JPH0418544B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a thermosensitive reversibly color-changing sheet material that changes color reversibly with changes in temperature.

(Prior Art and Problems) Various thermosensitive and reversible color-changing ink compositions that change color depending on temperature have been known, and have been put into practice in the fields of towels, rice cakes, and the like.

Attempts to apply this thermochromism phenomenon to textile products such as clothing are being considered, but even if a thermosensitive reversible color-changing ink composition is applied to fabric or stamped on it, the light fastness is very low, making it difficult to put it to practical use. It wasn't.

(Objective of the Invention) The object of the present invention is to provide a thermosensitive reversible color-changing sheet material that can stably exhibit thermochromism over a long period of time without impairing the characteristics of textile products such as knitted fabrics. It's about doing.

(Structure of the Invention) The heat-sensitive reversible color-changing sheet of the present invention comprises a fiber base layer, a synthetic resin layer containing a heat-sensitive reversible color-changing ink (hereinafter referred to as layer A), and at least one of an ultraviolet absorber and an antioxidant. It is a laminated structure having a synthetic resin layer (hereinafter referred to as layer B) containing The B layer is provided outside the A layer. The fiber base used in the present invention may be any sheet material containing fiber as an essential component, such as natural fibers such as cotton, sheepskin, silk, recycled fibers such as rayon and acetate, polyester, polyamide, etc. Fabrics made of synthetic fibers,
Examples include knitted fabrics and nonwoven fabrics. These base materials can also be used after being dyed or treated with water repellent treatment.

Any substance or composition that reversibly changes color depending on temperature can be used as the thermosensitive reversible color-changing ink. As such thermosensitive reversible color-changing inks, there are known ones that reversibly repeat color development and decoloring, and those that reversibly repeat clear color changes, and any of them can be used in the present invention. In particular, those that change color between -20 and 50°C are preferably used.

Examples of the heat-sensitive reversible color-changing ink used in the present invention include xanthene-based inks that develop a red to orange color, such as 3,6-bisdiethylaminoorthocarboxyphenylxanthenelactam and 3-diethylamino7chloroorthocarboxyphenylxanthenelactam. Compound, 4,4'-bisdimethylaminodiphenyl orthocarboxyphenylmethanelactam, 4,4'bisdiaminodiphenylorthocarboxyphenylmethanelactam, 4,4'bisdimethylaminodiphenylp-dimethylaminoorthocarboxyphenyl Purple like methane lactam~
Coloring components such as phthalide compounds that develop a blue color, compounds that develop a yellow color such as 3,6 ethoxyfluorane, etc. are added as necessary to salts, acidic compounds, etc.
Examples include those containing other third components. Specific examples of components that can coexist in these thermosensitive reversible color-changing inks include dibenzotriazole, 4 lauryl aminosulfonyl benzotriazole, 5 butylbenzotoarizole, 1,2,
3. Triazoles such as dibutyl triazoledicarboxylate, methyl bisparahydroxyphenylmethane β-oxynaphthoate, hydroxyl group-containing compounds such as phenol formaldehyde initial condensate, stearic acid, anthracenecarboxylic acid, phythenic acid, Unstable salts or acidic compounds such as anthranyl toluidic acid, ammonium stearate, acetylbenzotriazole, benzoylbenzotriazole, etc.
Ingredients include cetyl alcohol, dodecyl alcohol, oleyl alcohol, octyl alcohol,
Alcohols such as stearylamide,
Thermosensitive reversible color-changing inks include acidamides such as acetoacetylanilide and oleylamide, esters such as stearic acid glyceride and lanoline diphenyl phthalate, thermoplastic organic substances such as isophorone decalin naphthalene, wood wax, and paraffin wax. Any suitable ink that exhibits reversible discoloration at the temperature at which textile products are used may be used without being limited to the above examples, but it is preferable to use these in combination with a desensitizer. In the present invention, it is essential that the thermosensitive reversible color-changing ink is dispersed in a synthetic resin while being encapsulated in microcapsules. The coating that makes up the microcapsules is a hydrophilic polymer compound such as alginic acid, carrageenan, pectin, gelatin, cationic starch, carboxymethylcellulose, carboxymethylated starch, polyvinyl alcohol, polyvinylpyrrolidone, or acrylic acid amapolymaleic acid copolymer. is preferred.

The diameter of the microcapsules is usually preferably about 3 to 30 microns. Microcapsules are usually made by forming a mixture of various components constituting a heat-sensitive reversible color-changing ink into solid solution particles and coating them with a film typified by a hydrophilic polymer compound. When at least one of an ultraviolet absorber and an antioxidant is contained in the microcapsules, the effect of the present invention becomes even more remarkable. In the present invention, one or more synthetic resin layers containing such thermosensitive reversible color-changing ink are formed directly or indirectly on the fiber base material.

Specific examples of the synthetic resin used in the present invention include polyurethane, polyacrylic ester, polymethacrylic ester, polyamide, polyester, ABS resin, polyvinyl chloride, polyolefin, polysulfone, ethylene-vinyl acetate copolymer, polyethylene, Examples include polypropylene, polyvinylidene chloride, and fluorine resin.
The amount of microcapsules of thermosensitive reversible color-changing ink dispersed in the synthetic resin layer is not particularly limited as long as the amount is sufficient to visually confirm the discoloration of the obtained laminated structure, and it depends on the desired color density and use. It can be determined as appropriate depending on the sensitivity of the ink, etc. The synthetic resin layer containing the heat-sensitive reversibly color-changing ink may contain other components as appropriate, if necessary. In particular, the effects of the present invention become even more remarkable by containing one or both of an ultraviolet absorber and an antioxidant. It is also preferable to coat these with a hydrophilic polymer.

In the present invention, at least one of the B layers must be provided outside the A layer. Although the ultraviolet absorber and the antioxidant can be used alone, it is preferable to use both together. Well-known UV absorbers and antioxidants can be used, but preferred examples include 2(5-methyl-2-hydroxyphenyl).
Benzotriazole, 2[2hydroxy3,5bis(α,αdimethylbenzyl)phenyl]benzotriazole2(3,5ditbutyl2hydroxyphenyl)benzotriazole,2(3tbutyl5
Methyl 5-hydroxyphenyl) 5-chlorobenzotriazole, 2(3,5 di-t-butyl-2-hydroxyphenyl) 5-chlorobenzotriazole, 2(3,
Benzotriazole-based ultraviolet absorbers such as 5-di-t-amyl-2-hydroxyphenyl) benzotriazole, or 2-ethoxy 2'-ethyl acid bisanilide, 2-ethoxy 5-t-butyl
Oxalic acid amide ultraviolet absorbers such as 2'ethyloxychloride bisanilide, benzphenone ultraviolet absorbers such as 2hydroxy 4n octo-octobenzphenone, or bis(2,
2,6,6, tetramethyl 4-piperezyl) sebacate, bis(1,2,2,6,6, pentamethyl 4-piperezyl) sebacate, dimethyl succinate 1
(2hydroxyethyl)4hydro2,2,6,6,
Tetramethyl piperesine polycondensate, poly[[6
(1,1,3,3,tetramethylbutyl)amino1,3,5triazine2,4diyl][(2,2,
6,6tetramethyl4piperezyl)imino]hexamethylene[2,2,6,6,tetramethyl4piperezyl)imino]], [2[3(3,5ditbutyl4hydroxyphenyl)propionyloxy]ethyl] Contains hindered amine ultraviolet absorbers such as 4[3(3,5ditbutyl4hydroxyphenyl)propionyloxy]2,2,6,6tetramethylpiperezine, and as an antioxidant, triethylene Glycolbis[3tbutyl5rutyl4hydroxyphenyl)propionate]
1,6 hexanediol bis[3(3,5 dit-butyl 4-hydroxyphenyl)propionate],
2,4bis(n-octylthio)6(4hydroxy3,5di-t-butylanilino)1,3,5-triazine, pentaerythrityltetrakis[3(3,
5 dit-butyl 4-hydroxyphenyl) propionate], 2,2 thione diethylene bis [3(3,5
di-t-butyl 4-hydroxyphenyl) propionate], octadecyl 3(3,5 di-t-butyl 4-hydroxyphenyl) propionate, 2,2 thiobis(4-methyl 6t-butylphenol), N,N'hexamethylene bis(3,5 di-t-butyl phenol), t-butyl 4-hydroxy-hydrocinnamamide, 3,5 di-t-butyl 4-hydroxybenzyl phosphonate diethyl ester,
1,3,5 trimethyl 2,4,6 tris(3,5
Examples include hindered phenolic antioxidants such as dit-butyl (4-hydroxybenzyl) benzene, bis-3,5 di-t-butyl (4-hydroxybenzyl ethyl sulfonate) calcium salt, and the like.

These ultraviolet absorbers and antioxidants are preferably contained in the B layer in an amount of 0.01% by weight or more, particularly preferably 0.1 to 7.0% by weight, although it depends on the synthetic resin used.

In the present invention, the B layer is provided outside the A layer of the obtained laminated structure, and the A layer is provided outside the A layer of the obtained laminated structure.
It is laminated so that it is wrapped directly or indirectly between layers. In this case, the plurality of B layers may have the same composition or may have different compositions. If the fiber base material is C layer, for example, C-B-A-B, B-C-A-B, B
-Layered in order such as A-C-B. The laminated structure of the present invention can further improve water repellency and abrasion resistance by separately providing a protective layer as the outermost layer, if necessary.

As a protective layer, a synthetic resin layer with wear resistance,
For example, vinyl chloride, polymethyl methacrylate,
Preferably, the material has a hardness of 80 degrees or more, such as polyethyl methacrylate, polyamide, ABS resin, or polyvinylidene chloride. The thickness of each layer varies depending on the purpose of use, but the thickness of layer A is about 10 to 40 microns, and the thickness of layer B is about 3 to 20 microns.

Depending on the purpose of use, a matting agent such as titanium oxide or silicon oxide may be added to the outermost layer.
It is also preferable to add about 0.1 to 10% by weight. The method of applying each layer of the present invention can be direct coating, transfer coating, gravure coating, etc., and the method of removing the solvent can be either a wet method or a dry method.

(Effects of the Invention) The heat-sensitive reversible color change sheet of the present invention exhibits a long-term stable heat-sensitive reversible color change phenomenon, and is particularly excellent in light resistance. Furthermore, the heat-sensitive reversible color-changing sheet of the present invention retains the characteristics of a fiber base material, and can be widely used for clothing such as ski wear, casual wear, pants, coats, windbreakers, swimsuits, coats, umbrellas, bag materials, etc. .

Furthermore, with the conventionally known liquid crystal type, it was possible to enjoy only limited color changes, but with the thermosensitive reversible color-changing sheet material of the present invention, it is possible to enjoy various color combinations.

(Example) Next, the present invention will be explained with reference to Examples. Note that in the embodiments of the present invention, parts refer to important parts.

Example 1 210 70 denier nylon taffeta sheets, 100 parts of polyester polyurethane Rheocoat 9054 [manufactured by Daiichi Lace Co., Ltd.], 5 parts of melamine crosslinking agent Supervetsucomin 820J [manufactured by Dainippon Ink Co., Ltd.], Para-toluenesulfonic acid as a catalyst to promote crosslinking
0.15 parts, 35 parts of toluene as a solvent, and 5 parts of Tinuvin P [manufactured by Ciiba-Geigy (AG)] as an ultraviolet absorber.
% dimethylformamide (hereinafter referred to as DMF)
1 part solution, Sumilizer BBM as antioxidant
A coating solution consisting of 14 parts of a 5% DMF solution [manufactured by Sumitomo Chemical Co., Ltd.] was applied at 30 g/ ^m2 , and after drying, 30 parts of Superflex 300 [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] was applied. 150 parts of Thermochromic Color S-22-c/#A-103 [manufactured by Matsui Shiki Co., Ltd.], a red to white reversible color-changing ink composition encapsulated in microcapsules;
Melamine-based crosslinking agent Sumitekus M-3 [manufactured by Sumitomo Chemical Co., Ltd.] 6 parts and Sumitetsu quantizer
Apply a coating liquid consisting of 0.5 parts of ACX [manufactured by Sumitomo Chemical Co., Ltd.].
Apply 150g/ ^m2 , dry, and then add Crisbon 7667
[Manufactured by Dainippon Ink Co., Ltd.] 100 parts, UV absorber Tinuvin P [manufactured by Ciba-Geigy (AG)] 0.7 parts, Sumilizer BBM [manufactured by Sumitomo Chemical Co., Ltd.] 0.5 parts, DMF/methyl ethyl ketone (hereinafter referred to as MEK) mixed solvent of
After applying a coating solution consisting of 80 parts at a concentration of 25 g/m ² and drying, the mangle was further impregnated with a 3.5% aqueous solution of Scotchigard FC-453 [manufactured by Sumitomo 3M Co., Ltd.] to achieve a 40% reduction. After squeezing with
The temperature was set at 160°C for 30 seconds to form a coated fabric with three coating layers. The light fastness of this coated fabric is grade 3 or higher in the JIS-L-0842 standard fade test, and it can be used as a waterproof fabric for ski clothing, and it also has the function of a heat-sensitive reversible color-changing fabric. It was hot.

Furthermore, the obtained fabric polymethacrylate ester
A 25% ethyl nitrate solution was applied to the outermost layer at 25 g/m ² , and after drying, it was set at 160°C for 30 seconds.
A fabric with a surface hardness of 80 degrees was obtained. The obtained fabric showed no abnormalities in the JIS K-6328 kneading resistance test of 1 kg, 1000 times, and was sufficiently durable as practical clothing.

Example 2 Ultramid IC made of nylon resin [manufactured by Bayer (AG) Co., Ltd.] on release paper EV-130-TP-D [manufactured by Soken Kako Co., Ltd.]
Dissolve 8 parts in 100 parts of a mixed solvent of 7 parts methanol, 3 parts benzene, and 1 part water, and then add Tinuvin P, an ultraviolet absorber.
[Manufactured by Ciba-Geigy (AG)] 0.05 part, antioxidant Irganox 1222 [manufactured by Ciba-Geigy (AG)] 0.4
After coating the coating solution by mixing the two parts with a gravure coater at a concentration of 50 g/m ² and drying it, apply the urethane emulsion Izerax 40 [Hodogaya Chemical Co., Ltd.
Co., Ltd.] 50 parts, Thermochromic Color S-22-c/#-B103, a heat-sensitive reversible color-changing ink encapsulated in microcapsules and reversible blue-yellow color S-22-c/#-B103 [Matsui Shiki Co., Ltd.]
[Manufactured by Sumitomo Chemical Co., Ltd.] 100 copies, Sumitex M-3 [Manufactured by Sumitomo Chemical Co., Ltd.]
3 parts, Sumitetsu Quantizer ACX [manufactured by Sumitomo Chemical Co., Ltd.] 0.5 parts, Tinuvin P [Ciba-Geigy (AG)]
manufactured by Ciba-Geigy] 0.05 part, Irganox 1222 [Ciba-Geigy
100 parts of Crisbon 4070 [manufactured by Dainippon Ink Co., ^Ltd. ], 100 parts of Crisbon NX [manufactured by Dainippon Ink Co., Ltd.] and Dainippon Ink Co., Ltd.] 5 parts, ultraviolet absorber Tinuvin P [Ciba-Geigy (AG)] 5 parts
30 denier 32 gauge polyester and tricot dyed cloth coated with an adhesive consisting of 14 parts of %DMF solution at 100 g/m ² and left for 24 hours, then the release paper was peeled off and the temperature was measured. A knitted coated fabric with reversible color change properties was prepared.

The light fastness of this coated fabric is
It was grade 3 or higher in the fade test according to JIS-L-0842 standards, and there was no problem at all when it was used for clothing.

Example 3 In Example 2, the nylon resin Ultramid
Dissolve 8 parts of IC [manufactured by Bayer (AG)] in 100 parts of a mixed solvent of 7 parts methanol, 3 parts benzene, and 1 part water, and then add the UV absorber Nutivin P [manufactured by Ciba-Geigy (AG)].
0.05 part, antioxidant Irganox 1222 [Ciba
A coated fabric was obtained in the same manner as in Example 2, except that a coating solution containing 0.5 part of [manufactured by Geigy (AG)] was applied to a coating solution of 50 g/m ² using a gravure coater, and the coated fabric was not dried. Ta. The obtained fabric was grade 1 in the fade test according to JIS-L-0842 standards, and was not suitable for practical use.

Example 4 Nylon 30D lip stop, taffeta #3030
[Manufactured by Toray Industries, Inc.] Asahi Guard AG710
After impregnating with a water repellent solution consisting of 3 parts [manufactured by Asahi Glass Co., Ltd.], 1.5 parts Deitsku Silicone Softener [manufactured by Dainippon Ink & Chemicals Co., Ltd.] and 95.5 parts water, and squeezing and drying to a concentration of 30%, polyurethane Leo coat 9054 [first lace
Co., Ltd.] 100 parts, Super Betsucomin 820J [Dainippon Ink & Chemicals Co., Ltd.] 3 parts, paratoluenesulfonic acid 0.15, Rezamin 2200 [Dainippon Ink & Chemicals Co., Ltd.]
35 parts, toluene 40 parts, Tinuvin P [Ciba-Geigy
(AG)] 0.25 parts, Irganox 1222 [Ciba-
Made by Geigy (AG)] 20g/20g of coating solution consisting of 0.3 parts
After doctor-coating the film to a thickness of m ² , dry it and then coat it with Eyecerax 40 [Hodogaya Chemical Co., Ltd.]
[Manufactured by] 30 parts, thermochromic color composition encapsulated in microcapsules Thermochromic color S-22-c/#D with reversible discoloration from purple to light blue
-103 [manufactured by Matsui Shiki Kagaku Co., Ltd.] 80 parts, epoxy crosslinking agent Rezamin 2200 [manufactured by Dainichiseika Chemical Co., Ltd.] 8 parts,
Apply a coating solution consisting of 0.5 parts of Tinuvin P [manufactured by Ciba-Geigy (AG)] using a knife-over-roll type coater.
After coating and drying to a weight of 110 g/m ² , further apply Crysbon 3416 [manufactured by Dainippon Ink & Chemicals Co., Ltd.] 50
A coating solution consisting of 40 parts of a 1:1 mixed solvent of DMF/MEK, 0.4 parts of Tinuvin P [manufactured by Ciba-Geigy (AG)], and 0.6 parts of Irganox 1222 [manufactured by Ciba-Geigy (AG)] was applied to a gravure coater. After coating at 20g/ ^m2 , heat at 140℃ for 3 minutes, dry and further coat at 160g/m2.
℃ for 30 seconds to make ski clothing material with excellent texture. This material is an excellent thermostatic and reversibly color-changing coated fabric, and its light resistance was grade 4 or higher in the JIS-I-0842 light resistance test.

Example 5 nylon 210d denier oxford, polyester polyurethane Krisbon 4070 [manufactured by Dainippon Ink & Chemicals Co., Ltd.] 100 parts, Krisbon
6 parts of NX [manufactured by Dainippon Ink and Chemicals Co., Ltd.], 40 parts of a mixed solvent of toluene/ethyl acetate = 1:1, and a 5% DMF solution of Tinuvin P [manufactured by Ciba-Geigy (AG)]
1.5 parts, Sumilizer BBM [manufactured by Sumitomo Chemical Co., Ltd.] 5%
A coating solution consisting of 14 parts of DMF solution was applied at 25 g/m ² , and after drying, 30 parts of Superflex 300 [manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] and a thermosensitive reversible color-changing ink composition encapsulated in microcapsules were applied. Thermochromic color S-22-c/#A- with reversible color change from red to white
103 [manufactured by Matsui Color Co., Ltd.] 150 copies, Sumitex M-3
A coating solution consisting of 4 parts [manufactured by Sumitomo Chemical Co., Ltd.] and 0.5 parts of Sumitetsu Scatterizer ACX [manufactured by Sumitomo Chemical Co., Ltd.] was applied to 130 g/m ² and dried, and further coated with Crisbon #3416 [large Nippon Ink Co., Ltd.] 100 parts, silicon oxide powder 8 parts, Tinuvin P [Ciba-Geigy (AG)] 0.07
part, Sumilizer BBM [manufactured by Sumitomo Chemical Co., Ltd.] 0.5 part,
Apply 30 parts of coating solution consisting of 70 parts of DMF/MEK mixed solvent.
g/ ^m2 , dried, heated in a baking oven at 145℃ for 6 minutes, and then heated in a drawing machine.
The width setting was performed at 160°C for 30 seconds to obtain a coated fabric with a matte effect on the surface of the coating film. The light fastness of this product is JIS-L-
In the fade test based on the 0842 standard, it had a light resistance of grade 4 or higher, and was sufficiently usable as winter clothing, and was suitable as a thermosensitive reversible color-changing fabric that exhibits thermosensitivity.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing one embodiment of the present invention. 1...Synthetic resin layer containing at least one of an ultraviolet absorber and an antioxidant, 2...Synthetic resin layer containing thermosensitive reversible color-changing ink, 3...Synthetic resin containing at least one of an ultraviolet absorber and an antioxidant Layer 4...Fiber base material.

Claims (1)

[Scope of Claims] 1. A fiber base layer, a synthetic resin layer containing a thermosensitive reversible color-changing ink (layer A), and a synthetic resin layer containing at least one of an ultraviolet absorber and an antioxidant (layer B). A laminated structure having a thermosensitive reversible ink encapsulated in microcapsules and dispersed in a synthetic resin layer, and a synthetic resin layer containing at least one of an ultraviolet absorber and an antioxidant ( 1. A heat-sensitive reversible color-changing sheet material, characterized in that layer B) is provided outside a synthetic resin layer (layer A) containing a heat-sensitive reversible color-changing ink. 2. The heat-sensitive reversible color-changing sheet material according to claim 1, which contains at least one of an ultraviolet absorber and an antioxidant together with the heat-sensitive reversible color-changing ink in the microcapsules. 3. The thermosensitive reversible discoloration according to claim 1 or 2, wherein the synthetic resin layer (A layer) containing the thermosensitive reversible discoloration ink contains at least one of an ultraviolet absorber and an antioxidant outside the microcapsules. sexual sheet-like material. 4. A synthetic resin layer (layer A) containing a thermosensitive reversible color-changing ink is sandwiched between synthetic resin layers (layer B) containing at least one of an ultraviolet absorber and an antioxidant, and is provided on the fiber base material. A thermosensitive reversibly color-changing sheet material according to claim 1, 2, or 3, characterized in that: 5. A heat-sensitive reversibly color-changing sheet material according to claim 1, 2, 3, or 4, wherein the outermost layer contains a matting agent.