JP2014051537A - Heat discoloration solid drawing set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a set including a heat discoloration solid drawing material capable of drawing smoothly and deeply on normal sheets of paper or a smooth non-absorptive surface, and of drawing lines of which discolor by heat of scratch by using a friction body, and hardly making a sheet surface after discoloration stained, and the friction body, and to reproduce the friction body by cutting it when stained.SOLUTION: A heat discoloration solid drawing material set 10 contains a combination of a heat discoloration solid drawing material 20 containing at least a resin component, a wax component, a heat discoloration coloring material and white body material, and a friction body 40 having a hardness of durometer type A by JIS K 6253 of 50 or more.

Description

  In the present invention, not only paper such as ordinary high-quality paper, drawing paper, copy paper, but also smooth non-absorbing surfaces such as coated paper, plastic, metal, glass, whiteboard, etc. A thermochromic solid drawing material that can be drawn darkly. More specifically, the drawing line that chemically changes color due to the heat of weak rubbing using a friction body on a transparent plate surface such as transparent plastic or glass is dark and clear. When drawing on these non-absorbing surfaces, it can be easily physically erased with paper, such as cloth, tissue paper, whiteboard eraser, included friction body, etc. The present invention relates to a set of a thermochromic solid drawing material that can be cut with a vessel and a friction body. Moreover, it is a thermochromic solid drawing tool set in which a friction sheet is provided on the outer periphery of the thermochromic solid drawing material or a protective sheet made of a friction body is wound, and is used by cutting with a pencil sharpener like a conventional pencil Regarding what is possible.

The conventional solid drawing material adjusts hardness by adding oil, resin, etc. to the compound which consists of a wax, a pigment, and an extender as needed. However, when the amount of oil is increased for the purpose of softening the solid drawing material, the strength is lowered and the material tends to be broken. In such a case, it becomes impossible to perform thin drawing or sharpen the tip and cut, and fine drawing is impossible. In addition, when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc., there is a problem in that it cannot be drawn softly and darkly because it slides on the surface.
On the other hand, if the amount of resin is increased in order to increase the strength, it is hard even if it can be thinly molded, so it cannot be drawn on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. There is a problem.

  For example, as a color pencil of a non-fired core, a composition of a soft color core having excellent colorability containing a mixture of glycerin fatty acid ester and / or pentaerythritol fatty acid ester having a melting point of 65 ° C. or less and rosin and / or rosin modified product. (Patent Document 1). The purpose of this is to melt the drawing on the canvas with oil for oil painting to obtain an oil painting-like work, such as coated paper, plastic, metal, glass, whiteboard, etc. The purpose is different from that of the solid drawing material to be drawn.

  In addition, as a solid drawing material, it contains pigment, wax and mineral oil, and also contains a certain proportion of amorphous poly α-olefin and rosin, so that it can be drawn smoothly even on non-absorbing drawing surfaces. The composition of a solid drawing material is disclosed (Patent Document 2). However, in this composition, since it is a necessary requirement to contain 5% by weight or more of mineral oil, the strength is low and it cannot be formed into a thin shape. Actually, the examples in the same document do not mention the diameter of the molded body.

  Further, in the solid drawing material as described above, it is a well-known technique as used by the present applicant to include a color material other than the thermochromic color material, that is, a general dye / pigment, particularly titanium dioxide. (For example, patent document 3 and patent document 4). Titanium dioxide has a strong hiding power, and there is no problem if you want to hide and overwrite the underlying pattern or characters, but once you want to overwrite it so that you can see the underlying pattern or characters, draw it once It is inconvenient because it is impossible to discriminate unless the lines and filled portions are removed. Therefore, if you try to form a solid drawing material by blending titanium dioxide particles at a concentration that does not hide the pattern or characters on the ground, there will be fewer titanium dioxide particles that should act as a build material. The drawing material is easily broken.

  The solid drawing material according to the above prior art is a normal solid drawing material, and there is basically no change in the hue of the drawn line or the solid drawing material itself. Coloring materials that change color, such as leuco dyes or leuco dyes encapsulated in microcapsules, are weak against heat, and melt glycerin fatty acid esters, etc. or waxes when manufacturing the above solid drawing materials It is considered that there is a high risk of deterioration such as oxidation at that time. In addition, when microcapsules are used, if a strong force is applied to make an ink composition in a well dispersed state, it is easily expected that the microcapsules will be destroyed and deviated from the target.

  In recent years, when using a thermochromic ink as a means for changing the color-changing ink and attaching a friction body to a writing instrument or the like filled with the thermochromic ink as a means for generating heat, the ink color can be changed. For example, there is widely used a technique in which frictional heat is generated by rubbing a friction body against a drawn line to change the ink color (Patent Documents 5 and 6). Such a friction body of a product changes the hue of ink by frictional heat when rubbing the drawing portion. Therefore, it is attached with the premise that it is not contaminated by the ink and does not wear. Therefore, it is not premised on the physical removal of the drawn lines by ink, and these documents neither describe nor suggest countermeasures against the contamination of the friction body. Here, when the drawn line contains the following “wax”, it is easily considered that the “wax” is melted by this frictional heat and the drawn line is stretched simultaneously with rubbing.

  By the way, in the chemical definition, the wax means “ester of fatty acid and higher monovalent or divalent alcohol”. In this definition, some are liquid at room temperature, such as jojoba oil, and others are solid. However, usually, “solid or semi-solid organic matter at room temperature” and “melting in a temperature range from room temperature to near 100 ° C. and having a low melt viscosity” are collectively referred to as wax (non-patent document). 1). Specifically, in addition to waxes of the above chemical definition, trivalent (glycerin) or tetravalent (pentaerythritol) alcohol and fatty acid esters that are categories of fats and oils, paraffin wax, petrolatum, microcrystalline wax, etc. Petroleum hydrocarbons, fatty acids alone, and other substances are collectively referred to as waxes.

Among those collectively referred to as “waxes”, most of those defined as “fatty acids and higher mono- or dihydric alcohols” have poor compatibility with rosin and rosin-modified products such as glycerin esters of rosin.
On the other hand, trivalent (glycerin) or tetravalent (pentaerythritol) alcohol and fatty acid ester have good compatibility with rosin and rosin modified products such as glycerin ester of rosin.
From the above, in the present application, “solid or semi-solid organic matter at normal temperature”, “melting in a temperature range from normal temperature to around 100 ° C. and low melt viscosity”, in particular, the melting temperature (melting point) is Those having a temperature of 110 ° C. or lower are referred to as “wax”.

JP2008-45043 (Claims, Examples, etc.) JP 2010-37434 (Claims, Examples, etc.) JP-A-2002-348516 (Claims, Examples, etc.) WO2012 / 018107A1 (Claims, Examples, etc.) JP 2012-41459 A (Mode for carrying out the invention) JP 2009-107240 A (Best Mode for Carrying Out the Invention)

"Characteristics and application of wax", supervised by Kenzo Fusegawa, Sachishobo, September 10, 1983

  The present invention has been made in view of the above-described problems of the prior art. Specifically, the present invention has a smooth writing taste, and is particularly easy on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. by the heat of abrasion using a friction body. It is possible to draw drawn lines that are chemically discolored significantly darker, and when drawing drawn lines that are difficult to stain the discolored paper surface and thermally discolored on the non-absorbing surface, paper such as cloth, tissue paper, white Heat that can be easily physically erased with a board erasing tool, bundled friction body, etc., has excellent mechanical strength such as bending strength, and is hard to break, and is a combination of a friction body and a heat-discoloring solid drawing material. It is an object to provide a color-changing solid drawing material set. Another object of the present invention is to cut and regenerate the frictional body when it becomes dirty.

  As a result of intensive studies to solve the above-described conventional problems, the present inventor has found that at least a solid drawing material comprising a resin, a wax, a thermochromic color material, and a constitution material, a durometer type A in JIS K 6253 It was found that a more convenient thermochromic solid drawing material set for the above-mentioned purpose can be obtained by setting it with a friction body having a hardness of 50 or more, and the present invention has been completed as described below. It is.

(1) 1st invention In view of said subject, the thermochromic solid drawing material set 10 which concerns on 1st invention of this application is a thermochromic solid containing at least a resin component, a wax component, a thermochromic color material, and an extender. Drawing material 20,
It is characterized by being combined with a friction body 40 having a durometer type A hardness of 50 or more in JIS K 6253.

In the present invention, as the “resin component”, for example, rosin and modified rosin can be used. The rosin and rosin modified product used here are not particularly limited as long as they are generally classified as rosin and rosin modified products, and any of them can be used. It is also possible to use abithienic acid, which is the main component of rosin. Here, “rosin modified product” refers to glycerol ester of rosin and the like.
These can be used alone or as a mixture of two or more types without distinguishing chemical products and natural products, and are appropriately selected depending on the colorability and hardness of the target solid drawing material 20.
The resin component content is in the range of 0.5 wt% to 20 wt%. When this content is less than 0.5% by weight, the fixing property on a smooth surface is inferior, coloring is insufficient, the strength is weak, and it is not practical. On the other hand, if it exceeds 20% by weight, it is hard and the fixing property on a smooth surface is also inferior and coloring becomes insufficient.

  In the present invention, as the “wax component”, for example, glycerin fatty acid ester can be used. The glycerin fatty acid ester used here is not particularly limited as long as it has a melting point of 45 ° C. or higher and is generally classified as a glycerin fatty acid ester, and any of them can be used. For example, palmitic acid glycerides and stearic acid glycerides having a melting point of 45 ° C. or higher, and monoglycerides, diglycerides, and triglycerides can be used. Further, as other than these, natural products such as molasses such as hazelou and urushiro, which are mainly composed of glycerin fatty acid ester, and smack waxes such as yamahazero and yamaurushirou can be used.

  In the present invention, the pentaerythritol fatty acid ester used as the “wax component” is not particularly limited as long as it has a melting point of 45 ° C. or higher and is generally classified as a pentaerythritol fatty acid ester, and any of them can be used. For example, a pentaerythritol palmitate or a pentaerythritol stearate having a melting point of 45 ° C. or higher, and any of a monopentaeryslit, a dipentaeryslit, a tripentaeryslit, and a tetrapentaeryslit can be used. When the melting point is lower than 45 ° C., the practical strength is too weak, and the thermochromic solid drawing material is easily broken when it is thinly formed.

These glycerin fatty acid esters and pentaerythritol fatty acid esters used in the present invention can be used alone or in combination of two or more without distinguishing chemical products and natural products. It is appropriately selected depending on the colorability and hardness of the material.
The content of the wax component is in the range of 8 wt% to 50 wt%. If this content is less than 8% by weight, it is hard, the fixability on a smooth surface is inferior, and coloring is insufficient. On the other hand, if it exceeds 50% by weight, the strength becomes weak and impractical.

  The “thermochromic material” used in the present invention is, for example, a thermochromic composition composed of at least a leuco dye, a color developer, and a color-changing temperature adjusting agent. Are also included. In the microcapsule pigment, the wall material 21 of the microcapsule particle is made of a monomer, a polymer or a polymer containing a cross-linking material that can be cross-linked, in order to strengthen the wall material. It is desirable to encapsulate this thermochromic composition.

The leuco dye used in the present invention is not particularly limited as long as it is an electron donating dye and functions as a color former. Specifically, from the viewpoint of obtaining excellent color development characteristics, for example, 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-diethylaminofluorane, 2-chloro-3-methyl-6-dimethylaminofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- Anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 2- (2-chloroanilino) -6-dibutylaminofluorane 3,6-dimethoxyfluorane, 3,6-di-n-butoxyfluorane, 1,2-benz-6-diethylaminofluorane, 1,2-benz-6-dibutylaminofluorane, 1,2-benz -6-ethylisoamylaminofluorane, 2-methyl-6- (Np-tolyl-N-ethylamino) fluorane, 2- (N-phenyl-N-methylamino) -6- (Np- Tolyl-N-ethylamino) fluorane, 2- (3′-trifluoromethylanilino) -6-diethylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane, 3-methoxy-4-dodecoxystylinoquinoline, and the like. These may be used alone (one kind) or in combination of two or more kinds (hereinafter simply referred to as “at least Can be used).
Furthermore, a pyridine compound, a quinazoline compound, a bisquinazoline compound, or the like that develops yellow to red coloring can also be used.
These leuco dyes have a lactone skeleton, a pyridine skeleton, a quinazoline skeleton, a bisquinazoline skeleton, etc., and develop color when these skeletons (rings) are opened.

  The developer used in the present invention develops a leuco dye. As the developer that can be specifically used, for example, o-cresol, tert-butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, from the viewpoint of obtaining an ink having excellent color development characteristics. p-chlorophenol, p-bromophenol, o-phenylphenol, hexafluorobisphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, 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′-hydroxyphenyl) ethane, 1,1-bis (4′-hydroxyphenyl) -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-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-methylpe Tan, 2,2-bis (4′-hydroxyphenyl) hexafluoropropane, 2,2-bis (4′-hydroxyphenyl) n-heptane, 2,2-bis (4′-hydroxyphenyl) n-nonane, etc. These can be used, and at least one of them can be used.

  The color change temperature adjusting agent used in the present invention is a color change temperature adjusting agent by blocking the binding between the leuco dye and the developer in a heated and melted state to form a decolored state and cooling the color change temperature adjusting agent below the melting point again. Is repeatedly crystallized to become a colored state, and the change is reversibly exhibited at the melting point of the color change temperature adjusting agent. Moreover, even if the leuco dye and the developer are disconnected from each other in the state of being heated and melted to eliminate the color-erased state, and the cooling to the melting point of the color changing temperature adjusting agent is performed again, the color changing temperature adjusting agent does not crystallize at that melting point. Those that maintain a decolored state can be used. The latter discoloration temperature adjusting agent crystallizes by lowering the temperature by several to several tens of degrees below the melting point, and exhibits a quasi-reversible change having a hysteresis characteristic that forms a colored state, and is further heated and cooled again. Therefore, this change repeatedly exhibits decoloring.

  The discoloration temperature adjusting agent that can be used is not particularly limited as long as it has the above-mentioned function. For example, a compound having at least one polar group such as a hydroxyl group, an ester bond, an ether bond, and an amide bond, specifically Specifically, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, docosanoic acid, tetradocosanoic acid, hexadocosanoic acid, octadocosanoic acid and the like, caprylic alcohol, Higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, isostearyl alcohol, palmitoleyl alcohol, amides of the above fatty acids and amines, esters of the above fatty acids and alcohols , Ethers of the above higher alcohols with glycerin, propylene glycol, ethylene glycol, etc., and diphenylpropanedione, dibendioxybenzene, diphenoxybenzene, diisopropylnaphthalene, benzylbiphenyl, benzylnaphthyl ether, dibenzyl sulfoxide , Dimethyl terephthalate, diphenyl carbonate, diphenyl sulfone, fluoranthene, fluorene, methyl hydroxy naphthalate, phenyl hydroxy naphthalate, and stearanilide, and the like, and at least one of them can be used.

  The microcapsule pigment has an average particle size of 0.1 to 20 μm, and the wall film is an epoxy resin, polyamide resin, acrylonitrile resin, polyurethane resin, polyurea resin, urea-formaldehyde resin, melamine-formaldehyde resin, benzoguanamine resin. In addition to amino resins such as butylated melamine resin, butylated urea resin, urea-melamine resin, acrylic resin, maleic resin, silicone resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polystyrene, etc. The thermochromic composition is included. In addition to these resins, gelatin, starch, gum arabic, sodium polyacrylate, hydroxyethyl cellulose, methyl cellulose, polyacrylic ester, ethyl cellulose, cellulose acetate and the like may be used.

When the “thermochromic colorant” of the present invention is used as a microcapsule pigment, the thermochromic composition comprising at least the leuco dye, the developer, and the color change temperature adjusting agent has an average particle size of 0.1 to 20 μm. Thus, it can be manufactured by microencapsulation.
Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, Examples thereof include a medium suspension coating method and a spray drying method, which can be appropriately selected depending on the application.
For example, in a phase separation method from an aqueous solution, a leuco dye, a developer, and a color change temperature adjusting agent are heated and melted, then charged into an emulsifier solution, heated and stirred to disperse into oil droplets, and then as a capsule film agent, For example, after using a resin raw material that can be formed of an amino resin for the wall membrane, an amino resin solution, specifically, a methylol melamine aqueous solution, a urea solution, a benzoguanamine solution, etc., are gradually added and subsequently reacted to prepare The desired thermochromic microcapsule pigment can be produced by filtering the dispersion.

The content of these leuco dyes, developers, and color change temperature adjusters varies depending on the type of leuco dye, developer, color change temperature adjuster used, microencapsulation method, etc. The developer is 0.1 to 100 developer and 1 to 100 color changing temperature adjusting agent in mass ratio. Moreover, a capsule membrane agent is 0.1-1 by mass ratio with respect to the capsule content.
In the microcapsule pigment of the present invention, it is possible to obtain the color of each pigment, an arbitrary color development temperature, and a decoloration temperature by suitably combining the types and amounts of the leuco dye, the developer, and the color change temperature adjusting agent. .

When the “thermochromic colorant” of the present invention is used as a microcapsule pigment, the wall film is preferably formed of a resin, and more preferably a melamine resin from the viewpoint of manufacturability, storage stability, and writing properties. It is desirable to form with thermosetting resins, such as an amino resin containing.
The thickness of the wall film of the microcapsule pigment is appropriately determined according to the required strength of the wall film and the drawn line density.

In the case where the “thermochromic colorant” is a microcapsule pigment, the average particle size is from the viewpoint of colorability, color developability, easy decolorization, stability, and the adverse effect on writability. The thickness is preferably 1 to 20 μm, more preferably 0.2 to 5.0 μm. The “average particle size” defined in the present invention (including examples and the like) is determined by a laser diffraction / scattering particle size distribution analyzer (laser diffraction / scattering particle size distribution meter MT3000 (manufactured by Nikkiso Co., Ltd.)). It is a value obtained by measuring an average particle diameter (arithmetic average diameter based on volume-based distribution).
If the average particle size is less than 0.1 μm, sufficient drawn line density cannot be obtained. On the other hand, if the average particle size exceeds 20 μm, the writing property is deteriorated, the dispersion stability of the microcapsule pigment is lowered, and the writing surface is caused by friction. Desorption occurs, which is not preferable.
The microcapsule pigment having an average particle diameter in the above range (0.1 to 20 μm) varies depending on the microencapsulation method, but in the phase separation method from an aqueous solution, the stirring conditions for producing the microcapsule pigment Can be prepared by suitably combining them.

In the present invention, the content of the “thermochromic color material” is preferably 5 to 30% by mass (hereinafter simply referred to as “%”), more preferably 10 to 25%, based on the total amount of the ink composition. It is desirable to do.
When the content of the thermochromic color material (developed particles) is less than 5%, coloring power and color developability become insufficient. On the other hand, when it exceeds 30%, blurring tends to occur, which is not preferable.

  In addition to the “thermochromic color material” in the present invention, a normal pigment can be included as a color material. The pigments include disazo yellow AAA, azo organic pigments such as pyrazolone orange, cyanine organic pigments such as phthalocyanine blue and phthalocyanine green, higher organic pigments such as quinacridone red, dyes such as final colors, fluorescent pigments, carbon black Inorganic pigments such as iron black, petal, and bitumen can be used.

Examples of the “extrinsic material” in the present invention include known structural materials such as titanium dioxide, calcium carbonate, kaolin, talc, precipitated barium sulfate, mica, boron nitride, potassium titanate whisker, and basic magnesium sulfate whisker whiskers. And all the extenders which exhibit white can be used.
Here, as the “titanium dioxide”, any conventionally known titanium dioxide can be used regardless of rutile or atanase. However, for the purpose of drawing clear and clear on transparent plate surfaces such as transparent plastic and glass, titanium dioxide for catalysts has a fine particle diameter and a thin drawing surface, which is not preferable. On the contrary, it is convenient to use an underline marker to be seen through.
In addition, for example, by adding only these white constitutional materials without adding titanium dioxide, a discolored solid drawing material can be used as an underline marker that allows a transparent drawing line to be drawn. If a semi-transparent sheet is further put on the drawn line and a copy is made, the portion where the drawn line is drawn is erased in the copied material, and an instant hole filling problem collection is obtained.

  As the “friction body 40” in the present invention, a synthetic resin, in particular, a silicone resin, a resin containing styrene, a fluorine resin, a chloroprene resin, a nitrile resin, a polyester resin, an ethylene propylene diene rubber (EPDM) or other soft resin (EPDM) Rubber, elastomer), or a hard resin such as polyacetal resin, polyethylene resin, polypropylene resin, ABS resin, polycarbonate resin, or polyester resin. However, when this “friction body 40” is used as a tool for physically removing the drawn lines on the non-absorbing surface, the part used for rubbing becomes contaminated and unsightly. The surface must be exposed. Therefore, the friction body 40 is preferably a hard resin having a durometer type A hardness of 50 or more in JIS K 6253 among the hard resins described above. If the hardness is less than 50, it is too soft and difficult to cut. If it is preferably 60 or more and 100 or less, more preferably 70 or more and 95 or less, cutting can be performed without any problem.

  By combining the thermochromic solid drawing material 20 and the friction body 40, the thermochromic solid drawing material set 10 according to the present invention is formed. Here, for the combination of the thermochromic solid drawing material 20 and the friction body 40, for example, when the friction body 40 is detachably attached to the side surface or the end of the thermochromic solid drawing material 20 and is integrated. When such a friction body 40 is detachably attached to the thermochromic solid drawing material 20 like a cap (see FIG. 8), the thermochromic solid drawing as a completely separate article is also possible. This includes any case where the product is combined with the material 20 as a product.

(2) 2nd invention Moreover, in addition to the characteristic of the said 1st invention, the thermochromic solid drawing material set 10 which concerns on 2nd invention of this application,
The friction body 40 is provided on at least a part of the outermost peripheral surface of the protective sheet 30 wound around the outer peripheral surface of the thermochromic solid drawing material 20 two or more times.
The thermochromic solid drawing material 20 is characterized in that the protective sheet 30 including the friction body 40 can be cut with a pencil sharpener.

  That is, the friction body 40 having the same properties as described above is attached to a part of the outermost peripheral surface of the protective sheet 30. For example, the entire outermost peripheral surface of the protective sheet 30 can be formed of such a friction body 40. Moreover, it is possible to adhere the friction body 40 formed in the shape of a protrusion along the axial direction from the top of the protective sheet 30 wound around the outer peripheral surface of the thermochromic solid drawing material 20 (see FIG. 7).

In the second invention, the protective sheet 30 wound around the discolored solid drawing material for two or more turns is particularly limited as long as it can be cut with a pencil sharpener, plastic such as synthetic resin, natural resin, ceramic, metal, paper, wood, etc. Any of these materials can be used, but the material is appropriately selected in consideration of winding two or more times. That is, the material of the protective sheet 30 is preferably paper or a synthetic resin in consideration of flexibility by being wound a plurality of times, thickness, durability of the sharpener blade when cutting with a pencil sharpener, and machinability. .
Regarding the paper as the material of the protective sheet 30, in consideration of the fact that the fiber is swollen by moisture absorption and the machinability is deteriorated, the surface-treated paper such as art paper or coated paper, which hardly absorbs moisture or penetrates water, Synthetic paper containing a resin such as polypropylene is desirable.

The synthetic resin as the material of the protective sheet 30 is not particularly limited as long as it is a known sheet material or film material, and can be used. However, considering strength and machinability with a pencil sharpener, it is desirable to use polyester such as polyethylene terephthalate, nylon, polystyrene, polyvinyl chloride, or biaxially oriented polypropylene.
Further, all of the protective sheet 30 may be formed of the friction body 40. That is, the protective sheet 30 composed of the friction body 40 wound around the thermochromic solid drawing material 20 for two or more turns similarly to the above, flexibility, thickness by winding a plurality of times, and a scraper when cutting with a pencil sharpener. In view of the durability and machinability of the blade, a synthetic resin having a durometer type A hardness of 50 or more in JIS K 6253 is desirable. For example, like the above-described protective sheet 30 made of paper or synthetic resin, the thermochromic solid drawing material set 10 is prepared by adjusting and winding the thickness of the protective sheet 30 made of the friction body 40 around the outer peripheral surface of the thermochromic solid drawing tool. Is formed.
Further, it is desirable that an adhesive is applied to a part or all of the inner surface side of the protective sheet 30 in terms of strength and prevention of dust scattering during cutting. The material of the adhesive is not particularly limited as long as it has been used for seals, sheets, films and the like, and any material can be used.

In order to fix the thermochromic solid drawing material 20 and the protective sheet 30, it is desirable that an adhesive is applied to the portion corresponding to the innermost layer of the protective sheet 30. Further, the outermost layer of the protective sheet 30 needs to be fixed to the layer immediately below with an adhesive. These intermediate portions may or may not be coated with an adhesive, or may be selected as appropriate depending on the required characteristics, such as using an adhesive with weak adhesive strength. It is possible to do.
Further, in the present invention, the protective sheet 30 is wound around the thermochromic solid drawing material 20 two or more times. Moreover, if it is too thick, it will be easy to make a level | step difference in the part which overlaps with the edge of the innermost layer, it will be hard to wind at normal temperature, and will peel easily over time. Therefore, the thickness of the protective sheet 30 is preferably about 1 μm to 200 μm, more preferably 5 μm to 150 μm.

  Further, if the number of windings of the protective sheet 30 is less than two, the strength reinforcing effect is small. Therefore, it is desirable to adjust the diameter of the internal thermochromic solid drawing material 20 and the thickness of the protective sheet 30 and to wrap around 3 to 20 turns.

(3) Third invention In addition to the characteristics of the first or second invention, the third invention of the present application has a ratio of the resin component to the wax component in the range of 2: 1 to 1:25. It is characterized by that.
When the content of the resin component is less than 1:25 with respect to the wax component, the resulting thermochromic solid drawing material 20 is brittle, and the fixability on a smooth surface is inferior, resulting in insufficient coloring. On the other hand, if the content of the resin component is more than 2: 1 with respect to the wax component, the thermochromic solid drawing material 20 becomes hard and the colorability is insufficient.
In short, if the resin component and the wax component are mixed at a suitable ratio (that is, within a range of 2: 1 to 1:25), the discoloration solid drawing material having good fixability on a smooth surface and good coloration. Will be obtained.
The mixing of the resin component and the wax component can be performed by melt-mixing in advance, and in the manufacturing process of the thermochromic solid drawing material 20, it can be mixed with other compounds in a mixer or the like. The manufacturing method is not particularly limited.

(4) 4th invention Moreover, 4th invention of this application is characterized by including 5 weight% or more of said white body materials in addition to the characteristic in any one of said 1st-3rd invention.
When the content of the white constitution material is less than 5% by weight or not added, it is not possible to draw a dark and clear drawing on a transparent plate surface such as transparent plastic or glass, resulting in a thin drawing surface, but an underline marker It becomes a discoloration solid drawing material which can distinguish the character of the background.

(5) Fifth Invention Further, the fifth invention of the present application includes, in addition to any of the features of the first to fourth inventions, the resin component, the wax component, the thermochromic color material, and the white constitution material. In addition, a component having a melting point of 40 ° C. or less is contained in a range of 4.5% by weight or less.
That is, natural or synthetic oils such as glycerin fatty acid ester, pentaerythritol fatty acid ester having a melting point lower than 45 ° C., wax such as jojoba oil, spindle oil, liquid paraffin, squalane, squalene, α-olefin oligomer, and silicone oil. Can be used as long as it does not affect the preferred content of each component. In particular, a component having a melting point of 40 ° C. or lower (for example, an organic component such as wax or oil having a melting point of 40 ° C. or lower) is used as long as the total content of the thermochromic solid drawing agent 20 is 4.5% by weight or lower. can do. However, when it is desired to form the solid drawing material 20 into a thin shape or to sharpen the tip, it is desirable not to contain these low melting point components as much as possible from the viewpoint of strength.

(6) 6th invention Moreover, in addition to the characteristic in any one of the said 1st-5th invention, 6th invention of this application is polyethylene and ethylene-vinyl acetate co-polymerization as additional resin components other than the said resin component. Containing at least one of the coalescence in a range of 20 wt% or less,
As an additional wax component other than the wax component, one or a mixture of two or more selected from the group consisting of paraffin wax having a melting point of 45 ° C. or higher, ozokerite, Fischer-Tropsch wax, polyethylene wax is included in a range of 30% by weight or less. It is characterized by.
That is, as an additional resin component, 20% by weight or less of polyethylene and / or ethylene-vinyl acetate copolymer can be used in combination with the resin component for the purpose of improving strength, adjusting hardness, writing quality, and the like. If this additional resin component exceeds 20% by weight, the moldability and coloring power on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. are inferior, resulting in thin drawn lines.
In the above case, the total content of the resin component and the additional resin component is the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. Considering it, it is preferable to set it as 30 weight% or less.

Further, since the polyethylene and / or ethylene-vinyl acetate copolymer as the additional resin component and the glycerin fatty acid ester and / or pentaerythritol fatty acid ester having a melting point of 45 ° C. or more as the resin component are low in compatibility, As the additional wax component, one or a mixture of two or more selected from the group consisting of paraffin wax having a melting point of 45 ° C. or higher, ozokerite, Fischer-Tropsch wax, and polyethylene wax of 30% by weight or less is used in combination. Yes.
Conventionally known ozokerite, Fischer-Tropsch wax, and polyethylene wax can be used as the additional wax component, but paraffin wax preferably has a melting point of 45 ° C. or higher in terms of strength. The content is preferably 30% by weight or less in terms of the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard and the like.
The total content of the wax component and the additional wax component is preferably 70% by weight or less, but is preferably 65% by weight or less in terms of strength. Furthermore, in consideration of the drawing density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc., it is desirable to set it to 60% by weight or less.

(7) Seventh invention In addition to the features of the sixth invention, the seventh invention of the present application is selected from the group consisting of low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. One or a mixture of two or more
The ethylene-vinyl acetate copolymer has a vinyl acetate content of 30% by weight or less and a melt flow rate of 2 g / min or more.

That is, the polyethylene used in the present invention has kneadability with other compounding materials, moldability, drawn line density when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, and fixability. In view of the point, it is preferable to select from any one of low density polyethylene, linear low density polyethylene, and ultra low density polyethylene, or a mixture thereof. Furthermore, it is desirable to select from those having a melt flow rate of 2 g / min or more.
The ethylene-vinyl acetate copolymer used in the present invention is kneadable with other compounding materials, moldability, and when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc. In view of the drawn line density and fixability, it is preferable to select from those having a vinyl acetate content of 30% by weight or less and a melt flow rate of 2 g / min or more.

(8) Eighth Invention In addition to the features of the sixth or seventh invention, the eighth invention of the present application has a ratio of the additional resin component to the additional wax component of 3: 1 to 1: It is characterized by being in the range of 20.
Here, when the ratio of the additional resin component is more than 3: 1 with respect to the additional wax component, the thermochromic solid drawing material 20 becomes hard and the colorability becomes insufficient. On the other hand, when the ratio of the additional resin component is less than 1:20 with respect to the additional wax component, the resulting thermochromic solid drawing material 20 becomes brittle and is insufficient in strength.

(9) Other In addition to the above components, conventionally known carnauba wax, candelilla wax, rice wax, montan wax, microcrystalline wax, ketone wax, polypropylene wax, various fatty acid amide waxes, zinc stearate, Metal soap such as lithium stearate may be appropriately selected and blended.
In this case, the total content of these components and the wax component (or the wax component and the additional wax component) is preferably approximately 70% by weight or less. In view of strength, the amount is preferably 65% by weight or less, and further 60% in consideration of the line density and fixability when drawing on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard and the like. % Or less is desirable.
In addition, in the present invention, for the purpose of dissolving or wiping the drawn lines with water, conventionally known various additives such as surfactants and ultraviolet absorbers with water-soluble color pencils, etc. have been described so far. You may mix | blend in the range which does not reduce the characteristics, such as drawing on an absorption surface and easy erasability.

Since this invention is comprised as mentioned above, there exists an effect described below.
That is, according to the present invention, it has a smooth writing taste, and particularly easily on a smooth non-absorbing surface such as coated paper, plastic, metal, glass, whiteboard, etc., by the heat of rubbing using a friction body. It is possible to draw the lines that are chemically discolored much darker, the paper after the discoloration is less likely to get dirty, and when the drawn lines that are thermally discolored on the non-absorbing surface are drawn, paper such as cloth, tissue paper, whiteboard Thermal discoloration, which is a combination of a thermochromic solid drawing material that can be easily physically erased with an erasing tool, bundled friction body, etc., has excellent mechanical strength such as bending strength, and is hard to break, and a friction body. A solid drawing material set can be provided. Moreover, when this friction body becomes dirty, it can also cut and reproduce | regenerate.

Among the thermochromic solid drawing materials used in the examples of the present invention, those formed into a quadrangular prism shape (A) and those molded into a columnar shape (B) are respectively shown in perspective views. The thing by which the protective sheet was wound around the thermochromic solid drawing material of FIG. 1 is shown with a perspective view. FIG. 3 shows an enlarged part of the III-III cross section of FIG. 2. The heat discoloration solid drawing material of FIG. 2 cut with the pencil sharpener is shown with a perspective view. The thermochromic solid drawing material set which combined the thermochromic solid drawing material and friction body of this invention is shown with a perspective view. The heat discoloration solid drawing material set by which the protection sheet which consists of a friction body was wound around the heat discoloration solid drawing material of FIG. 1 is shown with a perspective view. FIG. 3 is a perspective view of a thermochromic solid drawing material in which the protective sheet of FIG. 2 is wound, and a discoloration solid drawing material set in which a friction body is attached to the side of the protective sheet. 1 is a perspective view of a thermochromic solid drawing material set in which a cap made of a friction body is attached to the thermochromic solid drawing material of FIG. FIG. 3 is a perspective view of a thermochromic solid drawing material set in which a cap made of a friction body is attached to the thermochromic solid drawing material of FIG. 2.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

(1) Microcapsule pigment: formulation of A-1 to A-5 (1-1) Pigment A-1
6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone (leuco dye): 1 part by weight Bisphenol A (developer): 2 parts by weight 4 , 4 ′-(Hexafluoroisopropylidene) bisphenol dilaurate (discoloration temperature adjusting agent): 24 parts by weight Methyl vinyl ether / maleic anhydride copolymer resin (GANTREZAN-179: GAFCHEMICALS) adjusted to 95 ° C. and pH 4 after heating and melting the above. The product was added to 400 parts by weight of an aqueous solution, and was heated and stirred to be dispersed in oil droplets. Subsequently, 20 parts by weight of 50% methylol melamine aqueous solution was gradually added as a capsule film agent, followed by reaction for 1 hour. The dispersion was filtered to obtain a microcapsule pigment. The average particle size of the finished microcapsule pigment was 0.3 μm.

(1-2) Pigment A-2
A microcapsule pigment having an average particle size of 0.6 μm was obtained by changing the stirring conditions in accordance with the formulation of Pigment A-1.

(1-3) Pigment A-3
6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone (leuco dye): 1 part by weight Bisphenol A (developer): 2 parts by weight 4 , 4 ′-(Hexafluoroisopropylidene) bisphenol dilaurate (discoloration temperature adjusting agent): 24 parts by weight After the above was heated and melted, the mixture was stirred in 276 parts by weight of water at 60 ° C. containing 0.1 part by weight of sodium dodecylbenzenesulfonate. Then, it was introduced and dispersed in the form of oil droplets. Further, after adding a solution obtained by adding 17 parts by weight of formalin (formaldehyde 37% aqueous solution) and 73 parts by weight of water to 10 parts by weight of urea and adjusting the temperature to 80 ° C., the mixture was adjusted to 80 ° C. A 5% by weight aqueous solution was added and reacted for 2 hours. The dispersion was filtered to obtain a microcapsule pigment. The average particle size of the completed microcapsule pigment was 0.8 μm.

(1-4) Pigment A-4
6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone (leuco dye): 1 part by weight Bisphenol A (developer): 2 parts by weight 4 , 4 '-(Hexafluoroisopropylidene) bisphenol dilaurate (discoloration temperature adjusting agent): 24 parts by weight Isocyanate (MR-200: manufactured by Nippon Polyurethane Industry Co., Ltd.): 5 parts by weight After heating and melting the above, tricalcium phosphate 2 weights And 400 parts by weight of an aqueous solution at 60 ° C. containing 0.04 part by weight of sodium dodecylbenzenesulfonate and dispersed by heating under stirring. Next, 2 parts by weight of xylylenediamine was added dropwise and stirred at 60 ° C. for about 3 hours to complete the reaction, followed by hydrochloric acid treatment. The dispersion was filtered to obtain a microcapsule pigment. The average particle size of the completed microcapsule pigment was 0.8 μm.

(1-5) Pigment A-5
6- (dimethylamino) -3,3-bis [4- (dimethylamino) phenyl] -1 (3H) -isobenzofuranone (leuco dye): 1 part by weight Bisphenol A (developer): 2 parts by weight 4 , 4 '-(Hexafluoroisopropylidene) bisphenol dilaurate (discoloration temperature adjusting agent): 24 parts by weight Epoxy resin (jER828: manufactured by Japan Epoxy Resin Co., Ltd.): 6 parts by weight The above was heated and melted, and then adjusted to 95 ° C and pH 4. The solution was added to 400 parts by weight of an aqueous solution of methyl vinyl ether / maleic anhydride copolymer (GANTREZAN-179: GAFCHEMICALS), and the mixture was heated and stirred to be dispersed in oil droplets. Next, 3 parts by weight of an amine curing agent (jER U: manufactured by Japan Epoxy Resin Co., Ltd.) was added, followed by reaction for 4 hours. The dispersion was filtered to obtain a microcapsule pigment. The average particle size of the completed microcapsule pigment was 0.6 μm.

(1-6) Developer particle A-6
A colorant solution was prepared by the following method.
Crystal violet lactone (leuco dye): 1 part by weight Hexafluorobisphenol A (developer, melting point about 130 ° C., heat capacity 60 J / g): 1 part by weight Behenyl alcohol 80 (discoloring temperature adjusting agent, melting point 60 ° C.): 8 parts by weight Sodium dodecyl sulfate (emulsifier, manufactured by Wako Pure Chemical Industries, Ltd.): 1 part by weight Ion exchange water: 89 parts by weight The above was heated at 80 ° C. for 2 hours and stirred at 15000 rpm with a homogenizer at high speed to give an average particle size of 0.13 μm The chemical solution was adjusted. 80% by weight urethane resin emulsion (WBR-2019, Tg 45 ° C., solid content 32 wt%, manufactured by Taisei Fine Chemical Co., Ltd.), 20% by weight α-methylstyrene acrylic resin (John Crill 61J, 30.5 wt% solid content, manufactured by BASF) was added to obtain a colored liquid, and the water was evaporated to obtain developer particles A-6.

(2) Composition and production method of Examples and Comparative Examples (2-1) Example 1
Hazerou (melting point: 52 ° C.): 43% by weight
Rosin: 16% by weight
Talc: 17% by weight
Titanium dioxide: 14% by weight
Pigment A-1: 10% by weight
The above blended composition is heated and mixed with a kneader, dispersed and then kneaded with two rolls, then heated and melted at about 60 ° C., added with pigment A-1, mixed and stirred, poured into a predetermined mold, cooled and solidified. Thus, a blue thermochromic solid drawing material 20 having a cross section of 8.0 mm × 8.0 mm on one side as shown in FIG. 1A was obtained.

(2-2) Example 2
Stearic acid glyceride (melting point 61 ° C.): 43% by weight
Rosin ester: 16% by weight
Talc: 18% by weight
Titanium dioxide: 12% by weight
Pigment A-2: 11% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-2 so as not to exceed 60 ° C., and extruded with a plunger type extruder. Thus, a thermochromic solid drawing material 20 having a diameter of 8.0 mm and having a blue color as shown in FIG. 1B was obtained.

(2-3) Example 3
Urushiro (melting point 52 ° C): 15% by weight
Rosin ester: 6% by weight
Fischer-Tropsch wax (melting point 110 ° C.): 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 15% by weight
Kaolin: 6% by weight
Pigment A-3: 25% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-3 so as not to exceed 60 ° C., and injection molded with an injection machine. A thermochromic solid drawing material 20 of blue when developing as shown in FIG.

(2-4) Example 4
Urushiro (melting point 52 ° C): 22% by weight
Rosin: 9% by weight
Paraffin wax 135F (Nippon Seiwa): 23% by weight
Microcrystalline wax (Nippon Seiwa): 5% by weight
Ethylene-vinyl acetate copolymer: 13% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 15 g / min)
Talc: 8% by weight
Titanium dioxide: 10% by weight
Pigment A-4: 10% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-4 so as not to exceed 60 ° C., and injection molded with an injection machine. A thermochromic solid drawing material 20 of blue when developing as shown in FIG.

(2-5) Example 5
Hazerou (melting point 52 ° C): 34% by weight
Rosin ester: 12% by weight
Paraffin wax 155F (Nippon Seiwa): 15% by weight
Low density polyethylene (Sumitomo Chemical): 5% by weight
Ethylene-vinyl acetate copolymer: 3% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 40 g / min)
Calcium carbonate: 6% by weight
Titanium dioxide: 15% by weight
Pigment A-5: 10% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-5 so as not to exceed 60 ° C., and injection molded with an injection machine. A thermochromic solid drawing material 20 of blue when developing as shown in FIG.

(2-6) Example 6
The blended composition in which the pigment A-1 in Example 1 was replaced with the developer A-6 was heated and mixed and dispersed with a kneader, then kneaded with two rolls, poured into a predetermined mold, cooled and solidified. As shown in FIG. 1A, the cross-section is 8.0 mm × 8.0 mm on one side, and a blue thermochromic solid drawing material 20 was obtained.

(2-7) Example 7
Stearic acid glyceride (melting point 61 ° C.): 43% by weight
Rosin ester: 16% by weight
Talc: 18% by weight
Titanium dioxide: 12% by weight
Pigment A-1: 11% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-1 so as not to exceed 60 ° C., and extruded with a plunger type extruder. Thus, a blue thermochromic solid drawing material 20 having a diameter of 7.0 mm and a length of 120 mm as shown in FIG. 1B was obtained. A protective sheet 30 made of polypropylene synthetic paper having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive is wound around the substrate 5 times as shown in FIG. 3 and has a diameter of 8.0 mm and a length as shown in FIG. A thermochromic solid drawing material 20 having a thickness of 120 mm was obtained.

(2-8) Example 8
Except that the protective sheet 30 of Example 7 was replaced with a protective sheet 30 made of biaxially stretched polypropylene having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive, the same production method as in Example 7 was used. A thermochromic solid drawing material 20 having a diameter of 8.0 mm and a length of 120 mm was obtained.

(2-9) Example 9
Except that the protective sheet 30 of Example 7 above was replaced with a protective sheet 30 made of art paper having a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive, the diameter was set to 8 by the same method as in Example 7 above. A thermochromic solid drawing material 20 having a thickness of 0.0 mm and a length of 120 mm was obtained.

(2-10) Example 10
Hazerou (melting point: 52 ° C.): 43% by weight
Rosin: 16% by weight
Talc: 17% by weight
Titanium dioxide: 14% by weight
Pigment A-2: 10% by weight
The above blended composition was heated and mixed with a kneader and dispersed, and then kneaded with two rolls. This kneaded product was further kneaded with pigment A-1 so as not to exceed 60 ° C., and extruded with a plunger type extruder. As shown in FIG. 1B, a blue thermochromic solid drawing material 20 having a diameter of 7.0 mm and a length of 120 mm was obtained. A protective sheet 30 made of polyvinyl chloride having a thickness of 80 μm, a width of 141 mm, and a length of 120 mm, including the adhesive, is wound around this around 6 turns, and a thermochromic solid having a diameter of 7.9 mm and a length of 120 mm as shown in FIG. Drawing material 20 was obtained.

(2-11) Example 11
Except that the protective sheet 30 of Example 10 was replaced with a protective sheet 30 made of styrene having a thickness of 80 μm, a width of 141 mm, and a length of 120 mm including the adhesive, a diameter of 7. A thermochromic solid drawing material 20 having a length of 9 mm and a length of 120 mm was obtained.

(2-12) Friction body 40
Polypropylene having a durometer type A hardness of 75 according to JIS K 6253 was molded into a rod shape with a diameter of 8.0 mm and a length of 120 mm, and the tip was tapered to obtain a friction body 40 as shown in FIG. A combination of the friction body 40 and the thermochromic solid drawing material 20 of Examples 1 to 11 is a thermochromic solid drawing material set 10 shown in FIG. In addition, the transparent polypropylene of the same grade was shape | molded as a transparent cap with an internal diameter of 8.0 mm, and it was set as the friction body 40 as shown in FIG. A combination of the friction body 40 and the thermochromic solid drawing material 20 of Examples 1 to 6 is a thermochromic solid drawing material set 10 shown in FIG. Moreover, what combined this friction body 40 with the thermochromic solid drawing material 20 of the said Examples 7-11 becomes the thermochromic solid drawing material set 10 shown in FIG. Even when the protective sheet 30 is wound, the hue of the thermochromic solid drawing material 20 can be confirmed through the friction body 40 on the cap.

(2-13) Example 12
A frictional body 40 made of polypropylene having a durometer type A hardness of 75 according to JIS K 6253, which is formed as a protrusion having a height of 2 mm along the axial direction, is thermally applied to the outer surface of the protective sheet 30 of Example 7 above. Except for the above, a thermochromic solid drawing material set 10 shown in FIG. 7 having a diameter of 8.0 mm and a length of 120 mm was obtained by the same production method as in Example 7.

(2-14) Example 13
The friction body 40 made of polypropylene having a durometer type A hardness of 75 according to JIS K 6253 formed on the outer surface of the protective sheet 30 of Example 8 as a protrusion having a protrusion height of 2 mm along the axial direction is heated. A thermochromic solid drawing material set 10 shown in FIG. 7 having a diameter of 8.0 mm and a length of 120 mm was obtained by the same production method as in Example 8 except that it was applied.

(2-15) Example 14
The protective sheet 30 of Example 7 was replaced with a protective sheet 30 made of a polypropylene friction body 40 having a thickness of 100 μm including an adhesive, a width of 138 mm, a length of 120 mm, and a durometer type A hardness of 75 according to JIS K 6253. Except that, a thermochromic solid drawing material set 10 shown in FIG. 6 having a diameter of 8.0 mm and a length of 120 mm was obtained by the same production method as in Example 7.

(2-16) Comparative Example 1
Hazerou (melting point 52 ° C): 40% by weight
Paraffin wax 155F (Nippon Seiwa): 10% by weight
White mineral oil: 10% by weight
Talc: 16% by weight
Titanium dioxide: 14% by weight
Pigment A-1: 10% by weight
The above blended composition is heated and mixed with a kneader, dispersed and then kneaded with two rolls, then heated and melted at about 60 ° C., added with pigment A-1, mixed and stirred, poured into a predetermined mold, cooled and solidified. As a result, a solid drawing material having a cross section of 8.0 mm × 8.0 mm on the side when developing was obtained.

(2-17) Comparative Example 2
Hazerou (melting point 52 ° C): 15% by weight
Paraffin wax 135F (Nippon Seiwa): 10% by weight
Rosin: 16% by weight
Amorphous poly α-olefin: 0.5% by weight
White mineral oil: 10% by weight
Talc: 24.5% by weight
Titanium dioxide: 14% by weight
Pigment A-1: 10% by weight
The above blended composition is heated and mixed with a kneader, dispersed and then kneaded with two rolls, then heated and melted at about 60 ° C., added with pigment A-1, mixed and stirred, poured into a predetermined mold, cooled and solidified. As a result, a solid drawing material having a cross section of 8.0 mm × 8.0 mm on the side when developing was obtained.

(2-18) Comparative Example 3
Urushiro (melting point 52 ° C): 15% by weight
Fischer-Tropsch wax (melting point 110 ° C.): 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 21% by weight
Kaolin: 6% by weight
Titanium dioxide: 15% by weight
Pigment A-1: 10% by weight
The above blended composition was heat-mixed and dispersed with a kneader and then kneaded with two rolls, and the kneaded product was injection molded with an injection machine to obtain a blue solid drawing material with a diameter of 8.0 mm.

(2-19) Comparative Example 4
Urushiro (melting point 52 ° C): 22% by weight
Paraffin wax 135F (Nippon Seiwa): 23% by weight
Microcrystalline wax (Nippon Seiwa): 5% by weight
Ethylene-vinyl acetate copolymer: 22% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 15 g / min)
Talc: 8% by weight
Titanium dioxide: 10% by weight
Pigment A-1: 10% by weight
The above blended composition was heat-mixed and dispersed with a kneader and then kneaded with two rolls, and the kneaded product was injection molded with an injection machine to obtain a blue solid drawing material with a diameter of 8.0 mm.

(2-20) Comparative Example 5
Hazerou (melting point 52 ° C): 34% by weight
Paraffin wax 155F (Nippon Seiwa): 15% by weight
Low density polyethylene (Sumitomo Chemical): 15% by weight
Ethylene-vinyl acetate copolymer: 5% by weight
(Vinyl acetate content: 28% by weight, melt flow rate: 40 g / min)
Calcium carbonate: 6% by weight
Titanium dioxide: 15% by weight
Pigment A-1: 10% by weight
The above blended composition was heat-mixed and dispersed with a kneader and then kneaded with two rolls, and the kneaded product was injection molded with an injection machine to obtain a blue solid drawing material with a diameter of 8.0 mm.

(2-21) Comparative Example 6
Except that the protective sheet 30 of Example 7 was replaced with a protective sheet made of high-quality paper with a thickness of 100 μm, a width of 138 mm, and a length of 120 mm including the adhesive, a diameter of 8. A solid drawing material having a length of 0 mm and a length of 120 mm was obtained.

(2-22) Comparative Example 7
The same composition as in Example 7 was heated and mixed and dispersed with a kneader, and then kneaded with two rolls. The kneaded product was extruded with a plunger-type extruder, and had a diameter of 7.8 mm and a length. A blue solid drawing material of 120 mm in color was obtained. A protective sheet made of polypropylene synthetic paper having a thickness of 80 μm, width of 28 mm, and length of 120 mm was wound around this, and the mating portion was bonded with an adhesive to obtain a solid drawing material having a diameter of 8.0 mm and a length of 120 mm. .

(2-23) Comparative Example 8
Except that the protective sheet of Comparative Example 7 was replaced with a protective sheet made of art paper having a thickness of 80 μm, a width of 28 mm, and a length of 120 mm, the manufacturing method was the same as that of Comparative Example 7, and the diameter was 8.0 mm and the length was 120 mm. A solid drawing material was obtained.

(2-24) Comparative Example 9
Urushiro (melting point 52 ° C): 15% by weight
Fischer-Tropsch wax (melting point 110 ° C.): 21% by weight
Montan wax: 12% by weight
Low density polyethylene (Sumitomo Chemical): 21% by weight
Kaolin: 6% by weight
Titanium dioxide: 15% by weight
Pigment A-1: 10% by weight
The above blended composition was heat-mixed and dispersed with a kneader and then kneaded with two rolls, and the kneaded product was injection molded with an injection machine to obtain a blue solid drawing material with a diameter of 8.0 mm.

(2-25) Comparative Example 10
An adhesive is applied to the outer peripheral surface of the solid drawing material similar to that in Example 7, and loaded onto a wooden shaft having an outer diameter of 8.0 mm and an inner diameter of 7.1. A solid drawing material having a diameter of 8.0 mm and a length of 120 mm is obtained. Obtained.

(3) Evaluation method (Examples 1-6, Comparative Examples 1-5)
The solid drawing materials of Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated and confirmed for strength, colorability and erasability when drawing on paper, PET film, glass, and whiteboard.

(3-1) Strength Three-point bending strength was measured for each solid drawing material at a temperature of 23 ° C. with a fulcrum of 40 mm, and the load (unit: N) when broken was determined.

(3-2) Copy Paper Colorability After each solid drawing material was reliably developed in a freezer below freezing for 24 hours, the solid drawing materials according to Example 1 and Comparative Examples 1 and 2 were cut with a cutter knife. Was sharpened by cutting. The solid drawing materials according to Examples 2 to 5 and Comparative Examples 3 to 5 were sharpened by cutting the tip with a small mini-sharpener. Each of these was used to draw on copy paper, and the colorability at that time was evaluated in five stages A ″ to C. Evaluation criteria were as follows.
A ″: The drawn line was too dark, and the underlying pattern and characters were not visible at all.
A ': The drawn line was too dark and it was difficult to see the pattern and letters on the groundwork.
A: The drawn lines are dark and clearly visible, but the pattern and characters on the ground are well discernable.
B: Although the drawn line was too thin and the marking was difficult to see, the pattern and characters on the ground were well discernable.
C: The drawn line is too thin and the marking is difficult to see, and the presence or absence of the marking is unknown.

(3-3) Non-absorbing surface colorability Each solid drawing material was sharpened in the same manner as in the above (3-2). Each of these was used to draw on a PET film, a glass slope, and a whiteboard (WB), and the colorability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: The drawn line is dark and clearly visible.
B: Although the drawing line is disturbed, it looks normal.
C: The drawn line is drowning and difficult to see.
D: The drawn line is drowning considerably and cannot be seen without care.
E: The drawn line is hardly visible or cannot be drawn.

(3-4) Erasability by rubbing The frictional body 40 mentioned in (2-10) above (FIG. 5) was scraped off with a tissue paper on the PET film, glass slope and whiteboard drawn in (3-3) above. ), And the erasability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: It disappears well and no trace remains.
B: Disappears but leaves a trace.
C: The shape of the drawn line remains without disappearing.
D: It hardly disappears.
E: Not disappeared at all (however, this evaluation was made when the evaluation in (3-2) above was D or E).

(3-5) Decoloring property by heating The drawn line drawn on the copy paper in (3-2) was heated to 70 ° C., and the decoloring property at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: The chromatic color (blue) disappears well and no trace is visible.
B: The chromatic color (blue) disappears but a trace remains.
C: The chromatic color (blue) disappears but a trace remains.
D: The chromatic color (blue) disappears slightly, but a trace remains.
E: The chromatic color (blue) does not disappear at all. (However, this evaluation was made when the evaluation in (2-2) was D or E).

(3-6) Decolorization by friction body 40 The hardness of durometer type A according to JIS K 6253, which is drawn on the copy paper in (3-2) above, is 75 and made of a rod-like polypropylene as shown in FIG. By rubbing and heating with the friction body 40, the color erasing property at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: The chromatic color (blue) disappears well and no trace is visible.
B: The chromatic color (blue) disappears but a trace remains.
C: The chromatic color (blue) disappears but a trace remains.
D: The chromatic color (blue) disappears slightly, but a trace remains.
E: The chromatic color (blue) does not disappear at all. (However, when the evaluation in (3-2) was D or E, this evaluation was used).

(3-7) Erasability through a copying machine A standard black and white copy of IMAGO MP C6001 manufactured by RICOH with a PET film having a light transmittance of 50% on the drawn line drawn on the copy paper in (3-2) above Copying was performed in the state, and the erasability at that time was evaluated in five stages of A to E. The evaluation criteria were as follows.
A: The characters on the ground completely disappeared and could not be discriminated at all.
B: Some characters on the background were visible but could not be identified.
C: The characters on the base are thin and can be distinguished by careful observation.
D: The characters on the background look a little thin and can be distinguished normally.
E: The characters on the background look normal and can be distinguished without problems.

(3-8) Evaluation Results Tables 1 and 2 below show the evaluation results for the above evaluation methods using Examples 1 to 6 and Comparative Examples 1 to 5.

  As described above, all the thermochromic solid drawing materials 20 according to Examples 1 to 6 of the present invention showed good results. That is, about intensity | strength, all of Examples 1-6 showed sufficient numerical value for practical use. Moreover, about any drawing target object, A evaluation was obtained in both coloring property and erasability. However, the erasability when drawn on the whiteboard was slightly inferior to the erasability of the commercially available whiteboard-specific marker, and therefore B was determined. Regarding Example 6, the erasability by the friction tool on the copy paper was evaluated as slightly B. This is thought to be due to the color material remaining in the gap between the paper fibers due to the melting of the wax, and the hue remaining.

On the other hand, the test results of Comparative Examples 1 to 5, which are outside the scope of the present invention, resulted in inferior evaluation except for the evaluation of colorability on copy paper.
First, since Comparative Example 1 was only hazel but no resin component such as rosin was blended, the tip was easily broken at the time of drawing. In addition, although it was soft, it slid against the smooth surface, resulting in a dark drawing.
In Comparative Example 2, since the amount of oil was large, the tip was easily broken at the time of drawing. Also, when rubbing the drawn lines on a smooth surface, the drawn lines were stretched and difficult to disappear.
In Comparative Examples 3 to 5, the strength was high, and there was almost no problem when drawing on paper. However, when drawing on a smooth surface, it was impossible to draw by sliding. Further, since the temperature was not taken into consideration when adjusting the solid drawing material, thermal discoloration was stopped, and no color development was already observed during the adjustment.

(4) Evaluation method (Examples 7 to 13, Comparative Examples 6 to 10)
The solid drawing materials of Examples 7 to 14 and Comparative Examples 6 to 10 were evaluated for strength and machinability with a pencil sharpener.

(4-1) Strength With respect to each solid drawing material, a three-point bending strength was measured at a temperature of 23 ° C. or 40 ° C. with a fulcrum of 60 mm, and a load (unit: N) when broken was obtained.

(4-2) Cutting performance with a pencil sharpener Five monitor monitors were used at room temperature and normal humidity (23 ° C, 50%) using a Mitsubishi pencil mini pencil sharpener (trade name: Pocket Sharpener DPS-101 PLT). After cutting with a sharp tip (see Fig. 4) in an environment and in an environment of high temperature and high humidity (35 ° C, 80%), the cutting performance is functionalized in the following 5 levels: 1-5 The average score was determined.
1: Remarkably bad.
2: Bad.
3: Not good or bad.
4: Good.
5: Remarkably good.

(4-3) Evaluation result The evaluation result about the said evaluation method using each Example and the comparative example is shown in following Table 2.

  As described above, the thermochromic solid drawing materials according to Examples 7 to 14 of the present invention showed good results in any of the evaluation methods. That is, the thermochromic solid drawing material set 20 according to Examples 7 to 11 which is used as the thermochromic solid drawing material set 10 in combination with the friction body 40 shown in FIG. As for Examples 12 to 14 constituting the same, the strength of itself showed a value of at least 50 N or more through both 23 ° C. and 40 ° C. temperature conditions. In addition, the machinability was also highly evaluated to exceed 4 points on average in any of the examples under the measurement conditions of normal temperature / normal humidity and high temperature / high humidity. Further, the protective sheet 30 was not peeled off or torn during the cutting.

On the other hand, in the test results of Comparative Examples 6 to 10, which are outside the scope of the present invention, the evaluation results were inferior in each of at least one item.
The high quality paper used as the protective sheet in Comparative Example 6 is hard and easily absorbs moisture. Therefore, in Comparative Example 6 in which this is wound, cutting performance is clearly inferior compared to Example 1 in which the same solid drawing material is used. It was. The result was that the protective sheet was torn especially under conditions of high temperature and high humidity.
In Comparative Examples 7 and 8, since the winding of the protective sheet was one round, it was weak and easily broken, and the strength was insufficient as a solid drawing tool. Moreover, since the adhesive of the protective sheet was applied only to the overlapping part, the protective sheet was easily peeled off from the solid drawing material. As a result, the machinability was clearly inferior to that of Example 6 using the same solid drawing material.
In Comparative Example 9, there was no problem with the machinability, but the strength was remarkably weak and it was easy to break, so it seems not suitable for practical use.
Comparative Example 10 was more robust and stronger than Example 6 using the same solid drawing material as much as it was equipped with a wooden shaft. However, since the thickness of the wood shaft was as thin as 0.1 mm, the adhesive strength with the solid drawing material was weak, and the shaft was cracked particularly under high humidity conditions, and the evaluation of machinability was significantly reduced compared to Example 6. It became a thing.

  By the way, the part of the rod-shaped polypropylene friction body 40 having a durometer type A hardness of 75 according to JIS K 6253, which was used in the experiment (3-4), was contaminated by scraping the drawn line. When cutting was performed under the same conditions as in 2) and the safety of the work was evaluated, it was possible to cut safely. The frictional body 40 having hardness 65 and hardness 95 was also evaluated in the same manner. However, the physical and chemical erasability was good, and cutting was possible safely. When the hardness exceeded 95, cutting with a pocket sharpener was difficult, and cutting with a cutter knife was possible. In addition, the friction body 40 having a hardness of 45 has no problem in physical and chemical erasability. However, cutting with a pocket sharpener cannot perform cutting well due to excessive cutting of the blade, and cutting with a cutter knife or the like. It was too soft and dangerous.

  The present invention can draw smoothly and darkly on smooth non-absorbing surfaces such as coated paper, plastic, metal, glass, whiteboard, as well as normal high-quality paper, drawing paper, copy paper, etc. It can be used for solid drawing materials.

10 Thermochromic solid drawing material set
20 Thermochromic solid drawing material 30 Protective sheet 40 Friction body

Claims (7)

A thermochromic solid drawing material containing at least a resin component, a wax component, a thermochromic color material and an extender; and
A friction body having a durometer type A hardness of 50 or more in JIS K 6253;
A thermochromic solid drawing material set characterized by combining the above.   The thermochromic solid drawing material set according to claim 1, wherein the friction body is made of a synthetic resin.   The thermochromic solid drawing material set according to claim 1, wherein the friction body is mounted integrally with the thermochromic solid drawing material.   The thermochromic solid drawing material set according to claim 1, wherein the friction body is detachably attached to the thermochromic solid drawing material. The friction body is provided on at least a part of the outermost peripheral surface of the protective sheet wound around the outer peripheral surface of the thermochromic solid drawing material two or more times,
The thermochromic solid drawing material set according to claim 3, wherein the thermochromic solid drawing material can be cut with a pencil sharpener together with the protective sheet including the friction body.   6. The thermochromic solid drawing material set according to claim 5, wherein the friction body is formed as a ridge provided along the axial direction on the outermost peripheral surface of the protective sheet.   6. The thermochromic solid drawing material set according to claim 5, wherein all of the protective sheets are formed of the friction body.

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