JPH0418543B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention relates to a thermosensitive reversible color-changing sheet 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 to practical use 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 or stamped on fabric, it can withstand practical use even if the light fastness is very low. It was nothing.

(Object of the invention) The object of the present invention is to provide a thermosensitive reversible color-changing sheet that can stably exhibit thermochromism over a long period of time without impairing the properties of textile products such as knitted fabrics. .

(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 containing (hereinafter referred to as B layer), and has a structure in which the B layer is provided outside the A layer when viewed from either the front or the back.

The fiber base material used in the present invention may be any sheet-like material containing fiber as an essential component,
Examples include woven, knitted, and nonwoven fabrics made of natural fibers such as cotton, wool, and silk, recycled fibers such as rayon and acetate, and synthetic fibers such as polyester and polyamide. 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 coloring and decoloring, and ones that reversibly repeat clear color changes.
Any of these can be used in the present invention, but especially -
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'-bisdimethylaminodiphenylorthocarboxyphenylethanelactam, 4,4'bisdimethylaminodiphenylparadimethylaminoorthocarboxif Purple like enylmethanelactam~
Coloring components of compounds that develop a yellow color, such as phthalide compounds that develop a blue color, 3,6-ethoxyfluoran, etc., are mixed with salts, acidic compounds,
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 aminophonyl benzotriazole, 5 butylbenzotriazole, 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, anthranil Unstable salts or acidic compounds such as toluidic acid, ammonium stearate, acetylbenzotriazole, benzoyltriazole, etc., alcohols such as cetyl alcohol, dodecyl alcohol, oleyl alcohol, octyl alcohol, etc., stearylamide, acetyl alcohol, etc. as a third component; Examples include acid amides such as acetylanilide 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. The heat-sensitive reversible color-changing ink is not limited to the above-mentioned examples, but any suitable ink exhibiting reversible color-changing property at the temperature at which textile products are used can be used, but it is more preferable to use these in combination with a desensitizer.

In the present invention, it is essential to mix such a thermosensitive reversible color-changing ink into a synthetic resin and provide it directly or indirectly on a fiber base material in one or more layers.

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, epoxy resin, and fluorine resin. The amount of heat-sensitive reversible color-changing ink in the synthetic resin is not particularly limited as long as it is sufficient to visually confirm the discoloration of the obtained laminated structure, and can be determined as appropriate depending on the desired color density and the sensitivity of the ink used. . 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 above 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 2-hydroxyphenyl) 5-chlorobenzotriazole, 2(3,5 di-t-butyl-2-hydroxyphenyl) 5-chlorobenzotriazole, 2(3,
benzotrizole-based UV absorbers such as 5-di-t-amyl-2-hydroxyphenyl) benzotriazole, or 2-ethoxy 2'-ethyl oxidized bisanilide, 2-ethoxy 5-t-butyl 2'-ethyl oxidized bisanilide, etc. Oxalic acid amide UV absorber, 2-hydroxy
Benzphenone ultraviolet absorber such as 4n octooctobenzphenone, 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 also contains antioxidants and Ethylene glycol bis[3t-butyl-5-rutyl-4-hydroxyphenyl)propionate]
1,6 hexanediol bis[3(3,5 dit-butyl 4-hydroxyphenyl)propionate],
2,4 bis(n-octylthio)6(4-hydroxy,
3,5 dit-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 di-t-butyl (4-hydroxybenzyl)benzene and bis-3,5-di-t-butyl (ethyl (ethyl) benzyl sulfonate) calcium salt.

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

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 having abrasion resistance such as vinyl chloride, polymethyl methacrylate, polyethyl methacrylate, polyamide, ABS resin,
A material having a hardness of 80 degrees or more, such as polyvinylidene chloride, is preferable. The thickness of each layer varies depending on the purpose of use.A
The layer is about 10 to 40 microns, and the B layer 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 previously unknown liquid crystal type, it was possible to enjoy only limited color changes, but with the heat-sensitive reversible color-changing sheet of the present invention, it is possible to enjoy various color combinations.

(Example) Next, the present invention will be explained with reference to Examples. In addition, parts in the examples of the present invention refer to parts by weight.

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 Ciba-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. Thermochromic Color L-22-5 (A), a heat-sensitive reversible color-changing ink composition with red to white reversible color-changing property [Matsui Shiki Co., Ltd.]
[manufactured] 150 parts, melamine crosslinking agent Sumitex M
A coating solution consisting of 6 parts of -3 [manufactured by Sumitomo Chemical Co., Ltd.] and 0.5 parts of Sumitetsu Quantizer ACX [manufactured by Sumitomo Chemical Co., Ltd.] was applied at 150 g/ ^m2 , dried, and further coated with Crisbon 7667 [Manufactured by Dainippon Ink Co., Ltd.] 100 parts, ultraviolet absorber Tinuvin P [manufactured by Ciba-Geigy (AG)] 0.7
part, Sumilizer BBM [manufactured by Sumitomo Chemical Co., Ltd.] 0.5 part,
After applying a coating solution consisting of 80 parts of a mixed solvent of DMF/methyl ethyl ketone (hereinafter referred to as MEK) at a coating density of 25 g/m ² and drying, add Scotch Guard FC-453 [manufactured by Sumitomo 3M Co., Ltd.] 3.5 % aqueous solution
After squeezing with a mangle to a 40% reduction, it was dried and set in a drawing machine at 160°C for 30 seconds to form a coated fabric with three coating layers. 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 could be sufficiently used as a waterproof fabric for ski clothing, and had the function of a heat-sensitive reversible color-changing fabric.

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 Nylon resin Ultamide IC [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 mixing medium 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 Irgatonox 1222 [Manufactured by Ciba-Ceigy (AG)]
A coating solution containing 0.5 parts of urethane emulsion was applied to a coating solution of 50 g/m ² using a gravure coater, and then dried. Blue-yellow reversible thermochromic color L-22-9
(B) [Manufactured by Matsui Color Co., Ltd.] 100 copies, Sumitsukus M-3
[Manufactured by Sumitomo Chemical Co., Ltd.] 3 parts, Sumitetsu Quantalizer ACX [manufactured by Sumitomo Chemical Co., Ltd.] 0.5 parts, Tinupin P
Transfer film obtained by applying a coating solution consisting of 0.05 part [manufactured by Ciba-Geigy (AG)] and 0.5 part Irganox 1222 [manufactured by Ciba-Geigy (AG)] at a concentration of 120 g/m ² and drying. 100 copies of Chrisbon 4070 [manufactured by Dainippon Ink Co., Ltd.], Chrisbon NX [Dainippon Ink Co., Ltd.]
Co., Ltd.] 5 parts, ultraviolet absorber Tinupin P [Ciba-
[Made by Geigy (AG)] Apply adhesive consisting of 14 parts of 5% DMF solution to 100g/m ² and 30 denier.
After 32-gate polyester and tricot dyed fabrics were bonded together and left for 24 hours, the release paper was peeled off to obtain a knitted coated fabric with temperature-indicating and reversible color-changing properties.

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 mixing medium of 7 parts methanol, 3 parts benzene, and 1 part water, and then add an ultraviolet absorber and Tinuvin 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 0.5 parts of the coating solution (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 210d denier oxford, polyester polyurethane Crysbon 4070 [manufactured by Dainippon Ink Chemical Co., Ltd.] 100 parts, Crysbon NX [manufactured by Dainippon Ink Chemical Co., Ltd.] 6 parts, toluene/ethyl acetate = 1 /1 mixed solvent, 40 parts of Tinuvin P [Ciba-
1.5 parts of 5% DMF solution of Geigy (AG), 14 parts of 5% DMF solution of Sumilizer BBM [manufactured by Sumitomo Chemical Co., Ltd.]
After applying 25 g/m ² of a coating solution consisting of
30 parts, thermochromic color L-22-5 (A), a red-white reversible color-changeable thermosensitive ink composition
150 copies, Sumitex M-3 [manufactured by Sumitomo Chemical Co., Ltd.] 4
Division, Sumitetsu Catalyzer ACX [Sumitomo Chemical
Co., Ltd.] 0.5 part coating solution was applied to 130 g/m ² and dried, followed by 100 parts of Crisbon #3416 [Dainippon Ink Chemical Co., Ltd.], 8 parts of silicon oxide powder, and Tinuvin P.
[Made by Ciba-Geigy (AG)] 0.07 part, Sumilizer
A coating solution consisting of 0.5 parts of BBM [manufactured by Sumitomo Chemical Co., Ltd.] and 70 parts of a DMF/MEK mixed solvent was applied at 30 g/m ² and dried, then heated in a paking oven at 145°C for 6 minutes. A width setting machine was used to set the width at 160°C for 30 seconds to obtain a coated fabric having a matte effect on the surface of the coating film. The light fastness of this product is 4 in the fade test according to JIS-L-0842 standard.
It had a light resistance of grade 1 or above, and could be sufficiently used as cold-weather clothing, and was suitable as a thermosensitive reversible color-changing fabric exhibiting 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 a thermosensitive reversible color-changing ink, 3...Containing at least one of an ultraviolet absorber and an antioxidant synthetic resin 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 synthetic resin layer (layer B) containing at least one of an ultraviolet absorber and an antioxidant from both the front and back sides of the synthetic resin layer (layer A) containing a thermosensitive reversible color-changing ink. A heat-sensitive reversible color-changing sheet characterized by being provided on the outside. 2. The heat-sensitive reversible color-changing sheet according to claim 1, wherein the synthetic resin layer (layer A) containing the heat-sensitive reversible color-changing ink contains at least one of an ultraviolet absorber and an antioxidant. 3. A synthetic resin layer (A layer) containing a thermosensitive reversible color-changing ink is sandwiched between synthetic resin layers (B layer) containing at least one of an ultraviolet absorber and an antioxidant, and is provided on a fiber base material. A heat-sensitive reversibly color-changing sheet according to claim 1 or 2. 4. The heat-sensitive reversible color-changing sheet according to claim 1, 2 or 3, wherein the outermost layer is a synthetic resin layer containing a matting agent.