JP6652348B2 - Thermochromic writing instrument - Google Patents

Description

The present invention relates to a thermochromic writing instrument that can be used for official documents.

  2. Description of the Related Art Conventionally, various writing instruments using discoloration or thermochromic ink that can erase written handwriting have been proposed. In particular, a reversible thermochromic composition comprising an electron-donating color-forming organic compound, an electron-accepting compound as a color developer, and a reaction medium serving as a color-changing temperature regulator for determining the temperature at which a color reaction occurs between the two is included. A reversible thermochromic microcapsule pigment, an ink containing at least water, and a writing instrument containing the ink, a technique capable of easily discoloring or decoloring a handwriting with less generation of erased dust due to rubbing heat is disclosed. (Patent Document 1).

International Publication No. 2008/105227

  However, the invention described in Patent Document 1 described above is unsuitable for official documents in which discoloration is not preferable because the handwriting can be discolored by an external action. Therefore, an object is to provide a thermochromic writing instrument that can be applied to official documents.

Then, in order to solve the above-mentioned problems, the inventor has made the following inventions after diligent development.
The writing implement of the present invention is a thermochromic writing implement in which one end of a barrel accommodates a writing core filled with thermochromic ink, and the other end accommodates a seal.

  In addition, a writing lead is mounted on one end of the barrel so that the tip of the writing lead can be selectively protruded and retracted from the tip of the shaft, and when the tip of the writing lead protrudes from the tip of the barrel, it is attached to the rear end of the barrel. The lead shaft can be extended by moving the provided rear shaft back and forth, and furthermore, a seal is fixed to the rear end of the rear shaft, and a cap is detachably fixed to an outer peripheral portion of the rear shaft. The seal is fixed to the rear end with the seal face on the rear end side, and the knock cylinder holding the vermilion on the front face in a state facing the seal face at a small interval is pressed against the cap by the spring force at the inner hole rear end of the cap. After being constantly urged rearward, and after being able to advance at an interval appropriately larger than the small interval against the spring force, a locking portion is provided so as to prevent further advancement. The rear end is provided so that it protrudes from the rear end of the cap, and a friction tool is fixed to the rear end. Further knock cover to the rear end outer periphery of the friction member by coating it is preferable that formed by secured.

  In addition, the shaft cylinder is composed of a front shaft and a center shaft, and a guide tube integrated with the center shaft is provided by providing engaging portions for fitting the front shaft and the center shaft to each other in a non-rotatable and non-rotatable manner. In each of the plurality of guide grooves of the guide cylinder, a writing core is fitted between the guide cylinder and the sliding piece so as to freely move back and forth by urging a return spring, and the cam slope displaced in the axial direction is circled at the front end. The circumferentially provided cylindrical cam is rotatably and axially movable with respect to the guide cylinder or the central shaft, and each sliding piece is brought into contact with the cam slope to alternately move forward and backward by the rotation of the cylindrical cam with respect to the front shaft or the central shaft. It is a writing instrument which is movable so that the tip of each writing lead can be selectively protruded and retracted from the tip opening of the front shaft, and it is preferable that a rear shaft is integrally provided on the rear outer periphery of the cylindrical cam. .

The thermochromic ink mentioned here is a color that maintains a predetermined color (first color) at normal temperature (for example, 25 ° C.) and changes to another color (second color) when heated to a predetermined temperature (for example, 65 ° C.). And then returns to the original color (first color) when cooled to a predetermined temperature (for example, −10 ° C.). In general, a configuration may be adopted in which the second color is colorless and the drawing line written in the first color (for example, red) is heated to be colorless. Therefore, the frictional body 9 rubs against the paper surface or the like on which the drawing line is written to generate frictional heat, thereby changing the drawing line to colorless. The second color may be a color other than colorless. More specifically, examples of the thermochromic microcapsule pigment serving as a coloring material of the thermochromic ink include a thermochromic composition containing at least a leuco dye, a developer, and a color changing temperature regulator, which is microencapsulated. Can be The reversible thermochromic microcapsule pigment preferably has an average particle diameter in the range of 0.1 to 5.0 μm, preferably 0.5 to 2 μm. The reversible thermochromic microcapsule pigment is preferably blended in an amount of 4 to 30% by weight based on the total amount of the ink composition. The average particle size was measured using a particle size measuring device N4Plus (manufactured by COULTER). At the time of measurement, the sample was diluted with water until the sample reached the recommended concentration of N4Plus, and the measurement was performed at a temperature of 25 ° C.

  The leuco dye that can be used is not particularly limited as long as it is an electron donating dye and functions as a color former. Specifically, triphenylmethane, spiropyran, fluoran, diphenylmethane, rhodamine lactam, indolyl phthalide, leuco auramine, and the like are conventionally known from the viewpoint of obtaining an ink having excellent coloring properties. They can be used alone (one type) or as a mixture of two or more types (hereinafter, simply referred to as “at least one type”).

  Specifically, 6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone, 3,3-bis (p-dimethylaminophenyl) -6 -Dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1 -Ethyl-2-methylindol-3-yl) -4-azaphthalide, 1,3-dimethyl-6-diethylaminofluoran, 2-chloro-3-methyl-6-dimethylaminofluoran, 3-dibutylamino-6 -Methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-xylidinofluor Orchid, 2- (2-chloroanilino) -6-dibutylaminofluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluoran, 1,2-benz-6-diethylaminofluoran, 1 , 2-Benz-6-dibutylaminofluoran, 1,2-benz-6-ethylisoamylaminofluoran, 2-methyl-6- (Np-tolyl-N-ethylamino) fluoran, 2- (N -Phenyl-N-methylamino) -6- (Np-tolyl-N-ethylamino) fluoran, 2- (3'-trifluoromethylanilino) -6-diethylaminofluoran, 3-chloro-6 -Cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 3-di (n-butyl) amino-6-methoxy-7-anilinofluoran 3,6-bis (diphenylamino) fluoran, methyl-3 ′, 6′-bisdiphenylaminofluoran, chloro-3 ′, 6′-bisdiphenylaminofluoran, 3-methoxy-4-dodecoxystyrino And quinoline. At least one of these can be used.

  These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, and the like, and develop color by opening these skeletons (rings). Preferably, use of a leuco dye which changes from colored to colorless by heat is desirable.

  The developer that can be used is a component having the ability to develop the color of the leuco dye, such as a phenol resin compound, a salicylic acid metal chloride, a salicylic acid resin metal salt compound, and a solid acid compound. Is mentioned. Specifically, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, hexafluorobisphenol, p -N-butyl hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcinol, dodecyl gallate, 2,2-bis (4'-hydroxyphenyl) propane, 4,4-dihydroxydiphenylsulfone, 1,1-bis (4'-hydroxyphenyl) ethane, 2,2-bis (4'-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, 1-phenyl-1,1-bis (4'-hydroxy Phenyl) ethane, 1,1-bis (4′- Droxyphenyl) -3-methylbutane, 1,1-bis (4′-hydroxyphenyl) -2-methylpropane, 1,1-bis (4′-hydroxyphenyl) n-hexane, 1,1-bis (4 '-Hydroxyphenyl) n-heptane, 1,1-bis (4'-hydroxyphenyl) n-octane, 1,1-bis (4'-hydroxyphenyl) n-nonane, 1,1-bis (4'- (Hydroxyphenyl) n-decane, 1,1-bis (4′-hydroxyphenyl) n-dodecane, 2,2-bis (4′-hydroxyphenyl) butane, 2,2-bis (4′-hydroxyphenyl) ethyl Propionate, 2,2-bis (4'-hydroxyphenyl) -4-methylpentane, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4'-hydr Kishifeniru) n- heptane, 2,2-bis (at least one 4'-hydroxyphenyl) n- nonane and the like.

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

  The discoloration temperature regulator is a substance that controls the discoloration temperature in the coloration of the leuco dye and the developer, and conventionally known substances can be used. Examples include alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons, and the like.

  Specifically, bis (4-hydroxyphenyl) phenylmethane dicaprylate (C7H15), bis (4-hydroxyphenyl) phenylmethanedilaurate (C11H23), bis (4-hydroxyphenyl) phenylmethanedimyristate (C13H27) Bis (4-hydroxyphenyl) phenylethane dimyristate (C13H27), bis (4-hydroxyphenyl) phenylmethane dipalmitate (C15H30), bis (4-hydroxyphenyl) phenylmethane dibehenate (C21H43), bis At least one kind such as (4-hydroxyphenyl) phenylethylhexylidene dimyristate (C13H27) is exemplified.

In addition, filling the thermochromic ink into the writing implement includes a structure in which the ink is directly filled into an ink storage tube housed in a cylindrical barrel, a barrel on the outer surface of the writing implement, or the like.
Further, the thermochromic ink may be not only a liquid but also a solid formed in a rod or the like.

  As described above, the thermochromic writing instrument of the present invention can provide a writing instrument that does not interfere with stamping with an official document or the like by storing a seal that does not use thermochromic ink in the barrel. it can. In addition, even if the knock cylinder is strongly knocked, the adhesion of the vermilion to the stamp surface is appropriate, and since the space between the stamp surface and the vermilion is in a non-contact state when not in use, the vermilion does not adhere as in the case of the constant contact. There is no problem of overflowing or unnecessary attachment of vermilion to the stamp surface, and there is no problem when using a friction tool protruding from the rear end of the knock cylinder.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an overall vertical cross-sectional view showing an embodiment of the present invention, and a part thereof is not cross-sectional. Further, in the knocked portion at the rear end, a state in which the knock cover is removed and a state in which the knock cover is fitted are shown in a half section. It is explanatory drawing which shows the engagement state of the protrusion of a cylindrical cam, and the peripheral groove of a center shaft. It is explanatory drawing which shows the other corresponding example of the engagement state of the protrusion of a cylindrical cam, and the peripheral groove of a center shaft. FIG. 4 is a cross-sectional view of a main part of an engaging portion in FIG. 3.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Corresponding components are denoted by common reference symbols throughout the drawings.
In the axial direction of the writing instrument, the writing portion side is defined as a “front” side, and the opposite side to the writing portion is defined as a “rear” side.

First, FIGS. 1 to 4 show an embodiment of the present invention.
The thermochromic writing instrument of the present invention includes a center shaft 1 integrally provided with a guide tube 2, a front shaft 3, a rear shaft 4 integrally provided with a cylindrical cam 5, a pair of sliding pieces 6a and 6b, a mechanical pencil writing core 7, The main components are a ballpoint pen writing core 8, a seal 37, a cap 40, a knock cylinder 41, and the like.

  First, as shown in FIG. 1, the center shaft 1 is made of a resin, and has a guide groove 9a which is long in the axial direction and is open to the side surface from a substantially central portion to a rear end, and a guide groove 9b having a similar guide groove 9b on the side surface opposite to the guide groove. A tube 2 is provided. In the front half of the guide tube 2, there is provided a tube portion 10 having a partition portion 16 having holes 32a, 32b in communication with the respective guide grooves 9a, 9b and having an open front end. A bulging engagement portion 13 is formed on the outer peripheral portion of the cylindrical portion 10 having a portion 31.

  As shown in FIG. 2, a narrow portion 54 is connected to the circumferential groove 19 through the inclined surface 53 at the front side, and a substantially L-shaped window is formed in the rear side surface of the center shaft 1. Have been. As will be described later, the protrusion 17 of the cylindrical cam 5 is inserted from the vertical groove 18, and the protrusion 17 elastically expands the inclined surface 53, passes through the narrow portion 54, and enters the circumferential groove 19. The cylindrical cam 5 rotates while the protrusion 17 abuts on the rear wall in the circumferential direction of the circumferential groove 19, and the writing portion of the mechanical pencil 7 or the ball-point pen 8 having the thermochromic property alternates from the tip end of the front shaft. It is a double thermochromic writing instrument that appears and disappears.

  The circumferential groove 19 is provided with a wide groove 55 so that the cylindrical cam 5 can be axially shifted at the position of the projection 17 when the mechanical pencil writing core 7 protrudes. An inclined surface 57b is connected between the rear wall 57a and the rear wall 57c of the peripheral groove 19 so that the cylindrical cam 5 cannot substantially shift at the position of the protrusion 17 when the protrusion 17 protrudes, and a narrow groove 56 is provided. ing. Further, as will be described later, it is set so that the wall 20 of the rear shaft 4 abuts the rear end of the center shaft 1 at the front end of the forward and backward movement, and the front end of the projection 17 does not abut the front wall 58 of the circumferential groove 19.

  The front end of the tip shaft 3 is tapered, and the tip end of the inner hole portion is provided with a tip opening through which a writing tip portion appears and disappears. In the rear end hole, an engagement groove 12 is provided, which engages with an engagement portion 13 provided on the outer peripheral portion of the tube portion 10 in front of the guide tube and prevents the tube portion 10 from slipping out and rotating. I have. The cylindrical portion 10 and the front shaft 3 are detachably fixed by an appropriate force. When refilling the pencil lead 7 or replacing the ballpoint pen 8, the leading shaft 3 is pulled out from the center shaft 1. In order to simplify the above, it is desirable that the joint between the cylindrical portion 10 and the rear end hole of the front shaft 3 be a screw.

  The rear shaft 4 is made of resin and integrally has a cylindrical cam 5 at the tip. The cylindrical cam 5 has a cylindrical shape, and has a cam slope 14 that is displaced circumferentially back and forth at a front end edge, and a notch 15 is formed at the foremost end of the cam slope 14. Further, the tip of the mechanical pencil 5 is inserted into the longitudinal groove 18 of the center shaft 1 and elastically fitted into the circumferential groove 19 to rotate in a certain range (approximately 180 degrees) and project from the side surface of the cylindrical cam 5. A projection 17 is formed to keep the shaft from shifting in this state.

  Further, the rear shaft 4 is provided with a front outer cylinder portion 33 and a rear outer cylinder portion 34 which are connected to each other behind the cylindrical cam 5 by a wall 20 to be integrated, and are provided at the front end of the outer cylinder portion 33. Is formed with a flange portion 35 that abuts a front end of a cap 40, which will be described later, and an engaging portion 36 that engages with an inner peripheral portion of the cap 40 is formed on an outer peripheral portion.

  If the cap 40 is made of resin, the engaging portion 36 can be selected from an uneven engaging portion, a frictional engagement such as a rib, and a screw. If the cap 40 is made of metal, a metal cylinder is fixed to the outer periphery of the outer cylinder 33, and a rib-shaped engaging portion is provided on the peripheral surface of the cylinder, or the cap 40 is engaged with the inner periphery of the cap 40. Various means are selected, such as installing a wig having a joint.

The seal 37 is a hard seal, which has a stamp surface engraved on a stamp material such as tsuge, ivory, zirconia, etc., and has a stamp surface 39 for attaching vermilion and stamping.
The seal 37 is detachably fitted to the inner surface of the outer cylindrical portion 34 with the seal surface 38 on the rear end side.

The knock cylinder 41 has a vermilion accommodating portion 42 at a front end, and a front shaft portion 43a, a flange portion 43c, and a rear shaft portion 43b are integrally provided behind the same. A step 43d is provided at the front end of the front shaft 43a at an appropriate distance from the rear end of the vermilion accommodating portion 42.
The fixing tool 44 is fixed to the rear end of the step portion 44a in a state where the front end of the step portion 44a is in contact with the rear end of the vermilion accommodating portion 42 behind the inner hole portion of the cap 40, and the rear end of the step portion 44a and the front end of the flange portion 43c. A knock 48 is always urged to the rear of the cap 40, and the rear end of the flange 43c substantially abuts the inner step 46 at the rear end of the cap 40.
Further, the rear shaft portion 43b of the knock cylinder appropriately protrudes from the rear end of the cap 40, and the frictional tool 51 fixed to the rear end hole by the stopper 52 is fixed.
Further, a locking spring 47 having an elastic piece-shaped locking portion 47b at a predetermined position is fixed to the outer peripheral portion of the rear shaft portion 43b, and a knock cover 49 having a crown 50 attached to the outer periphery thereof is detachable. It is fitted to. The crown 50 may not be provided.

  The friction tool 51 is for discoloring the thermochromic ink, and is capable of discoloring or erasing the handwriting of the mechanical pencil, the mechanical pencil writing lead 7 and the ballpoint pen writing lead 8 containing the thermochromic ink. . The frictional tool 51 is formed so as to be appropriately worn so as not to damage the paper surface and to prevent the printed characters on the paper surface from being blurred. Specifically, under a wear test (ASTM D1044) load of 9.8 N and 1000 rpm specified in JIS K7204, the Taber abrasion amount of the wear wheel CS-17 of the Taber abrasion tester is preferably 10 mg or more. . If the friction member has a Taber abrasion amount of less than 10 mg, the paper surface will be damaged at the time of rubbing, and the printed characters will be blurred.

  As a material for forming the friction tool 51, rubber such as thermosetting rubber such as silicone rubber, nitrile rubber, ethylene propylene rubber, and ethylene propylene diene rubber, and thermoplastic elastomer such as styrene elastomer, olefin elastomer, and polyester elastomer. The friction tool 51 may be formed by forming an elastic material, a mixture of two or more rubber elastic materials, and a mixture of the rubber elastic material and the synthetic resin so that the Taber abrasion amount is 10 mg or more. Further, a friction tool 51 may be formed by forming a mixture of a polypropylene resin and a styrene-based thermoplastic elastomer or a mixture of a polypropylene resin and a polypropylene-based thermoplastic elastomer so that the Taber abrasion amount is 10 mg or more.

  Furthermore, in order to adjust the Taber abrasion amount to be 10 mg or more, an alkyl sulfonate phenyl ester, a cyclohexanedicarboxylic acid ester, or a phthalic acid-based plasticizer for giving more flexibility to the material of the friction tool 51. May be added. Since the friction tool 51 contains the plasticizer, the friction tool 51 is more likely to be worn, so that the handwriting can be discolored without damaging the paper surface and without blurring the printed characters and the like. In addition, the friction tool 51 is also applicable as a touch pen and a stylus pen.

  Further, it is desirable that the friction tool 51 has a durometer D hardness specified in JIS K6203 of 30 or more. Thereby, a predetermined hardness can be secured, and a more stable rubbing operation can be performed.

Further, a cap 40 is fitted around the outer circumference of the outer cylindrical portion 33, the front end of the cap 40 abuts against the flange 35, and the cap 40 is detachably fixed by the engaging portion 36.
In this state, the space between the seal surface 38 of the seal 37 and the front surface of the vermilion 45 faces at a small interval, and the interval between the step 43d of the knock cylinder 41 and the step 44a of the fixing tool 44 is smaller than the small interval. It is set appropriately large. At this time, when the knock cylinder 41 moves forward, the vermilion 45 bites into the stamp surface 38 by a predetermined amount, and an appropriate amount of vermilion sticks to the stamp surface. Further, when the step 43d abuts (locks) on the step 44a, the forward movement of the knock cylinder 41 can be prevented.

  The ink composition for vermilion used for vermilion 45 used for the seal 37 includes at least one organic solvent selected from the group consisting of glycol ethers, glycol ether acetates, and esters, and pigments and / or dyes. And a dispersing resin having a solubility in water and ethanol at 25 ° C. of 7% or less when the colorant is a pigment, and water and ethanol at 25 ° C. when the colorant is a dye. It contains a fixing resin whose solubility in water is 1% or less and a fluorine-based surfactant.

The organic solvent must have an SP value of 5 to 15, preferably 7 to 13, and a vapor pressure at 20 ° C. of 0.001 mmHg to 45 mmHg, preferably 0.01 mmHg to 20 mmHg. The SP (Solubility Parameter) value (dissolution parameter (δ)) of the organic solvent is limited in terms of the material that can be dissolved in the ink, and if the SP value is less than 5, it is used in the ink. When the SP value exceeds 15, the polarity as a solvent increases, and a resin which is easily dissolved in ethanol is also included as a resin to be used in the ink. This is not desirable.

Note that the SP value [dissolution parameter (δ)] defined in the present invention is expressed as a measure of the mixing property between components when mixing and dissolving, and the dissolution is expressed as follows. When two components, component 1 and component 2, dissolve, and the heat balance is considered assuming that the bond between 1-1 and 2-2 changes to 1-2 between the molecules, each molecule and its surroundings Since releasing from the intermolecular force of molecules means vaporization, the change in internal energy when the vaporized materials are mixed and aggregated as it is is represented by the following equation.
ΔE = ΔE1 + ΔE2-2 (ΔE1 · ΔE2) ^0.5
ΔE = [(ΔE1) ^0.5 − (ΔE2) ^0.5 ] ²
[ΔE1; internal energy change when component 1 is vaporized,
ΔE2: change in internal energy when component 2 is vaporized,
(ΔE1 · ΔE2) ^0.5 ; energy recovered by the binding energy created between 1 and 2]
That is, as (ΔE1) ^0.5 − (ΔE2) ^0.5 is smaller, the enthalpy change ΔH of dissolution is smaller and the dissolution is easier. When ΔE per unit volume of each component is referred to as cohesive energy, ΔE has a relation of enthalpy of evaporation ΔHV and ΔH = ΔE + RT. Therefore, ΔH is obtained from the temperature dependence of vapor pressure by the Clausius-Clapeyron equation. You can know.
Here, the square root of the cohesive energy density is called a dissolution parameter and is represented by the following equation.
δ = (ΔE / V) ^0.5
[ΔE: molecular aggregation energy (cal / mol), V: molecular volume (ml / mol)]
There are various methods for obtaining the values, and slightly different values are obtained depending on the measurement method and the calculation method. Specific examples thereof include a latent heat of vaporization method (Hildebrand method), a vapor pressure method (Hoy method), a dissolution method, a swelling method, a surface tension method, a critical pressure method, a thermal expansion coefficient method, and a molecular attraction constant method. In the present invention, it basically means a numerical value based on the latent heat of evaporation method.

On the other hand, if the vapor pressure (20 ° C.) of the organic solvent is less than 0.001 mmHg, drying becomes poor when printing as an ink, which is not preferable, and if the vapor pressure (20 ° C.) exceeds 45 mmHg, In terms of product performance, it is not preferable since the dry-up (drying) on the stamped surface of the infiltration stamp and on the board surface of the stamp stand and vermilion stand severely affect the stamping performance.

By using an organic solvent having the above-mentioned SP value (δ), the desired pigment can be dispersed and the sticking property (stability) can be exhibited, and the vapor pressure (20 ° C.) [p] can be obtained. By using an organic solvent, it can exhibit excellent quick-drying properties, and imprints imprinted on non-permeable surfaces such as adhesive tape, paraffin paper, plastic, ceramics, metal, etc. with poor wettability can be quickly fixed. Become.

  The organic solvent used in the present invention is not particularly limited as long as it is an organic solvent within the range of the SP value and the vapor pressure (20 ° C.), but from the viewpoint of cost, safety, handleability, and the like, It is desirably at least one selected from the group consisting of glycol ethers, glycol ether acetates, and esters.

As glycol ethers, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol dimethyl ether, ethylene glycol Dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether , Tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene Glycol monobutyl ether, propylene glycol monophenyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxy -1-butanol, diethylene glycol methyl ethyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-hexyl ether.
Examples of the glycol ether acetates include, for example, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol diacetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, and propylene glycol. Examples include diacetate, dipropylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, and 3-methoxybutyl acetate.

As the esters, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, 2-methylpentyl acetate, acetic acid-1 -Methylamyl, heptyl acetate, octyl acetate, 2-ethylhexyl acetate, nonyl acetate, decyl acetate, n-methyl acetate, isobutyl isobutylate, methyl caproate, ethyl caproate, ethyl caprylate, ethyl lactate, n-butyl lactate , Diethyl succinate, ethyl 3-toxoxypropionate, and the like.

These organic solvents can be used alone or as a mixture of two or more kinds. From the viewpoint of safety and oral toxicity, it is more preferable to use an organic solvent other than an ethylene glycol derivative or the like. .

The amount of the organic solvent that satisfies the above conditions used in the present invention varies depending on the usage mode of the organic solvent, that is, the amount of the organic solvent used alone or in the case of using a mixture of two or more kinds. And it is 20 to 97% by weight, preferably 30 to 93% by weight based on the total amount of the ink composition. When the amount of the organic solvent is less than 20% by weight, the fluidity of the ink becomes poor. When the amount exceeds 97% by weight, the ratio of the colorant, the resin and other additives decreases, and the quality of the product increases. It is not preferable because it has an effect.

Examples of the colorant used in the present invention include pigments and / or dyes. The dye is preferably a dye having low solubility in water and ethanol. As the pigment, an organic pigment or an inorganic pigment can be used, and a pigment which is hardly dissolved in an organic solvent to be used is preferable. In the case of organic pigments, those having an average particle diameter after dispersion of 30 nm to 700 nm are preferable, and in the case of inorganic pigments, those having an average particle diameter after dispersion of 30 nm to 10 μm are preferable. The dye is not particularly limited as long as it has low solubility in water and ethanol, but its solubility is 10% or less at room temperature and 3% or more soluble in main solvent at room temperature. Is mentioned. In addition, a combination of a dye and a pigment may be used as long as the stability such as the sedimentation of the pigment and the increase in viscosity is not bad.

The compounding amount of the pigment is 0.5 to 25% by weight, preferably 0.5 to 20% by weight, and the dye is 0.1 to 35% by weight, preferably 0.5 to 25% by weight, based on the total amount of the ink composition. It can be blended as needed within the range of up to 20% by weight.

Examples of usable inorganic pigments include, for example, carbon black, titanium black, zinc white, red iron oxide, titanium oxide, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, and cadmium. Red, yellow lead, molybdenum orange, zinc chromate, strontium chromate, white carbon, clay, talc, ultramarine, sedimentable barium sulfate, barite powder, calcium carbonate, lead white, navy blue, manganese violet, aluminum powder, brass powder, etc. And inorganic pigments.

Examples of usable organic pigments include aniline-based, cyanine-based, azo-based (monoazo-based, disazo-based), phthalocyanine-based, and azine-based pigments. These can be used alone or in combination of two or more. . Typical specific examples include yellow organic pigments such as Hansa Yellow and Benzidine Yellow, orange organic pigments such as Benzidine Orange and Permanent Orange, lake organic pigments such as Lake Red and Permanent Carmine, quinacridone violet, and dioxazine violet. Organic pigments such as purple organic pigments, blue organic pigments such as phthalocyanine blue and fast sky blue, and green organic pigments such as phthalocyanine green and permanent brown.

Further, styrene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, a resin emulsion obtained by polymerizing olefinic monomers, and a hollow resin emulsion that swells in ink and becomes amorphous. Alternatively, an organic multicolor pigment composed of dyed resin particles obtained by dyeing these emulsions themselves with a coloring agent may be used.

Dyes soluble in the above organic solvents and suitable for the present invention include, for example, C.I. I. solvent black 3, C.I. I. solvent black 5, C.I. I. solvent black 7, C.I. I. solvent black 27, C.I. I. solvent black 29, C.I. I. solvent black 34, C.I. I. solvent yellow 2, C.I. I. solvent yellow 14, C.I. I. solvent yellow 16, C.I. I. solvent yellow 29, C.I. I. solventyellow 33 C.I. I. solvent yellow 56, C.I. I. solvent yellow 77, C.I. I. solvent yellow 79, C.I. I. solvent yellow 82, C.I. I. solvent yellow 93, C.I. I. solvent red 1, C.I. I. solvent red 3, C.I. I. solvent red 4, C.I. I. solvent red 8, C.I. I. solvent red 18, C.I. I. solvent red 24, C.I. I. solvent red 27, C.I. I. solvent red 49, C.I. I. solvent red 111, C.I. I. solvent red 132, C.I. I. solvent red 135, C.I. I. solvent red 179, C.I. I. solventred 218, C.I. I. solvent blue 14, C.I. I. solvent blue 25, C.I. I. solvent blue 35, C.I. I. solvent blue 70, C.I. I. solvent blue 94, Basic blue 7, C.I. I. solvent orange 45, C.I. I. solvent orange 60, C.I. I. solvent orange 62, C.I. I. solvent green 3, C.I. I. solvent violet 8, C.I. I. solvent violet 13, C.I. I. solvent violet 14, C.I. I. solvent brown 5 and the like, and other examples thereof include salt derivatives of these derivatives and water-resistant dyes.

The resin used in the present invention differs in the properties of the resin depending on the colorant used.When a pigment is used as the colorant, the resin can serve as a dispersant or a dispersant-fixing agent, and is dissolved in the organic solvent. What is necessary is just to disperse the pigment, and when a dye is used as the colorant, it is compounded as a fixing agent.

In the present invention, when the colorant is a pigment alone, one or more of a dispersing resin or a dispersing / fixing resin having a solubility in water and ethanol at 25 ° C. of 7% or less is used. Further, a fixing resin may be further added. When the colorant is a dye alone, a fixing resin having a solubility in water and ethanol at 25 ° C. of 1% or less is used, and when the colorant is a combination of a pigment and a dye, the fixing resin at 25 ° C. One or more of a dispersing resin or a dispersing and fixing resin having a solubility in water and ethanol of 7% or less is used, and the fixing resin is used according to the performance of the ink.

By using a resin under these conditions, it is possible to exhibit the stability of the ink, the water resistance and alcohol resistance of the imprint, and the fixability (fastness) of the imprint. If the dispersing resin has a solubility of more than 7% in water and ethanol at 25 ° C. and a fixing resin having a solubility of more than 1%, the water resistance and alcohol resistance of the imprint will be poor, and the colorant will be resistant to water and alcohol. Is undesirably reduced or disappears.

It is necessary that the dispersing resin used in the present invention has a solubility in water and ethanol at 25 ° C. of 7% or less, preferably 3% or less, more preferably 1% or less. There is no particular limitation, and the solubility of the fixing resin in water and ethanol at 25 ° C. must be 1% or less.

Examples of the resins satisfying these physical properties include vinyl resins such as vinyl chloride / vinyl acetate copolymer, hydroxyl-modified vinyl chloride / vinyl acetate copolymer, carboxyl-modified vinyl chloride / vinyl acetate copolymer, and modified vinyl resins thereof, and methacrylic acid. And acrylic resins such as polymers using special acrylic monomers using homo- and copolymers of homo- and copolymers of esters of acrylic acid or their derivatives, fluoroolefins and multiple alkyl vinyl ethers Fluorinated resin (for example, trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), trade name "Fluonate K-702, K-705" (manufactured by Dainippon Ink and Chemicals, Inc.)), and other synthetic resins Rosin-modified maleic resin and rosin-modified Lumpur resin and the like can also be used if low acid value [for example, trade name "Becca site" (manufactured by Dainippon Ink and Chemicals, Inc.)].

Other resins belonging to the range of solubility as resins used in the present invention include, for example, trade names “Solsperse 24,000SC”, “Solsperse 24,000GR”, “Solsperse 26,000”, “Solsperse 28, 000 "(manufactured by Zeneca, (formerly ICI)).
Further, resins other than these can be used without any particular limitation as long as they are within the above-mentioned range of physical properties and do not adversely affect the stability of the ink.
These resins may be blended in an amount of at least 1% by weight or more, preferably in the range of 1 to 15% by weight.

In the above resin, a resin produced by a solution polymerization method, for example, an acrylic resin or lumiflon is dissolved in an organic solvent (eg, ethyl acetate, butyl acetate, toluene, etc.) in 30 to 70%. Therefore, these resins were used after insolubilizing the solid content once and drying them, and then confirming their solubility in ethanol and water.

Examples of the fluorine-based surfactant used in the present invention include a surfactant having a perfluoroalkyl group or a fluorinated alkyl group, or an oligomer thereof. Specifically, perfluoroalkyl alkoxylate [trade name "FC-171" (manufactured by Sumitomo 3M)], fluorinated alkyl ester [trade name "FC-430", "FC-431" (manufactured by Sumitomo 3M) And perfluoroalkyl-containing oligomers (trade names “S-381”, “S-383”, “S-393”, “SC-101”, “SC-105” (manufactured by Asahi Glass Co., Ltd.)) and perfluoroalkyl ethylene oxide Additives [trade name “KH-40” (manufactured by Asahi Glass Co., Ltd.)], special compound containing perfluoroalkyl [trade name “SA-100” (manufactured by Asahi Glass Co., Ltd.)], and oligomers containing perfluoroalkyl group and hydrophilic group [Product name "F-171" (manufactured by Dainippon Ink and Chemicals, Inc.)], oligomer containing perfluoroalkyl group and lipophilic group [Product name "F-172", "F-173" (Dainichi) Ink Chemical Co., Ltd.)], a perfluoroalkyl group / (hydrophilic group / lipophilic group) -containing oligomer [trade name "F-177" (Dainippon Ink Chemical Co., Ltd.)], a perfluoroalkyl group-containing oligomer [trade name "F-178A", "F-178K", "F-179" (manufactured by Dainippon Ink and Chemicals, Inc.)], urethanes containing perfluoroalkyl groups and lipophilic groups [trade names "F-183", "F-184" (Manufactured by Dainippon Ink and Chemicals, Inc.)], oligomers containing a perfluoroalkyl group and a lipophilic group (trade names “EF-801” and “EF-351” (manufactured by Mitsubishi Materials Corporation), perfluoroalkyl groups and hydrophilic properties) Group-containing oligomers such as EF-802 and EF-352 (manufactured by Mitsubishi Materials Corporation) can be used, and these can be used alone or in combination of two or more.

The amount of these fluorine-based surfactants is 0.01 to 15% by weight, preferably 0.1 to 7% by weight, based on the total amount of the ink composition. If the amount of the fluorine-containing surfactant is less than 0.01% by weight, the effect on the printing surface having releasability or water repellency is extremely reduced in terms of product performance. On the other hand, if it exceeds 15% by weight, the ink viscosity, the ink stability, and the drying property when printing are reduced, which is not preferable.

Furthermore, in the present invention, if necessary, other dispersants, dispersing aids, and preservatives, fungicides, surfactants, rust inhibitors, and lubricants that can be compatible without adversely affecting the ink. An agent and a wetting agent can be blended, and an auxiliary solvent can be blended in terms of product performance as long as the stability of the ink is not impaired. In addition, a non-volatile solvent (for example, a castor oil-modified product) that is compatible with the main solvent as long as it does not adversely affect the product properties can be blended as an auxiliary solvent for suppressing drying.

Examples of preservatives or fungicides include phenol, sodium omazine, sodium pentachlorophenol, 1,2-benzisothiazoline 3-one, 2,3,5,6-tetrachloro-4 (methylsulfonyl) pyridine, Examples thereof include alkali metal salts of benzoic acid such as sodium benzoate, sorbic acid and dehydroacetic acid, and benzimidazole compounds.

Examples of the rust preventive include benzotriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, tolyltriazole and the like.

Examples of the lubricant and the wetting agent include polyether-modified silicone such as polyethylene glycol adduct of dimethylpolysiloxane.
In addition, additives other than these can be blended within a range that does not adversely affect the intended ink composition.

The ink viscosity of the ink composition for penetrating printing, stamping board, and vermilion ink of the present invention needs to be 10 to 3000 mPa · s (25 ° C., E-type viscometer, 20 rpm measured value). The viscosity is appropriately adjusted within the above viscosity range depending on the use of the stamp base. By setting the viscosity in the above range, the ink can be transferred to the printing surface as a penetrating mark, a stamp stand, and a vermilion, and if the viscosity is less than 10 mPa · s, it is impossible to adjust the outflow amount of the ink. If the viscosity exceeds 3,000 mPa · s, the amount of ink flowing out is small and the sharpness of the imprint is poor, which is not preferable.

Further, the ink composition for penetrating printing, stamping and vermilion of the present invention preferably has a surface tension of the ink of 13 to 40 dyn / cm, preferably 14 to 30 dyn / cm. When the surface tension of the ink is less than 13 dyn / cm, bleeding as a product performance and direct current (ink dripping) from an outflow mechanism (pen core or the like) become problems, and if the surface tension exceeds 40 dyn / cm. The solvent is in a range that does not dissolve the ink composition material, which is not preferable.

In order to produce the ink compositions for penetrating printing, stamping and vermilion of the present invention, various conventionally known methods can be employed. For example, the above-mentioned components are blended and mixed and stirred by a stirrer such as a dissolver, or mixed and pulverized by a ball mill, a three roll, a bead mill, a sand mill, etc., and then centrifuged or filtered to obtain pigment particles or oxidized particles. It can be easily obtained by removing coarse particles of titanium particles, undissolved matter, and mixed solid matter.

  The sliding piece 6a has a projection 22a on the outer surface, a central portion protruding from the rear end surface of the projection 22a, and both sides thereof have a cam slope having substantially the same gradient as the cam slope 14 of the cylindrical cam 5 described above. I have. Further, a hole is provided which abuts against the flange portion 24 of the core pipe 23 to protrude and fit the rear of the core pipe 23 long. Further, the sliding piece 6b has a projection 22b and a cam slope like the sliding piece 6a, and is provided at its tip with a locking portion 26 for fastening the rear end of the ballpoint pen writing lead 8. Note that the locking portion may be formed in a pipe shape and the rear end of the writing lead may be fitted thereto.

  The mechanical pencil writing lead 7 has a built-in general chuck mechanism, is joined to the core pipe 23 via a joint 29 connected to the chuck mechanism at the rear end, and comes into contact with a flange portion 24 provided behind the core pipe 23. The sliding piece 6 is fitted to the sliding piece 6a, and the rear end hole of the core pipe 23 projecting from the rear end of the sliding piece 6a is closed by a tail plug 25 or the like. The leading of the lead is performed by moving the chuck by moving the sliding piece 6a while the step 28 at the tip of the mechanical pencil 7 is in contact with the inner step 27 of the front shaft 3.

  Next, a description will be given in assembling order. The mechanical pencil 7 and the ball-point pen 8 are respectively connected to the sliding pieces 6a and 6b at the rear ends thereof, so that the guide grooves 9a and 9b of the above-mentioned center axis guide cylinder 2 are formed. And is urged rearward by return springs 30a, 30b interposed between the front end surfaces of the sliding pieces 6a, 6b and the partition portions 16 on the front surfaces of the guide grooves 9a, 9b.

The rear shaft 4 is formed by inserting the cylindrical cam 5 into the rear end hole of the center shaft 1 so that the protrusion 17 is elastically fitted into the circumferential groove 19, and is rotatable at substantially 180 degrees in the circumferential direction with respect to the center shaft 1 and is prevented from coming off. And is stopped.
In the state where the mechanical pencil writing lead 7 is protruded, the rear shaft 4 can be shifted by the stroke necessary for feeding the center with respect to the center shaft 1, and when the writing lead is stored or the ballpoint pen writing lead 8 is projected. The axis transition is made impossible.
Since the sliding pieces 6a, 6b are constantly urged rearward by the return springs 30a, 30b, the cam slopes of the projections 22a, 22b are always kept in contact with the cam slope 14 of the cylindrical cam 5.

    In addition, separately from the above-described embodiment, a flange-shaped protrusion is provided in the inner hole of the cylindrical cam, a circumferential groove is provided on the outer periphery of the rear end of the guide cylinder, and the protrusion is elastically fitted into the circumferential groove, It is also possible to constitute so that the cylindrical cam is rotatable with respect to the guide cylinder and is prevented from falling off.

  Also, with the rear end surface of the front shaft 3 in contact with the front surface of the step portion 31 of the center shaft 1, the engaging portion 13 of the tubular portion 10 is elastically fitted into the engaging groove 12 of the front shaft 3. The shaft 3 and the center shaft 1 are fixed in a state where they are stopped from rotating and come off. The tip shaft 3 is detachable with an appropriate force. In this state, when the rear shaft 4 is rotated in one direction with respect to the front shaft 3 or the center shaft 1, the sliding piece 6a moves forward and the notch 15 at the foremost end of the cam slope 14 of the cylindrical cam 5 becomes one of the mechanical pencil writing cores. 7 is locked to the projection 22a of the sliding piece 6a, so that the writing tip projects from the tip end of the front shaft. When the rear shaft 4 is rotated in the other direction with respect to the front shaft 3 or the center shaft 1, the sliding piece 6a is retracted, and the writing tip of the mechanical pencil writing lead 7 is immersed from the tip of the front shaft. 6b moves forward, and the writing tip of the other ball-point pen writing core 8 projects from the tip of the front shaft.

In the case where the cap 40 is fitted to the rear shaft 4, when the cap 40 is rotated in one direction with respect to the front shaft 3 or the center shaft 1, the sliding piece 6 a moves forward and the top of the cam slope 14 of the cylindrical cam 5 is moved. The notch 15 at the front end is engaged with the projection 22a of the sliding piece 6a of the one mechanical pencil writing lead 7, so that the writing tip projects from the tip end of the front shaft. If the rear end of the cap 40 (rear end of the crown 50) is knocked with respect to the front shaft 3 and the center shaft 1, the step 28 of the mechanical pencil writing lead 7 is in contact with the inner step 27 of the front shaft 3. The chuck mechanism operates and the lead is extended.
When the cap 40 is rotated in the other direction with respect to the front shaft 3 or the center shaft 1, the sliding piece 6a is retracted so that the writing tip of the mechanical pencil writing lead 7 is immersed from the tip of the front shaft and the sliding piece 6b is rotated. Moves forward, and the writing tip of the other ball-point pen writing core 8 projects from the tip end of the front shaft.

  FIGS. 3 and 4 show another example of the engagement between the projection 17 of the cylindrical cam and the center shaft 1a. In this case, as a means for fitting the protrusion 17 into the circumferential groove 60, a partition wall 62 having an inclined surface 63 is provided on the upper wall of the guide groove 61 for fitting the protrusion 17 from the rear end of the center shaft 1a. . The reason for providing the partition wall 62 is to enhance the rigidity of the center shaft 1a in the engaging portion.

As described above, when the cap 40 is rotated in one direction with respect to the front shaft 3 or the center shaft 1, the notch 15 provided at the tip of the cam slope 14 of the cylindrical cam 5 as shown in FIG. , And its writing tip protrudes from the tip end of the front shaft.
At this time, the projection 17 of the cylindrical cam 5 is located in the wide groove 55 in the circumferential groove 19 of the center shaft 1.
In this state, when the rear end of the crown 50 is knocked and the cylindrical cam 5 is moved forward, the operation is transmitted to the sliding piece 6a, the core pipe 23, and the mechanical pencil writing core 7, and the step 28 of the writing tip is firstly moved. The chuck advances together with the joint 29 from the state in which it comes into contact with the inner step portion 27 of the shaft 3, and the lead is fed out.
By the way, when the rear end of the crown 50 is knocked, the interval between the step portion 43d of the knock tube 41 and the step portion 44a of the fixing tool 44 is set appropriately larger than the small interval, so that the knock tube 41 moves forward. The vermilion 45 bites into the stamp surface 38 by a predetermined amount, and an appropriate amount of vermilion adheres to the stamp surface. Therefore, the vermilion is usually abundantly attached to the stamp surface without knocking to attach the vermilion to the stamp surface with particular consciousness.

  When the cap 40 is rotated to the other end with respect to the front shaft 3 or the center shaft 1, the mechanical pencil writing lead 7 is retracted, and the writing tip of the ball-point pen writing lead 8 protrudes from the tip of the front shaft instead. When the writing lead is stored and the ball-point writing lead 8 is projected, the projection 17 is located in the narrow groove 56 of the circumferential groove 19 and knocks, and the wall 20 of the rear shaft 4 is knocked at the rear end of the center shaft 1. Since the projection 17 does not contact the front wall 58 of the circumferential groove 19 in the contact state, the projection and the like do not break.

Next, when the cap 40 is removed from the outer cylindrical portion 33 of the rear shaft 4, the stamped surface 38 of the seal 37 is exposed, so that the stamped surface 38 can be stamped downward. Further, when the knock cover 49 with the crown at the rear end of the cap 40 is removed, the friction tool 51 is exposed, and erroneous characters can be corrected when a mechanical pencil is used.
When the knock cover 49 is removed from the rear shaft portion 43b of the knock cylinder 41, the locking portion 47a of the locking spring 47 fixed to the outer periphery of the rear shaft portion 43b is substantially in contact with the rear end of the cap 40. Even if the friction tool 51 is pressed, the knock cylinder 41 does not retreat. Accordingly, since the front surface of the vermilion 45 does not contact the stamped surface 38, there is no concern that the stamped surface 38 will be stained with vermilion even if the friction tool is violently pryed off. When the knock cover 49 is attached, the locking portion 47a is elastically deformed, the contact state between the locking portion 47a and the rear end of the cap 40 is released, and the knock cylinder 41 moves forward at a predetermined interval. It becomes possible.
Further, the locking spring 47 is desirably made of metal having excellent spring properties, but may be formed integrally with a resin knock cylinder.

By the way, the configuration of the knocking portion on which the vermilion is mounted is not limited to the above-described embodiment. For example, when the knocking cylinder 41 is knocked, the advancement is stopped when the stepped portion 43d comes into contact with the stepped portion 44a of the fixing tool 44, so that the stamp face 38 is usually extremely dirty with vermilion when the friction tool is erased. Problems can be prevented. Therefore, it may not be necessary to provide the locking spring 47. Further, the structure for attaching the knock cylinder to the cap and the contact structure for preventing advancement are not limited to the above-described embodiment, and can be provided.
Further, by providing the front end of the crown 50 so as to be in contact with the rear end of the cap 40, it is possible to omit the contact portion between the cap and the knock cylinder.
In addition, the mechanism that allows a plurality of writing cores to be mounted so that the tip of the writing core can be selectively protruded and retracted from the shaft tip is not limited to the above-described structure for rotating the cylindrical cam, but also includes a slider type, a knock type, and a pendulum type. For example, a structure used for a conventional double-type writing instrument can be applied.

DESCRIPTION OF SYMBOLS 1 Middle shaft 1a Middle shaft 2 Guide cylinder 3 Front shaft 4 Rear shaft 5 Cylindrical cam 6a Sliding piece 6b Sliding piece 7 Mechanical pencil writing lead 8 Ballpoint writing lead 9a Guide groove 9b Guide groove 10 Tube part 11 Knock spring 12 Engagement groove 13 Engaging part 14 Cam slope 15 Notch 16 Partition part 17 Projection 18 Vertical groove 19 Peripheral groove 20 Wall 22a Projection 22b Projection 23 Core pipe 24 Flange part 25 Tail plug 26 Locking part 27 Inner part 28 Step part 29 Joint 30a Return spring 30b Return spring 31 Stepped portion 32a hole 32b hole 33 Outer tube portion 34 Outer tube portion 35 Flange portion 36 Engagement portion 37 Seal stamp 38 Stamped surface 39 Clip 40 Cap 41 Knock tube 42 Vermilion accommodating portion 43a Front shaft portion 43b Rear shaft portion 43c flange Part 43d Step 43e Hole 44 Fixture 44a Step 45 6 Inner Step 47 Locking Spring 47a Locking Portion 48 Spring 49 Knock Cover 50 Crown 51 Friction Tool 52 Stopper 53 Slope 54 Narrow Part 55 Wide Groove 56 Narrow Groove 57a Rear Wall 57b Slope 57c Rear Wall 58 Front wall 60 Peripheral groove 61 Guide groove 62 Partition wall 63 Inclined surface

Claims (2)

Housing the writing lead that one end filled with thermochromic ink of the barrel houses a friction device to discolor the seal and thermochromic inks without using a thermochromic ink with a ink pad at the other end, the thermochromic The thermochromic microcapsule pigment as a coloring material of the water-based ink is blended in an amount of 4 to 30% by weight based on the total amount of the ink composition, and the vermilion is selected from the group consisting of glycol ethers, glycol ether acetates, and esters. At least one organic solvent, a coloring agent comprising a pigment and / or a dye, and a dispersing resin having a solubility in water and ethanol at 25 ° C. of 7% or less at 25 ° C. when the coloring agent is a pigment, When the colorant is a dye, the ink composition contains a fixing resin having a solubility of 1% or less in water and ethanol at 25 ° C. and a fluorine-based surfactant. Thermochromic writing instrument characterized by comprising the addition of an alkyl sulfonic acid phenyl ester, cyclohexane dicarboxylic acid esters and phthalic acid-based plasticizer. A ballpoint pen writing core containing thermochromic ink is mounted in the shaft cylinder, and the tip of the writing core can be protruded and retracted from the shaft tip, a seal is fixed to the rear end of the rear shaft, and the outer periphery of the rear shaft A long fountain pen-shaped cap was removably fixed, and a seal was fixed to the rear end of the rear shaft with the seal face facing the rear end side, and the vermilion was held in front with the seal face facing the seal face at small intervals. The knock cylinder is constantly urged rearward against the cap by a spring force at the rear end of the cap inner hole, and after being able to advance at an appropriately larger interval than the small interval against the spring force, A locking portion is provided to prevent forward movement, and a rear end of the knock cylinder is provided so as to protrude from the rear end of the cap. A friction tool is fixed to the rear end, and further covers the friction tool. The knock cover is fixed to the outer periphery of the rear end Thermochromic writing instrument according to claim 1.