JPH0637746B2 - Thermochromic cloth - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A. The present invention relates to a thermochromic fabric whose color reversibly changes with temperature.

Industrial field of application The thermochromic cloth of the present invention is in the form of woven cloth, non-woven cloth, knitted cloth, and pile cloth, which is used as a basic material for various textile products such as clothing, bedding, interior goods, toys and the like. It can be applied.

Conventional technology Conventionally, regarding yarns that change color due to temperature change, Japanese Patent Publication 5
An application example of a liquid crystal ink is disclosed in Japanese Patent Laid-Open No. 1-2532. The present invention is characterized in that liquid crystal ink is coated on one or both sides of a sheet-shaped dark-colored substrate such as black or dark blue to form a flat yarn, or the flat yarn is wound around a core yarn to form a twisted yarn. Therefore, this yarn is rather a sheet and has a peculiar shape different from ordinary fibers, the degree of freedom of morphology and properties is suppressed, and it cannot take various shapes according to the purpose. Since it is used, its moisture resistance is extremely poor, it cannot be washed at all, and its color is only based on a dark color, so the color change temperature cannot be freely obtained, and it is expensive and has not been put into practical use. Explaining this sheet a little further, even if there are color change layers on both the upper and lower sides, there is no color change layer on both the left and right cross sections, and if a thin sheet is used, the color change layer will drop to less than 1/2 of the entire surface, and the color change effect will be extremely high. It has the drawback of becoming worse and has not been put to practical use. Therefore, there has been a strong demand for cloths that can change the color change temperature and change colors in various ways.

Problem to be Solved by the Invention The present invention eliminates the above-mentioned restrictions at all and provides a thermochromic fabric applicable to any fabric product.

(B) Structure and Effect of the Invention Means for Solving the Problem The present invention provides [R: particle size (μm) of pigment, D: denier number (denier) of elementary fiber, d: specific gravity (g / cm ³ ) of elementary fiber] A thermochromic pigment comprising a thermochromic material composed of a developer and a thermochromic temperature controlling agent encapsulated in microcapsules, and a thermochromic layer comprising a binder, wherein the thermochromic layer is an individual fiber. On the other hand, the present invention relates to a thermochromic cloth composed of thermochromic fibers having an adhesion amount of 3% by weight to 90% by weight and the thermochromic pigment being 5% by weight to 80% by weight in the thermochromic layer.

In the present invention, the particle size of the pigment is It is necessary to satisfy [r: particle diameter of pigment (μm, D: denier number (denier) of elementary fiber, d: specific gravity of elementary fiber (g / cm ³ )]. Each of the elementary fibers that make up the cloth is provided with a thermochromic layer independently of each other, so the thermochromic pigment is evenly distributed over the fibers, which gives the cloth a good texture and thermochromic property. In order to do this, the particle size of the pigment must be within a certain range.According to our research, the discoloration unevenness of a cloth composed of fibers coated with a thermochromic pigment is observed. It was clarified that it was due to the non-uniform distribution of the pigment, and this non-uniform distribution was caused by the cross-linking of the pigment across multiple fibers, that is, the particle size and the thickness of the fiber. If the pigment bonds multiple elementary fibers in a bridging pattern, this part As a result, a large amount of thermochromic pigments tend to gather, which results in non-uniform distribution of the pigments, causing thermal discoloration unevenness. However, it is not possible to prevent it, and the relationship between the thickness of the fiber and the fiber becomes an important problem. To By satisfying the relationship, the above phenomenon can be prevented and the discoloration unevenness has been successfully prevented.

Next, the present invention is also characterized in that a thermochromic layer composed of a pigment and a binder is provided on the surface of each elemental fiber of the fibers constituting the cloth. Since the thermochromic layer is provided on the surface of each individual fiber, the thermochromic pigment has a uniform distribution throughout the cloth, and many features are that the texture, flexibility, and pigment adhesion strength are uniform. This new structural unit is a novel thermochromic element fiber that is not known at all, and the cotton-like material and the yarn made of this element fiber have uniform thermochromic property, texture, and pigment adhesion strength. It is a new one. Therefore, a thermochromic fabric composed of these thermochromic fibers, more specifically a thermochromic woven fabric,
Thermochromic non-woven fabrics, thermochromic knitted fabrics, thermochromic pile fabrics, etc. are all novel, which have not been known at all, exhibiting uniform thermochromic property, texture and pigment adhesion strength.

In the present invention, a particular relationship between the thickness of the elementary fiber and the particle size of the thermochromic pigment is [R: particle diameter of pigment (μm, D: denier number (denier) of elementary fiber, d: specific gravity of elementary fiber (g / cm ³ )] is defined by the cross-sectional shape of the elementary fiber used This is because there is also a case of irregular shapes such as a flat shape and the like, and in order to prevent the bridging phenomenon of the pigment particles, it is meaningless to simply define the filament diameter and the pigment particle diameter. This configuration is indispensable in order to achieve the purpose of (1) and to exert a unique effect.

The thermochromic layer in the present invention is suitably 8% by weight to 90% by weight, particularly 5% by weight, based on the fiber constituting the cloth.
Approximately 70% by weight is suitable from the viewpoint of thermochromic discoloration effect.

The reason for this is that as a result of examining various amounts of adhesion, the following became clear. That is, when it is less than 3% by weight, the texture is good, but the density is low and the color change is not clear, so that it is not practical as a cloth. Further, when the amount of adhesion is more than 90% by weight, the density is high and the color change is clear, but binding between the elementary fibers is likely to occur, and it is difficult to make the individual fibers exist independently, so the texture is impaired. I cannot obtain a soft feeling, so it is not practical. Therefore 3% by weight
The range of up to 90% by weight is a practicable range satisfying both the density, the clearness of color change and the soft texture. Further, in the range of 5% by weight to 70% by weight among them, the density and color change are sufficiently clear, and there is no binding between the elementary fibers, so that the individual fibers can exist completely independently. A thermochromic fiber of the best quality with a soft texture and a well-balanced pigment adhesion strength was obtained, and the cloth composed of this fiber exerts an extremely excellent effect.

Action The thermochromic fabric of the present invention is provided with a thermochromic layer on each filament, and since the thermochromic pigment having a particle diameter suitable for the denier number of the filament used is used, the thermochromic cloth is uniform and flexible. It has extremely excellent properties, texture, scratchability, washability, and processability, so it can be applied to all types of fabric products.

The thermochromic pigment used in the present invention is effectively a conventionally known reversible thermochromic material obtained by combining an electron-donating color developing agent and an electron-accepting color developing agent. One example of these is JP-B-51-44706. JP-B, JP-B-51-44707, JP-B-51-44708, and JP-B-51-8
The thermochromic material disclosed in Japanese Patent No. 5216 can be mentioned. For example, (a) an electron-donating color former, (b) a compound having a phenolic hydroxyl group and a metal salt thereof, an aromatic carboxylic acid and an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid salt, an acidic phosphoric acid ester. And their metal salts, 1,
Electron-accepting developers such as 2,3-triazole and its derivatives, halohydrin compounds, (c) alcohols, esters, ketones, ethers, acid amides, aliphatic carboxylic acids having 6 or more carbon atoms, A thermochromic pigment comprising a color-changing temperature controlling agent such as thiols, sulfides, disulphides, sulfoxides and sulfones is used.

Specific examples are shown in Table 1. The numbers in parentheses indicate the blending amount (parts by weight).

These thermochromic materials are colored from red to blue, yellow, green, orange, purple, brown, black, and other subtle colors at temperatures between approximately -30 ° C and + 100 ° C, from subtle colors to colorless and from colorless to colored. It can be reversibly and instantly changed to, and a brightening agent can be added to increase the vividness of white in colorlessness and further increase the contrast. Further, the color change can be colored by adding and using color compounds such as general dyes, fluorescent dyes, pigments, fluorescent pigments, and phosphorescent pigments (I).
It is effective because it can be changed from one to another different colored (II). In addition, light can be transmitted, and it can be made transparent in response to changes in temperature to reveal the base. In order to make these thermochromic materials into pigments, the thermochromic materials are encapsulated in microcapsules or blended with various resins and cured after emulsification or by spray-drying after curing or solidification after curing, crushing after curing, etc. Fine particles can be obtained with.

When the surface of the fiber is coated with this pigment, a thermochromic fiber that changes its color to colorless depending on the temperature change is formed.

Next, to make a thermochromic fiber that changes color (I) and colorless (II) using these thermochromic pigments that change color and colorless, add a color component to the thermochromic composition. The surface of the fiber is coated with the thermochromic pigment that changes color (I) and colorless (II), or the thermochromic pigment that changes color and colorless and general pigment, fluorescent pigment, phosphorescent pigment or Dyes and fluorescent dyes can be microencapsulated and made into particles and coated on the surface of the fiber, or the surface of the fiber dyed with general dyes or general pigments can be coated with a colored colorless thermochromic pigment. . Further, it is possible to use a method in which the elementary fiber coated with a thermochromic pigment that changes color to colorless and the elementary fiber colored with a general dye or a general pigment are mixed and spun.

As the binder for binding the obtained thermochromic pigment to the elemental fiber, conventionally known wax, low melting point thermoplastic resin,
Examples thereof include rubber, natural resin, synthetic resin and the like. For example, low-molecular-weight polyethylene, low-melting point polyester, ethylene-vinyl acetate copolymer, chlorinated rubber, polyvinyl acetate emulsion, polyethylene emulsion, acrylic emulsion, styrene resin emulsion, butadiene-nitrile emulsion, seratec, zein , Unsaturated polyester resin, epoxy resin, cellulosic resin, polyurethane resin, phenol resin, vinyl chloride resin, vinyl acetate resin, silicon resin, polyvinyl alcohol, polyvinyl methyl ether, etc.

It is effective to use various kinds of materials and forms for the monofilament, and specifically, other chemical fibers such as natural fiber, semi-synthetic fiber, synthetic fiber, copolymer fiber, inorganic fiber, metal fiber and the like can be mentioned. ， In addition, as an example, cotton, wool, goat hair, camel hair, rabbit hair, silk, silkworm silk thread, casein fiber, soy protein fiber, zein fiber, peanut protein fiber, regenerated silk thread,
Viscose rayon, copper ammonia rayon, saponified acetate, natural rubber fiber, alginic acid fiber, acetate fiber, triacetate fiber, acetic acid staple fiber, ethyl cellulose fiber, chlorinated rubber fiber, polyamide fiber, polyester fiber, polyurethane fiber, polyethylene Fiber, polypropylene fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyfluoroethylene fiber, polyacrylonitrile fiber, polyvinyl alcohol fiber, promics fiber, benzoate fiber, polyclar fiber, polynodic fiber, acrylonitrile-alkylvinylpyridine Copolymer fiber, acrylonitrile-ethylene copolymer fiber, acrylonitrile-vinyl chloride copolymer fiber, vinyl chloride-vinylidene chloride copolymer fiber, vinyl chloride - vinyl copolymer fibers acetate, vinyl chloride - acrylonitrile copolymer fibers, vinyl chloride - ethylene copolymer fibers, glass fibers, Rotsukuuru, ceramic poke off Ivor, and carbon fiber.

Moreover, in addition to the usual fiber forms, there are triangular, pentagonal, octagonal, Y-shaped, L-shaped, star-shaped, dockbone-shaped, horseshoe-shaped, flat-shaped, etc. cross-section fibers, macaroni-shaped, lotus root-shaped, sponge-shaped, Hollow fibers such as rice fields, side. pie.
Side type, sheath. Examples include core type and matrix type conjugate fibers. The modified cross-section fiber and the hollow fiber have a large surface area and are easily attached with a pigment, so that the concentration can be high.

The production of the thermochromic cloth coated with the thermochromic pigment is carried out by the following method although it slightly varies depending on the form of the cloth. First, the production of fibers constituting the thermochromic woven fabric will be described. The target elemental fiber (which may be crimped if necessary) is dipped in a coating composition consisting of a thermochromic pigment, a binder and a color-developing agent and then dried or sprayed. If necessary, the thermochromic element fibers obtained by drying treatment such as spraying, brushing, direct coating with a roll coater, etc. are crimped and used as they are as thermochromic filaments. Further, a plurality of bundles are twisted and twisted to form a thermochromic filament yarn. Alternatively, a thermochromic raw cotton cut to an appropriate length after crimping, or a target raw cotton is dipped in the above-mentioned coating composition and then centrifuged,
After removing excess composition with a roll squeezer or an air gun, dry treatment or spraying with a spray, direct coating with a brush, roll coater, etc. and drying treatment, and then applying the thermochromic raw cotton to the card. After being made into a sliver, a thermochromic spun yarn is obtained through a spinning process. These thermochromic fibers are woven by a loom, plain weave, ridge weave, twill weave, satin weave, twill weave,
It is obtained by weaving into a layered weave and the like.

Next, the thermochromic nonwoven fabric will be described. First, a fiber assembly for processing into a non-woven fabric will be described. After the target fiber (which may be crimped if necessary) is dipped in the coating composition and then dried, treated or sprayed with a spray or brush, or directly applied by a roll coater, etc. A filament sheet is obtained in a filament state by crimping the thermochromic element fibers obtained by the drying treatment, if necessary. Further, the thermochromic fiber obtained in the same manner is cut into an appropriate length to obtain a thermochromic raw cotton which is a fiber assembly. In addition, after dipping the target raw cotton in the coating composition, remove excess composition with centrifugal separation, roll squeezing, air gun, etc. and then dry it or spray it with a spray etc., or directly by a roll coater etc. After coating, etc., it is dried to obtain a thermochromic raw cotton which is a fiber assembly. Of the thermochromic fiber aggregates thus obtained, the filament sheet can be directly processed into a non-woven fabric, but the raw cotton must be a web. Therefore, the raw cotton is put on a card and made into a web. Next, processing into a nonwoven fabric will be described. If necessary, pile up filament sheets or webs and mechanically bond them by stitch bonding or needling, or immerse them in an adhesive, spray the adhesive, powder adhesive, thread adhesive, fibrous It can be obtained by mixing an adhesive or applying pressure or heat to bond them.

Next, the thermochromic knitted fabric will be described. Thermochromic filaments, thermochromic filament yarns, thermochromic spun yarns, and other thermochromic fibers obtained in the same manner as for thermochromic woven fabrics are knitted with a knitting machine into circular knitting, flat knitting, pearl knitting, and rubber knitting. , Denby edition,
It can be obtained by knitting atlas, cord, double denby, double atlas, double cord, lace, etc.

Next, the thermochromic pile fabric means various pile fabrics such as thermochromic high pile fabric and thermochromic flocked fabric. The thermochromic pile fabric is prepared by using the thermochromic filament or thermochromic filament yarn or thermochromic spun yarn described above as warp yarn, and weaving it with warp piles such as velvet and platter, or weft yarn Weave a pile such as heaven, and cut it at an appropriate position to cover the woven surface with fluff. In addition, it can be covered with a loop, such as a towel or jiyutan. In addition to this, the pile fabric preformed in advance is impregnated with the coating composition, followed by printing, coating, spraying, etc., followed by drying, and hair splitting. The thermochromic high-pile fabric is obtained by putting the thermochromic raw cotton described above on a card to make a sliver and knitting with a high-pile knitting machine. This high-pile fabric has long naps and a large amount of thermochromic pigments, so it is characterized by a particularly excellent thermochromic effect.

The thermochromic flocking fabric is made by cutting the thermochromic filament described above into an appropriate length to form a pile, and by mechanical flocking process such as spraying type, vibration type, spraying type or electrostatic flocking process. can get.

The thermochromic layer in the present invention is suitable in an amount of 3% by weight to 90% by weight, and particularly 5% by weight to 70% by weight based on the thermochromic discoloring effect, based on the filaments constituting the thermochromic cloth. It is suitable. The thermochromic pigment is contained in the thermochromic layer in an amount of 5% by weight to
80% by weight is suitable, especially 10% to 60% by weight
Is preferable from the viewpoint of thermochromic discoloration effect.

That is, when the amount is less than 5% by weight, the color density is low and the color change cannot be clearly seen, while when the amount is more than 80% by weight, it is difficult to visually recognize a clear decolored state. The 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 the above-mentioned binders, and if necessary, an antioxidant, an ultraviolet absorber, an anti-aging agent, etc. may be blended to further make the thermochromic function permanent.

Next, some specific examples of the present invention will be described with reference to the drawings.
FIG. 1 shows the thermochromic cloth of the present invention. 1 is a thermochromic fiber and 2 is a fiber which is not thermochromic. A pattern as shown in FIG. 2 is formed by the thermochromic fiber and the non-thermochromic fiber, but if both fibers are kept in the same color at room temperature, the pattern will appear only when the temperature changes. The thermochromic cloth 3 of FIG. 3 has different color-changing temperatures A to J.
It is composed of multiple types of thermochromic fibers shown in groups. In this thermochromic cloth, the fibers of the groups A to J discolor at their respective discoloring temperatures. Therefore, when characters, patterns, figures, etc. are formed by using these fiber groups, the pattern can be changed or moved. FIG. 4 shows a state in which the thermochromic fiber 1 hides the non-thermochromic fiber 2.
Therefore, 2 cannot be seen under normal conditions. If a pattern of characters, a pattern, a figure, etc. is formed with the non-thermochromic fiber 2, the pattern will appear when the thermochromic fiber changes to colorless and pale due to temperature change. The expression and deletion of such patterns can be made more complicated. That is, the thermochromic fiber 1 and the non-thermochromic fiber 2 are respectively formed with a pattern, and the thermochromic fiber is thermally discolored, so that the pattern formed by the non-thermochromic fiber 2 can be exposed. Furthermore, if both fibers are combined to form a pattern, and the thermochromic fiber alone is also used to form a pattern, the pattern changes to a combined pattern of both fibers due to temperature changes. FIG. 5 shows changes in the three-dimensional pattern, which is particularly effective for a cloth such as pile cloth having fibers with long fibers on the surface. When a pattern is formed by combining fibers with long hair and short fibers and the color is changed by temperature change, the pattern is three-dimensional and the change in color becomes clear. In this case, of course, the fibers of either fiber may be long. FIG. 6 shows a fabric in which the fibers on the surface of the cloth are thermochromic at the front end and not thermochromic at the rear end. The color or pattern of the fiber that is not thermochromic appears due to the thermochromic change of the tip. In this case, it is possible to change the color at the front end and the rear end of the thermochromic fiber, or to change the color in multiple stages such as three stages and four stages. Thus, the thermochromic fabric of the present invention has an excellent effect that not only the color change of a single color but also multicolor and various patterns can be formed.

Furthermore, the present invention is capable of reversible changes between natural colors and other colors, especially white. A thermochromic fiber obtained by using a reversibly changing thermochromic pigment of yellow-white, a reversible thermochromic pigment of magenta white, and a reversible thermochromic pigment of cyan white, respectively, is used to obtain three primary colors with a computer. The decomposed pattern is woven by a computer loom, or the cloth woven by a computer knitting machine shows and disappears a natural color pattern depending on the temperature change. In addition, the cloth decomposed into the three primary colors by a computer using these three types of thermochromic fibers was stabbed with a non-thermochromic cloth by the computer, and a natural color pattern was expressed by the temperature change. Disappear.

Furthermore, using a coating agent adjusted with each of the three pigments, the pattern decomposed into the three primary colors by a computer is printed on a non-thermochromic fabric by computer printing, and the printed part is made a thermochromic fabric to form a natural color pattern. be able to.

Examples Next, specific examples will be shown, but the present invention is not limited thereto.

The parts in the formulation are parts by weight.

Example 1 A thermochromic composition consisting of 1 part of crystal violet lettactone, 3 parts of benzyl 4-hydroxybenzoate and 25 parts of stearyl alcohol was encapsulated by a coacervation method using gelatin / gum arabic. Thermochromic microcapsules 150 having a particle size of 8 μm
Parts, solid urethane about 41% aqueous urethane resin emulsion 4
In a coating composition obtained by uniformly mixing 50 parts and 24 parts of an aqueous epoxy resin, 7D polyurethane fiber (d =
1.21) Take out 500 parts after soaking and dry at 100 ° C. for 5 minutes to obtain a thermochromic polyurethane element fiber, which is crimped and bundled with 30 pieces to obtain a twist of 35 times / m. The thermochromic filament yarn thus obtained is woven into a plain weave by a loom,
A thermochromic polyurethane plain weave fabric was obtained.

The thermochromic plain woven fabric is blue below 53 ° C,
When the temperature was raised to 53 ° C or higher, the color changed to colorless, and when the temperature was lowered to 53 ° C or lower again, the color returned to blue, showing reversible thermochromic property.

Example 2 Spiro [12-H-benzo [α] xanthene-12,12
1 '(3'H) -isobenzofuran] -3'-one, 9
-(Diethylamino) -1 part, bisphenol A 2 parts,
15 parts myristyl alcohol, 10 stearyl caprylate
Part of thermochromic composition was encapsulated by interfacial polymerization method with epoxy resin / amine curing agent Thermochromic microcapsules 60 with a particle size of 5 μm
Parts, 200 parts of glycidyl ether type epoxy resin, and 80 parts of amine curing agent are uniformly mixed, and a 5D nylon raw fiber (d = 1.14) crimped with a coating composition.
The thermochromic nylon fiber obtained by spraying 300 parts with a spray gun and drying at 80 ° C for 30 minutes is 70 mm ~ 13
The thermochromic nylon raw cotton obtained by bias cutting to 0 mm was sliver laid on a card, and the thermochromic spun yarn obtained through the spinning process was woven into a diagonal weave by a loom, and the thermochromic nylon diagonal A woven fabric was obtained.

The above-mentioned thermochromic slanted woven fabric is pink at 25 ° C or lower, changes to colorless at 25 ° C or higher, and returns to pink at 25 ° C or lower again to show reversible thermochromism. It was

Example 3 Spiro [isobenzofuran-1 (3H), 9 '-[9
[H] xanthene] -3-one, 2'-chloro-6'-
A thermochromic composition comprising (diethylamino) -3'-methyl-1 part, zinc benzoate 2 parts, and diphenyl ether 25 parts was solidified to the inside with an epoxy resin / amine curing agent. Particle 200 having a particle diameter of 12 μm satisfying the above conditions
Part, 800 parts of acrylic ester resin emulsion having a solid content of about 42% were uniformly mixed, and a 10D sponge-like hollow polyacrylonitrile (d = 1.17) raw cotton 1 was bias cut to 80 mm to 130 mm in a coating composition.
After immersing 000 parts of the composition by centrifugation to remove excess composition and drying at 90 ° C. for 10 minutes, thermochromic hollow polyacrylonitrile raw cotton was applied to a card to make a sliver and then a thermochromic spinning obtained through a spinning process. The yarn was woven into a satin fabric with a loom to obtain a thermochromic hollow polyacrylonitrile satin fabric fabric.

The thermochromic satin woven fabric showed vermilion at 10 ° C. or lower, changed to colorless at 10 ° C. or higher, and returned to vermilion at 10 ° C. or lower again to show reversible thermochromism.

Example 4 Spiro [isobenzofuran-1 (3H), 9 '-[9
[H] xanthene] -3-one, 6 '-(diethylamino) -3'-methyl-2'-(phenylamino) -1
Part, 4-chlorobenzoic acid 3 parts, stearic acid amide 25
Parts were uniformly kneaded to 750 parts of polypropylene, cooled and finely pulverized. 200 parts of thermochromic fine particles having a particle diameter of 4 μm
In a coating composition in which 800 parts of vinyl acetate-ethylene-vinyl chloride terpolymer (emulsion) having a solid content of about 50% were uniformly mixed, 3D equivalent silk fiber (d = 1.3) was used.
3) A thermochromic silk filament yarn obtained by soaking 1000 parts after dipping and drying at 100 ° C. for 5 minutes to bundle 30 thermochromic silk fibers and twisting 40 times / m Was woven with a loom to obtain a thermochromic silk ridge woven fabric.

The thermochromic ridged woven fabric is black below 95 ° C,
When the temperature was raised to 95 ° C or higher, it turned colorless, and when it was lowered to 95 ° C or lower again, it returned to black and showed reversible thermochromic property.

Example 5 1 (3H) -isobenzofuranone, 3,3-bis (1-
Ethyl-2-methyl-1H-indol-3-yl)-
A thermochromic composition consisting of 1 part, 2 parts of bisphenol A zinc salt and 25 parts of cetyl alcohol was solidified to the inside with an epoxy resin / amine curing agent. 100 parts of thermochromic fine particles having a particle size of 4 μm,
A crimped 5D vinyl chloride-vinyl acetate copolymer fiber (d = 1.34) 800 in a coating composition obtained by uniformly mixing 700 parts of acrylic-vinyl acetate copolymer emulsion having a solid content of about 45%. After soaking the part, take it out 1
Thermochromic vinyl chloride obtained by drying at 00 ° C for 10 minutes
Vinyl acetate copolymer fiber cut to 45 mm, made into a web with a card, then laminated in parallel with 4 sheets, immersed in SBR resin emulsion solution, squeezed and dried with a roll, and thermochromic vinyl chloride-vinyl acetate copolymer non-woven fabric was gotten.

The thermochromic non-woven fabric showed pink color at 40 ° C. or higher, changed to colorless at 40 ° C. or higher, and returned to pink color when lowered to 40 ° C. or lower again, showing reversible thermochromic property.

Example 6 A thermochromic composition comprising 1 part of crystal biolettolactone, 3 parts of octyl 4-hydroxybenzoate and 25 parts of butyl stearate was included by an interfacial polymerization method using a polyisocyanate / amine curing agent. Thermochromic microcapsules 10 with a particle size of 12 μm
10 parts of polyester raw cotton (d = 1.38) in a coating composition in which 650 parts of ethylene-vinyl acetate copolymer emulsion having a solid content of about 50% was uniformly mixed.
After dipping 00 parts and removing the excess coating composition by centrifugation and drying at 90 ° C. for 15 minutes, the thermochromic polyester raw cotton was made into a web with a card, and then three sheets were laminated in an intersecting manner to obtain NBR resin emulsion. The liquid was sprayed from a spray nozzle and dried to obtain a thermochromic polyester nonwoven fabric.

The thermochromic non-woven fabric exhibits a blue color at 10 ° C or lower, and
When it became 0 ° C or higher, it turned colorless, and when it was lowered to 10 ° C or lower again, it returned to blue and showed reversible thermochromic property.

Example 7 A thermochromic composition comprising 1 part of crystal bio-leptlactone, 2 parts of 4,4-methylenediphenol and 25 parts of butyl palmitate was encapsulated by an interfacial polymerization method using an acrylic resin / amine curing agent. Thermochromic microcapsules 30 with a particle size of 12 μm
In a coating composition in which 0 parts and 400 parts of an acrylic ester emulsion having a solid content of about 45% were uniformly mixed, 10 D vinyl chloride-vinylidene chloride copolymer raw cotton (d) was added.
= 1.7) After dipping 500 parts of the coating composition with an air gun and then removing the excess coating composition and drying at 100 ° C for 10 minutes, thermochromic vinyl chloride-vinylidene chloride copolymer raw cotton obtained was slivered on a card. The thermochromic spun yarn obtained through the above was knitted into a circular knit by a knitting machine to obtain a circular knit fabric made of thermochromic vinyl chloride-vinylidene chloride copolymer fiber.

The thermochromic circular knitted fabric exhibits a blue color at -10 ° C or lower, changes to colorless at -10 ° C or higher, and again at -10 ° C.
When it was lowered below, it returned to blue and showed reversible thermochromism.

Example 8 Spiro [12-H-benzo [α] xanthene-12,12
1 '(3'H) -isobenzofuran] -3'-one, 9
-(Diethylamino) -1 part, dodecyl gallate 2 parts,
Obtained by uniformly kneading 25 parts of stearone into 800 parts of polyethylene, cooling and pulverizing. Thermochromic fine particles 500 having a particle size of 10 μm
Parts, solid resin about 25% polyester resin emulsion 5
7D in a coating composition in which 00 parts are uniformly mixed
Polyester triangular cross-section shape elementary fiber (d = 1.38) 8
A thermochromic polyester triangular cross-section elemental fiber obtained by dipping 00 parts after immersion and drying at 100 ° C. for 5 minutes was crimped to obtain 35 bundles and twisted 30 times / m. The thermochromic filament yarn was knitted with a knitting machine into a double denby knitted fabric to obtain a thermochromic polyester double denby knitted fabric.

The above thermochromic double denby knitted fabric shows pink color at 85 ° C or lower, changes to colorless at 85 ° C or higher, and returns to pink color when lowered to 85 ° C or lower again, and exhibits reversible thermochromic property. Indicated.

Example 9 Spiro [isobenzofuran-1 (3H), 9 '-[9
H] xanthene] -3-one, 6 '-(diethylamino) -2'-[cyclohexyl (phenylmethyl) amino] -1 part, 5,5-bis (1,2,3-benzotriazole) 2 parts, caprylic acid A thermochromic composition consisting of 25 parts was encapsulated by the coacervation method with gelatin / gum arabic. Thermochromic microcapsules 500 with particle size of 8 μm
Part, 700 parts of acrylonitrile-vinyl acetate copolymer fiber of 6D dyed yellow in a coating composition in which 450 parts of acrylic acid ester resin emulsion having a solid content of about 42% are uniformly mixed and taken out after being dipped at 90 ° C. Thermochromic acrylonitrile-vinyl acetate copolymer fiber (d = 1.18) obtained by drying for 10 minutes was cut into 3 mm to make a thermochromic pile for flocking, and flocking was applied to coated paper by an electrostatic processing method. , A thermochromic flocked fabric was obtained.

The above-mentioned thermochromic flocked fabric shows a green color at 15 ° C or lower,
When the temperature was raised to 15 ° C or higher, the color changed to yellow, and when the temperature was lowered to 15 ° C or lower, the color returned to green, showing reversible thermochromic property.

Example 10 Spiro [isobenzofuran-1 (3H), 9 '-[9
A thermochromic composition consisting of [H] xanthene] -3-one, 3 ′, 6′-dimethoxy-1 part, naphthoic acid 2 parts, myristyl alcohol 25 parts was solidified to the inside with an epoxy resin / amine curing agent. Of thermochromic particles 600 having a particle size of 12 μm
Parts, a coating composition in which 1000 parts of vinyl acetate copolymer resin emulsion having a solid content of about 50% is uniformly mixed is sprayed onto an 8D nylon fiber (d = 1.14) with a spray gun to dry at 100 ° C. for 10 minutes. The thermochromic nylon fiber obtained by cutting was cut into 5 mm to make a thermochromic pile for flocking, and flocking was performed on the urethane surface of the base material, which was made by fusing urethane foam on nylon fabric, by electrostatic processing, A thermochromic flocked fabric was obtained.

The above-mentioned thermochromic flocked fabric exhibits a yellow color at 38 ° C or lower,
When the temperature was raised to 38 ° C or higher, the color changed to colorless, and when the temperature was lowered to 38 ° C or lower again, the color returned to yellow, showing reversible thermochromic properties.

Example 11 Spiro [isobenzofuran-1 (3H), 9 '-[9
H] xanthene] -3-one, 6 '-(cyclohexylmethylamino) -3'-methyl-2'-(phenylamino) -1 part, 1,1-bis (4-hydroxyphenyl)
-A thermochromic composition comprising 2 parts of cyclohexane, 12.5 parts of palmitic acid and 12.5 parts of decyl caprylate was encapsulated by an interfacial polymerization method using acid chloride / phenol. Of thermochromic microcapsules 200 having a particle size of 8 μm
Part, 500 parts of cotton (d = 1.54) corresponding to 5D was immersed in a coating composition in which 800 parts of an acrylic ester emulsion having a solid content of about 45% were uniformly mixed, and then an excess composition was obtained by centrifugation. After removing the heat, the thermochromic cotton obtained by drying at 100 ° C for 10 minutes is sliver laid on a card, and then the thermochromic spun yarn obtained through the spinning process is woven into a towel cloth with a loom to produce a thermochromic towel. A dough was obtained.

The above-mentioned thermochromic towel cloth exhibited black at -3 ° C or lower, changed to colorless at -3 ° C or higher, and returned to black when lowered to -3 ° C or lower, and showed reversible thermochromic property. .

Example 12 1 (3H) -isobenzofuranone, 3- (1-ethyl-
2-Methyl-1H-indol-3-yl) -3- (4
-Diethylaminophenyl) -1 part, 5-chloro-1,
A thermochromic composition comprising 3 parts of 2,3-benzotriazole and 25 parts of dilauryl ether was included by a coacervation method. Thermochromic microcapsules 60 with a particle size of 7 μm
Part, 200 parts of glycidyl ether type epoxy resin, and 80 parts of amine curing agent are uniformly mixed, and the coating composition is sprayed onto a ratcell knitted pile fabric made of 5D polyester fiber (d = 1.38) with a pile length of 15 mm. Spraying, drying at 80 ° C. for 30 minutes, and subjecting to hair splitting, a thermochromic polyester pile fabric was obtained.

The thermochromic pile fabric exhibited a blue color at 30 ° C. or lower, changed to colorless at 30 ° C. or higher, and returned to blue color when lowered to 30 ° C. or lower, showing reversible thermochromic properties.

Example 13 Spiro [isobenzofuran-1 (3H), 9 '-[9
H] xanthene] -3-one, 3 '-(diethylamino) -6', 8'-dimethyl-1 part, 4-phenylphenol 3 parts, 1,10-decanediol 25 parts Was solidified to the inside with acrylic resin / amine curing agent 400 parts of thermochromic fine particles having a particle size of 4 μm,
Vinyl acetate-ethylene-vinyl chloride terpolymer having a solid content of about 50% 600 parts of 3D polypropylene elemental fibers (d = 0.91) crimped in a coating composition in which 600 parts of emulsion were uniformly mixed. The thermochromic polypropylene raw fiber obtained by picking up the part after dipping and drying at 100 ° C for 5 minutes is cut into 50 mm to make thermochromic polypropylene raw cotton, sliver hung on a card, and then knitted with a high pile knitting machine and shearing By processing, a thermochromic polypropylene high pile fabric having a pile length of 20 mm was obtained.

The thermochromic high-pile fabric exhibited an orange color at 70 ° C. or lower, changed to colorless at 70 ° C. or higher, and returned to orange color when lowered to 70 ° C. or lower again, showing reversible thermochromic properties.

Example 14 Spiro [isobenzofuran-1 (3H), 9 '-[9
[H] xanthene] -3-one, 6 '-(diethylamino) -2'-[cyclohexyl (phenylmethyl) amino] -1 part, 4,4-thio-bis (3-methyl-6-te
rt-butyl-phenol) 3 parts, 12-hydroxystearic acid triglyceride 30 parts polypropylene 75
It was obtained by uniformly kneading to 0 part, cooling and finely pulverizing. 600 parts of thermochromic fine particles having a particle diameter of 8 μm,
In a coating composition obtained by uniformly mixing 400 parts of acrylic-vinyl acetate copolymer emulsion having a solid content of about 45%, from a 7D acrylonitrile-vinyl chloride copolymer flat section fiber (d = 1.25) having a cut length of 70 mm. After dipping 400 parts of the raw cotton, the excess composition was removed with an air gun and dried at 100 ° C for 10 minutes, the thermochromic acrylonitrile-vinyl chloride copolymer raw cotton was sliver laid on a card and then knitted with a high pile knitting machine. Then, shearing was performed to obtain a thermochromic acrylonitrile-vinyl chloride copolymer high pile fabric having a pile length of 35 mm.

The above thermochromic high-pile fabric exhibited a green color at 50 ° C. or lower, changed to colorless at 50 ° C. or higher, and returned to green when lowered to 50 ° C. or lower again, showing reversible thermochromic properties.

Example 15 1 (3H) -isobenzofuranone, 3 constituting three primary colors
-(1-Ethyl-2-methyl-1H-indole-3-
Yl) -3- (4-diethylaminophenol) -1
Part, 2 parts of bis (4-hydroxyphenyl) sulfone, and 25 parts of butyl stearate, a thermochromic composition for color change of cyan white, spiro [12H-benzo [α]
Xanthene-12,1 '(3'H) -isobenzofuran] -3'-one, 9- (diethylamino) -1 part, bis- (4-hydroxyphenyl) sulfone 2 parts, butyl stearate 25 parts Thermochromic composition that changes color of magenta white and spiro [isobenzofuran-1]
(3H), 9 '-[9H] xanthene] -3-one,
A thermochromic composition of 3 ', 6'-dimethoxy-1,2 parts of bis- (4-hydroxyphenyl) sulfone, and 25 parts of butyl stearate and having a yellow-white color change was prepared with gelatin / gum arabic, respectively. Included by the coacervation method, The thermochromic microcapsules satisfying the above condition and having a particle diameter of 8 μm were prepared. Three kinds of thermochromic microcapsules 300 obtained
Parts, 700 parts of an acrylic ester emulsion having a solid content of about 48% were uniformly mixed, and a 5D polyacrylonitrile fiber having a cut length of 50 mm (d =
After dipping 400 parts of raw cotton consisting of 1.17) and removing the excess composition by centrifugation and drying at 90 ° C for 10 minutes, the thermochromic raw cotton obtained was sliver by applying it to a card The heat-discoloring polyacrylonitrile high pile fabric having a pile length of 22 mm was obtained by knitting with a computer high pile knitting machine into a pattern in which the sex sliver was decomposed into three primary colors with a computer and shearing.

The above thermochromic high-pile fabric shows a natural color picture at 10 ° C or lower, and changes to white at 10 ° C or higher, and again 10
When the temperature was lowered to below ℃, a natural color picture appeared and exhibited reversible thermochromism.

Comparative Example 1 For comparison with Example 1, the particle size of thermochromic microcapsules having the same composition as in Example 1 was measured. Was changed to 30 μm, and a thermochromic plain woven fabric for comparison was obtained in the same manner as above.

Comparative Example 2 For comparison with Example 6, the particle size of thermochromic microcapsules having the same composition as in Example 6 was measured. Was changed to 35 μm, and a thermochromic non-woven fabric for comparison was obtained in the same manner as above.

Comparative Example 3 For comparison with Example 7, the particle size of thermochromic microcapsules having the same composition as in Example 7 was measured. Was changed to 30 μm, and the thermochromic circular knitted fabric for comparison was obtained in the same manner as above.

Comparative Example 4 For comparison with Example 10, the particle size of thermochromic fine particles having the same composition as in Example 10 was measured. Was changed to 29 μm, and a thermochromic flocked fabric for comparison was obtained in the same manner as above.

Comparative Example 5 For comparison with Example 11, the particle size of thermochromic microcapsules having the same composition as in Example 11 was measured. Was changed to 25 μm, and a thermochromic towel cloth for comparison was obtained in the same manner as above.

Comparative Example 6 For comparison with Example 12, the particle size of thermochromic microcapsules having the same composition as in Example 12 was measured. Was changed to 22 μm, and the other thermochromic pile fabric for comparison was obtained in the same manner.

Comparative Example 7 For comparison with Example 13, the particle size of thermochromic fine particles having the same composition as in Example 13 was measured. Was changed to 20 μm, and the thermochromic high pile fabric for comparison was obtained by the same method as above.

Comparative Test 1 When the appearance and texture of the thermochromic plain woven fabrics of Example 1 and Comparative Example 1 were compared, the plain woven fabric of Example 1 showed a uniform blue color, and no discoloration unevenness was observed during the discoloration. Although it had a soft texture, the plain woven fabric of Comparative Example 1 had a non-uniform blue color, and when it was discolored, remarkable discoloration unevenness that could not be put to practical use was observed, and the texture was also extremely hard to put it to practical use. Further, when both of them were subjected to a washing test according to JIS L0844A-2, the plain woven cloth of Example 1 retained the same concentration as the cloth before washing, but the plain woven cloth of Comparative Example 1 was a pigment. The heat discoloration effect was almost eliminated by washing once.

Comparative Test 2 When the appearance and texture of the thermochromic non-woven fabrics of Example 6 and Comparative Example 2 are compared, the non-woven fabric of Example 6 shows a uniform blue color, no discoloration unevenness at the time of discoloration, and a very soft texture. However, the non-woven fabric of Comparative Example 2 had a non-uniform blue color, and when it was discolored, it showed remarkable discoloration unevenness that could not be put to practical use, and the texture was also extremely hard to put it to practical use. Also JI
When a washing test based on S L0844A-2 was conducted, the non-woven fabric of Example 6 retained the same concentration as that of the non-laundered fabric, but the non-woven fabric of Comparative Example 2 had a large loss of pigment and was washed once. As a result, the heat discoloration effect has almost disappeared.

Comparative Test 3 When the appearance and texture of the thermochromic circular knitted fabrics of Example 7 and Comparative Example 3 are compared, the circular knitted fabric of Example 7 shows a uniform blue color, and there is no discoloration unevenness at the time of discoloration. Although it had a soft texture, the circular knitted fabric of Comparative Example 3 had a non-uniform blue color, and when it was discolored, it showed remarkable discoloration unevenness that could not be put to practical use, and the texture was also extremely hard to put it to practical use. Further, when both were subjected to a washing test in accordance with JIS L0844A-2, the circular knitted fabric of Example 7 retained the same density as the fabric before washing, but the circular knitted fabric of Comparative Example 3 contained pigments. Dropout is large,
The heat discoloration effect was almost eliminated by one wash.

Comparative Test 4 When the appearance and texture of the thermochromic flocked fabrics of Example 10 and Comparative Example 4 are compared, the flocked fabric of Example 10 shows a uniform yellow color, no discoloration unevenness is observed during discoloration, and a very soft texture. However, the flocked fabric of Comparative Example 4 had a non-uniform yellow color, showed unevenness in discoloration that could not be put to practical use at the time of discoloration, and had a texture that was extremely hard to put into practical use. Further, when both were subjected to a washing test in accordance with JIS L0844A-2, the flocked fabric of Example 10 retained the same concentration as that of the fabric before washing, but the flocked fabric of Comparative Example 4 had a loss of pigment. The heat discoloration effect was almost eliminated by washing once.

Comparative Test 5 When the appearance and texture of the thermochromic towel fabrics of Example 11 and Comparative Example 5 are compared, the towel fabric of Example 11 shows a uniform black color, no discoloration unevenness is observed at the time of discoloration, and a very soft texture. However, the towel cloth of Comparative Example 5 had a non-uniform black color, and when it was discolored, it showed remarkable discoloration unevenness that could not be put to practical use, and the texture was also extremely hard to put it to practical use. Further, when both were subjected to a washing test in accordance with JIS L0844A-2, the towel cloth of Example 11 retained the same concentration as the cloth before washing, but the towel cloth of Comparative Example 5 did not drop the pigment. The heat discoloration effect was almost eliminated by a single wash.

Comparative Test 6 When the appearance and texture of the thermochromic pile fabrics of Example 12 and Comparative Example 6 were compared, the pile fabric of Example 12 showed a uniform blue color, no discoloration unevenness was observed during the color change, and a very soft texture. However, the pile fabric of Comparative Example 6 had a non-uniform blue color, and when it was discolored, there was noticeable discoloration unevenness that could not be put to practical use, and the texture was also extremely hard to put to practical use. When both were subjected to a brushing step and a polishing step in the finishing step, the pile fabric of Example 12 retained the same density as before the finishing process and finished better in texture, but the pile fabric of Comparative Example 6 was obtained. As a result, the pigment was largely removed due to strong abrasion, and the thermal discoloration effect was almost eliminated by the finishing process.

Comparative Test 7 When the appearance and texture of the thermochromic high-pile fabrics of Example 13 and Comparative Example 7 are compared, the high-pile fabric of Example 13 shows a uniform orange color, no discoloration unevenness is observed during the discoloration, and a very soft texture. However, in the high pile fabric of Comparative Example 7, the orange color was nonuniform, and when the color changed, there was noticeable discoloration unevenness that could not be put to practical use, and the texture was also extremely hard to put to practical use. Further, when both were subjected to a brushing step and a polishing step in the finishing step, the high pile fabric of Example 13 retained the same concentration as before the finishing process and finished better, but the high pile fabric of Comparative Example 7 The strong discoloration caused a large amount of pigment to fall off, and the thermal discoloration effect was almost eliminated by going through the finishing process.

As described above, the present invention eliminates any restrictions on thermochromic fibers obtained by coating with a conventional liquid crystal ink, resulting in thermochromic properties, flexibility, texture, and abrasion resistance not seen in the past. It provides a thermochromic fabric that is extremely washable and processable and can be applied to all kinds of fabric products.

An example of using the present invention is shown below.

Sweaters, cardigans, vests, sports shirts, polo shirts, weisshats, T-shirts, blouses, suits,
Blazers, jackets, slacks, skirts, jerseys, jumpers, training wear, men's / women's clothing, children's clothing, baby clothing, school uniforms, work clothes, etc.
Kimono, Kimono fabric such as obi, coat, raincoat, gown, pajyama, bathrobe, socks, gloves, underwear, swimwear, scarf, chor, muffler, hat, ear pads, slippers, tie, veil, ski wear, socks, watsupen ， Hand bag, bag, bag, furoshiki, towel,
Handkerchiefs, blankets, sheets, knees, duvets, futon cotton, carpets, chair upholstery, jeuyutan, cushions, moquettes, kotatsu coats, kotatsu underlays, sheet fabrics, wall covering fabrics, artificial flowers, stabs, laces, ribbons , Curtains, cloth, goodwill, rugs, ropes, canvas, tents, clothes, hoses, hoods, sheets, hiking shoes, carrying bags, lifeboats, relieving shoes, wrapping cloths, parasites, belts, nets, plush toys, doll clothes, Doll hair, Christmas tree cotton, false beard, false eyelashes, wigs, hairpieces, balls, sound absorbing curtains, heat insulating materials, napkins, lamp shades, thinning screens, blinds,
It can be applied to all textile products.

[Brief description of drawings]

FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5, and FIG. 6 are configuration diagrams showing some of the specific examples of the thermochromic fabric of the present invention. 1 ... Thermochromic fiber 2 ... Non-thermochromic fiber 3 ... Thermochromic cloth

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location D06Q 1/00 (72) Inventor Kito, 3-17 Midoricho, Showa-ku, Nagoya, Aichi Prefecture Pilotot Ink stock In-house (72) Inventor Masaharu Ozaki 3-17, Midori-cho, Showa-ku, Nagoya, Aichi Prefecture Pilot Tok Ink Co., Ltd. (72) Inventor Nobuaki Matsunami 3--17, Midori-cho, Showa-ku, Nagoya, Aichi In Pilot Ink Co., Ltd. (72 ) Inventor Naoya Ishimura, 3-17, Midoricho, Showa-ku, Nagoya, Aichi Prefecture, Pilot Ink Co., Ltd. (72) Inventor, Katsuyuki Fujita, 3-17, Midori-cho, Showa-ku, Nagoya City, Aichi Prefecture, Pilot Ink Co., Ltd. Toranosuke Hashimoto (56) ) References Japanese Patent Publication No. 51-44708 (JP, B1)

Claims (5)

[Claims] 1. The following formula is applied to each surface of a fiber composed of a plurality of elementary fibers. [R: particle size (μm) of pigment, D: denier number (denier) of elementary fiber, d: specific gravity (g / cm ³ ) of elementary fiber] A thermochromic pigment comprising a thermochromic material composed of a color developer and a thermochromic temperature controlling agent encapsulated in microcapsules, and a thermochromic layer comprising a binder, wherein the thermochromic layer is formed on each individual fiber. On the other hand, a thermochromic cloth composed of thermochromic fibers having an adhesion amount of 3% by weight to 90% by weight and the thermochromic pigment being 5% by weight to 80% by weight in the thermochromic layer. 2. The thermochromic cloth according to claim 1, wherein the thermochromic cloth is a woven cloth. 3. The thermochromic cloth according to claim 1, wherein the thermochromic cloth is a non-woven fabric. 4. The thermochromic cloth according to claim 1, wherein the thermochromic cloth is a knitted cloth. 5. The thermochromic cloth according to any one of claims 1 to 4, wherein the thermochromic cloth is a pile cloth.