JP2014010305A - Drawing set and drawing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a drawing set configured to easily form a fine and clear image on a thermochromic sheet using an image forming sheet without displacing the image forming sheet, and a drawing method using the same.SOLUTION: A drawing set comprises a thermochromic sheet formed by arranging a thermochromic layer including a thermochromic material on a support surface, an image forming sheet with an image of an arbitrary shape formed thereon, and a friction body. The image forming sheet includes a transparent resin film as a substrate. On one surface of the substrate, an adhesive layer removable from the thermochromic sheet is disposed. On the opposite surface of the substrate, a lubricating layer is disposed.

Description

  The present invention relates to a drawing set and a drawing method using the drawing set. More specifically, the present invention relates to a drawing set including a thermochromic sheet provided with a thermochromic layer, an image forming sheet formed with an arbitrary shape image and a friction body, and a drawing method using the drawing set.

  Conventionally, when an image such as a figure or a figurative object is imitated with a writing instrument or the like, an image is formed by using a template on which an image punch is formed. (For example, Patent Documents 1 and 2).

  However, when writing with a template, there are problems that the template is shifted, the outline becomes unclear depending on the design, and a fine image cannot be formed.

JP-A-7-241389 Utility Model Registration No. 3096167

Kondo Yasuo and Koishi Masumi, "Microcapsules-Manufacturing Method, Properties and Applications-" Sankyo Publishing Co., Ltd. 1977

  The present invention provides a drawing set capable of clearly and easily forming a fine image without shifting the image forming sheet even when an image is formed on the thermochromic sheet using the image forming sheet. A drawing method using the same is provided.

The present invention solves the above problems by drawing a thermochromic sheet having a thermochromic layer provided on the support surface, a drawing set comprising a specific image forming sheet and a friction body, and drawing using the drawing set. It came to complete.
That is, the present invention
“1. In the drawing set comprising a thermochromic sheet having a thermochromic layer containing a thermochromic material on the surface of the support, an image forming sheet formed with an arbitrarily shaped image, and a friction body, the image The forming sheet has a transparent resin film as a base material, and an adhesive layer having removability to the thermochromic sheet is provided on one surface of the base material, and an image forming sheet is formed with a friction body on the opposite surface of the base material. A drawing set comprising a slipping layer capable of lowering frictional resistance and suppressing generation of frictional heat when rubbing.
2. The thermochromic sheet is formed on the surface of the support with (a) an electron-donating color-forming compound, (b) an electron-accepting compound, and (c) the electron-receiving reaction by the components (a) and (b) at a specific temperature. A reaction medium that occurs reversibly in the region, the first color development state and the second color development state are interchangeably exhibited, and the holding temperature range of each color development state is in a certain temperature range, in the colored state, in the process of temperature rise begins to change color from a first colored state is reached the temperature t _3, at a temperature t ₄ above temperature range than the temperature t _3, become completely second colored state in the course of temperature in the second colored state is lowered and reaches the temperature t ₂ less than the t ₃ begins to change color from a second colored state, at low temperatures t ₁ following temperature range than t ₂ become completely first colored state, first in the temperature range between the temperature t ₂ and the temperature t ₃ Item 1 is a reversible thermochromic sheet comprising a reversible thermochromic layer containing a reversible thermochromic material exhibiting hysteresis characteristics in which a color state and a second color development state are selectively maintained. The drawing set described.
3. The temperature t _{4 at} which the reversible thermochromic material is completely in the second coloring state is 40 to 90 ° C., and the temperature t ₁ at which it is completely in the first coloring state is 10 ° C. or less. The drawing set according to item 2.
4). A drawing method using the drawing set according to any one of Items 1 to 3, wherein an image forming sheet formed by forming a mold image of an arbitrary shape on a thermochromic sheet is used as an adhesive layer. And the thermochromic sheet are in contact with each other, and the image forming sheet is rubbed with a friction body to heat the portion where the thermochromic sheet and the friction body are in direct contact with the heat of friction to a temperature equal to or higher than the discoloration temperature. A drawing method comprising forming an image on the portion. ".

  According to the present invention, an image in a specific color development state can be formed and held in a certain temperature range, and the image forming state can be visually confirmed by using a transparent resin film as the base material of the image forming sheet. Image formation can be performed. Further, by providing the image forming sheet with an adhesive layer having removability, it is possible to form an image without shifting the image forming sheet from the thermochromic sheet when an image is formed. It can be clearly formed. Furthermore, by providing a slipping layer on the image forming sheet, when forming an image by rubbing with a friction body, the frictional resistance on the surface of the image forming sheet is reduced, so that frictional heat is generated except for the portion where the image is formed. In addition, the frictional heat is less likely to be transmitted, so that an excellent effect is achieved such that a fine image can be formed clearly and easily.

It is a perspective view which shows an example of the drawing set of this invention. It is sectional drawing which shows an example of the image forming sheet used for this invention. It is a front view which shows an example of the image formability sheet | seat used for this invention. It is a front view of the state which has arrange | positioned the image forming sheet in the thermochromic sheet | seat used for this invention. It is a front view of the state which formed the image in the thermochromic sheet | seat used for this invention. It is explanatory drawing which shows the discoloration behavior of the reversible thermochromic material used for this invention.

  The drawing set (1) of the present invention comprises a thermochromic sheet (2) having a thermochromic layer provided on a support and a transparent resin film as a base material and has removability on one surface of the base material. The minimum unit is composed of an image forming sheet (3) provided with an adhesive layer and a slipping layer on the opposite surface, and a friction body (4). In the present invention, the image forming sheet of the drawing set has a transparent resin as a base material, and an adhesive layer having removability to the thermochromic sheet is provided on one surface of the base material, and the opposite surface of the base material is provided. It is characteristic that a slipping layer capable of reducing the frictional resistance and suppressing the generation of frictional heat when the image forming sheet is rubbed with a friction body is provided.

  An example of the image forming sheet used in the present invention will be described with reference to FIGS. FIG. 2 is a cross-sectional view of the image forming sheet (3) used in the present invention, and the constitution thereof is a pressure-sensitive adhesive layer (32) that can be re-peeled on one surface of a substrate (31) made of a transparent resin film. And a slipping layer (33) is provided on the opposite surface of the substrate. FIG. 4 is a front view of the image forming sheet used in the present invention. The image forming sheet (3) used in the present invention is provided with the image forming sheet (3) on the thermochromic sheet (2), and when the image forming sheet is rubbed with a friction body, the friction body and the thermochromic property. An image forming punching portion (34) is provided so that the sheet is in direct contact and frictional heat is applied to the thermochromic sheet so that the sheet can be discolored.

  The image forming sheet used in the present invention is preferably about 25 μm to 250 μm. If it is larger than this range, a step between the slipping layer surface of the image forming sheet and the thermochromic sheet becomes large, so that a clear image may not be obtained. Further, a portion other than the image forming punch portion of the image forming sheet is transmitted to the thermochromic sheet, and unnecessary portions may be discolored. Especially preferably, it is 50-125 micrometers, and since a clear image is obtained in the shape of the image formation punching part of an image forming sheet, it is preferable.

  The transparent resin film used in the present invention is not particularly limited as long as it has transparency and can recognize that the thermochromic sheet is colored, decolored or discolored. Specific examples include films made of polyolefin resins, polyester resins, polystyrene resins, acrylic resins, polyamide resins, and fluororesins.

  Moreover, it is preferable that the transparent resin film used for this invention is about 12 micrometers-200 micrometers from the preferable range of the said image forming sheet.

  The transparency of the transparent resin film used in the present invention means that it is colorless or colored and has a light transmittance that can recognize a change such as coloring, decoloring, or discoloration of the thermochromic sheet.

  The pressure-sensitive adhesive layer of the image forming sheet used in the present invention can be formed by disposing a pressure-sensitive adhesive on the transparent resin film of the substrate by coating, printing or the like. Specific examples of the adhesive used in the adhesive layer include acrylic resins such as acrylic resins and acrylic styrene resins, ethylene vinyl acetate resins, ethylene vinyl chloride resins, ethylene vinyl acetate vinyl chloride resins, ethylene vinyl acetate acrylic resins, and ethylene vinyl chloride. Examples thereof include ethylene vinyl acetate resins such as acrylic resins, synthetic resins such as olefin resins, urethane resins, vinyl chloride resins, and silicone resins, and thermoplastic elastomers such as styrene butadiene resins and styrene isoprene resins.

  If the image forming sheet is repeatedly used for another position of the thermochromic sheet or another thermochromic sheet, or if the image forming sheet is removed from the thermochromic sheet after image formation, the thermochromic sheet is too strong. Since the surface of the adhesive may be damaged, a weak adhesive material that can be removed again is preferable as the adhesive. Among these, acrylic resins, ethylene vinyl acetate resins, and urethane resins are particularly preferable.

  The slipping layer of the image forming sheet used in the present invention can be formed by disposing a slipping agent on the transparent resin film of the base material by coating, printing, film lamination, or the like. The lubricant to be used is not particularly limited as long as it can reduce the frictional resistance when the image forming sheet is rubbed with a friction body, but is not limited to a polymer material such as silicone resin and fluorine resin, hydrocarbon wax, fatty acid amide. Examples thereof include waxes such as wax. In addition, a material in which the film itself is slippery, for example, a highly functional polyolefin film such as poly-4-methylpentene-1 can also be used. Since the frictional resistance is reduced by the slipping layer, frictional heat is less likely to be generated when rubbing with a friction body, and unnecessary discoloration can be prevented in areas other than the portion where the image of the thermochromic sheet is desired to be formed.

  The thickness of the slipping layer is preferably about 0.01 to 10 μm. Within this range, the image-forming sheet can be prevented from becoming unnecessarily thick, a clear image can be formed, and durability against repeated rubbing by the friction body can be maintained, which is preferable.

By providing a slipping layer on the image forming sheet used in the present invention, it is possible to suppress the generation of frictional heat at portions other than the image forming punched portion as compared with the case where no slipping layer is provided. Can be made thinner. By making the image forming sheet thin with the above configuration, it becomes possible to sufficiently scrape the image forming punched portion with the friction body, and by providing the slipping layer, the frictional heat generated can be reduced. The difference between the end of the image forming punch and the end of the image forming sheet can be increased. That is, the temperature of the image forming vent part exceeds the t _4, since the temperature of the image forming sheet portion does not reach the t ₄ even if exceed t _3, the image forming finer, be clearer It becomes possible. Furthermore, since the image forming sheet used in the present invention is provided with an adhesive layer, even when the thickness of the image forming sheet is reduced, the adhesive layer is not inadvertently displaced during rubbing. Compared to the case where there is no image, it is possible to reliably scrape the image forming punched portion with the friction body, and the image to be formed becomes finer and clearer. By providing both the pressure-sensitive adhesive layer and the slipping layer on the image forming sheet of the present invention, a finer image can be obtained in a clear, accurate and simple manner.

  As an example of the method for producing the image forming sheet (3) used in the present invention, an adhesive to be an adhesive layer (32) is formed on the transparent resin film (31) by coating, printing or the like. Subsequently, on the opposite side of the transparent resin film (3) provided with the adhesive layer, a slipping agent to be the slipping layer (33) is formed by coating, printing, etc., and then punched into the shape of the image to be formed. The image forming sheet (3) can be obtained by providing the image forming punching portion (34) using the above. After providing the adhesive layer and / or the slipping layer, the image forming punching portion (34) may be provided, or after providing the image forming punching portion (34) from the transparent resin film, the adhesive layer and the slipping layer are provided. May be provided to obtain the image forming sheet (3).

  The thermochromic sheet used in the present invention is not particularly limited as long as it can be discolored by frictional heat generated when rubbing with a friction body, and the discolored state can be maintained in a certain temperature range. Alternatively, a reversible type thermochromic sheet or an irreversible type thermochromic sheet can be used. Examples of the reversible thermochromic sheet include a reversible thermochromic sheet using a reversible thermochromic material as a reversible thermochromic layer, a liquid crystal sheet using a liquid crystal material or the like as a reversible thermochromic layer, and the like. As a type of thermochromic sheet, a temperature indicating sheet provided with a thermochromic layer in which a wax or an organic compound that melts at a preset temperature is laminated in a coarse state on a colored substrate such as thermal paper or colored paper Is mentioned.

  As the thermochromic sheet used in the present invention, it is preferable to use a reversible type thermochromic sheet because it can be used repeatedly. In particular, a reversible thermochromic sheet using a reversible thermochromic material for the reversible thermochromic layer is particularly preferable because its discoloration state can be variously adjusted.

  The reversible thermochromic sheet used in the present invention can alternately exhibit the first color development state and the second color development state. According to the present invention, the first color development state and the second color development state are expressed in two colors: a colored state (α) and a colored state (β), a colored state and a decolored state or a decolored state. This means that the state and the coloring state are interchangeably exhibited. That is, when the temperature rises from the first color development state and changes to the second color development state, the color (α) changes to the color (β), the color change state changes to the color disappearance state, that is, the heat disappears. It includes a change in color type, a change from a decolored state to a colored state, that is, a change in the heated color type.

  The reversible thermochromic material used in the present invention has a non-thermochromic coloring such as a dye or a pigment when the first coloring state and the second coloring state change between colored (α) and colored (β). This can be achieved by blending an agent.

The discoloration behavior of an image when drawn with the drawing set of the present invention will be described with reference to FIG. In FIG. 6, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter, also referred to as a complete decoloring temperature) that reaches a completely decolored state, and B is a temperature t ₃ (hereinafter, decolorized) at which decolorization is started. C is a point indicating a density at a temperature t _{2 at} which color development is started (hereinafter sometimes referred to as a color development start temperature), and D is a complete color development state. temperature t ₁ to reach a point showing the density at _{(hereinafter,} sometimes referred to complete coloring temperature).

The discoloration temperature range is a temperature range between t ₁ and t ₄ , and can exhibit either a colored state or a decolored state between t ₂ and t ₃ , which is a region having a large difference in color density. The temperature range is substantially the discoloration temperature range. The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. Further, when the ΔH value is large, it is easy to maintain each state before and after the color change. The reversible thermochromic material having a large ΔH value can alternatively hold either the colored state or the decolored state over the entire color holding temperature range (t ₃ -t ₂ ).

In the present invention, after the image forming sheet (3) is disposed on the reversible thermochromic sheet (2) in a colored state, the image forming sheet is abraded with the friction body (4). Friction heat is generated in the part. At that time, when the temperature of the portion where the frictional body and the reversible thermochromic sheet are in direct contact with each other is heated to t ₄ or more, the colored state changes to the decolored state. At this time, the temperature of the reversible thermochromic sheet does not rise to t _{4 in the} part where the friction body and the reversible thermochromic sheet are not in direct contact with each other through the image forming sheet, that is, the friction body and the reversible thermochromic sheet. The colored state will be maintained. As a result, an image (21) is formed on the reversible thermochromic sheet. When this image is erased, it can be erased by heating the reversible thermochromic sheet to a temperature of t ₄ or higher by directly rubbing it with a friction body or cooling to a temperature of t ₁ or lower. .

  The reversible thermochromic sheet used in the present invention has a minimal configuration in which a reversible thermochromic layer containing a reversible thermochromic material comprising at least the components (A), (B) and (C) is provided on a support. It has a configuration.

  As the component (a) of the reversible thermochromic material used in the present invention, a so-called leuco dye that is usually used for a heat sensitive material such as a thermal paper can be used. Specific examples include diphenylmethane phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans, styrinoquinolines, diazarhodamine lactones, and the like.

  More specifically, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) ) Phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- [2 -Ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3,6-diphenylaminofluorane, 3,6-dimethoxyfluorane 3,6-di-n-butoxyfluorane, 2-methyl-6- (N-ethyl-Np-tolylamino) fluorane, 3-chloro-6-cyclohexylaminofluor Lan, 2-methyl-6-cyclohexylaminofluorane, 2- (2-chloroanilino) -6-di-n-butylaminofluorane, 2- (3-trifluoromethylanilino) -6-diethylaminofluorane, 2- (N-methylanilino) -6- (N-ethyl-Np-tolylamino) fluorane, 1,3-dimethyl-6-diethylaminofluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2 -Anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di-n-butylaminofluorane, 2-xylidino-3-methyl-6-diethylaminofluorane, 1,2- Benz-6-diethylaminofluorane, 1,2-benz-6- (N-ethyl-N-isobutylamino) fluorane, 1, -Benz-6- (N-ethyl-N-isoamylamino) fluorane, 2- (3-methoxy-4-dodecoxystyryl) quinoline, spiro [5H- (1) benzopyrano (2,3-d) pyrimidine- 5,1 ′ (3′H) isobenzofuran] -3′-one, 2- (diethylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine -5,1 '(3'H) isobenzofuran] -3-one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl-spiro [5H- (1 ) Benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) isobenzofuran] -3-one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) isobenzofuran] -3-one, 2- (di-n-butylamino) -8- (N-ethyl-Ni-amylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidin-5,1 '(3'H) isobenzofuran] -3-one, 3- (2-methoxy-4-dimethylamino Phenyl) -3- (1-butyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1 -Ethyl-2-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-pentyl-2-methylindole -3-yl) -4,5,6,7-te Lachlorophthalide, 3 ', 6'-bis [phenyl (2-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9'-[9H] xanthen] -3-one, 3 ', 6'-bis [Phenyl (3-methylphenyl) amino] -spiro [isobenzofuran-1 (3H), 9 '-[9H] xanthen] -3-one, 3', 6'-bis [phenyl (3-ethylphenyl) amino ] -Spiro [isobenzofuran-1 (3H), 9 '-[9H] xanthen] -3-one.

  Furthermore, there can be mentioned pyridine-based, quinazoline-based, bisquinazoline-based compounds and the like that are effective in developing fluorescent yellow to red color development.

  The (b) component electron-accepting compounds used in the present invention include compounds having active protons and pseudo-acidic compounds (not acids, but compounds that act as an acid in the composition and cause component (I) to develop color. Group), and a group of compounds having electron vacancies. Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., a phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group can also be used.

  More specifically, phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, p- N-butyl 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-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, 1,1-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) ethylpropionate, 2,2-bis (4-hydroxy) Phenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) n-hepta , 2,2-bis (4-hydroxyphenyl) such as n- nonane, and the like.

  In addition, the compound having a phenolic hydroxyl group can exhibit the most effective thermochromic property, but aromatic carboxylic acid and aliphatic carboxylic acid having 2 to 5 carbon atoms, carboxylic acid metal salt, acidic phosphate ester and A compound selected from those metal salts, 1,2,3-triazole and derivatives thereof can also be used.

  Further, as an electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms (Japanese Patent Laid-Open No. 11-129623), a specific hydroxybenzoic acid ester (Japanese Patent Laid-Open No. 2001-105732). Gazette), gallic acid esters (Japanese Patent Laid-Open No. 2003-253149), and the like, and a heat coloring type reversible thermochromic composition can also be applied.

  The component (c) of the reaction medium for reversibly causing the electron transfer reaction by the components (a) and (b) used in the present invention in a specific temperature range includes alcohols, esters, ketones, and ethers. Can be mentioned.

  The component (c) is preferably a large hysteresis characteristic regarding the color density-temperature curve (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side and the high temperature side to the low temperature side). A carboxylic acid ester compound that exhibits a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition that exhibits color memory, and changes color when changing to the side) For example, a carboxylic acid ester having a substituted aromatic ring in the molecule, an ester of a carboxylic acid having an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester having a cyclohexyl group in the molecule, 6 carbon atoms Fatty acid and unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid And esters of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like can be used.

  Also, fatty acid ester compounds obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even number of fats having 10 to 16 carbon atoms. A fatty acid ester compound having a total carbon number of 17 to 23 obtained from a group carboxylic acid may be used.

  Specifically, as esters, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, capryl N-undecyl acid, n-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-laurate -Pentyl, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate , N-undecyl myristate, myristic N-tridecyl acid, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n stearate Nonyl, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate , N-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like.

  As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, and 5-undecanone. 2-dodecanone, 3-dodecanone, 4-dodecanone, 5-dodecanone, 2-tridecanone, 3-tridecanone, 2-tetradecanone, 2-pentadecanone, 8-pentadecanone, 2-hexadecanone, 3-hexadecanone, 9-heptadecanone, 2 -Pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.

  Furthermore, as arylalkyl ketones having 12 to 24 carbon atoms, for example, n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetra Decanophenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone N-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropio Phenone, n-heptaphenone, 4-n-pentyl Acetophenone, phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, like cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether. , Ditridecyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether Etc.

（式中、Ｒ１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ１、Ｘ２のいずれか一方は−（ＣＨ２）ｎＯＣＯＲ２又は−（ＣＨ２）ｎＣＯＯＲ２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ１及びＹ２は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。） Furthermore, a compound represented by the following general formula (1) is preferably used as the component (c).

(In the formula, R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, one of X1 and X2 represents — (CH2) nOCOR2 or — (CH2) nCOOR2, and the other represents a hydrogen atom. , N represents an integer of 0 to 2, R2 represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y1 and Y2 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen. , R and p represent an integer of 1 to 3)

  Of the compounds represented by (Chemical Formula 1), when R1 is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width can be obtained, and R1 is a hydrogen atom, and m It is more preferable that is 0.

（式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０〜２４のアルキル基、更に好ましくは炭素数１２〜２２のアルキル基である。） Of the compounds represented by (Chemical Formula 1), compounds represented by the following general formula (Chemical Formula 2) are more preferably used.

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.)

  Specific examples of the compound include octanoic acid-4-benzyloxyphenylethyl, nonanoic acid-4-benzyloxyphenylethyl, decanoic acid-4-benzyloxyphenylethyl, undecanoic acid-4-benzyloxyphenylethyl, and dodecanoic acid. -4-benzyloxyphenylethyl, tridecanoic acid-4-benzyloxyphenylethyl, tetradecanoic acid-4-benzyloxyphenylethyl, pentadecanoic acid-4-benzyloxyphenylethyl, hexadecanoic acid-4-benzyloxyphenylethyl, heptadecanoic acid Examples thereof include -4-benzyloxyphenylethyl and octadecanoic acid-4-benzyloxyphenylethyl.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲンを示す。） Furthermore, as the component (c), a compound represented by the following general formula (Formula 3) can also be used.

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represents an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon, respectively. (The alkoxy group of Formula 1-4 is shown, and a halogen.)

  Specific examples of the compound include 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-dodecanoic acid 1,1- Diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1-diphenylmethyl, octadecanoic acid Examples thereof include 1,1-diphenylmethyl.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。） Furthermore, a compound represented by the following general formula (Formula 4) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20)

  Examples of the compound include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol, a diester of succinic acid and 2- (4-benzyloxyphenyl) ethanol, succinic acid and 2- Diester with [4- (3-methylbenzyloxy) phenyl)] ethanol, diester with glutaric acid and 2- (4-benzyloxyphenyl) ethanol, glutaric acid and 2- [4- (4-chlorobenzyloxy) Phenyl)] ethanol diester, adipic acid and 2- (4-benzyloxyphenyl) ethanol diester, pimelic acid and 2- (4-benzyloxyphenyl) ethanol diester, suberic acid and 2- (4- Diester with benzyloxyphenyl) ethanol, suberic acid and 2- [4- (3-methyl Benzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4- (4-chlorobenzyloxy) phenyl)] ethanol diester, suberic acid and 2- [4- (2,4-dichlorobenzyloxy) ) Phenyl)] ethanol diester, azelaic acid and 2- (4-benzyloxyphenyl) ethanol diester, sebacic acid and 2- (4-benzyloxyphenyl) ethanol diester, 1,10-decanedicarboxylic acid And 2- (4-benzyloxyphenyl) ethanol diester, 1,18-octadecanedicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol diester, 1,18-octadecanedicarboxylic acid and 2- [4- (2-Methylbenzyloxy) phenyl)] die with ethanol Etc. can be exemplified ether.

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１乃至３の整数を示す。） Furthermore, a compound represented by the following general formula (Formula 5) can also be used as the component (c).

(In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).

  Examples of the compound include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid, and 1,3-bis (2 -Hydroxyethoxy) benzene and lauric acid diester, 1,3-bis (2-hydroxyethoxy) benzene and myristic acid diester, 1,4-bis (hydroxymethoxy) benzene and butyric acid diester, 1,4 Diesters of bis (hydroxymethoxy) benzene and isovaleric acid, diesters of 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, and 1,4-bis (2-hydroxyethoxy) benzene and propionic acid Diester, diester of 1,4-bis (2-hydroxyethoxy) benzene and valeric acid Diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and caprylic acid, 1,4-bis (2-hydroxyethoxy) benzene And a diester of 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, a diester of 1,4-bis (2-hydroxyethoxy) benzene and myristic acid, and the like.

（式中、Ｘは水素原子、炭素数１乃至４のアルキル基、炭素数１乃至４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１乃至２０の整数を示す。） Furthermore, a compound represented by the following general formula (6) can also be used as the component (c).

(Wherein, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20) Indicates an integer.)

  Examples of the compound include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, a diester of 1,10-decanedicarboxylic acid and 2-phenoxyethanol, Examples include a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

  The blending ratio of the three components (A), (B), and (C) used in the present invention is determined by the concentration, the color change temperature, the color change form, and the type of each component. The ratio is (m) component: (b) component: (b) component: (c) component = 1: 0.1-50: 1-800, preferably (b) component: (b) component :( C) Component = 1: 0.5-20: 5-200. Each of these components may be used in combination of two or more.

  For use in the present invention, various additives such as an antioxidant, an ultraviolet absorber, an infrared absorber, a dissolution aid, and an antiseptic / antifungal agent can be added as long as the function is not affected. .

  The reversible thermochromic material is effective when applied as it is, but is preferably used as a microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic material is maintained in the same composition under various use conditions, and can exhibit the same effects without receiving external factors such as other additives.

The reversible thermochromic material or microcapsule pigment has a complete color development temperature t ₁ that can be obtained only in a refrigerator or freezer, that is, 10 ° C. or lower, preferably 5 ° C. or lower, more preferably 0 which does not require freezing. ° C. or higher, and a temperature of 5 ° C. or less and complete decoloring temperature _{t 4} the temperature obtained from the frictional heat generated by friction body, i.e. 40 to 90 ° C., preferably 45 to 85 ° C., more preferably 45 to By specifying the range of 80 ° C. and specifying the ΔH value of 30 to 100 ° C., it is possible to effectively function to maintain colors exhibited in the daily living temperature range.

If the complete color erasing temperature t ₄ is 40 ° C. or higher, the state before discoloration can be maintained even under high-temperature conditions such as summer, and if it is 90 ° C. or lower, the reversible thermochromic sheet is rubbed on the surface. It can be sufficiently discolored or discolored by frictional heat due to several rubbing by the body.

When the complete color erasing temperature t ₄ exceeds 90 ° C., the frictional heat obtained by rubbing with the friction body may not easily reach the complete color erasing temperature. There is a risk that the reversible thermochromic sheet may be damaged because of an increase in the amount or a tendency to rub against an excessive load.

Further, in the temperature setting of the complete coloring temperature t _1, is preferably a lower temperature to be maintained in the developed state or decolored state is normal use, it is preferable 10 ° C. or less. Furthermore, the reversible thermochromic composition needs to be in a colored state. As a cooling means, it is preferable to cool with a general-purpose refrigerator or freezer, but considering the cooling capacity of the freezer, the limit is up to −50 ° C.

  The microcapsule pigment used in the reversible thermochromic sheet of the present invention is not particularly limited, but preferably has an average particle size of 0.1 to 30 μm. If it is smaller than this range, the color density tends to be lowered, and if it is larger than this range, the workability tends to be inferior when a reversible thermochromic layer is provided on the reversible thermochromic sheet. More preferably, it is 1.0-10.0 micrometers. Within this range, the color development state is good, and it is effective because it is highly sensitive to discoloration and excellent processability.

  The average particle diameter of the microcapsule pigment referred to in the present invention is represented by the value of D50 expressed on a volume basis when the outer diameter of the particle is measured. Here, a laser diffraction / scattering particle size distribution measuring apparatus is used. (Measured using Horiba, Ltd .; LA-300) and the average particle diameter (median diameter) calculated based on the numerical value is used.

  In the microcapsule pigment used in the present invention, the mass ratio between the inclusion and the wall membrane is preferably inclusion: wall membrane = 1: 1 to 7: 1. If the ratio of inclusions is larger than this range, the thickness of the wall film becomes thinner and weakens against pressure and heat, and the microcapsules tend to be destroyed. Tend to decrease. More preferably, the inclusion: wall membrane = 1: 1 to 6: 1. If it is within this range, the density and visibility in the colored state are high, and the microcapsules are not destroyed.

  The method for producing the microcapsule pigment is described in, for example, Non-Patent Document 1 (Takeshi Kondo and Masumi Koishi, “Microcapsules—Production, Properties, and Applications—Sankyo Publishing Co., Ltd., 1977)”. Such generally known methods can be used. Specifically, the coacervate method, interfacial polymerization method, interfacial polycondensation method, in-situ polymerization method, submerged drying method, submerged curing method, suspension polymerization method, emulsion polymerization method, air suspension coating method, spray Examples thereof include a dry method, which is appropriately selected depending on the strength of the microcapsules.

  The reversible thermochromic sheet used in the present invention can be obtained by providing a reversible thermochromic layer containing a reversible thermochromic material on the support surface. For example, screen printing, offset printing, gravure printing using inks and paints dispersed in a vehicle containing various synthetic resin emulsions, water-soluble or oil-based synthetic resins, ultraviolet curable resins, and other resins selected from glues, etc. It can be provided on the surface of the support by a printing method such as coater or transfer printing, or a coating method such as spray coating.

  The binder resin is not particularly limited as long as it does not affect the thermochromic property of the reversible thermochromic material, but may be either water-soluble or oil-soluble resin, and can be appropriately selected and used depending on the purpose. . Specifically, general-purpose resins such as ionomer resin, isobutylene-maleic anhydride resin copolymer resin, acrylonitrile-acryl styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorine. Polyethylene-styrene copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinylidene chloride resin, vinyl chloride resin, chlorinated vinyl chloride resin, Vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polystyrene resin, Polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin, phenol resin modified alkyd resin, epoxy resin modified alkyd resin, styrene Modified alkyd resin, acrylic modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyurethane resin, alkyd resin, natural rubber, polyisobutylene, butyl rubber , Polyvinyl alkyl ether, rosin, rosin ester, rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum hydrocarbon resin, shellac, cyclization , Vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylic ester emulsion resin, aqueous silicone rubber emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble Examples thereof include epoxy resins, water-soluble polybutadiene resins, cellulose acetate, cellulose nitrate, and ethyl cellulose. Moreover, the said resin can be used together 1 type, or 2 or more types.

  The thermoreversible color-changing sheet used in the present invention has a structure in which the reversible thermochromic layer is provided on the support surface, but it can also be a label in which an adhesive layer is provided on the back surface of the support.

  The reversible thermochromic sheet used in the present invention is provided with a transparent protective layer on the reversible thermochromic layer to provide scratch resistance, or a metal gloss layer containing a transparent metallic luster pigment to provide light resistance. You can also

  As the transparent metallic luster pigment, a transparent metallic luster pigment in which the surface of a core material such as natural mica, synthetic mica, flat glass piece, and flaky aluminum oxide is coated with a metal oxide, a cholesteric liquid crystal type metallic luster pigment is used. It is done.

  Effective examples of transparent metallic luster pigments with natural mica as the core material include natural mica particles whose surface is coated with titanium oxide, and whose upper layer is coated with iron oxide or non-thermochromic dyes. The surface of the natural mica is coated with 41 to 44% by mass of titanium oxide, and the metallic metallic luster pigment having a particle size of 5 to 50 μm. The surface of the natural mica is coated with 30 to 38% by mass of titanium oxide, Gold metallic luster pigment having a particle size of 5 to 60 μm coated with 0.5 to 10% by mass of non-thermochromic colored pigment, particle size of 5 to 100 μm coated with 16 to 39% by mass of titanium oxide on the surface of natural mica Silver metallic luster pigment, metallic metallic luster pigment with natural mica surface coated with 45-58 mass% titanium oxide, natural mica surface coated with 45-58 mass% titanium oxide, 0.5 on top -10 mass% Metallic color metallic luster pigments coated with a thermochromic colored dye pigments.

  Specific examples of pigments obtained by coating the surface of the natural mica with a metal oxide such as titanium oxide include trade names “Iriodin” manufactured by Merck & Co., Inc., product number: 100 (particle size distribution: 10 to 60 μm: silver pearl), 120 (particle size distribution) 5-25 μm: raster satin), 201 (particle size distribution 5-25 μm: rutile fine gold), 205 (particle size distribution 10-60 μm: rutile platinum gold), 221 (particle size distribution 5-25 μm: rutile fine blue), 225 (particle size Distribution: 10-60 μm: rutile blue pearl), 231 (particle size distribution: 5-25 μm: rutile fine red), 235 (particle size distribution: 10-60 μm: rutile green pearl), trade name “Lumina Colors” manufactured by Engelhard Inc. Product number: Lumina Gold (particle size distribution 10 to 48 μm: gold color), Lumina red (particle size distribution 10 to 4 μm: metallic red), lumina red blue (particle size distribution 10-48 μm: metallic blue), lumina aqua blue (particle size distribution 10-48 μm: metallic blue), lumina green (particle size distribution 10-48 μm: metallic green), lumina turquoise (particle size) Distribution 10 to 48 μm: metallic green) and the like can be exemplified.

  As a transparent metallic luster pigment with synthetic mica as the core material and coated with a metal oxide such as titanium oxide, it becomes a coloring factor such as impurities and iron as compared with the system using natural mica as the core material. The content of metal ions is small, the glitter is excellent, it has a glittering appearance, and the transparency is also excellent. The metallic luster pigment exhibits a metallic luster of gold, silver or metallic color depending on the coverage of the metal oxide covering the surface of the synthetic mica. An example of the synthetic mica is KMg3 (AlSi3O10) F2. Moreover, although the shape of the mica is not specified, a flat shape or a scale shape can be mentioned. Examples of the metal oxide that covers the surface of the synthetic mica include metal oxides such as titanium, zirconium, chromium, vanadium, and iron. Preferred examples include metal oxides mainly composed of titanium oxide. The metallic luster pigment has an average thickness of 0.1 to 5 μm and an average particle diameter of 2 to 200 μm, preferably 2 to 100 μm.

  Specific examples of pigments in which the surface of the synthetic mica is coated with a metal oxide are trade names “ultimica” manufactured by Nippon Koken Kogyo Co., Ltd., product number: SB-100 (5 to 30 μm: silver), SD-100 ( 10-100 μm: silver), SE-100 (15-100 μm: silver), SF-100 (44-150 μm: silver), SH-100 (150-600 μm: silver), YB-100 (5-30 μm: gold) YD-100 (10-60 μm: gold), YE-100 (15-100 μm: gold), YF-100 (44-150 μm: gold), RB-100 (5-300 μm: metallic red), RD-100 ( 10-60 μm: metallic red), RE-100 (15-100 μm: metallic red), RF-100 (44-150 μm: metallic red), RBB- 00 (5-30 μm: metallic purple), RBD-100 (10-60 μm: metallic purple), RBE-100 (15-100 μm: metallic purple), RBF-100 (44-150 μm: metallic purple), VB-100 ( 5-30 μm: metallic violet), VD-100 (10-60 μm: metallic violet), VE-100 (15-100 μm: metallic violet), VF-100 (44-150 μm: metallic violet), BB-100 (5- 30 μm: metallic blue), BD-100 (10-60 μm: metallic blue), BE-100 (15-100 μm: metallic blue), BF-100 (44-150 μm: metallic blue), GB-100 (5-30 μm: metallic Lean), GD-100 (10~60μm: metallic green), GE-100 (15~100μm: metallic green), GF-100 (44~150μm: metallic green), and the like.

  A transparent metallic luster pigment having a flat glass piece as a core material and the surface thereof coated with a metal oxide such as titanium oxide exhibits a metallic luster of gold, silver or metallic color depending on the coverage of the metal oxide. Specifically, as a pigment in which the surface of the flat glass piece is coated with a metal oxide, a trade name “META SHINE” MC5090RS (90 μm: silver) manufactured by Nippon Sheet Glass Co., Ltd., in which a scaly glass piece is coated with titanium oxide. MC5090RY (90 μm: gold), MC5090RR (90 μm: red), MC5090RV (90 μm: purple), MC5090RB (90 μm: blue), MC5090RG (90 μm: green), MC1080RS (80 μm: silver), MC1080RY (80 μm: gold), MC1080RR (80 μm: red), MC1080RB (80 μm: blue), MC1080RG (80 μm: green), MC1040RS (40 μm: silver), MC1040RY (40 μm: gold), MC1040RR (40 μm: red), MC1040RB (40 μm) Blue), MC1040RG (40 μm: Green), MC1020RS (20 μm: Silver), MC1020RY (20 μm: Gold), MC1020RR (20 μm: Red), MC1020RB (20 μm: Blue), MC1020RG (20 μm: Green), MC1080RSS1 (80 μm: Silver) ), MC1080RYS1 (80 μm: gold), and the like.

  The transparent metallic luster pigment with flaky aluminum oxide as the core material and the surface coated with a metal oxide such as titanium oxide has less impurity content than the system of natural mica, making it brilliant. Are better. Examples of the metal oxide covering the surface of the aluminum oxide include metal oxides such as titanium, zirconium, chromium, vanadium, iron, etc., preferably a metal oxide mainly composed of titanium oxide is applied, Depending on the coverage of the metal oxide, it exhibits a metallic color such as gold, silver or metallic. The metallic luster pigment has an average thickness of 0.1 to 5 μm and an average particle diameter of 2 to 200 μm, preferably 2 to 100 μm.

  Specific examples of pigments obtained by coating the surface of the flaky aluminum oxide with a metal oxide include trade names “Silary” manufactured by Merck Co., Ltd .: T50-10 (10-30 μm: silver), T60-10 WNT (10-30 μm). : Silver), T60-20WNT (10-30 μm: Gold), T60-24WNT (10-30 μm: Metallic Green), T60-23WNT (10-30 μm: Metallic Blue), and the like.

  Examples of the transparent metallic luster pigment having color flop include a cholesteric liquid crystal type metallic luster pigment and a transparent metallic luster pigment formed by coating silicon oxide with one or more metal oxides. The cholesteric liquid crystal type bright pigment will be described below.

  The liquid crystal polymer used as the cholesteric liquid crystal type bright pigment has a property that only a part of the incident light is reflected in a wide spectral region due to the interference effect of light, and the light is transmitted through all other regions. The region of the reflection spectrum is determined by the pitch width of the helical polymer and the refractive index of the material, and the reflection spectral region is divided into light components polarized in the left and right helices, with the direction of rotation of the helix. Accordingly, one can be reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type glittering material has the property of transmitting and reflecting over the entire spectral region, that is, the color flop property in which the hue changes depending on the excellent metallic luster and the viewpoint. Further, the cholesteric liquid crystal type glitter pigment has transparency as well as glitter. Examples of the cholesteric liquid crystal glitter pigment include materials based on a siloxane skeleton having a mesogen in the side chain.

  Specific examples of the cholesteric liquid crystal type bright pigment include trade name “Helicone HC” manufactured by Wacker Chemie, product number: Sapphire (SLM90020) [blue → dark], Scarabeus (SLM90120) [green → blue], Jade (SLM90220). ) [Gold color → green blue], Maple (SLM90320) [red copper color → green], and the like. The cholesteric liquid crystal type bright pigment preferably has an average thickness of 3 to 15 μm, preferably 5 to 10 μm, and an average particle size of 1 to 100 μm, preferably 10 to 60 μm.

  The metallic luster pigment formed by coating the silicon oxide with one or more kinds of metal oxides has light transmittance and expresses various colors depending on the viewing angle and the light hitting angle by the interference effect of light. Can have color flop and metallic luster. Further, when silicon oxide is coated in multiple layers with two or more kinds of metal oxides, color flop properties and metal gloss can be more effectively imparted by using metal oxides having different light reflectivities. Examples of the metal oxide include tin oxide, titanium oxide, and iron oxide.

  Specific examples of the metallic luster pigment include trade names made by Merck Co., Ltd .: Colorstream T10-01 Viola Fantasy, Colorstream T10-00 Autum Mystery, and the like.

  The metallic luster pigment can be used with any particle size as long as it has color flop properties, but preferably has an average particle size of 1 to 100 μm, preferably 5 to 50 μm.

  Furthermore, a light stabilizer layer can be appropriately provided between the uppermost layer of the reversible thermochromic sheet or between each layer. Specifically, the light stabilizer layer is selected from an ultraviolet absorber, an antioxidant, an anti-aging agent, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, a visible light absorber, and an infrared absorber. It is a layer in which the light stabilizer is fixed in a dispersed state.

  As the friction body used in the present invention, an elastic body such as rubber, elastomer or plastic foam which is rich in elasticity and can generate appropriate friction during friction to generate frictional heat is preferably used. Examples of the material of the friction body include silicone resin, SBS resin (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene copolymer), fluorine-based resin, chloroprene resin, and nitrile resin. , Polyester resin, ethylene propylene diene rubber (EPDM) and the like. In particular, it is preferable to use a low-abrasion elastic material that does not generate wear debris during friction because it efficiently generates frictional heat due to friction.

  The shape of the friction body is not particularly limited, but in addition to a spherical shape, a polyhedral shape such as a square, a rectangle, a triangular weight, a square weight, a cone, a cylinder, a doll, an animal, a plant, a vehicle, a building, a food, etc. It may be a form. Further, the friction body can be provided on a molded product such as plastic, glass, ceramics, wood, stone, or metal.

    Furthermore, the friction body can be provided on a writing instrument. The location where the friction body is provided is not particularly limited, but includes a cap tip portion, a shaft tube tip portion, and the like because of the ease of rubbing as a friction body.

Example 1
(Manufacture of image forming sheet I)
A 50 μm polyethylene terephthalate film (hereinafter sometimes referred to as “PET film”) was used as the transparent resin film, and the acrylic resin emulsion was coated with a wire bar and dried to provide a 30 μm adhesive layer. A silicone emulsion liquid was applied to the opposite surface provided with the adhesive layer with a wire bar and then dried to provide a 3 μm-sliding layer. At the center of the obtained sheet, a star-shaped punching die was used to cut out a star-shaped shape to provide an image-forming punching portion, whereby an image-forming sheet I having a total thickness of 83 μm was obtained.

(Create drawing set)
Using thermal paper as the thermochromic sheet, the image forming sheet I was combined with a rectangular parallelepiped (15 mm × 25 mm × 40 mm) made of SEBS resin as the friction body (4) to obtain a drawing set.
Drawing was performed by the following method using the obtained drawing set. The image forming sheet I was disposed on the thermal paper so that the adhesive layer and the thermal paper were in contact with each other, and the image forming sheet was rubbed with a friction body (4). The part directly abraded by the friction body (4) of the thermal paper developed color, and a star-shaped clear image was obtained on the thermal paper, and this image was maintained at room temperature.

(Example 2)
(Production of microcapsule pigment A)
4.5-part 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a), 1,1-bis (4-hydroxyphenyl) -2-methylpropane 6 as component (b) 0.0 part, a reversible thermochromic material consisting of 50.0 parts of p-methylbenzyl palmitate as component (c) is heated and dissolved, and 30.0 parts by weight of an aromatic isocyanate prepolymer as a wall film material, a cosolvent 40 The solution in which 0.0 part by mass was mixed was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and stirring was continued while heating, then 2.5 parts by weight of a water-soluble aliphatic modified amine was added, and stirring was further continued. A thermochromic microcapsule suspension was obtained. The suspension was centrifuged to isolate thermochromic microcapsules. The average particle size of the microcapsule pigment is 6.0 μm, t ₁ : 3 ° C., t ₂ : 10 ° C., t ₃ : 38 ° C., t ₄ : 45 ° C., ΔH: 35 ° C., reversible thermochromic property. Material: Wall film = 2.6: 1.0 A behavior having hysteresis characteristics was exhibited, and the color changed reversibly from black to colorless and from colorless to black.

(Production of reversible thermochromic sheet a)
Microcapsule pigment A 30 parts by weight Acrylic emulsion resin 50 parts by weight Thickener 2 parts by weight Leveling agent 0.5 parts by weight Antifoaming agent 0.5 parts by weight Crosslinking agent 5 parts by weight A dispersed reversible thermochromic ink was obtained. The obtained ink was solid-printed on a 50 μm PET film using a 120-mesh screen and dried and cured to obtain a reversible thermochromic sheet. When the obtained reversible thermochromic sheet was cooled to 3 ° C. or lower, the entire surface turned black, and the state was maintained at room temperature (25 ° C.).

(Create drawing set)
The reversible thermochromic sheet a, the image forming sheet I, and a rectangular parallelepiped (15 mm × 25 mm × 40 mm) made of SEBS resin as a friction body (4) were combined to obtain a drawing set.
Drawing was performed by the following method using the obtained drawing set. On the entire black reversible thermochromic sheet a, the image forming sheet I was disposed so that the adhesive layer and the reversible thermochromic sheet were in contact with each other, and the image forming sheet was rubbed with a friction body (4). . The portion of the reversible thermochromic sheet a directly abraded by the friction body (4) is heated to 45 ° C. or more and decolored, and a star-shaped clear image is obtained on the reversible thermochromic sheet a. Was maintained at room temperature.
When the reversible thermochromic sheet was placed in a refrigerator and cooled to 3 ° C. or lower, the entire surface turned black. When drawing was performed again by the above method, an image could be formed.

(Example 3)
(Production of microcapsule pigment B)
(A) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- [1-ethyl-2-methyl-1H-indol-3-yl] as component -1 (3H) -isobenzofuranone 1.5 parts (b) As component 2,5.0 parts of 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 4,4 '-(2-methylpropylidene) A reversible thermochromic material comprising 3.0 parts of bisphenol and 50.0 parts by mass of capric acid-4-benzyloxyphenylethyl as component (c) is dissolved by heating, and an aromatic isocyanate prepolymer 30.0 is used as a wall film material. A solution prepared by mixing 4 parts by mass of the solvent and 40.0 parts by mass of the co-solvent is emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. After stirring while heating, 2.5 parts by mass of the water-soluble aliphatic modified amine is added. For example, further continued agitation to obtain a thermochromic microcapsule suspension. The suspension was centrifuged to isolate the microcapsule pigment. The average particle diameter of the microcapsule pigment is 2.5 μm, t ₁ : −16 ° C., t ₂ : −8 ° C., t ₃ : 48 ° C., t ₄ : 58 ° C., ΔH: 65 ° C., reversible heat Color-changing material: wall film = 2.6: 1.0 A behavior having a hysteresis characteristic was exhibited, and the color changed reversibly from blue to colorless and from colorless to blue.

(Production of reversible thermochromic sheet b)
A reversible thermochromic sheet b was obtained by the same method as the production of the reversible thermochromic sheet a except that the microcapsule pigment A was changed to the microcapsule pigment B.

(Manufacture of image forming sheet II)
Image forming sheet I, except that the adhesive layer was 20 μm thick ethylene vinyl acetate resin and the substrate was a 50 μm thick poly-4-methylpentene-1 film (trade name: manufactured by Opulan Mitsui Chemicals, Inc.). An image forming sheet II was obtained in the same manner as in the production of

(Create drawing set)
A drawing set was obtained by combining the reversible thermochromic sheet b, the image forming sheet II, and a cylindrical body (diameter 10 mm × length 150 mm) made of SEBS resin as the friction body (4).
Drawing was performed by the following method using the obtained drawing set. The image forming sheet II was disposed on the reversible thermochromic sheet b whose entire surface was blue so that the adhesive layer and the reversible thermochromic sheet were in contact with each other, and the image forming sheet was rubbed with the friction body (4). . The portion of the reversible thermochromic sheet b directly abraded by the friction body (4) is heated to 58 ° C. or more and decolored, and a star-shaped clear image is obtained on the reversible thermochromic sheet b. Was maintained at room temperature.
When the reversible thermochromic sheet was placed in a freezer and cooled to −16 ° C. or lower, the entire surface turned blue. When drawing was performed again by the above method, an image could be formed.

Example 4
(Production of microcapsule pigment C)
(I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5,1 '(3'H)- Isobenzofuran] -3-one 1.0 part, (2) 2,2-bis (4'-hydroxyphenyl) hexafluoropropane as component (4), 4,4 '-(2-methylpropylidene) bisphenol 0 part, a reversible thermochromic material comprising 50 parts of 4-benzyloxyphenylethyl laurate as component (c) is heated and dissolved, 30.0 parts by weight of an aromatic isocyanate prepolymer as a wall film material, and 40. The solution in which 0 part by mass was mixed was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and after stirring while heating, 2.5 parts by mass of a water-soluble aliphatic modified amine was added, and further stirred. Only to obtain a thermochromic microcapsule suspension. The suspension was centrifuged to isolate thermochromic microcapsules. The average particle diameter of the microcapsule pigment is 3.0 μm, t ₁ : −8 ° C., t ₂ : −1 ° C., t ₃ : 52 ° C., t ₄ : 65 ° C., ΔH: 63 ° C., reversible heat Discoloring material: wall film = 2.6: A behavior having a hysteresis characteristic of 1.0 was exhibited, and the color changed reversibly from pink to colorless and from colorless to pink.

(Production of reversible thermochromic sheet c)
A reversible thermochromic sheet c was obtained in the same manner as the production of the reversible thermochromic sheet a except that the microcapsule pigment A was changed to microcapsule pigment C.

(Create drawing set)
A drawing set was obtained by combining the reversible thermochromic sheet c, the image forming sheet I, and a cylinder (diameter 10 mm × length 150 mm) made of SEBS resin as the friction body (4).
Drawing was performed by the following method using the obtained drawing set. An image forming sheet I is disposed on the reversible thermochromic sheet c, which is entirely pink, so that the adhesive layer and the reversible thermochromic sheet are in contact with each other, and the image forming sheet is rubbed with a friction body (4). did. The portion of the reversible thermochromic sheet c directly rubbed with the friction body (4) is heated to 65 ° C. or more and decolored, and a star-shaped clear image is obtained on the reversible thermochromic sheet c. Was maintained at room temperature.
When the reversible thermochromic sheet was cooled to −8 ° C. or lower, the entire surface turned blue. When drawing was performed again by the above method, an image could be formed.

(Comparative Example 1)
(Manufacture of image forming sheet III)
An image forming sheet III was obtained in the same manner as the image forming sheet I except that the adhesive layer was not provided.

(Create drawing set)
A drawing set was obtained by combining the reversible thermochromic sheet a, the image forming sheet III, and a cuboid (15 mm × 25 mm × 40 mm) made of SEBS resin as the friction body (4).
Drawing was performed by the following method using the obtained drawing set. The image forming sheet III was disposed on the black reversible thermochromic sheet a so that the pressure-sensitive adhesive layer and the reversible thermochromic sheet were in contact with each other, and the image forming sheet was rubbed with a friction body (4). . At this time, the image forming sheet was displaced, and a star-shaped image could not be formed.

(Comparative Example 2)
(Manufacture of image forming sheet IV)
An image forming sheet IV was obtained in the same manner as the image forming sheet I except that the slipping layer was not provided.

(Create drawing set)
A drawing set was obtained by combining the reversible thermochromic sheet a, the image forming sheet IV, and a cuboid (15 mm × 25 mm × 40 mm) made of SEBS resin as the friction body (4).
Drawing was performed by the following method using the obtained drawing set. On the entire black reversible thermochromic sheet a, the image forming sheet IV was disposed so that the adhesive layer and the reversible thermochromic sheet were in contact with each other, and the image forming sheet was rubbed with a friction body (4). . A part of the reversible thermochromic sheet a rubbed directly with the friction body (4) and a part of the reversible thermochromic sheet a and the rubbed body (4) rubbed through the image forming sheet are 45 ° C. As a result of the above-described heating and decoloration, a star-shaped image was partially broken on the reversible thermochromic sheet a.

  As is clear from the results of the above-described examples and comparative examples, the drawing set of the present invention can easily form a clear image and has an excellent function as a drawing set as compared with the conventional case. It is clear.

The drawing set of the present invention can be used for toys, stickers, notebooks, and the like.

DESCRIPTION OF SYMBOLS 1 Drawing set 2 Reversible thermochromic sheet 21 Image 3 Image forming sheet 31 Transparent resin film 32 Adhesive layer 33 Sliding layer 34 Image forming punching part 4 Friction body t ₁ Handwriting of the heat-erasing type solid writing body of the present invention Complete color development temperature of t ₂ Color development start temperature of handwriting of the heat-erasable type solid cursive material of the present invention t ₃ Temperature of color erase start of handwriting of the heat-erasable type solid cursive material of the present invention t ₄ Completely decoloring temperature of handwriting of color type solid cursive letters ΔH Temperature range indicating the degree of hysteresis

Claims (4)

  In a drawing set consisting of a thermochromic sheet comprising a thermochromic layer containing a thermochromic material on the surface of the support, an image forming sheet formed with an image of an arbitrary shape, and a friction body, the image forming sheet comprises: The adhesive layer having removability to the thermochromic sheet was provided on one side of the base material using the transparent resin film, and the image forming sheet was rubbed with a friction body on the opposite side of the base material A drawing set comprising a slipping layer capable of reducing frictional resistance and suppressing generation of frictional heat. The thermochromic sheet is formed on the surface of the support with (a) an electron-donating color-forming compound, (b) an electron-accepting compound, and (c) the electron-receiving reaction by the components (a) and (b) at a specific temperature. A reaction medium that occurs reversibly in the region, the first color development state and the second color development state are interchangeably exhibited, and the holding temperature range of each color development state is in a certain temperature range, in the colored state, in the process of temperature rise begins to change color from a first colored state is reached the temperature t _3, at a temperature t ₄ above temperature range than the temperature t _3, become completely second colored state in the course of temperature in the second colored state is lowered and reaches the temperature t ₂ less than the t ₃ begins to change color from a second colored state, at low temperatures t ₁ following temperature range than t ₂ become completely first colored state, first in the temperature range between the temperature t ₂ and the temperature t ₃ 2. The reversible thermochromic sheet comprising a reversible thermochromic layer containing a reversible thermochromic material exhibiting hysteresis characteristics in which the color state and the second color development state are selectively maintained. The drawing set described. The temperature t _{4 at} which the reversible thermochromic material is completely in the second coloring state is 40 to 90 ° C., and the temperature t ₁ at which it is completely in the first coloring state is 10 ° C. or less. The drawing set according to claim 2.   It is a drawing method using the drawing set of any one of Claims 1-3, Comprising: The image forming sheet formed in the arbitrary shape on a thermochromic sheet | seat is an adhesion layer and a heat | fever. The discolorable sheet is disposed so as to be in contact, and the portion where the thermochromic sheet and the friction body are in direct contact is heated by frictional heat to a temperature equal to or higher than the discoloration temperature by rubbing the image forming sheet with a friction body. A drawing method comprising forming an image on a portion.

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