model name SPI3800N manufactured by Seiko Epson Corporation).

[0151] The material used for the balls is not particularly limited, and examples thereof include superhard alloy balls mainly composed of tungsten carbide, metal balls such as stainless steel, ceramic balls such as silicon carbide, silicon nitride, alumina, silica, and zirconia, and ruby ​​balls.

[0152] In addition, the material constituting the ballpoint pen tip of the ballpoint pen refill used as the thermochromic writing body and the non-thermochromic writing body of the present invention can include metal materials such as stainless steel, zinc white copper, brass, aluminum bronze, aluminum, and resin materials such as polycarbonate, polyacetal, and ABS. If the wear and stability of the ball seat are taken into consideration, the pen tip body made of stainless steel is preferred.

[0153] In addition, the amount of movement of the ball of the ballpoint pen tip constituting the non-thermochromic writing body of the present invention in the length direction of the ballpoint pen tip is preferably 3 μm to 30 μm. This is to obtain good handwriting and writing experience. If further consideration is taken, it is preferably 10 μm to 25 μm, and preferably 12 μm to 25 μm.

[0154] The ink holding cylinders used for thermochromic writing materials and non-thermochromic writing materials respectively use, for example, molded bodies made of thermoplastic resins such as polyethylene, polypropylene, polyethylene terephthalate, and nylon, or metal tubes such as stainless steel.

[0155] When the ink is directly contained in the ink containing cylinder, an ink backflow preventing body may be filled at the rear end of the ink.

[0156] The ink backflow prevention body composition is composed of a nonvolatile liquid or a low-volatile liquid.

[0157] Specifically, vaseline, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, oligomers or cooligomers of α-olefin, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, fatty acid-modified silicone oil, etc. can be mentioned, and one or more kinds thereof can be used in combination.

[0158] The nonvolatile liquid and / or the low-volatile liquid is preferably thickened to a suitable viscosity by adding a thickener. Examples of the thickener include silica having a hydrophobic surface, microparticle silica having a methylated surface, aluminum silicate, swelling mica, clay-based thickeners such as hydrophobic bentonite or montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, etc., tribenzylidene sorbitol, fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrin-based compounds such as fatty acid dextrin, and cellulose-based compounds.

[0159] Furthermore, the above-mentioned liquid ink backflow preventing body and a solid ink backflow preventing body may be used together.

[0160] (Friction parts)

[0161] The multi-core writing tool of the present invention is preferably equipped with a friction component. The friction component is used to discolor (decolorize) thermochromic handwriting by frictional heat generated by friction, and can be installed around the front end of the barrel or the handle, the rear end of the barrel or the clip of the multi-core writing tool.

[0162] As friction parts and friction bodies, elastic bodies such as elastomers and plastic foams that are rich in elasticity and can generate friction heat by generating moderate friction when rubbing are preferred, but plastic molded bodies, stones, wood, metals, cloth, etc. can also be used.

[0163] It should be noted that a common eraser for erasing pencil-based handwriting can be used to erase the handwriting, but since scraps are generated when rubbing, it is preferable to use the above-mentioned friction member and friction body that hardly generate scraps.

[0164] As the material of the friction part and the friction body, preferably silicone resin, SEBS resin (styrene-ethylene-butadiene-styrene block copolymer), SEPS resin (styrene-ethylene-propylene-styrene block copolymer), polyester resin, EPDM (ethylene propylene diene monomer rubber), polyolefin resin or a mixture of at least two of them. Among them, considering that the colorant is not easy to adhere to the friction part, SEBS resin and polyolefin resin are more preferred. If the removability of thermochromic handwriting is further considered, SEBS resin is most preferred. By using a material that is not easy to adhere to the friction part as the material of the friction part, when the thermochromic handwriting is removed by friction, it is possible to suppress the paper surface pollution caused by the colorant contained in the thermochromic handwriting adhering to the friction part and the paper surface pollution during repeated writing.

[0165] The friction member can be a member (friction body) of any shape separated from the writing tool, but by being fixed to the writing tool, it is excellent in portability, so it is preferred. In addition, the position where the friction member is fixed is preferably the front end (top) of the cap or the rear end of the shaft cylinder.

[0166] (Multi-core writing tools)

[0167] Next, a specific example of the multi-core writing instrument of the present invention will be described.

[0168] Figure 1 and Figure 2 It is a schematic diagram of an example of the structure of the multi-core writing instrument 1 of the present invention. Figure 1 It is a cross-sectional view of the multi-core writing tool 1 of the present invention. Figure 2 It is an appearance diagram of the multi-core writing tool 1 of the present invention.

[0169] The multi-core writing tool 1 has a cylindrical shaft 9 that is long in a predetermined direction. A front end opening 9H is provided at one end of the shaft 9 in the length direction, and a friction component 10 is provided at the other end in the length direction. A plurality of writing bodies 2 are accommodated in the shaft 9. The plurality of writing bodies 2 include at least one thermochromic writing body 2A and at least one non-thermochromic writing body 2C.

[0170] The plurality of writing bodies 2 are respectively configured to include: a ballpoint pen tip 3; a ball rotatably held at the end portion of the front end opening 9H side of the ballpoint pen tip 3 in the longitudinal direction; and an ink container 4 connected to the ballpoint pen tip 3. The ballpoint pen tip 3 is provided with a coil spring for pressing the ball directly against the inner wall of the tip edge in the ballpoint pen tip 3.

[0171] Ink is contained in the ink containing tube 4 of each of the plurality of writing bodies 2. Specifically, a reversible thermochromic ink composition is contained as ink in the ink containing tube 4 of the thermochromic writing body 2A. In addition, a non-thermochromic ink composition is contained as ink in the ink containing tube 4 of the non-thermochromic writing body 2C. The end portion of the ink containing tube 4 of each of the plurality of writing bodies 2 on the opposite side of the ball side in the longitudinal direction is filled with an ink follower 8 having viscoelasticity.

[0172] Sliding bodies 5 having operating parts 6 are provided at the ends on the opposite sides of the front end openings 9H in the longitudinal direction of each of the plurality of writing bodies 2. In the present invention, the operating parts 6 provided in the thermochromic writing body 2A and the operating parts 6 provided in the non-thermochromic writing body 2C are configured in different shapes.

[0173] For example, when the hue of the ink composition contained in the thermochromic writing body 2A and the non-thermochromic writing body 2C contained in the barrel 9 is the same, sometimes it is a combination that is difficult to judge by the previous appearance display. Specifically, it is a case where the hue of the reversible thermochromic ink composition in the thermochromic writing body 2A and the non-thermochromic ink combination in the non-thermochromic writing body 2C is the same, such as black. Even in such a case, since the operating parts 6 provided separately are of different shapes from each other, the user can easily distinguish and identify the thermochromic writing body 2A and the non-thermochromic writing body 2C without hesitation. Therefore, a multi-core writing tool 1 that can be quickly selected can be provided.

[0174] In the thermochromic writing body 2A containing a reversible thermochromic ink composition, or the non-thermochromic writing body 2C containing a non-thermochromic ink composition in the writing body 2 of the multi-core writing instrument 1, it is preferred to provide a distinguishable identification display portion at or near the writing tip. Specifically, the identification display portion can be provided by providing a coloring layer 7 at the writing tip of the thermochromic writing body 2A or the non-thermochromic writing body 2C.

[0175] As described above, when writing with the writing body 2, there is no need to write temporarily and confirm the handwriting, and the handwriting can be distinguished through the identification display part at the tip of the writing, which is preferred.

[0176] As described above, in the multi-core writing tool 1 of the present invention, the plurality of writing bodies 2 contained in the barrel 9 include at least one thermochromic writing body 2A containing a reversible thermochromic ink composition and at least one non-thermochromic writing body 2C containing a non-thermochromic ink composition. Therefore, as described above, the present invention can provide a multi-core writing tool with excellent practicality.

[0177] Example

[0178] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0179] (Reversible Thermochromic Ink Compositions A and B)

[0180] A mixture of the following materials other than the thickener in the following blending amounts was heated and stirred at room temperature using a magnetic stirrer to prepare a base ink. Thereafter, the following thickener in the following blending amount was added to the above-prepared base ink, and the mixture was fully mixed and stirred using a homogenizer until it became uniform, thereby obtaining reversible thermochromic ink compositions A and B. The specific blending amounts are as follows.

[0181] (Preparation of reversible thermochromic ink composition A: color changes from black to colorless)

[0182]

[0183] It should be noted that the viscosity of the reversible thermochromic ink composition A was measured at 20°C using an E-type rotational viscometer (trade name: DV-II viscometer, manufactured by Brookfield, rotor: conical rotor CPE42) at a shear rate of 3.84 sec. -1 (1rpm) is 700mPa·s, at a shear rate of 384sec -1 (100rpm) is 30mPa·s.

[0184] (Reversible Thermochromic Ink Composition B)

[0185] Reversible thermochromic ink composition B was obtained by the same method as that of reversible thermochromic ink composition A except that the types and addition amounts of the components to be blended were changed as shown below.

[0186] (Preparation of reversible thermochromic ink composition B: color changes from blue to colorless)

[0187]

[0188]

[0189] (Non-thermochromic ink composition C1)

[0190] A mixture obtained by mixing the following components in the following blending amounts was heated and then completely dissolved using a disperser to obtain a non-thermochromic ink composition 1 (oil-based ink composition). The specific blending amounts are as follows.

[0191] (Preparation of non-thermochromic ink composition C1 (oil-based ink composition): black ink)

[0192]

[0193] (Preparation of non-thermochromic ink compositions C2 to C31 (oil-based ink compositions): black ink)

[0194] Except for changing the components and pen tip specifications as shown in the table, the inks were mixed in the same procedure as for the non-thermochromic ink composition 1 and completely dissolved using a disperser to obtain non-thermochromic ink compositions C2 to C31 (oil-based ink compositions).

[0195] It should be noted that for the non-thermochromic ink composition, the viscosity of the non-thermochromic ink composition C1, the non-thermochromic ink composition C2, and the non-thermochromic ink composition C3 was measured using a viscometer RVDVII+Pro CP-52 spindle manufactured by Brookfield Co., Ltd. The results were as follows: -1 At the rotation speed of 2.5 rpm, the non-thermochromic ink composition C1 had an ink viscosity of 5000 mPa·s, the non-thermochromic ink composition C10 had an ink viscosity of 2000 mPa·s, and the non-thermochromic ink composition C11 had an ink viscosity of 3000 mPa·s.

[0196] (Production of Thermochromic Writing Material)

[0197] The thermochromic ink composition A prepared as described above is contained in an ink container 4. A ballpoint pen tip 3 rotatably holding a ball having a ball diameter of 0.7 mm is installed in the ink container 4. Then, the ink container 4 is further filled with an ink follower 8 having viscoelasticity and containing polybutene as a main component to obtain a thermochromic writing body 2A (water-based ballpoint pen refill) (see Figure 1 , Figure 2 ).

[0198] Similarly, the prepared thermochromic ink composition B is contained in an ink container 4. A ballpoint pen tip 3 rotatably holding a ball with a ball diameter of 0.7 mm is installed in the ink container 4. Then, the ink container 4 is further filled with a viscoelastic ink follower 8 containing polybutene as a main component to obtain a thermochromic writing body 2B (water-based ballpoint pen refill) (not shown).

[0199] (Production of non-thermochromic writing material (oily writing material))

[0200] The non-thermochromic ink composition C1 (non-thermochromic ink composition C2 to 31 (oily ink composition)) prepared as described above is contained in an ink container 4. A ballpoint pen tip 3 that rotatably holds a ball with a ball diameter of φ0.7 mm is installed in the ink container 4. Then, a viscoelastic ink follower 8 with polybutene as the main component is further filled in the ink container 4 to obtain a non-thermochromic writing body 2C (oily ballpoint pen core). The amount of movement of the ball in the ballpoint pen tip 3 in the longitudinal direction of the ink container 4 is 10 μm, and the arithmetic mean roughness (Ra) of the ball surface is 3 nm.

[0201] (Example 1)

[0202] Production of multi-core writing instruments

[0203] The three writing bodies 2 (thermochromic writing body 2A, thermochromic writing body 2B (not shown) and non-thermochromic writing body 2C) obtained as described above are accommodated in the shaft cylinder 9. In addition, a front end opening portion 9H is formed on one end side of the shaft cylinder 9 in the longitudinal direction. In addition, a friction component 10 is installed on the other end of the shaft cylinder 9 in the longitudinal direction. In Example 1, as the friction component 10, a friction component 10 made of SEBS resin is used. Through these steps, etc., a multi-core writing tool 1 with a telescopic mechanism is manufactured, and by sliding the operating portion (rod) 6 of the sliding body 5 protruding from the window hole provided on the side wall of the shaft cylinder 9, one of the multiple writing bodies 2 can be selectively extended and retracted from the front end opening portion 9H of the shaft cylinder 9.

[0204] The multi-core writing tool 1 can form black and blue thermochromic handwriting and black non-color-changing handwriting using one writing tool.

[0205] Thermochromic handwriting (text or pattern) formed by writing with the thermochromic writing body 2A can be easily removed by rubbing with the friction part 10 at the part where correction is desired, and black non-colorful handwriting can be formed by using the non-thermochromic writing body 2C near the thermochromic handwriting.

[0206] In addition, since the shape of the operating portion 6A, 6B (not shown) of the sliding body 5 of the thermochromic writing body 2A, 2B (not shown) is different from the shape of the operating portion 6C of the sliding body 5 of the non-thermochromic writing body 2C, it is a shape that is easy for users to recognize and can be distinguished.

[0207] Furthermore, a non-thermochromic writing body 2C is prepared in which a black circumferential colored layer 7 is provided at the writing tip of the non-thermochromic writing body 2C (see Figure 1). By providing a coloring layer 7 at the writing tip of the non-thermochromic writing body 2C, it is possible to easily distinguish between the thermochromic writing bodies 2A and 2B without the coloring layer and the non-thermochromic writing body 2C.

[0208] (Examples 2 to 29, Comparative Examples 1 to 2)

[0209] As shown in the table, a non-thermochromic writing body 2C containing an ink composition in which each component is changed is contained in a barrel 9, and a multi-core writing tool 1 is obtained in the same manner as in Example 1.

[0210] (Examples 30 to 32)

[0211] In the same manner as in Example 1, except that a friction component 10 made of polyolefin is used instead of the friction component 10 made of SEBS resin used in Example 1, a non-thermochromic writing body 2C containing an ink composition in which each component is changed is contained in a shaft tube 9, as shown in the table, to obtain a multi-core writing tool 1.

[0212] The evaluation results are shown in the table. In addition, writing paper JIS P3201 was used as writing test paper, and the following tests and evaluations were performed.

[0213] Scratch resistance test: Write with a non-thermochromic writing medium near the thermochromic writing medium to form non-thermochromic writing. Immediately thereafter, apply friction to each of the formed writings with a friction member and observe the writings.

[0214] ◎···Staining of non-thermochromic writing is slightly noticeable, but good writing is maintained.

[0215] ○···Stains of non-thermochromic writing were observed, but good writing was maintained.

[0216] △···Stains of non-thermochromic writing were observed in large quantities, but writing that was not a problem in practical use was maintained.

[0217] ×···Non-thermochromic writing is severely stained

[0218] Writing experience: Conduct a handwriting-based sensory test and evaluate it.

[0219] ◎···Very smooth

[0220] ○···Smooth

[0221] △···The smoothness is at a level that does not pose a problem in practical use.

[0222] ×···Heavier

[0223] Ink aging test: The ink in the pen tip body was observed under a microscope after one month at 50°C.

[0224] ◎···No precipitate, good.

[0225] ○···A small amount of precipitate was generated.

[0226] △···Deposits were generated, but there was no problem in practical use.

[0227] ×···Precipitation is produced, resulting in unclear writing, poor writing, etc.

[0228] [Table 1]

[0229]

[0230] [Table 2

[0231]

[0232] [Table 3]

[0233]

[0234] [Table 4]

[0235]

[0236] [Table 5]

[0237]

[0238] [Table 6]

[0239]

[0240] [Table 7]

[0241]

[0242] [Table 8]

[0243]

[0244] [Table 9]

[0245]

[0246] [Table 10]

[0247]

[0248] [Table 11]

[0249]

[0250] [Table 12]

[0251]

[0252] It should be noted that the numbers shown in the column "Non-thermochromic ink composition" in the table represent the manufacturing company name and product name of each composition. Specifically, the manufacturing company name and product name of each number and the corresponding non-thermochromic ink composition in the table are as follows. It should be noted that for some numbers, only the manufacturing company name is shown.

[0253] 1: Made by Fuji Color Co., Ltd. Contains 20% pigment component and 20% polyvinyl butyral resin

[0254] 2: Made by ORIENT CHEMICAL Co., Ltd.

[0255] 3: SC-P750 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.

[0256] 4: SC-P400 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.

[0257] 5: SC-P1000 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.

[0258] 6: SC-P1600 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.

[0259] 7: SC-E350 manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.

[0260] 8: Plysurf manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0261] 9: Phosphanol manufactured by Toho Chemical Industry Co., Ltd.

[0262] 10: JP series manufactured by Johoku Chemical Industry Co., Ltd.

[0263] 11: Made by Kao Co., Ltd.

[0264] 12: NYMEEN L201 manufactured by NOF Co., Ltd.

[0265] 13: PVP K-90 manufactured by ISB Japan Co., Ltd.

[0266] 14: Made by Sekisui Chemical Co., Ltd.

[0267] 15: Made by YASUHARA CHEMICAL Co., Ltd.

[0268] 16: Made by Hitachi Chemical Co., Ltd.

[0269] 17: ADK STAB LS-12 made by ADEKA Co., Ltd.

[0270] In Examples 1 to 32, good performance was obtained in the scratch resistance test, writing feel, and ink aging test. Furthermore, a pigment was used as a colorant, but the pigment had good dispersibility and was stable.

[0271] In Example 1, the non-thermochromic writing body 2C ballpoint pen tip was changed to a ballpoint pen tip with a changed amount of movement of the ball in the longitudinal direction and additional tests were conducted, and good performance was obtained in the rubbing test, writing feeling, and ink time test. Specifically, the amount of movement of the ball in the longitudinal direction was set to 14μm, 18μm, and 22μm, and good results were obtained as in Example 1.

[0272] In addition, Examples 1 to 29 using the friction member 10 made of SEBS resin obtained good scratch resistance test results compared with Examples 30 to 32 using the friction member 10 made of polyolefin.

[0273] In Comparative Examples 1 and 2, since no pigment was used in the non-thermochromic ink composition, the stain of the non-thermochromic writing became serious.

[0274] Industrial Applicability

[0275] The present invention can use thermochromic writing and non-thermochromic writing closely with one writing tool, and can be widely used as a multi-core writing tool with excellent practicality. The multi-core writing tool of the present invention is not limited to a multi-core writing tool that accommodates three ballpoint pen refills, and can be widely used as a composite writing tool that accommodates more than three multi-core writing tools, at least mechanical pencil refills or marker refills, etc.

[0276] Explanation of symbols

[0277] 1 Multi-core writing tool

[0278] 2. Script

[0279] 2A Thermochromic Writing Font

[0280] 2C non-thermochromic writing

[0281] 3 ballpoint pen nibs

[0282] 4Ink container

[0283] 5 Sliding body

[0284] 6. 6A Operation Department

[0285] 7 Coloring Layers

[0286] 8Ink Follower

[0287] 9-axis barrel

[0288] 9H front opening

[0289] 10 Friction parts

Claims

1. A multi-core writing tool, which contains a plurality of writing bodies in a shaft tube, and is provided with a telescopic mechanism, wherein the telescopic mechanism can selectively extend and retract one of the plurality of writing bodies from a front end opening provided at one end of the shaft tube in the length direction, wherein the multi-core writing tool is characterized in that: The plurality of said writing styles include: At least one thermochromic writing element containing a reversible thermochromic ink composition; and at least one non-thermochromic writing element containing a non-thermochromic ink composition, The non-thermochromic ink composition is an oil-based ink composition containing a pigment. A friction member is provided at the other end portion of the shaft cylinder in the longitudinal direction.

2. The multi-core writing tool according to claim 1, characterized in that: The content of the pigment is 50% by mass or more relative to 100% by mass of the colorant contained in the non-thermochromic ink composition.

3. The multi-core writing tool according to claim 1 or 2, characterized in that: The oil-based ink composition contains an alkylene oxide derivative of glycerol.

4. The multi-core writing tool according to claim 1 or 2, characterized in that: The average particle size of the pigment is greater than or equal to 1 nm and less than or equal to 500 nm.

5. The multi-core writing tool according to claim 1 or 2, characterized in that: The oil-based ink composition includes a surfactant.

6. The multi-core writing tool according to claim 1 or 2, characterized in that: The oil-based ink composition contains at least one selected from the group consisting of polyvinyl butyral resin, ketone resin, and terpene phenol resin.

7. The multi-core writing tool according to claim 1 or 2, characterized in that: It has a sliding body, which is arranged at one end of the length direction of each of the plurality of writing bodies and has an operating part. The operating portion provided on the thermochromic writing body and the operating portion provided on the non-thermochromic writing body have different shapes from each other.

8. The multi-core writing tool according to claim 1 or 2, characterized in that: The pigment is spherical.

9. The multi-core writing tool according to claim 1 or 2, characterized in that: The pigment includes a carbon black pigment (X) and a diketopyrrolopyrrole pigment (Y), and the content ratio of the carbon black pigment (X) to the diketopyrrolopyrrole pigment (Y) in the pigment is 0.5≤X / Y≤5.

10. The multi-core writing tool according to claim 1 or 2, characterized in that: The non-thermochromic ink composition contains polyoxypropylene glyceryl ether having an average added mole number of propylene oxide of 1 to 30.

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