JPH0563197B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Object of the invention Field of industrial application The present invention relates to a thermochromic stuffed animal that reversibly changes color depending on temperature. The thermochromic stuffed animal of the present invention differs from conventional stuffed animals in that it has the ability to change color reversibly and reversibly due to temperature changes, and relates to a completely new stuffed animal that has the ability to change color in response to temperature changes. . Prior Art Conventionally, no effective proposals have been disclosed regarding thermochromic stuffed animals that change color in a variety of ways due to temperature changes, and such stuffed animals have been eagerly awaited. Problems to be Solved by the Invention The present invention provides a stuffed animal with a thermochromic function that reversibly changes color in response to changes in temperature, which has not been possible in the past. (B) Structure and Effects of the Invention Means for Solving the Problems The present invention provides a surface of each elementary fiber of a fiber composed of a plurality of elementary fibers having the following formula: r≦10√ [r: pigment particle size (μm). D: Denier number of basic fiber (denier). d: Specific gravity of elementary fiber (g/cm ³ )]
A thermochromic layer consisting of a thermochromic pigment and a binder made of a thermochromic material consisting of a combination of an electron-donating color former, an electron-accepting color developer, and a discoloration temperature regulator, with a particle size that satisfies the above conditions. The thermochromic layer has an adhesion amount of 3% to 90% by weight with respect to each elementary fiber, and the thermochromic pigment has an adhesion amount of 5% to 90% by weight in the thermochromic layer.
The present invention relates to a thermochromic stuffed toy in which at least a portion of the surface of the stuffed toy is made of a thermochromic cloth composed of 80% by weight thermochromic fiber. In the present invention, in order for the stuffed animal to exhibit a good and uniform thermochromic effect, the particle size of the pigment must be r≦10√ [r: particle size of pigment, D: denier number of elementary fiber, d: specific gravity of elementary fiber]. It is necessary to satisfy. In the present invention, each of the basic fibers constituting the thermochromic cloth used for stuffed animals is independently provided with a thermochromic layer, so the distribution of the thermochromic pigment to the fibers is uniform. As a result, the stuffed animal has a good texture and uniform thermochromic properties. For this purpose, the particle size of the pigment must be within a specific range. According to research by the present inventors, the uneven discoloration of stuffed animals made of fabrics made of fibers coated with thermochromic pigments is due to uneven distribution of the pigments, and this uneven distribution is caused by the presence of multiple pigments. It was clarified that this is due to cross-linking across the fibers. In other words, depending on the particle size and the thickness of the elementary fibers, if the pigment binds multiple elementary fibers together in a bridge-like manner, a large amount of the thermochromic pigment tends to gather in this area, resulting in uneven distribution of the pigment. This causes uneven heat discoloration. Since uneven discoloration is caused by the cross-linking phenomenon, it cannot be prevented simply by regulating the particle size of the pigment, and the relationship with the thickness of the elementary fibers becomes an important issue. Based on this new knowledge, the present inventors conducted research to solve the conventional problems, and as a result,
By satisfying the relationship r≦10√ between the pigment and the basic fibers, the above-mentioned phenomenon can be prevented, and uneven discoloration can be successfully prevented. Another feature of the present invention is that a thermochromic layer made of a pigment and a binder is provided on the surface of each individual fiber of the fibers constituting the thermochromic cloth used for stuffed animals. Because the thermochromic layer is provided on the surface of each individual fiber, the distribution of the thermochromic pigment throughout the fabric is uniform, and the texture, flexibility, and pigment adhesion strength are uniform throughout. This new structural unit is a novel thermochromic fiber that has not been previously known. Therefore, the cotton-like materials and yarns made of these basic fibers are novel and exhibit uniform thermochromic properties, texture, and pigment adhesion strength. Therefore, thermochromic fabrics composed of these thermochromic fibers, more specifically thermochromic woven fabrics, thermochromic non-woven fabrics, thermochromic knitted fabrics, thermochromic pile fabrics, etc. all have uniform thermochromic properties. Thermochromic plush toys that use these thermochromic fabrics on at least part of their surface have good texture, uniform thermochromic properties, pigment adhesive strength, etc. This is a completely new stuffed toy that exhibits excellent performance. In the present invention, the specific relationship between the thickness of the elementary fiber and the particle size of the thermochromic pigment is particularly determined by r≦10√
d [r: particle size of pigment, D: denier number of elementary fiber,
d: Specific gravity of the elementary fiber] is specified in order to prevent the bridging phenomenon of the pigment particle size since the cross-sectional shape of the elementary fiber used may have an irregular shape, such as a polygonal shape or a flattened shape, as described later. This is because it is meaningless to specify simply by the wire diameter of the elementary fiber and the particle diameter of the pigment.
This configuration is essential in order to achieve the purpose of the present invention and to produce specific effects. The thermochromic layer in the present invention is 3% to 90% by weight based on the basic fibers constituting the cloth used for stuffed toys.
The amount by weight is appropriate, and 5 to 70 weight % is particularly preferable in view of the thermochromic color change effect. The reason for this is that as a result of examining various adhesion amounts, the following became clear. i.e. 3% by weight
If it is less than that, the texture is good, but the density is low and the color change is not clear, so it is not practical as a stuffed animal. In addition, if the amount of coating exceeds 90% by weight, the concentration is high and the color change is clear, but the texture is impaired because binding between elementary fibers tends to occur and it is difficult to make each elementary fiber exist independently. However, it is not practical as a stuffed animal because it does not have a flexible feel. Therefore, a range of 3% to 90% by weight is a practical range that satisfies both the density, clarity of color change, and soft texture. Furthermore, in the range of 5% to 70% by weight, the density and color change are clear enough, and there is no binding between the elementary fibers, making each fiber unique.
The best quality thermochromic fiber is obtained, which has a very flexible texture as the book can exist completely independently, and has sufficient pigment adhesion strength. Stuffed toys made with this product have extremely excellent effects. The surface of the stuffed toy in the present invention refers to the visible parts of the stuffed toy, such as the inside of the mouth, ear holes,
Also refers to the pouch of a marsupial, the inside of a stuffed animal that can be separated or opened, etc. Function The thermochromic stuffed toy of the present invention uses a thermochromic pigment with a particle size suitable for the denier of the basic fibers, so there is no cross-linking between the fibers, resulting in uniformity, flexibility, texture, and
It can possess extremely excellent performance in terms of scratch resistance and washability. In other words, thermochromic cloth made of fibers that are not cross-linked with pigments is extremely soft and has a good feel because the gaps between the fibers are not cross-linked, and stuffed toys made from this cloth are shows an extremely excellent texture. The thermochromic stuffed animal of the present invention exhibits a thermochromic effect that cannot be obtained with ordinary stuffed animals. Specifically, for example, a brown bear changes to blue when you breathe on it, a green crocodile changes to yellow when you hold it due to body heat, and a red dog changes to yellow due to internal heat when you hug it. , We took a bath together, and the blue male seal turned pink depending on the temperature of the water.
By taking it outside from the room, the white rabbit changes to pink due to the change in temperature, and by using multi-stage changes, the color changes from black to red to yellow to white by continuously changing the temperature. By incorporating hidden multi-colored designs, completely new functions and effects can be achieved, such as a message appearing when you blow on it, or letters, patterns, and designs appearing or changing. As the thermochromic pigment used in the present invention, conventionally known reversible thermochromic materials consisting of a combination of an electron-donating color former and an electron-accepting color developer are effective. Examples include thermochromic materials disclosed in Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 51-44708, and Japanese Patent Publication No. 51-35216. For example, (a) electron-donating color formers, (b) compounds with phenolic hydroxyl groups and their metal salts, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylates, acidic phosphoric acid esters. and metal salts thereof, 1,2,3-triazole and its derivatives, electron-accepting color developers such as halohydrin compounds, (c) alcohols, esters, ketones, ethers, acid amides, carbon number 6 or more aliphatic carboxylic acids, thiols, sulfides,
Disulfides, sulfoxides, sulfones,
A thermochromic pigment consisting of a color-changing temperature regulator such as Specific examples are shown in the attached table.
The numbers in parentheses indicate parts by weight.

[Table] These thermochromic materials are approximately -30℃ to +100℃
At temperatures between red, blue, yellow, green, orange, purple,
Brown, black, and other combinations can reversibly change subtle colors from colored to colorless and from colorless to colored, and by adding a fluorescent whitening agent, the vividness of white in colorless is increased. You can also make the contrast even stronger. Furthermore, the color can be changed from one color () to another different color () by adding and using colored compounds such as general dyes, fluorescent dyes, pigments, fluorescent pigments, and phosphorescent pigments. Therefore, it is effective. It also allows light to pass through it, and can become transparent in response to changes in temperature, revealing the underlying layer. In order to turn these thermochromic materials into pigments, the thermochromic materials are encapsulated in microcapsules or blended with various resins, and then hardened after emulsification, or cured or solidified after being sprayed using a spray drying method, and pulverized after hardening. It can be made into fine particles using When the surface of the fiber is coated with this pigment, a thermochromic fiber is formed that changes color and colorless depending on temperature changes. Next, in order to create thermochromic fibers that change from colored () to colored () using these thermochromic pigments that change from colored to colorless, a colored component is added to the thermochromic composition. Thermochromic pigments that change from colored () to colored () are coated on the surface of basic fibers, or thermochromic pigments and general pigments that change from colored to colorless, fluorescent pigments, phosphorescent pigments or dyes, and fluorescent pigments are used. The surface of the basic fibers may be coated with microcapsules or particles of the dye, or the surface of the basic fibers colored with general dyes or general pigments may be coated with a colorless thermochromic pigment. Also,
A method may be used, such as blending raw fibers coated with a thermochromic pigment that changes color and colorless and raw fibers colored with general dyes or pigments. Examples of the binder for binding the obtained thermochromic pigment to the basic fibers include conventionally known waxes, low-melting thermoplastic resins, rubbers, natural resins, synthetic resins, and the like. For example, low molecular polyethylene, low melting point polyester, ethylene-vinyl acetate copolymer,
Chlorinated rubber, polysulfuric acid vinyl emulsion, polyethylene emulsion, acrylic emulsion, styrene resin emulsion, brassiene-nitrile emulsion, shellac, zein, unsaturated polyester resin, epoxy resin, cellulose resin, polyurethane resin, phenolic resin , vinyl chloride resin, vinyl acetate resin, silicone resin, polyvinyl alcohol, polyvinyl methyl ether, etc. Various materials and forms of single fibers are effective, and specific examples include natural fibers, semi-synthetic fibers, synthetic fibers, other chemical fibers such as copolymer fibers, inorganic fibers, and metal fibers. Examples include cotton, wool, goat hair, camel hair, rabbit hair,
Silk, natural silk thread, casein fiber, soy protein fiber,
Zein fiber, peanut protein fiber, regenerated silk thread, viscose lace, copper ammonia lace,
Saponified acetate, natural rubber fiber, alginate fiber, acetate fiber, triacetate fiber, acetate staple fiber, ethyl cellulose fiber, chlorinated rubber fiber, polyamide fiber, polyester fiber, polyurethane fiber, polyethylene fiber, polypropylene fiber, polyvinyl chloride polyvinyl chloride fiber, polyfluoroethylene fiber, polyacrylonitrile fiber, polyvinyl alcohol fiber, promix fiber,
Benzoate fiber, polyclar fiber, polynosic fiber, acrylonitrile-alkylvinylpyridine copolymer fiber, acrylonitrile-ethylene copolymer fiber, acrylonitrile-vinyl chloride copolymer fiber, vinyl chloride-vinylidene chloride copolymer fiber, vinyl chloride-vinyl acetate copolymer fiber , vinyl chloride-acrylonitrile copolymer fiber, vinyl chloride-ethylene copolymer fiber, glass fiber, rock wool, ceramic fiber, carbon fiber and the like. In addition to the normal fiber shapes, the shapes include triangular, pentagonal, octagonal, Y-shaped, L-shaped, star-shaped, dogbone-shaped, horseshoe-shaped, uneven cross-section fibers, macaroni-shaped, lotus root-shaped, sponge-shaped, Hollow fibers such as field shapes, side. by. Examples include conjugate fibers of side type, sheath type, core type, matrix type, etc. The hollow fibers of irregular cross-section fibers have a large surface area and are easy to adhere to pigments, so they have the characteristic of being able to be concentrated. The production of thermochromic cloth coated with thermochromic pigment used in thermochromic stuffed animals is carried out by the following method, although it differs slightly depending on the form of the cloth. First, the production of the fibers constituting the thermochromic woven fabric will be explained. The target elementary fibers (which may be crimped if necessary) are dipped in a coating composition consisting of a thermochromic pigment, a binder, and a coloring agent, and then dried, or blown by spraying, etc. The thermochromic fibers obtained by direct coating with a brush, roll coater, etc., and then drying are crimped if necessary to form thermochromic filaments. In addition, a thermochromic filament yarn is made by bundling and twisting a plurality of filament yarns. Alternatively, after crimping, the thermochromic raw cotton cut into an appropriate length or the target raw cotton is immersed in the above-mentioned coating composition, and then centrifuged, rolled, squeezed with an air gun, etc. to remove the excess composition, and then dried. The thermochromic raw cotton obtained by treatment, spraying, brushing, direct application with a roll coater, etc. and drying treatment is applied to a card to make a sliver, and then goes through a spinning process to become a thermochromic spun yarn. . These thermochromic fibers are plain woven using a loom. Rim weave. Oblique weave. Satin weave. Twill weave. Obtained by weaving into a layered weave or the like. Next, the thermochromic nonwoven fabric will be explained. First, a fiber aggregate to be processed into a nonwoven fabric will be explained. The target elementary fibers (which may be crimped if necessary) are dipped in the coating composition and then dried, or sprayed, brushed, or applied directly with a roll coater, etc., and then dried. A filament sheet is obtained in the form of a filament by crimping the thermochromic fibers obtained by the treatment, if necessary. In addition, thermochromic fibers obtained in the same manner are cut into appropriate lengths to obtain thermochromic raw cotton, which is a fiber aggregate. After immersing the target raw cotton in the coating composition, it is centrifuged.
Roll aperture. Air gun. After removing excess composition, dry it, or spray it or brush it. After direct coating using a roll coater or the like, drying treatment is performed to obtain thermochromic raw cotton, which is a fiber aggregate. Of the thermochromic fiber aggregate thus obtained, the filament sheet can be processed into a nonwoven fabric as it is, but the raw cotton must be made into a web. Therefore, the raw cotton is carded and made into a web. Next, processing into a nonwoven fabric will be explained.
Filament sheets or webs are overlapped as necessary and bonded mechanically by stitch bonding or needling, or immersed in adhesive. Spray adhesive. Powder adhesive. Fibrous adhesive. It can be obtained by mixing a filamentous adhesive or bonding by applying pressure or heat. Next, the thermochromic knitted fabric will be explained. Thermochromic filament obtained in the same manner as for thermochromic woven fabric. Thermochromic filament yarn. Circular knitting of thermochromic fibers such as thermochromic spun yarn using a knitting machine. Flat version. Pearl edition. Rubber edition. Edited by Denby. Atlas edition. Code edition. Double Denby edition. Double Atlas edition. Double chord edition. Race edition. It can be obtained by knitting. Next, thermochromic pile fabric is thermochromic high pile fabric. Refers to various pile fabrics such as thermochromic flocked fabrics. The thermochromic pile fabric uses the thermochromic filament, thermochromic filament yarn, or thermochromic spun yarn as described above for the warp. Velvet. Do you use warp pile weaving such as plassy? Betutin is used for the weft. Weft pile weave such as coal.
Cut it at an appropriate position to make the surface of the fabric covered with fluff. Another towel. It can also be made into a looped form, such as in a jiyutan. In addition to this, the preformed pile fabric is impregnated with the coating composition. printing. coat. It can be obtained by a method such as spraying, drying, and splitting. The thermochromic high pile fabric is obtained by knitting the thermochromic raw cotton described above by carding it into a sliver using a high pile knitting machine.
This high pile fabric has long piles and a large amount of thermochromic pigments, so it has a particularly excellent thermochromic effect. The thermochromic flocked fabric is made by cutting the thermochromic filament described above to an appropriate length, making a pile, and scattering it. Vibration type. It can be obtained by a method such as mechanical flocking such as a blowing method or electrostatic flocking. A thermochromic stuffed toy using the thermochromic fabric of the present invention can be obtained by cutting the thermochromic fabric according to a pattern for the intended stuffed toy and sewing it. In this case, by sewing thermochromic fabrics of various colors, a stuffed animal that changes color can be obtained. Of course, adhesion or fusing may be used as appropriate instead of sewing. In addition, a stuffed animal was formed in advance using a cloth that was not a thermochromic cloth. This stuffed toy is coated with a coating agent containing a thermochromic pigment and a binder whose pigment particle size satisfies r≦10√ [r: particle size of pigment, D: denier number of elementary fiber, d: specific gravity of elementary fiber]. It is also possible to treat the entire surface or a portion thereof with thermochromic to make the treated area thermochromic. In addition, thermochromic fabric is sewn onto stuffed animals made of non-thermochromic fabric.
Adhesion. It is also possible to make a thermochromic stuffed toy by partially arranging the stuffed toy. A stuffed animal constructed using thermochromic cloth is sewn with other thermochromic cloth. It may be arranged by adhesive or the like to make a multicolored thermochromic stuffed animal. Furthermore, a stuffed toy made of a non-thermochromic cloth can be embroidered with the aforementioned thermochromic filament, thermochromic filament yarn, thermochromic spun yarn, etc. to impart thermochromic properties. In this case, when a stuffed toy made of thermochromic cloth is subjected to the same treatment, it becomes a multicolored thermochromic stuffed toy. The thermochromic layer in the present invention is suitably 3% to 90% by weight, particularly 5% to 70% by weight based on the basic fibers constituting the thermochromic cloth used for stuffed toys.
% by weight is preferable in view of thermochromic color change effect. In addition, the thermochromic pigment is 5% by weight or more in the thermochromic layer.
80% by weight is suitable, especially 10% to 60% by weight
is preferable from the viewpoint of thermochromic color change effect. That is, if it is less than 5% by weight, the coloring density is so low that a color change cannot be clearly seen, while if it exceeds 80% by weight, it is difficult to clearly see a decolorized state. The above range of 10% by weight to 60% by weight is the optimum range in which the balance between density and color change is maintained. The resin to be applied is appropriately selected from among the binders described above, and if necessary, antioxidants, ultraviolet absorbers, anti-aging agents, etc. can be added to make the thermochromic function permanent. Parts in the following examples are parts by weight. Example 1 Spiro[12-H-benzo[2]xanthene-
12,1′(3′H)-isobenzofuran]-3′-one,9
-(diethylamino)-1 part, zinc benzoate 2 parts,
A thermochromic composition consisting of 25 parts of butyl stearate is solidified to the inside with an epoxy resin/amine curing agent. 200 parts of thermochromic microparticles with a particle size of 12 μm satisfying r≦10√, solid content of approximately 42%. After immersing 1000 parts of 10D sponge-like hollow polyacrylonitrile raw cotton (d = 1.17) bias-cut into a size of 80 mm to 130 mm into a coating composition in which 800 parts of acrylic acid ester resin emulsion was uniformly mixed, the excess composition was removed by centrifugation. After removal, the thermochromic hollow polyacrylonitrile raw cotton obtained by drying at 90°C for 10 minutes was carded to make a sliver, and the thermochromic spun yarn obtained through the spinning process was woven into satin fabric using a loom. A thermochromic stuffed rabbit was obtained by sewing a thermochromic hollow polyacrylonitrile satin fabric. The stuffed toy made from the thermochromic satin fabric of the rabbit described above turns pink at temperatures below 10℃;
At temperatures above this temperature, it turned colorless, and when the temperature was lowered to below 10°C, the color returned to pink, showing reversible thermochromic properties. Example 2 1(3H)-isobenzofuranone, 3,3-bis(1-ethyl-2-methyl-1H-indole-3
-1 part of bisphenol A, 2 parts of bisphenol A. A thermochromic composition consisting of 25 parts of cetyl alcohol is solidified to the inside with an epoxy resin/amine curing agent.r≦10
100 parts of thermochromic microparticles with a particle size of 4 μm that satisfy √. CIPigment Yellow 32 copies. Solid content approx.
45% acrylic-vinyl acetate copolymer emulsion
After immersing 800 parts of crimped 5D vinyl chloride-vinyl acetate copolymer fiber (d=1.34) in a coating composition in which 700 parts were uniformly mixed, the resulting mixture was taken out and dried at 100°C for 10 minutes. The resulting thermochromic vinyl chloride-vinyl acetate copolymer fibers were cut into 45 mm pieces, made into a web using a card, and then four sheets were laminated in parallel, immersed in an SBR resin emulsion solution, and then squeezed and dried with a roll. A thermochromic stuffed tomato was obtained by sewing a thermochromic vinyl chloride-vinyl acetate copolymer nonwoven fabric. The above-mentioned stuffed toy using thermochromic nonwoven fabric made of tomato exhibits a red color at temperatures below 40°C, changes to yellow at temperatures above 40°C, and returns to red when the temperature is lowered to below 40°C, demonstrating reversible thermochromic properties. showed that. Example 3 1 part of Crustal Violet lactone, 2 parts of dodecyl gallate, 15 parts of myristyl alcohol, and 10 parts of decyl caprate were uniformly kneaded into 800 parts of polyethylene, cooled, and finely pulverized. r≦10√
7D polyester triangular cross-sectional fiber (d =1.38) Take out 800 parts after soaking and heat at 100℃5
The thermochromic polyester triangular cross-sectional fibers obtained by drying for minutes are crimped and 35 fibers are bundled into 30
A thermochromic stuffed toy of a cow is obtained by sewing the thermochromic polyester double denby knitted fabric obtained by knitting the thermochromic filament yarn obtained by twisting the yarn at a twist rate of twists/m into a double denby knitted fabric using a knitting machine. It was done. The stuffed animal made with the thermochromic double denby knitted fabric of the cows mentioned above turns blue at temperatures below 25 degrees.
At temperatures above 25°C, it turned colorless, and when the temperature was lowered again below 25°C, the color returned to blue, showing reversible thermochromic properties. Example 4 Spiro[isobenzofuran-1(3H),9'-
[9H)xanthene]-3-one, 6'-(diethylamino)-2'-[cyclohexyl (phenylmethyl)
A thermochromic composition consisting of 2 parts of amino]-1 part, 5,5-bis(1,2,3-benzotriazole) and 25 parts of caprylic acid was encapsulated using gelatin/gum arabic using a coacervation method. r≦10√
6D acrylonitrile dyed yellow is added to a coating composition in which 500 parts of thermochromic microcapsules with a particle size of 8 μm satisfying D/d and 450 parts of an acrylic acid ester resin emulsion with a solid content of approximately 42% are uniformly mixed. - Vinyl acetate copolymer fiber (d=
1.18) After soaking, 700 parts were taken out and dried at 90°C for 10 minutes. The resulting thermochromic acrylonitrile-vinyl acetate copolymer fibers were cut into 4 mm pieces to make thermochromic piles for flocking, and electrostatically coated on coated paper. A thermochromic stuffed toy of a crocodile was obtained by sewing thermochromic flocked fabric with a pile length of 3.8 mm obtained by flocking using the processing method. The stuffed toy made from the above-mentioned crocodile thermochromic flocked fabric turns green at temperatures below 15 degrees Celsius, changes to yellow at temperatures above 15 degrees Celsius, and returns to green when the temperature drops below 15 degrees Celsius, resulting in reversible thermal discoloration. showed his sexuality. Example 5 Spiro [isobenzofuran-1 (3H), 9' [9H]
xanthene]-3-one, 1 part of 6'-(cyclohexylmethylamino)-3'-methyl-2'-(phenylamino)-, 2 parts of 1,1-bis(4-hydroxyphenyl)-cyclohexane, palmitic acid 12.5
A thermochromic composition consisting of 12.5 parts of decyl caprylate is encapsulated by an interfacial polymerization method using acid chloride/phenol, and the particle size satisfies r≦10√.
200 parts of 8μm thermochromic microcapsules, solid content approx. 45
5D in a coating composition in which 800 parts of acrylic acid ester emulsion of
After soaking 500 parts of equivalent cotton (d = 1.54), remove the excess composition by centrifugation, and drying at 100°C for 10 minutes. The resulting thermochromic spun yarn was woven into a towel fabric with a pile length of 2.5 mm using a loom, and the resulting thermochromic towel fabric was sewn with a regular white towel fabric with a pile length of 2.5 mm. I got a stuffed animal. In the stuffed toy using the thermochromic panda towel fabric mentioned above, the thermochromic towel fabric part turns black at temperatures below -3°C, giving it the hue of a panda.
When the temperature reached 3° C. or higher, the color changed to white, and when the temperature was lowered to −3° C. or lower, the color returned to black and the color to that of a panda, showing reversible thermochromic properties. Example 6 1(3H)-isobenzofuranone, 3-(1-ethyl-2-methyl-1H-indol-3-yl)-
3-(4-diethylaminophenyl)-1 part, 5-
3 parts of chloro-1,2,3-benzotriazole,
60 parts of thermochromic microcapsules with a particle diameter of 7 μm that satisfies r≦10√, containing a thermochromic composition consisting of 25 parts of dilauryl ether by coacervation method using gelatin/gum arabic, glycidyl ether type epoxy 200 parts resin, amine curing agent
Coating composition uniformly mixed with 80 parts
A thermochromic polyester pile fabric made of 5D polyester fibers (d = 1.38) with a pile length of 10 mm was sprayed with a spray gun, dried at 80℃ for 30 minutes, and then the resulting thermochromic polyester pile fabric was sewn. A thermochromic stuffed toy of a penguin was obtained. The above-mentioned penguin stuffed animal made of thermochromic pile fabric exhibits a blue color at temperatures below 30℃, changes to colorless when the temperature rises above 30℃, and returns to blue when the temperature is lowered to below 30℃, which is a reversible thermochromic color change. showed his sexuality. Example 7 Spiro[isobenzofuran-1(3H),9'-
[9H]xanthene]-3-one, 1 part 3'-(diethylamino)-6',8'-dimethyl, CISolvent
Blue 25 0.15 parts. 4-chlorobenzoic acid 3 parts, 1,
A thermochromic composition consisting of 25 parts of 10-decanediol is encapsulated using an interfacial polymerization method using an acrylic resin/amine curing agent, and the particle size satisfies r≦10√.
A 3D film was crimped into a coating composition in which 400 parts of thermochromic microparticles of 4 μm and 600 parts of a vinyl acetate-ethylene-vinyl chloride terpolymer emulsion with a solid content of about 45% were uniformly mixed. After soaking, 500 parts of polypropylene fibers (d=0.91) were taken out and dried at 100°C for 5 minutes.The resulting thermochromic polypropylene fibers were cut into 50 mm pieces to obtain thermochromic polypropylene raw cotton, which was carded to make slivers. A thermochromic stuffed koala was obtained by sewing thermochromic polypropylene high pile fabric with a pile length of 20 mm obtained by knitting and shearing using a high pile knitting machine. The above-mentioned koala stuffed animal made of thermochromic high pile fabric turns brown at temperatures below 70℃;
At temperatures above 70°C, the color changed to blue, and when the temperature was lowered to below 70°C, the color returned to brown, showing reversible thermochromic properties. Example 8 Spiro [isobenzofuran-1 (3H), 9′-
[9H]xanthene]-3-one, 6'(diethylamino)-2'-[cyclohexyl(phenylmethyl)amino]-1 part, 4,4'-thio-bis(3-methyl-6-tert-butyl-phenol) ) 3 parts, 30 parts of 12-hydroxystearic acid triglyceride is uniformly kneaded into 750 parts of polypropylene, cooled, and finely pulverized. Particle size satisfying r≦10√
A 7D acrylonitrile-vinyl chloride copolymer flat cross section with a cut length of 70 mm is mixed into a coating composition in which 600 parts of thermochromic microparticles of 8 μm and 400 parts of an acrylic-vinyl acetate copolymer emulsion with a solid content of approximately 45% are mixed uniformly. Raw cotton consisting of elementary fibers (d=1.25)
After soaking 400 parts, remove the excess composition with an air gun and drying at 100°C for 10 minutes.The obtained thermochromic acrylonitrile-vinyl chloride copolymer raw cotton was applied to a card to make a sliver, then knitted with a high pile knitting machine and sheared. Processed pile length 35mm
A thermochromic stuffed bear was obtained by sewing thermochromic acrylonitrile-vinyl chloride copolymer high pile fabric. The above-mentioned stuffed animal using thermochromic high pile fabric of the bear exhibits a green color at temperatures below 50℃, turns colorless at temperatures above 50℃, and returns to green when the temperature is lowered to below 50℃, which is a reversible thermochromic color change. showed his sexuality. Example 9 A thermochromic composition consisting of 1 part of crystal violet lactone, 3 parts of octyl 4-hydroxybenzoate, and 25 parts of butyl stearate was encapsulated using an interfacial polymerization method using an acrylic resin/amine curing agent. 100 parts of thermochromic microcapsules with a satisfactory particle size of 12 μm and 650 parts of ethylene-vinyl acetate copolymer emulsion with a solid content of about 50% are mixed uniformly into a coating composition, and 700 parts of 10D polyester raw cotton (d=1.38) is added to the coating composition. 15 at 90°C after removing excess coating composition by centrifugation after soaking.
The thermochromic polyester raw cotton obtained by drying for minutes was made into a web using cards, and three sheets were laminated crosswise.
A thermochromic stuffed zebra was obtained by sewing a thermochromic polyester nonwoven fabric obtained by spraying an NBR resin emulsion liquid from a spray nozzle and drying it and a general white nonwoven fabric. The thermochromic nonwoven fabric part of the stuffed animal made from the thermochromic nonwoven fabric of the zebra mentioned above turns blue at temperatures below 10°C, giving it the hue of a zebra, but when the temperature rises above 10°C, the color changes to white and the whole becomes white. It changes to a white horse, and when the temperature is lowered to below 10 degrees Celsius, the thermochromic nonwoven fabric part returns to blue, returning to the hue of a zebra.
It exhibited reversible thermochromic properties. Example 10 Spiro[isobenzofuran-1(3H),9′-
[9H]xanran]-3-one, 2'-chloro-6'-
(diethylamino)-3'-methyl-0.6 part, spiro[isobenzofuran-1(3H), 9'[9H]xanthene]-3-one, 2'[bis(phenylmethyl)amino]-4'-methyl-6 '-(diethylamino)-0.4 parts,
A thermochromic composition consisting of 3 parts of benzyl 4-hydroxybenzoate and 25 parts of stearin alcohol is encapsulated by a coacervation method using gelatin/gum arabic, and the particle size satisfies r≦10√.
150 parts of 8μm thermochromic microcapsules, solid content approx. 45
% acrylic-vinyl acetate copolymer emulsion
500 parts of the coating composition was uniformly mixed on a polyacrylonitrile pile with a pile length of 10 mm (d=
1.17) Spray the pale yellow tail of a regular squirrel stuffed toy made of fabric with a spray gun90
After drying at ℃ for 10 minutes, a thermochromic stuffed squirrel was obtained. The thermochromic squirrel stuffed animal mentioned above has a reversible thermochromic color change in which the tail part turns brown when the temperature is below 53℃, changes to light yellow when the temperature rises above 53℃, and returns to brown when the temperature is lowered to below 53℃. showed his sexuality. Example 11 Crystal Violet Lactone 1 part, 4,4
- A thermochromic composition consisting of 2 parts of methylene diphenol and 25 parts of butyl palmitate is mixed with an acrylic resin/
r≦ encapsulated by interfacial polymerization method using amine curing agent
10D vinyl chloride-vinylidene chloride copolymer in a coating composition in which 300 parts of thermochromic microcapsules with a particle size of 12 μm satisfying 10√ and 400 parts of an acrylic acid ester emulsion with a solid content of approximately 45% are mixed uniformly. After soaking 500 parts of raw cotton, remove excess coating composition with an air gun and heat to 100℃.
The thermochromic vinyl chloride-vinylidene chloride copolymer raw cotton obtained by drying for 10 minutes is applied to a card to make a sliver, and then the thermochromic spun yarn obtained through the spinning process is used to make the back part of a regular cloth turtle stuffed toy. A thermochromic stuffed toy of a turtle was obtained by embroidering a pattern on it. The thermochromic stuffed turtle mentioned above has a blue pattern on its carapace when the temperature is below -10℃, but the pattern disappears when the temperature is above -10℃, and when the temperature is lowered to below -10℃ again, it becomes blue. The pattern is restored,
It exhibited reversible thermochromic properties. As explained above, the present invention has the ability to reversibly change color due to temperature changes, and has extremely excellent uniformity, flexibility, texture, scratch resistance, and washability that are the same as those of general stuffed animals. The present invention provides a novel thermochromic stuffed toy that has functions and effects that have not been previously known.

Claims (1)

[Claims] 1. The surface of each elementary fiber of a fiber consisting of a plurality of elementary fibers has the following formula r≦10√ [r: pigment particle size (μm). D: Denier number of basic fiber (denier). d: Specific gravity of elementary fiber (g/cm ³ )]
A thermochromic layer consisting of a thermochromic pigment and a binder made of a thermochromic material consisting of a combination of an electron-donating color former, an electron-accepting color developer, and a discoloration temperature regulator, with a particle size that satisfies the above conditions. The thermochromic layer has an adhesion amount of 3% to 90% by weight with respect to each elementary fiber, and the thermochromic pigment has an adhesion amount of 5% to 90% by weight in the thermochromic layer.
A thermochromic stuffed toy comprising a thermochromic cloth made of 80% by weight thermochromic fibers on at least a part of the surface of the stuffed toy. 2 Claim 1 in which the thermochromic cloth is a woven cloth
Thermochromic stuffed animal described in section. 3. The thermochromic stuffed toy according to claim 1, wherein the thermochromic fabric is a nonwoven fabric. 4. The thermochromic stuffed toy according to claim 1, wherein the thermochromic cloth is a knitted fabric. 5. The thermochromic stuffed toy according to any one of claims 1 to 4, wherein the thermochromic cloth is a pile fabric. 6. The thermochromic stuffed toy according to any one of claims 1 to 5, wherein the thermochromic cloth is a pile fabric with a pile length of 3 mm or more.