JP2014101440A - Metallic sheen-imparting reversible thermochromic adhesive tape and method for manufacturing a metallic sheen-imparting reversible thermochromic adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic sheen-imparting reversible thermochromic adhesive tape having a high marketability and capable of imparting a visually recognizable metallic sheen color having a sufficient luminance and a method for manufacturing a metallic sheen-imparting reversible thermochromic adhesive tape.SOLUTION: The provided metallic sheen-imparting reversible thermochromic adhesive tape 1 is obtained by providing, in proper order on the rear surface of a transparent tape substrate 2, a metallic sheen layer 3 in which a transparent flat metallic sheen pigment is bound within a binder resin in a dispersion state; a reversible thermochromic layer 4 in which a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition including (i) an electron-donative coloring organic compound, (ii) an electron-receptive compound, and (iii) a reaction medium determining the temperature at which a coloring reaction of the former two components is induced is bound within a binder resin in a dispersion state; and an adhesive layer 5. A method for manufacturing the metallic sheen-imparting reversible thermochromic adhesive tape is also provided.

Description

  The present invention relates to a method for producing a metallic glossy reversible thermochromic adhesive tape and a metallic glossy reversible thermochromic adhesive tape. More specifically, the present invention relates to a method for producing a metallic glossy reversible thermochromic pressure-sensitive adhesive tape and a metallic glossy reversible thermochromic pressure-sensitive adhesive tape capable of visually recognizing a high-gloss metallic glossy color due to temperature changes.

Conventionally, a reversible thermochromic adhesive tape having a reversible thermochromic layer provided on the front surface or the back surface of a substrate has been disclosed (for example, see Patent Document 1). Further, a reversible temperature-sensitive color-changing pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer is provided on a base material containing a reversible thermochromic material is disclosed (for example, see Patent Document 2).
The reversible temperature-sensitive color-changing adhesive tape is a tape that can set various color types and color-changing temperatures, has improved temperature detection and color-change visualizing effect, and has a transparency on the reversible thermochromic layer. It is disclosed that a metallic gloss color can be visually recognized in a configuration in which a metallic gloss layer containing a gloss pigment is provided.
The reversible thermochromic pressure-sensitive adhesive tape is a reversible thermochromic layer in which a reversible thermochromic material is dispersed in a binder resin even if a metallic gloss layer is provided on the reversible thermochromic layer and the metallic gloss color is visible. Since fine irregularities are formed on the surface, forming a metallic luster layer including a transparent flat metallic luster pigment on the reversible thermochromic layer results in poor orientation of the metallic luster pigment in the metallic luster layer. For this reason, the visually recognized metallic luster color does not easily exhibit sufficient luminance.

JP 2001-234134 A JP 2001-247828 A

  The present invention is intended to solve the problem of a metallic luster tone reversible thermochromic adhesive tape in which a metallic luster layer is formed on a reversible thermochromic layer, that is, a visible metallic luster color has sufficient luminance. It is intended to provide a method for producing a metallic luster-tone reversible thermochromic pressure-sensitive adhesive tape and a metallic luster-tone reversible thermochromic pressure-sensitive adhesive tape.

The present invention relates to a metallic luster layer in which a transparent flat metallic luster pigment is fixed in a dispersed state in a binder resin on the back surface of a transparent tape substrate, (a) an electron-donating color-forming organic compound, (b) A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition containing an electron accepting compound and (c) a reaction medium that determines the temperature at which the color reaction of both occurs is dispersed in a binder resin. A metallic glossy reversible thermochromic pressure-sensitive adhesive tape in which fixed reversible thermochromic layers are sequentially provided is a requirement.
Further, the transparent flat metallic luster pigment is a pigment obtained by coating the surface of a transparent core material with a metal oxide, an adhesive layer is provided under the reversible thermochromic layer, and the reversible heat The binder resin in the discoloration layer is an adhesive resin, which itself forms an adhesive layer, and the reversible thermochromic microcapsule pigment is required to change color at 30 ° C. to 50 ° C. .
Further, a metallic glossy layer is provided on a transparent tape base material by applying a metallic glossy ink containing a transparent flat metallic glossy pigment and a binder resin, and (a) an electron donating coloration is provided on the metallic glossy layer. Reversible thermochromic microcapsule pigment and binder containing a reversible thermochromic composition containing a reactive organic compound, (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of the two occurs. A requirement is a method for producing a metallic glossy reversible thermochromic adhesive tape in which a reversible thermochromic ink containing a resin is applied to provide a reversible thermochromic layer.
Furthermore, the manufacturing method of the metallic luster tone reversible thermochromic adhesive tape which provides the adhesive layer containing adhesive resin on the said reversible thermochromic layer is made into requirements.

  The present invention provides a metal glossy reversible thermochromic pressure-sensitive adhesive tape and a metal glossy tone reversible thermochromic pressure-sensitive adhesive tape that are capable of exhibiting sufficient brightness for a visually recognized metal glossy color and a method for producing a metal glossy tone reversible thermochromic pressure-sensitive adhesive tape. Can do.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition which has color memory property. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heating coloring type reversible thermochromic composition. It is a perspective view which shows one Example of the metallic luster tone reversible thermochromic adhesive tape of this invention. It is longitudinal cross-sectional explanatory drawing which shows one Example of the metallic luster tone reversible thermochromic adhesive tape of this invention.

As the transparent tape base material, a general-purpose base material is effective, and examples thereof include a plastic film.
Examples of the plastic film include a polyethylene film, a polypropylene film, a polyester film, a polycarbonate film, a polyvinyl chloride film, a polyvinylidene chloride film, a polystyrene film, and a polyamide film.

The metallic luster layer is a layer in which a transparent flat metallic luster pigment is fixed in a dispersed state in a binder resin.
As the transparent flat metallic luster pigment, a pigment in which the surface of a transparent core material is coated with a metal oxide is useful.
Specific examples of the transparent flat metallic luster pigment include a transparent metallic luster pigment in which the surface of a core material such as natural mica, synthetic mica, flat glass pieces, and flaky aluminum oxide is coated with a metal oxide, a cholesteric liquid crystal type A metallic luster pigment is used.

Transparent metallic luster pigments with natural mica as the core material are effective when the surface of natural mica particles is coated with titanium oxide, and the top layer of titanium oxide is coated with iron oxide or non-thermochromic dyes. There is a golden metallic luster pigment having a particle size of 5 to 50 μm in which the surface of natural mica is coated with 41 to 44% by mass of titanium oxide, and the surface of natural mica is coated with 30 to 38% by mass of titanium oxide, on which 0 .Golden metallic luster pigment with a particle size of 5 to 60 μm coated with 5 to 10% by mass of non-thermochromic colored pigment, silver color with a particle size of 5 to 100 μm with the surface of natural mica coated with 16 to 39% by mass of titanium oxide Metallic pigment, metallic metallic luster pigment coated with 45 to 58 mass% titanium oxide on the surface of natural mica, surface of natural mica coated with 45 to 58 mass% titanium oxide, and 0.5 to 10% non-thermal change Sex colored dye or pigment metallic color metallic luster pigment obtained by coating the like.
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 BASF Corporation Product number: Lumina Gold (Particle size distribution 10 to 48 μm: gold), Lumina red (particle size distribution 10 to 48 μm) Metallic red), lumina red blue (particle size distribution 10 to 48 μm: metallic blue), lumina aqua blue (particle size distribution 10 to 48 μm: metallic blue), lumina green (particle size distribution 10 to 48 μm: metallic green), lumina turquoise (particle size distribution 10 ˜48 μm: metallic green).

Transparent metallic luster pigments with synthetic mica as the core material and coated with a metal oxide such as titanium oxide are metal ions that become coloring factors such as impurities and iron compared to systems using natural mica as the core material. In addition to being excellent in glitter, it has a glittering appearance and excellent transparency.
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.
As the synthetic mica, KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ may be mentioned.
Although the shape of the mica is not specified, a flat shape or a scale shape can be exemplified. 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 can be exemplified.

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.
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.
Examples of the metallic luster pigment include trade names manufactured by Merck & Co., Inc .: 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.

Examples of the binder resin for fixing the transparent flat metallic luster pigment in a dispersed state include general-purpose resins such as ionomer resins, isobutylene-maleic anhydride copolymer resins, acrylonitrile-acrylic styrene copolymer resins, acrylonitrile-styrene copolymers. Polymerization resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile chlorinated 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, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenol resin, rosin modified alkyd resin , Phenolic 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 S Rosin derivative, polyterpene resin, oil-soluble phenol resin, petroleum hydrocarbon resin, shellac, cyclized rubber, vinyl acetate emulsion resin, styrene-butadiene emulsion resin, acrylate emulsion resin, water-soluble alkyd resin, Examples thereof include water-soluble melamine resins, water-soluble urea resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble polybutadiene resins, cellulose acetate, cellulose nitrate, and ethyl cellulose.
The transparent flat metallic luster pigment and binder resin are dissolved or dispersed in an appropriate solvent such as water or an organic solvent to prepare ink (including paint), applied to the back surface of the transparent tape substrate, and dried. Thus, a metallic luster layer is formed.

  Ink containing transparent flat metallic luster pigment (including paint) is applied on a transparent tape base material with smoothness, so that transparent flat metallic luster in the metallic luster layer formed by drying The pigment is easily oriented in the direction parallel to the metallic luster layer, and the visually recognized metallic luster color has sufficient luminance.

The reversible thermochromic layer provided on the back surface of the metallic luster layer is a layer in which a reversible thermochromic microcapsule pigment is fixed in a dispersed state in a binder resin.
The reversible thermochromic microcapsule pigment comprises (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible heat containing a reaction medium that determines a temperature at which the color reaction of the both occurs. A pigment in which a discoloring composition is encapsulated by a capsule wall film.
Examples of the reversible thermochromic microcapsule pigment include a predetermined temperature (discoloration point) described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. Before and after the color change, the color disappears in the temperature range above the high temperature side discoloration point, and the color develops in the temperature range below the low temperature side discoloration point. The other state is maintained while the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. Applying a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition that has a relatively small characteristic (ΔH = 1 to 7 ° C.) (decolored by heating and develops color by cooling) (Fig. 1 Irradiation).

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (t ₄ ). A reversible thermochromic composition having a color memory property in a temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range) (decolored by heating and developed by cooling). Reversible thermochromic micro Capsule pigments can also be applied (see FIG. 2).

The hysteresis characteristic in the color density-temperature curve of the reversible thermochromic microcapsule pigment encapsulating the reversible thermochromic composition will be described below with reference to the graph of FIG.
In FIG. 2, 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 referred to as a complete decoloring temperature) reaching a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature) at which decoloring starts. C is a point indicating a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D is a temperature t ₁ at which a fully colored state is reached (hereinafter referred to as a color development start temperature). , Referred to as a complete color development temperature).
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). It is easy to maintain each state before and after the color change.
Here, the difference between t ₄ and t ₃ , or the difference between t ₂ and t ₁ (Δt) is a scale indicating the sensitivity of discoloration.

  The reversible thermochromic microcapsule pigment changes color at 30 ° C. to 50 ° C., and can be easily changed by changing the environmental temperature, or touching or rubbing with a finger or hand. .

Furthermore, in order to allow only one specific state (coloring state) to exist in the normal temperature range among the color development and decoloration states of the reversible thermochromic microcapsule pigment, the complete decolorization temperature (t ₄ ) is 50 ° C. or higher. In addition, the color development start temperature (t ₂ ) is preferably 5 ° C. or lower.
Here, it is explained why the complete color erasing temperature (t ₄ ) is 50 ° C. or more and the color development start temperature (t ₂ ) is 5 ° C. or less in order to maintain the color development state in the normal temperature range (around 25 ° C.). Then, if the heating is stopped from the color development state through the decoloration start temperature (t ₃ ) and not reaching the complete decolorization temperature (t ₄ ), a phenomenon of returning to the first state occurs again, and Even if the cooling is stopped in a state where the color state does not reach the complete color development temperature (t ₁ ) through the color development start temperature (t ₂ ), the color development state is maintained, so that the complete color erasing temperature (t ₄ ) If the temperature is 50 ° C. or more exceeding the normal temperature range, the color development state is maintained in the normal use state, and if the color development start temperature (t ₂ ) is 5 ° C. or less below the normal temperature range, the color disappearance state is maintained. Is maintained in normal use.
In the temperature setting of the above-mentioned complete decoloring temperature (t ₄ ), it is preferable that the temperature is higher in order to maintain the color development state in the normal use state, and the complete decoloring temperature (t ₄ ) is 55 ° C. Is preferable, and 60 ° C. or higher is more preferable.
Furthermore, in the temperature setting of the color development start temperature (t ₂ ) described above, a lower temperature is preferable in order to maintain the decolored state in a normal use state, and 0 ° C. or less is preferable, and −5 C. or less is more preferable.
In order to make the microcapsule pigment encapsulating the reversible thermochromic composition into a colored state in advance, it is preferable to cool it in a general-purpose freezer as a cooling means, but considering the cooling capacity of the freezer, it is −50 ° C. The complete color development temperature (t ₁ ) is -50 ° C to 5 ° C, preferably -50 ° C to 0 ° C, more preferably -50 ° C to -5 ° C.
The hysteresis width (ΔH) is in the range of 40 ° C. to 100 ° C., preferably 50 to 100 ° C., more preferably 60 to 100 ° C.

Hereinafter, the components (a), (b) and (c) constituting the reversible thermochromic composition will be described.
Examples of the electron donating color-forming organic compound as the component (a) include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, Fluoranes, stylinoquinolines, diazarhodamine lactones and the like.
Examples of these compounds are given below.
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-cyclohexylaminofluorane,
2-methyl-6-cyclohexylaminofluorane,
2- (2-chloroamino) -6-dibutylaminofluorane,
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,
1,2-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) pyrimidine-5,1 ' (3′H) isobenzofuran] -3-one,
2- (Dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- (1) benzopyrano (2,3-g) pyrimidine-5,1 '(3'H) -isobenzofuran] -3 -On,
3- (2-methoxy-4-dimethylaminophenyl) -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-methylindol-3-yl) -4,5,6,7-tetrachlorophthalide,
4,5,6,7-Tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1 (3H ) -Isobenzofuranone,
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,
4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine and the like can be mentioned.

As the electron-accepting compound of the component (b), a compound group having active protons, a pseudo-acidic compound group (a compound group that is not an acid but acts as an acid in the composition to cause the component (I) to develop color), There is 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. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, 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-methylbu 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, , 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, 1,1-bis (4-hydroxyphenyl) 2-ethylhexane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ethyl Propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2 Bis (4-hydroxyphenyl) n- heptane, there is 2,2-bis (4-hydroxyphenyl) n- nonane.
The compound having a phenolic hydroxyl group can develop the most effective thermochromic property, but aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, acidic phosphate esters and their It may be a compound selected from metal salts, 1,2,3-triazole and derivatives thereof.

Examples of the (c) component of the reaction medium that causes the electron transfer reaction by the (a) and (b) components to occur reversibly in a specific temperature range include alcohols, esters, ketones, and ethers.
Among the components (c), those having a low molecular weight evaporate out of the capsule when subjected to a high heat treatment. Therefore, a compound having 10 or more carbon atoms is preferably used in order to stably hold the component in the capsule.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc. are mentioned.
As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring. Esters, aliphatic and alicyclic rings obtained from any combination of esters, aliphatic and alicyclic or aromatic polyvalent carboxylic acids obtained from the above and monohydric alcohols having aliphatic and alicyclic or aromatic rings Or esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and aliphatic and alicyclic or polyhydric alcohol having an aromatic ring, specifically, ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl acid, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate , Distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, azelaic acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprate, xylene glycol distearate, etc. Can be mentioned.
In addition, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and esters of fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-stearate Mechi Butyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3, stearate 7-Jime Luoctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, isostearic acid Examples include stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate. It is done.

  In addition, as the component (c) for obtaining a reversible thermochromic composition having color memory, a carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., for example, in a molecule A carboxylic acid ester having a substituted aromatic ring, 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, a fatty acid having 6 or more carbon atoms, and Unsubstituted aromatic alcohol or ester of phenol, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid and ester of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate , Dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearate adipate , Trilaurin, trimyristin, tristearin, Dimyristate, distearate and the like are 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 fat 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 is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

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.
Further, arylalkyl ketones having 12 to 24 carbon atoms in total, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecano Phenone, 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-butylpropiophenone, n-heptaphenone, 4-n-pentylacetophene Emissions, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, may be mentioned 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、Ｒ_１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ_１、Ｘ_２のいずれか一方は−（ＣＨ_２）_ｎＯＣＯＲ_２又は−（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２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。〕
前記式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好適であり、更にＲ_１が水素原子であり、且つ、ｍが０の場合がより好適である。
なお、式（１）で示される化合物のうち、より好ましくは下記一般式（２）で示される化合物が用いられる。

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。
前記化合物として具体的には、オクタン酸−４−ベンジルオキシフェニルエチル、ノナン酸−４−ベンジルオキシフェニルエチル、デカン酸−４−ベンジルオキシフェニルエチル、ウンデカン酸−４−ベンジルオキシフェニルエチル、ドデカン酸−４−ベンジルオキシフェニルエチル、トリデカン酸−４−ベンジルオキシフェニルエチル、テトラデカン酸−４−ベンジルオキシフェニルエチル、ペンタデカン酸−４−ベンジルオキシフェニルエチル、ヘキサデカン酸−４−ベンジルオキシフェニルエチル、ヘプタデカン酸−４−ベンジルオキシフェニルエチル、オクタデカン酸−４−ベンジルオキシフェニルエチルを例示できる。 Moreover, the compound shown by following General formula (1) can also be used as said (c) component.

[Wherein, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and _one of X ₁ and X ₂ represents — (CH ₂ ) _n OCOR ₂ or — (CH ₂ ) _n COOR ₂ , the other represents a hydrogen atom, n represents an integer of 0 to 2, R ₂ represents an alkyl or alkenyl group having 4 or more carbon atoms, Y ₁ and Y ₂ represent a hydrogen atom, 1 to 4 carbon atoms An alkyl group, a methoxy group, or halogen, and r and p each represent an integer of 1 to 3. ]
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.
Of the compounds represented by the formula (1), a compound represented by the following general formula (2) is more preferably used.

R in the formula 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。）
前記化合物として具体的には、オクタン酸１,１−ジフェニルメチル、ノナン酸１,１−ジフェニルメチル、デカン酸１,１−ジフェニルメチル、ウンデカン酸１,１−ジフェニルメチル、ドデカン酸１,１−ジフェニルメチル、トリデカン酸１,１−ジフェニルメチル、テトラデカン酸１,１−ジフェニルメチル、ペンタデカン酸１,１−ジフェニルメチル、ヘキサデカン酸１,１−ジフェニルメチル、ヘプタデカン酸１,１−ジフェニルメチル、オクタデカン酸１,１−ジフェニルメチルを例示できる。 Furthermore, a compound represented by the following general formula (3) can also be used as the component (c).

(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 An example is 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。）
前記化合物としては、マロン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、こはく酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、グルタル酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アジピン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２−〔４−(３−メチルベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(４−クロロベンジルオキシ）フェニル）〕エタノールとのジエステル、スベリン酸と２−〔４−(２，４−ジクロロベンジルオキシ）フェニル）〕エタノールとのジエステル、アゼライン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１０−デカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−（４−ベンジルオキシフェニル）エタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−〔４−(２−メチルベンジルオキシ）フェニル）〕エタノールとのジエステルを例示できる。 Furthermore, a compound represented by the following general 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 It 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。）
前記化合物としては、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４−ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４−ビス（２−ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステルを例示できる。 Furthermore, a compound represented by the following general 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 diester of capric acid, 1,4-bis (2-hydroxyethoxy) benzene and lauric acid, and 1,4-bis (2-hydroxyethoxy) benzene and myristic acid.

（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。）
前記化合物としては、こはく酸と２−フェノキシエタノールとのジエステル、スベリン酸と２−フェノキシエタノールとのジエステル、セバシン酸と２−フェノキシエタノールとのジエステル、１，１０-デカンジカルボン酸と２−フェノキシエタノールとのジエステル、１，１８-オクタデカンジカルボン酸と２−フェノキシエタノールとのジエステルを例示できる。 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, An example is a diester of 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol.

  Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms may be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters and the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) are used. A microcapsule pigment containing a reversible thermochromic composition that is decolored by cooling) can also be applied (see FIG. 3).

  The blending ratio of the components (a), (b), and (c) depends on the concentration, the color change temperature, the color change form, and the type of each component. In general, the component ratio at which a desired color change characteristic is obtained is as follows. (B) Component 1 is in the range of (b) Component 0.1-50, preferably 0.5-20, (c) Component 1-800, preferably 5-200. Part by mass). Moreover, you may use each component in mixture of 2 or more types, respectively.

The reversible thermochromic composition is used as a reversible thermochromic microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic composition can be kept in the same composition under the various use conditions and can exhibit the same effects.
Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The microcapsule pigment may have a circular cross section or a non-circular cross section.
Here, the mass ratio of the reversible thermochromic composition to the microcapsule wall membrane satisfies the range of 7: 1 to 1: 1, preferably 6: 1 to 1: 1.
When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

The microcapsule pigment has an average particle diameter of 0.1 to 30 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, satisfying practicality.
When the average particle size exceeds 30 μm, the microcapsules may lack dispersion stability, and when the average particle size is less than 0.1 μm, it is difficult to exhibit high density color development.
The particle size is measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd .; LA-300), and the average particle size (median diameter) is calculated on the basis of the numerical value. To do.

The reversible thermochromic microcapsule pigment is made into ink (including paint) by dispersing a predetermined amount in an aqueous or oily vehicle containing the same binder resin as that of the metallic luster layer. A reversible thermochromic layer is disposed on the back surface of the metallic gloss layer (a surface different from the surface on which the transparent tape substrate is provided). Here, the reversible thermochromic microcapsule pigment is blended at a ratio of 20 to 400 parts by mass with respect to 100 parts by mass of the binder resin. If it is less than 20 parts by mass, no clear thermochromic property is exhibited. On the other hand, when it exceeds 400 parts by mass, a color residue at the time of decoloring tends to occur, and it is preferably applied within the range of 50 to 350 parts by mass.
The binder resin may be an adhesive resin, or may be configured to function as a reversible thermochromic adhesive layer by application of the adhesive resin.

  When the reversible thermochromic layer does not have adhesiveness, a general-purpose acrylic resin-based, urethane resin-based, styrene-butadiene copolymer, vinyl ether copolymer, natural rubber or the like is known on the back surface of the reversible thermochromic layer. The tackifier is appropriately used in combination to form an adhesive layer.

The reversible thermochromic layer is not limited to the one containing a kind of reversible thermochromic pigment in the layer, and a plurality of reversible thermochromic microcapsule pigments having different discoloration points can also be contained and subjected to multistage discoloration. .
In addition, as a form of the reversible thermochromic layer, a plurality of reversible thermochromic layers containing microcapsule pigments having different hues, densities, or discoloration characteristics are overprinted to form a multilayer structure, and the color changes at different temperatures. Examples include a plurality of reversible thermochromic layers arranged in parallel in the axial direction, and a plurality of reversible thermochromic layers that discolor at different temperatures arranged in blocks at appropriate intervals.
The metallic gloss layer and the reversible thermochromic layer are not limited to solid prints, and may be printed images of letters, numbers, symbols, designs, and the like.

The back surface of the reversible thermochromic layer can be diversified by providing a non-thermochromic layer. The non-thermochromic layer is not limited to a solid shape, and may be a non-color-changing printed image such as letters, numbers, symbols, and designs. By disposing the non-color-changing layer, it is possible to play a role of complementing the temperature visual effect due to the color change of the reversible thermochromic layer.
Furthermore, a non-thermochromic image can be provided at a location where the reversible thermochromic layer is not provided.

Furthermore, a light stabilizer layer can be appropriately provided on the reversible thermochromic 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 decolorant, a visible light absorber, and an infrared absorber. This is a layer in which the light stabilizer is fixed in a dispersed state.
The metallic glossy reversible thermochromic pressure-sensitive adhesive tape of the present invention is a general-purpose ink using an ink in which a transparent flat metallic glossy pigment is dispersed in a vehicle containing a binder resin on the back surface of a transparent tape substrate. A metallic luster layer is disposed by printing or coating means, and reversible thermochromic color is produced by printing or coating means using ink in which a reversible thermochromic microcapsule pigment is dispersed in a vehicle containing a binder resin on the back surface of the metallic gloss layer. After disposing the layer, an adhesive layer is formed by applying a general-purpose adhesive. In the case where the binder resin is a pressure-sensitive adhesive system, a form in which the reversible thermochromic layer also serves as the pressure-sensitive adhesive layer is effective.

In addition, the said metallic luster tone reversible thermochromic adhesive tape can be discolored by heating or cooling in the stuck state.
Examples of the heating means include an energizing heating color changing tool equipped with a resistance heating element, a heating color changing tool filled with warm water, a hair dryer, and a method of rubbing with a finger or hand, but means that can be changed by a simple method. A friction body can be used.
As the friction body, an elastic body such as rubber, elastomer or plastic foam which is rich in elasticity and can generate frictional heat upon rubbing to generate frictional heat is suitable.
As the material of the friction body, silicone resin, SBS resin (styrene-butylene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene copolymer), and polyester resin are preferably used.
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 used by being attached to a molded article or writing instrument such as plastic, glass, ceramics, wood, stone, or metal.
Examples of the cooling means include a cold / hot color changing tool using a Peltier element, a cold / hot color changing tool filled with a coolant such as cold water and ice pieces, a refrigerator and a freezer.

  The metallic luster tone reversible thermochromic adhesive tape of the present invention can be easily visually recognized by cutting and sticking to an appropriate shape and size on an object requiring temperature measurement, beverage, food field, clothing field, It has applicability to a wide range of fields such as quality, process control, maintenance and security fields as well as household goods, freezing and refrigeration fields and packaging fields.

Examples of the metallic luster tone reversible thermochromic adhesive tape of the present invention will be described below.
In addition, the part in an Example shows a mass part.
Example 1 (see FIGS. 4 and 5)
Metallic blue transparent flat metallic luster pigment (trade name, manufactured by BASF Corporation) with the surface of a natural mica coated with 51% by weight of titanium oxide on the back side of a 25 μm thick polyester film as the transparent tape substrate 2 ; Luminous Red Blue) 15 parts coated with metallic luster ink added to vehicle containing 3 parts benzotriazole UV absorber, 80 parts polyester resin (solid content 30% by weight) and 2 parts antifoam leveling agent The metallic luster layer 3 having a thickness of 10 μm was provided by drying.
On the metallic luster layer, 3 parts of 2- (2-chloroanilino) -6-dibutylaminofluorane as component (a) and 1,1-bis (4-hydroxyphenyl) -2-methylpropane as component (b) A reversible thermochromic microcapsule comprising 5 parts of a reversible thermochromic composition composed of 50 parts of myristyl myristate as component (c) in an epoxy resin film microcapsule obtained by an epoxy prepolymer / amine compound interfacial polymerization method. 65 parts of pigment (discolored black at 30 ° C. or lower, colorless at 40 ° C. or higher), 150 parts of polyester resin (solid content 30% by mass), 5 parts of antifoam leveling agent, 2 parts of viscosity modifier, 35 parts of water A reversible thermochromic layer 4 having a thickness of 20 μm was provided by applying and drying using a thermochromic ink dispersed in an aqueous vehicle containing.
Next, an adhesive was applied on the reversible thermochromic layer to provide the adhesive layer 5, and slitted to a width of 10 mm to obtain a metallic glossy reversible thermochromic adhesive tape 1.
The metallic luster tone reversible thermochromic pressure-sensitive adhesive tape exhibits a reversible discoloration that becomes a metallic blue color having a high brightness at a temperature of less than 30 ° C. and becomes colorless at a temperature of 40 ° C. or more, and has an arbitrary size at an arbitrary position. It can be cut into a shape and pasted on any part of the object for practical use.
When the metallic glossy reversible thermochromic adhesive tape was attached to the printed material, the metallic blue color was visible when the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
Since the surface of the transparent tape base material was not damaged by rubbing with a friction body, a high-luminance metallic blue color could be visually recognized again at a temperature lower than 30 ° C.

Example 2
Metallic violet colored transparent flat metallic luster pigment (trade name: Super Violet 5303V) made by coating the surface of natural mica with titanium oxide on the back of a 25 μm thick polyester film as a transparent tape substrate 15 parts of a metallic gloss ink added in a vehicle containing 75 parts of a polyester resin emulsion (solid content 30% by weight) and 2 parts of a defoaming leveling agent, 3 parts of a viscosity modifier, and 5 parts of water are coated and dried. A metallic luster layer having a thickness of 10 μm was provided.
On the metallic luster layer, 3 parts of 2- (2-chloroanilino) -6-dibutylaminofluorane as component (a) and 1,1-bis (4-hydroxyphenyl) -2-methylpropane as component (b) A reversible thermochromic microcapsule comprising 5 parts of a reversible thermochromic composition composed of 50 parts of myristyl myristate as component (c) in an epoxy resin film microcapsule obtained by an epoxy prepolymer / amine compound interfacial polymerization method. 65 parts of pigment (discolored black at 30 ° C. or lower, colorless at 40 ° C. or higher), 150 parts of polyester resin (solid content 30% by mass), 5 parts of antifoam leveling agent, 2 parts of viscosity modifier, 35 parts of water A reversible thermochromic layer having a thickness of 20 μm was provided by applying and drying using a thermochromic ink dispersed in an aqueous vehicle containing.
Next, an adhesive was coated on the reversible thermochromic layer to provide an adhesive layer, and slitted to a width of 10 mm to obtain a metallic glossy reversible thermochromic adhesive tape.
The metallic luster tone reversible thermochromic pressure-sensitive adhesive tape exhibits a reversible discoloration that becomes a metallic violet color having a high brightness at a temperature of less than 30 ° C. and becomes colorless at a temperature of 40 ° C. or higher, and has an arbitrary size at an arbitrary position. It can be cut into a shape and pasted on any part of the object for practical use.
When the metallic glossy reversible thermochromic adhesive tape was attached to the printed material, the metallic violet color was visually recognized when the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
Since the surface of the transparent tape base material was not damaged by rubbing with a friction body, a high-luminance metallic violet color could be visually recognized again at a temperature lower than 30 ° C.

Example 3
15 parts of a metallic green transparent flat metallic luster pigment (made by BASF, trade name: Lumina Green) on the back of a 12 μm thick polyester film as a transparent tape substrate, with the surface of natural mica coated with titanium oxide Is coated with a metallic gloss ink added to a vehicle containing 3 parts of a benzotriazole ultraviolet absorber, 80 parts of a polyester resin (solid content 40% by weight) and 2 parts of an antifoam leveling agent, and dried to a thickness of 8 μm. The metallic luster layer was provided.
Next, on the metallic luster layer, 3-dibutylamino-6-methyl-7-anilinofluorane 3 parts as component (ii) 1,1-bis (4-hydroxyphenyl) -2- Micropart of epoxy resin film obtained by interfacial polymerization method of epoxy prepolymer / amine compound with reversible thermochromic composition comprising 5 parts of methylpropane, 47 parts of paramethylbenzyl palmitate as component (c) and 3 parts of behenyl behenate. 65 parts of reversible thermochromic microcapsule pigment encapsulated in capsules (discolored black at 30 ° C. or lower, colorless at 45 ° C. or higher), 90 parts of acrylic resin (solid content 40% by mass), 50 parts of adhesive, A reversible thermochromic adhesive ink dispersed in an aqueous vehicle composed of 2 parts of a foaming agent is applied and dried to provide a reversible thermochromic layer having tackiness, and a slit is added to a width of 10 mm. To obtain a metal luster thermochromic adhesive tape and.
The metallic glossy reversible thermochromic pressure-sensitive adhesive tape exhibits a reversible discoloration that becomes a metallic green color having a high luminance at a temperature of less than 30 ° C. and becomes colorless at a temperature of 45 ° C. or more, and has an arbitrary size and shape at an arbitrary position. And can be put to practical use by sticking it to any part of the object.
When the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was attached to the printed material, the metallic green color was visible when the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
Since the surface of the transparent tape substrate was not damaged by rubbing with a friction body, a high-luminance metallic green color could be visually recognized again at a temperature lower than 30 ° C.

Example 4
Metallic silver transparent flat metallic luster pigment (trade name; Bright Silver 1303Z) 15 with a metallic mica surface coated with titanium oxide on the back side of a 12 μm thick polyester film as a transparent tape substrate 15 Part is coated with a metallic gloss ink added to a vehicle containing 75 parts of polyurethane resin emulsion (solid content 35% by weight), 2 parts of antifoam leveling agent, 3 parts of viscosity modifier and 5 parts of water, dried and thickened. A metallic luster layer having a thickness of 8 μm was provided.
Next, on the metallic luster layer, 3-dibutylamino-6-methyl-7-anilinofluorane 3 parts as component (ii) 1,1-bis (4-hydroxyphenyl) -2- Micropart of epoxy resin film obtained by interfacial polymerization method of epoxy prepolymer / amine compound with reversible thermochromic composition comprising 5 parts of methylpropane, 47 parts of paramethylbenzyl palmitate as component (c) and 3 parts of behenyl behenate. 65 parts of reversible thermochromic microcapsule pigment encapsulated in capsules (discolored black at 30 ° C. or lower, colorless at 45 ° C. or higher), 90 parts of acrylic resin (solid content 40% by mass), 50 parts of adhesive, A reversible thermochromic adhesive ink dispersed in an aqueous vehicle composed of 2 parts of a foaming agent is applied and dried to provide a reversible thermochromic layer having tackiness, and a slit is added to a width of 10 mm. To obtain a metal luster thermochromic adhesive tape and.
The metallic glossy reversible thermochromic pressure-sensitive adhesive tape exhibits a reversible discoloration that becomes a metallic silver color with high brightness at a temperature of less than 30 ° C. and becomes colorless at a temperature of 45 ° C. or more, and has an arbitrary size and shape at an arbitrary position. And can be put to practical use by sticking it to any part of the object.
When the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was adhered to the printed material, the metallic silver color was visually recognized in the state where the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
Since the surface of the transparent tape base material was not damaged by rubbing with a friction body, a high-luminance metallic silver color could be visually recognized again at a temperature lower than 30 ° C.

Example 5
Metallic gold-colored transparent flat metallic luster pigment (trade name; manufactured by BASF) on the back of a 25 μm thick polyester film as a transparent tape substrate and the surface of natural mica coated with 51 wt% titanium oxide Metal added to a vehicle containing 15 parts of Lumina Gold (particle size distribution 10 to 48 μm: gold color) in a vehicle containing 3 parts of a benzotriazole UV absorber, 80 parts of a polyester resin (solid content 30% by mass) and 2 parts of an antifoaming agent A glossy ink was applied and dried to provide a 10 μm thick metallic luster layer.
Subsequently, 3 parts of 2- (2-chloroanilino) -6-dibutylaminofluorane as component (A) and 1,1-bis (4-hydroxyphenyl) -2- A reversible thermochromic composition comprising 5 parts of methylpropane and 50 parts of stearyl caprate as component (c) encapsulated in microcapsules of an epoxy resin film obtained by an epoxy prepolymer / amine compound interfacial polymerization method. 65 parts of microcapsule pigment (discolored black at 25 ° C or lower, colorless at 35 ° C or higher), 180 parts of polyester resin (solid content 25% by mass), 5 parts of antifoam leveling agent, 2 parts of viscosity modifier, water A reversible thermochromic layer having a thickness of 20 μm was provided by applying and drying using a thermochromic ink dispersed in 35 parts of an aqueous vehicle.
Next, an adhesive was coated on the reversible thermochromic layer to provide an adhesive layer, and slitted to a width of 10 mm to obtain a metallic glossy reversible thermochromic adhesive tape.
The metallic luster tone reversible thermochromic pressure-sensitive adhesive tape exhibits a reversible color change that becomes a metallic green color having a high luminance at a temperature of less than 25 ° C. and becomes colorless at a temperature of 35 ° C. or more, and has an arbitrary size and shape at an arbitrary position. And can be put to practical use by sticking it to any part of the object.
When the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was attached to the printed material, the metallic green color was visible when the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
Since the surface of the transparent tape substrate was not damaged by rubbing with a friction body, a high-luminance metallic green color could be visually recognized again when the temperature was lower than 25 ° C.

Comparative Example 1
On the surface of a polyester film having a thickness of 25 μm as a tape substrate, 3 parts of 2- (2-chloroanilino) -6-dibutylaminofluorane as component (a) and 1,1-bis (4- A reversible thermochromic composition comprising 5 parts of hydroxyphenyl) -2-methylpropane and 50 parts of myristyl myristate as component (c) is used as an epoxy resin film microcapsule obtained by an epoxy prepolymer / amine compound interfacial polymerization method. 65 parts of encapsulated reversible thermochromic microcapsule pigment (black at 30 ° C. or lower, colorless at 40 ° C. or higher), 180 parts of polyester resin (solid content 25% by mass), 5 parts of defoaming leveling agent, viscosity Applying and drying with thermochromic ink dispersed in an aqueous vehicle containing 2 parts of modifier and 35 parts of water, reversible thermochromic with a thickness of 20 μm A layer was provided.
Next, 15 parts of a metallic blue transparent flat metallic luster pigment (BASF, trade name: Lumina Red Blue) in which the surface of natural mica is coated with 51% by weight of titanium oxide is added to a benzotriazole ultraviolet absorber 5 The metallic luster ink added to the vehicle containing 80 parts of acrylic resin (solid content 40% by mass) and 2 parts of antifoaming agent was applied and dried to provide a metallic luster layer having a thickness of 10 μm.
Next, an adhesive was applied to the back surface of the tape base material, an adhesive layer was provided, and slitting was performed to a width of 10 mm to obtain a metallic glossy reversible thermochromic adhesive tape.
The metallic glossy reversible thermochromic pressure-sensitive adhesive tape becomes metallic blue in a temperature range of less than 30 ° C. and becomes colorless in a temperature range of 40 ° C. or higher, but has insufficient glitter.
When the metallic glossy reversible thermochromic adhesive tape was attached to the printed material, the metallic blue color was visible when the reversible thermochromic layer was colored, so that the characters formed on the printed material could be concealed.
When the surface of the metallic glossy reversible thermochromic pressure-sensitive adhesive tape was rubbed with a friction body made of SEBS resin, the reversible thermochromic layer was discolored by frictional heat, and the characters formed on the printed matter in the lower layer could be visually recognized.
The surface of the metallic gloss layer was easily damaged by rubbing with a friction body, and the metallic blue color visually recognized at a temperature of less than 30 ° C. was not clear compared with the initial stage, and the appearance was impaired.

t ₁ Complete color development temperature of reversible thermochromic microcapsule pigment with heat decoloring type t ₂ Color development start temperature of reversible thermochromic microcapsule pigment with heat decoloration type t ₃ Reversible thermochromic microcapsule pigment with heat decoloration type Decoloration start temperature of t ₄ Complete decolorization temperature of reversible thermochromic microcapsule pigment of heat decoloring type T ₁ Complete decoloration temperature of reversible thermochromic microcapsule pigment of ₁ heating color developing type T ₂ Reversible heat of color developing type of heat decoloring type Discoloration start temperature of the color-changing microcapsule pigment T ₃ Color development start temperature of the reversible thermochromic microcapsule pigment of the ₃ heating coloring type T ₄ Color development temperature of the reversible thermochromic microcapsule pigment of the heating and coloring type ΔH Hysteresis width 1 Metal gloss Reversible thermochromic adhesive tape 2 Transparency tape substrate 3 Metal gloss layer 4 Reversible thermochromic layer 5 Adhesive layer

Claims (7)

  A metallic luster layer in which a transparent flat metallic luster pigment is fixed in a dispersed state in a binder resin on the back surface of a transparent tape substrate, (b) an electron-donating color-forming organic compound, (b) an electron-accepting compound And (c) a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition containing a reaction medium that determines the temperature at which the color reaction of both occurs is fixed reversibly in a binder resin. A metallic luster reversible thermochromic pressure-sensitive adhesive tape characterized by sequentially providing thermochromic layers.   The metallic glossy reversible thermochromic pressure-sensitive adhesive tape according to claim 1, wherein the transparent flat metallic luster pigment is a pigment obtained by coating the surface of a transparent core material with a metal oxide. The metallic glossy reversible thermochromic adhesive tape according to claim 1 or 2, wherein an adhesive layer is provided below the reversible thermochromic layer. The metallic glossy reversible thermochromic pressure-sensitive adhesive tape according to claim 1 or 2, wherein the binder resin in the reversible thermochromic layer is a pressure-sensitive resin and itself forms a pressure-sensitive adhesive layer. 5. The metallic glossy reversible thermochromic adhesive tape according to claim 1, wherein the reversible thermochromic microcapsule pigment changes color at 30 ° C. to 50 ° C. 6.   A metallic gloss ink containing a transparent flat metallic gloss pigment and a binder resin is applied to a transparent tape base material to provide a metallic gloss layer, and (a) an electron-donating color-forming organic compound on the metallic gloss layer. A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition containing (b) an electron-accepting compound, and (c) a reaction medium that determines the temperature at which the color reaction of both occurs. A method for producing a metallic glossy reversible thermochromic pressure-sensitive adhesive tape in which a reversible thermochromic ink is applied to provide a reversible thermochromic layer.   The method for producing a metallic glossy reversible thermochromic adhesive tape according to claim 5, wherein an adhesive layer containing an adhesive resin is provided on the reversible thermochromic layer.

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