JPH10146204A - Thermosensitive discoloring footwear - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain thermosensitive discoloring footwear which exhibits a slight color change in spite of a slight temp. change and makes a variety of color tones sensible by applying a specific reversible thermodiscoloring compsn. which exhibits a first hue, a second hue and an intermediate hue between the first hue and the second hue with respect to a temp.-color density curve. SOLUTION: The surface of the footwear 2 is provided with a reversible thermodiscolorable layer 3 by reversible thermodiscoloring ink uniformly, dispersed with microcapsule pigments of about 0.5 to 50μm in grain size enclosing the reversible thermodiscoloring compsn. of -20 to 40 deg.C in discoloration temp. changing from red to colorless or vice versa and is provided thereon with a coating layer 4. The thermosensitive discoloring footwear 1 is made red by the color development of the reversible thermodiscoloring layer 3 at <=13 deg.C. When the temp. exceeds 20 deg.C, the color tone is made gradually paler, by which the footwear is discolored from pale red to pink. When the temp. exceeds 30 deg.C, the reversible thermodiscoloring compsn. is discolored and is changed to white. The thermosensitive discolorable footwear 1 has the reversibility to discolor to pink, pale red and red when the temp. falls again down to 13 deg.C from 23 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to thermochromic footwear. More specifically, in response to a temperature change in the ambient temperature range, the color tone of the surface of the footwear continuously shows the same color in shades or shades, or exhibits an approximate color tone, and further exhibits an intermediate color tone. The present invention relates to thermosensitive discolorable footwear.

[0002]

2. Description of the Related Art Conventionally, temperature indicating footwear colored with a temperature indicating material is disclosed in Japanese Utility Model Laid-Open No. 57-131105.

[0003] The above-mentioned conventional thermal shoes have a temperature of 5 ° C or more.
A shoe that discolors in three stages in accordance with a change in air temperature is disclosed using a temperature indicating material that discolors at a temperature of 5 ° C. to −5 ° C. and a temperature of −5 ° C. or less. However, even if the temperature indicating footwear exhibits a gradual color change due to a temperature change, each color tone presented at each stage is monotonous, and the shades and shades of the same color, an approximate color tone, and an intermediate color tone are displayed. It is difficult to present and continuously discolor. It is also difficult to obtain footwear that exhibits a color change with a stepwise and continuous gradation over a relatively wide range of environmental temperatures.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned disadvantages by applying a specific reversible thermochromic composition with respect to a temperature-color density curve, and allows a subtle color change even with a slight temperature change. An object of the present invention is to provide a thermochromic footwear that exhibits a change and allows visualization of various color tones.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a thermosensitive color-changing footwear provided with a reversible thermochromic layer which changes color variously with temperature change, wherein the reversible thermochromic layer has a color change temperature of -20.degree.
A particle size of about 0. 0 containing a reversible thermochromic composition at 0 ° C.
A layer in which a 5 to 50 μm microcapsule pigment is fixed in a binder in a dispersed state, wherein the reversible thermochromic composition is in a first hue state with respect to a temperature-color density curve, and in a process of increasing the temperature. When the temperature reaches the second temperature T ₃ , the first hue begins to change color, and completely becomes the second hue in a temperature range equal to or higher than the temperature T ₄ higher than the second temperature T ₃ , and the reversible thermochromic composition becomes In the process of falling in temperature in the second hue state, when the temperature reaches the first temperature T ₂ , the second hue begins to change color, and completely falls within a temperature range lower than the first temperature T ₂ and lower than the temperature T _1. A first hue, wherein the temperature difference between T ₁ and T _{2 and} the temperature difference between T ₃ and T ₄ are in the range of 2 ° C. to 30 ° C., and a function of exhibiting an intermediate hue between the first hue and the second hue. Thermochromic footwear having a thermosensitive layer or a reversible thermochromic layer that changes color with temperature change In the discolorable footwear, the reversible thermochromic layer has a plurality of discoloration temperatures ranging from -20 ° C to 4 ° C.
A particle size of about 0. 0 containing a reversible thermochromic composition at 0 ° C.
A layer formed by blending or laminating 5 to 50 μm microcapsule pigments, wherein the reversible thermochromic composition is in the first hue state with respect to the temperature-color density curve, and in the process of increasing the temperature, the second Upon reaching the temperature T _3, the first color begins to discolor, become completely second color at a second higher temperature T ₄ or more temperature range than the temperature T _3, the reversible thermochromic composition a second color In the process of falling temperature in the state,
When first reaches a temperature T _2, the second color begins to discolor, it becomes completely the first color at a first low temperature T ₁ of the following temperature range than the temperature T _2, the midpoint of the T ₁ and T ₂ T ₅ and T ₃ and T
_The hysteresis width (ΔH) indicating the temperature width of the midpoint T ₆ of ₄ is 7 ° C. or less, and the temperature T ₃ ′ and T ₁ ′ of the adjacent reversible thermochromic compositions are represented by the following general formula (1). ) And (2) are required. T ₄ + 2 ≧ T ₃ ′ (1) T ₂ +2 ≧ T ₁ ′ (2) Furthermore, the general formula is the following general formula: T ₄ ≧ T ₃ ′ ((1) 1) T ₂ ≧ T ₁ ′ (2) The reversible thermochromic composition has a hysteresis width (ΔH) of 5
C. or lower, a thermochromic die-cut image is stuck or sewn on the surface of the footwear to form a reversible thermochromic layer, and a light-shielding pigment and / or It is required that a coating layer containing a light stabilizer is formed, a non-thermochromic layer is disposed below the reversible thermochromic layer, and the reversible thermochromic layer is configured to be concealable by a temperature change. .

As the reversible thermochromic composition, a composition containing three components of an organic compound medium which reversibly causes a color reaction between an electron-donating color-forming organic compound and an electron-accepting compound is used. Specifically, Japanese Patent Publication No. 51-35414,
JP-B-51-44706, JP-B-51-4470
8, No. 52-7774, Tokiko 1-17154
Gazette, Japanese Patent Publication No. 1-29398, and JP-A-7-18
No. 6546 and the like. The color changes before and after a predetermined temperature (discoloration point) as a boundary, and only one specific state can exist in a normal temperature range between the two states before and after the change. That is, the other state is maintained while the heat or cold required for the state to develop is applied, but returns to the state exhibited in the normal temperature range if the application of the heat or cold disappears, so-called, This type changes color by showing a small hysteresis width (ΔH) for temperature-color density due to temperature change.

The above-described reversible thermochromic composition is used by being encapsulated in microcapsules. This is because the composition is maintained at the same composition under various conditions of use and can exhibit the same effects. By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the particle diameter is in the range of 0.5 to 50 μm, preferably 2 to 50 μm.
When a non-thermochromic layer is provided as a lower layer, the layer can be effectively hidden. The microencapsulation is carried out by a conventionally known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Furthermore, on the surface of the microcapsule, a secondary resin film is further provided according to the purpose to impart durability,
The surface properties can be modified for practical use.

The microcapsule pigment containing the reversible thermochromic composition is dispersed in a medium containing a binder which is a film-forming material and applied as a coloring material such as ink or paint to form a reversible thermochromic layer. it can.

As the above-mentioned binder, for example, various kinds of general-purpose binders such as various synthetic resin emulsions, water-soluble or oil-soluble synthetic resins, and UV-curable resins can be used.
For example, ionomer resin, isobutylene-maleic anhydride resin 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, chlorine 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 resin modified alkyd resin, epoxy resin 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, acrylate ester emulsion resin, polyurethane emulsion resin, water-soluble alkyd resin, water-soluble melamine resin, water-soluble urea resin, water-soluble phenol resin, water-soluble epoxy resin, Examples thereof include a water-soluble polybutadiene resin, cellulose acetate, cellulose nitrate, and ethyl cellulose.

Here, the microcapsule pigment accounts for 1 to 40% by weight in the reversible thermochromic layer. 1% by weight
If it is less than 10, it is difficult to visually recognize the color density. On the other hand, if it exceeds 40% by weight, there is a residual color at the time of decoloration, which is not preferable.

In the temperature-color density curve, the temperature difference between T ₁ and T ₂ is 2 ° C. to 30 ° C. so that the reversible thermochromic composition can change color with environmental temperature in various regions. , Preferably 3 ° C. to 25 ° C., and T ₃ and T ₄
Temperature difference between 2 ° C and 30 ° C, preferably between 3 ° C and 25 ° C
Is used. Temperature in the above temperature range-
By using the reversible thermochromic composition having a color density curve, it is possible to exhibit a continuous color tone change due to a temperature change without having selectivity even in a relatively hot area or a cold area. The temperature difference between T ₁ and T ₂ mentioned above and T ₃ and T ₄
By using the composition having the above temperature difference, the color can be delicately changed from dark to light and from light to dark in response to a slight temperature change. Incidentally, T ₁ is the temperature the temperature, i.e. the -20 ° C. or higher to discolor in a cold region or the like, also,
T ₄ is a temperature temperature, i.e. of 50 ° C. or less discolored even at a relatively hot region.

In the present invention, a plurality of reversible thermochromic compositions having the above-mentioned temperature-color density curve can be used. Further, the reversible thermochromic composition has a hysteresis width (ΔΔ) indicating the temperature width between the temperatures T ₁ and T ₂ and between T ₃ and T _4.
H) is preferably 7 ° C. or lower. Further, the hysteresis width (ΔH) is more preferably 5 ° C. or less. If the hysteresis width exceeds 7 ° C., the appearance of the color change due to the temperature change is stored and retained, so that it is difficult to exhibit a reversible color change with a change in the environmental temperature.

[0013] Further, in order to obtain a thermochromic footwear exhibiting a similar color change, the temperature - the midpoint T ₅ and T ₃ of the T ₁ and T ₂ of the reversibly thermochromic composition having a color density curve and T _The hysteresis width (ΔH) indicating the temperature width of the middle point T ₆ of ₄ is 7 ° C. or less, preferably 5 ° C. or less, more preferably 3 ° C. or less, and the temperature of adjacent reversible thermochromic compositions. A plurality of reversible thermochromic compositions satisfying the following general formulas (1) and (2) can be used for T ₃ ′ and T ₁ ′ of the color density curve. T ₄ + 2 ≧ T ₃ ′ (1) T ₂ + 2 ≧ T ₁ ′ (2) Explaining the general formula (1), the first reversible thermochromic composition is converted from the first hue to the first hue. In the process of discoloring to two hues, T ₄
Before reaching, or at the same time as, or before reaching 2 ° C., the temperature T ₃ ′ at which the reversible thermochromic composition starts discoloring adjacent to the temperature range, thereby setting the environmental temperature. A continuous tone change can be seen against the rise. If the temperature T ₃ ′ of the reversible thermochromic composition adjacent to the temperature obtained by adding 2 ° C. to the above T ₄ is set, it is difficult to visually recognize the color change that continuously occurs as the environmental temperature increases. Therefore, the general formula (1) is expressed as follows: T ₄ ≧ T ₃ ′
Is more preferable. The general formula (2) will be described. In the process in which the reversible thermochromic composition changes color from the second hue to the first hue, the temperature decreases by 2 ° C. before reaching, or simultaneously with, or after reaching T ₁ ′. Temperature at which the reversible thermochromic composition adjacent to the temperature range before the color change starts discoloring
By setting _2, with respect to the fall of the environmental temperature,
You can see the continuous color change. 2 ° C higher than T ₁ '
Temperature T of the reversible thermochromic composition adjacent to the above low temperature
_{When 2} is set, it becomes difficult to visually recognize the aspect in which the color continuously changes as the environmental temperature decreases. Therefore, the general formula (2) more preferably satisfies T ₂ ≧ T ₁ ′.

The light-shielding pigment used in the coating layer is
It is a pigment selected from pearlescent pigments, transparent titanium oxide, transparent iron oxide, transparent cesium oxide, transparent zinc oxide, etc., and the light stabilizer is an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, A layer in which a light stabilizer selected from a superoxide anion quencher, an ozone decolorizer, a visible light absorber, and an infrared absorber is fixed in a dispersed state, and is effective for improving light fastness. In addition, an antioxidant, an antistatic agent, a polarity imparting agent, a thixotropic agent, an antifoaming agent, and the like can be added to the pearlescent pigment layer as needed to improve the function.

In the above description, the pearlescent pigment system will be described. The surface of natural mica is coated with 14 to 68% by weight of titanium oxide, and the coating layer has an optical thickness of 110 to 41%.
A pearlescent pigment having a particle size of 5 nm and a particle size of 5 to 300 μm is effective, and a layer fixed in a dispersed state in an appropriate binder can be laminated on the reversible thermochromic layer.

The above-mentioned attempt to give a pearlescent color change by applying a pearlescent pigment has been proposed by the present applicant in Japanese Patent Application Laid-Open Nos. Hei 6-1067 and Hei-6.
The technology disclosed in Japanese Patent Application Laid-Open No. 1068/1994 and Japanese Patent Application Laid-Open No. 6-8628 can be applied. Furthermore, specifically, the optical thickness of the coating layer obtained by coating the surface of natural mica with 26 to 57% by weight of titanium oxide is 180 to 240 nm, and the particle size is 5 to 5.
~ 125μm golden pearlescent pigment, natural mica surface 1
The optical thickness of the coating layer coated with 4 to 43% by weight of titanium oxide is 110 to 170 nm, and the particle size is 1 to 180 μm.
m, a silver pearl luster pigment, a natural mica having a surface coated with 29 to 68% by weight of titanium oxide having an optical thickness of 24
A metallic pearlescent pigment having a particle size of 5 to 415 nm and a particle size of 5 to 125 μm can be exemplified.

The pearlescent pigment layer is capable of changing the color from gold, silver, and other various metallic colors due to the correlation between the iris effect and the transmission effect caused by the selective interference of visible light and the brightness of the reversible heat layer. In addition, light resistance is remarkably improved by absorbing or reflecting at least a part of ultraviolet light or visible light which adversely affects the function of the color storage layer.

The reversible thermochromic layer may be blended with a general dye, pigment, or the like to make the color tone more complicated. It is also possible to provide a discoloration layer so that the color can be hidden. The non-thermochromic layer may be used for the purpose of coloring footwear,
Images such as figures, characters, and numbers may be provided.

The reversible thermochromic layer, coating layer and non-thermochromic layer can be formed by conventionally known methods, for example, screen printing, offset printing, gravure printing, coater, tampo printing,
It can be formed by printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating and the like. Further, in addition to providing the layer directly on the surface of the shoe, a layer may be provided on the cloth, synthetic resin, leather, synthetic leather, or the like by the above-described forming means, and then cut and sewn or attached to the shoe as a die cut image. Further, a layer formed of a synthetic resin formed by blending the reversible thermochromic composition, non-thermochromic colored dye or pigment, light-shielding pigment, and light stabilizer, or a plastic material may be used.

[0020]

Embodiments of the present invention will be described below. The parts in the examples are parts by weight.

Example 1 (Refer to FIGS. 1 and 8) As the footwear 2, the surface of the white athletic shoe is red-colorless (when cooled from 23 ° C. to 13 ° C.), the density of red gradually increases, and conversely, 20%. As the temperature is raised from 30 ° C. to 30 ° C., the density of the red color gradually becomes thinner: T ₁ : 13 ° C., T ₂ : 23 ° C., T
_{3: 20 ℃, T 4:} 30 ℃, temperature difference 10 of T ₁ and T ₂
° C., T ₃ and the temperature difference 7 ° C. of T _4, the reversibly thermochromic layer 3 at the reversible thermochromic ink uniformly dispersed microcapsules pigments containing a reversible thermochromic composition which changes color ΔH7 ℃) provided Further, 40 parts of an acrylate resin, 4 parts of an ultraviolet absorber, 0.4 part of a silicone-based defoamer, 20 parts of butyl acetate
Parts, and 15 parts of an aromatic medium boiling point solvent were uniformly mixed and screen-printed to form a coating layer 4.

The thermochromic footwear 1 obtained as described above comprises:
At an environmental temperature of 13 ° C. or lower, the reversible thermochromic layer develops a color and exhibits red. When the ambient temperature exceeds 20 ° C., the color tone of the reversible thermochromic composition in the reversible thermochromic layer gradually decreases,
The color changes continuously from light red to pink, and when it exceeds 30 ° C., the reversible thermochromic composition is decolorized and appears white. When the white thermochromic footwear 1 falls from 23 ° C. to 13 ° C. again due to a change in environmental temperature, it becomes pink,
It changes color to light red and red continuously and has reversibility.

Example 2 (See FIGS. 2 and 9) After the non-thermochromic layer 5 is provided by printing a yellow non-thermochromic ink on the surface of the white campus cloth 21, the color is blue →→ colorless on the non-thermochromic layer. (As the temperature is reduced from 30 ° C. to 10 ° C., the density of blue gradually increases, and conversely, when the temperature is increased from 15 ° C. to 35 ° C., the density of blue gradually decreases. T ₁ : 1
_{0 ℃, T 2: 30 ℃} , T 3: 15 ℃, T 4: 35 ℃, T
₁ and the temperature difference 20 ° C. of T _2, T ₃ temperature difference and T ₄ 20 ° C.,
ΔH: 5 ° C.) The reversible thermochromic layer 3 is provided with a reversible thermochromic ink in which a microcapsule pigment enclosing the reversible thermochromic composition that changes color is changed to 40 parts of an acrylic ester resin on the uppermost layer. 4 parts of ultraviolet absorber, 0.4 parts of silicone defoamer, 20 parts of butyl acetate, aromatic medium boiling point solvent 15
Screen printing was performed with an ink in which the portions were uniformly mixed, and a coating layer 4 was provided. After cutting the reversible thermochromic fabric obtained as described above, the thermochromic footwear 1 was obtained by attaching the thermochromic fabric to the surface of the shoe via the adhesive layer 6.

In the thermochromic footwear 1, at an environmental temperature of 10 ° C. or less, the non-thermochromic layer and the reversible thermochromic layer A develop a color to bluish green. When the ambient temperature exceeds 15 ° C., the color tone of the reversible thermochromic composition in the reversible thermochromic layer A gradually decreases, and the color gradually changes to green and yellowish green. The thermochromic composition fades and appears yellow. When the temperature drops from 35 ° C. to 10 ° C. again due to a change in the environmental temperature, the yellow thermochromic footwear continuously changes color to yellow-green, green, and blue-green, and has reversibility.

Example 3 (see FIGS. 3 and 10) Blue ← → colorless (T ₁ : 13 ° C., T
_{2: 22 ℃, T 3:} 15 ℃, T 4: 24 ℃, ΔH: 2
C)). The reversible thermochromic layer A31 was provided with a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that changes color to (° C) was uniformly dispersed. Furthermore, on the upper surface, blue ←
→ Colorless (T ₁ ′: 24 ° C., T ₂ ′: 33 ° C., T ₃ ′: 26 ° C.,
_{T 4 ': 35 ℃, ΔH} ': 2 ℃) reversibly thermochromic layer formed by the reversible thermochromic ink which the microcapsule pigment was uniformly dispersed containing therein a reversibly thermochromic composition changes color B3
2, the uppermost layer is an ink obtained by uniformly mixing 40 parts of an acrylate resin, 4 parts of an ultraviolet absorber, 0.4 parts of a silicon-based defoamer, 20 parts of butyl acetate, and 15 parts of an aromatic medium boiling point solvent. Then, screen printing was performed, and a coating layer 4 was provided. Thus, thermochromic footwear 1 was obtained.

The thermochromic footwear 1 has a reversible thermochromic layer A31 and a reversible thermochromic layer B at an environmental temperature of 13 ° C. or less.
32 develops color and appears blue-violet. On the other hand, when the temperature exceeds 15 ° C., the reversible thermochromic composition in the reversible color-changing layer A31 loses its color, and the blue color gradually becomes thinner, and the color becomes reddish at 24 ° C. . When the temperature further rises and exceeds 26 ° C., the reversible thermochromic composition in the reversible color-changing layer B32 starts to lose color, and the blue color becomes thinner and 35 ° C.
When it reaches, it appears pink. The above-mentioned color change is visually observed continuously in the course of heating from 15 ° C. to 35 ° C. In addition, the pink thermosensitive discolorable footwear has a reversibility by visually discoloring continuously from pink to bluish purple when the outside temperature falls from 33 ° C. to 13 ° C. again due to a change in environmental temperature. .

Example 4 (see FIGS. 4 and 10) Blue ← → colorless (T ₁ : 13 ° C., T
_{2: 23 ℃, T 3:} 18 ℃, T 4: 28 ℃, ΔH: 7
C)). The reversible thermochromic layer A31 was provided with a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that changes color to (° C) was uniformly dispersed. Furthermore, on the upper surface, blue ←
→ Colorless (T ₁ ′: 20 ° C., T ₂ ′: 30 ° C., T ₃ ′: 25 ° C.,
(T ₄ ′: 35 ° C., ΔH ′: 7 ° C.) A reversible thermochromic layer B3 formed of a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that uniformly changes color is uniformly dispersed.
2, the uppermost layer is an ink obtained by uniformly mixing 40 parts of an acrylate resin, 4 parts of an ultraviolet absorber, 0.4 parts of a silicon-based defoamer, 20 parts of butyl acetate, and 15 parts of an aromatic medium boiling point solvent. Then, screen printing was performed, and a coating layer 4 was provided. Thus, thermochromic footwear 1 was obtained.

The thermochromic footwear 1 has a reversible thermochromic layer A31 and a reversible thermochromic layer B at an environmental temperature of 13 ° C. or less.
32 develops color and appears blue-violet. On the other hand, when the temperature exceeds 18 ° C., the reversible thermochromic composition in the reversible color-changing layer A31 loses its color, and the blue color gradually becomes thinner and appears purple, and at around 25 ° C. it appears reddish purple. . In addition, 25 ° C
Is exceeded, the reversible thermochromic composition in the reversible color-changing layer B32 also begins to lose color, and the blue color becomes lighter. The above color change is from 18 ° C to 3
In the process of heating to 5 ° C., it is visible continuously. In addition, the pink thermochromic footwear has a reversibility by continuously changing color from pink to bluish purple when the outside temperature falls from 30 ° C. to 13 ° C. due to a change in environmental temperature again.

Example 5 (see FIGS. 5 and 10) Blue ← → colorless (T ₁ : 13 ° C.)
T ₂ : 23 ° C., T ₃ : 20 ° C., T ₄ : 30 ° C., ΔH: 7
C)). The reversible thermochromic layer A31 was provided with a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that changes color to (° C) was uniformly dispersed. Furthermore, on the upper surface, blue ←
→ Colorless (T ₁ ′: 18 ° C., T ₂ ′: 28 ° C., T ₃ ′: 25 ° C.,
_{T 4 ': 35 ℃, ΔH} ': 7) reversibly thermochromic layer formed by the reversible thermochromic ink which the microcapsule pigment was uniformly dispersed containing therein a reversibly thermochromic composition changes color B32
Is provided on the uppermost layer with an ink obtained by uniformly mixing 40 parts of an acrylate resin, 4 parts of an ultraviolet absorber, 0.4 parts of a silicon-based antifoaming agent, 20 parts of butyl acetate, and 15 parts of an aromatic medium boiling point solvent. Screen printing was performed, and the coating layer 4 was provided.
Thus, thermochromic footwear 1 was obtained.

The thermochromic footwear 1 has a reversible thermochromic layer A31 and a reversible thermochromic layer B at an environmental temperature of 13 ° C. or less.
32 develops color and appears blue-violet. If the temperature exceeds 18 ° C., the reversible thermochromic composition in the reversible color-changing layer A31 is decolorized and the blue color becomes thin. If the temperature exceeds 25 ° C., the reversible thermochromic composition in the reversible color-changing layer B32 also becomes As the color starts to fade, the blue color becomes lighter and reddish purple, and when it reaches 35 ° C., it becomes pinkish. The above color change is from 20 ° C to 3
In the process of heating to 5 ° C., it is visible continuously. In addition, the pink thermosensitive color-change footwear changes color from red to purple and purple continuously when the temperature falls from 30 ° C. to 13 ° C. again due to a change in environmental temperature, and has reversibility.

Example 6 (See FIGS. 6 and 11) After the pink non-thermochromic ink is printed on the surface of the white campus fabric 21 to provide the non-thermochromic layer 5, a blue color is formed on the non-thermochromic layer 5. → colorless _{(T 1: 20 ℃, T} 2: 26 ℃, T
₃ : 22 ° C., T ₄ : 28 ° C., ΔH: 2 ° C.) A reversible thermochromic layer A3 using a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that uniformly changes color is uniformly dispersed.
1 was provided. Further, on the upper surface, blue ← → colorless (T ₁ ': 2
2 ° C., T ₂ ′: 28 ° C., T ₃ ′: 24 ° C., T ₄ ′: 30 ° C., Δ
H ′: 2 ° C.) A reversible thermochromic layer B32 formed of a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that changes color to H ′: 2 ° C. is uniformly dispersed, and then blue →→ colorless (T ₁ ) _{: 24 ℃, T 2 ":} 30 ℃, T 3": 26
C., T ₄ ": 32 ° C., ΔH": 2 ° C.) provided with a reversible thermochromic layer C33 formed of a reversible thermochromic ink in which a microcapsule pigment containing a reversible thermochromic composition that uniformly changes color is dispersed. Acrylate resin 40 on the top layer
Parts, an ultraviolet absorber 4 parts, a silicon-based antifoaming agent 0.4 parts, butyl acetate 20 parts, and an aromatic medium boiling point solvent 15 parts were uniformly screen-printed with an ink to form a coating layer 4. . After cutting the reversible thermochromic fabric obtained as described above, it was sewn on the surface of the shoe 2 as footwear to obtain thermochromic footwear 1.

In the thermochromic footwear 1, at an ambient temperature of 20 ° C. or less, the reversible thermochromic layers A33, B32, and C31 develop a color and exhibit a blue-violet color. When the ambient temperature exceeds 22 ° C,
The color of the reversible thermochromic composition in the reversible thermochromic layer A31 starts to fade, and the blue color becomes pale and purple. In addition, 24
When the temperature exceeds ° C, the reversible thermochromic composition in the reversible color-changing layer B32 also starts to lose color, and the blue color becomes lighter and reddish purple. Further, when the temperature exceeds 26 ° C., the reversible thermochromic composition in the reversible color-changing layer C33 starts decoloring, and the blue color becomes thinner. When the temperature reaches 32 ° C., the reversible thermochromic compositions in all the reversible color-changing layers are changed. It fades and appears pink. The above-mentioned color change is continuously observed during the process of heating from 22 ° C to 32 ° C. In addition, the temperature change discoloration footwear of the pink color has a temperature of 30 ° C. to 20 ° C. again due to a change in environmental temperature.
As it descends, it changes color continuously to reddish purple, purple, and blue purple, and has reversibility.

Example 7 (See FIGS. 7 and 12) Dark green ← → colorless (T ₁ : 20)
_{℃, T 2: 24 ℃,} T 3: 24 ℃, T 4: 28 ℃, Δ
H: 4 ° C.), a microcapsule pigment A containing a reversible thermochromic composition, and blue →→ colorless (T ₁ ′: 24)
_{℃, T 2 ': 28 ℃} , T 3': 28 ℃, T 4 ': 32 ℃, Δ
H ′: 4 ° C.), a microcapsule pigment B containing a reversible thermochromic composition, and a pink color →→ colorless (T ₁ ):
_{28 ℃, T 2 ": 32} ℃, T 3": 32 ℃, T 4 ": 36 ℃,
ΔH ″: 4 ° C.) The reversible thermochromic layer 3 is provided by a microcapsule pigment C containing a reversible thermochromic composition that changes color to 4 ° C.) and an ink in which a yellow non-thermochromic ink is uniformly dispersed.
In the upper layer, 40 parts of polyurethane resin and ultraviolet absorber 4
Parts, a silicone-based antifoaming agent 0.5 parts, xylene 25 parts, and cyclohexanone 20 parts were uniformly screen-printed with an ink to form a coating layer 4. After cutting the reversible thermochromic fabric obtained as described above, shoes 2 are used as footwear.
To obtain a thermochromic footwear 1.

In the thermochromic footwear 1, the microcapsule pigments A, B, and C in the reversible thermochromic layer 3 develop color at an environmental temperature of 20 ° C. or less, and exhibit a black color. Environmental temperature is 24 ° C
Is exceeded, the microcapsule pigment A in the reversible thermochromic layer 3 begins to lose color, and is visually observed from black to dark brown and brown. When the temperature exceeds 28 ° C., the color of the microcapsule pigment B starts to be erased, and the color is observed from brown to reddish brown. Further 32 ° C
When the temperature exceeds 36 ° C., the microcapsule pigment C starts to lose color, and the color changes from reddish brown to red and orange. When the temperature exceeds 36 ° C., the yellow color due to the yellow non-thermochromic ink is observed. In the process of heating the color change from 24 ° C to 36 ° C,
Visually continuous. In addition, the yellow thermochromic footwear changes its temperature from 32 ° C. to 20 ° C. again due to a change in environmental temperature.
As it descends, it changes color continuously from yellow to orange, red, reddish brown, brown, dark brown and black, and has reversibility.

Example 8 (see FIG. 7) Green ← → colorless on white synthetic fabric surface (T ₁ : 20 ° C.,
T ₂ : 24 ° C., T ₃ : 24 ° C., T ₄ : 28 ° C., ΔH: 4
C), and a microcapsule pigment A containing a reversible thermochromic composition that changes color to blue (→ T ₁ ′: 24 ° C.
T ₂ ′: 28 ° C., T ₃ ′: 28 ° C., T ₄ ′: 32 ° C., ΔH ′:
(4 ° C.), a microcapsule pigment B containing a reversible thermochromic composition, and a pink color →→ colorless (T ₁ ): 28
_{℃, T 2 ": 32 ℃} , T 3": 32 ℃, T 4 ": 36 ℃, Δ
H ": 4 ° C.) A reversible thermochromic layer is provided with a microcapsule pigment C containing a reversible thermochromic composition discoloring to 4 ° C.) and an ink in which a yellow non-thermochromic ink is uniformly dispersed. Silver pearlescent pigment 10 having a particle size of 10 to 60 μm, the surface of which is coated with 29% by weight of titanium oxide
Parts, polyurethane resin 40 parts, ultraviolet absorber 4 parts, silicon-based antifoaming agent 0.5 part, xylene 25 parts, cyclohexanone 20 parts, and uniformly screen-printed with silver pearlescent pigment ink. Layers were provided.
After the reversible thermochromic fabric obtained as described above was cut, it was sewn on the surface of the shoe 2 as footwear to obtain a metallic luster thermochromic footwear.

In the thermochromic footwear, the microcapsule pigments A, B, and C in the reversible thermochromic layer 3 are colored and blackened at an environmental temperature of 20 ° C. or less, so that the pearlescent pigment layer reflects the light. Silver color is visible. When the environmental temperature exceeds 24 ° C., the microcapsule pigment A in the reversible thermochromic layer 3 starts to lose color, and is visually observed from silver to blue through a metallic silvery purple. When the temperature exceeds 28 ° C., the color of the microcapsule pigment B starts to disappear, and a pink color is visually perceived through purple and reddish purple. Further, when the temperature exceeds 32 ° C., the microcapsule pigment C starts to lose color. The color changes from pink to pale pink. The above-mentioned color change is continuously observed in the course of heating from 24 ° C. to 36 ° C. In addition, the yellow thermochromic footwear is white, pale pink, pink, magenta, purple, bluish purple when the temperature falls again from 32 ° C. to 20 ° C. due to a change in environmental temperature. It has a reversibility by continuously discoloring to silver metallic bluish purple and silver.

[0037]

According to the present invention, the color of the surface of the footwear is continuously changed to the same color in shades, similar colors, or intermediate colors in various regions where the temperature and the temperature change are different. It is possible to provide thermochromic footwear with high convenience and decorativeness. In addition, by providing a non-thermochromic layer below the reversible thermochromic layer, while exhibiting the color change described above, it is possible to see a more versatile color tone or pattern,
A highly versatile thermochromic footwear can be provided.

[Brief description of the drawings]

FIG. 1 is a graph showing a temperature-color density curve of a reversible thermochromic composition of an example of the present invention.

FIG. 2 is a graph showing a temperature-color density curve of a reversible thermochromic composition of another example of the present invention.

FIG. 3 is a graph showing a temperature-color density curve of a reversible thermochromic composition of another example of the present invention.

FIG. 4 is a graph showing a temperature-color density curve of a reversible thermochromic composition according to another example of the present invention.

FIG. 5 is a graph showing a temperature-color density curve of a reversible thermochromic composition of another example of the present invention.

FIG. 6 is a graph showing a temperature-color density curve of a reversible thermochromic composition of another example of the present invention.

FIG. 7 is a graph showing a temperature-color density curve of a reversible thermochromic composition of another example of the present invention.

FIG. 8 is an explanatory longitudinal sectional view of an essential part of another embodiment of the thermochromic footwear of the present invention.

FIG. 9 is an explanatory longitudinal sectional view of an essential part of another embodiment of the thermochromic footwear of the present invention.

FIG. 10 is an explanatory longitudinal sectional view of a main part of another example of the thermochromic footwear of the present invention.

FIG. 11 is an explanatory longitudinal sectional view of a main part of another embodiment of the thermochromic footwear of the present invention.

FIG. 12 is a vertical sectional view of a main part of another embodiment of the thermochromic footwear of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermochromic footwear 2 Footwear 21 Fabric 3 Reversible thermochromic layer 31 Reversible thermochromic layer A 32 Reversible thermochromic layer B 33 Reversible thermochromic layer C 4 Coating layer 5 Non-thermochromic layer 6 Adhesive layer

Claims (7)

[Claims] 1. A thermosensitive color-changing footwear provided with a reversible thermochromic layer that variously discolors with a change in temperature, wherein the reversible thermochromic layer has a color change temperature of -20 ° C to 40 ° C. A microcapsule pigment having a particle size of about 0.5 to 50 μm is fixed in a dispersed state in a binder, and the reversible thermochromic composition has a first temperature-color density curve. In the process of increasing the temperature in the hue state, when the temperature reaches the second temperature T ₃ , the first hue begins to change color, and the second hue is completely removed in a temperature range higher than the second temperature T ₃ and higher than the temperature T ₄ . Hue, the reversible thermochromic composition is in the second hue state, and in the process of decreasing the temperature, the first temperature T
_When the second hue is reached, the second hue begins to change color and the first temperature T ₂
The first hue is completely obtained in a temperature range equal to or lower than the lower temperature T ₁ , wherein the temperature difference between T ₁ and T _{2 and} the temperature difference between T ₃ and T ₄ are in the range of 2 ° C. to 30 ° C. A thermochromic footwear having a function of exhibiting an intermediate hue between the hue and the second hue. 2. A thermosensitive color-changing footwear provided with a reversible thermochromic layer that changes color by a change in temperature, wherein the reversible thermochromic layer comprises:
A layer formed by blending or laminating a plurality of microcapsule pigments each containing a plurality of reversible thermochromic compositions each having a discoloration temperature of −20 ° C. to 40 ° C. and a particle size of about 0.5 to 50 μm, reversible thermal discoloration composition temperature - with respect to color density curve, in the process of temperature in the first color state is increased and reaches the second temperature T _3, the first color begins to discolor, the second temperature become completely second color at a temperature T ₄ or more temperature range from T _3, in the process of the reversible thermochromic composition temperature in the second color state is lowered, the first temperature T
_When the second hue is reached, the second hue begins to change color and the first temperature T ₂
Become completely the first color at a lower temperature T ₁ below the temperature range, the midpoint T of the T ₁ midpoint T ₅ and T ₃ of the T ₂ and T _4
The hysteresis width (ΔH) showing the temperature width of ₆ is 7 ° C. or less, and the following general formulas (1) and (2) are obtained with respect to the temperatures T ₃ ′ and T ₁ ′ of the adjacent reversible thermochromic compositions. Thermochromic footwear characterized by satisfying. T ₄ + 2 ≧ T ₃ ′ (1) T ₂ +2 ≧ T ₁ ′ (2) 3. The thermochromic footwear according to claim 2, wherein said general formula satisfies (1) and (2). T ₄ ≧ T ₃ ′ (1) T ₂ ≧ T ₁ ′ (2) 4. The thermochromic footwear according to claim 1, wherein the reversible thermochromic composition has a hysteresis width (ΔH) of 5 ° C. or less. 5. A reversible thermochromic layer is formed by pasting or sewing a thermochromic die-cut image on the surface of footwear.
Thermochromic footwear. 6. The thermochromic footwear according to claim 1, wherein a coating layer containing a light-shielding pigment and / or a light stabilizer is formed on an upper layer of the reversible thermochromic layer. 7. The thermochromic footwear according to claim 1, wherein a non-thermochromic layer is provided below the reversible thermochromic layer, and is configured to be concealable by a change in temperature.