JPH11128540A - Reversible thermal color change stuffed toy set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have a moderate feeling of holding and be visible of sufficient color changing by fixing a cloth that fabric weight is a specific value with a reversible thermal color change member and constructing a stuffed toy using the reversible thermal color change cloth in specific value of thickness as a sin part and a heating and cooling color changing tool of which edge part is made with a hard member. SOLUTION: It prints a rotary screen print with a reversible thermal color change ink (80 g/m<2> ) consists of acrylic emulsion 70 and micro capsule pigment 30 containing a temperature changing color memory component on Tetron(R) and cotton mixed spinning broadcloth (fabric weight 30 to 200 g/m<2> ) as a cloth, to make a reversible thermal color change layer. And it coats with oil based top coat ink consisting of acrylic resin, benzotriazolo ultraviolet absorber and toluene as a photogravure print to make a top coat layer and gets a reversible thermal color change cloth with thickness of 5 to 200 μm. Sewing bear shaped, filling polyester short fiber cotton inside, it gets the reversible thermal color change stuffed toy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reversible thermochromic plush set. More specifically, the present invention relates to a reversible thermochromic stuffed animal set in which a thermochromic image appears by applying heating or cooling means.

[0002]

2. Description of the Related Art A reversible thermochromic stuffed animal in which a reversible thermochromic layer is provided on the surface of a stuffed animal has been disclosed (JP-A-8-19669). It is disclosed that the above-mentioned conventional reversible thermochromic stuffed animal forms a desired pattern by discoloring the reversible thermochromic layer by applying heating or cooling means. However, when applying a heating or cooling heat discoloring tool having a versatile tip formed of a hard member such as a metal as the heating or cooling means, since the tip is hard, the area in contact with the stuffed toy surface is compared. Therefore, if the contact time is short, it is difficult to form a sufficient reversible thermochromic image. In addition, it is conceivable to increase the area in contact with the discoloring tool by imparting flexibility to the stuffed toy. Has the disadvantage of impairing

[0003]

SUMMARY OF THE INVENTION The present invention has an appropriate holding feeling which is indispensable for a stuffed toy and has a sufficient color change even when a heating or cooling tool whose tip is formed of a hard member is applied. An object of the present invention is to provide a reversible thermochromic stuffed animal set that can be visually recognized.

[0004]

Means for Solving the Problems The present inventor specifies the basis weight of a cloth used as a stuffed skin material and the thickness of a reversible thermochromic cloth obtained by fixing a reversible thermochromic material to the cloth. By doing so, it has been found that a suitable discolored image can be produced by applying a heating or cooling discoloration tool having a writing tip made of a hard member without impairing the appropriate flexibility of the stuffed toy. That is, the present invention provides a reversible thermochromic material comprising a reversible thermochromic material having a basis weight of 30 to 200 g / m ² fixed to a reversible thermochromic material and having a thickness of 5 to 200 μm as a skin material. A reversible thermochromic stuffed animal set consisting of a stuffed animal and a heating or cooling color changing device having a tip formed of a hard material is required. Further, the basis weight of the cloth is 40 to 160 g / m ² , and the heat source of the heating or cooling discoloration device is hot water, cold water, or ice chips,
A C element or a Peltier element, wherein the reversible thermochromic material comprises: (a) an electron-donating color-forming organic compound;
(B) an electron-accepting compound, (c) a reversible thermochromic composition comprising a reaction medium which reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range, and The composition must have a hysteresis width of 5 to 50 ° C. in a temperature-color density curve.

[0005] The fabric used for the stuffed skin material is a knitted fabric formed of natural fibers, synthetic fibers, or the like.
Fabrics such as woven fabrics, braided fabrics, and raised fabrics are preferably used. The cloth used has a basis weight of 30 to 200 g / m ² , preferably 40 to 160 g / m ² . If the basis weight of the cloth is less than 30 g / m ^2, it is difficult to fix the thermochromic material uniformly and sufficiently, and it is not possible to produce a reversible thermochromic image having a desired color density. And it is difficult to produce a uniform image. In addition, when the stuffed animal is formed, there is a risk that the inside of the stuffed animal may be visually recognized or the stuffed animal may leak out in some cases. On the other hand, if the basis weight of the fabric exceeds 200 g / m ² , the soft feeling as a stuffed skin material is impaired, and it is difficult to form a reversible thermochromic fabric having a desired thickness.

The reversible thermochromic composition contained in the reversible thermochromic material fixed to the cloth includes an electron-donating color-forming organic compound, a color developer of the compound, and a color reaction between the two. Thermochromic composition containing three components of a compound serving as a medium to be caused (for example, JP-B-51-35414,
JP-B-51-44706, JP-B-52-7774
And Japanese Patent Publication No. 1-29898). 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 is a type in which a small hysteresis width is displayed on a temperature-color density curve due to a temperature change to change the color.

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. It is a type of composition that discolors 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. As the thermochromic color memory composition, a composition having a hysteresis width of 5 to 50 ° C. is suitably used, and the color development state or the decoloration state of the composition is easily maintained at ambient temperature. Characters and designs can be stored and stored in the stuffed toy.

It is preferable that the above-mentioned reversible thermochromic composition is used by being encapsulated in microcapsules. That is, under various use conditions, the reversible thermochromic materials are maintained in 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 particle diameter is 0.1 to
The range of 100 μm, preferably 1 to 50 μm, more preferably 2 to 30 μm satisfies the practicality. The microencapsulation is performed by a conventionally known interfacial polymerization method, in sit
There are u polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air suspension coating method, spray drying method, etc., which are appropriately selected according to the application. Is done. 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 binder containing a resin and applied as a reversible thermochromic material such as ink or paint. The resin may be water-based or oil-based, and is determined in consideration of adhesiveness, workability, and economy.
To be specific, acrylate resin, urethane resin, ethylene-vinyl acetate resin, vinyl chloride resin,
Examples include styrene resin, alkyd resin, polyester resin, urea resin, melamine resin, epoxy resin, phenol resin, epoxy acrylate resin, amide resin, cellulose acetate, cellulose nitrate, and ethyl cellulose. The resin may be used alone or in combination of two or more, and 100 parts by weight (solid content) of the reversible thermochromic composition.
25 to 400 parts by weight of resin solids can be used. If the amount is less than 25 parts by weight, the durability of the film is poor, and
If it exceeds 400 parts by weight, the texture of the fabric may be impaired or the heat discoloration performance may be adversely affected.

[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 to form a reversible thermochromic material fixed in a dispersed state in a vinyl chloride-vinyl acetate copolymer resin matrix, or the reversible thermochromic composition is mixed in a saturated copolymerized polyester resin matrix with fine particles. A reversible thermochromic material dispersed and dispersed can also be used. Further, a colorant such as a general dye or pigment, a fluorescent dye or a pigment may be added to the reversible thermochromic material to change the color change.

The above-described reversible thermochromic material is coated on a cloth by a known method, for example, screen printing, offset printing,
Forming continuously or discontinuously by means of printing such as gravure printing, coater, tampo printing, transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating A reversible thermochromic layer is formed, and a reversible thermochromic fabric is obtained. The discontinuous shape is an appropriate pattern such as a dot shape, a lattice pattern, a mesh shape, a character or a figure.

The reversible thermochromic fabric to which the reversible thermochromic material is fixed has a thickness of 5 to 200 μm, preferably 1 to 200 μm.
The thickness is set to 0 to 100 μm. When the thickness of the reversible thermochromic fabric is less than 5 μm, the content of the reversible thermochromic composition is reduced, so that it is difficult to obtain a sufficient color density in a color-developed state of the composition, and Discolorable fabric thickness of 20
If the thickness exceeds 0 μm, thermal conductivity is poor, so that a clear reversible thermochromic image cannot be produced depending on the application conditions of the color changing device, and the flexibility of the fabric is impaired.

Further, if the above thickness is satisfied, a non-color-changing layer may be provided below and / or above the reversible thermochromic layer as long as the flexibility of the fabric is not impaired, or a metallic gloss layer, a protective layer and a light stabilizer layer may be provided. It can also be provided as appropriate. Specifically, as the colorant contained in the non-color-changing layer, a general-purpose general colored dye or pigment, a fluorescent dye or pigment has been conventionally used, and if desired, a pearl pigment, a metal powder pigment, a luminous pigment, titanium dioxide White pigments and the like can also be used. The colorant is dispersed in a binder containing a resin or the like, an ink,
It is applied as a coloring material such as a paint and can form a non-discoloring layer. The shape of the non-color-changing layer may be an appropriate pattern such as a dot shape, a lattice pattern, a mesh shape, a character, a figure, or the like, in addition to being provided on the entire surface. The metallic luster layer is titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica,
A layer containing a metallic luster pigment such as guanine, sericite, basic lead carbonate, lead acid arsenate, bismuth oxychloride, etc., and can impart metallic luster. Further, when provided on the reversible thermochromic layer, it also has the effect of improving the light resistance of the reversible thermochromic composition.
The protective layer is formed for the purpose of waterproofing, surface protection, imparting glossiness, and the like. The light stabilizer layer is a light stabilizer 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. This is a layer fixed in a dispersed state. Incidentally, an antistatic agent, a polarity imparting agent, a thixotropic agent,
The function can be improved by adding an antifoaming agent or the like as necessary.

Further, Japanese Patent Application Laid-Open No. Sho 60-179371,
You may use the reversible thermochromic fabric of the said unit weight and thickness which weaved thermochromic fiber described in Unexamined-Japanese-Patent No. 60-225369.

The reversible thermochromic stuffed toy is obtained by cutting and sewing the reversible thermochromic fabric obtained as described above into an appropriate shape and filling the inside with a filling. As the filling to be filled in the reversible thermochromic stuffed toy, a filling such as cotton, cloth, feather, sponge and the like, which has elasticity and has a soft touch and a soft texture is suitably used. In addition, a granular resin molded product, styrene foam, or the like can be filled.

The reversible thermochromic stuffed toy set of the present invention is obtained by the reversible thermochromic stuffed toy and the heating / cooling color changing device obtained as described above.

The heating and cooling discoloring device will be exemplified.
The heating or cooling discoloration tool includes a writing form with a tapered tip, or a stamp with an image of a character, a pattern, or a pattern formed on the tip, and is provided with a resistance heating element. Energizing heating discoloration tool (Japanese Utility Model Showa 62-1395)
No. 73, Japanese Utility Model Laid-Open No. 4-50100), PTC
A heating discoloring device using an element, a heating pen filled with warm water or the like (disclosed in Japanese Utility Model Application Laid-Open No. 2-106299, etc.), and a cooling discoloring device using a Peltier element as a cooling discoloring device (JP-A-5-318915) For example, a cooling pen filled with a refrigerant such as cold water or ice chips can be used.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The reversible thermochromic fabric is cut and sewn, and then filled with fillings for dolls, animals, plants, fruits, vehicles,
Stuffed animals that imitate forms such as buildings, food and drink, indoor equipment, play equipment, celestial bodies such as the moon, stars, and the sun, sports equipment, etc.
A reversible thermochromic stuffed toy set can be obtained by using a heating or cooling thermochromic tool.

[0019]

【Example】

Example 1 (See FIGS. 1 and ² ) A thermosensitive color-changing color memory composition (black at 18 ° C. or higher, colorless at 24 ° C. or lower) was applied to a Tetron / cotton blended fabric (basis weight 120 g / m ² ) as the fabric 22. ) microcapsule pigment 30 parts containing therein a so that the reversible thermochromic ink consisting of 70 parts of acrylic emulsion 80 g / m ^2, printing rotary screen reversibly thermochromic layer 2
3 was formed, and then an oil-based top coat ink consisting of 1.9 parts of an acrylic resin, 1 part of a benzotriazole-based ultraviolet absorber and 80 parts of toluene was gravure-printed at 20 g / g.
m ² to form a top coat layer 24 to obtain a reversible thermochromic fabric 21 having a thickness of 80 μm. The reversible thermochromic fabric 21 was cut into bear-shaped skin pieces. The above-mentioned epidermis piece is sewn, and the filling 25
Was filled with polyester short fiber cotton to obtain a reversible thermochromic stuffed animal 2 in the form of a bear. A reversible thermochromic stuffed animal set 1 was obtained by using the stuffed animal and a color changing tool having a metal tip inside a medium as a heating or cooling color changing tool 3. At room temperature of 25 ° C., the stuffed toy was a white stuffed bear. When the stuffed surface is traced around the eyes, the ears, and the body using the discoloring tool containing cold water at 10 ° C., the thermochromic color memory composition develops a color and becomes black, It turned into a stuffed handle. When the stuffed toy of the panda was allowed to stand at room temperature, the portion that developed black gradually returned to white, and after a while, returned to the original white stuffed bear. In addition, when tracing a stuffed animal with the above-mentioned thermochromic discoloration device, the contact property is good, and the reversible thermochromic layer in the contact portion is sufficiently colored. The stuffed animal also had a soft texture, and the stuffed toy was satisfactory. The appearance change could be repeated.

Example 2 Yellow polyester taffeta (weight per unit area: 40 g / m 2)
² ) 15 g / m of a reversible thermochromic ink comprising 30 parts of microcapsule pigments containing a thermochromic color memory composition (red at 30 ° C. or higher, colorless at 18 ° C. or lower) and 70 parts of a urethane emulsion. ² , printing with a doctor coat, then 50 parts of urethane emulsion,
An aqueous topcoat ink consisting of 50 parts of water was applied by spray coating to a concentration of 5 g / m ² to obtain a reversible thermochromic fabric having a thickness of 10 μm. The reversible thermochromic fabric was cut and cut into star-shaped skin pieces. The skin portion piece was sewn, and a cotton short fiber made of polyester and a power source of a thermochromic discoloration device using a Peltier element were built therein as a filling to obtain a reversible thermochromic stuffed animal in the form of a star. A reversible thermochromic stuffed animal set was obtained by using the stuffed animal and a thermochromic discoloration device connected to a power source inside the stuffed animal via a cord. When the stuffed animal was heated to 30 ° C. or more, the entire surface became a yellow star-shaped stuffed animal, and this aspect was maintained in a temperature range exceeding 18 ° C. When a character is written on the stuffed surface using the thermochromic discoloring device using the Peltier element, the thermochromic color memory composition develops a color and turns red, leaving a message at 30 ° C. The temperature was kept below. In addition, if letters are written on the stuffed animal with the above-mentioned thermochromic discoloration device, the contact property is good, and the reversible thermochromic layer at the contact portion is sufficiently colored. The stuffed animal also had a soft texture, and the stuffed toy was satisfactory. When heated again to a temperature of 30 ° C. or higher, the whole surface became a yellow star-shaped stuffed animal, and this change in appearance could be repeated. or,
When the stuffed animal was cooled to 18 ° C. or less, the whole surface became a red star-shaped stuffed animal, and this aspect was maintained in a temperature range of less than 30 ° C. The power supply inside the stuffed animal is P
When a character is written using a heating discoloring device using a TC element, the thermochromic color memory composition is decolorized to yellow and a message can be left, and this aspect is observed in a temperature range exceeding 18 ° C. Held.

Example 3 Nylon tricot (basis weight 190 g /
m ² ), a reversible thermochromic composition (blue at 15 ° C. or more, 1
Microcapsule pigment 30 containing (colorless at less than 5 ° C.)
100 g / m of a reversible thermochromic ink consisting of 1 part of a fluorescent pink pigment and 68 parts of a urethane oil / fat (solid content: 30%).
² silk screen printing, thickness 40μm
Was obtained. The reversible thermochromic fabric was cut into car-shaped skin pieces. The skin portion piece was sewn and filled with polyester short fiber cotton as a filling to obtain a reversible thermochromic stuffed animal in the form of a car. A reversible thermochromic stuffed animal set was obtained by using the stuffed animal and a discoloration tool that accommodates a medium in a metal tip. The stuffed toy is in the form of a pink car at room temperature of 25 ° C. When the surface is traced using the color changing device containing cold water of 10 ° C., the reversible thermochromic composition develops a color and becomes purple. , Changed to a car with a purple design. The above-mentioned aspect shows that the purple design part is 15
When the temperature reached over ℃, it returned to its original state. In addition, when tracing a stuffed animal with the above-mentioned thermochromic discoloration device, the contact property is good, and the reversible thermochromic layer in the contact portion is sufficiently colored. The stuffed animal also had a soft texture, and the stuffed toy was satisfactory. Also, the reversible thermochromic plush set has a simple structure,
It can also be applied as a bath toy, and in addition to the discoloration tool, a brush that contains hot or cold water can be used in combination as heating or cooling means.

Comparative Example 1 A reversible thermochromic fabric was obtained in the same manner as in Example 1 except that a Tetron / cotton blended gather fabric (basis weight 220 g / m ² ) was used as the fabric. The thickness of the cloth is 240μ
m. Similarly, a stuffed bear was prepared to obtain a reversible thermochromic stuffed animal. The stuffed animal was poor in flexibility and uncomfortable to hold, and the reversible thermochromic layer at the contact portion did not sufficiently develop color even when the stuffed animal was traced using the same color changing device containing cold water.

Comparative Example 2 As a cloth, a polyester organza (basis weight 20 g /
A reversible thermochromic fabric was obtained in the same manner as in Example 1 except for using m ² ). The thickness of the cloth was 3 μm, and a stuffed bear was similarly produced to obtain a reversible thermochromic stuffed animal. When the stuffed animal was traced using the same discoloring tool containing cold water, the reversible thermochromic layer at the contact portion developed color, but had uneven color tone and low color density. In addition, the stuffed toy has poor durability because the filling comes out from the gap of the cloth as it is used.

COMPARATIVE EXAMPLE 3 A cotton / linen-blend waterproof canvas (basis weight 300 g /
A reversible thermochromic fabric was obtained in the same manner as in Example 1 except for using m ² ). The thickness of the cloth was 100 μm. Similarly, a stuffed bear was prepared to obtain a reversible thermochromic stuffed animal. Even if the stuffed animal traced the stuffed animal with a thermochromic discoloration device, the contactability was poor, and the reversible thermochromic layer did not sufficiently develop color. Moreover, it was poor in flexibility and uncomfortable.

Comparative Example 4 A reversible thermochromic fabric was obtained in the same manner as in Example 1 except that nylon taffeta (basis weight 45 g / m ² ) was used as the fabric. The thickness of the cloth was 300 μm. Similarly, a stuffed bear was prepared to obtain a reversible thermochromic stuffed animal.
The stuffed toy had poor flexibility, and even when the stuffed animal was traced using the color changing tool, the reversible thermochromic layer at the contact portion did not develop color smoothly and was poor in practicality.

[0026]

According to the present invention, there is provided a game in which a user can have a comfortable hugging feeling and can visually recognize a sufficient color change even when a heating or cooling color changing device having a tip formed of a hard member is applied. It is possible to provide a reversible thermochromic stuffed animal set rich in properties. Also, the heat source of the heating or cold discoloration tool is hot water, cold water,
Alternatively, it is possible to provide a reversible thermochromic stuffed toy set which can be easily discolored by using ice pieces and can be used in a bathroom or the like. Further, the heat source of the heating or cooling color changer is PT
By being a C element or a Peltier element, a heating or cooling function can be instantaneously generated when necessary,
It is possible to provide a reversible thermochromic stuffed animal set that can be played without selecting a place of use.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a use state of a reversible thermochromic plush set of the present invention.

FIG. 2 is a sectional view of a main part of the reversible thermochromic stuffed toy of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reversible thermochromic plush set 2 Reversible thermochromic stuffed toy 21 Reversible thermochromic cloth 22 Cloth 23 Reversible thermochromic layer 24 Top coat layer 25 Filling 3 Heating or cold thermochromic tool

Claims (5)

[Claims] 1. A fabric having a basis weight of 30 to 200 g / m ² and a reversible thermochromic material fixed to a fabric having a thickness of 5 to 200 g / m ^2.
A reversible thermochromic stuffed animal set comprising a reversible thermochromic stuffed animal using a μm reversible thermochromic fabric as a skin material and a heating or cooling thermochromic tool having a tip formed of a hard material. 2. The fabric having a basis weight of 40 to 160 g /
The thermochromic stuffed animal set according to claim 1, which has a m ² of ² . 3. The reversible thermochromic plush set according to claim 1, wherein the heat source of the heating or cooling color changing tool is hot water, cold water, or ice chips. 4. A heat source of the heating or cooling color changer is PT.
The reversible thermochromic plush set according to claim 1, which is a C element or a Peltier element. 5. The reversible thermochromic material comprises: (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound,
(C) a thermochromic color-memory composition comprising a reaction medium which reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range; The hysteresis width in the temperature-color density curve is 5
The reversible thermochromic plush set according to claim 1, which has a temperature of from about 50 ° C. to about 50 ° C. 4.