JPH11315277A - Reversible thermosensitive multicolor color-changing composition, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reversible thermosensitive multicolor color-changing compsn. with enhanced multicolor color changing, charm of color changing and unexpectedness, by blending two kinds of thermally color-changing pigments different from each other in color tone at color developing and hysteresis breadth, in order to satisfy a specific condition. SOLUTION: This is a reversible thermosensitive multicolor color-changing compsn. prepd. by having a thermally color-changing pigment A which changes color indicating a large hysteresis breadth (ΔHA) and a termally color-changing pigment B which has a color tone different from that of the component A in color changing, indicates a hysteresis breadth (ΔHB) smaller than ΔHA, and changes color within the color- changing temp. range of the pigment A, exist in a mixed state, wherein formulae I-VI are satisfied (where T1 , T2 , T3 and T4 respectively indicate the complete color developing temp., color developing initiation temp., color fading initiation temp. and complete color fading temp. of the pigment A; and t1 , t2 , t3 and t4 respectively indicate those of the pigment B) in regard to the temp.-color density curve. The pigment A is an electron-donating type color developing org. compd. and the pigment B is an electron-accepting type compd. They were fixed to a binder resin in a dispersed state.

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 applying a simple heat or cooling means in a living environment temperature range or daily, and a laminate thereof.

[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, a plurality of types of thermochromic granules having different hysteresis widths and colors are applied to each other, and a thermochromic pigment that exhibits a large hysteresis width and undergoes a color change and exhibits a small hysteresis width in a 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 color-changing material which manifests a multicolor by such a temperature change, and changes the color with a high sensitivity by using a living environment temperature range or a simple heat or cold means. In the specific temperature range at room temperature, any of the colors before and after the change can be alternately stored and held, and furthermore, in the cooling process and the heating process, the same temperature range can be obtained. Reversible thermosensitive multi-colors that are effective for toys, decorations, accessories, writing sheet materials, temperature history detection fields, etc. An object of the present invention is to provide a discolorable composition and a laminate. Among them, plastic moldings that imitate the shapes of insects, dinosaurs, and other animals, show various discoloration patterns due to temperature changes, significantly improve the taste of discoloration, unexpectedness, etc., toys, mascots, etc. The present invention intends to disclose a proposal that is suitable for:

[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 was different from the color tone of the time, [Delta] H _a exhibits a smaller hysteresis width ([Delta] H _B), formed by the presence of the thermochromic pigment B which changes color inherent in discoloration temperature region of the thermochromic pigment a in a mixed state reversible The reversible thermosensitive multicolor discolorable composition, which satisfies all of the following general formulas (1) to (6), is required. 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 10 ° C. (2) (t ₁ −T ₂ ) ≧ 1 ° C. (3) (T ₃ −t ₄ ) ≧ 1 ° C. (4) T ₄ = 28 ° C. to 55 ° C. (5) T ₁ = 5 ° C. to 23 ° 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 thermochromic layer in which a thermochromic layer fixed to a binder resin in a dispersed state is formed on a support. Further, in the first and second inventions, t ₁ is 25 ° C. or more, ΔH _B is 0.5 to 5 ° C., a non-thermochromic colorant C is mixed, The color of the 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 capable of alternately storing and storing a state in a normal temperature range (see FIG. 1). As the thermochromic pigment B, there is Japanese Patent Publication No. Sho 5 proposed by the present applicant.
JP-A-1-35414, JP-B-51-44706, JP-B-1-17154, and JP-A-7-1865.
No. 46, etc., in which a thermochromic material having a relatively small hysteresis width or a fatty acid ester having a ΔT value (melting point−cloud point) of 3 ° C. or less is applied as the component (c), 3 ° C. or less (See FIG. 2), which is a high-sensitivity reversible thermochromic material (Japanese Patent Publication No. 1-29898) that expresses the hysteresis width (ΔH _B ) of the present invention. This type of reversible thermochromic material changes color before and after a color change temperature, and only one specific state can exist in a normal temperature range between the two states before and after the color change. In other words, the other state is maintained while the heat or cold required to develop the state is applied, but returns to the original state exhibited in the normal temperature range when the application of the heat or cold is stopped. Is a 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
Coloring or decoloring by living environment temperature or simple heat or cooling means by specifying the temperature in the range of ~ 50 ° C, preferably 15-35 ° C, and changing the color in the color-developing state or decoloring state to the normal temperature range. Can be alternately stored. [Delta] H _A value color-memory function is less than 10 ° C. is insufficient, although fulfilling exceeds the color-memory function 50 ° C., depending on the living environment temperature or simple heat or cold unit, the tautomeric colors memory function Difficult to express. On the other hand, the ΔH _B value of the thermochromic pigment B satisfies the range of 0.5 to 10 ° C., preferably 0.5 to 5 ° C., more preferably 0.5 to 3 ° C., and the thermochromic pigment A It is required that the color change is inherent in the color change temperature range. 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 satisfies both the relationship of the temperature difference between t ₁ and T ₂ of 1 ° C. or more and the difference of temperature between T ₃ and t ₄ of 1 ° C. or more to visually determine the discoloration state of the thermochromic pigment B. To properly recognize the visible time for color change. If the temperature is less than 1 ° C., the generation and decoloration of the thermochromic pigments A and B become continuous, and it is difficult to recognize the color change. Further, T ₄ is 28 ° C. to 55 ° C., T ₁ is 5 ° C. to 23 ° C.
By satisfying ° C., it is possible to suitably visually recognize a change in appearance due to discoloration in a living environment temperature range in a normal temperature range.

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. In the above, t ₁ of the pigment B is 25 ° C. or more, ΔH _B is 0.5 to 5 ° C., and t ₄ is 36 ° C. to 37 ° C.
When the temperature is not more than 0 ° C., the color of the pigment B is extinguished by body temperature (36 ° C. to 37 ° C.) such as a finger touch, and in a room temperature region below that, the color develops. The second color is developed by body temperature due to finger touch, etc., the third color is developed by heating by friction or hot water, etc., and the fourth color is developed by temperature drop to room temperature area, room temperature, tap water or ice water, etc. Thus, the color change state of the first color can be returned again. As described above, various color changes can be easily expressed by heat or cold means in the living environment temperature range to allow visual observation, and a special color changing device or the like is not required.

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. In addition, even if the base layer 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 visually recognized. Since the color change is through, 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)
In addition, the color (fourth color) presented in the temperature decreasing process exhibits a different color, which contributes to multicoloring and can further enhance the exquisiteness and unexpectedness of discoloration. The non-thermochromic colorant C
Examples thereof include conventionally known dyes, ultraviolet light emitting dyes, general pigments, fluorescent pigments, luminous pigments, luminous pigments, metal powders, pearl pigments, extender pigments, photochromic colorants, and fluorescent brighteners. Here, the color of the colorant C is
By selecting and using any of the three primary colors of yellow, cyan, and magenta, or a color similar to any of the three primary colors, a sharp color change, more specifically, the first color, the second color, or the fourth color In particular, it contributes to making the color tones of the second and fourth colors clearly visible. The thermochromic pigments A and B in the present invention
Alternatively, the composition obtained by blending the non-thermochromic colorant C with the above A and B is prepared by melt-blending 0.1 to 40% by weight (preferably 0.2 to 25% by weight) in a thermoplastic resin. And molded articles of various forms can be formed, but in general, the composition is dispersed in a vehicle containing a binder resin, and the composition is formed into a paint or ink form, coated on various supports, sprayed, and the like. The thermochromic layer can be formed and 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 thermochromic layer is 5 to 5.
The range of 80% by weight (preferably 10 to 60% by weight) is effective in view of the thermochromic effect. That is, when the content is less than 5% by weight, the color density is low, and the color change cannot be clearly seen.
When the content exceeds 0% by weight, the residual color is visually recognized, and it is difficult to visually recognize a clear decolored state. The thermochromic layer has a thickness of at least 0.1.
5 μm or more, preferably 1 to 400 μm, more preferably 10 to 200 μm, and if it is less than 0.5 μm, the color change lacks sharpness.On the other hand, a system exceeding 400 μm tends to impair the aesthetic appearance, and is preferably Absent. 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, Polymethyl methacrylate resin, epoxy acrylate resin, alkyl phenol resin, rosin-modified phenol 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-acetic acid Vinyl resin, styrene-butadiene resin, epoxy resin, unsaturated polyester resin, polyurethane resin, vinyl acetate resin Rujon resins, styrene - butadiene emulsion resin, acrylic ester emulsion resin, water-soluble phenolic resin, water-soluble epoxy resin, water-soluble butadiene resins, cellulose acetate, nitrate cellulose, ethyl cellulose and the like.

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. As the support, plastic, glass, metal, ceramic, cloth,
All materials such as paper, synthetic paper, synthetic leather, wood, and stone are effective. Among these supports, fabric, paper, synthetic paper,
In the case of application to a support having a small heat capacity such as synthetic leather and a temperature change relatively fast, a difference in the color development and decolorization temperatures of the pigments A and B is set to be large, and the second color and the fourth color are developed. It is effective to set the temperature range wide. Meanwhile, plastic,
In a system in which a thermochromic layer is formed on a support that has a large heat capacity such as glass, metal, ceramics, wood, and stone and has a slow temperature change, the temperature of the support itself changes slowly and the temperature at which the color changes is sensitive. To the pigment, the coloring of the pigments A and B,
Even if the temperature difference of the decoloring is set to be small, the second color and the fourth color can be surely 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. Specifically, like dinosaurs, reptiles, insects, flora and fauna, imaginary creatures such as mermaids, fish, etc., horns, fangs, haptics, tentacles, hands, feet, tails, fins, mustaches, etc. In toys such as shaped articles and stuffed toys, the spray ink in which the multicolor discolorable composition according to the present invention is dispersed in a vehicle containing a binder resin is sprayed on the surface of the toy and dried to obtain a large amount due to a temperature change. It can be changed to a color, depending on the inhomogeneity of the heat capacity of the support itself, to produce various discolored patterns.
In particular, when the object is large enough to fit in the palm, it is easy to change the color from the first color to the second color and the third color due to body temperature, discoloration to the fourth color at room temperature, room temperature, and water supply. Since the color can be easily changed to the first color by water, ice water, or the like, it is suitable not only for toys but also for accessories and mascots. To form a multicolor thermochromic layer on a support, conventionally known coating methods, for example, screen printing, offset printing,
Printing means such as gravure printing, coater, tampo printing, transfer and the like, means such as brush coating, spray coating, electrostatic coating, electrodeposition coating and the like are all effective. The support is a cloth,
In the case of a permeable material such as paper, an undercoat layer made of a resin thin film or the like is provided on the base in advance to prevent the penetration of the thermochromic ink at the time of forming the thermochromic layer, and to provide a clear color tone. Contributes to the formation of a thermochromic layer that makes

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermosensitive multicolor discolorable composition of the present invention can be melt-blended with a thermoplastic resin and molded into a sheet or a molded product. Usually, the composition is dispersed in a vehicle containing a binder resin. As a paint or printing ink, a thermochromic layer is fixed to a support by spraying or coating, and is practically used as a laminate. Examples of toys, accessories, seals, and the like will be described below, but the present invention is not limited thereto.

[0012]

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

Example 1 Thermochromic pigment A (ΔH _A : 16 ° C., T ₁ : 15 ° C.,
T ₂ : 17 ° C., T ₃ : 31 ° C., T ₄ : 33 ° C., 3.5 parts of cyan color →→ colorless color change, thermochromic pigment B (Δ)
_{H B: 1 ℃, t 1} : 26 ℃, t 2: 28 ℃, t 3: 27
° C, t ₄ : 29 ° C, magenta color ← → colorless) 6.5 parts, and non-thermochromic coloring agent C [yellow fluorescent pigment (trade name: Epocolor FP-117, manufactured by Nippon Shokubai Co., Ltd.)] Using an oil-based spray ink in which 5 parts were dispersed in a vehicle containing a binder resin, the entire surface of an ant-shaped object molded from a white soft vinyl chloride resin was spray-painted to form a mini animal toy. The animal toy is placed in water at a temperature of 15 ° C. or less, 29
C. to 31.degree. C., hot water of 33.degree. C. or more, water of 17.degree. C. to 26.degree. C., and water of 15.degree. C. or less, the black (first color), green (second color), yellow ( The entire color could be changed in the order of (the third color), red (the fourth color), and black (the first color). Next, when the user touched a part of the surface of the toy which was colored in black as a whole, the touched portion changed color from black to green, and the portion changed to green became yellow by further touching the toy, The surface was in a state of simultaneously displaying three colors of black, green, and yellow. When the discolored toy was allowed to stand at room temperature of 24 ° C., the green portion turned black again, and the yellow portion turned red. As a result, the discolored state consisting of black and red was visually recognized.
This discolored state could be maintained in a room temperature range of 17 ° C. or more and 27 ° C. or less. When touching a part of the toy,
Since the black portion turned green and the red portion turned yellow, it was possible to simultaneously show the non-contact portion of black, red, and the green and yellow portions of the color changed by touch with the finger. Further, in this state, when the device was left at room temperature of 24 ° C., the color changed again to black and red. Next, by immersing the toy in this state in water at 15 ° C. or lower, the whole could be returned to black. The toy has a tactile sensation, the discoloration of the projections such as the feet is faster than that of the body, so that the entire heating, such as heating the toy in the palm of the hand, causes the specific parts such as the projections to be formed. The color could be selectively changed. As described above, the toy can easily make the four discolored states of black, green, yellow, and red visible by applying ice water, tap water, room temperature, body temperature, hot water, and the like. Since it is possible to simultaneously present four discolored states on the surface of the toy, it is possible to obtain a variety of color changes despite the entire painting with a single spray ink, and the color changes can be repeatedly reproduced. did it.

Example 2 Thermochromic pigment A (ΔH _A : 16 ° C., T ₁ : 21 ° C.,
T ₂ : 23 ° C., T ₃ : 37 ° C., T ₄ : 39 ° C., magenta color →→ colorless color change) 4.0 parts, thermochromic pigment B (ΔH
_B : 6 ° C., t ₁ : 26 ° C., t ₂ : 28 ° C., t ₃ : 32
° C, t ₄ : 34 ° C, yellow ← → colorless) 6.0 parts, and non-thermochromic coloring agent C [water dispersion of cyan pigment, (trade name:
An aqueous screen printing ink was prepared by dispersing 0.05 parts of SANDYE SUPER BLUE GLL, a pigment content of about 24% by weight, manufactured by Sanyo Dyeing Co., Ltd. in an aqueous vehicle containing a binder resin. Using a 109-mesh screen printing plate, a white synthetic paper having a pressure-sensitive adhesive layer on the back surface with the aqueous screen printing ink [trade name:
SS Yupo (PATI), 10 μm thickness, manufactured by FSK Corporation]
On top, solid printing was performed, and after drying, a transparent polyester film (film thickness: 25 μm) having an adhesive layer on the back surface was laminated to form a reversible thermochromic seal. The seal is attached to the hood portion of a black amphibious toy in the form of an amphibious vehicle.
2 ° C hot water, 39 ° C or higher hot water, 23 ° C to 26 ° C water, 2
When sequentially immersed in water at 1 ° C. or lower, the seal portion of the bonnet was black (first color), purple (second color),
Cyan (third color), green (fourth color), black (first
Color), and color change in this order. Next, hot water of 39 ° C. or higher was applied to the entirety of the seal portion that had been changed to black by using a brush, and the color changed from black to purple and further to cyan. From this discolored state, when the amphibious toy was left at room temperature of 24 ° C., the cyan bonnet turned green. Further, water of 21 ° C. or less was applied to the green bonnet portion using a brush to partially develop a black color, thereby forming a discoloration pattern of black numerals. This discolored state is 23 ° C or higher,
The temperature could be maintained at room temperature of 32 ° C. or lower. In this discolored state, a part of the black numeral part is discolored to purple by touch, and a part of the green part is touched by finger.
By changing the color to cyan, black in the non-touch area,
A discolored state of simultaneously exhibiting four colors of green and purple and cyan of the touch portion was obtained. When the discolored state was allowed to stand at room temperature of 24 ° C., the discolored state returned to the pattern of green and black numbers again. Next, by immersing the toy in this state in water at a temperature of 21 ° C. or lower, the whole could be returned to black. As described above, the toy is ice water, tap water, room temperature,
By applying body temperature, hot water, etc., it is possible to easily change the color into four discolored states of black, purple, cyan and green, and it is possible to simultaneously show four discolored states on the same printed matter in the room temperature region Therefore, despite the solid printing with a single screen ink, various color changes could be obtained, and the above-described color changes could be repeatedly reproduced.

Example 3 Thermochromic pigment A (ΔH _A : 18 ° C., T ₁ : 13 ° C.,
T ₂ : 15 ° C., T ₃ : 31 ° C., T ₄ : 33 ° C., yellow ← →
6.0 parts of colorless color change), thermochromic pigment B (ΔH _B : 2)
_{℃, t 1: 18 ℃,} t 2: 20 ℃, t 3: 20 ℃,
t ₄ : 22 ° C., cyan color ← → colorless) 4.0 parts, and non-thermochromic colorant C [magenta fluorescent pigment (trade name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.)] 0.3 part Using an oil-based spray ink dispersed in a vehicle containing a binder resin, the entire surface of a dinosaur-shaped object formed of white soft vinyl chloride resin was spray-painted to form a mini animal toy. Water below ℃,
22 ° C to 31 ° C water, 33 ° C or higher hot water, 15 ° C to 18
C. water and 15 ° C. or lower water in order to obtain dark green (first color), orange (second color), magenta (third color)
Color), blue-violet (fourth color), and dark green (first color). Next, when the toy, which was entirely colored dark green, was allowed to stand at room temperature of 24 ° C., the color of the dinosaur began to change, and the entire color changed to orange when left to stand. When the user touched the toy in this state, the touched portion changed color to magenta, and a spot-like magenta pattern could be formed. This state could be maintained in a room temperature range of 20 ° C. to 31 ° C. The toy having vermilion spots in the orange portion is
When immersed in water at -18 ° C, the orange portion turns dark green and the magenta portion turns blue-violet,
A state with blue-violet spots in the dark green portion was obtained. Further, when left in this state at a room temperature of 24 ° C.,
Again, it returned to a state having magenta spots in the orange portion. Next, by immersing the toy in this state in water at 13 ° C. or lower, the whole could be returned to dark green. As described above, the toy can be easily changed to four discolored states of dark green, orange, magenta, and blue-purple by applying ice water, tap water, room temperature, body temperature, hot water, and the like,
Despite the whole painting with a single spray ink,
Various color changes could be obtained, and the above-mentioned color changes could be repeated and reproduced.

[0016] Example 4 thermochromic pigment _{A (ΔH A: 10 ℃,} T 1: 21 ℃,
T ₂ : 23 ° C., T ₃ : 31 ° C., T ₄ : 33 ° C., yellow ← →
7.0 parts of a colorless color change), thermochromic pigment B (ΔH _B : 2)
_{℃, t 1: 26 ℃,} t 2: 28 ℃, t 3: 28 ℃,
t ₄ : 30 ° C., cyan color ← → colorless) 3.0 parts, and non-thermochromic colorant C [magenta fluorescent pigment, trade name: Epocolor FP-1000N, manufactured by Nippon Shokubai Co., Ltd.] 1.5 Part was spray-coated over the entire surface of a white ABS resin star-shaped pendant using an oil-based spray ink dispersed in a vehicle containing a binder resin. Using a white non-thermochromic oil-based spray ink, spray coating is performed in a heart shape, and a magenta fluorescent pigment [trade name: Epocolor FP-1000] is applied on the white non-thermochromic ink.
N, manufactured by Nippon Shokubai Co., Ltd.] to form a heart-shaped magenta non-thermochromic coloring layer. When the coated object was immersed in water of 21 ° C. or less, warm water of 30 ° C. to 31 ° C., warm water of 33 ° C. or more, water of 23 ° C. to 26 ° C., and water of 21 ° C. or less, the heart of the painted object was obtained. In the thermochromic portion other than the portion, the discoloration state changes in the order of brown (first color), orange (second color), magenta (third color), purple (fourth color), and brown (first color). did. In the discoloration process, since the heart portion is a magenta non-thermochromic coloring layer, the contrast with the background color changes significantly in each discoloration state, especially when immersed in warm water at 33 ° C. or higher. Since the thermochromic portion became magenta, the shape of the heart was not visually recognized. Then, when touching the star-shaped protrusion of the painted material in which the thermochromic portion was changed to brown, the touched portion changed from brown to orange, and the portion changed to orange continued to touch. The color changed to magenta, and the thermochromic portion simultaneously exhibited three colors of brown, orange, and magenta. When the coated material in the discolored state was left at room temperature of 24 ° C., the orange portion turned brown again, and the magenta color changed to purple. The center portion of the was composed of a magenta heart shape and a brown background color. This discolored state could be maintained in a room temperature range from 23 ° C. to 28 ° C. In addition, in this discolored state, when touching a part of the thermochromic portion, the brown portion changes color to orange, and the purple portion changes color to magenta, so only the thermochromic portion changes color.
It was possible to simultaneously exhibit four colors of brown and purple in the non-touching part and orange and magenta in the touching part. Further, in this state, when the coated object was left at room temperature of 24 ° C.,
The thermochromic portion returned to a state of exhibiting two colors of brown and purple again. Next, by immersing the coated product in this state in water at a temperature of 21 ° C. or lower, the thermochromic portion could be returned to brown again. As described above, the painted object can be easily changed to four discolored states of brown, orange, magenta, and purple by application of ice water, tap water, room temperature, body temperature, hot water, and the like, At the same time, the contrast between the thermochromic portion and the non-thermochromic coloring material layer laminated on the reversible thermochromic laminate could be greatly changed. Further, in the room temperature region, it is possible to simultaneously exhibit four discolored states on the same painted object, so that various color changes can be obtained despite the entire painting with a single reversible thermochromic spray ink. The above-mentioned discoloration could be repeatedly reproduced.

[0017] Example 5 thermochromic pigment _{A (ΔH A: 21 ℃,} T 1: 15 ℃,
T ₂ : 17 ° C., T ₃ : 36 ° C., T ₄ : 38 ° C., 3.0 parts of cyan color → colorless color change), thermochromic pigment B (Δ)
H _B : 2 ° C., t ₁ : 27 ° C., t ₂ : 29 ° C., t ₃ : 29
° C, t ₄ : 31 ° C, magenta color → colorless) 7.0 parts of a reversible thermochromic aqueous screen printing ink was prepared by dispersing 7.0 parts in an aqueous vehicle containing a binder resin. After solid printing a white non-thermochromic aqueous screen printing ink on the entire surface of the polyester tricot fabric, solid printing was performed using the reversible thermochromic aqueous screen printing ink using a 109-mesh screen printing plate. Was.
Next, using a purple, cyan, white, and magenta non-thermochromic aqueous screen printing ink, a floral pattern composed of four colors was printed on the reversible thermochromic layer. The printing cloth is water of 15 ° C. or less, warm water of 31 ° C. to 36 ° C., 38 ° C.
When immersed sequentially in the above warm water, water at 17 ° C. to 27 ° C., and water at 15 ° C. or less, the thermochromic portion of the printed matter is:
Purple (first color), cyan (second color), white (third color)
(Color), magenta (fourth color), and purple (first color). In the discoloration process, since the floral pattern portion is a non-thermochromic coloring layer composed of the four colors,
In each discoloration state, the contrast with the background color greatly changed, and a pattern portion having the same color as the color tone of the thermochromic portion became invisible. By attaching a swimsuit for a doll sewn with the printing fabric to the doll and immersing it in different water temperatures,
As described above, a toy capable of various color changes could be constructed. As described above, the printed matter is ice water, tap water,
Room temperature, body temperature, thermochromic part purple by application of hot water, etc.
It is possible to change the color into four color change states of cyan, white and magenta, and in each color change state, the non-thermochromic coloring of the flower pattern laminated on the thermochromic part and the reversible thermochromic laminate The contrast with the agent layer can be greatly changed, and the visual recognition state of the non-thermochromic colorant layer can also be changed.

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.
An oil-based screen printing ink in which 5 parts were dispersed in a vehicle containing a binder resin was prepared, and a butterfly pattern was printed on a white polyester film (100 μm thick) using a 109-mesh screen printing plate. The printed matter shows the same color change at the same discoloration temperature as the animal toy of Example 1, but compared with the animal toy of Example 1, the first color to the second color, the third color, Discoloration to a color, discoloration from a third color to a fourth color when left at room temperature, and discoloration from a fourth color to the first color due to cold water or the like are easy, and the above-mentioned color is easily obtained in a short time. The change could be repeated. Cut out the printed matter in the shape of a butterfly, as a doll accessory,
By attaching to a doll dress, hair, and the like, and applying finger touch, room temperature standing, cold water, and the like as described above, a toy capable of various color changes could be constructed. As described in the above embodiments, the present invention provides a more versatile and diverse pattern by providing a print image with a non-thermochromic ink (a general-purpose printing ink) on the upper layer or the lower layer of the reversible thermosensitive multicolor discoloring layer. The color change can be seen visually.

[0019]

According to the present invention, the color is changed with high sensitivity by a living environment temperature range or a simple heat or cold means, and multiple colors are effectively developed. Any color can be stored alternately, and furthermore, different colors can be expressed in the same temperature range during the cooling process and the heating process. To provide a reversible thermosensitive multicolor discolorable composition and a laminate effective for toys, decorations, accessories, thermochromic writing sheet materials, temperature history detection fields and the like. Above all, in miniature animal toys and mascots, etc., which are shaped into animal shapes by plastic materials, the heat capacity differs in each part,
A variety of color change patterns can be exhibited, and the toy characteristics and saliency can be enhanced.

[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 external view showing a uniform phase of a dinosaur toy which is one embodiment of the laminate of the present invention.

FIG. 4 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 multicolored laminate 2 Reversible thermosensitive multicolored layer

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 10 ° C. (2) (t ₁ −T ₂ ) ≧ 1 ° C. (3) (T ₃ −t ₄ ) ≧ 1 ° C. (4) T ₄ = 28 ° C. to 55 ° C. (5) T ₁ = 5 ° C. to 23 ° 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 t ₁ is 25 ° C. or more, and ΔH _B is 0.1.
The reversible thermosensitive multicolor discolorable composition according to claim 1, which has a temperature of 5 to 5 ° C. 4. 4. The reversible thermosensitive multicolor discolorable composition according to claim 1, wherein a non-thermochromic colorant C is mixed. 5. The reversible thermosensitive multicolored 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 layer having a hysteresis width (ΔH _B ) smaller than H _A, and a thermochromic pigment B, which is inherently discolored in the color-changing temperature region of the thermochromic pigment A and fixed to a binder resin in a dispersed state, is formed. A reversible thermosensitive multicolor discolorable laminate 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 10 ° C. (2) (t ₁ −T ₂ ) ≧ 1 ° C. (3) (T ₃ −t ₄ ) ≧ 1 ° C. (4) T ₄ = 28 ° C. to 55 ° C. (5) T ₁ = 5 ° C. to 23 ° 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 1, wherein t ₁ is 25 ° C. or more, and ΔH _B is 0.1.
The reversible thermosensitive multicolor discolorable laminate according to claim 6, which is at 5 to 5C. 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.