JPH10323930A - Sheeny thermochromic laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance uniquely fine sight and also unique device effects and thereby make a product best suited to requirements in the field of toys and decorations by forming a reversibly thermochromic layer on the surface of a support and then a protecting layer on the reversibly thermochromic layer and finally a sheeny pattern layer on the protecting layer. SOLUTION: A tricot cloth of 50-denier white nylon fiber as a support 2 is printed with reversibly thermochromic properties and the printed coat cured by drying to obtain a reversibly thermochromic layer 3. Further, a pattern of a plurality of starts is printed on the reversibly thermochromic layer 3 using a 60-mesh screen process printing with a hot melt adhesive of an ethylene-vinyl acetate copolymer sin emulsion to form an adhesive layer 4. After drying the adhesive layer 4, it is joined with the metallic sheen layer side of a hologram film transfer film and these layers are brought into contact with each other under pressure for 10 sec. using a hot plate heated at 150 deg.C. Next, the layers are cooled down to a room temperature and the base sheet of the transfer film is peeled to obtain a sheeny thermochromic laminate 1 with the reversibly thermochromic layer 3, on the upper surface of which a sheeny star pattern layer 5 with a silvery metallic sheen is transferred.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a brilliant thermochromic laminate. More specifically, the present invention relates to a brilliant thermochromic laminate capable of giving a brilliant design a different taste by a thermochromic effect.

[0002]

2. Description of the Related Art There has been disclosed a brilliant thermochromic body in which a thermochromic layer is provided on the surface of a support, and fine particles having a brilliant property are fixed on the thermochromic layer in a dispersed state (Japanese Patent Laid-Open No. Hei 7 (1999)). -2
No. 76805). The brilliant thermochromic material described above has a brilliant effect of fine particles having a brilliancy fixed in a dispersed state,
It has a feature that it is effectively or hardly seen depending on the color tone of the thermochromic layer, and can be applied to various decorative fields. However, the color effect obtained by fixing the glittering fine pieces on the reversible thermochromic layer in a dispersed state, so-called disorder, is monotonous,
Therefore, its use is limited.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned disadvantages of the conventional thermochromic material which fixes a photoluminescent material in a dispersed state on the thermochromic layer. That is, by providing a pattern layer having glitter on the reversible thermochromic layer, it is possible to enhance a more specific aesthetic and decorative effect, and to provide a glitter thermochromic laminate suitable for toys and decorative fields. .

[0004]

According to the present invention, there is provided a photothermographic layer comprising a reversible thermochromic layer provided on the surface of a support, and a glitter pattern layer partially provided on the reversible thermochromic layer. A requirement is a brilliant thermochromic laminate in which a reversible thermochromic material is dispersed in a support, or a brilliant design layer is partially provided on the support. Furthermore, the area ratio between the visible reversible thermochromic part and the glittering pattern is 10:90.
９９99: 1, a reversible thermo-discolored portion is visible around the glittering pattern, and the glittering pattern layer has a brightness reflection property, a light interference property, an iris property, a hologram property, a metal glossiness,
A layer exhibiting optical properties selected from pearl luster, that the pattern of the glittering pattern layer is formed by aggregation of glittering fine pieces, a protective layer is provided on the reversible thermochromic layer, It is required that a glitter pattern layer is disposed thereon, that the support is a fabric, that a glitter thermochromic laminate is used to form a doll costume, and the like.

As the support, paper, synthetic paper, synthetic leather, leather, plastic, glass, porcelain, wood, stone, etc. are used, and preferably, plastic films, woven fabrics, knits, braids, non-woven fabrics, lace fabrics And the like. Further, the form may be a planar form or an uneven form. Further, as the support, specifically, toys such as doll costumes, accessories, indoor equipment,
Clothes, footwear, rugs, sports equipment and the like can be mentioned.

The reversible thermochromic layer provided on the support has a reversible thermochromic layer containing three components of an organic compound medium which reversibly causes a color reaction between the electron-donating color-forming organic compound and the electron-accepting compound. A discolorable composition is used. In particular,
JP-B-51-35414, JP-B-51-4470
No. 6, JP-B-51-44708, JP-B-52-44
No. 7764, Japanese Patent Publication No. 1-17154, Japanese Patent Publication No.
No. 29398, JP-A-7-186546 and the like. The above is the predetermined temperature (discoloration point)
The color changes before and after the boundary, and only one specific state can exist in the room 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 appear is applied, but returns to the state exhibited in a normal temperature range when the heat or cold is not applied, that is, a so-called temperature change. Is a type in which a small hysteresis width (ΔH) is shown for the temperature-one-color density due to the color change.

Also, Japanese Patent Publication No. 4-171 proposed by the present applicant.
No. 54, JP-A-7-179777, JP-A-7-179777
The thermosensitive color-changing color memory composition which exhibits large hysteresis characteristics and discolors described in, for example, JP-A-339997, that is, the shape of a curve plotting a change in coloring density due to a temperature change indicates a temperature in a discoloration temperature range. A type of discoloring material that changes color following a significantly different path when the temperature is increased from a lower temperature side and conversely when the temperature is decreased from a higher temperature side than the discoloration temperature. A reversible thermochromic composition having a characteristic of being able to memorize and retain a state changed at a temperature below the low-temperature side discoloration point or above the high-temperature side discoloration point in a normal temperature range between the points is also effective.

Although the above-mentioned reversible thermochromic composition is effective when used as it is, it is preferable to use it in a microcapsule. That is, under various use conditions, the reversible thermochromic composition is maintained at the same composition and can exert the same function and effect. By being encapsulated in the microcapsules, a chemically and physically stable pigment can be constituted, and the range of particle diameter of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm satisfies practicality. 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. Further, a secondary resin film may be further provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

The reversible thermochromic composition or the microcapsule pigment containing the same is dispersed in a medium containing a binder which is a film-forming material and applied as a reversible thermochromic material such as ink or paint. A thermochromic layer can be formed. The reversible thermochromic composition or the microcapsule pigment containing the same is contained in the binder in an amount of 0.5 to 1%.
00% by weight, preferably 1 to 75% by weight. If the amount is less than 0.5% by weight, a clear thermochromic effect is difficult to visually recognize, and if it exceeds 100% by weight, the color is excessive, is in a decolored state, and residual color is observed.

[0010] The reversible thermochromic composition may be a vinyl chloride-vinyl acetate copolymer resin, a hindered amine compound selected from piperidine derivatives, a vinyl chloride-vinyl acetate-vinyl alcohol copolymer, a vinyl chloride-vinylidene chloride copolymer. A polymer or the like is blended in a dispersed state in a vinyl chloride-vinyl acetate copolymer resin matrix to form a reversible thermochromic layer, or the reversible thermochromic material is mixed in a saturated copolymerized polyester resin matrix with fine particles. And then dispersed to form a reversible thermochromic layer.

The reversible thermochromic layer can be formed by a conventionally known method, for example, printing means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition. It can be formed by means such as coating, flow coating, roller coating, and dip coating.

The reversible thermochromic layer is not limited to a layer formed as a coating film, but may be formed of a plastic material formed by blending a thermochromic composition or a microcapsule pigment containing the same. Good. Further, the reversible thermochromic composition or a microcapsule pigment containing the same can be blended in a support.

As a method for forming the glitter pattern layer provided on the reversible thermochromic layer, for example, a glitter transfer foil which is generally commercially available is used. The glittering transfer foil has a structure in which a release layer, a glittering layer, a generally used adhesive layer or a hot melt adhesive layer are sequentially laminated on a film substrate. In addition, even if the adhesive or the hot melt adhesive is not applied, it can be used by providing an adhesive layer.

Further, a hologram film can be used. The hologram film is formed by pressing a hologram master plate having a hologram image formed on various resins, performing embossing, and forming an Al, C on the embossed resin layer.
r, Ni, Sn, Fe, Co, Cu, Pb, Sb, M
Those formed by evaporating a metal such as g, Cd, or Bi are preferably used.

When a hologram is used as the glittering design layer, a commercially available hologram transfer foil is preferably used. The hologram transfer foil has a configuration in which a release layer, an embossed resin layer, a metal deposition layer, a generally used adhesive layer or a hot melt adhesive layer are sequentially laminated on a film substrate. In addition, even if the adhesive or the hot melt adhesive is not applied, it can be used by providing an adhesive layer. As the hologram transfer foil suitably used in the present invention, a PET film (biaxially-stretched polyethylene terephthalate) having a thickness of 12 to 75 μm, a nylon film having a thickness of 12 to 100 μm, and a thickness of 12 to 50 μm
A film using a polypropylene film having a thickness of m, a hard vinyl chloride film having a thickness of 16 to 50 μm, or the like is suitably used in terms of dimensional stability and cost. The release layer is used to facilitate peeling of the film substrate at the time of transfer, and an acrylic resin, an amino alkyd resin, a urethane resin, an epoxy resin, a vinyl acetate resin or the like having a thickness of 0.5 to 5 μm can be used. .

Also, an iris thin film can be used. As the iris thin film, a conventionally known structure is effective. Specifically, one composed of a transparent thin film layer and a transparent thin film layer having irregularities (the transparent thin film layer is titanium oxide,
Metal compound thin film layers exemplified by silicon oxide, zinc oxide, antimony oxide, zinc sulfide, magnesium fluoride, calcium fluoride, etc., copolymers of vinylidene chloride with vinyl chloride, vinyl acetate, vinyl alcohol or polyvinyl chloride Thin film layer with fine bubbles due to gas generated by decomposition of any of polyvinylidene chloride, polystyrene and thermoplastic resin such as vinyl chloride, styrene and copolymer by light, heat, etc., vinyl copolymer , A cellulose-based copolymer, a urethane-based copolymer and various curing agents for curing the same, a composition having a curable functional group, a thin film layer comprising an organic-substituted silicon-based compound, and oxidation with the organic material. A thin film layer made of inorganic fine particles such as titanium, aluminum oxide, and zirconium oxide. The layer and the refractive index difference is 0.05 or more, the visible light transmittance is about 10% or more is an uncolored or colored transparent thin film layer, and may further have light scattering on the surface and inside of the film, Visible light transmittance 50%
Examples thereof include a release layer, a resin layer, if necessary, the iris thin film layer, a generally used adhesive layer and a hot melt adhesive on a film substrate. An iris transfer foil in which layers are sequentially laminated is preferably used. In addition, even if the adhesive or the hot melt adhesive is not applied, it can be used by providing an adhesive layer. Also, an iris film provided with the iris thin film layer on a transparent film, and an optical interference pattern film provided on one or both surfaces with a vapor deposited layer comprising one or more of oxides, sulfides, and fluorides (Japanese Patent Application Laid-Open No. No. 60-32645)) A transparent multilayer film exhibiting a light interference phenomenon in which at least 100 layers made of polymers having different refractive indices made of two or more polymers are provided in an intermediate layer (US: THE MEARL)
CORPORATION, trade name: MEARL I
RIDESCENTFILM) or the like can also be used.

Further, pearlescent pigments can also be used.
The pearlescent pigments include conventionally known pearlescent pigments such as titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, lead acid arsenate, and bismuth oxychloride. Can be applied, and dispersed in a medium containing a binder and applied as a form of paint, ink, or the like. Alternatively, the pigment may be contained in a dispersed state in a thermoplastic resin or a thermosetting resin.

As the pearlescent pigment, a metallic pearlescent pigment in which the surface of natural mica particles is coated with titanium oxide, and a metallic pearlescent pigment in which the titanium oxide layer is coated with iron oxide are also used. In addition, dichroic pearlescent pigments coated on a titanium oxide coating with a non-thermochromic colored dye are also used.

The pearlescent pigment can be formed into a paint by dispersing the pearlescent pigment in a medium containing a binder. Further, in the case of a thermoplastic binder, the binder is in a molten state, a pearlescent pigment layer is blended in a dispersed state, and a glittering pattern layer is formed using a thin film and a pearlescent pigment layer in the form of a film which are integrally formed. It may be formed.

In the case where the glitter pattern layer is in the form of a film, the glitter pattern layer is formed by an appropriate means selected by a conventionally known method, for example, a method such as high frequency fusing, cutting, Thomson punching, punching, etching and the like. A pattern layer can be formed. Further, the above-mentioned material exhibiting the glittering property is finely cut to form minute pieces, and is fixed regularly on the reversible thermochromic layer, so that characters, symbols, figures, and the like, which are visible as an aggregate of minute pieces, are formed. Symbols can be formed as appropriate. When the individual minute pieces form characters, symbols, figures, and the like, the glitter pattern layer may be formed by being irregularly fixed on the reversible thermochromic layer. The size and shape of the minute piece are not particularly limited, but examples of the shape of the minute piece include polygons such as a triangle and a quadrangle, a star, a circle, and a line. In the system in which the pattern is formed by the fine pieces, even if the support is a flexible material such as cloth,
Since the performance is not hindered and the light is irregularly reflected, the thermochromic effect and the brilliant effect can be seen regardless of the visual position. Further, in a system in which a pattern is formed by the aggregate of the fine pieces, the fine pieces in the layer are non-planarly fixed by forming the layer three-dimensionally by containing various resins in the design layer, The diffuse reflection of light can be further emphasized. Further, when the base material on which the minute pieces are provided is a mesh-shaped member such as lace cloth, it is difficult to fix the minute pieces. Therefore, a pattern layer is formed in advance on the surface or the back surface of the member with an appropriate material. Thereafter, the minute piece can be fixed to the portion where the symbol layer is provided.

The laminated structure of the brilliant thermochromic layer includes:
It is formed by laminating a glitter layer exhibiting optical properties such as light luminance reflectivity, light coherence, iris, hologram, metallic luster, and pearl luster on the reversible thermochromic layer. When a material having no light transmittance as a layer, for example, an aluminum vapor-deposited film or a hologram film in which a metal is vapor-deposited on an embossed surface is used, a laminate having more glitter and thermochromic properties can be obtained.

The glitter pattern layer may be formed by laminating a plurality of glitter pattern layers having different optical properties or may be used in combination. Similarly, the reversible thermochromic layer may be formed by laminating a plurality of reversible thermochromic layers having different colors and / or color-changing temperatures, or may be used in combination.

The adhesive for fixing the glitter pattern layer includes acrylic resin, vinyl acetate resin, urethane resin, epoxy resin, diacryl phthalate resin, olefin resin, vinyl chloride resin, polyester resin, polyamide resin and the like. No. Examples of the bonding method include a method such as heat fusion and ultrasonic fusion in addition to bonding with an adhesive.

The area ratio between the reversible thermochromic portion and the glitter pattern, which can be visually recognized in the glitter thermochromic laminate thus constituted, is 10:90 to 99: 1, preferably 15:85.
When it is within the range of from 95: 5, more preferably from 25:75 to 90:10, both the glittering effect and the thermochromic effect can be satisfied. 1 visible reversible thermochromic area
When the content is 0% or less, the thermochromic effect is not sufficiently observed, so that the brilliancy due to the brilliant design is emphasized, and the brilliant thermochromic laminate that should show two different states is less likely to cause a difference. Lack of taste. On the other hand, if the visible reversible thermochromic portion exceeds 99%, the color change is emphasized, making it difficult for the glitter effect to be sufficiently recognized, and lacking in decorativeness. Furthermore, when the reversible thermochromic portion is configured to be visible around the glittering pattern, the outline of the glittering pattern is emphasized or not emphasized by the color change of the reversible thermochromic portion that changes color due to temperature change. Therefore, a brilliant thermochromic laminate that is more variable can be obtained.

A protective layer of a film, a transparent resin or the like can be provided between the support and the glitter pattern layer or on the glitter pattern layer. By providing the protective layer, it is possible to protect the thermochromic function and the glittering property, so that it is possible to prevent a decrease in quality during production and to prevent a decrease in the glittering property and thermochromic property during use.

In the above-described structure of the brilliant thermochromic laminate, a light stabilizer is contained in the reversible thermochromic layer or the protective layer.
A layer containing a light stabilizer can be provided as appropriate. Specifically, the light stabilizer is selected from an ultraviolet absorber, an antioxidant, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone decolorant, a visible light absorber, and an infrared absorber. It is a light stabilizer. In addition, an anti-aging agent, an antistatic agent, a polarity-imparting agent, a thixotropic agent, an antifoaming agent and the like can be added to each layer as needed to improve the function.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to embodiments. The term "parts in the compounding" means parts by weight. Example 1 (see FIGS. 1, 2, and 3) A microcapsule pigment in which a reversible thermochromic composition is encapsulated in a tricot cloth made of 50-denier white nylon fiber as a support 2 [blue ← → colorless, color change temperature 30 ° C. ] 3
0 parts, 5 parts of pink fluorescent pigment, 50 parts of acrylate emulsion resin, 2 parts of thickener, 0.5 leveling agent
Parts, a defoamer 0.5 part, and a cross-linking agent 5 parts were uniformly dispersed, and after printing, the ink was dried and cured to form a reversible thermochromic layer 3.

On the reversible thermochromic layer 3, an adhesive layer 4 was formed by printing a hot-melt adhesive composed of an ethylene-vinyl acetate copolymer resin emulsion using a 60-mesh screen plate to form a plurality of star patterns. . After the adhesive layer is dried, it is bonded to the metallic gloss layer side of the hologram transfer film having silver metallic gloss, pressed on a hot plate heated to 150 ° C. for 10 seconds, and then cooled to room temperature and transferred. The film base sheet was peeled off, and a glittering thermochromic laminate 1 having a star-shaped glittering design layer 5 having a silver metallic luster transferred onto the upper surface of the reversible thermochromic layer 3 was obtained. In addition, the area ratio of the reversible thermochromic part and the glitter pattern visually observed from the upper surface of the glitter thermochromic laminate was 50:50.

At a temperature lower than about 30 ° C., the reversible thermochromic layer exhibits a purple color at a temperature of less than about 30 ° C. Thus, a star-shaped design having silvery metallic luster is visually recognized on the purple cloth, and the temperature of 30 ° C. or higher is observed. Then, since the reversible thermochromic layer changes color from purple to pink, a star-shaped design having silver metallic luster is visually recognized on the pink fabric. It should be noted that this aspect change is again 3
When the temperature is lower than 0 ° C., a star-shaped design having a silver metallic luster is visually recognized on the purple cloth, and can be repeated. In addition, in the laminate, a glittering design layer having hologram properties reflects light, and a star-shaped design having glitteriness is always visible, and the reversible thermochromic layer changes color due to a temperature change. An attractive fabric can be obtained.

Example 2 (see FIG. 4) A microcapsule pigment (green to colorless, discoloration temperature of 28) containing a reversible thermochromic composition in a tricot cloth made of 40-denier white polyester fiber as a support 2 was used.
30 ° C., 10 parts of a yellow fluorescent pigment, 50 parts of an acrylate emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent uniformly dispersed. The reversible thermochromic ink is printed on a 100-mesh screen plate and dried and cured to form a reversible thermochromic layer 3. Further, on the upper surface thereof, 5 parts of a benzotriazole-based ultraviolet absorber, 50 parts of an acrylic polyol resin, A resin solution comprising 0.5 part of a crosslinking agent, 25 parts of toluene and 25 parts of ethyl acetate was applied using a gravure plate having a plate depth of 120 μm, and dried and cured to form a protective layer 6.

Next, on the upper surface of the aluminum deposition, on the transfer surface side of a rainbow-colored metallic glossy multicolor transfer film colored red, pink, orange, yellow, green, blue, and purple with transparency, A hot melt adhesive made of a polyester resin emulsion is printed on a screen plate of 80 mesh with ABC characters, dried to form an adhesive layer, and then joined to the protective layer 6 and heated to 160 ° C. After pressing on a hot plate for 10 seconds,
After cooling to room temperature, the base film of the transfer film was peeled off, to obtain a glitter thermochromic laminate 1 in which the glitter layer 5 composed of the adhesive layer 4 and the letters ABC was formed on the protective layer 6. In addition, the area ratio of the reversible thermochromic part and the glitter pattern visually observed from the upper surface of the glitter thermochromic laminate was 80:20.

At a temperature of less than 28 ° C., the laminate is a multicolor AB having metallic luster on a yellow-green cloth.
The letter C is visible. At a temperature of 28 ° C. or higher, the yellow-green fabric turns yellow, so that multicolored ABC characters having metallic luster are visually recognized on the yellow fabric. When the temperature changes again to a temperature lower than 28 ° C., multicolor ABC characters are visually recognized on the yellow-green fabric and can be repeated. Further, in the laminate, a multi-colored character having a metallic luster reflects light, a character having a shining property is always visible, and the reversible thermochromic layer changes color due to a change in temperature. Can be obtained.

Example 3 (see FIG. 4) A microcapsule pigment containing a reversible thermochromic composition in a tricot cloth made of 40-denier white polyester fiber as a support 2 [green ← → colorless, discoloration temperature 28
30 ° C., 10 parts of a yellow fluorescent pigment, 50 parts of an acrylate emulsion resin, 2 parts of a thickener, 0.5 parts of a leveling agent, 0.5 parts of an antifoaming agent, and 5 parts of a crosslinking agent uniformly dispersed. The reversible thermochromic ink is printed on a 100-mesh screen plate, dried and cured to form a reversible thermochromic layer 3, and a benzotriazole-based ultraviolet absorber 5
, 50 parts of an acrylic polyol resin, 0.5 part of an isocyanate-based cross-linking agent, 25 parts of toluene, and 25 parts of ethyl acetate, using a gravure plate having a plate depth of 120 μm, followed by drying and curing to form a protective layer 6. Was formed.

Then, using a gold transfer foil film coated with a hot melt resin in advance, the protective layer side and the transfer surface of the transfer foil film are joined to form a continuous scale pattern in a convex shape. After pressing at 180 ° C. for 3 seconds on a hot plate and cooling to room temperature, the base film of the transfer foil film is peeled off, and the adhesive layer 4 and the golden scale pattern 5 on the protective layer 6 are formed. Brilliant thermochromic laminate 1 having
I got The area ratio between the reversible thermochromic portion and the glitter pattern as viewed from the upper surface of the glitter thermochromic laminate was 90:10.
Met.

At a temperature of less than 28 ° C., a continuous golden scale pattern was observed on the yellow-green fabric,
At a temperature of not less than ° C., the yellow-green color changes to yellow, and a golden continuous scale is visible on the yellow fabric. In addition, when the temperature changes again to a temperature lower than 28 ° C., a continuous scale pattern is visually recognized on the yellow-green fabric, and can be repeatedly performed. Further, in the laminate, a scale pattern having a metallic luster reflects light, and a scale pattern having a brilliant property is always visible, and the reversible thermochromic layer changes color due to a change in temperature, so that the laminate has a different taste. A fabric having the same can be obtained.

Example 4 (see FIG. 5) A microcapsule pigment containing a thermochromic color memory composition on a white polyester satin fabric as a support 2 [pink →→ colorless, coloring temperature 15 ° C., Color temperature 30
℃] 30 parts, acrylate emulsion resin 50
Part, thickener 2 parts, leveling agent 0.5 parts, defoamer 0.5
Parts, a reversible thermochromic ink formed by uniformly dispersing 5 parts of a cross-linking agent, and drying and curing to form a reversible thermochromic layer 3,
5 parts of a benzotriazole UV absorber from the upper surface,
A resin solution comprising 50 parts of an acrylic polyol resin, 0.5 part of an isocyanate-based crosslinking agent, 25 parts of toluene, and 25 parts of ethyl acetate is applied using a gravure plate having a plate depth of 120 μm, and dried and cured to form a protective layer 6. did.

On the upper surface of the protective layer 6, one side is 0.3-0.
An ink composed of 25 parts of silver hologram film fine pieces cut into a square of 5 mm, 75 parts of an acrylic emulsion adhesive, 0.5 parts of a thickener, and 0.1 parts of a defoamer was applied to a 40-mesh screen plate. Then, a continuous pattern having a wave pattern was printed and dried and cured to form a glittering design layer 5, thereby obtaining a glittering thermochromic laminate 1. The area ratio between the reversible thermochromic portion and the glitter pattern as viewed from the upper surface of the glitter thermochromic laminate is 9
5: 5.

When the laminate is cooled to 15 ° C. or lower, a continuous silver pattern of hologram film is visually observed on a pink satin cloth, and this aspect is maintained at a temperature of less than 30 ° C. When the laminate is heated to 30 ° C. or more, the pink color of the satin fabric changes to white, so that a continuous silver pattern is visually observed on the white satin fabric. It is kept at a temperature exceeding.
When the temperature changes to 15 ° C. or lower again, a continuous wave pattern can be visually recognized on the pink satin fabric, and the appearance change can be repeated. Further, in the laminate, the hologram film fine pieces having a metallic luster reflect light, and a wave pattern having a luminous property is always visible, and the reversible thermochromic layer changes color due to a change in temperature. An attractive fabric can be obtained.

Example 5 (See FIG. 6) As a support 2, a tricot fabric made of 15 denier white nylon fiber was used, and 40 parts of a reversible thermochromic pigment (blue →→ colorless, color change temperature 30 ° C.), polyurethane emulsion resin 50 parts, leveling agent 0.5 parts, defoaming agent 0.5
Parts were uniformly dispersed, a reversible thermochromic ink was prepared, applied using a spray gun, dried and cured to form a reversible thermochromic layer 3.

On the reversible thermochromic layer 3, an adhesive solution consisting of 80 parts of an ethylene-vinyl acetate copolymer resin emulsion-based adhesive, 2.0 parts of a thickener, and 0.2 parts of an antifoaming agent was applied to 40 parts.
A star screen pattern is printed on a mesh screen plate to form an adhesive layer 4, and from the upper surface thereof, a small piece of silver-evaporated aluminum foil cut into a rectangular shape of about 0.3 mm is placed on the adhesive layer 4.
After the adhesive layer was dried and cured through a 5-mesh sieve, the glitter pattern layer 5 was formed by removing the small pieces of the vapor-deposited foil fixed to the adhesive layer. Further, 25 parts of an acrylic polyol resin, 25 parts of a polyurethane resin,
A topcoat resin consisting of 5 parts of an isocyanate-based crosslinking agent, 50 parts of ethyl acetate, and 0.2 parts of an antifoaming agent was 150 μm deep.
Is coated using a gravure plate, dried and cured to form a protective layer 6
Was formed, and a brilliant thermochromic laminate 1 was obtained. The area ratio between the reversible thermochromic portion and the glitter pattern as viewed from the upper surface of the glitter thermochromic laminate was 40:60.

At room temperature below 30 ° C., a silver star is visible on the blue tricot fabric,
The blue tricot fabric having the above temperature turns white, and a silver star is visually recognized on the white tricot fabric.
When the temperature changes again to a temperature lower than 30 ° C., a silver star is visually recognized on the blue cloth, and this change can be repeated. In addition, the laminate is a small piece of aluminum vapor-deposited foil having a metallic luster reflects light, and a star having a luminous property is always visible, and the reversible thermochromic layer changes color due to a change in temperature. Fabrics having different flavors can be obtained.

Example 6 (see FIG. 7) 30 parts of a microcapsule pigment (blue ← → colorless, discoloration temperature 30 ° C.) in which a reversible thermochromic composition was encapsulated in a transparent polyester film 25 μm thick as a support 2 , 5 parts of a pink fluorescent pigment, 50 parts of an acrylic ester emulsion resin, 2 parts of a thickener, and a silicone leveling agent 1.0
Parts, a defoamer 0.5 part and a cross-linking agent 5 parts were uniformly dispersed and printed, and dried and cured to form a reversible thermochromic layer 3.

On the reversible thermochromic layer 3, one side is 0.3 to
25 parts of a silver hologram film fine piece cut into a square of 0.5 mm, 75 parts of an acrylic emulsion adhesive,
An ink consisting of 0.5 parts of a thickener and 0.1 parts of a defoamer
A star pattern was printed on a 0-mesh screen plate, dried and cured to form a glittering design layer 5 to obtain a glittering thermochromic laminate 1. The area ratio between the reversible thermochromic portion and the glitter pattern as viewed from the upper surface of the glitter thermochromic laminate is 3
0:70.

At temperatures below about 30 ° C., the laminate
An iris-shaped star pattern is visible on the purple reversible thermochromic layer. When the temperature of the reversible thermochromic layer becomes higher than 30 ° C, the purple color of the reversible thermochromic layer changes to pink. A star pattern having a characteristic is visible. When the temperature again becomes lower than 30 ° C., a star-shaped pattern is visually recognized on the purple film, and the appearance change can be repeated.
Further, in the laminate, a star-shaped pattern having iris reflects light, always has brilliancy, and since the reversible thermochromic layer changes color due to a change in temperature, it is possible to obtain a film having a different character. it can.

Example 7 (See FIG. 8) Pink, orange, yellow, green, and green were applied to a tricot cloth made of 40-denier white polyester fiber as the support 2.
A non-color-changing ink of blue and purple was printed in a band shape to form a rainbow-like non-color-changing layer 7. On the non-color-changing layer, 30 parts of a microcapsule pigment enclosing a reversible thermochromic composition (black ← → colorless, color change temperature 28 ° C.), 50 parts of an acrylate emulsion resin, 2 parts of a thickener, a leveling agent A reversible thermochromic ink prepared by uniformly dispersing 0.5 part, 0.5 part of an antifoaming agent and 5 parts of a crosslinking agent is printed on a 100-mesh screen plate, dried and cured to form a reversible thermochromic layer 3. Then, a gravure plate having a plate depth of 120 μm was further coated on the upper surface with a resin solution consisting of 5 parts of a benzotriazole-based ultraviolet absorber, 50 parts of an acrylic polyol resin, 0.5 part of an isocyanate-based crosslinking agent, 25 parts of toluene, and 25 parts of ethyl acetate. The protective layer 6 was formed by applying and drying and curing.

Then, on the transfer surface side of a rainbow-colored metallic glossy multicolor transfer film colored red, pink, orange, yellow, green, blue and purple with transparency on the upper surface of the aluminum vapor deposition, A hot-melt adhesive made of a polyester resin emulsion is printed on an 80-mesh screen plate with a pattern combining a star pattern and a straight line, dried to form an adhesive layer, and then joined to the protective layer 6, On a hot plate heated to 160 ° C,
After pressing for 10 seconds, the base film of the transfer film is peeled off by cooling to room temperature, and the glittering heat is formed on the protective layer 6 by forming the adhesive layer 4 and the glittering design layer 5 combining the star pattern and the straight line. A discolorable laminate 1 was obtained. In addition, the area ratio between the reversible thermochromic portion and the glitter pattern visually observed from the upper surface of the glitter thermochromic laminate was 85:15.

At a temperature of less than 28 ° C., a multicolor star pattern having metallic luster and a straight line are visually observed on the black fabric. When the temperature reaches 28 ° C or higher,
Since the reversible thermochromic layer becomes colorless, a rainbow-like color is visually recognized by the lower non-color-changing layer, and a star-shaped pattern having metallic luster and a straight line are visually recognized on the rainbow-colored fabric.
Note that, when the temperature changes again to a temperature lower than 28 ° C., a star-shaped pattern and straight-line characters are visually recognized on the black fabric, and this aspect change can be repeated. Further, in the laminate, a multi-colored pattern having a metallic luster reflects light, and a pattern having a brilliant property is always visible, and the reversible thermochromic layer changes color due to a change in temperature. Can be obtained.

Example 8 (See FIG. 5) Microcapsule pigment [blue-green to colorless, discoloration temperature 15 ° C.] on a white polyester satin cloth as a support 2
30 parts, yellow fluorescent pigment 10 parts, acrylate emulsion resin 50 parts, thickener 2 parts, leveling agent 0.5
Parts, an antifoaming agent 0.5 parts, and a cross-linking agent 5 parts uniformly dispersed, a reversible thermochromic ink discoloring from green to yellow, and a microcapsule pigment [blue ← → colorless, discoloration temperature 15 ° C.]
30 parts, a reversible thermochromic ink discolored from purple to pink prepared in the same manner except that 5 parts of pink fluorescent pigments were used, and microcapsule pigment [pink ← →
Colorless, discoloration temperature 15 ° C] A reversible thermochromic ink that changes color from red to yellow and a microcapsule pigment [pink ← → colorless] prepared by the same method except that 30 parts and 10 parts of a yellow fluorescent pigment were used. And a discoloration temperature of 15 ° C.] A reversible thermochromic layer 3 was printed by using a reversible thermochromic ink which changes color from purple to blue prepared in the same manner except that 30 parts and 2 parts of blue pigment were used. From the upper surface, 5 parts of a benzotriazole-based ultraviolet absorber, 50 parts of an acrylic polyol resin, 0.5 part of an isocyanate-based crosslinking agent,
A resin solution composed of 25 parts of toluene and 25 parts of ethyl acetate was applied using a gravure plate having a plate depth of 120 μm, and dried and cured to form a protective layer 6.

On the upper surface of the protective layer 6, one side is 0.3-0.
An ink composed of 25 parts of silver hologram film fine pieces cut into a square of 5 mm, 75 parts of an acrylic emulsion adhesive, 0.5 parts of a thickener, and 0.1 parts of a defoamer was applied to a 40-mesh screen plate. Then, a continuous pattern having a wave pattern was printed and dried and cured to form a glittering design layer 5, thereby obtaining a glittering thermochromic laminate 1. The area ratio between the reversible thermochromic portion and the glitter pattern as viewed from the upper surface of the glitter thermochromic laminate is 9
5: 5.

At a temperature of less than 15 ° C., a glittering wavy pattern is observed on green, purple and red fabrics. At a temperature of 15 ° C. or higher, the reversible thermochromic layer changes color, so that a glittering wavy pattern is visually observed on the yellow, pink and blue fabrics. In addition, this aspect change
When the temperature again becomes lower than 15 ° C., a wavy pattern is visually recognized on the green, purple, and red fabrics, and can be repeated.
In addition, the laminate has a different character because a glittering wave pattern reflects light, a glittering pattern is always visible, and the reversible thermochromic layer changes color due to a change in temperature. Can be obtained.

Application Example After the laminate obtained in Example 1 was cut and sewn, a doll dress was obtained. The doll dress showed a color change similar to that of Example 1, and a dress having rich glitter and having a different taste depending on the color change could be obtained.

Comparative Example 1 In the same manner as in Example 4, a brilliant thermochromic laminate in which the area ratio between the reversible thermochromic portion and the brilliant pattern viewed from the top surface was 99.9: 0.1 was formed. did. In the glitter thermochromic laminate, although the wave pattern by the glitter pattern layer is visible, the area of the reversible thermochromic portion is large, and the color change that reversibly changes from pink to white due to temperature change is emphasized. As a result, the glitter effect is hardly visually recognized and lacks decorativeness.

Comparative Example 2 In the same manner as in Example 4, a brilliant thermochromic laminate having a reversible thermochromic part and a brilliant design area ratio of 5:95 as viewed from the upper surface was formed. The brilliant thermochromic laminate, in which a wave pattern due to the brilliant design layer is visible, since the area of the brilliant design is large, the color reversibly changes from pink to white due to a temperature change in the reversible thermochromic portion. Because the color change is hard to be seen, and the thermochromic effect is not sufficiently seen, the glitter by the glitter pattern is emphasized, and it is difficult for the glitter thermochromic laminate, which should show two different states, to make a difference,
Lack of discoloration.

[0054]

The brilliant heat-modified laminate of the present invention is characterized in that a brilliant design layer is provided on the reversible thermochromic layer.
Since the glittering pattern can be given a different taste by the temperature change, it is possible to provide a glittering thermochromic laminate exhibiting a unique beauty and having a high decorative effect.
In addition, since the area ratio between the visible reversible thermochromic portion and the glitter pattern is in the range of 10:90 to 99: 1, the glitter thermochromic laminate excellent in balance between glitter effect and thermochromic effect. Can be provided. Furthermore, when the design of the glittering design layer is formed by a collection of glittering fine pieces, the applicable range can be expanded and a laminate excellent in the glittering effect can be provided.
In addition, by forming the support with a fabric, the texture of the fabric itself and the brilliancy and thermochromic properties are effectively exhibited while maintaining the flexibility, and the brilliancy excellent in remarkableness in the toy, decoration and the like fields. A thermochromic fabric can be provided, and the commercial value of doll costumes and the like can be further improved.

[Brief description of the drawings]

FIG. 1 is an explanatory longitudinal sectional view of one embodiment of a glitter thermochromic laminate of the present invention.

FIG. 2 is an explanatory diagram showing a state in which a reversible thermochromic layer of the glitter thermochromic laminate of the present invention is colored.

FIG. 3 is an explanatory view showing a state in which a reversible thermochromic layer of the glitter thermochromic laminate of the present invention is in a decolored state.

FIG. 4 is an explanatory longitudinal sectional view of another embodiment of the brilliant thermochromic laminate of the present invention.

FIG. 5 is an explanatory longitudinal sectional view of another embodiment of the brilliant thermochromic laminate of the present invention.

FIG. 6 is an explanatory longitudinal sectional view of another embodiment of the brilliant thermochromic laminate of the present invention.

FIG. 7 is an explanatory longitudinal sectional view of another embodiment of the brilliant thermochromic laminate of the present invention.

FIG. 8 is an explanatory longitudinal sectional view of another embodiment of the glittering thermochromic laminate of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Brilliant thermochromic laminate 2 Support 3 Reversible thermochromic layer 4 Adhesive layer 5 Brilliant design layer 6 Protective layer 7 Non-color-changing layer

Claims (9)

[Claims] 1. A glitter thermochromic laminate comprising a support having a reversible thermochromic layer provided thereon, and a glitter pattern layer partially provided on the reversible thermochromic layer. 2. A brilliant thermochromic laminate comprising a support in which a reversible thermochromic material is dispersed and a brilliant pattern layer partially provided on the support. 3. The area ratio between the visible reversible thermochromic portion and the glittering pattern is in the range of 10:90 to 99: 1.
Or the glittering thermochromic laminate of 2. 4. The glitter thermochromic laminate according to claim 1, wherein a reversible thermochromic portion is visible around the glitter pattern. 5. The glitter pattern layer is a layer exhibiting optical properties selected from the group consisting of brightness reflection, light interference, iris, hologram, metallic luster, and pearl luster.
Brilliant thermochromic laminate. 6. The glitter thermochromic laminate according to claim 1, wherein the pattern of the glitter pattern layer is formed by a collection of glitter fine pieces. 7. The glitter thermochromic laminate according to claim 1 or 2, wherein a protective layer is provided on the reversible thermochromic layer, and a glitter pattern layer is provided on the protective layer. 8. The method according to claim 1, wherein the support is a fabric.
Brilliant thermochromic laminate. 9. A doll costume formed by the glittering thermochromic laminate of claim 8.