TEXTILE MATERIAL THERMOCHROMIQUE

The present invention relates to a textile material thermochromic that changes color reversibly The temperature. More particularly, the invention relates to a textile material such as fibers, filaments, fabrics, andc, wherein the surface of each fiber is coated with a thermochromic coating containing a binder and a thermochromic pigment having a specific particle size. Thermochromic The textile material of the present invention is applicable to a wide range of textile products such as drapery, bedding, interior decoration, toys, andc.

In the production of fibres that undergo a color change with temperature, is has specified a liquid crystal ink in the Japanese Patent Publication n " 2532/76. This technique comprises applying an ink liquid crystal on one or both sides of a supporting sheet of deep color, e.g., black or deep blue, and The cutting the coated sheet to form filaments flat or twisting of the flat filament around a core yarn twisted to form a filament. Therefore, the product is a sheet rather than a fiber, because it has a special shape different fibre in general. The freedom of shapes and properties are so limited that is cannot satisfy the requirement for various shapes depending on the goals. The use of liquid crystals themselves reduced dramatically moisture resistance, which makes it impossible to wash the product. Furthermore, this technique has disadvantages in that additional The products are limited to only deep coloring; the color change temperatures cannot be arbitrarily selected; and the products are of a high cost. In The detail, although the sheet material has a thermochromic coating same on both upper and lower faces, its two cut edges are not coated with the thermochromic layer if, in a thin ribbon of the sheet coated with the thermochromic layer, the proportion of the surface coated with the thermochromic layer is reduced to one half or even less, which results in an effect thermochromic extremely deteriorated.

These drawbacks have failed The practical use of these products. Therefore, Most is sought to develop fibers that can change color in a wide range

at temperatures optional.

An object of the present invention is to provide

thermochromic a textile material in the form of fibers, wad raw, filaments, fabrics, etc, which can eliminate limitations described above and which can be used with any type of textile products.

The present invention relates to a textile material comprising fibres having thermochromic The surfaces are coated with a thermochromic layer containing a binder and a thermochromic pigment having a particle size satisfying the following relation:

0,01 < r < 1θ/D/d

wherein r represents the particle size of the pigment ; μπΐ D is the fineness of the fiber denier; and d is the density of the fiber by g/cm ^.

The invention be included at the reading the description which will follow, with reference to the accompanying drawings in which Figures 1 to 6 each represent one embodiment of the fabric thermochromic according to the present invention, wherein the references figures 1 to 3 designate the thermochromic fibres, the fibres the fabric and non- thermochromiquës thermochromic, respectively.

The size of particles of the thermochromic pigment which can be used in the present invention must satisfy the above relationship, so that the resulting fiber can exert a thermochromism satisfactory and uniform. In the textile material according to the present invention, as each of the fibers the component is independent, the thermochromic pigment is uniformly distributed in the fibers and the resulting fibers have good texture and are free of irregularities in the thermochromic properties. The invention has been found according to the invention that Changes irregular color coated fibers with a pigment thermochromîque is due to an uneven distribution of the pigment and that it is assigned to the bridging the pigment to more fibers. That is, when the pigment is connected to a plurality of fibers in a bridge, the thermochromic pigment tends more to join thereto bridged. As a result, the distribution of the pigment becomes non-uniform, which ultimately leads to irregular a thermochromism. Having since the irregular color change is from bridging phenomenon of the pigment, cannot avoid irregular The color change by simply adjusting the particle size of the pigment and the relationship between the size of particles of the pigment and the fineness of the fiber is an important issue.

Following further searches based on the discovery described above, the applicant is aware has now discovered that it is possible to properly avoid this bridging phenomenon leading to irregular a color change when the pigment and the fiber are linked by the relationship r < 10/575. It should be noted herein, however, than the minimum dimension of pigment particles generally available is about 0.01 pm.

The, it specifies the relationship between the fineness of the fiber and the particle size of the thermochromic pigment by the three following variables: r dimension

of particles of the pigment pm, D denier of the fiber density and d

3

of the fiber by g/cm, is that the specification simply by the fineness of the fiber and the size of particles of the pigment is not intended in no way prevent bridging above mentioned pigment particles in If of fibers having straight sections modified, such as a polygon and flattened shape.

The present invention is further characterized

by the thermochromic layer comprising a pigment and a binder which covers the individual fibers. Because of this feature, the entire textile material has not only a uniform distribution of the thermochromic pigment, but also a texture, flexibility and adhesion to the uniform pigment. Thermochromic The fiber is a new constituent unit which has never been described. For example, the thermochromic material according to the Japanese Patent Publication no.2532/76 is not provided with the thermochromic coating. over its entire surface. Therefore, the raw linters, ^ fabrics filaments, andc, fibres compounds according to the invention are all new materials having a thermochromism, texture and adhesion to uniform pigment.

In the present invention, can be used effectively as thermochromic pigments of the invention reversible thermochromic materials comprising combinations of known conventional chromogenic compounds electron donors and developers of electron acceptors. Examples reversible thermochromic materials are described in the known patent EUA of n, British Patent no. 1,405 701, patent RFA 2,327 723, the French patent 2,186 516 and Canadian patent 1,025 200.

More particularly, the thermochromic pigments for use according to the invention include a combination of: (a) a chromogenic compound electron donor, (b) a developer electron acceptor, such as a compound having a phenolic hydroxyl group or a salt thereof, an aromatic carboxylic acid, an aliphatic carboxylic acid in ^C 2~^C 5' ^^{es is} *-^s aliphatic carboxylic acids, alicyclic or aromatic, and acid esters phosrhorique and their metal salts, 1, 2, 3-triazole and its derivatives, the halohydrins, andc, and (c) an agent for regulating the temperature of color change, such as alcohols, esters, ketones, ethers, acid amides, aliphatic carboxylic acids or more, thiols, sulfides, disulfides, sulfoxides, sulfones, andc.

Specific combinations of these components (a),

(b) and (c) and their color change temperatures are indicated in the following table.

Temperature changes color stands

40 °C

orange colourless

50 °C

green --^ colourless

υΐ

20 °C

blue.^v colourless

green

33 °C colourless

r noi

45 °C

colourless The thermochromic pigments described above may change color reversibly and a colored state such as red, blue, yellow, green, magenta red, brown, black and any other delicate color tone obtained by mixing, to a colorless state or vice versa at a temperature between about -30_e t +100 °C. Can be added to these thermochromic materials a fluorescent brightener agent for whiteness to the colorless state and increasing the contrast.

The thermochromic pigments can transmit the light to become transparent in the temperature variation to view the bottom through the thermochromic transparent layer. The thermochromic materials described above can be formulated into pigments by reducing the particle size, for example by micro-encapsulation, emulsification in various resins followed by curing, curing sufvre spraying by spray drying or solidification or curing and spray end.

The thermochromic pigment thus prepared is mixed with a binder to form a thermochromic coating composition.

The binders for use according to the invention include waxes, thermoplastic resins low-melting, rubbers, natural resins and conventional synthetic resins. Examples of such binders are the low molecular weight polyethylene, polyesters low-melting, ethylene-vinyl acetate, the chlorinated rubber, the polyvinyl acetate emulsion, polyethylene emulsions, acrylic emulsions, the emulsions of styrene resins, butadiene-nitrile emulsions, shellac, zein, unsaturated polyester resins, epoxy resins, resins of the cellulosic type, of the polyurethane resins, phenolic resins, vinyl chloride resins, vinyl acetate resins, silicone resins, polyvinyl alcohol, polyvinyl methyl ether The, andc.

In addition The above components, may also be used in combination of components such as dyes, fluorescent dyes, pigments, fluorescent pigments, luminescent pigments f ' light-storing "), etc The addition of these color components performs reversible color changes between a colored state and another colored state. More particularly, fibers can be obtained which undergo a reversible color change between two colored states Ca) by adding the above colored component to a thermochromic composition to form a thermochromic color changing pigment reversibly between colored states and application of the resultant pigment to fibers, Cb) by encapsulation or fine spray of a mixture comprising the thermochromic pigment changes color reversibly between a colored state and a colorless and the dye component above and application to the fibers of the microcapsules or of the composite material in the resulting particles, or (c) by applying the thermochromic pigment to reversible change in color between a colored state and a colorless state onto fibres which have been colored by dyes or pigments general. It is also possible to use a method comprising mixing coated fibers by the reversible thermochromic pigment change between states and colored fibers colored by dyes or pigments general.

The thermochromic pigment is ordinarily present in the thermochromic composition in the total amount of 5 to 80 % by weight and preferably from 10 to 60% by weight, solids, the point effect thermôchromiques. If the pigment content is less than 5% by weight, The, color density is too low for viewing significantly the color changes. Contents For against exceeding 80% by weight do not allow for complete disappearance of the color. Therefore, the range of 10 to 60% by weight specified above is the optimum range for maintaining a good balance between the density and the color change.

Thermochromic The coating composition to form a layer which comprises the thermochromic thermochromic pigment and the binder described above and, if desired, a colored component may also comprise conventional additives such as antioxidants, ultraviolet absorbers, andc, for prolonging the thermochromic functions.

Thermochromic The coating composition thus prepared is applied to fibers to obtain theromchromicfibres of the present invention, which change color reversibly between a colored state and a colorless state or between two. colored states in accordance with changing temperature.

Thermochromic The coating composition is suitably applied in an amount of 3 to 90% by weight, based on the dry fiber weight of, an amount of 5 to 70% by weight being particularly preferred in color shift effects of thermochromism. The specific amount or concentration of the thermochromic layer has been determined from the following conclusions of intensive studies of which the applicant is aware. Quantities of less than 3% by weight are favorable for texture, but too low to produce a color change net, which makes the fiber unable in, practice. If the amount exceeds 90% by weight, the color density is sufficiently high for a color change net, but can be easily producing a fusion between the fibers whereby it is difficult for each fiber exist independently. Therefore, the texture of the resulting textile material is so altered that are not producible a soft feel. Fibers having the high concentration of thermochromic The layer are therefore suitable not practice.

Therefore, The concentration in The range of 3 to 90% by weight enables the practical use, in which all the conditions of color density, color change net and soft texture are satisfied. In particular, a range of 5 to 70% by weight gives a sufficient color density and a color change sufficiently net and allows each fiber exist quite independently without fusion with the other fibers. Thus the fiber having the preferred concentration of the thermochromic layer presents results quite excellent due to

of these good balance such as soft texture and sufficient bonding strength of the pigment.

Individual fibers can be used of various materials and various shapes to the coating with the thermochromic pigment according to The present invention. For example, can be used natural fibers, semi-synthetic fibers, synthetic fibers, other fibers such as copolymers chemical fibers, inorganic fibers, metal fibers, andc. Specific examples of such fibers are cotton The, the wool, goat hair. The camel hair, the hair Bunny, silk, the raw silk filament, the fibers of casein, soy protein The fibers, the fibers of zein, The fibers of peanut protein, the floss regenerated, Viscose, rayon cuprammoniacale , saponified acetate, the fibers of natural rubber, the fibers of alginic acid, the acetate fibers, triacetate fibers, staple fibers The acetylated, The fibers of ethyl cellulose, chlorinated rubber The fibers, polyamide fibers, polyester fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, the fibers of polyfLuoroéthylène , polyacrylonitrile fibres, polyvinyl alcohol fibres, the fibres "Promix", benzoate the fibers, the fibers of " polychlal ", polynosic the fibers, the fibers of acrylonitrile- alkylvinylpyridine , the fibers of acrylonitrile -vinyl chloride copolymers, the fibers of copolymers of vinyl chloride-vinylidene chloride, the.

fibres copolymers of vinyl chloride-vinyl acetate, The fibers of copolymers of vinyl chloride-acrylonitrile, The fibers of vinyl chloride-ethylene copolymers, the glass fibers, the rock wool, The ceramic fibers, The carbon fibers, andc.

For The fiber shapes, the fibers which may be applied to the present invention include not only those having a general shape of fibres, but fibers modified sectionsdroites such as triangular cross-section fibers, pentagonal, octagonal, the fibers cross-section in the Y, L-shaped, star, dumbbell, horseshoe, to planar shape, andc; the hollow fibers having hollow straight sections as the fibers in macaroni, The fibers-section nidsd' abeilies , sponge, checkerboard, andc; and the conjugate fibers such as those of the type "side by side", core type and envelope, matrix type, andc. Fibers to modified cross section and the hollow fibers are advantageous to obtain high concentrations of pigments because they are high specific surfaces and readily accept pigments"

As described above, since the textile materials according to the invention include fibers that are each coated with a thermochromic layer by use of a thermochromic pigment having a particle size selected according to the fineness of the fibers for use, they have excellent performances with respect to uniformity, flexibility, the texture, the frictional resistance, cleaning ability and finish properties and are therefore applicable to a wide range of textile products as described below.

The methods for obtaining textile materials

according to the present invention from theromchromicfibres are described in detail below.

Although with more or less variations according to the form of fibers, typically can be produce theromchromicfibres each coated by a thermochromic pigment by the method wherein there is applied a coating composition comprising a thermochromic pigment and a binder to fibers to be coated, which may have been corrugated if desired, by dipping, brushing, spraying, roll coating or a coating technique like, followed by drying. If desired, the resulting coated fibers may then be corrugated.

The wad (or fiber) raw thermochromic can be pro weft by cutting theromchromicfibres described above (crimped or corrugated or not) at the proper lengths. Furthermore, the wad blank can be produced by dipping the wad to be coated in raw The above described coating composition, removal of the excess composition by centrifugation or by the use of rollers squeezing or of an air gun and compressed air drying /; or application of the coating composition on the^has wad raw brush coating, to the cylinder, by spraying, etc, and then drying.

Thermochromic yarn may be produced using the thermochromic fibres described above (or non-corrugated) thermochromic as filaments. Thermochromic Several of these filaments may be twisted together to form continuous filaments thermochromic. Furthermore, the wad thermochromic raw above can be soumiseau carding to form a ribbon thermochromic which is then spun to provide spun yarns thermochromic.

A woven fabric can be produced by weaving the thermochromic thermochromic fibres described above to a loom in various structures such as plain weave fabrics, grooved weave, twill weave, satin weave, double weave, andc.

éfoffe can be obtained from a non-woven fibre mass which is obtained as follows. A form of a sheet of the thermochromic fibres filaments described above (is * corrugated or non-corrugated) or cut into appropriate lengths to form a wad raw thermochromic. Raw The wad thermochromic may also be formed by dipping the wad raw revêti r in the coating composition, removal of the composition under test using a centrifuge, of squeezing rollers, of an air gun andc compressed air, and drying or coating raw The wad directly with the composition by spraying, brushing, roll coating, andc and drying. The sheet of filaments of the fiber mass thermochromic thus obtained can be finished non-woven fabric as it is, but the raw material is to be formed into a tissue by carding. The stratifies with each other the necessary number of filament sheet or tissues and mechanically binds into one body by bonding, stitching or needling, or bonded to each other by soaking the laminate in an adhesive, by an adhesive spraying, incorporation of a powdered adhesive, in the form of wires or fibers between the sheets or tissues, or application of heat or pressure on the laminate.

Can be obtained by knitting the knitted fabric filament, thread or yarn thermochromic, andc The prepared same manner as in the production of a woven fabric thermochromic, tubular at the point, at point simple (plain knit), at the point (mesh) pearlescent, the rib stitch, at point simple " denbigh ", at point "simple atlas", the rib stitch simple, double point at " denbigh ", at point "double atlas", the rib stitch/double, at the point of lace, andc.

The sheet (pile fabric) thermochromic mentioned herein includes various sheets such as the fabric long-poi Is or "high-cell", the flocked fabric, andc. The sheet or fabric poi Is thermochromic is obtained by weaving the filament, thread or yarn thermochromic above as a warp yarn a velour structure chain as pile, plush, andc, or weft thread into a pile structure frame such as frame velvet, corduroy, andc, loops and cut at an appropriate position of bristles so as to cover the surface of the fabric. The loops may not be cut in the production of sponge cloth, carpet, andc.

Furthermore, the pile fabric sheet or thermochromic may also be obtained by applying the coating composition to a fabric poilspréalablement formed by a temper printing, coating, spraying or the like, drying the coated fabric loops and then cut. The fabric "High-cell" thermochromic is obtained by subjecting the raw material thermochromic described below to carding to form a wick which is then woven using a knitting machine "high-cell". Since the fabric "high-cell" has long-hair and a high content of a pigment thermochromic, it has properties thermochroraiques particularly excellent.

May be produced by cutting the flocked fabric thermochromic filament thermochromic described above into appropriate lengths to form flock and bonding the flock to a base by a technique such as spread mechanical flocking, vibration, spraying, etc, or a technique of electrostatic flocking.

Can be mixed thermochromic fibres according to the invention with uncoated fibers that do not have a thermochromic layer and that include the dyed fibers and the fibers undyed. The proportion of uncoated fibers mixing ranges from 0.01 to 20 weight parts e n, preferably 0.1 to 10 parts by weight, per part by weight theromchromicfibres. The mixing with the uncoated fibers is effective to increase the gloss, the volume and viewing color changes and also in order to decrease the net loads imposed directly to the thermochromic fibres by application of heat, exposure to light or ultraviolet, andc.

When increases the proportion of uncoated fibers mixing, the surface gloss of the textile material, resulting is further enhanced. However, if it exceeds 20 parts by weight, it becomes difficult to view the thermochromism significantly. Accordingly the range. of 0.1 to 10 parts by weight is particularly suitable for the thermochromism, the gloss and smoothness to the eye.

Embodiments textile materials of the invention are described below with reference to the accompanying drawings.

In the figures 1 to 6, the references 1, 2 and 3 denote theromchromicfibres, non-fabric thermochroraiques and a thermochromic, respectively. Figure 2 represents a pattern by a combination of fibers, and non-thermochromic thermochromic fiber having the cross-section shown in Figure 1. When the two types of fibres have the same color at room temperature, the drawing appears only the temperature change. Figure 3 represents a thermochromic fabric composed of a plurality of kinds of fibers thermochromic A to J with different colour change temperatures, in which a pattern, such as letters, drawings or digits, formed thereof can change or thermochromic

move with the temperature change. Figure 4 represents a fabric in which fibres 2 are masked by non-thermochromic theromchromicfibres 1 so that the fibers non-thermochromic 2 are hidden from view under normal conditions. If a drawing, for example letters, drawings, andc digits, is formed by the fibers non-thermochromic, the design appears when the thermochromic fibres states colorless or pale colored with change in temperature.

The occurrence and such disappearance of a design can be made more complicated. In detail, a design is formed in each case by the thermochromic fibres 1 and the fibers non-thermochromic 2, so that the pattern consisting of 2 may occur by a change in the color theromchromicfibres 1. Further a drawing can be formed by a combination of the fibres fibres 1 and 2 and another pattern is formed by the thermochromic fibres only such a pattern is converted into the drawing consisting of the combination of the two types of fibers with the temperature change. Figure 5 represents the variation of a three-dimensional pattern includes a combination of long fibers and short fibers, regardless of those thermochromic, the other being non-thermochromic. In the embodiment, the color change with temperature is excellent due to the three-dimensional design. Said effect is particularly strong in the case of a fabric covered with long fibers, for example a pile fabric. Figure 6 represents one embodiment wherein the ends of the fibers at the surface of the fabric are thermochromic and their "roots" are not thermochromic. The colour or non-thermochromic the fiber pattern appears when the ends of the fibers pass to a colorless state by change of temperature. In this case, the color of the fiber ends may be different from those of the root, or the fibers may be of different colors in three or more portions.

Therefore, thermochromic the fabric does not affect color only between a colored state and a colorless state ^ but also forms drawings of various colors.

The present invention can further a reversible color change between a natural color and another color, especially white. For example, when the pattern is formed by weaving or knitting natural color fiber thermochroraiques each coated with a reversible thermochromic pigment color changing between yellow and white, a reversible thermochromic pigment color changing magenta and between the white pigment and a reversible thermochromic color changing between the cyan and white, by means of a computer in accordance with each of the drawings, formed by splitting the design into natural couleuis designs in the three primary colors by means of a computer, the design true color appears and disappears with temperature changes. When these three types of thermochromic fibres are embroidered on a thermochromic with a computer to form the pattern of respective color selection, the design true color appears or disappears égaetement on the fabric of temperature changes.

Furthermore, when printing each of the coating compositions prepared from each of the three non-thermochromic pigments on a fabric using a printer to computer to form each of the patterns obtained by selecting three-color, a design true color appears and disappears to the printed area.

The textile materials according to the present invention can be applied to any type of textile products. Examples of textile products which The invention can be applied are the garments, such as sweaters, cardigans, body vests, Shirts, shirts, blouses, costumes, ', jackets, trousers, skirts, knitted fabrics, jumpers, sports clothing, work clothes, clothes Japanese, mantles, impermeable, dresses, pajamas, bathrobes, ski clothing, underwear, display, andc; tailored items or hosiery, such as socks, gloves, scarves, shawls, pass mountain, Barber, guard oreiLies , slippers, ties, webs or veils, belts, sanitary towels, tissues, bags, andc; the bedding Bed for example sheets, covers, gowns, cover feet, duvets, andc; the interior decorative articles for example carpet, / bootscraper, covers, cushions, carpet, curtains, scrim, wall hanging, drapery sound-insulating, packing coatings, lampshade, screens, blinds, andc; the safety locking device, by free artificial flowers, wire lapping b, ' tape, string, stuffed toys, doll's hair, vêtementsde doll, artificial snow for Christmas tree; the articles to the outside, by free sail cloth, tents, butter muslin, hoses, covers, tarpaulins, mountain boots, Lifeboats, backpacks, packaging web, parachutes, threads, etc;

and other, e.g. fake beard or moustache, false eyelashes, wigs, extension strands, balls, napkins, andc.

In the case of plush toys, for example, can be produced by cutting plush toys thermochromic thermochromic of the fabric of the invention to the dimensions of the paper patterns for the desired toy and sewing the cut pieces of the fabric. To this occasion, can be used different types of étoffesthermochromiquesayant various colors to obtain stuffed toys multiple changes of color. In reality the seam can be replaced by a glued joint or melt. Furthermore, the fabric can be partially set thermochromic to a plush toy a cloth made of non-thermochromic for manufacturing the toy thermochromic multi-color.

The The invention following examples illustrate but not limit the scope. In these examples, the parts and percentages include all by weight, except other indication.

Unfettered 1

The encapsulation a thermochromic composition comprising 1 part of the crystal violet lactone, 3 parts of benzyl 4-hydroxybenzoate and 25 parts of alcohol stéarytique by coacervation system in a gelatin-gum arabic to form microcapsules thermochromic having a particle diameter of 8 pm which satisfies the relationship r < VD/cT.

Is dipped 500 g of polyurethane fibers (d=1,21) of fineness 7D in a coating composition prepared by mixing uniformly 150 g of microcapsules obtained above, 450 g of an aqueous emulsion of urethane resin (solids content: about 41%)and 24 g of aqueous an epoxy resin, are removed from the coating composition, and is dried at 110 °C during 2 minutes to obtain 550 g of thermochromic polyurethane fibers. Resulting fibers were a blue color at temperatures below 53 °C, became colorless at temperatures of more than 53 °C and pass back to the blue at temperatures below 53 °C, indicating a reversible thermochromism.

Example 2

The encapsulation a thermochromic composition comprising 1 part 9-(diethylamino)-1-H-benzo-Cot spirod2 3xanthène -12, 1¹ (3 'H)-isobenzofuran -3' -one, 2 parts of bisphenol A, 15 parts of myristyl alcohol and stearyl caprate 10 parts by interfacial polymerization using a system epoxy resin-curing agent amine to obtain microcapsules of thermochromic having a particle size of 5 pm which satisfies the relationship r < Jl0 D/d. Is mixed uniformly 60 g of microcapsules thermochromic, 200 g of epoxy resin type diglycidyl ether and 80 g of a curing agent and amine coating composition is applied is 300 g fiber "nylon" (d=1,14), of fineness 5D with a spray gun, is then dried to 80 °C during 30 minutes to obtain 360 g of thermochromic nylon fibers.

Thermochromic The nylon fibers have a pink color at temperatures of -25°C, they become colorless at temperatures above 25 °C and saw again rose by lowering The temperature below 25 °C, indicating a reversible thermochromism.

Example 3

Is solidified to the heart a thermochromic composition comprising 1 part 2 '-chloro -6' -(diethylamino)-3 'methyl- spiroCisobenzofuranne -1 (3:00), 9' - C9H5xanthène ]-3-one, 2 parts of zinc benzoate and 25 parts of diphenyl ether using a system epoxy resin to hardener amine thermochromic to be fine particles having a particle size of 12 pm which satisfies γ ≤ 1θ7073. Is mixed uniformly 200 g of thermochromic microparticles and 800 g of an emulsion of acrylic ester resin having a solid content of about 42% and immersing copolymer fibers 1000 g of vinyl chloride-vinyl acetate (d=1,34) D of fineness 10 resulting in the coating composition, The is removed from the coating composition is dried at 90 °C and during 10 minutes to obtain copolymer fibers 1280 g of vinyl chloride-vinyl acetate thermochromic.

The fibers have a color vermilion at temperatures of less than 10 °C, they became colorless at a temperature of more than 10 °C and saw again at vermilion by lowering the temperature below 10 °C, indicating a reversible thermochromism.

Example 4

The portion to uniformly 1 '-(diethylamino)-3' -methyl -2'-(phenylamino)-1- spiroCisobenzofuranne (3Η), 9¹ C9H3 xan - thène ]-3-one, 3 parts 4-chlorobenzoic acid and 25 parts of stearic amide with 750 parts of polypropylene. The mixture is cooled and sprayed finely thermochromic to obtain fine particles having a particle diameter of 4 Committee pm which the relationship r < 10/D/cJ. Is mixed uniformly 200 g of the fine particles and thermochromic 800 g of an emulsion of vinyl acetate-ethylene terpolymer-vinyl chloride having a solid content of about 50% and is immersed in the resulting coating composition 1000 g of silk fibers (d=1,33) having a fineness corresponding to 3D, removed and dried at 100 °C during 5 minutes to obtain g silk fibers 1080 thermochromic.

Resulting silk fibers have a black color below 9S°C, became colorless above 95 °C and black again below 95 °C, indicating a reversible thermochromism.

Example 5

Is solidified to the heart a thermochromic composition comprising 1 part of 3, 3-bis (1-ethyl-2-methyl-lH-indole-3-yl)- isobenzofuranmone -1 (3:00), 2 parts of zinc salt of bisphenol A parts and 25 cetyl alcohol using a system epoxy resin to hardener amine thermochromic to obtain fine particles having a particle size of 4 pm which satisfies < The relationship r loJÔTd. Is mixed uniformly 100 g of the fine particles and thermochromic 700 g of an emulsion of acrylic ester copolymer vinyl acetate copolymer having a solids content of about 45% for preparing a coating composition. Is dipped in the coating composition 800 g fiber acrylonitrile-vinyl chloride copolymer of fineness 5D having a flattened cross-section, is The in then removed and dried to 100 °C during 10 minutes to obtain fibres with copolymer acrylonitri the-vinyl chloride (d-1,25) thermochromic. The fibers are subjected to the undulation and cut to a length of 127 mm 880 g of fluffy material to obtain crude acrylonitrile-vinyl chloride copolymer thermochromic.

The resulting material has a color pink below 40 °C, becomes colourless above 40 °C and again rose below 40 °C indicating a reversible thermochromism.

Example 6

Is subjected to encapsulation by interfacial polymerization a thermochromic composition consisting of 1 i e of crystal violet lactone, 3 portions 4-octyl hydroxybenzaote and 25 parts butyl stearate using a system acrylic resin/amine curing agent to obtain the thermochromic microcapsules having a particle size of 12 pm that satisfies the relationship r < 1o/d7S. Is mixed uniformly 100 g of microcapsules and 650 g of an emulsion of ethylene vinyl acetate copolymer having a solid content of about 50% for preparing a coating composition. 0n projects the coating composition to 700 g fiber-vinyl chloride copolymer vinylidene chloride (d=1,7) of fineness 10D which have been subjected to the corrugation, using a gun

spray, and then dried to 90 °C during 15 minutes.

The fibers are cut obliquely thermochromic copoLymère vinyl chloride-vinylidene chloride resulting lengths of 50 to 90 mm to obtain 790 g raw linters thermochromic copolymer vinyl chloride-vinylidene chloride.

The wad resulting raw a blue color below 10 °C, becomes colourless above 10 °C and to novel blue by lowering the temperature below 10 °C, indicating a reversible thermochromisree.

Example 7

The uniformly 1 portion of crystal violet lactone, 2 parts 4.4 '-methylene-bisphenol and 25 parts stéarone with 800 parts of polyethylene and the mixture is cooled and sprayed thermochromic to form fine particles having a particle size of 8 pm which satisfies γ ≤ 10ΑΤ73. Is mixed uniformly fine particles thermochromic 300 g and 400 g of an emulsion of acrylic ester having a content solidesd' about 45% for preparing a coating composition. Is dipped in the coating composition g 500 raw stripped. polyacrylonitrile of fineness 7D (d=1,17) cut obliquely at lengths of 80 to 130 mm and after removal of the excess of the composition by centrifugation, is dried at 100 °C during 10 minutes to obtain 650 g of a crude staple polyacrylonitrile thermochromic.

The material resultant crude has a blue color below 85 °C, it becomes colourless above 85 °C blue and again below 85 °C, indicating a reversible thermochromism Example 8

The microencapsulation a thermochromic composition consisting of 1 part 3 ', 6' -dimethoxy-spiro- Cisobenzofuranne -1 (3:00), 9 '- C9H ] xanthene]-3-one, 2 parts of dodecyl gallate and 25 parts of caprylic acid by coacervation system in a gelatin/gum arabic to obtain microcapsules of thermochromic having a particle size of 10 pm which satisfies the relationship r < 10/D/d.' is mixed uniformly 500 g of microcapsules and 500 g of a resin emulsion acrylic ester having a content solidesd' strate ron 42% for preparing a coating composition and is immersed in the coating composition 800 g of cotton (d=1,54) having a fineness corresponding to 5D, be wrung out and used between squeezing rollers and is dried at 110 °C during 3 minutes to obtain 980 g of thermochromic cotton.

Cotton thermochromic resulting yellow below 15 °C, it becomes colourless above 15 °C and yellow again by lowering the temperature below 15 °C, indicating a reversible thermochromism.

Example 9

The microencapsuLation by interfacial polymerization a thermochromic composition consisting of 1 part 6 '-(cyclohexylamino)-3' -methyl -2 '-(phenylamino)- spiroEisobenzo -furan -1 < 3:00), 9' - E9H3xanthène3 -3-one, 2 parts 5.5 '-bis < 1, 2, 3-benzotriazole) and 25 parts of myristyl alcohol using a system/phenol acid chloride to obtain microcapsules of thermochromic having a particle size of 4 pm which satisfies 1a γ ≤ relationship lo/V/d. Is mixed uniformly 500 g of microcapsules thermochromic and 450 g of an emulsion of vinyl acetate-ethylene terpolymer-vinyl chloride having a solid content of about 50% for preparing a coating composition, is immersed in the composition 750 g of polypropylene fibres < d = 0, 91) of fineness 3D, needed then removed and the.

dry 100 °C during 5 minutes to obtain polypropylene fibers thermochromic. The resulting fibers are formed of a bundle of fibers that the 30 is twisted with the number of twists of 30 by m to obtain a polypropylene yarn thermochromic.

The resulting wire is black temperatures less than 38 °C, becomes colourless above 38 °C and black again by lowering the temperature below 38 °C indicating a reversible thermochromism.

Example 10

Is solidified to the heart a thermochromic composition consisting of 1 3-(1-ethyl-2-methyl -1:00-indole-3-yl)-3-(4-diethylaminophenyl)-1 < 3:00)- isobenzofurannone , 2 parts naphthoic acid, 12.5 parts palmitic acid and 12.5 parts of decyl caprylate system èpoxydique with a resin to hardener amine thermochromic to obtain fine particles having a particle size of 10 pm which satisfies The relationship γ ≤ 10^0/ ℮ Τ. is. sprayed a coating composition prepared by uniform mixture of 60 g of the fine particles resulting thermochromic, 200 g of an epoxy resin and 80 g of a curing agent amine on 300 g Nylon fiber fineness 5D corrugated, is then dried to 80 °C during 30 minutes to obtain nylon fibres thermochromic (d=1,14). The The nylon fibers and bundles of fibers 25 is twisted The with the number of twists of 40 by m to obtain 350 g of a nylon yarn thermoch romique.

The nylon yarn resulting blue color below -3°C, becomes colourless above -3°C blue and again below -3°C, indicating a reversible thermochromism. Example 11

The uniformly 1 portion 3 '-(diethylamino)-6' , 8 '-dimethyl- spiroCisobenzofuranne -1 (3:00), 9' - C9HDxanthèneD -3-one, 2 parts of 1, 1-bis (4-hydroxyphenyl) cyclohexane and 25 parts ether dilaurylique with 750 g of polypropylene and the mixture is cooled and sprayed finely thermochromic to obtain fine particles having a particle size of 8 pm which satisfies < The relationship r 1o/O/d. Is mixed uniformly 500 g of the fine particles and thermochromic 500 g of a resin emulsion acrylic ester having a solids content of 45% for preparing a coating composition and is immersed into The coating composition 500 g hollow fiber polyacrylonitrile cndulées (friséesO of fineness 7D, sponge cross-section, is The in then removed and dried to 100 °C during 10 minutes to obtain fibres with polyacrylonitrile thermochromic (d=1,17). Are cut obliquely the resulting fibers to lengths of 100 to 150 mm to form a raw staple polyacrylonitrile thermochromic. The The wad pig unruban carding to form which is then spun to obtain 600 g of yarn comprising hollow fibers of polyacrylonitrile thermochromic.

Spun The thermochromic resulting orange color below 30 °C_/ colourless becomes above 30 °C and orange again by decreasing temperature below 30 °C and indicates a reversible thermochromism.

Example 12

A thermochromic composition, consisting of 1 part to '- Cdiéthylamino)-Z' - Ccyclohexyl (phenylmethyl) amino]-1- spiroCisobenzofuranne (3:00), 9' HI8H3xanÎhène3 -3-one, 3 parts of 5-chloro -1, 2, 3-benzotriazole and 25 parts of butyl palmitate, for the microencapsulation by interfacial polymerization using a polyisocyanate system/amine-type curing agent to obtain microcapsules of thermochromic having a particle size of 10 pm which satisfies γ ≤ 10 ^ Β7Η. Is mixed uniformly 100 g of microcapsul. and 500 g of a polyester resin emulsion having a solid content of about 25% for preparing a coating composition. Is dipped in the coating composition 500 g of fluffy material raw polyester (d=1,38) of fineness 8D, which has been teinteen yellow and after removing the excess composition by means of an air gun to air, is dried at 100 °C during 5 minutes. Polyester raw The wad thermochromic resulting soumiseau carding to obtain a ribbon which is extruded to obtain 600 g of yarn thermochromic.

The spun resulting green below -10°C, turns yellow above -10°C and back to the green by lowering the temperature below -10°C < > indicating a reversible thermochromism.

Example 13

Is subjected to the undulation the polyurethane fibers obtained to the thermochromic example 1 and is twisted fiber bundles 30 each corrugated to the number of twists of 35/m. The thermochromic fit twisted resulting plain weave woven on a loom. The resulting cloth thermochromism has the same as the example 1.

Example 14

The taper of nylon fibers obtained to the thermochromic example 2 in lengths of 70 to 130 pm, the wad resulting raw to carding to form a ribbon which is then filéen a spun yarn. Spun yarn is woven on a loom with the twill weave serge to obtain a nylon thermochromic.

Thermochromism The fabric has the same as the example 2.

Example 15

The taper of the hollow fibers of polyacrylonitrile (d=1,17) of fineness 10D sponge having a straight section into lengths of 80 to 130 mm is immersed and 1000 g of the wad resulting raw in the same amount of the same coating composition as the example 3. After removal of the excess composition by centrifugation, is dried raw The wad 90 °C during 10 minutes, subjected to the carding to form a ribbon and is

the queue to form the. Resulting The spun yarn is woven on a loom with the satin weave satin polyacrylonitrile to obtain a hollow fiber thermochromic thermochromism having the same as the example 3.

Example 16

Fiber bundles are formed each comprising

in 30 silk fibers obtained to the thermochromic example 4 and are twisted with a number of twists of 40/m. The continuous filament The queue silk thermochromic resulting on a loom with the rep weave to obtain a silk fabric having thermochromic to rep weave The same thermochromism as the example 4.

Example 17

Is dipped 800 g of curled fibers (crimped), cfe ccpdymère vinyl chloride-vinyl acetate Cd=1,34) of fineness 5D in

the same amount of the same coating composition as the example -5, needed then removed and dried to 100 °C during 10 minutes. Severance thermochromic fibres copolymer vinyl chloride-vinyl acetate resulting to a length of 45 mm and

moulded to form a sail with a carding machine. The stratifies in parallel layers 4 sheets of the resulting web and the laminate is immersed in a resin emulsion SBR, is expressed by rollers and dried to a non-woven fabric thermochromic copolymer vinyl chloride-vinyl acetate. Thermochromism The fabric has the same as the example 5.

Example 18

Encapsulated thermochromic the same composition as the example 6 by interfacial polymerization using a system polyisocyanate/amine curing agent to obtain microcapsules having a thermochromic dimensioned particles pm 12 which satisfies The relationship r < 1 oJÔ /' d. Is mixed uniformly 100 portions of the microcapsules and 650 parts of an emulsion of ethylene-vinyl acetate copolymer having a solid content of about 50% for preparing a coating composition. 700 parts is dipped polyester raw linters (d=1,38) of fineness 10D in the coating composition, is centrifuged to separate the excess of coating composition and is dried at 90 °C during 15 minutes to obtain a raw wad thermochromic polyester. The wad pig carding to form a web.

The cross-ply laminate sheets of the web 3 and sprayed thereon a resin emulsion NB. R through a spray nozzle and then dried to a thermochromic polyester non-woven fabric.

Nonwoven The éfoffe thermochromism has the same as the example 6.

Example 19

Encapsulated by interfacial polymerization a thermochromic composition consisting of 1 part of crystal violet lactone, 2 parts of 4, 4- méthylènediphénol and 25 parts of butyl palmitate using a system acrylic resin/amine curing agent to obtain microcapsules of thermochromic having a particle size of 12 pm which satisfies the < relationship r 1 ojo/d. Is mixed portions of the microcapsules uniformly 300 and 400 parts of an emulsion acrylic ester having a solid content of about 45% for preparing a coating composition is immersed parts 500 raw linters-vinyl chloride copolymer vinylidene chloride (d=1,7) of fineness 10D and, after removal of the excess of the composition using a air gun compressed air, is dried at 100 °C during 10 minutes. The raw The wad thermochromic copolymer vinyl chloride-vinylidene chloride resulting carding to form a sliver which is then spun to. obtain a thermochromic spun.

The filament is knitted using tubular to obtain thermochromic a knitted fabric.

The knitted fabric is blue color below -10°C, it becomes colourless above -10°C and blue again by decreasing the temperature below -10°C indicating a reversible thermochromic.

Example 20

The portion uniformly 1 9-( diéthymaino)-H- benzoCaJxanthène spiroC12 -12, 1 * (3 'H)-isobenzofuran -3' -one,

2 dodecyl gallate portions 25 and portions stéarone with 800 parts of polyethylene and the mixture is cooled, and is then powdered thermochromic to obtain fine particles having a particle size of 10 μΐη r which satisfies the relationship <10>/D/d. Is mixed uniformly 500 portions of the fine particles and 500 parts of a polyester resin emulsion having a solid content of about 25% to result in a coating composition and is immersed in the coating composition 800 parts of polyester fibers (d=1,38) of fineness: 7D having a triangular cross-section, needed then removed and dried to 100 °C during 5 minutes. The polyester fibers are subjected to the resulting thermochromic frizzing and turning the crimped fibers in fiber bundles each consisting of 35 and fibers are twisted to the number of twists of 30/m. The filament yarn (continuous wire) thermochromic resulting knitted using double denbigh on a knitting machine to produce a fabric.

The fabric is pink color below 85 °C, it becomes colourless above 85 °C and again rose by lowering the temperature below 85 °C, indicating a reversible thermochromism.

Example 21

Is encapsulated by coacervation a thermochromic composition consisting of 1 part 6 '-(diethylamino -2' Ccyclohexyl (phénylméthy U- aminoIl -spiro [isobenzofuran -1 (3Η), 9 '- C9H3xanthène3 -3-one, 2 parts 5.5' -bis (1, 2, 3-benzotriazole) and 25 parts of caprylic acid using a system gelatin/gum arabic to obtain microcapsules of thermochromic having a particle size of 8 pm which satisfies the < relationship r 1 ojb /d. Is mixed uniformly 500 portions of the microcapsules with 450 parts of a-emulsion acrylic ester resin having a solid content of about 42% for preparing a coating composition and is immersed in the coating composition 700 fiber portions vinyl copolymer acrylonitrileacétate of fineness ôD dyed yellow, ? needed then removed and dried to 90 °C during 10 minutes. Severance thermochromic fibres copolymer acrylonitrile- acêtate resulting vinyl Cd -1^183 to a length of 3 mm to form hair thermochromic for flocking, , which are then flocked electrostatically, on a coated paper to obtain a flocked fabric thermochromic.

The resulting flocked fabric is green color below 15 °C ^ it turns yellow above 15 °C and back to the green below 15 °C indicating a reversible thermochromism me.

Example 22

Is solidified to the heart a thermochromic composition consisting of 1 part 3%6 '-dimethoxy-spiro [isobenzofuran -1 (3:00) , 9 '-[ 9:00] xanthène3 -3-one^2 parts naphthoic acid and 25 parts of myristyl alcohol using a system epoxy resin/hardener amine thermochromic to obtain fine particles having a particle size of 12 pm which satisfai. t the relationship r :? l0jB /d. Is mixed uniformly 600 thermochromic portions of the fine particles with 1000 parts of an emulsion copolymer resin acrylic ester-vinyl acetate having a solid content of about 50% for preparing a coating composition. The coating composition is applied to fibers of NyLon of fineness (d=1,14) 80 by means of a spray gun and is dried at 100 °C during 10 minutes, , and then cut the nylon fibers resulting thermochromic at a

of 5 mm to obtain bristles thermochromic for the flocking " The bristles are electrostatically flocked on a nylon fabric having a urethane fusion bonded expanded to produce a fabric flocked thermochromic.

The flocked fabric is coloured yellow below 38 °C, it becomes colourless above 38 °C and yellow again below 38 °C, indicating a reversible thermochromism.

Example 23

Is encapsulated thermochromic composition consisting of 1 part 6'-(cyclohexylmethylamino)-3^, 2-methyl-^, -( phényt -amino)-1- spiroCisobenzofuranne (3:00), 9'- E9H3xanthène ]-3-one, 2 parts of 1, 1-bis (4-hydroxyphenyl)-cyclohexane, 12.5 parts palmitic acid and 12.5 parts of decyl caprylate by interfacial polymerization in a system/phenol acid chloride to obtain microcapsules of thermochromic having a particle size of 8 pm < satisfying the relationr | 10, D/d. Is mixed uniformly 200 portions of the microcapsules with 800 parts of an emulsion acrylic ester having a solid content of about 45% for preparing a coating composition is immersed 500 parts of cotton (d=1,54) having a fineness corresponding to 5D, is centrifuged to separate the excess composition is dried at 100 °C and during 10 minutes. The thermochromic the resulting raw staple carding to obtain a ribbon which is then spun. The yarn is woven on a loom for producing a sponge cloth thermochromic.

The cellulose sponge cloth is black below

-3 °C, becomes colourless above -3°C and again black by temperature decrease below -3°C, indicating a reversible thermochromism.

Example 24

Is encapsulated thermochromic composition, 3-C1 portion consisting of 1-ethyl-2-methyl -1:00-indole-3- yl)-3-(4-diethylaminophenyl)- isobenzofurannone -1 (3:00), 3 parts of 5-chloro -1, 2, 3-benzotriazole and 25 parts ether di ' lauryl, by coacervation to obtain microcapsules of thermochromic having a particle size of 7 pm satisfying ^ iojo r/d ". Is mixed uniformly 60 portions of the microcapsules, 200 parts of an epoxy resin and glÿcidylique ether 80 parts of an amine curing agent for preparing a coating composition. The composition is sprayed on a napped fabric at the point of biarritz having a pile length of 15 mm polyester fiber (d=1,38) of fineness 5D, is then dried to 80 °C during 30 minutes. The loops are cut to obtain a pile fabric polyester thermochromic.

The thermochromic resulting pile fabric

blue color below 30 °C, becomes colourless above 30 °C and blue again by decreasing temperature below 30 °C indicating a reversible thermochromism.

Example 25

Is solidified to the heart a thermochromic composition consisting of 1 part 3 '- Cdièthylamino)-6' , 8 '- diméthylspi roCisobenzofuranne -1 (3:00), 9' -[ 9:00] xanthèneIl -3-one, 3-phenylphenol portions 4 and 25 parts 1, 10-decanediol using a system acrylic resin/hardener amine thermochromic to obtain fine particles having a particle size of 4 pm < satisfying D | r 10/d. Is mixed uniformly 400 portions of the thermochromic fine particles and 600 parts of an emulsion terpolymer of vinyl acetate-ethylene-vinyl chloride having a solid teneuren of about 50% for preparing a coating composition. Is dipped in the coating composition 500 parts of polypropylene fibres (d=0,91) crimped fineness 3D, needed then removed and dried to 100 °C during 5 minutes to obtain polypropylene fibers thermochromic. The fibers are cut to a length of 50 mm to form a wad raw, is subjected to carding to form a ribbon and is knitted on a knitting machine for the web, and then is subjected to clip to obtain a polypropylene fabric shag thermochromic having a pile length of 20 mm.

Shaggy The fabric resulting orange color is below 70 °C, becomes colourless above 70 °C

orange and again by decreasing temperature below 70 °C, indicating a reversible thermochromism.

Example 26

The uniformly 1. of portion 6 '- Cdiéthylamino)-2' -[ cyclohexyl (phenylmethyl)-1-- spiroCisobenzofuranne amino3 (3:00), 9 '-[ 9inxanthène ;]-3-one, 3 parts 4.4' - thiobis (3-methyl-6-tert-butylphenol) and 30 parts of triglyceride of 12-hydroxystearic acid with 750 parts of polypropylene and the mixture is cooled and is The will spray finely thermochromic to obtain fine particles having a particle size of 8 satisfying μηΐ The relationship r ^ lo. JÔTd. Is mixed uniformly 600 portions of the fine particles and 400 parts of an emulsion acrylic ester copolymer vinyl acetate copolymer having a solids content of about 45% for preparing a coating composition. Is dipped in the coating composition 400 parts composed of raw linters fibers acrylonitriLe -vinyl chloride copolymer (d=1,25) of fineness 7D having a flat cross-section and a length of cut pile of 70 mm and, after removal of the composition attached by an air gun to compressed air, is dried at 100 °C to obtain a raw wad thermochromic. The wad pig carding to obtain a ribbon that is knitted in a knitting machine tissue

shaggy and is subjected to clip to obtain a fabric Longs bristles of acrylonitrile-vinyl chloride copolymer thermochromic having a pile length of 35 mm.

The fabric fleece is green resulting below 50 °C, it becomes colourless above 50 °C and green again by decreasing temperature below 50 °C indicating a reversible thermochromism.

Example 27

Is prepared three thermochromic compositions constituting the three primary colors, i.e. a composition-' a of the reversible change to white consisting of cyan.

1 3-(1-ethyl-2-methyl -1:00-indole-3-yl)-3-(4-diethylamino-phenol)- isobenzofurannone -1 (3:00), 2 parts of bis-(4-hydroxyphenyl) sulfone and 25 parts butyl stearate, a composition for magenta reversible change to white consisting of 1 part (diethylamino)-9-H- benzoCa spiroC12 ] xanthene -12, 1 '(3:00)- isobenzofuranne3 -3' -one, 2 parts of bis-(4-hydroxyphenyl) sulfone and 25 parts butyl stearate composition and a reversible change from yellow to white consisting of 1 part 3 ', 6' -dimethoxy- spiroCiso -benzofuran -1 (3:00), 9'- C9HIlxanthène ]-3-one, 2 parts of bis-(4- hydroxyphényDsulfone and 25 parts butyl stearate, each composition is encapsulated by coacervation system using a gelatin/gum arabic to obtain the corresponding thermochromic microcapsules having a particle size of 8 pm satisfying < r lO ^ D/cL is mixed uniformly each case 300 parts of the one of the three types of microcapsules with 700 parts of an emulsion acrylic ester having a solid content of about 48 % for preparing a coating composition.

Is dipped in the coating composition 400 parts of a raw wad composed of polyacrylonitrile fibers d=1,17) d e fineness 5D and, after removal of excess composition by centrifugation, is dried at 90 °C during 10 minutes. The thermochromic the resulting raw staple carding to form a ribbon. Knitted The the three types of tape on a knitting machine for the web to computer in accordance with the three-color drawings obtained by selection with a computer, and then to obtain a base fabric shag polyacrylonitrile thermochromic having a pile length of 22 mm.

Shaggy The resulting fabric has a true color drawing below 10 °C and becomes white above 10 °C. The figure true color appears again by lowering the temperature below 10 °C, indicating a reversible thérmochromisme.

Example 28

Beams are produced each consisting of 23 thermochromic fibres polyurethane obtained to the example 1 and 7 crimped fibers (corrugated) polyurethane fineness 7D uncoated (corresponding to approximately 0.3 part by portion of the fibers t. herao-■ chromic polyurethane) and twisted to the number of twists of 40/m. Thermochromic resulting the yarn is woven on a weaving machine to obtain a plain-weave fabric polyurethane thermochromic plain weave.

Example 29

300 is mixed raw nylon wad parts thermochromic obtained by cutting to a length of 100 mm nylon the thermochromic fibres prepared and the example 2

1200 parts polyester raw linters of fineness 7D using a card and into a web. The stratifies in parallel layers 4 sheets of the web, by quenching the laminate in a resin emulsion SBR, expresses and is dried to a thermochromic non-woven fabric.

Example 30

In the same coating composition as that used to the example 4, 800 is immersed fiber portions copolymer acrylonitrile-vinyl acetate Cd=1,18) of fineness 3D, needed then removed and dried to 100 °C during 5 minutes. Severance resulting thermochromic fibres to a length of 3 mm to obtain bristles for flocked finish. Is mixed uniformly 800 portions of the thermochromic bristles with 1000 bristle sections primer rayon flocked of fineness 3D uncoated having a pile length of 3 mm and is electrostatically flocked the bristles mixed on a cloth nylon having fusion bonded expanded urethane, to obtain a thermochromic flocked fabric having a pile length of 2.7 mm.

Example 31

The uniformly 1 portion 3 ', 6' - diméthoxyspiroCisobenzofuranne -1 (3:00), 9'- L9HDxanthène ]-3-one, 2 parts naphthoic acid, 12.5 parts palmitic acid and 12.5 parts of decyl caprylate with 800 parts of polyethylene and The mixture is cooled, and then finely The sprayed thermochromic to obtain fine particles having a particle size of 12 pm satisfying 1oÿD r $/ dl is mixed uniformly 200 parts of the resulting fine particles and 750 parts of an emulsion acrylic ester resin having a solid content of about 42% for preparing a coating composition and is immersed in the composition of raw parts 750 wad acrylonitriLe -vinyl chloride copolymer (d=1,25) of fineness 10D having a pile length of 51 mm and cut, after removing the excess composition nip rolls, is dried at 90 °C during 15 minutes. Furthermore, is uniformly mixed 750 parts of the resulting raw wad thermochromic, 150 parts raw linters acrylonitrile-vinyl chloride copolymer uncoated, of a fineness of 3D having a pile length of 38 mm cut and 150 parts of polyester raw linters a fineness of 5D, uncoated, having a pile length of 38 mm cut using a card in order to form a ribbon which is then knitted on a knitting machine for the web and is subjected to clip to obtain a thermochromic to long pile fabric having a pile length of 20 mm.

The fabric shaggy resulting yellow color below -3°C, it becomes colourless above -3°C and yellow again by decreasing temperature below

-3 °C, indicating a reversible thermochromism.

Each fabrics 28 obtained in the examples

thermochromism to 31 has a satisfactory and has a gloss and feel sufficient.

To evaluate the results of the textile materials according to the present invention, comparative samples are prepared as indicated in the following comparative examples and are subjected to comparative test as indicated in the examples following comparative test.

Is encapsulated by coacervation thermochromic the same composition as the example 1 in a system gêlatine /gum arabic to obtain microcapsules of thermochromic having a particle size of 30 pm, which is greater than 10*10/3.

A coating composition is prepared by mixing uniformly 150 g of microcapsules thermochromic, 450 g of an aqueous emulsion of urethane resin having a solids content d '-about 41% and 24 g of an epoxy resin and is immersed aqueous 500 g of polyurethane fibers (d=1,21) of fineness 7D, needed then removed and dried to 110 °C during 2 minutes to obtain 580 g of thermochromic fibres polyurethane.

Is achieved thermochromic-weave fabric

joined in the same way as to the example 13, except that the thermochromic microcapsules have a particle size of 30 μπΐ , which is greater than 10/ d7cL \

Is achieved thermochromic nonwoven fabric

in the same way as to the example 18, except that thermochromic The microcapsules have a particle size of 35 pm, which is greater than IOJdTcL

Thermochromic is achieved at point tubular knitted fabric in the same way as to the example 19, except that the thermochromic microcapsules have a particle size of 30 4m, which is greater than 1 o/o/d ".

Is achieved of thermochromic flocked fabric

the same way as to the example 2? , thermochromic except that the fine particles have a particle size of 29 μπΐ , ςυΐest greater than 1o/O/d.

A terry cloth thermochromic in the same way as to the example 23, except that the thermochromic microcapsules have a particle size of 25 μΐη ^ υ1 is greater than 10/57d.

Thermochromic The resulting fabric pile in the same way as to the example 24, except that the thermochromic microcapsules have a particle size of 22^ υ1 μηΐ is greater than 10, jD/d ".

The resulting fabric thermochromic shag the same way as to the example 25, except that the thermochromic fine particles have a particle size of 20 μΐη ,. ςυΐ 10,/d7cL is greater than

The in bundles the thermochromic fibres obtained to the example 1 and those obtained to the comparative free 1 and the appearance of the beams is compared. The bundle of fibers of the example 1 has a blue color and the uniform is not observed irregularities of the color change with temperature.

However, the beam of the fibres of the comparative example 1 of a blue color is non-uniform and has the disadvantage that large unevenness of the color change with temperature, which makes the fiber unusable in practice.

The twisted beams each consisting of 10 thermochromic fibres obtained to the example 1 or comparative example 1, with the number of twists of 30/m and resulting thermochrorniques the filaments are woven on a weaving machine to obtain a thermochromic woven fabric. Irradiation The fabric testing fastness to washing according to the L 0844A-2, J IS l ' fabric prepared from the fibers of the example 1 has the same concentration of pigment that before wash, while the pigment decreases seriously in the fabric made from the fibres of the comparative example 1, so that it substantially loses its function thermochromic after washing.

The thermochromic The crimped fibres obtained to the example 1 or comparative example 1, respectively, are cut into lengths dê 90 mm, is the card to form a ribbon ' and are woven thermochromic pile fabric having a pile length of 45 mm. Exposing fabrics for cleaning and polishing in step textile finishing, the pile fabric of the fibres of the example 1 gives a finished cloth of high flexibility and excellent texture, while maintaining the pigment at a concentration equal to that before finishing textile.

Instead the pile fabric of the fibres of the comparative example 1 is a pigment loss due to friction and intense loses most of the thermochromic effect..

The results of the comparative test examples

1 to 3 reveal that the relationship γ ≤ lOjD /d between the particle size of the pigment (r) thermochromic and the denier (D > fiber having a density (d) is effective to provide the textile material upper thermochromic features such as color change uniform, washing resistance and frictional resistance.

Comparisons are made of the appearance and texture between the following fabrics: thermochromic plain-weave the fabric of the example 13 and that of the comparative example 2;

The thermochromic nonwoven fabric of the example 18 The and that of comparative example 3 ; the thermochromic tubular knitted fabric at the point of the example 19 and that of the comparative example 4;

the flocked fabric of the thermochromic that of example 22 and comparative example 5 The; the towel thermochromic example 23 and that of the comparative example 6 ; the fabric pile thermochromi that of the comparative example 24 and that of comparative example 7 The; the fabric and thermochromic shag the example and that of the comparative example 8. Each sample according to the present invention has a uniform color and without irregularity at the color change and a soft. However, each of the comparative samples has a non-uniform color, has strong irregularities of the color change and a texture very hard which do not permit practical use. Furthermore, when the samples are subjected to the test according to JIS L 0844A-2, each of the samples of the present invention retains the pigment at a concentration equal to that before the washing test, while each of the comparative samples undergoes high pigment loss and loses substantially all of the thermochromic properties after washing.

At brushing and polishing each of the pile fabrics thermochromic The example 24 etcbl' comparative example 7 fabrics and thermochromic shag the example 25 and comparative example 8 in the step of finishing textiles.

The samples of the present invention are finished with a good texture/while maintaining the pigment at the same concentration that before the finishing, while any of the comparative samples undergoes high decrease of the pigment due to friction intense during the finishing of the fabric, substantially losing its thermochromic properties.

As described above, the present invention eliminates all the limitations imposed on the thermochromic fibres obtained by conventional fiber coating with an ink ' liquid crystal thermochromic and provides textile materials having excellent thermochromism, flexibility, texture, frictional resistance, resistance to washing and finishing or finishing.

Is solidified to the heart a thermochromic composition consisting of 1 part of 3, 3-bis (1-ethyl-2-methyl -1:00-indole-3- yl)- isobenzofurannone -1 (3:00), 2 parts of bisphenol A parts and 25 cetyl alcohol using a system epoxy resin/amine curing to obtain fine particles. Thermochromiques having a particle size of 4 pm which satisfies r|ao 10jD /d. Is mixed uniformly 100 parts of the fine particles with thermochromic 700 parts of an emulsion acrylic ester copolymer vinyl acetate copolymer having a solids content of about 45 % for preparing a coating composition and is immersed into The coating composition 800 fiber portions copolymer vinyl chloride-vinyl acetate (d=1,34) of fineness 5D that have been subjected to the crimping, removed and dry 100 °C The during 10 minutes. The resulting thermochromic fibres are cut to a length of 45 mm and transformed in a card into a web. 4 The laminate sheets of the web in parallel layers. The laminate is dipped in a resin emulsion SBR, is expresses between squeezing rollers and dried so as to obtain a nonwoven fabric thermochromic copolymer vinyl chloride-vinyl acetate. From the fabric a plush toy tomato-shaped. Plush The tomato is red in colour below 40 °C, becomes yellow above 40 °C and again becomes red below 40 °C, with a reversible thermochromism.

Is mixed uniformly 1 portion of the crystal violet lactone, 2 parts of dodecyl gallate, 15 parts of myristyl alcohol and 10 parts of decyl caprylate with 800 parts of polyethylene and the mixture is cooled and sprayed finely to obtain fine particles having a size cfe thermochromic particles μΐΐΐ 10 which satisfies the relationship γ≤ lo/O/d. Is mixed uniformly 500 portions of the thermochromic fine particles with 500 parts of a polyester resin emulsion having a solid content of about 25% for preparing a coating composition and is immersed in the coating composition 800 parts of polyester fibers Cd=1,38) of fineness 7D having a triangular cross-section, needed then removed and the dry 100 °C during 5 minutes. At crimping, the resulting thermochromic fibres, produced in the beams 35 and each consisting of fibers are twisted to the number of twists of thermochromic 30/m to obtain a spun yarn. The yarn is knitted on a knitting machine at point denbigh double and is cut and the knitted fabric are sewn resulting in the form of a plush beef thermochromic.

In the same coating composition as

the example 21, is immersed 700 fiber portions copolymer acrylonitrile-vinyl acetate Cd=1,18) of fineness 6D dyed yellow, needed then removed and dried to 90 °C during 10 minutes. Severance thermochromic fibres resulting acylonitrile -vinyl acetate copolymer to a length of 4 mm to obtain bristles thermochromic for flocking.

The bristles is applied by electrostatic flocking on a coated paper is cut and are sewn and the thermochromic resulting flocked fabric having a pile length of 3.8 mm a crocodile thermochromic plush.

Crocodile The plush yellow color is below 15 °C, it turns yellow above 15 °C and again becomes green by temperature decrease below 15 °C, indicating a reversible thermochromism-

The métieur woven on a weaving the same spun thermochromic obtained in example 23 to obtain a sponge cloth having a pile length of 2.5 mm. A plush panda giant thermochromic in ' using the sponge cloth thermochromic thereof and a commercial white sponge cloth having a pile length of 2.5 mm.

The plush toy is black in the parts made with the sponge cloth thermochromic and resembles a giant panda below -3°C. Black areas become white The above -3°C so that no white the body, but are rendered black by lowering the temperature to -3°C or below, indicating a reversible therrnoc bromisme.

The pistoLet the same coating composition as The example 24 on a napped fabric at the point of biarritz having a pile length of 10 mm which has been obtained from polyester fibers (d=1,38) of fineness 5D, is then dried to 80 °C during 30 minutes. The loops are cut and is cut and the pile fabric are sewn thermochromic polyester in the form of " plush pinguin a thermochromic.

The pinguin plush pile fabric made with the thermochromic is blue color below 30 °C, becomes colourless above 30 °C and blue again by decreasing temperature below 30 °C indicating a reversible thermochromism.

700 parts is dipped polyester raw linters (d=1,38) of fineness 10D in the same coating composition as the example 6, is centrifuged to remove excess The composition and is dried at 90 °C during 15 minutes. At carding raw the wad thermochromic resulting polyester to form a web. The three laminate sheets of the web cross-ply and is sprayed onto the laminate a resin emulsion NBR by means of a spray nozzle and dried. A plush zebra thermochromic using the nonwoven fabric thermochromic resulting polyester non-woven fabric and a commercial white.

The parts made with the non-woven fabric are blue thermochromic below 10 °C, making it resemble the plush toy to a zebra, they saw to white above 10 °C making the whole body white, and become blue, indicating a reversible thermochromism.

At carding the same wad raw thermochromic copolymer vinyl chloride-vinylidene chloride as prepared in the example 19 to form a ribbon which is then spun to form the thermochromic. The spun resulting is embroidered accordance with the pattern of a turtleback the back of a toy shaped peLuche tortoise manufactured with a commercial fabric.

The turtleback faiteavec the yarn thermochromic is blue color below -10^Q C. The drawing of the shell disappears above -10°C but reappears by decreasing the temperature below -10°C, indicating a reversible thermochromism.

Is solidified to the heart a thermochromic composition consisting of 1 part 3 '-< diethylamino)-6' , 8 '-di-methyl- spiroCisobenzofuranne -l (3:00), 9' - C9H3xanthène3 -3-one, 3-phenylphenol portions 4 and 25 parts butyl stearate thermochromic to obtain fine particles having a particle size of 6 pm which satisfies γ ≤ 10^D/d. Is mixed uniformly 600 parts of the fine particles with thermochromic 400 parts of an emulsion of vinyl acetate copolymer resin having a solid content of about 50% for preparing a coating composition. Is dipped in the coating composition 400 raw linters parts acrylonitrile-vinyl chloride copolymer as a fineness of 10b having a flat cross-section and a cut length of 51 mm and, after the removal of the excess of the composition by means of an air gun to compressed air.

is dried at 100 °C during 10 minutes. Is mixed uniformly 400 parts of the resulting raw wad thermochromic, 200 paities raw staple polyacrylonitrile as a fineness of 7D cut to a length of 51 mm which have been dyed blue and 200 parts raw staple polyacrylonitrile fibers uncoated, of a fineness of 3D and cut to a length of 38 mm and form of a sliver by means of a card.

The tape is knitted on a knitting machine with long bristles and the knitted fabric is subjected to the clip to obtain a thermochromic to long pile fabric having a pile length of 25 mm. The fabric are cut long-bristled, the stitching is in a plush koala thermochromic.

Plush The koala has a very good texture and has a brown color below 10 °C, blue turns above 10 °C by decreasing and again becomes brown The temperature below 10 °C, indicating a reversible thermochromism.

9 Example of use

The same is sprayed coating composition that that in the example 1 by means of a spray gun on 800 parts nylon fibers (d=1,14) d ' a fineness of 8D The 100 °C and is dry during 10 minutes. Severance nylon fibers resulting thermochromic to a length of 5 mm to obtain bristles for flocking. The bristles is applied by electrostatic flocking on a nylon fabric on which has been adhered by melt-expanded urethane and is cut and the resulting flocked fabric are sewn on a doll head for manufacturing a doll having a thermochromic hair.

Encapsulated by interfacial polymerization a thermochromic composition consisting of 1 part of 3, 3-bis (1-ethyl-2-methyl -1:00-indole-3-yl)- isobenzofurannone -1 (3:00), 2 parts of naphthoic acid and parts 25 cetyl alcohol using a system acrylic resin/hardener amine to obtain microcapsules thermochromic having a particle diameter of 7 pm which satisfies γ The ≤ 1/ dZcT. Is mixed uniformly 500 portions of the microcapsules with 500 parts of an emulsion acrylic ester resin having a solid content of about 45% for preparing a coating composition and is immersed in the composition 800 parts polyacrylonitrile fibers (d=1,17) of fineness 7D, needed then removed and dried to 100 °C during 5 minutes. The resulting crimped The thermochromic fibres and chamfer cuts in lengths of 80 to 130 mm to obtain a raw wad thermochromic. The wad pig carding and then twisted in the usual manner to obtain the bulked yarns. Thus the bulked yarns into bundles of wires and 3 are twisted wool of obtaining yarns having an outer diameter of about 3 mm. Severance wool yarns

at the proper lengths and bonds their ends on a doll head for manufacturing a doll having hair thermochromic.

Is dipped 800 g wool fibers (d=1_r 32 ; fineness corresponding to 4-20D; fibres40 length of -130 mm) in the same coating composition as that used to the example 10, needed then removed and dried to 100 °C during 5 minutes. At clip the wad thermochromic resultant raw

the usual manner to form yarn having an outer diameter of about 3 mm. A doll having hair thermochromic using the wool yarn resulting in the same way as to the example 10.

The doll's hair obtained in the examples of use 2 and 3 are pink color below 40° ^ but became colorless above 40 °C, having a reversible thermochromism.

It is understood that the invention is not limited

with the preferred embodiments described above as illustrative and that those skilled in the art can be ameliorated various modifications and various changes without departing the frame and scope of the invention.