JP2003034005A - Metal gloss-like reversible temperature-sensitive multicolor color-changeable laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal gloss-like reversible temperature-sensitive multicolor color-changeable laminate using a thermally color-changeable pigment showing a large hysteresis width with respect to a temperature-color density curve to be discolored and showing metal gloss such as a gold color, a silver color, a metallic color or the like by a temperature change to generate a color change and showing varicolored phase. SOLUTION: The metal gloss-like reversible temperature-sensitive multicolor color-changeable laminate 1 is constituted by laminating a metal gloss pigment layer 4 on the specific reversible temperature-sensitive multicolor color- changeable layer 3 provided on a support 2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metallic luster reversible temperature-sensitive multicolor discoloring laminate. More specifically, the present invention relates to a metallic luster reversible temperature-sensitive multicolor discoloring laminate that exhibits a variety of appearances by exhibiting a metallic luster such as gold, silver, and metallic colors due to temperature changes, and exhibiting various aspects.

[0002]

2. Description of the Related Art The applicant of the present invention is concerned with a color-changing material which develops multiple colors by a temperature change, as disclosed in JP-A-11-315277, JP-A-2000-80359, and JP-A-2000.
-80360 is disclosed.

[0003]

In the above-mentioned multicolor revealing color changing material, since a plurality of types of thermochromic pigments are applied, in the state where all these thermochromic pigments are colored, In many cases, the color tone is a dark color such as black or brown, or a dull color, and the color tone has been constrained. The present invention solves the above-mentioned restriction of color tone by adding a variety of colors of a new metallic luster tone, and effectively develops a multicolor manifestation discoloration effect due to temperature change, and toys, teaching materials, temperature indication, and decoration fields. The present invention is intended to provide a metal glossy reversible temperature-sensitive multicolor discoloring laminate which is effective in various fields.

[0004]

DISCLOSURE OF THE INVENTION The present invention is a laminate comprising a reversible temperature-sensitive multicolor color changing layer on a support, and a metallic luster pigment layer on the reversible temperature-sensitive multicolor color changing layer. The reversible temperature-sensitive multicolor discoloration layer exhibits a large hysteresis width (ΔH _A ) with respect to the temperature-color density curve and discolors, and the thermochromic pigment A.
And a thermochromic pigment _B having a hysteresis width (ΔH _B ) smaller than ΔH _A and having a hysteresis width (ΔH _B ) which is inherent in the color-changing temperature region of the thermochromic pigment A and is fixed in a dispersed state on the binder resin in a mixed state. The metallic luster pigment layer is a layer formed by fixing a metallic luster pigment having a material selected from natural mica, synthetic mica, flat glass pieces, or flaky aluminum oxide as a core substance to a binder resin in a dispersed state. It requires a metallic luster reversible temperature-sensitive multicolor discolorable laminate characterized by being a layer. More specifically, the thermochromic pigment A and the thermochromic pigment B all satisfy the following (1) to (4): ΔH _A = [(T ₄ −T ₃ ) / 2− (T ₂₋ T ₁ ) / 2] = 10 to 50 ° C. (1) ΔH _B = [(t ₄ −t ₃ ) / 2− (t ₂ −t ₁ ) / 2] = 0.5 to 20 ° C. (2) (T ₁ −T ₂ ) ≧ 1 ° C. (3) (T ₃ −t ₄ ) ≧ 1 ° C. (4) Here, T ₁ , T ₂ , T ₃ , and T ₄ are thermochromic pigments A.
The full color development temperature, the color development start temperature, the color erasure start temperature, and the complete color erasure temperature are shown respectively. Also, t ₁ , t ₂ , t ₃ , t ₄
Is the complete color development temperature, color development start temperature of the thermochromic pigment B,
The decolorization start temperature and the complete decolorization temperature are shown. Furthermore,
T ₁ is 5 ° C to 23 ° C, T ₄ is 28 ° C to 55 ° C, T ₁ is 23 ° C to 90 ° C, and T ₄ is 33 ° C to 10 ° C.
0 ° C., T ₁ is −30 ° C. to 18 ° C., and T ₄ is −20 ° C. to 28 ° C. Further, a non-thermochromic colorant C is added to the reversible temperature-sensitive multicolor color changing layer. Containing, the color of the non-thermochromic colorant is any of the three primary colors of yellow, cyan, magenta, or a color similar to the three primary colors,
The support has an inhomogeneous heat capacity part, and the reversible temperature-sensitive multicolor discoloration layer is provided at the part, the inhomogeneous heat capacity part has an inhomogeneous wall thickness, and the inhomogeneous heat capacity part. Is an uneven surface, and the support is a toy-shaped object or a beverage container.

The above-mentioned formation of the reversible temperature-sensitive multicolor discoloration layer has been previously proposed by the present applicant and is disclosed in Japanese Patent Laid-Open No. 11-31527.
No. 7, JP-A-2000-80359, JP-A 20
The technique disclosed in Japanese Patent Publication No. 00-80360 can be applied, and will be specifically described below. In the above, T ₁ is 5 ° C. to 2
By satisfying the temperature condition of 3 ° C. and T ₄ of 28 ° C. to 55 ° C., it is possible to effectively visually recognize the modal change accompanying the discoloration in the living environment temperature range in the normal temperature range. Also, T ₁ is −
By satisfying the temperature conditions of 30 ° C. to 18 ° C. and T ₄ of −20 ° C. to 28 ° C., various color changes are exhibited in the low temperature range below room temperature. Also, T ₁ is 23 ° C to 90 ° C, and T 1
₄ satisfies the temperature condition of 33 ° C to 100 ° C,
It produces various color changes in the high temperature range above room temperature.

In the above, the thermochromic pigments A and B are
(A) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) an organic compound medium that reversibly causes a color reaction due to the electron-accepting reaction of (a) and (b) above. Examples thereof include a reversible thermochromic material containing three components, a pigment exhibiting reversible thermochromic properties in the form of fine particles of the resin solid solution of the three components, and a microcapsule pigment having the three components encapsulated in microcapsules. The particle size of the reversible thermochromic microcapsule pigment is in the range of 0.2 to 30 μm, preferably 1 to 30 μm, more preferably 2 to 15 μm. It is effective in terms of etc.

As the thermochromic pigment A, Japanese Patent Publication No. 4-17154 and Japanese Patent Application Laid-Open No. 7-3399 proposed by the present applicant.
No. 7, JP-A No. 7-179777, and No. 8-
No. 39936, etc., a thermosensitive color-changing thermochromic material that exhibits a large hysteresis characteristic (ΔH _A ) and changes color, that is, the shape of a curve plotting the change in coloring density due to temperature change is , When the temperature is increased from the lower temperature side than the discoloration temperature range, and conversely, when the temperature is decreased from the higher temperature side than the discoloration temperature range, the color discolors by following a significantly different route, and the low temperature range of T ₁ or lower or It is effective to use a material that retains a state of change in a high temperature range of T ₄ or higher in a specific temperature range in an alternating manner (see FIG. 4).

As the thermochromic pigment B, JP-B-51-35414 and JP-B-51-4 proposed by the present applicant are proposed.
No. 4,706, Japanese Patent Publication No. 1-17154, JP-A No. 7-186546 and other thermochromic materials having a relatively small hysteresis width, and ΔT values (melting point-clouding point) of 3 ° C. or less. Hysteresis width (ΔH _B ) of 3 ° C. or less to which the fatty acid ester shown is applied as the component (C)
High-sensitivity reversible thermochromic material that develops
9398) (see FIG. 5).
This type of reversible thermochromic material discolors before and after the discoloration temperature as a boundary, and only one specific state can exist in a specific temperature range of both states before and after the discoloration. That is, the other state is maintained as long as the heat or cold required to develop that state is applied, but returns to the original state exhibited in the specific temperature range when the heat or cold is no longer applied. It is a type of thermochromic material.

The reversible temperature-sensitive multicolor discoloration layer in the present invention is
Large hysteresis width (ΔH _A ) And discolor
Of the thermochromic pigment A and the thermochromic pigment A
Different key, ΔH_A Smaller hysteresis width (ΔH
_B ), And is inherent in the color change temperature region of the thermochromic pigment A.
And a thermochromic pigment B that discolors by
Further satisfying specific temperature characteristics between the pigments A and B
Allow both related pigments to exist in a mixed state and
High-sensitivity discoloration, color memory, multicolor discoloration, meaning of discoloration
Effectively exhibits externality, subtleties of discoloration, detectability of temperature history, etc.
And effectively functions as a base layer of the metallic luster pigment layer.
Explaining this point, ΔH of the thermochromic pigment A_A Value 10
To 50 ° C, preferably 15-35 ° C
By the T of the pigment A₁ Below low temperature range or T_Four that's all
Alternating the color changed in the high temperature range of T₁ ~ T_Four Temperature
Region, and in effect, T₂ ~ T₃ Stored in the temperature range of
In relation to the color change of the thermochromic pigment B due to the temperature change,
You can effectively bring out multiple colors. ΔH_A The value is 1
If the temperature is below 0 ℃, the color memory function is insufficient.
Memory retention temperature even if the color memory function is fulfilled
The range is too wide and it is difficult to change the color easily with daily temperature means.
However, the above-mentioned range of 10 to 35 ° C. is practically preferable.
On the other hand, ΔH of thermochromic pigment B_B The value is 0.5 to 20 ° C,
Preferably 0.5 to 10 ° C, more preferably 0.5 to 3
The temperature range of the thermochromic pigment A, which satisfies the range of
The requirement is that there is a natural discoloration relationship with. Heat change
ΔH of color pigment B_B By specifying the value in the range
It is sensitive to temperature changes and the heat or cold required for the changes
If you remove the application of the
Change is ΔH_A Is reversibly expressed in the region of
, The above ΔH_ADiscoloration stored in memory
By mixing with the color of pigment A, various color changes can be visualized.
It The present invention further provides t₁ And T₂ Temperature difference of 1 ℃ or more, T
₃ And t_Four To satisfy the temperature difference of 1 ° C or more together
Therefore, it is possible to visually determine the discolored state of the thermochromic pigment B.
The visual time is properly maintained and the color change is recognized. Less than 1 ° C
Then, the thermochromic pigments A and B are continuously emitted and decolored,
It is difficult to recognize the color change.

Next, the discoloring behavior due to the temperature change will be specifically described. 1) In the temperature range of T ₁ or lower, the colors of the thermochromic pigments A and B are both in a color-developing state, and the color mixture (first color) of the colors of the pigments A and B is visually recognized and 2) t ₄ ~
In the temperature range of T _3, the pigment B is decolored, the pigment A maintains the colored state, and the color (second color) of the pigment A is visually recognized. 3) In the temperature range of T ₄ or higher, the pigment is Both A and B have been decolorized and become colorless (third color), and 4) lowering the temperature t ₁ ~
In the temperature range of T ₂ , the pigment B is visualized as a color (fourth color). When the temperature is further lowered, the temperature returns to 1) in the temperature range of T ₁ or less, and the color mixture of the colors of the pigments A and B is visually recognized.

By mixing the non-thermochromic colorant C in addition to the mixed system of the thermochromic pigments A and B satisfying the above requirements, it is possible to further increase the number of colors. That is, 1) in the temperature range of T ₁ or lower, a color mixture (first color) of the colors of the pigments A, B and the colorant C is visually recognized, and 2) in the temperature range of t _{4 to} T ₃ , the pigment A and B are colored. The mixed color (second color) of Agent C is visualized and 3) T ₄
In the above temperature range, to visual color (third color) colorants C, 4) in the temperature range of t ₁ through T _2, mixed colors colorants C and pigment B (fourth color) is visually . Even in a system in which the underlayer is colored with a non-thermochromic colorant without mixing the colorant C in the same layer, the same color change as above can be visually recognized, but the thermochromic layer is transparent. Since it is a change in color after that, it is unavoidable that the sharpness is lowered. As described above, by mixing the non-thermochromic colorant C in the same layer, four different vivid colors can be expressed in the heating-cooling process, and the color exhibited in the heating process ( Second color),
The colors (fourth color) exhibited in the temperature lowering process are different from each other, effectively functioning as memory retention of the temperature history and serving as an indicator, and further enhancing the strangeness and unexpectedness of discoloration. Examples of the thermochromic colorant C include conventionally known dyes, ultraviolet light emitting pigments, general pigments, fluorescent pigments, phosphorescent pigments, luminescent pigments, metal powders, pearl pigments, extender pigments, photochromic colorants, fluorescent whitening agents, Etc. Here, the colors of the colorant C are yellow, cyan,
A clear color change by selecting and using one of the three primary colors of magenta or a color similar to any of the three primary colors, more specifically, the first color, the second color or the fourth color, particularly the second color. This contributes to making the color tones and the color tones of the fourth color visible clearly. The thermochromic pigments A and B in the present invention or the composition obtained by blending the non-thermochromic colorant C with the A and B is 0.1 to 40% by weight (preferably 0.2) in the thermoplastic resin. Sheets, filaments and shaped articles of various forms can be molded by melt blending (about 25% by weight), but in general, the composition is dispersed in a vehicle containing a binder resin to form a paint or an ink. Then, a reversible temperature-sensitive multicolor discoloration layer is formed by coating or spraying on various supports.

In the system based on the coloring material such as the above-mentioned paint and ink,
The thermochromic pigments A and B are effectively in the form of microcapsule pigments, and the occupancy rate in the reversible temperature-sensitive multicolor discoloring layer is 5 to 80% by weight (preferably 10 to 60% by weight).
The range is effective from the viewpoint of thermochromic effect. That is, when the amount is less than 5% by weight, the color density is low and the color change cannot be clearly seen. On the other hand, when the amount is more than 80% by weight, the residual color is visible and it is difficult to visually recognize a clear decolored state. The thickness of the reversible temperature-sensitive multicolor discoloration layer is at least 0.5 μm or more, preferably 1 to 4
00 μm, more preferably 10 to 200 μm,
If it is less than 0.5 μm, the vividness of the color change is lacking.
A system of more than 0 μm tends to impair the appearance and is not preferable. The binder resin contained in the vehicle is preferably a transparent film-forming resin, which is exemplified below. Ionomer resin, isoprene-maleic anhydride copolymer resin, acrylonitrile-acrylic styrene copolymer resin, acrylonitrile-styrene copolymer 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, high density polyethylene resin, medium density polyethylene resin, linear low density polyethylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate Resin, polystyrene resin, high impact polystyrene resin, polypropylene resin, polymethylstyrene resin, polyacrylic acid ester resin, polymethylmethacrylate resin,
Epoxy acrylate resin, alkylphenol resin,
Rosin modified phenolic resin, rosin modified alkyd resin,
Phenol modified alkyd resin, epoxy 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, polyurethane resin, vinyl acetate resin Examples thereof include emulsion resins, styrene-butadiene emulsion resins, acrylic ester emulsion resins, water-soluble phenol resins, water-soluble epoxy resins, water-soluble butadiene resins, cellulose acetate, cellulose nitrate, ethyl cellulose and the like.

As the support, all materials such as plastic, glass, metal, ceramics, cloth, paper, synthetic paper, synthetic leather, wood and stone are effective. Among these supports, when applied to a support having a small heat capacity such as cloth, paper, synthetic paper, and synthetic leather and having a relatively rapid temperature change,
It is effective to set a large difference between the coloring and decoloring temperatures of the pigments A and B and set a wide temperature range in which the second color and the fourth color develop. On the other hand, in a system that forms a reversible temperature-sensitive multicolor discoloration layer on a support that has a large heat capacity such as plastic, glass, metal, ceramics, wood, stone, etc. and has a slow temperature change, the temperature change of the support itself Since the temperature is slow and the temperature reaching the color change is delayed, the second color and the fourth color are surely visible even if the temperature difference between the coloring and decoloring of the pigments A and B is set small. . Although the support has an influence as a temperature factor on the discoloring behavior depending on the material as described above, the discolored state can be diversified by providing non-uniform heat capacity locations even if the same material is used. By providing a reversible temperature-sensitive multicolor discoloration layer on a support that intentionally arranges inhomogeneous heat capacity areas, it gives heterogeneity to the reaction speed and holding time etc. to heat or cold heat, and changes in appearance due to color change. To give a heterogeneity, causing partial discoloration or discoloration with a time delay, and making various discolored patterns visible.On the contrary, to improve unexpectedness, toyiness, and conspicuousness Function. Specifically, as with imaginary creatures such as robot dinosaurs, reptiles, insects, animals and plants, mermaids, fish, etc., uneven parts such as horns, fangs, tactile senses, tentacles, hands, feet, tails, fins, whiskers, etc. In many toys such as shaped objects and stuffed animals that have many, it can be changed into multiple colors by temperature change by spraying it on the surface of the toy and drying it as a spray form ink, and the heat capacity of the support itself Depending on the heterogeneity, a variety of discolored patterns are revealed. In particular, if the object is of a size that fits in the palm of the hand, it can be easily discolored due to body temperature, so it can be applied not only to toys but also to accessories and mascots.

Next, the metallic luster pigment layer provided on the reversible temperature-sensitive multicolor discoloration layer will be described. The metallic luster pigment layer is a layer in which a metallic luster pigment having a core substance of a material selected from natural mica, synthetic mica, flat glass flakes, or flaky aluminum oxide is fixed in a binder resin in a dispersed state. The metallic luster pigment layer not only imparts a variety of metallic luster-like colors to the reversible temperature-sensitive multicolor discoloration layer as described above, but also acts as a light-shielding pigment layer and has a light absorbing (or light reflecting) function. The light-shielding function adversely affects the function deterioration of the reversible temperature-sensitive multicolor color changing layer, and improves the light resistance of the reversible temperature-sensitive multicolor color changing layer by absorbing or reflecting at least part of ultraviolet rays and visible light. Has the effect of

The metallic luster pigments containing natural mica fine particles as a core substance include natural mica particles whose surface is coated with titanium oxide, and those whose upper layer is coated with iron oxide.
Alternatively, a non-thermochromic dye or pigment is coated (preferably 0.5 to 1).
0% by weight) is effective, and more specifically, the surface of natural mica is coated with 41 to 44% by weight of titanium oxide, a golden metallic luster pigment having a particle size of 5 to 50 μm, natural The surface of the mica is coated with 30 to 38% by weight of titanium oxide, and 0.5 to 10% by weight of the non-thermochromic colored pigment is coated on the surface of the mica. Silver-colored metallic luster pigment having a particle size of 5 to 100 μm, whose surface is coated with 16 to 39% by weight of titanium oxide, metallic colored metallic luster pigment having a surface of natural mica coated with 45 to 58% by weight of titanium oxide, and surface of natural mica 45 ~
Coated with 58% by weight of titanium oxide, on which 0.5 to 1
Examples thereof include metallic metallic luster pigments coated with 0% by weight of non-thermochromic colored dyes and pigments.

Compared to the natural mica system, the metallic luster pigment containing the particles of synthetic mica as a core substance has a smaller content of metal ions such as impurities and coloring factors such as iron, and is rich in glitter and shimmers. Take on the appearance. Specifically, it is effective that the surface of the synthetic mica is coated with a metal oxide containing titanium oxide as a main component, the average thickness is 0.1 to 5 μm, and the average particle diameter is 2 to 1000 μm. is there. Depending on the coverage of the metal oxide, it exhibits a metallic luster of gold, silver, or metallic color, is highly transparent, and the color tone of the lower reversible temperature-sensitive multicolor discoloration layer can be clearly recognized. Examples of synthetic mica include KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ . The shape of the mica is not specified, but a flat shape or a scale shape can be exemplified. Examples of the metal oxide that coats the surface of the synthetic mica include metal oxides such as titanium, zirconium, chromium, vanadium, and iron, but metal oxides containing titanium oxide as a main component are preferable, and the average. Having a thickness of 0.1 to 5 μm and an average particle diameter of 2 to 1000 μm, preferably 2 to 500 μm, and more preferably 2 to 200 μm. Here, the said average particle diameter shows a laser diffraction method average particle diameter, and is a particle diameter whose volume-based median diameter corresponds to 50% of cumulative distribution. As the metallic luster pigment in which the surface of the synthetic mica is coated with a metal oxide, specifically, the product name “Ultimica” manufactured by Nikko Kogyo Co., Ltd. product number: SB-10
0 (5 to 30 μm: silver), SD-100 (10 to 60)
μm: silver), SE-100 (15 to 100 μm: silver), SF-100 (44 to 150 μm: silver), SH
-100 (150 to 600 μm: silver), YB-100
(5 to 30 μm: gold), YD-100 (10 to 60 μm)
m: gold), YE-100 (15 to 100 μm: gold), YF-100 (44 to 150 μm: gold), RB
-100 (5-300 μm: metallic red), RD
-100 (10-60 μm: metallic red), RE
-100 (15 to 100 μm: metallic red), R
F-100 (44 to 150 μm: metallic red),
RBB-100 (5 to 30 μm: metallic purple), RBD-100 (10 to 60 μm: metallic purple), RBE-100 (15 to 100 μm: metallic purple), RBF-100 (44 to 150 μm:
Metallic purple), VB-100 (5 to 30 μm:
Metallic violet), VD-100 (10-60
μm: metallic violet), VE-100 (15
˜100 μm: metallic violet), VF-10
0 (44 to 150 μm: metallic violet), B
B-100 (5 to 30 μm: metallic blue), BD
-100 (10-60 μm: metallic blue), BE
-100 (15 to 100 μm: metallic blue), B
F-100 (44 to 150 μm: metallic blue),
GB-100 (5 to 30 μm: metallic green),
Examples thereof include GD-100 (10 to 60 μm: metallic green), GE-100 (15 to 100 μm: metallic green), and GF-100 (44 to 150 μm: metallic green).

Examples of the metallic luster pigment having a flat glass piece as a core substance and its surface coated with titanium oxide include metallic luster pigments of gold, silver or metallic color depending on the coverage of titanium oxide. Specifically, a product name “Metashine” manufactured by Nippon Sheet Glass Co., Ltd., in which scale-like glass pieces are coated with titanium oxide, product number: RCFSX-5450
TS (6041) [average thickness 5 ± 2 μm, average particle size 45
0 ± 145 μm, gold], RCFSX-5200TS
(6042) [average thickness 5 ± 2 μm, average particle size 200 ±
70 μm, silver], RCFSX-5140TS (604
3) [Average thickness 5 ± 2 μm, average particle size 140 ± 45 μ
m, silver], RCFSX-5080TS (6044)
[Average thickness 5 ± 2 μm, average grain size 80 ± 30 μm, silver color], RCFSX-2080TS (6046) [Average thickness 2 ± 1 μm, average grain size 80 ± 30 μm, silver color], RC
FSX-K120TS (6043) [Average thickness 20 ± 5
μm, average particle size 120 ± 20 μm, silver color], RCFSX
-5090RC (8052) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, gold color], RCFSX-5090
RC (8053) [Average thickness 5 ± 2 μm, average particle size 90]
± 30 μm, metallic green], RCFSX-50
90RC (8069) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic blue], RCFSX-5
090RC (8070) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic purple], RCFSX
-5090RC (8071) [average thickness 5 ± 2 μm, average particle size 90 ± 30 μm, metallic red], RCFS
X-1040RC (9543) [average thickness 1 μm, average particle size 40 μm, silver), RCFSX-1040RC (9
544) [average thickness 1 μm, average particle size 40 μm, gold), RCFSX-1040RC (9546) [average thickness 1 μm, average particle size 40 μm, metallic red], R
CFSX-1040RC (9548) [Average thickness 1μ
m, average particle size 40 μm, metallic blue], RCF
SX-1040RC (9549) [average thickness 1 μm, average particle size 40 μm, metallic green], RCFSX-
1020RC (9550) [average thickness 1 μm, average particle size 20 μm, silver color] RCFSX-1020RC (955
1) [Average thickness 1 μm, average particle size 20 μm, gold color], R
CFSX-1020RC (9553) [Average thickness 1μ
m, average particle size 20 μm, metallic red], RCFS
X-1020RC (9555) [average thickness 1 μm, average particle size 20 μm, metallic blue] and the like can be mentioned.

With flaky aluminum oxide as the core substance,
A metallic luster pigment whose surface is coated with a metal oxide will be described. Since the core substance of this kind of metallic luster pigment is flaky aluminum oxide, the content of impurities is small and the glitter is excellent as compared with the system of natural mica. Examples of the metal oxide that coats the surface of the aluminum oxide include titanium, zirconium, chromium, vanadium, and metal oxides such as iron, but a metal oxide containing titanium oxide as a main component is preferably applied. Depending on the coverage of the metal oxide, metallic luster pigments of gold color, silver color, metallic color and the like can be mentioned. The metallic luster pigment has an average thickness of 0.1 to 5
The average particle diameter is 2 to 200 μm. By using the metallic luster pigment exhibiting the above-mentioned thickness and average particle diameter, it is possible to exhibit uniform glitter of the metallic luster layer and a clear color change due to discoloration of the reversible temperature-sensitive multicolor discoloration layer. Here, the said average particle diameter shows a laser diffraction method average particle diameter, and is a particle diameter whose volume-based median diameter corresponds to 50% of cumulative distribution. As the metallic luster pigment in which the surface of the flaky aluminum oxide is coated with a metal oxide, specifically, a product name “Chiraric” manufactured by Merck & Co., Inc. product number: T50-
10 (10 to 30 μm: silver) can be exemplified.

The various metallic luster pigments described above are dispersed in an appropriate amount in a vehicle containing the binder resin described above,
In the form of paint or printing ink, conventionally known coating methods, for example, screen printing, offset printing, gravure printing, coater, tampo printing, printing means such as transfer,
A metallic luster pigment layer is formed on the reversible temperature-sensitive multicolor discoloration layer by means of brush coating, spray coating, electrostatic coating, electrodeposition coating or the like. The reversible temperature-sensitive multicolor discoloration layer and / or the metallic luster pigment layer are not limited to those solid-printed, and print images of letters, numbers, symbols, designs, etc. are effective.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Examples will be described below. The parts in the examples are parts by weight.

[0021]

EXAMPLES Example 1 Thermochromic pigment A (ΔH _A : 17.5 ° C., T ₁ : 16 ° C.,
_{T 2: 17 ℃, T 3} : 32 ℃, T 4: 36 ℃, reversible color change cyan ← → colorless) 3.5 parts, thermochromic pigments B
(ΔH _B : 1 ° C., t ₁ : 26 ° C., t ₂ : 28 ° C., t ₃ :
27 ° C., t ₄ : 29 ° C., magenta color ← → colorless reversible color change) 6.5 parts, and non-thermochromic colorant C [yellow fluorescent pigment, trade name: Epocolor FP-117, Japan Co., Ltd. Catalyst-made] 0.5 part was dispersed in a vehicle containing a binder resin, and black (first color), green (second color)
A thermochromic oily spray ink exhibiting a color), a yellow color (a third color) and a red color (a fourth color) was prepared. Using the thermochromic oil-based spray ink, spray painting is applied to the entire surface of a monster robot shaped object formed of a white soft vinyl chloride resin, and after forming a reversible temperature-sensitive multicolor discoloration layer, on the discoloration layer. , A metallic luster pigment obtained by coating a flat glass piece with titanium oxide [trade name: Metashine RCFSX-1040
RC (9544), Nippon Sheet Glass Co., Ltd., average thickness: 1
μm, average child diameter 40 μm, gold color] and a spray paint of an oil-based spray ink containing a binder resin to construct a mini monster robot toy. The toy water below 16 ° C,
29 ° C-32 ° C water, 36 ° C or higher warm water, 17-26 ° C
Subsequent immersion in 16 ℃ or less of water, golden metallic luster color (first color), green (second color), yellow (third color)
Color, with a slightly golden metallic sheen), red (4th
The entire color could be changed in the order of (color) and gold metallic luster color (first color). Next, when touching a part of the surface of the toy, which was made to develop a golden metallic luster color throughout, the touched part changed color from the golden metallic luster color to green, and a part of the green discolored part was further fingered. By continuing to touch, the surface became yellow, and the toy surface was in a state of simultaneously exhibiting three metallic colors of gold, green and yellow. 2 of the above discolored toys
When left at room temperature of 4 ° C, the green part changed to a golden metallic luster color again, and the yellow part changed to red,
A discolored state consisting of two colors, a golden metallic luster color and a red color, was visualized. This discolored state could be maintained in a room temperature range of 17 ° C. or higher and 27 ° C. or lower. When a part of the toy is touched with a finger, the golden metallic luster color portion changes color to green, and the red portion changes color to yellow, so the non-contact portion of the metallic metallic luster color, red and green color changed due to finger touch, It was possible to simultaneously present four colors of the yellow part. Further, in this state, when it was allowed to stand at room temperature of 24 ° C., it was again in a discolored state composed of two colors of metallic luster color of gold and red. Next, by dipping the toy in this state in water at 16 ° C. or lower, the whole could be restored to a golden metallic luster color. The toy, because the discoloration of the protruding parts of the head, arms, legs, tail, etc. is faster than that of the body, the toy is heated in the palm, etc. As described above, it was possible to selectively change the color of a specific portion such as a protruding portion.The toy can be easily treated by applying ice water, tap water, room temperature, body temperature, warm water, etc. to a golden metallic luster color, green, yellow. , It is possible to visualize the four discolored states of red, and it is also possible to present the four discolored states simultaneously on the surface of the toy in the room temperature range. In addition, various color changes could be visually recognized, and the discoloration could be repeatedly reproduced. Further, the type of the metallic luster pigment obtained by coating a flat glass piece with titanium oxide is represented by Metashine RCFSX-1040R.
C (9546) [manufactured by Nippon Sheet Glass Co., Ltd., average thickness: 1 μ
m, average particle diameter 40 µm, metallic red color], Metashine RCFSX-1040RC (9548) [manufactured by Nippon Sheet Glass Co., Ltd., average thickness: 1 µm, average particle diameter 40 µm
m, metallic blue color], a mini monster robot toy was constructed in the same manner, and the color tones of the first color exhibited metallic red color and metallic blue color (second color, third color, fourth color, respectively). The color tone is the same as that of the toy), and various color changes could be obtained from the same reversible temperature-sensitive multicolor discoloration layer by changing the type of the metallic luster pigment.

Example 2 Thermochromic pigment A (ΔH _A : 10 ° C., T ₁ : 22 ° C., T
₂ : 23 ° C., T ₃ : 32 ° C., T ₄ : 33 ° C., reversible color change of magenta color ← → colorless) 4.0 parts, thermochromic pigment B
(ΔH _B : 2.5 ° C., t ₁ : 26 ° C., t ₂ : 28 ° C., t
₃ : 29 ° C., t ₄ : 30 ° C., yellow ← → colorless reversible color change) 6.0 parts, and non-thermochromic colorant C [water dispersion of cyan color pigment, trade name: SANDAY SUPER BL
UE GLL, pigment content about 24% by weight, Sanyo Dye Co., Ltd.
[Production] Disperse 0.05 part in an aqueous vehicle containing a binder resin, and black (first color), purple (second color), cyan (third color), green (fourth color) due to temperature change. A thermochromic water-based screen printing ink exhibiting the following was prepared.
After solid-printing a white non-thermochromic water-based screen printing ink on the entire surface of the polyester taffeta fabric, after solid printing with the thermochromic water-based screen printing ink, after forming a reversible temperature-sensitive multicolor discoloration layer Further, a metallic luster pigment [Trade name: ULTIMICA YD-100, manufactured by Nippon Koken Kogyo Co., Ltd., particle diameter 10 to 60 μm, gold color] and a binder resin in which the surface of synthetic mica is coated on the discoloration layer with titanium oxide. An oil-based screen-printing ink containing was screen-printed. Water the printing cloth at 22 ° C. or below, 30
When sequentially immersed in water of ℃ ~ 32 ℃, warm water of 33 ℃ or more, water of 23 ~ 26 ℃, water of 22 ℃ or less, golden metallic luster color (first color), purple (second color) , Cyan (third color), green (fourth color), gold metallic luster color (first color)
The discolored state changed in the order of. A doll toy for boys was constructed by sewing the printed material on a cloak for a doll and mounting it on the doll. When a metal star stamp immersed in water at 30 ° C to 32 ° C was pressed against the cloak part of the toy that had been changed to a golden metallic luster color, the pressed part turned purple and
By leaving it at room temperature of ℃, it returned to a golden metallic luster color again. Further, when the stamp immersed in warm water at 33 ° C. or higher was pressed against the cloak portion, the pressed portion changed color to purple, and further pressing changed the color to cyan. When the toy is left in this state at room temperature of 24 ° C., the cyan-colored part turns green and the purple-colored part turns gold metallic luster color. It became a discolored state with a star-shaped green discoloration part on. In this discolored state, when touching a part of the golden metallic luster color part and a part of the star-shaped green discolored part, the touched parts changed color to purple and cyan, respectively, and the non-finger touched part of the golden metal It was possible to simultaneously present four colors of glossy color, green and purple and cyan which were discolored by touch. Next, by cooling the toy in this state to a temperature of 22 ° C. or lower in a refrigerator or the like, the entire cloak portion could be returned to a golden metallic luster color. As mentioned above, the toys are ice water, refrigerators,
By applying tap water, room temperature, body temperature, warm water, etc., it is possible to easily visualize the four discolored states of golden metallic luster color, purple, cyan, and green. Since it is possible to exhibit the discolored state at the same time, it is possible to visually perceive various color changes and repeatedly reproduce the color changes, even though the entire screen is printed with a single screen printing ink. In addition, the type of the metallic luster pigment in which the surface of the synthetic mica is coated with titanium oxide is Ultimika RD-100 [manufactured by Nippon Koken Kogyo Co., Ltd., particle diameter 10 to 60 μm, metallic red color], Ultimika BD-100 [Japan Koken Industry Co., Ltd.
Manufactured, particle size 10 to 60 μm, metallic blue color] in the same manner except that the printing material was prepared and the toy was constructed. The first color tone was metallic red color or metallic blue color, respectively. (The color tones of the second color, the third color, and the fourth color were the same as those of the toy), and various color changes could be obtained from the same reversible temperature-sensitive multicolor discoloration layer.

Example 3 Thermochromic pigment A (ΔH _A : 14 ° C., T ₁ : 37 ° C., T ₂ :
40 ° C, T ₃ : 51 ° C, T ₄ : 54 ° C, magenta color ← →
Colorless reversible color change) 4.5 parts, thermochromic pigment B (ΔH
_B : 1.5 ° C., t ₁ : 45 ° C., t ₂ : 46 ° C., t ₃ : 4:
Reversible color change of 6 ℃, t ₄ : 48 ℃, cyan color ← → colorless) 5.5 parts, and non-thermochromic colorant C [yellow fluorescent pigment, trade name: Epocolor FP-117, Japan Co., Ltd. Made of catalyst] 0.7 part was dispersed in an oil vehicle containing a binder resin, and black (first color), red (second color), yellow (third color), green (fourth color) due to temperature change. A thermochromic oily screen printing ink exhibiting the following is prepared, curved surface printing is applied to the surface of a ceramic mug using a screen printing plate on which a blank character pattern is formed, and heat-cured at about 70 ° C for 1 hour to reversibly A temperature sensitive multicolor discoloration layer was formed. Furthermore, a metallic luster pigment in which the surface of flat aluminum oxide is coated with titanium oxide on the color-changing layer [trade name: Silaric T50-1
0 crystal silver, manufactured by Merck Japan Ltd., particle size 10 to 30 μm, silver] and a screen printing by adding a curing agent to an oil-based screen printing ink containing a reactive binder resin, and then heat curing the ink. Thus, a reversible temperature-sensitive multicolor discoloring mug was obtained. The drawn character pattern of the mug has a metallic luster color of silver at room temperature (24 ° C.).
When sequentially immersed in water at each temperature of 8 to 51 ° C., 54 ° C. or higher, 40 to 45 ° C., 37 ° C. or lower, red (second color), yellow (third color) in each warm water, Green (4th
Color) and a silver metallic luster color (first color).
Then, when hot water at 70 ° C. was put into the mug in which the drawn character pattern was in a discolored metallic luster color at room temperature, the color changed from red to yellow and then to yellow, and from the bottom, yellow, red, and silver metallic luster. The discolored state consisting of three colors was visualized. When left at room temperature in the discolored state,
As the temperature of the mug surface decreased, the red portion turned into a silver metallic luster color, the yellow portion turned into a green color, and a silver metallic luster color, three colors of green and yellow were exhibited. Subsequently, when it was allowed to stand at room temperature, it was changed to a silver metallic luster color and a green discolored state, and then again exhibited a silver metallic luster color. Since the mug exhibits the above-described discoloring behavior, when the hot beverage at a predetermined temperature is filled in the mug, silver metallic luster color, red, yellow, and different colors of green can be expressed, and Not only can it detect temperature changes, but it also meets the wonder of discoloration and unexpectedness. Furthermore, since the color change can be repeatedly reproduced by a temperature change, the color change mug satisfies the commercial characteristics.

Example 4 Thermochromic pigment A (ΔH_A : 10 ° C, T₁ : 27 ° C, T₂ :
29 ° C, T₃ : 37 ° C, T_Four: 39 ° C, yellow ← → colorless
Reversible color change) 6.0 parts, thermochromic pigment B (ΔH _B : 2
℃, t₁ : 30 ° C, t₂ : 32 ° C, t₃ : 32 ° C, t
 _Four: 34 ° C., cyan color ← → colorless reversible color change) 4.0
Part and non-thermochromic colorant C [magenta color fluorescent pigment, quotient
Product name: Epocolor FP-1000N, Nippon Shokubai Co., Ltd.
Manufactured] 1.5 parts dispersed in a vehicle containing a binder resin
To change to brown (first color), orange (second color)
Color), magenta (third color), purple (fourth color)
A thermochromic oily spray ink was prepared. The thermochromic property
White soft vinyl chloride resin with oil-based spray ink
Spray painting on the entire surface of the monster figure molded by
After forming the reversible temperature-sensitive multicolor discoloration layer,
A flat glass piece was coated with titanium oxide on the tarnish layer.
Metallic luster pigment [Product name: Metashine RCFSX-1
040RC (9544), manufactured by Nippon Sheet Glass Co., Ltd., average thickness:
1 μm, average diameter 40 μm, gold color] and binder resin
Spray the oil-based spray ink that it contains to
Made up a beast toy. The monster toy is at room temperature (24 ℃)
Has a golden metallic luster color, and the toy
37 ° C, 39 ° C or higher, 29 to 30 ° C, 27 ° C or lower
Subsequent dipping in water at various temperatures
Is orange (second color), magenta (third color), purple (second color)
4 colors) and gold metallic luster color (1st color)
It was Then, the toy exhibited a golden metallic luster color at room temperature
When you touch a part of the finger, the touched part turns orange and
A color spot pattern could be formed. From this discolored state, the toy
If left at a temperature below 30 ° C, the orange part will become golden again.
It has a metallic luster color and the toy has a golden metallic luster on the entire surface.
Became a color. Furthermore, the entire surface is in a discolored state with a golden metallic luster color.
When the toy in 1 is immersed in warm water at 39 ° C or higher,
It begins to change color from the protrusions to orange and then to magenta.
The entire toy is discolored with magenta. The strange
The colored toys should be left at room temperature below 27 ° C.
Changes the color of the protrusions to purple and then to a golden metallic luster color.
By changing the color and then letting it stand, the entire surface becomes golden again.
The metallic luster color changed. The toy changes in temperature
Since it exhibits the above-described discoloration behavior, environmental temperature, water,
Gold metallic luster due to body temperature and other simple thermal means
Repeated four color changes of color, orange, magenta and purple
However, it can be reproduced and visualized, and the taste of discoloration
Satisfies the characteristics of toys that require externality.

Example 5 Thermochromic pigment A (ΔH_A : 15 ℃, T₁ : 5 ° C, T₂ :
7 ° C, T₃ : 20 ° C, T_Four: 22 ℃, yellow ← → colorless
Reverse color change) 7.0 parts, thermochromic pigment B (ΔH _B : 2
℃, t₁ : 15 ° C, t₂ : 17 ° C, t₃ : 17 ° C, t
 _Four: 19 ° C, cyan ← → colorless reversible color change) 3.0
Part and non-thermochromic colorant C [magenta color fluorescent pigment, quotient
Product name: Epocolor FP-1000N, Nippon Shokubai Co., Ltd.
Manufactured] 1.5 parts dispersed in a vehicle containing a binder resin
To change to brown (first color), orange (second color)
Color), magenta (third color), purple (fourth color)
A thermochromic oily spray ink was prepared. The thermochromic property
Acrylonitrile polystyrene is used with oil-based spray ink.
Of a spot pattern on the surface of a plastic cup made of a copolymer resin
Spray coating was applied to form a reversible temperature-sensitive multicolor discoloration layer.
After that, a flat glass piece is further oxidized on the discoloration layer.
Metallic luster pigment coated with tongue [Product name: Metashine R
CFSX-1040RC (9544), Nippon Sheet Glass
Co., Ltd., average thickness: 1 μm, average particle size 40 μm, gold
Color] and an oil-based spray ink containing a binder resin
Spray painted and reversible temperature sensitive multicolor tarnishing plastic
I made a cup. The spot pattern on the cup is room temperature (24 ° C)
Shows a magenta color, 7 ° C to 15 ° C, 5 ° C or higher
Below, the cup in water at 19 ℃ ~ 20 ℃, 22 ℃ or more
When sequentially immersed, purple in water at each temperature,
Discolored to golden metallic luster, orange, and magenta
I was able to make it. Then, the spotted pattern is magenta at room temperature.
When iced water was put into a colored cup,
Is purple from the part near the ice, and then a golden metallic light
Turns amber and has a golden metallic sheen, purple and magenta
A speckled pattern consisting of three colors was visible. The cup
When left at room temperature in the discolored state, the temperature of the cup surface
As it rises, purple spots turn magenta and golden metal
The glossy spots turn orange, and then the orange spots
The dots also turn magenta, and the entire spots are magenta again.
Returned to. The cup exhibits the discoloration behavior described above.
Then, when you fill the cup with a low-temperature drink at a specified temperature,
Different colors such as lustrous color, orange color, magenta color and purple color are displayed.
Of course, it can be served and the temperature of the beverage can be detected.
The theory, discoloration, and unexpectedness are satisfied. The color change is repeated
Since it can be reproduced, it has commercial characteristics as a color change cup
It

Example 6 Thermochromic pigment A (ΔH _A : 11 ° C., T ₁ : 8 ° C., T ₂ :
10 ° C., T ₃ : 19 ° C., T ₄ : 21 ° C., cyan color ← → colorless reversible color change) 3.5 parts, thermochromic pigment B (ΔH
_B : 2 ° C., t ₁ : 14 ° C., t ₂ : 16 ° C., t ₃ : 16
C, t ₄ : 18 ° C., magenta color ← → colorless reversible color change) 6.5 parts, and non-thermochromic colorant C [yellow fluorescent pigment, trade name: Epocolor FP-117, Nippon Shokubai Co., Ltd.] [Production] 0.5 part is dispersed in an aqueous vehicle containing a binder resin to produce black (first color), green (second color), yellow (third color), red (fourth color) due to temperature change. A thermochromic water-based screen printing ink was prepared. On white synthetic paper having an adhesive layer on the back side, solid printing is performed with the thermochromic water-based screen printing ink to form a reversible temperature-sensitive multicolor discoloration layer, and then the surface of the natural mica is oxidized on the discoloration layer. Metallic luster pigment coated with titanium [Product name: Ir
iodin 205 Rutile Platinum
Gold, manufactured by Merck Japan Ltd., particle diameter 10 to 60 μm
m, gold] and a binder resin and screen printing an oil-based screen printing ink, and then pasting a transparent polyester film having an adhesive layer on the back surface onto the metallic luster pigment layer to provide reversible temperature-sensitive multicolor discoloration. A seal was made. At room temperature (24 ° C), the seal is yellow (third
Color, having a slightly golden metallic luster color), and the seal is 10 ° C to 14 ° C, 8 ° C or less, 18 ° C to 19 °
When sequentially immersed in water of each temperature of ℃, 21 ℃ or more, in the water of each temperature, red (fourth color), gold metallic luster color (first color), green (second color) The discolored state changed in order. Cut out the seal into a star shape and attach it to the bonnet part of a black amphibious toy, and the seal part shows a yellow discoloration state at room temperature.
When it was immersed in ice water at a temperature of not higher than 0 ° C., the seal portion turned red and then changed to a golden metallic luster color. When left at room temperature in the discolored state, the seal portion changed to a green discolored state and turned yellow again. Since the seal exhibits the above-described discoloring behavior, four color changes of gold metallic luster color, green, red, and yellow are repeated by familiar thermal means such as environmental temperature, ice water, tap water, and body temperature. It can be reproduced and visualized, and it satisfies the characteristics of toys that require strangeness of discoloration and unexpectedness.

[0027]

INDUSTRIAL APPLICABILITY The present invention effectively combines a multicolor revealing thermochromic material and a metallic luster material, and changes the color with high sensitivity by applying living environment temperature or daily simple heat or cold heat means to obtain a glittering property. As a metal glossy reversible temperature-sensitive multicolor discolorable laminate capable of visualizing various color changes of rich metal glossy, it has applicability to various fields such as toys, teaching materials, beverage containers, and decoration fields.

[Brief description of drawings]

FIG. 1 is a longitudinal cross-sectional explanatory view of a metallic luster reversible temperature-sensitive multicolor discoloration laminate of the present invention.

FIG. 2 shows a monster robot toy according to an embodiment of the present invention.
It is an external view which shows a uniform phase.

FIG. 3 is an external view showing a partially discolored appearance of the monster robot toy.

FIG. 4 shows a temperature-color density curve of thermochromic pigment A.

FIG. 5 shows a temperature-color density curve of thermochromic pigment B.

[Explanation of symbols]

T ₁ thermochromic pigment A complete color development temperature T ₂ thermochromic pigment A color initiation temperature T ₃ thermochromic pigment A decolorization initiation temperature T ₄ thermochromic pigment A complete decolorization temperature t ₁ thermodiscoloration Of the thermochromic pigment B t ₂ Color development start temperature of the thermochromic pigment B t ₃ Decolorization start temperature t _{4 of the} thermochromic pigment B ₄ Decolorization temperature ΔH _{A of the} thermochromic pigment B Hysteresis width ΔH _B Hysteresis width of thermochromic pigment B 1 Metallic luster reversible temperature-sensitive multicolor color changing laminate 2 Support 3 Reversible temperature-sensitive multicolor color changing layer 4 Metal luster pigment layer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F100 AA19C AC05C AG00C AK01B                       AK01C AR00B AR00C AT00A                       BA03 BA07 BA10A BA10C                       CA13B CA13C DD01A DE02C                       DE10C GB16 GB84 JJ10B                       JN24 JN24C JN28B YY00B                 4J038 BA051 BA081 CA021 CA071                       CB021 CB091 CB171 CC031                       CC051 CD051 CD081 CF021                       CF041 CG111 CG191 DA191                       DB001 DD071 DD121 DE001                       DG001 HA066 HA216 HA486                       HA546 KA08 KA12 KA15                       KA20 NA01 PA19 PC01 PC02                       PC03 PC04 PC08 PC09 PC10

Claims (10)

[Claims] 1. A reversible temperature-sensitive multicolor discoloration layer is provided on a support,
A laminate in which a metallic luster pigment layer is provided on the reversible temperature-sensitive multicolor discoloration layer, wherein the reversible temperature-sensitive multicolor discoloration layer exhibits a large hysteresis width (ΔH _A ) with respect to a temperature-color density curve and discolors. And a thermochromic pigment _B having a hysteresis width (ΔH _B ) smaller than ΔH _A and having a hysteresis width (ΔH _B ) smaller than that of ΔH _A and being discolored in the thermochromic pigment A in a mixed state. The metallic luster pigment layer is a layer fixed to a resin in a dispersed state, and the metallic luster pigment layer uses a metallic luster pigment whose core substance is a material selected from natural mica, synthetic mica, flat glass pieces, or flaky aluminum oxide as a binder resin. A metal glossy reversible temperature-sensitive multicolor discoloration laminate, which is a layer fixed in a dispersed state. 2. The thermochromic pigment A and the thermochromic pigment B are
The metal glossy reversible temperature-sensitive multicolor discolorable laminate according to claim 1, wherein all of the following (1) to (4) are satisfied. ΔH _A = [(T ₄ −T ₃ ) / 2− (T ₂ −T ₁ ) / 2] = 10 to 50 ° C. (1) ΔH _B = [(t ₄ −t ₃ ) / 2− (t ₂ − t ₁ ) / 2] = 0.5 to 20 ° C. (2) (t ₁ −T ₂ ) ≧ 1 ° C. (3) (T ₃ −t ₄ ) ≧ 1 ° C. (4) where T ₁ and T ₂ , T ₃ and T ₄ are thermochromic pigments A
The full color development temperature, the color development start temperature, the color erasure start temperature, and the complete color erasure temperature are shown respectively. Also, t ₁ , t ₂ , t ₃ , t ₄
Is the complete color development temperature, color development start temperature of the thermochromic pigment B,
The decolorization start temperature and the complete decolorization temperature are shown. 3. T ₁ is 5 ° C. to 23 ° C., and T ₄ is 28 ° C.
The reversible temperature-sensitive multicolor discoloration laminate having metallic luster according to claim 2, which has a temperature of ˜55 ° C. 4. 4. T ₁ is 23 ° C. to 90 ° C., and T ₄ is 33.
3. The metallic luster reversible temperature-sensitive multicolor discolorable laminate according to claim 2, which has a temperature of from 100 to 100 ° C. 5. T ₁ is −30 ° C. to 18 ° C., and T ₄ is −
The temperature is 20 ° C. to 28 ° C., and the metallic luster reversible temperature-sensitive multicolor discoloration laminate according to claim 2. 6. The reversible temperature-sensitive multicolor discoloration layer contains a non-thermochromic colorant C, wherein the color of the non-thermochromic colorant is any one of the three primary colors of yellow, cyan and magenta, or The metallic luster tone reversible temperature-sensitive multicolor discolorable laminate according to any one of claims 1 to 5, which has a color similar to the three primary colors. 7. The support has an inhomogeneous heat capacity portion, and a reversible temperature-sensitive multicolor discoloration layer is provided at the portion.
7. The metallic luster reversible temperature-sensitive multicolor discolorable laminate according to any one of items 1 to 6. 8. The metallic luster tone reversible temperature-sensitive multicolor discoloration laminate according to claim 7, wherein the nonuniform heat capacity portion has a nonuniform thickness. 9. The reversible temperature-sensitive multicolor discoloration laminate having a metallic luster tone according to claim 7, wherein the non-uniform heat capacity portion is an uneven surface. 10. The reversible temperature-sensitive multicolor discolorable laminate according to claim 1, wherein the support is a toy-shaped object or a beverage container.