JP2000080359A - Temperature sensitive and reversibly multi-color changeable composition and laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which highly sensitively changes a color at high temperatures and effectively indicates multi colors by making the composition contain a mixture of a thermally changeable pigment A having a specific hysteresis width and a thermally changeable pigment B having a specific hysteresis width which changes a color in a color changing temperature range of the pigment A. SOLUTION: A composition of the present invention comprises a thermally changeable pigment A which changes a color showing a big hysteresis width (δHA) of a temperature-color concentration curve, a thermally changeable pigment B which changes a color showing a small hysteresis width (ΔHB) in a color changing temperature range of the pigment A and further a non-thermally changeable pigment C each dispersed in a vehicle containing a binding resin. The composition satisfies all of formulae I, II and formulas: (t1-T2)>=1 deg.C, (T3-t4)>=1 deg.C, T4=33-100 deg.C and T1=23-90 deg.C, wherein T1, T2, T3 and T4 are a complete coloring temperature, a color change initiating temperature, a discoloring initiating temperature and a complete discoloring temperature of the thermally color changeable pigment A, respectively and t1, t2, t3 and t4 are the same temperatures of the thermally color changeable pigment B, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reversible thermosensitive multicolor discolorable composition and a laminate. More specifically, the present invention relates to a reversible thermosensitive multicolor discolorable composition which exhibits various color changes by a temperature change, and a laminate such as a toy, a beverage container, an indicator, etc. provided with a thermochromic layer of the composition.

[0002]

2. Description of the Related Art Several proposals have been disclosed in the past as attempts to realize multicolor by temperature change. For example, applying a plurality of types of thermochromic particles having different hysteresis widths and colors to each other, discoloring the thermochromic pigment exhibiting a large hysteresis width and discoloring by exhibiting a small hysteresis width in the discoloration temperature range. (Japanese Unexamined Patent Publication (Kokai) No. 3-76783) and a plurality of dyes having a large hysteresis width (so-called thermochromic color memory dyes). Attempt (actual fairness 7
No. 36719) is disclosed.

[0003]

The present inventor has further pursued a discoloration material which manifests multicolor by such a temperature change, and particularly, a color change material having high sensitivity at a specific temperature in a high temperature range above normal temperature. In a specific temperature range, any of the colors before and after the change can be stored and stored alternately. Further, the cooling process and the heating process can be performed within the same temperature range. An object of the present invention is to provide a reversible thermosensitive multicolor discolorable composition capable of expressing different colors and a laminate of a toy-shaped object, a beverage container, an indicator, etc., provided with a thermochromic layer formed of the composition.

[0004]

SUMMARY OF THE INVENTION The first aspect of the present invention, the temperature - relates color density curve, a thermochromic pigment A whose color changes exhibit a large hysteresis width ([Delta] H _A), the heat discoloring pigment A color _A thermochromic pigment _B having a hysteresis width (ΔH _B ) smaller than ΔH _A , having a different color tone at the time, and being present in the color changing temperature region of the thermochromic pigment A and discoloring is present. The reversible thermosensitive multicolor discoloring composition is characterized by satisfying all of the following general formulas (1) to (6). 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) T ₄ = 33 to 100 ° C. 5) T ₁ = 23 to 90 ° C. (6) Here, T ₁ , T ₂ , T ₃ and T ₄ are thermochromic pigments A
, The color development temperature, the color development start temperature, the color erasure start temperature, and the complete color erasure temperature. Also, t ₁ , t ₂ , t ₃ , t ₄
Is the complete color development temperature, color development start temperature of thermochromic pigment B,
The erasing start temperature and the complete erasing temperature are shown. The second invention meets all of the above general formula (1) to (6), the temperature - color density large hysteresis width with respect to the curve ([Delta] H _A)
And a thermochromic pigment _B having a hysteresis width (ΔH _B ) smaller than the ΔH _A and having a color change inherent in the color changing temperature region of the thermochromic pigment A.
And a reversible thermosensitive multicolor-changeable laminate characterized in that a reversible thermosensitive multicolor-changeable layer fixed to a binder resin in a dispersed state is formed on a support. Further, in the first and second inventions, ΔH _B is 0.5 to 10 ° C.
That the non-thermochromic colorant C is mixed,
The color of the non-thermochromic coloring agent C is required to be any one of the three primary colors of yellow, cyan, and magenta, or a color similar to any of the three primary colors.

[0005] 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 generates a color reaction by the electron transfer reaction of (a) and (b). Examples thereof include a reversible thermochromic material containing three components, a pigment exhibiting reversible thermochromic properties in the form of fine particles of the three-component resin solid solution, and a microcapsule pigment in which the three components are encapsulated in microcapsules. The microcapsule pigment in the above can be prepared by a known microencapsulation technique, for example, an interfacial polymerization method, an in situ polymerization method, a curing in liquid coating method, a phase separation method from an aqueous solution, a phase separation method from an organic solvent, a melting dispersion cooling method. , An air suspension coating method, a spray drying method and the like. By using the above-mentioned reversible thermochromic material encapsulated in microcapsules, the reversible thermochromic material is maintained in the same composition under various use conditions, and can exhibit the same function and effect. A physically stable pigment can be constituted. Incidentally, 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 30 μm.
Those having a size of 15 μm are effective in terms of sharpness of discoloration, durability, workability and the like. As the thermochromic pigment A,
It is described in Japanese Patent Publication No. 4-17154, Japanese Patent Application Laid-Open No. 7-33997, Japanese Patent Application Laid-Open No. 7-179777, Japanese Patent Application Laid-Open No. 8-39936, etc. proposed by the present applicant.
_A thermochromic material that changes color by showing a large hysteresis characteristic (ΔHA), that is, a thermochromic material, that is, the shape of a curve plotting a change in color density due to a change in temperature, indicates that the temperature is lower than the color change temperature range. It followed a very different path and when going lowered from the high temperature side than the color change temperature range in the opposite case to continue at elevated temperature discoloration, was varied in the low temperature range or T ₄ or more high temperature zone of the T ₁ or less It is effective to use a material that can alternately store and maintain the state in a specific temperature range (see FIG. 1). Examples of the thermochromic pigment B include JP-B-51-35414 and JP-B-51-4470 proposed by the present applicant.
6, JP-B-1-17154, JP-A-7-1
A thermochromic material having a relatively small hysteresis width described in JP-A-86546 or a fatty acid ester having a ΔT value (melting point−cloud point) of 3 ° C. or less, which is applied as the component (C), 3 ° C. or less High sensitivity reversible thermochromic material exhibiting a hysteresis width (ΔH _B ) (Japanese Patent Publication No. 1-2939)
No. 8 publication) (see FIG. 2). This type of reversible thermochromic material changes color before and after the color change temperature, and only one specific state can exist in a specific temperature range between the two states before and after the color change. That is, the other state is maintained while the heat or cold required for the state to appear is applied, but returns to the original state exhibited in the specific temperature range when the heat or cold is no longer applied. Type of thermochromic material.

[0006] The present invention comprises a thermochromic pigment A to discolor exhibiting the the large hysteresis width ([Delta] H _A), the heat discoloring pigment A was different in color tone upon color development, [Delta] H _A smaller hysteresis width (ΔH _B ), and a thermochromic pigment B that is inherently discolored in the color changing temperature region of the thermochromic pigment A and discolors is essential, and a specific temperature is further set between the thermochromic pigments A and B. Both pigments that have a relationship that satisfies the characteristics are present in a mixed state, and high sensitivity discoloration, color memory, multicolor discoloration, unexpected discoloration, strangeness of discoloration, detectability of temperature history, etc. in a specific temperature range Is intended to be effectively expressed.
To explain this point, the ΔH _A value of the thermochromic pigment A is 10
By specifying the pigment A in the range of from 50 ° C. to 50 ° C., preferably from 15 ° C. to 35 ° C., the color of the pigment A changed in the low-temperature range below T ₁ or in the high-temperature range above T ₄ is changed to T _{1 to} T _4. , More substantially in the temperature range of T _{2 to} T ₃ , and multiple colors can be effectively produced in relation to the color change due to the temperature change of the thermochromic pigment B. . ΔH _A value of 1
If the temperature is lower than 0 ° C, the color memory function is insufficient.
If the temperature exceeds the range, even if the color storage function is achieved, the storage temperature range is too wide and it is difficult to easily change the color by a daily temperature means, and the above range of 10 to 35 ° C. is practically preferable.
On the other hand, the ΔH _B value of the thermochromic pigment B is 0.5 to 20 ° C.
Preferably 0.5 to 10C, more preferably 0.5 to 3C.
It is required that the thermochromic pigment A satisfies the range of ° C and that the thermochromic pigment A is inherently discolored and discolored. By specifying the ΔH _B value of the thermochromic pigment B within the above range, it is sensitive to a temperature change, and immediately returns to the original color when the application of heat or cold required for the change is removed. There would be reversibly expressed in the region of the [Delta] H _a, thereby visually colorful color change by color mixing and color of the [Delta] H _a thermochromic pigments a which is stored and held in the region of. The present invention further provides a temperature difference between t ₁ and T ₂ of 1 ° C. or more,
_When the temperature difference between ₃ and t ₄ satisfies the relationship of 1 ° C. or more, the visible time for visually discriminating the discolored state of the thermochromic pigment B is properly maintained, and the color change is recognized. If the temperature is less than 1 ° C., the development and decoloration of the thermochromic pigments A and B become continuous,
It is difficult to recognize color changes. Further, when T ₄ satisfies the temperature in the range of 33 to 100 ° C. and T ₁ satisfies the temperature in the range of 23 to 90 ° C., it effectively contributes to developing various color changes in a high temperature range above normal temperature.

Next, the discoloration behavior due to a temperature change will be specifically described. The T ₁ following the temperature range, the thermochromic pigments A, there are both a colored state colors exhibited by B, the pigment A, the color of the color mixture exhibited by B (first color) is visual, t ₄ by heating the temperature range of the through T _3, the pigment B is decolored, pigment a has maintained the colored state, the pigment a color (second color)
There is visual, the T ₄ above temperature range, pigments A, B and discolored together, colorless (third color), and in a temperature range of t ₁ through T ₂ lowering the temperature, the pigment B color development ( (4th color). Further lowering the temperature, said return to the by T ₁ following temperature range pigments A, color mixing of the colors exhibited by B is visually.

By mixing a non-thermochromic colorant C in addition to the mixed system of thermochromic pigments A and B satisfying the above requirements, further multicoloring can be achieved. That is, in the T ₁ following temperature range, pigments A, B, and mixing colors of colorants C (first color) is visualized, at the temperature range of t ₄ through T _3, the mixing of the pigment A and a colorant C The color (second color) is visible and T ₄
In the above temperature range, the color (third color) of the colorant C is visually recognized, and in the temperature range of t _{1 to} T ₂ , the mixed color (fourth color) of the pigment B and the colorant C is visually recognized. It should be noted that even in a system in which the underlayer is colored with a non-thermochromic coloring agent without mixing the coloring agent C in the same layer, the same color change as described above can be seen, but the thermochromic layer is transparent. Because of this color change, the sharpness is inevitably reduced. As described above, by mixing the non-thermochromic colorant C in the same layer, four different clear colors can be developed in the heating to cooling process, and the color ( Second color),
The color (fourth color) presented during the cooling process has a different color, and functions effectively for storing and retaining the temperature history to serve as an indicator, and further enhances the exquisiteness and unexpectedness of the discoloration. As the thermochromic colorant C, conventionally known dyes, ultraviolet light-emitting dyes, general pigments, fluorescent pigments, luminous pigments, luminous pigments, metal powders, pearl pigments, extender pigments, photochromic colorants, fluorescent brighteners, And the like. Here, the color of the colorant C is yellow, cyan,
By selecting and using one of the three primary colors of magenta or a color similar to any of the three primary colors, a vivid color change, more specifically, the first color, the second color or the fourth color, particularly the second color This contributes to making the color and the fourth color tone clearly visible. In the present invention, the thermochromic pigments A and B or the composition in which the non-thermochromic coloring agent C is blended with A and B are contained in the thermoplastic resin in an amount of 0.1 to 40% by weight (preferably 0.2 to 0.2%). To 25% by weight) can be melt-blended to form sheets, filaments and various forms of shaped articles. Generally, however, the composition is dispersed in a vehicle containing a binder resin to form a coating or ink. Then, a thermochromic layer is formed on various supports by coating, spraying, or the like, and is put to practical use.

In the system using the coloring materials such as paints and inks,
Each of the thermochromic pigments A and B is effective in the form of a microcapsule pigment, and the occupancy in the reversible thermosensitive multicolor discoloring layer is 5 to 80% by weight (preferably 10 to 60% by weight).
Is effective in view of the thermochromic effect. That is, if the content is less than 5% by weight, the color density is low and the color change cannot be clearly seen. On the other hand, if it exceeds 80% by weight, the residual color is visible, and it is difficult to see a clear decolored state. The thickness of the reversible thermosensitive multicolor discoloring layer is at least 0.5 μm or more, preferably 1-4.
00 μm, more preferably 10 to 200 μm,
If it is less than 0.5 μm, the color change lacks sharpness.
A system having a thickness of more than 0 μm tends to impair the aesthetic appearance, which is not preferable. The resin contained in the vehicle is preferably a transparent film-forming resin, and 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, polyacrylate 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, acryl-modified alkyd resin, amino alkyd resin, vinyl chloride-vinyl acetate resin, styrene- Butadiene resin, epoxy resin, unsaturated polyester resin, polyurethane resin, vinyl acetate emulsion resin, styrene Butadiene emulsion resin, acrylic ester emulsion resin, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble butadiene resin,
Examples thereof include cellulose acetate, cellulose nitrate, and ethyl cellulose.

Next, the second invention will be described. The second invention is a reversible thermosensitive multicolor discolorable laminate in which a thermochromic layer in which the thermochromic pigment A and the thermochromic pigment B are fixedly dispersed in a binder resin is formed on a support. Require body. Furthermore, the non-thermochromic colorant C is used in combination, and further, the support has a heterogeneous heat capacity portion, and a reversible thermosensitive multicolor discoloring layer is provided in the portion, It is required that the uniform heat capacity portion has an inhomogeneous wall thickness, the uneven heat capacity portion has an uneven surface, and the support is a toy-shaped object, a beverage container, 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. Of these supports, fabrics,
In the application to a support having a small heat capacity such as paper, synthetic paper, and synthetic leather and a temperature change relatively fast, the difference between the coloring and decoloring temperatures of the pigments A and B is set to be large, and the second color and the second color are used. It is effective to set a wide temperature range in which the four colors appear. On the other hand, in a system in which a heat discoloration layer is formed on a support having a large heat capacity such as plastic, glass, metal, ceramics, wood, and stone, and a slow temperature change, the temperature change of the support itself is slow.
Since the temperature at which the color change is sensitive is slowed down, pigment A,
Even if the temperature difference between the coloring and erasing of B is set to be small, the second color and the fourth color can be reliably recognized. The support has an effect as a temperature factor on the discoloration behavior depending on the material as described above. However, even if the support is made of the same material, the discoloration state can be diversified by the presence of a non-uniform heat capacity portion. By providing a thermochromic layer on a support on which heterogeneous heat capacity points are intentionally arranged, it imparts inhomogeneity to the response speed to heat or cold and the holding time, etc. To cause partial discoloration or discoloration with a time delay, thereby causing a variety of discolored patterns to be visualized, which rather functions to enhance unexpectedness, toy characteristics, and saliency. To form the multicolor thermochromic layer on the support, conventionally known coating methods, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, Means such as electrostatic coating and electrodeposition coating are mentioned, and all are effective. When the support is made of a permeable material such as a cloth or paper, an undercoat layer made of a resin thin film or the like is provided on the underlayer in advance so that the permeability of the thermochromic ink at the time of forming the thermochromic layer is improved. This contributes to the formation of a thermochromic layer that allows a clear color tone to be seen.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The reversible thermosensitive multicolor discolorable composition of the present invention can be melt-blended with a thermoplastic resin to form sheets and various forms of shaped articles. Usually, the composition is contained in a vehicle containing a binder resin. As a paint or printing ink in a dispersed state, a thermosensitive multicolor discoloring layer is formed on a support by spraying or coating to be put into practical use as a laminate. Examples are described below, but the present invention is not limited to these.

[0012]

Examples are shown below. The parts in the examples are parts by weight.

[0013] Example 1 (see FIGS. 4-5) thermochromic pigment _{A (ΔH A: 10 ℃,} T 1: 27 ℃,
T ₂ : 29 ° C., T ₃ : 37 ° C., T ₄ : 39 ° C., yellow ← →
7.0 parts of a colorless reversible color change), thermochromic pigment B (ΔH
_{B: 2 ℃, t 1:} 30 ℃, t 2: 32 ℃, t 3: 32
° C, t ₄ : 34 ° C, cyan color ← → colorless reversible color change)
3.0 parts and 1.5 parts of a non-thermochromic colorant C [magenta fluorescent pigment (trade name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.)] are dispersed in an oil vehicle containing a binder resin. An oil-based spray ink was prepared. The oil-based spray ink was sprayed onto the entire surface of the dinosaur-shaped object molded from the white soft vinyl chloride resin, and the miniature animal toy 1 having the reversible thermosensitive multicolor discoloring layer 2 was obtained. The animal toy 1 has a brown color at room temperature (25 ° C.).
When sequentially immersed in water at temperatures of 30 ° C. and 27 ° C. or lower, in the warm water, the color changed to orange, magenta, purple, and brown, respectively. Next, when a part of the toy 1 which turned brown at room temperature was touched, the touched part turned orange and a spotted orange pattern was formed. When the toy 1 in the discolored state was left in a room temperature of 30 ° C. or lower or in water, the spotted orange portion turned brown again, and the toy 1 again exhibited the entire brown color. Further, when the toy 1 in a brown discoloration state was immersed in warm water of 39 ° C. or higher, the projection changed color from orange to magenta, and the toy 1 changed to a magenta discoloration state. When the toy 1 in the discolored state was allowed to stand at room temperature of 27 ° C. or lower or in water, the protruding portion was discolored to purple and then brown. Since the toy 1 exhibits the discoloration behavior described above due to a temperature change, environmental temperature changes, water, body temperature, and other simple thermal means, brown, orange, magenta, and purple color changes are repeated, It can be reproduced and visualized, and satisfies toy characteristics that require the taste of discoloration and unexpectedness.

[0014] Example 2 thermochromic pigment _{A (ΔH A: 10 ℃,} T 1: 34 ℃,
T ₂ : 35 ° C., T ₃ : 43 ° C., T ₄ : 46 ° C., yellow ← →
6.0 parts of colorless reversible color change), thermochromic pigment B (ΔH
_B : 2.5 ° C., t ₁ : 38 ° C., t ₂ : 39 ° C., t ₃ : 4
0 ° C., t ₄ : 42 ° C., 4.0 parts of cyan color → colorless reversible color change) 4.0 parts, and non-thermochromic colorant C [magenta fluorescent pigment (trade name: Epocolor FP-1000N, Co., Ltd.)
Nippon Shokubai)] to prepare an oil-based spray ink in which 0.3 part was dispersed in an oil-based vehicle containing a binder resin.
Using the oil-based spray ink, the surface of a plastic cup made of an acrylonitrile-styrene copolymer resin was spray-painted with a speckled pattern to obtain a plastic cup having a spotted reversible thermosensitive multicolor discoloring layer. The spotted pattern of the cup has a dark green color at room temperature (25 ° C.)
42-43 ° C, 46 ° C or more, 35 ° C-3
When immersed sequentially in water at each temperature of 8 ° C. and 34 ° C. or lower, orange, magenta, blue-purple, and dark green were exhibited in each warm water. Then, when warm water at 60 ° C. was put into a cup in which the spot pattern had a dark green color at room temperature, the color turned orange from the bottom of the spot pattern, and then changed to magenta, three colors of magenta, orange, and dark green. Was visually observed. When left at room temperature in the discolored state, as the temperature of the glass surface drops, the orange spots turn dark green, the magenta spots turn blue-violet, and dark green, blue-violet, and magenta exhibit three colors. It became a state. Further, when left at room temperature, the spotted pattern became dark green again after passing through two discoloration states of blue-violet and dark green. Since the cup exhibits the discoloration behavior described above, when the cup is filled with a hot beverage of a predetermined temperature, dark green, orange, magenta, and blue-violet colors can be displayed, and the temperature of the beverage can be detected. Of course, it is possible to provide a cup satisfying the taste of discoloration and the unexpectedness. Since the color change can be repeatedly reproduced by a temperature change, the color change cup has merchantability.

[0015] Example 3 thermochromic pigment _{A (ΔH A: 14.5 ℃,} T 1: 36 ℃,
T ₂ : 39 ° C., T ₃ : 50 ° C., T ₄ : 54 ° C., 3.5 parts of thermochromic pigment B)
(ΔH _B : 1.5 ° C., t ₁ : 45 ° C., t ₂ : 46 ° C., t
_{3: 46 ℃, t 4:} 48 ℃, reversible color change) 6.5 parts magenta ← → colorless, and non-thermal discoloring colorant C [yellow fluorescent pigment (trade name: Epokara FP-117, (strain ) Made by Nippon Shokubai)] to prepare an ink in which 0.5 part is dispersed in an oil vehicle containing a reactive binder resin, and then 10 parts of the ink is mixed with 3.0 parts of a curing agent to prepare a two-part curable oil. Using a screen printing ink and a stainless steel screen printing plate with a blank character pattern, a curved surface printing was performed on the surface of the ceramic mug at about 70 ° C.
The composition was cured by heating for 1 hour to obtain a reversible temperature-sensitive multicolor discolorable mug having a pattern of various characters that were changed in color. The drawn character pattern of the mug is black at room temperature (25 ° C.), and the cup is placed in water at each temperature of 48 ° C. to 50 ° C., 54 ° C. or more, 39 ° C. to 45 ° C. and 36 ° C. or less. Each of the hot waters exhibited green, yellow, red, and black colors. Then, when warm water at 70 ° C. was put into the mug in which the lettering pattern was black at room temperature, the color changed from the bottom to green, then yellow, and the three colored states of yellow, green, and black were visualized. Was. When the mug surface was left at room temperature in the discolored state, as the temperature of the mug surface decreased, the green portion turned black, the yellow portion turned red, and became a state of three colors of yellow, red, and black. Subsequently, when the mixture was allowed to stand at room temperature, the color changed to two colors, red and black, and then changed to black again.
Since the mug exhibits the discoloration behavior described above, when a mug is filled with a hot beverage of a predetermined temperature, black, green, yellow, and red can be displayed in different colors, and of course, the temperature of the beverage can be detected. , The taste of discoloration,
Meet unexpectedness. Further, since the color change can be repeatedly reproduced by a temperature change, the color change mug satisfies the merchantability.

[0016] Example 4 thermochromic pigment _{A (ΔH A: 10 ℃,} T 1: 24 ℃,
T ₂ : 26 ° C., T ₃ : 34 ° C., T ₄ : 36 ° C., 3.0 parts of cyan color →→ colorless reversible color change), thermochromic pigment B
(ΔH _B : 2 ° C., t ₁ : 28 ° C., t ₂ : 30 ° C., t ₃ :
30 ° C., t ₄ : 32 ° C., magenta color →→ colorless reversible color change) A thermochromic aqueous screen printing ink was prepared in which 7.0 parts were dispersed in an aqueous vehicle containing a binder resin. After solid printing of white non-thermochromic aqueous screen printing ink on the entire surface of the polyester tricot fabric, solid printing was performed using the thermochromic screen printing ink using a 109-mesh screen printing plate. . Next, using a purple, cyan, white, and magenta non-thermochromic screen printing ink, a floral pattern consisting of four colors was formed by printing on the reversible thermosensitive multicolor discoloring layer. When the discolored layer of the printing fabric is in a purple discolored state at room temperature (25 ° C.), the printing fabric is heated to 32 ° C. to 34 ° C.
Of water at a temperature of 36 ° C. or higher, water at a temperature of 26 ° C. to 28 ° C., and water at a temperature of 24 ° C. or lower, showed cyan, white, magenta, and purple in the water at each temperature. In the process of discoloring the multicolor discoloring layer, the four-colored floral pattern does not change color due to a temperature change, but changes the contrast between the two to make it visible. In a combination where both colors are the same,
The floral pattern becomes invisible. By wearing a doll swimsuit sewn with the printed fabric on a doll and immersing it in water with different touch or water temperature, the same appearance change is given, and the appearance change is repeatedly reproduced, so that the toy property is satisfied. Can be.

[0017] Example 5 thermochromic pigment _{A (ΔH A: 14.5 ℃,} T 1: 36 ℃,
T ₂ : 39 ° C., T ₃ : 50 ° C., T ₄ : 54 ° C., magenta color → colorless reversible color change) 4.0 parts, thermochromic pigment B
(ΔH _B : 1.5 ° C., t ₁ : 45 ° C., t ₂ : 46 ° C., t
_{3: 46 ℃, t 4:} 48 ℃, yellow ← → reversible color change color) 6.0 parts, and non-thermal discoloring colorant C [aqueous dispersion of cyan pigment (trade name: SANDYE SUPER BL
UE GLL, pigment content: about 24% by weight, Sanyo Dyeing Co., Ltd.
Aqueous screen printing ink was prepared by dispersing 0.05 part of a vehicle containing a binder resin. 1
Using a 09-mesh screen printing plate, a white synthetic paper having a pressure-sensitive adhesive layer on the back surface (trade name, SS YUPO (PATI), 1) with the thermochromic aqueous screen printing ink.
0 μm thickness, manufactured by FSK Co., Ltd.]
0 mm), and the following message was printed in the vicinity of the mark with a non-thermochromic screen printing ink to form a print sheet. "When the mark is black, warm it up.""When the mark is purple, warm it up a little more.""When the mark is cyan, it's hot.""When the mark is green, it's time to eat." A transparent polyester film having an adhesive layer on the back surface (film thickness: 25 μm) was laminated to produce a thermochromic seal. The mark portion of the seal has a black color at room temperature (25 ° C.), and the seal is formed at 48 ° C. to 50 ° C., 54 ° C. or more, 39 ° C. to 45 ° C.
When sequentially immersed in water at a temperature of 36 ° C. or lower, the color of the water could be changed in the order of purple, cyan, green, and black with each of the warm water. In addition, the seal is made of hot water of 48 ° C. to 50 ° C., hot water of 45 ° C. or more,
When sequentially immersed in warm water below ℃, purple, black,
Only the color changed in the order of As described above, since the discoloration state of the seal is different between the heating process and the cooling process, whether the seal has been heated to a temperature equal to or higher than a predetermined temperature (complete decoloring temperature T ₄ of thermochromic pigment A: 54 ° C.) Not only can the temperature history be displayed, but also the current temperature can be displayed according to the discoloration state of the thermochromic pigment B,
Has indicator function.

Example 6 3.5 parts of the thermochromic pigment A of Example 1, 6.5 parts of the thermochromic pigment B of Example 1, and the non-thermochromic colorant C0.
5 parts, 2.0 parts of an ultraviolet absorber, 0.5 parts of an antioxidant, and 200 parts of a low molecular weight polypropylene (softening point: 150 ° C.) were uniformly dispersed in a tumbler mixer, and then formed into pellets using an extruder. Melt spinning was performed using the pellets to obtain a reversible thermosensitive multicolor discolorable filament. The filament shows the same color change at the same discoloration temperature as the animal toy of Example 1, but is easily discolored as compared with the animal toy of Example 1 and can repeat the discoloration in a short time. Was. The filament was planted on the head of the doll as the hair of the doll, and a toy capable of various color changes could be constituted by familiar thermal means such as environmental temperature change, tap water, hot water, body temperature, etc. . Further, by processing the filament into a woven yarn and weaving it into a plain woven fabric by a loom, a fabric applicable to various daily uses could be formed.

[0019]

According to the present invention, the color can be changed with high sensitivity at a specific temperature in a high temperature range of room temperature or higher, and multiple colors can be effectively exhibited. In a specific temperature range, any of the colors before and after the change can be exchanged. It is also possible to provide a reversible thermosensitive multicolor discolorable composition which can be stored and stored in a strange manner, and which can exhibit different colors in the same temperature range during the heating process and the cooling process. Further, by forming a single color-changing layer by applying the reversible thermosensitive multicolor-color-changing composition, a laminate capable of exhibiting multicolor color change can be formed. We can provide toys, beverage containers, other various shaped objects and sheet materials with discoloration function, have various color changes, discoloration taste, unexpectedness, and also have temperature history detection function, so it is effective in various fields It is.

[Brief description of the drawings]

FIG. 1 shows a temperature-color density curve of thermochromic pigment A.

FIG. 2 shows a temperature-color density curve of thermochromic pigment B.

FIG. 3 is an enlarged vertical cross-sectional explanatory view of the laminate of the present invention.

FIG. 4 is an external view showing a uniform state of a dinosaur toy which is an embodiment of the laminate of the present invention.

FIG. 5 is an external view showing a partially discolored appearance of the dinosaur toy.

[Explanation of symbols]

T ₁ complete decoloring temperature t ₁ thermochromic the complete coloring temperature T ₂ color start thermochromic pigment A temperature T ₃ of the thermochromic pigment A decolorization initiation temperature T ₄ thermochromic pigments A thermochromic pigment A the complete coloring temperature t ₂ color start thermochromic pigment B temperature t ₃ complete decoloring temperature [Delta] H _a thermochromic pigments a decoloring starting temperature t ₄ thermochromic pigment B thermochromic pigment B sex pigment B Hysteresis width ΔH _B Hysteresis width of thermochromic pigment B 1 Reversible thermosensitive multicolor discolored laminate 2 Reversible thermosensitive multicolor discolored layer 3 Support

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C09D 17/00 C09D 17/00 F term (reference) 2C150 BA09 CA02 DC17 FB20 FB22 FD31 4F100 AK01A AL05A AT00B BA02 BA26 BA42 CA13A DA01 DA20 DD01B EC15A GB23 GB61 GB84 JA20A JJ10B JL10 JN28 JN28A YY00A 4J037 AA30 CB28 CC11 CC21 DD05 EE06 EE28 FF06 FF07 FF08 4J038 BA021 CA021 CA041 CA051 CB021 CB031 CB051 CB161 CB171 CC031 CC041 CC051 CC071 CD031 CD051 CD081 CF021 CF031 CF041 CG141 CG161 CH031 CP081 DA041 DA081 DB001 DB221 DB471 DD071 DD181 DD231 DD241 DE001 DG001 DH001 KA08 KA12 NA16 PB02 PB04 PC02 PC03 PC04 PC06 PC08 PC09 PC10 4J039 BE01 CA04 EA21 FA02 FA03 FA06 FA07 GA01 GA02 GA03 GA05 GA10

Claims (13)

[Claims] 1. A temperature - relates color density curve, thermochromic pigments A which changes color exhibits a large hysteresis width ([Delta] H _A)
And the thermochromic pigment A is different from the thermochromic pigment A in color tone at the time of color development.
_A reversible thermosensitive multicolor discolorable composition which exhibits a hysteresis width (ΔH _B ) smaller than _A and is present in a mixed state with the thermochromic pigment B, which is inherently discolored in the discoloration temperature region of the thermochromic pigment A and is discolored. , A reversible thermosensitive multicolor discolorable composition characterized by satisfying all of the following general formulas (1) to (6). 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) T ₄ = 33 to 100 ° C. 5) T ₁ = 23 to 90 ° C. (6) Here, T ₁ , T ₂ , T ₃ and T ₄ are thermochromic pigments A
, The color development temperature, the color development start temperature, the color erasure start temperature, and the complete color erasure temperature. Also, t ₁ , t ₂ , t ₃ , t ₄
Is the complete color development temperature, color development start temperature of thermochromic pigment B,
The erasing start temperature and the complete erasing temperature are shown. 2. The reversible thermosensitive multicolor discolorable composition according to claim 1, wherein the thermochromic pigment A and the thermochromic pigment B are dispersed in a mixed state in a vehicle containing a binder resin. 3. The method according to claim 1, wherein ΔH _B is 0.5 to 10 ° C.
Or the reversible thermosensitive multicolor discolorable composition according to 2. 4. The reversible thermosensitive multicolor discolorable composition according to claim 1, wherein a non-thermochromic colorant C is mixed. 5. The reversible thermosensitive multicolor colorant according to claim 4, wherein the color of the non-thermochromic colorant C is one of three primary colors of yellow, cyan, and magenta or a color similar to any of the three primary colors. Composition. 6. satisfy all the following general formula (1) to (6), the temperature - and thermochromic pigments A which changes color exhibits a large hysteresis width ([Delta] H _A) with respect to color density curve, the Δ
_A thermochromic pigment _B having a hysteresis width (ΔH _B ) smaller than H _A and having a thermochromic pigment B inherently discolored in the color changing temperature region of the thermochromic pigment A fixed to a binder resin in a dispersed state. A reversible thermosensitive multicolor discolorable laminate characterized in that a color discoloring layer is formed on a support. 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) T ₄ = 33 to 100 ° C. 5) T ₁ = 23 to 90 ° C. (6) Here, T ₁ , T ₂ , T ₃ and T ₄ are thermochromic pigments A
, The color development temperature, the color development start temperature, the color erasure start temperature, and the complete color erasure temperature. Also, t ₁ , t ₂ , t ₃ , t ₄
Is the complete color development temperature, color development start temperature of thermochromic pigment B,
The erasing start temperature and the complete erasing temperature are shown. 7. The method according to claim 6, wherein ΔH _B is 0.5 to 10 ° C.
The reversible thermosensitive multicolor discolorable laminate described. 8. The reversible thermosensitive multicolor-changeable laminate according to claim 6, wherein a non-thermochromic colorant C is mixed. 9. The reversible colorant according to claim 6, wherein the color of the non-thermochromic colorant C is any one of the three primary colors of yellow, cyan, and magenta, or a color similar to any of the three primary colors. Thermosensitive multicolor discolorable laminate. 10. The support has non-uniform heat capacity locations,
The reversible thermosensitive multicolor discolorable laminate according to any one of claims 6 to 9, wherein a reversible thermosensitive multicolor discoloring layer is provided at the location. 11. The reversible thermosensitive multicolor discolorable laminate according to claim 10, wherein the thickness of the non-uniform heat capacity portion is non-uniform. 12. The reversible thermosensitive multicolor discolorable laminate according to claim 10, wherein the inhomogeneous heat capacity portion is an uneven surface. 13. The reversible thermosensitive multicolor discolorable laminate according to claim 6, wherein the support is a toy-shaped object or a beverage container.