JP2005231234A - Thermally color changing writing material and writing material set using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermally color changing writing material which can form a script of an arbitrary writing line width changing according to writing pressure in a low writing pressure region and can form conveniently various thermally color changing images of characters, line drawings, patterns and others, and a writing material set the same. <P>SOLUTION: In the thermally color changing writing material and the writing material set using the same, a writing tip member is provided with a tapering contracted diameter part which can enlarge the writing line width by bending the writing tip in adaptation to an increase of the writing pressure in the limits of the writing pressure of 1-60 g and reduces the writing line width by recovery from bending due to lessening of the writing pressure. Through the intermediary of this writing tip member, an arbitrary image is formed by a thermally color changing coloring material which is prepared by dispersing in a water-based medium a reversible thermal-color changing microcapsule pigment which has transitory color changing temperature regions on the low and high temperature sides and presents a transitory color in a process to a complete color change. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermochromic writing material. Specifically, in a writing material that forms an arbitrary temperature-sensitive color-change image using a temperature-sensitive color-changing color material in which a reversible thermochromic microcapsule pigment is dispersed in an aqueous medium via a writing tip member, a low writing pressure region A thermosensitive color-changing writing material capable of easily forming various temperature-sensitive color-change images such as letters, line drawings, and patterns by forming handwriting of any writing line width adapted to the strength of writing pressure in It relates to the writing material set used.

Conventionally, several proposals have been disclosed regarding a writing instrument for forming a thermochromic handwriting (see, for example, Patent Documents 1 to 3).
However, an effective proposal that satisfies the merchantability has not yet been disclosed with respect to a convenient writing material that forms a wide variety of temperature-sensitive color-change images having an arbitrary handwriting width in the low writing pressure region.
Japanese Patent No. 2540341 JP-A-9-124993 JP 2001-207101 A

Conventional thermochromic writing tools can form handwriting with a fixed writing line width depending on the ball diameter when the writing tip is a rolling element such as a metal ball, but the user can write handwriting with any writing line width when writing. It cannot be formed.
Also, resin processed or fused processed bodies of fibers forming capillary gaps, felt bodies, plastic porous bodies having continuous pores, etc. are disclosed, but the writing angle is changed or the specific shape portion of the writing tip is written. Even if the writing line width can be changed by contacting the surface, it is not possible to form a handwriting having a writing line width that changes in accordance with the writing pressure in the low writing pressure region.
Furthermore, even if the writing tip is deformed at a writing pressure of 100 g or more and the writing line width can be widened, the writing pressure tends to be applied directly to the writing surface and damage the paper surface.
The present invention can easily form a handwriting with a writing line width that adapts to the writing pressure in a low writing pressure range, particularly in the range of the writing pressure of 1 to 60 g, without damaging the writing surface. It is possible to form a pattern by a variety of temperature-sensitive color-changing images in combination with the application of temperature-sensitive and various color-changing color materials. It is intended to provide a thermochromic writing material suitable for use and a writing material set using the same.

The present invention will be described with reference to the drawings (see FIGS. 1 to 7).
The present invention is a writing material 1 or 11 for forming an arbitrary image by the thermochromic color material 5 through the writing tip member 2, and the writing tip member 2 has a reduced diameter portion 21 having a tapered shape. In response to an increase in writing pressure in the range of 1 to 60 g of writing pressure, the reduced diameter portion 21 is bent to widen the writing line width, and in response to a decrease in writing pressure, the bending is recovered to reduce the writing line width. The temperature-sensitive color-changing color material 5 is restored to its original shape and the temperature-sensitive color-changing color material 5 has a high-temperature side color change start temperature (t ₃ ) and a high-temperature side complete color change temperature (t ₄ ) in the temperature-color density curve. ), And the temperature range of each transitional discoloration temperature region between the low temperature side discoloration start temperature (t ₂ ) and the low temperature side complete discoloration temperature (t ₁ ) is in the range of 1 to 10 ° C. Temperature-sensitive color-changing writing material comprising 3 to 40% by weight of an aqueous microcapsule pigment dispersed in an aqueous medium , It is a requirement 11.
Furthermore, the temperature-sensitive color-changing color material 5 is selected from any one of temperature-sensitive color-changing inks, pastes, or semi-solids or solids, and the temperature-sensitive color-changing writing materials 1 and 11 are temperature-sensitive color-change materials. Writing instrument form 1 (see FIG. 1) in which the ink is accommodated in the shaft cylinder 4 and led out continuously from the writing tip member 2, or temperature-sensitive color changing ink, paste, semi-solid or solid The storage body 6 in which the container is housed in the container and the writing body 7 to which the writing tip member 2 is attached (see FIG. 2), and the base body of the writing tip member 2 is made of fibers. Selected from fiber bundles closely bundled in the longitudinal direction, plastic porous body having continuous pores, synthetic resin fiber heat fusion or resin processed body, soft resin or elastomer extrusion processed body, writing tip member 2 substrate has an outer diameter of 2 to 10 m It has an arbitrary outer diameter (D) selected from the range of Φ, and the outer diameter (D) and the length (L) of the tapered portion of the tapered tapered diameter portion 21 are L / D = 2-5. The tapered diameter-reduced portion 21 has a fiber converging body in which the tapered sides of the synthetic resin fiber processed into a tapered shape are closely arranged in the same direction, or different fibers are closely arranged. It consists of a fiber concentrator configured in a tapered shape, and is formed by joining, fusing, or bundling the base end, and in the range of 1 to 60 g of writing pressure, the writing line width is adapted to increase in writing pressure. The maximum value of the writing line width at the time of widening, writing at a writing angle of 90 ° and applying the writing pressure approximates the outer diameter (D) of the base body of the writing tip member 2, and writing at a writing angle of 60 ° The maximum value of the writing line width approximates the length (L) of the tapered portion, and the writing line width that has reached each of the maximum values. , Be restored by reducing to accommodate the reduction in writing pressure based on the writing line width, the hot side complete discoloration temperature of the reversible thermal discoloration microcapsule pigment (t ₄₎ is 21 ° C. to 65 ° C., the low temperature side complete Two or more types in which the color change temperature (t ₁ ) is in the range of −30 ° C. to + 20 ° C., the high temperature side color change start temperature (t ₃ ) and the low temperature side color change start temperature (t ₂ ) are different, and the hues are different. A reversible thermochromic microcapsule pigment, a non-thermochromic colorant is blended in the reversible thermochromic microcapsule pigment, or in an aqueous medium, and the hue is changed in a transient color change temperature range. The requirement is to show multi-stage changes due to changes, and to incorporate a metallic luster pigment.
Furthermore, among the thermochromic writing materials 1 and 11, three kinds of writing materials that exhibit red, blue, and yellow handwriting at the time of color development are essential, and the writing material that exhibits black handwriting or A writing material set in which a fiber bundle for attaching and applying water is set as a requirement.

The temperature-sensitive color-changing writing material of the present invention can form handwriting with a writing line width that adapts to the writing pressure in the low writing pressure (1 to 60 g) region, and enables the formation of individual characters, line drawings, patterns, etc. A wide variety of temperature-sensitive color change images can be formed in combination with the color change effect of the temperature-sensitive color change colorant.
In particular, in the formation of a pattern or the like by overdrawing, there is no damage to the writing surface, and in combination with the characteristics of the aqueous medium, it is possible to provide color mixing and shading on the writing surface.
In addition, red, blue and yellow writing materials are essential for color development, black writing materials, and writing material sets equipped with a fiber bundling body for attaching and applying water. Therefore, it is possible to improve the convenience and convenience of the user as a multicolored writing material or as an art material for forming a shading pattern or the like.

The tapered diameter-reduced portion 21 of the writing tip member 2 bends in accordance with the writing pressure at the time of writing in the low writing pressure (1 to 60 g) region, thereby writing the writing line width with the writing pressure adaptability. Form.
Since the handwriting that can be widened and shrunk can be formed in the low writing pressure region, it is possible to form a pattern by individual character formation, overdrawing, and color mixing, without causing fuzz or damage on the surface of the writing.
The system in which the base of the writing tip member 2 is made of a fiber bundling body is a type in which the tapered side of a synthetic resin fiber processed into a tapered shape is closely arranged in the same direction to form a tapered taper-shaped reduced diameter portion 21. And the like, in which the fibers are closely arranged and the tapered diameter-reduced portion 21 is formed.
The tapered taper fibers include polyamide (6-nylon, 6, 6 nylon, 6, 10-nylon, 6, 12-nylon, 12-nylon, etc.), polyester (polyethylene terephthalate, poly, etc.) having a single fiber denier of 1 to 20d. Butylene terephthalate, etc.), polyolefin (polyethylene, polybutylene, etc.), polyurethane, polyacrylonitrile, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and other synthetic fibers can be exemplified, such as fibers having crimps, straight fibers, Highly elastic fibers and fibers having different cross-sections can be appropriately blended and applied.
In addition, as the system using the different kinds of fibers, it is effective to arrange fibers having different fiber diameters and rigidity, irregular cross-section fibers, and fibers having different cut lengths to form a tapered shape.
The system using the fiber bundle does not require a diameter reduction step by post-processing, and can be configured as a tapered diameter reduction portion 21, and the base end portion of the fiber bundle is bonded, fused, or bound and held. Attached to the part 3 for practical use. In addition, the system using a fiber bundle is rich in flexibility, resilience, and softness, and is effective for the formation of various handwriting with low writing pressure adaptability.Furthermore, when applying overdrawing, color mixing, blurring, etc. Does not cause damage to the writing surface.
The continuous porous plastic porous body is a molded body having a porosity of 30 to 80% made of a relatively soft material such as polyamide, polyurethane, polyolefin, elastomer, etc., and the tapered reduced diameter portion 21 is integrally formed during the molding process. Although it is molded, it can also be formed by grinding by post-processing.
The synthetic resin fiber heat-sealed or resin-processed system uses conventional synthetic resin fibers such as polyamide and polyester, highly elastic fibers, composite fibers, low-melting fibers, and the like. Examples include those having a porosity of 30 to 80% formed by the above, composite structure coalescence of synthetic resin fiber and elastomer resin, and the like.
The system by the extrusion molding which provides the ink conduction path in the internal axial direction by melt extrusion molding of the soft resin or elastomer is a processing body made of general-purpose materials such as polyamide, polyester, polyamide elastomer, polyurethane elastomer and polyester elastomer. It can be illustrated.
In the system of the heat-sealed or resin processed body and the extrusion-molded body, one end portion of the rod-shaped body is ground into a tapered shape to form a tapered reduced diameter portion 21.

The base body of the writing tip member 2 having an outer diameter in the range of 2 to 10 mmΦ satisfies suitability as a component of a writing instrument having formability of letters and pictures and portability.
Furthermore, by setting the outer diameter (D) of the substrate and the length (L) of the tapered portion of the tapered tapered diameter portion 21 to a relationship of L / D = (2-5) / 1, Appropriate deflection and resilience to adapt to the writing pressure can be given, and handwriting with a desired writing line width can be freely formed, satisfying repeated practicality.
In the system where the (L) value exceeds 5, the restoring property is insufficient and the ink outflow property is impaired. On the other hand, when the (L) value is less than 2, the flexibility is insufficient and it is difficult to satisfy the variable effect of the writing line width.
Furthermore, in the range of 1 to 60 g of the writing pressure, the maximum value of the writing line width when the writing pressure is increased by adapting to the increase of the writing pressure and writing at a writing angle of 90 °, Desirably, the writing tip member 2 has a flexibility sufficient to give a value approximate to the outer diameter (D) of the base body.
To further explain this point, the minimum writing line width in a substantially non-deflection state at a constant pressure in the range of 1 to 3 g of writing pressure, the writing line width that widens in accordance with the increase in writing pressure, and the writing pressure 50 to 60 g showing the maximum bending state and having the flexibility to repeatedly form the maximum writing line width corresponding to the diameter of the base end of the tapered reduced diameter portion 21, that is, the outer diameter (D) of the substrate. Is desirable.
Furthermore, in the range of the writing pressure of 1 to 60 g, the writing pressure adaptability is shown, and the maximum value of the writing line width when the writing pressure is applied by writing at a writing angle of 60 ° is the length of the tapered portion (L It is desirable to have a flexibility that gives a handwriting with a writing line width approximating to) in an area before the writing pressure of 50 to 60 g.
By adopting a configuration capable of forming a writing pressure-adaptive writing line width according to the writing angle, it is possible to effectively form handwriting having various desired writing line widths.
The tapered tapered reduced diameter portion 21 described above may be a pyramid shape, but a conical shape does not have directionality during use and satisfies the convenience. Here, the tapered portion is not limited to a linear shape, and may be a slight curved shape. Further, the tip is not limited to the pointed end, and may have an appropriate thickness and curved surface.

The reversible thermochromic microcapsule pigment applied to the present invention is selected from pigments exhibiting intermediate colors before and after complete color change in a specific temperature range, and contributes to versatility. Specifically, it is between the high temperature side color change start temperature (t ₃ ) and the high temperature side complete color change temperature (t ₄ ), or between the low temperature side color change start temperature (t ₂ ) and the low temperature side complete color change temperature (t ₁ ). Each transitional discoloration temperature range is selected from pigments in the range of 1 to 10 ° C. (preferably 3 to 8 ° C.), thereby achieving a color discrimination effect.
When the temperature range is less than 1 ° C., it is difficult to distinguish substantially. When the temperature range exceeds 10 ° C., the change in appearance is too slow to satisfy the visual effect.
In a colored-colorless system with a single thermochromic pigment, an intermediate color density is visualized, and in a system using a plurality of thermochromic pigments having different color-changing characteristics, the appearance of multistage discoloration is visualized and non-thermochromic. In a system in which a sex colorant coexists, an intermediate color between colored (1) and colored (2) is made visible. Furthermore, in a system in which a plurality of thermochromic pigments are applied, the discoloration visual temperature range can be widened in a combination system in which the discoloration temperature ranges of the pigments do not exist within each other. .
As shown in the temperature-color density curve (see FIGS. 3, 4, and 5), the color density in the transient color change temperature range is the color density in the complete color development temperature range and the complete color change state (including decoloring). It exhibits an intermediate color density with respect to the color density, and in the multi-stage color changing system, the appearance accompanying the change in hue is made visible.
The reversible thermochromic microcapsule pigment is 3 to 40% by weight, preferably 10 to 25% by weight, in an aqueous medium that forms the temperature-sensitive color-changing colorant 5 in the form of ink, paste, or semi-solid. Blended.
If the blending amount is less than 3% by weight, the color density in the colored state is low. On the other hand, if it exceeds 40% by weight, ink outflow from the writing tip member, homogeneous application, adhesion, etc. are impaired, and an afterimage tends to occur.

The reversible thermochromic microcapsule pigment determines conventionally occurring (i) electron-donating color-forming organic compound, (b) electron-accepting compound, and (c) occurrence temperature of the color reaction of both. The reversible thermochromic composition containing the essential three components of the reaction medium is effective when encapsulated in microcapsules, and the present applicant has proposed as a heat decoloring type that decolorizes by heating from a colored state. Those described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398 and the like can be used.
As shown in the temperature-color density curve of FIG. 3, the pigment discolors before and after a predetermined temperature (discoloration point), and exhibits a decolored state in a temperature range higher than the high temperature side complete discoloration temperature (t ₄ ). It exhibits a colored state in the temperature range below the complete color change temperature (t ₁ ) on the low temperature side, and only one specific state exists in the normal temperature range among the two states. That is, the other state is maintained while the heat or cold necessary to develop the state is applied, but when the heat or cold is not applied, the state returns to the state exhibited in the normal temperature range. The width is relatively small (ΔH _A = 1-8 ° C.).
Further, as a heat-decoloring type thermochromic pigment, Japanese Patent Publication No. 4-17154, Japanese Patent Application Laid-Open No. 7-179777, Japanese Patent Application Laid-Open No. 7-33997, Japanese Patent Application Laid-Open No. 8-39936, etc. proposed by the present applicant. The color memory holding type described in (1) can be used.
In the case of the pigment, the shape of the curve in which the change of the color density due to the temperature change is plotted as shown in the temperature-color density curve of FIG. The color changes by following a path that is largely different from when the temperature is lowered from the high temperature side, and the color development state in the low temperature range below the complete low temperature side discoloration temperature (t ₁ ), or the complete high temperature side discoloration temperature (t ₄ ) The above decolored state in the high temperature range is a large hysteresis characteristic (ΔH _B = 8 that can be stored and held alternately in a specific temperature range [temperature range (substantially two-phase holding temperature range) between t _{2 and} t _3]. ~ 80 ° C).
Furthermore, a system in which a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms as an electron-accepting compound is applied as a heat-coloring type thermochromic pigment that develops color by heating from a decolored state. (JP-A-11-129623, JP-A-11-5973), a system to which a specific hydroxybenzoic acid ester is applied (JP-A-2001-105732), a system to which a specific gallic acid ester is applied (special feature) No. 2003-253149) can be used (see FIG. 5).

The pigment applied to the present invention is, among the heat decoloring type thermochromic pigments, between the high temperature side color change start temperature (t ₃ ) and the high temperature side complete color change temperature (t ₄ ), or the low temperature side color change start. The temperature range of each transitional discoloration temperature range between the temperature (t ₂ ) and the low temperature side complete discoloration temperature (t ₁ ) is 1 to 10 ° C., preferably 3 to 7 ° C. It is preferable in terms of visual effect in the temperature range.
The low temperature side discoloration start temperature (t ₂ ) can be set to an arbitrary temperature selected from the range of −30 ° C. to + 20 ° C., and the high temperature side discoloration start temperature (t ₃ ) can be selected from the range of 25 ° C. to 60 ° C.
Here, even in the multi-stage color changing system (FIG. 6) to which the heat decoloring type thermochromic pigment is applied, the above relationship can be applied. In the heat coloring type thermochromic pigment system (FIG. 5), the relationships (t ₃ ) and (t ₄ ), (t ₂ ) and (t ₁ ) are respectively represented by (T ₃ ) and (T ₄ ). ), (T ₂ ) and (T ₁ ), the effect in the transient discoloration temperature range can be explained.

The microcapsule pigment does not refuse application in the form of a circular cross section, but is effective in the form of a noncircular cross section (see FIG. 7).
In the thermochromic handwriting 8 formed by the writing tip member 21, the microcapsule pigment is densely oriented and fixed with the long diameter side (maximum outer diameter side) in close contact with the writing surface, and has a high concentration. In addition to exhibiting color developability, the microcapsule pigment is slightly elastically deformed into a shape that reduces the external force against the external force associated with the formation of handwriting, the destruction of the wall film of the microcapsule pigment is suppressed, and the thermochromic function is impaired. And can be expressed effectively. Here, the non-circular cross-sectional shape microcapsule pigment has an average maximum outer diameter of 1 to 6 μm, preferably 1 to 5 μm, and a reversible thermochromic composition / wall film = 7/1 to 1. It is preferable to satisfy the range of 1/1 (weight ratio), preferably 6/1 to 1/1 (weight ratio).
In a system in which the average value of the maximum outer diameter of microcapsule pigments (including those having a circular cross-sectional shape) exceeds 6.0 μm, the flowability from the capillary gap tends to decrease, whereas the average value of the maximum outer diameter is 1 μm. If it is less than this, it will be difficult to show a high color density.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the wall film becomes too thin, and the resistance to pressure and heat tends to decrease. On the other hand, when the ratio of the wall film to the reversible thermochromic composition is larger than the above range, the color density and sharpness during color development tend to decrease.

  For the microencapsulation of the reversible thermochromic composition, known means such as an interfacial polymerization method, an interfacial polycondensation method, an in-situ polymerization method, a coacervate method and the like can be applied. In order to obtain a microcapsule pigment having a circular cross-sectional shape, it is preferable to apply an interfacial polymerization method or an interfacial polycondensation method that hardly causes aggregation and coalescence.

The writing materials 1 and 11 of the present invention are the writing instrument form 1 in which the temperature-sensitive color-changing ink is accommodated in the shaft cylinder 4 and is continuously derived from the writing tip member 2, or the temperature-sensitive color-changing ink, paste, or Any of a combination form 11 with a writing body 7 to which a semi-solid or solid body is appropriately stored in a container having a shape and size to form a storage body 6 and a writing tip member 2 prepared separately. Is effective.
In the system of the writing instrument form 1, various types of writing instruments that have been conventionally used can be used.
For example, the ink stored in the shaft cylinder or cartridge is led out to the writing tip by a knock mechanism provided at the rear of the shaft cylinder, the ink is stored in the flexible shaft cylinder, and the side of the shaft cylinder is placed on the fingertip In which the ink is led to the writing tip, and the needle valve for controlling the supply of ink is arranged in the path from the ink tank to the writing tip member 2 to provide the mechanism for controlling the ink drawing property, the shaft cylinder Examples include a mode in which the ink contained in the ink is led out to the writing tip through a valve mechanism, a mode in which the ink occlusion body impregnated with the ink is contained in the shaft cylinder, and the ink is led out to the writing tip by a capillary action. it can.
The temperature-sensitive color-changing ink is obtained by dispersing the reversible thermochromic microcapsule pigment in an aqueous medium at a ratio of 3 to 40% by weight, and a binder resin can be blended for adjusting the viscosity or imparting stickiness. It can be used for the writing instrument form or filled in the container in the combination form. In the latter case, water can be used in an appropriate amount and added, and a stirring ball for stirring is incorporated. May be.
Even if the binder resin is blended, it is water-soluble immediately after writing, and does not hinder color mixing due to overdrawing or imparting lightness and darkness.
In addition, in order to delay the sticking property of a handwriting, the below-mentioned wetting agent and its compounding quantity can also be adjusted suitably.
As temperature-sensitive color-changing inks, inks in the above-mentioned dispersed state, inks that are easily dispersible by stirring means such as stirring balls, shear-thinning inks that contain shear-thinning substances, and water-soluble polymers Examples thereof include agglomerated ink in which capsule pigments are suspended in a gentle agglomerated state, and a specific gravity control type ink in which the specific gravity difference between the pigment and the aqueous vehicle is adjusted to 0.05 or less.
The viscosity of each ink is in the range of 3 to 90 mPa · s (25 ° C.) depending on the form of the writing instrument and the structure of the writing tip member 2.
For example, Japanese Patent Application Laid-Open No. 9-124993 proposed by the present applicant is applied to the shear-thinning ink, and the reversible thermochromic microcapsule pigment is 3 to 40% by weight, and the shear-thinning substance 0.1 to 0. 5 parts by weight, containing 5 to 35% by weight of a water-soluble organic solvent, blending an appropriate amount of a non-thermochromic colorant as required, and the balance consisting of water, with a viscosity of 40 to 300 mPa · s (EM type rotation) (Value at a rotation speed of 10 rpm by a viscometer), adjusted to a range of shear thinning viscosity index of 0.1 to 0.8, writing pressure adaptable handwriting formation process at the time of writing, shearing in overdrawing and coating process An appropriate viscosity adjusting function can be achieved according to the force load.
For example, JP-A-2001-207101 proposed by the present applicant is applied to the agglomerated ink, and the binder resin containing 3 to 40% by weight of a reversible thermochromic microcapsule pigment and a water-soluble polymer flocculant is used. 05 to 25% by weight, if necessary, an appropriate amount of a non-thermochromic colorant is blended, and the remainder is blended with water containing a humectant or the like as needed.
The specific gravity control type ink can be prepared by applying Japanese Patent No. 2540341 (Japanese Patent Application No. 62-210721) proposed by the present applicant.

  The shear thinning substance in the above is a nonionic surfactant having an HLB value in the range of 8 to 12, xanthan gum, succinoglycan whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose (average molecular weight of about 100) To 8 million), guar gum, locust bean gum and derivatives thereof, hydroxycellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 based on alkyl esters of methacrylic acid, glycomannan, agar and carrageenan Examples thereof include carbohydrates having a gelling ability extracted from seaweed, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymers, and the like, which can be used alone or in combination. Xanthan gum, succinoglycan, and crosslinkable acrylic acid polymer are particularly excellent in storage stability.

As the water-soluble polymer flocculant, a nonionic water-soluble polymer compound is preferably used. Specific examples include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, nonionic water-soluble cellulose derivatives, and the like. Among these, specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, and cyclodextrin, and specific examples of nonionic water-soluble cellulose derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl. Examples thereof include methyl cellulose and hydroxypropyl methyl cellulose. Any water-soluble polymer exhibiting a loose bridging action between the microcapsule pigment particles applied to the present invention can be applied, and among these, the nonionic water-soluble cellulose derivatives function most effectively. .
The polymer flocculant can be blended in an amount of 0.05 to 20% by weight based on the total amount of the ink composition.

As moisturizers to suppress drying at the writing tip, glycols such as glycerin, propylene glycol, ethylene glycol, diethylene glycol, low molecular weight polyethylene glycol and their lower alkyl ethers, 2-pyrrolidone, N-vinylpyrrolidone, urea, etc. An appropriate amount of the above can also be blended.
The humectant can be blended in an amount of 5 to 40% by weight based on the total amount of ink.

An appropriate amount of a binder resin can be added for adjusting the handwriting stickiness and viscosity, and a resin emulsion, an alkali-soluble resin, a water-soluble resin, or the like can be applied.
Examples of the resin emulsion include polyacrylic acid ester, styrene-acrylic acid copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacrylic acid-maleic acid copolymer, ethylene- Examples include aqueous dispersions such as methacrylic acid copolymers, α-olefin-maleic acid copolymers, polyesters, and polyurethanes. Examples of the alkali-soluble resins include styrene-maleic acid copolymers, ethylene-maleic acid copolymers, Examples of the water-soluble resin such as a styrene-acrylic acid copolymer include polyvinyl alcohol and polyvinyl butyral, and one or a mixture of two or more can be used.
Moreover, conventionally various various dispersing agents, such as surfactant, can also be mix | blended as needed.

  The temperature-sensitive color-changing paste is prepared according to the temperature-sensitive color-changing ink. Etc., filled in an appropriate container to form a storage body 6, and a writing body 11 having a writing tip member 2 as a set to form a combined writing material 11. Viscosity, concentration, etc. can be adjusted by adding water.

  The temperature-sensitive color-changing semi-solid or solid is formed by blending various water-soluble resins, low-melting-point wax-like substances, and if necessary, wetting agents. The storage 6 is contained in a container and impregnated with water. A temperature-sensitive discoloration image 8 is formed by adhering and penetrating the writing tip member 2 with the writing tip member 2 or by adding an appropriate amount of water to the container to make it water-soluble. The semi-solid or solid body is not limited to a pellet shape, and may be a spherical shape or a granular shape.

As the non-thermochromic colorant, general-purpose dyes, pigments, fluorescent pigments, phosphorescent pigments, metallic luster pigments, cholesteric liquid crystal type luster pigments, and the like can be blended to enhance the color effect.
As the metallic luster pigment, aluminum luster or metallic luster pigment whose surface is treated with a colored resin, metallic luster pigment in which a metal vapor deposition film such as aluminum is formed on a transparent or colored transparent film, aluminum formed on a substrate such as a film A metallic luster pigment having a thickness of 0.01 to 0.1 μm obtained by peeling off a metal vapor-deposited film such as colloidal particles having an average particle size of 5 to 30 nm selected from gold, silver, platinum and copper, and natural as a core substance Examples include mica, synthetic mica, glass pieces, alumina, and pearl pigments in which the surface of a transparent film piece is coated with a metal oxide.
Specific examples of the pearl pigment include those in which the surface of natural or synthetic mica is coated with titanium oxide, and the upper layer thereof is coated with iron oxide or a non-thermochromic dye / pigment. Depending on the oxide coverage, a metallic glossy color of gold, silver or metallic can be provided. Furthermore, the surface of the flat glass piece is coated with a metal mainly composed of titanium oxide, gold, silver, nickel and iron oxide, the surface of the flaky aluminum oxide is coated with titanium oxide, and the upper layer is made of metal. The thing etc. which coat | covered with the oxide can be illustrated.
The cholesteric liquid crystal-type glitter pigment can impart a metallic luster color change due to the light interference effect.

Moreover, a fragrance | flavor component is mix | blended and aromaticity can be provided, and an aromatic function can be expressed with a temperature-sensitive discoloration function by environmental temperature, fingertip temperature, or frictional heat.
As the fragrance component, a conventionally used fragrance component is effective, and the fragrance component is encapsulated in a microcapsule in order to maintain sustained release. Although the fragrance component can be used alone as an inclusion liquid, liquid properties such as polarity and water solubility differ depending on the fragrance component, which may cause problems in microencapsulation, and the types of fragrance that can be applied to microencapsulation are limited. Is done.
By dissolving the fragrance component in a non-volatile high-boiling organic compound to form an inclusion liquid, the liquidity such as water solubility of the inclusion liquid is homogenized, so the high-boiling organic compound suitable for microencapsulation is applied. By doing so, it becomes possible to microencapsulate various perfume ingredients having different substances, and furthermore, controlled release can be controlled.
Specific examples of the perfume include essential oils such as grapefruit oil, orange oil, lemon oil, lime oil, lavender oil, and cypress oil, alcohols, aldehydes, esters, aromatic compounds, terpene oil, and the like. .
Specific examples of nonvolatile high-boiling organic compounds include hydrocarbons, halogenated hydrocarbons, sulfides, ethers, ketones, esters, acid amides, alcohols, waxes, etc. Organic compounds that have been commonly used as plasticizers are preferred in terms of odorlessness, compatibility with perfume ingredients, low toxicity, variety of types, and cost. For example, citric acids such as acetyl triethyl citrate and tributyl acetyl citrate, and phosphate plasticizers such as tricresyl phosphate, triethyl phosphate, tributyl phosphate, and tris (2-ethylhexyl) phosphate can be exemplified.
The range of the said fragrance | flavor component / non-volatile high boiling point compound = 1-50 / 99-50 (weight ratio) satisfies retentivity and aroma divergence.
The said microcapsule can be mix | blended in the range of 2-20 weight% in all the components of a thermochromic color material. In this case, the microcapsule may be a mixture of an aromatic component and a thermochromic component.

Examples are shown below. In addition, the part in an Example is a weight part.
Example 1
Heat-decolorable reversible thermochromic microcapsule pigment (from high temperature side color change point (t ₃ : 26 ° C., t ₄ : 32 ° C.), low temperature side color change point (t ₁ : 24 ° C., t ₂ : 28 ° C.), from red Colorless color change, average particle size: 2.5 μm, reversible thermochromic composition / wall membrane = 2.6 / 1.0] of 44.0 parts of microcapsule slurry (solid content of 13.2 parts) was added to glycerin. 5.00 parts, antifungal agent (trade name: Proxel XL-2, manufactured by Zeneca Corp.) 0.70 parts, silicone-based antifoaming agent (trade name: SN deformer 381, manufactured by San Nopco Corp.) 0.1 Parts, water 43.35 parts uniformly dispersed in an aqueous medium, hydroxyethyl cellulose [trade name: Cellosize WP-09L, Union Carbide Japan Co., Ltd., water-soluble polymer flocculant] 5.00% by weight While stirring 8.00 parts of an aqueous solution containing It was prepared a reversible thermochromic microcapsule pigment gradual suspended in aggregation state aggregation system thermochromic ink (thermochromic colorant 5) was added in the liquid in the dispersed state.
Manufacture of writing instrument A fiber focusing system writing tip member 2 (base end outer diameter 4 mmΦ, taper length 15 mm) is attached to the holding part 3 and the side of the flexible shaft cylinder 4 is pressed to press the writing tip. The ink (temperature-sensitive color-changing color material 5) was filled in the ink containing part of the mechanism for deriving the ink to constitute the temperature-sensitive color-changing writing instrument 1 (see FIG. 1).
Changes in writing line width due to changes in writing pressure At a writing angle of 90 °, the writing pressure was gradually increased from the initial writing pressure of 1 to 3 g, and a straight line having a length of 10 cm was written in 2 seconds in the range of the writing pressure of 50 g. However, a handwriting that was proportionally widened from the initial writing line width of 1 to 2 mm was formed, and a writing line width of 4 mm was formed at a writing pressure of 50 g, and then the writing pressure was gradually reduced. However, the writing line width was gradually reduced to return to the initial writing line width.
When writing under the same conditions as described above at a writing angle of 60 °, a handwriting with the writing line width increased proportionally from the initial writing line width of 1 to 2 mm was formed, and the writing pressure was 50 g and the width was 15 mm. Then, when the writing pressure was gradually reduced in the same manner as described above, the writing line width was gradually reduced to return to the initial writing line width of 1 to 2 mm.
Change in appearance due to temperature change of handwriting Between high temperature side color change start temperature (t ₃ : 26 ° C) and high temperature side complete color change temperature (t ₄ : 32 ° C), and low temperature side color change start temperature (t ₂ : 28 ° C) Light red in each transitional discoloration temperature range between the low temperature side complete discoloration temperature (t ₁ : 24 ° C.), red in the complete color development temperature range, and colorless in the high temperature side complete discoloration temperature range The appearance was visually discriminated in three stages according to the difference in visual density.

Example 2
In place of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side color change point (t ₃ : 26 ° C., t ₄ : 32 ° C.), low temperature side color change point (t ₁ : 24 ° C., t ₂ : 26 ° C.), blue to colorless color change, average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0] Similarly, an agglomerated temperature-sensitive color change ink was prepared and a temperature-sensitive color change writing instrument 1 was constructed.
When the test similar to Example 1 was done about the change of the writing line | wire width by a writing pressure change, the substantially similar result was obtained. Also in the following Examples 3 and 4, when the same test was performed with the thermochromic writing instrument having the same form, almost the same result was obtained.
Aspect change due to temperature change of handwriting Between high temperature side discoloration start temperature (t ₃ : 26 ° C) and high temperature side complete discoloration temperature (t ₄ : 32 ° C), and low temperature side discoloration start temperature (t ₂ : 26 ° C) Light blue is visualized in each transitional color temperature range between the low-temperature side complete color change temperature (t ₁ : 24 ° C.) and each of the blue color displayed in the complete color development temperature range and the colorless color displayed in the high-temperature side complete color change temperature range The appearance was visually discriminated in three stages according to the difference in visual density.

Example 3
In place of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side color change point (t ₃ : 25 ° C., t ₄ : 32 ° C.), low temperature side color change point (t ₁ : 24 ° C., t ₂ : 27 ° C.), yellow to colorless color change, average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0] Similarly, an agglomerated temperature-sensitive color-changing ink was prepared.
Aspect change due to temperature change of handwriting Between high temperature side color change start temperature (t ₃ : 25 ° C) and high temperature side complete color change temperature (t ₄ : 32 ° C), and low temperature side color change start temperature (t ₂ : 27 ° C) Light yellow is visualized in each transitional color temperature range between the low temperature side complete color change temperature (t ₁ : 24 ° C.) and each of the yellow color displayed in the complete color development temperature range and the colorless color displayed in the high temperature side complete color change temperature range The appearance was visually discriminated in three stages according to the difference in visual density.

Example 4
In place of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side color change point (t ₃ : 27 ° C., t ₄ : 32 ° C.), low temperature side color change point (t ₁ : 25 ° C., t ₂ : 28 ° C.), color change from black to colorless, average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0] Similarly, an agglomerated temperature-sensitive color-changing ink was prepared.
Aspect change due to temperature change of handwriting Between high temperature side discoloration start temperature (t ₃ : 27 ° C) and high temperature side complete discoloration temperature (t ₄ : 32 ° C), and low temperature side discoloration start temperature (t ₂ : 28 ° C) Gray color is visible in each transitional discoloration temperature range between the low-temperature side complete discoloration temperature (t ₁ : 25 ° C.), and each color is black in the complete color development temperature range and colorless in the high-temperature side complete discoloration temperature range Was visually discriminated in three stages according to the difference in visual density.

Example 5
Instead of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side color change point (t ₃ : 30 ° C., t ₄ : 36 ° C.), low temperature side color change point (t ₁ : 28 ° C., t ₂ : 30 ° C.), color change from blue to colorless, average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0], and 0. An agglomerated thermosensitive color-changing ink was prepared in the same manner as in Example 1 except that 15 parts were blended.
Preparation of writing instrument In a fiber-focused ink occlusion body (porosity of about 83%) coated with a polyester resin sliver, the ink is impregnated immediately after being stirred in a uniform state and accommodated in the shaft cylinder. A temperature-sensitive color-changing writing instrument 1 was constructed by assembling it in a connected state with a writing tip member formed by resin processing of a polyester fiber attached to the part.
Here, the writing tip member 21 has an outer diameter of 3 mmΦ with a porosity of about 60%, and is ground into a tapered shape to form a reduced diameter portion. The length of the tapered portion is 6 mm. Met.
Change in writing line width due to change in writing pressure At a writing angle of 60 °, the writing pressure was gradually increased from the initial writing pressure of 1 to 3 g, and a straight line having a length of 10 cm was written in 2 seconds in the range of the writing pressure of 60 g. However, a handwriting that was proportionally widened from the initial writing line width of 1-2 mm was formed, and a writing line width of 4 mm was formed at a writing pressure of 60 g, and then the writing pressure was gradually reduced to write. However, the writing line width was gradually reduced to return to the initial writing line width.
Changes in handwriting due to temperature changes
Between the high temperature side color change start temperature (t ₃ : 30 ° C.) and the high temperature side complete color change temperature (t ₄ : 36 ° C.), and the low temperature side color change start temperature (t ₂ : 30 ° C.) and the low temperature side complete color change temperature (t ₂ : 28 ° C) in each transitional discoloration temperature range, a reddish purple color is visualized, and each of blue-purple color exhibited in the complete color development temperature range and pink color exhibited in the high temperature side complete discoloration temperature range It was visually discriminated separately from the aspect.

Example 6
Instead of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side discoloration point (t ₃ : −6 ° C., t ₄ : 4 ° C.), low temperature side discoloration point (t ₁ : −8] , T ₂ : 2 ° C.), color change from blue to colorless, average particle size: 2.5 μm, reversible thermochromic composition / wall film = 2.6 / 1.0]. In the same manner as in No. 1, an agglomerated temperature-sensitive color change ink was prepared.
Creation of a writing instrument Instead of the writing tip member by resin processing of the polyester fiber of Example 5, a writing tip member in which polyamide-based fibers are bound by an elastomer (the outer diameter of the base portion having a porosity of about 60%; 3 mmΦ, tapered tapered shape) The temperature-sensitive color-changing writing instrument 1 having the same form as that of Example 5 was configured using the length of the tapered portion of the reduced diameter portion that had been ground; 6 mm).
Change in writing line width due to change in writing pressure When the same test as in Example 5 was performed, handwriting with the same writing line width could be repeatedly formed.
Change in appearance due to temperature change of handwriting Between high temperature side discoloration start temperature (t ₃ : -6 ° C) and high temperature side complete discoloration temperature (t ₄ : 4 ° C), and low temperature side discoloration start temperature (t ₂ : 2 ° C) Light blue in each transitional discoloration temperature region between the low temperature side complete discoloration temperature (t ₁ : -8 ° C), blue color presenting in the complete color development temperature region, and colorlessness presenting in the high temperature side complete discoloration temperature region Each of these aspects was visualized in three stages depending on the difference in visual density.

Example 7
In place of the pigment of Example 1, a heat decoloring type reversible thermochromic microcapsule pigment [high temperature side color change point (t ₃ : 16 ° C., t ₄ : 24 ° C.), low temperature side color change point (t ₁ : 14 ° C., t ₂ : 22 ° C., color change from blue to colorless) and heat decolorable reversible thermochromic microcapsule pigment (high temperature side discoloration point (t ₃ : 26 ° C., t ₄ : 34 ° C.), low temperature side discoloration point (T ₁ : 25 ° C., t ₂ : 32 ° C., color change from pink to colorless) and Example 1 except that 30 parts of microcapsule slurry (solid content 18 parts) were blended in equal amounts. Similarly, an agglomerated temperature-sensitive color-changing ink was prepared, and a temperature-sensitive color-changing writing tool having the same writing instrument form as Example 1 was constructed.
Change in writing line width due to change in writing pressure When the same test as in Example 1 was performed, handwriting with the same writing line width could be repeatedly formed.
Change in appearance due to temperature change of handwriting In the complete coloring state below the high temperature side discoloration start temperature of blue (t ₃ : 16 ° C), it exhibits a bluish purple color, and in the temperature range of 16 ° C to 24 ° C, a reddish purple color (first Transitional discoloration state), and changes to pink (second transitional discoloration state) at 26 ° C or higher, and light pink (third transitional discoloration state) in the temperature range of 26 ° C to 34 ° C. And was colorless at 34 ° C. or higher.

Example 8
Instead of the pigment of Example 1, a heat decoloring type (color memory retention type) microcapsule pigment [high temperature side color change point (t ₃ : 46 ° C., t ₄ : 64 ° C.), low temperature side color change point (t ₁ : − 16 ° C., t ₂ : −4 ° C.), and a change in color from blue to colorless was applied in the same manner as in Example 1 except that 0.15 part of edible red No. 3 was blended. An ink was prepared to constitute a temperature-sensitive color-changing writing instrument in the same writing instrument form as in Example 1.
Change in writing line width due to change in writing pressure When the same test as in Example 1 was performed, handwriting with the same writing line width could be repeatedly formed.
Change in appearance due to temperature change of handwriting Between high temperature side discoloration start temperature (t ₃ : 46 ° C) and high temperature side complete discoloration temperature (t ₄ : 64 ° C), and low temperature side discoloration start temperature (t ₂ : -4 ° C) In each transitional discoloration temperature range between the low temperature side complete discoloration temperature (t ₁ : -16 ° C.), a reddish purple color is visualized, a blue purple color presenting in the complete color development temperature region, and the high temperature side complete discoloration It was visually discriminated separately from each pink color aspect in the discoloration temperature range.

Example 9
Heat-decolorable reversible thermochromic microcapsule pigment microcapsule slurry of Example 1 25.0 parts (solid content 15.0 parts), xanthan gum (shear thinning substance) 0.33 parts, water 51.0 parts, 11.0 parts of urea, 11.0 parts of glycerin, Nopco SW-WET-366 (nonionic permeability imparting agent, manufactured by San Nopco) 0.55 parts, Nopco 8034 (modified silicone-based antifoaming agent, manufactured by San Nopco) 0 .13 parts, Proxel XL-2 (an antifungal agent, manufactured by Zeneca Co., Ltd.) 0.13 part of a shear-thinning-type temperature-sensitive color-changing ink was prepared, and the temperature-sensitive color change property of the writing instrument form similar to Example 1 was prepared. Writing instrument 1 was constructed.
Change in writing line width due to change in writing pressure When the same test as in Example 1 was performed, handwriting with the same writing line width could be repeatedly formed.
As a result of measuring the viscosity of the ink with an EMD viscometer at 25 ° C., it showed a value of 30 mPa · s at a measurement rotation speed of 100 rpm.
Change in appearance due to temperature change of handwriting The same discoloration behavior as in Example 1 was exhibited.

Example 11
Heat decoloring type reversible thermochromic microcapsule pigment (high temperature side color change point (t ₃ : 27 ° C., t ₄ : 32 ° C.), low temperature side color change point (t ₁ : 27 ° C., t ₂ : 24 ° C.), from black Colorless color change, average particle size: 2.3 μm, reversible thermochromic composition / wall film = 2.3 / 1.0] 44.0 parts of microcapsule slurry (solid content 12.5 parts), and 12.5 parts of metal oxide-coated alumina luster pigment [trade name: Silaric T50-10, manufactured by Merck Japan Ltd.], 5.0 parts of glycerin, antifungal agent [trade name: Proxel XL-2, Geneca ( Co., Ltd.)) 0.7 part, silicone-based antifoaming agent (trade name: SN deformer 381, San Nopco Co., Ltd.) 0.1 part, after being uniformly dispersed in an aqueous medium consisting of 29.7 parts of water, Hydroxyethyl cellulose [Brand name: Cello size WP-09L, Uni With stirring down carbide Japan Ltd.] solution 8.0 parts containing 4.0 wt%, to prepare a thermosensitive color-changing ink is added in the liquid in said dispersed state.
As a result of measuring the viscosity of the ink with a No. 3 rotor using a B-type viscometer, the viscosity was 90 mPa · s at a measurement rotation speed of 60 rpm.
Creation of a writing instrument A knock mechanism is provided at the rear part of the shaft cylinder, and the temperature-sensitive color-changing ink is filled in a writing instrument type cartridge that draws ink to the tip of the writing by the operation of the knock mechanism, and a stirring sphere is incorporated to collect fibers. A system-writing tip member (outer diameter 4 mmΦ at the base end and length 15 mm at the tapered portion) was attached to the holding portion to constitute the temperature-sensitive color change writing instrument 1.
Change in writing line width due to change in writing pressure The writing line width of the writing pressure adaptability similar to that in Example 1 was shown, and a glittering handwriting was obtained.
Aspect change due to temperature change of handwriting Between high temperature side discoloration start temperature (t ₃ : 27 ° C) and high temperature side complete discoloration temperature (t ₄ : 32 ° C), and low temperature side discoloration start temperature (t ₁ : 27 ° C) At each transitional discoloration temperature between the low-temperature side complete color change temperature (t ₂ : 24 ° C.), a light silver color is visualized, and a dark silver color exhibited in the complete color development temperature range and a colorless color exhibited in the high temperature side complete color change temperature range Each of these aspects was visually discriminated in three stages according to differences in visual temperature.

Example 12
Writing materials suitable for writing letters, line drawings, illustrations, and art materials, with each writing instrument having red, blue, and yellow handwriting in Examples 1, 2, and 3 and black writing instrument of Example 4 as a set Configured the set.

Example 13
A storage body 6 in which the temperature-sensitive color-changing inks of Examples 1 to 11 are respectively housed in a container, and a writing tip member 2 (which is selected from Examples 1, 5, and 6) that writes the ink by adhering and penetrating the ink. The writing material 11 of the combination form which set the writing body 7 which attached | subjected the arbitrary thing) was comprised (refer FIG. 2).
Here, the writing body 7 has a temperature-sensitive color-changing ink attached and penetrated to form a temperature-sensitive color-change image, and water is attached and applied to function as a color mixture on a writing paper surface or to form a shading pattern. be able to.

It is explanatory drawing of the use condition of the thermochromic writing material (writing instrument form) of this invention. It is explanatory drawing of the thermochromic writing material (combination form of a storage body and a writing body) of this invention. It is explanatory drawing of the temperature-color density curve of the heat decoloring type reversible thermochromic microcapsule pigment applied to this invention. It is explanatory drawing of the temperature-color density curve of the heat decoloring type reversible thermochromic microcapsule pigment (color memory retention type) applied to this invention. It is explanatory drawing of the temperature-color density curve of the heat coloring type | mold reversible thermochromic microcapsule pigment applied to this invention. It is explanatory drawing of the temperature-color density curve which shows a multistep change in the transitional discoloration temperature range in the system which applies a heat decoloring type reversible thermochromic microcapsule pigment. It is model explanatory drawing of one form of a reversible thermochromic microcapsule pigment, (A) shows an external appearance, (B) shows a cross section.

Explanation of symbols

1 Temperature-sensitive discoloring writing material (writing instrument form)
11 Temperature-sensitive discoloring writing material (set of storage and cursive)
2 Writing tip member 21 Reduced diameter portion L Length of tapered portion D Diameter of proximal end portion of tapered portion 3 Holding portion 4 Shaft cylinder 5 Temperature-sensitive color-changing colorant 6 Storage body 7 Writing body 8 Temperature-sensitive discolored image 9 Reversible heat Discolorable microcapsule pigments a Wall membrane
b Indentation c Reversible thermochromic composition ΔHA _A hysteresis temperature range (heating decoloring type)
ΔH _B hysteresis temperature range (heat decoloration-color memory retention type)
ΔH _C Hysteresis temperature range (heating coloring type)
t ₁ Low temperature side complete discoloration temperature of heat decolorable microcapsule pigment t ₂ Low temperature side discoloration start temperature of heat decolorable microcapsule pigment t ₃ High temperature side discoloration start temperature of heat decolorable microcapsule pigment t ₄ Heat decoloration High temperature side complete discoloration temperature of T type heated microcapsule pigment T ₁ Heated color development type microcapsule pigment low temperature side complete color change temperature T ₂ Heated color development type microcapsule pigment low temperature side color change start temperature T ₃ Heated color development type microcapsule pigment high temperature side color change Starting temperature T ₄ Complete color change temperature on the high-temperature side of the heating type microcapsule pigment

Claims (12)

A writing material for forming an arbitrary image with a temperature-sensitive color-changing colorant through a writing tip member, wherein the writing tip member has a tapered diameter-reduced portion, and writing in a range of writing pressure of 1 to 60 g. The deformed diameter part is flexed in response to an increase in pressure to widen the writing line width, and the bending line width is reduced in response to a reduction in writing pressure to restore the original shape by restoring the bending line width. The temperature-sensitive color-changing colorant is provided between the high-temperature side color change start temperature (t ₃ ) and the high-temperature side complete color change temperature (t ₄ ) in the temperature-color density curve, and the low-temperature side color change start temperature ( t ₂₎ and a reversible thermal discoloration microcapsule pigment temperature width of each transient discoloration temperature region is in the range of 1 to 10 ° C. between the cold side complete discoloration temperature (t ₁₎ in an aqueous medium 3-40 A thermochromic writing material characterized in that it is dispersed at a ratio of% by weight.   The temperature-sensitive color-changing coloring material according to claim 1, wherein the temperature-sensitive color-changing color material is selected from temperature-sensitive color-changing inks, pastes, and semi-solid or solid materials.   A thermosensitive color-changing ink is accommodated in the shaft cylinder, and a writing instrument form in which the thermosensitive color-changing ink is led out continuously from the writing tip member, or a temperature-sensitive color-changing ink, paste, or semi-solid or solid body is contained in the container. The temperature-sensitive color-changing writing material according to claim 2, wherein the temperature-sensitive color-changing writing material is one of a combination form of a housed storage body and a writing body to which a writing tip member is attached.   The base of the writing tip member is a fiber bundling body in which fibers are closely bundled in the longitudinal direction, a plastic porous body having continuous pores, a heat-bonded or resin processed body of synthetic resin fibers, an extrusion molding of a soft resin or an elastomer The temperature-sensitive color-changing writing material according to claim 1, which is selected from a processed body.   The base body of the writing tip member has an arbitrary outer diameter (D) selected from the range of an outer diameter of 2 to 10 mmΦ, and the outer diameter (D) and the length of the tapered portion of the tapered tapered portion (L ) Is in a relationship of L / D = 2 to 5/1, the temperature-sensitive color-changing writing material according to any one of claims 1 to 4.   The tapered diameter of the tapered portion is a fiber bundling body in which the tapered side of a synthetic resin fiber processed into a taper taper shape is closely arranged in the same direction, or a fiber bundling body in which different kinds of fibers are closely arranged to form a tapered taper shape. The temperature-sensitive color-changing writing material according to any one of claims 1 to 5, wherein the temperature-sensitive color-changing writing material is formed by bonding, fusing, or binding the base end portion.   In the range of 1 to 60 g of writing pressure, the writing line width is increased in accordance with the increase of the writing pressure, and the maximum value of the writing line width when the writing pressure is applied by writing at a writing angle of 90 ° is the value of the writing tip member. Approximate to the outer diameter (D) of the substrate, the maximum value of the writing line width when writing at a writing angle of 60 ° approximates the length (L) of the tapered portion, and the writing line width reaching the maximum value is The thermochromic writing material according to any one of claims 1 to 6, wherein the temperature-sensitive color-changing writing material returns to the original writing line width in accordance with a decrease in writing pressure. The reversible thermochromic microcapsule pigment has a high temperature side complete color change temperature (t ₄ ) of 21 ° C to 65 ° C, and a low temperature side complete color change temperature (t ₁ ) of -30 ° C to + 20 ° C. The temperature-sensitive color-changing writing material according to any one of the above. The two or more reversible thermochromic microcapsule pigments having different hues at different high temperature side color change start temperatures (t ₃ ) and low temperature side color change start temperatures (t ₂ ) are blended. The thermochromic writing material according to any one of the above.   The non-thermochromic colorant is blended in the reversible thermochromic microcapsule pigment or the thermochromic colorant, and exhibits a multistage change due to a hue change in a transitional color temperature range. The thermochromic writing material according to any one of the above.   The temperature-sensitive color-changing writing material according to any one of claims 1 to 3, wherein a metallic luster pigment is blended.   Among the temperature-sensitive color-changing writing materials according to any one of claims 1 to 11, three types of writing materials that exhibit red, blue, and yellow writings at the time of color development are essential, and black writing is performed. A writing material set in which a fiber bundling body for adhering and applying water is used as a set.

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