JP2022104277A - Reversible heat discoloration twisted yarn, fabric using the same, head ornament, and toy - Google Patents

Abstract

To provide a reversible heat discoloration twisted yarn good in visibility of reversible discoloration by temperature change, and suppressed in generation of delamination by providing adhesive layers to improve adhesiveness between layers, excellent in durability of a reversible heat discoloration layer by protecting the reversible heat discoloration layer, having glossiness, and having applicability to a variety of fields such as a toy field, a decorative field, and a design field so as to be high in merchantability.SOLUTION: A reversible heat discoloration twisted yarn (1) comprises a reversible heat discoloration flat yarn (2) comprising sequentially: a first transparent adhesive layer (4); a reversible heat discoloration layer (5) fixed with a reversible discoloration microcapsule pigment containing a reversible heat discoloration composition comprising at least (a) an electron-donating coloring organic compound, (b) an electron-accepting compound, and (c) a reaction medium for controlling a coloration reaction of the above (a) and (b) in a binder resin in a dispersed state; a second transparent adhesive layer (6); and a transparent resin layer (7) on one side broad surface of a flat yarn composed of a transparent resin film (3).SELECTED DRAWING: Figure 4

Description

The present invention relates to a reversible thermochromic twisted yarn and a fabric, a headdress, and a toy using the same. More specifically, the present invention relates to a reversible thermochromic twisted yarn that reversibly changes its color due to a temperature change, and a fabric, a headdress, and a toy using the same.

Conventionally, a reversible thermal discoloration layer formed of a composition composed of a thermal discoloring material and a fixing agent (hereinafter referred to as “binder”) is provided on a substrate, and a protective layer covering the reversible thermal discoloration layer is further provided. Disversible thermochromic yarns and twisted yarns to which the yarns are applied are disclosed (see, for example, Patent Document 1).
The above-mentioned reversible thermochromic yarn reversibly changes color from colored to colorless or from colorless to colored by using a heat-changing material encapsulated in microcapsules as a colorant. Since the heat-changing material is encapsulated, the color of the thread tends to be lighter than when a general non-heat-changing colorant is used, and the color change tends to be difficult to visually recognize.
It is conceivable to increase the blending ratio of the heat-discoloring material in the composition in order to deepen the color of the thread, but if the blending ratio of the heat-discoloring material is increased, the adhesiveness of the reversible heat-discoloring layer to the substrate or the protective layer is increased. In particular, when the above-mentioned reversible heat-discoloring yarn is applied to a twisted yarn, delamination occurs between the reversible heat-discoloring layer and the substrate, or between the reversible heat-discoloring layer and the protective layer due to the stress applied to the yarn. As a result, the reversible thermal discoloration layer is not protected from external factors, and there is a problem that the thermal discoloration function of the reversible thermal discoloration layer is easily impaired.

Microfilm of No. 60-165477

INDUSTRIAL APPLICABILITY The present invention is intended to provide a reversible thermochromic twisted yarn having good visibility of reversible color change due to temperature change and having excellent luster in durability of the reversible thermochromic layer.

In the present invention, a first transparent adhesive layer, (a) an electron-donating color-developing organic compound, and (b) an electron-accepting compound are formed on one wide surface of a plain yarn made of a transparent resin film. C) A reversible thermochromic microcapsule pigment containing at least a reversible thermochromic composition comprising a reaction medium for controlling the color reaction of (a) and (b) above was fixed in a dispersed state in a binder resin. The requirement is a reversible thermochromic twisted yarn composed of a reversible thermochromic flat yarn in which a reversible thermochromic layer, a second transparent adhesive layer, and a transparent resin layer are sequentially provided.
Further, the first transparent adhesive layer and the second transparent adhesive layer contain a light stabilizer, the transparent resin layer is a transparent resin film, and the reversible thermal discoloration property. The average particle size of the microcapsule pigment is 0.1 to 50 μm, and the reversible thermochromic microcapsule pigment is blended in the range of 50 to 200 parts by mass with respect to 100 parts by mass of the solid content of the binder resin. The average thickness of the reversible thermochromic layer is 1 to 50 μm, and the average particle size (D) of the reversible thermochromic microcapsule pigment and the average thickness (T) of the reversible thermochromic layer. However, the following formula (I) is satisfied. 0.002 ≦ D / T <1 (I)
Is a requirement.
Further, a reversible thermochromic twisted yarn composed of the reversible thermochromic flat yarn and the yarn is required.
Further, the reversible thermochromic flat yarn is provided around the yarn, and the yarn has any of metallic luster, pearl luster, hologram property, iris property, light interference property, and light reflection property. It is a requirement that the brilliant yarn has a selected optical property, and that the brilliant yarn is a transparent brilliant yarn having further transparency.
Further, a cloth made of the reversible thermochromic plying, a headdress provided with the reversible thermochromic plying, and a toy made of the reversible thermochromic plying are required.

In the present invention, the visibility of reversible color change due to temperature change is good, and the occurrence of delamination is suppressed by providing an adhesive layer to improve the adhesiveness between each layer, resulting in a reversible thermal discoloration layer. By being protected, the reversible thermal discoloration layer has excellent durability and gloss, and it has high commercial reversible thermal discoloration with applicability to various fields such as toy field, decoration field, design field, etc. It is possible to provide twisted yarn and products such as fabrics, headdresses, toys and the like using the twisted yarn.
Further, by further containing a light stabilizer in the adhesive layer, the reversible heat-discoloring layer has excellent durability and light resistance, and further has gloss, a reversible heat-discoloring twisted yarn, and fabrics and headdresses using the same. , Toys and other products can be provided.

It is a graph explaining the hysteresis characteristic in the color density | temperature curve of the heat decolorizing type reversible thermochromic composition. It is a graph explaining the hysteresis characteristic in the color density | temperature curve of the heat decolorizing type reversible thermochromic composition. It is a graph explaining the hysteresis characteristic in the color density | temperature curve of the heat color development type reversible thermochromic composition. It is explanatory drawing of one Example of the reversible thermochromic plying of this invention. It is explanatory drawing of another Example of the reversible thermochromic plying of this invention. It is explanatory drawing of another Example of the reversible thermochromic plying of this invention. It is a vertical sectional view of an Example of the reversible thermochromic flat yarn used in this invention. It is a vertical sectional view of another Example of a reversible thermochromic flat yarn used in this invention. It is a vertical sectional view of another Example of a reversible thermochromic flat yarn used in this invention.

The reversible thermochromic twisted yarn (1) (hereinafter, may be referred to as “twisted yarn”) of the present invention is formed on one wide surface of a plain yarn made of a transparent resin film (3) shown in FIG. One transparent adhesive layer (4), a reversible thermal discoloration layer (5) in which a reversible thermochromic microcapsule pigment is fixed in a dispersed state in a binder resin, a second transparent adhesive layer (6), a transparent resin. It is composed of a reversible thermochromic flat yarn (2) in which layers (7) are sequentially provided.
Here, the first transparent adhesive layer or the second transparent adhesive layer may be hereinafter referred to as "transparent adhesive layer" or "adhesive layer".

The transparent resin film applied to the present invention can impart glossiness to the reversible heat-discoloring twisted yarn, and further, the stress when the reversible heat-discoloring flat yarn is processed into a twisted yarn, scratching, etc. It is possible to prevent damage to the first transparent adhesive layer and the reversible thermal discoloration layer due to a certain factor, and to obtain a reversible thermal discoloration twisted yarn having excellent durability and glossiness of the reversible thermal discoloration layer. .. The transparent resin film is not particularly limited as long as the design of the reversible thermal discoloration layer, characters, and color change due to temperature change can be visually recognized.
Examples of the transparent resin film include polyolefin resins such as polyethylene and polypropylene, cellulose derivatives such as cellulose acetate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers. Examples thereof include a film made of a general-purpose resin such as vinyl alcohol resin, vinyl chloride resin, vinylidene chloride resin, acrylic acid ester resin, polyacrylic acid, rayon, and cupra.

The thickness of the transparent resin film is in the range of 3 to 50 μm, preferably 6 to 25 μm, more preferably 6 to 12 μm, which satisfies the practical use. When the thickness of the transparent resin film exceeds 50 μm, it is difficult to process the reversible thermochromic flat yarn into twisted yarn, and the soft texture of the yarn is easily impaired. On the other hand, if the thickness is less than 3 μm, the strength of the film is poor because the thickness is too thin, and the effect of protecting the first transparent adhesive layer and the reversible thermal discoloration layer from external factors such as stress and scratching is obtained. It tends to be scarce.

The transparency of the transparent resin film is a property of transmitting light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079), and is a visible light region of the transparent resin film. The light transmission rate (visible light transmission rate) in the above is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance is less than 5%, it becomes difficult to visually recognize the color change due to the design, characters, and temperature change of the reversible thermal discoloration layer.
For the above-mentioned visible light transmittance, a transparent resin film is provided on a transparent substrate that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210]. Was measured in the wavelength region from 380 nm to 780 nm, and was set as an intermediate value between the maximum value and the minimum value.

The reversible thermochromic layer constituting the twisted yarn of the present invention has a color reaction of (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, (c) (a) component and (b) component. A reversible thermochromic microcapsule pigment in which a reversible thermochromic composition comprising a reaction medium for determining the occurrence temperature of the above is encapsulated in microcapsules is contained.
The reversible thermochromic composition is described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-229398, etc., before and after a predetermined temperature (discoloration point) as a boundary. Discoloration occurs in the temperature range above the high temperature side discoloration point, and the color develops in the temperature range below the low temperature side discoloration point. The state of is maintained as long as the heat or cold required for the state to develop is applied, but when the heat or cold is no longer applied, the state returns to the state exhibited in the normal temperature range, and the hysteresis width (ΔH) is A heat-decoloring type (decolorizes by heating and develops color by cooling) reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) can be used (see FIG. 1).

Further, the hysteresis width described in JP-A No. 4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. The shape of the curve, which shows a large characteristic (ΔH = 8 to 70 ° C.) and plots the change in color density due to temperature change, is higher than the discoloration temperature range, contrary to the case where the temperature is raised from the lower temperature side than the discoloration temperature range. The color changes by following a path that is significantly different from the case of descending from the side, and the color development state in the temperature range of the complete color development temperature t ₁ or less, or the decolorization state in the high temperature range of the complete decolorization temperature t ₄ or more, Heat decolorization type with color memory in a specific temperature range [temperature range between color development start temperature t ₂ and decolorization start temperature t ₃ (substantial two-phase holding temperature range)] (decolorization by heating and color development by cooling) It is also possible to use a reversible thermochromic composition (see FIG. 2).

The components (a), (b), and (c) will be specifically described below.

The component (a), that is, the electron-donating color-developing organic compound is a component that determines a color and is a compound that donates electrons to the component (b), which is a color developer, to develop a color.
Examples of the electron-donating color-developing organic compound include a phthalide compound, a fluorine compound, a stirinoquinoline compound, a diazarodamine lactone compound, a pyridine compound, a quinazoline compound, a bisquinazoline compound, and the like, among which a pyridine compound, a quinazoline compound, and the like. And bisquinazoline compounds are preferred.

Examples of the phthalide compound include diphenylmethanephthalide compound, phenylindrill phthalide compound, indrill phthalide compound, diphenylmethane azaphthalide compound, phenyl indolyl azaphthalide compound, and derivatives thereof. Of these, a phenylindrill azaphthalide compound and a derivative thereof are preferable.
In addition, examples of the fluorin compound include an aminofluorane compound, an alkoxyfluorane compound, and a derivative thereof.

The compounds that can be used for the component (a) are illustrated below.
3,3-Bis (4-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-Diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) phthalide,
3,3-bis (1-n-butyl-2-methylindole-3-yl) phthalide,
3,3-Bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-n-Hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- [2-ethoxy-4- (N-ethylanilino) phenyl] -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide,
3- (2-Acetamide-4-diethylaminophenyl) -3- (1-propyl-2-methylindole-3-yl) -4-azaphthalide,
3,6-bis (diphenylamino) fluorane,
3,6-Bis (N-Phenyl-N-p-Trillamino) Fluoran,
3,6-dimethoxyfluorane,
3,6-di-n-butoxyfluolane,
2-Methyl-6- (N-ethyl-N-p-trillamino) fluorane,
3-Chloro-6-cyclohexylaminofluorane,
2-Methyl-6-cyclohexylaminofluorane,
2-Chloroamino-6-di-n-butylaminofluorane,
2- (2-Chloroanilino) -6-di-n-butylaminofluorane,
2- (3-Trifluoromethylanilino) -6-diethylaminofluorane,
2- (3-Trifluoromethylanilino) -6-di-n-pentylaminofluorane,
2-Dibenzylamino-6-diethylaminofluorane,
2- (N-Methylanilino) -6- (N-ethyl-Np-trillamino) fluorane,
1,3-dimethyl-6-diethylaminofluorane,
2-Chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluorane,
2-anilino-3-methoxy-6-diethylaminofluorane,
2-anilino-3-methyl-6-di-n-butylaminofluorane,
2-anilino-3-methoxy-6-di-n-butylaminofluorane,
2-Xylidino-3-methyl-6-diethylaminofluorane,
2-Anilino-3-methyl-6- (N-ethyl-N-p-tolylamino) fluorane,
6-diethylamino-1,2-benzofluorane,
6- (N-ethyl-N-isobutylamino) -1,2-benzofluorine,
6- (N-Ethyl-N-Isopentylamino) -1,2-benzofluorine,
2- (3-Methoxy-4-dodecoxystylyl) quinoline,
2-diethylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on,
2-Di-n-butylamino-8-di-n-butylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-On,
2-Di-n-butylamino-8-diethylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-on ,
2-Di-n-butylamino-8- (N-ethyl-N-isoamylamino) -4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -Isobenzofuran] -3'-on,
2-Di-n-butylamino-8-di-n-pentylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] pyrimidine-5,1'(3'H) -isobenzofuran] -3'-On,
4,5,6,7-Tetrachloro-3- (4-dimethylamino-2-methoxyphenyl) -3- (1-n-butyl-2-methyl-1H-indole-3-yl) -1 (3H) ) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -iso Benzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-pentyl-2-methyl-1H-indole-3-yl) -1 (3H) -Isobenzofuranone,
4,5,6,7-Tetrachloro-3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methyl-1H-indole-3-yl) -1 (3H) -iso Benzofuranone,
3', 6'-bis [Phenyl (2-methylphenyl) amino] Spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [Phenyl (3-methylphenyl) amino] Spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
3', 6'-bis [Phenyl (3-ethylphenyl) amino] Spiro [isobenzofuran-1 (3H), 9'-[9H] xanthene] -3-one,
2,6-bis (2'-ethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2,6-bis (2', 4'-diethyloxyphenyl) -4- (4'-dimethylaminophenyl) pyridine,
2- (4'-Dimethylaminophenyl) -4-methoxyquinazoline,
4,4'-Ethylenedioxy-bis [2- (4-diethylaminophenyl) quinazoline]

As the fluorans, in addition to the compound having a substituent on the phenyl group forming the xanthene ring, the phenyl group having the substituent on the phenyl group forming the xanthene ring and the phenyl group forming the lactone ring also has a substituent (for example,). It may be a compound exhibiting a blue color or a black color having an alkyl group such as a methyl group and a halogen atom such as a chlorine atom).

The component (b), that is, the electron-accepting compound is a compound that receives electrons from the component (a) and functions as a color developer of the component (a).
Examples of the electron-accepting compound include a group of compounds having an active proton, a group of pseudo-acidic compounds [a group of compounds that are not acids but act as acids in a reversible thermochromic composition to develop color of component (a)], and electrons. Examples thereof include compounds selected from a group of compounds having pores. Among the above components (b), a compound selected from the group of compounds having an active proton is preferable.

The group of compounds having an active proton includes a compound having a phenolic hydroxyl group and its derivative, a carboxylic acid and its derivative, an acidic phosphoric acid ester and its derivative, an azol-based compound and its derivative, 1,2,3-triazole and the like. Examples thereof include derivatives thereof, cyclic carbosulfoimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. As the carboxylic acid and its derivative, an aromatic carboxylic acid and its derivative, or an aliphatic carboxylic acid having 2 to 5 carbon atoms and its derivative thereof are preferable.
The group of pseudoacidic compounds includes metal salts of compounds having a phenolic hydroxyl group, metal salts of carboxylic acids, metal salts of acidic phosphoric acid esters, metal salts of sulfonic acid, aromatic carboxylic acid anhydrides, and aliphatic carboxylic acid anhydrides. , Aromatic carboxylic acid and sulfonic acid mixed anhydride, cycloolefin dicarboxylic acid anhydride, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, halogenated alcohols and the like.
Examples of the compound group having electron vacancies include borates, boric acid esters, inorganic salts and the like.

Among the above-mentioned components (b), a compound having a phenolic hydroxyl group is preferable because it can more effectively exhibit the thermal discoloration property.
Compounds having a phenolic hydroxyl group include a wide range of compounds from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensed resins and the like. The compound having a phenolic hydroxyl group preferably has at least two or more benzene rings. Further, the compound having a phenolic hydroxyl group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxyl group and an ester or amide group thereof, a halogen atom and the like.

Metals contained in metal salts such as compounds having a phenolic hydroxyl group include, for example, sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum. Etc. can be exemplified.

The compounds that can be used for the component (b) are illustrated below.
Phenol, o-cresol, tertiary butylcatechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, p-hydroxybenzoate n-butyl , P-Hydroxybenzoate n-octyl, resorcin, dodecyl asbestosate, 4,4-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 1,1-bis (4-hydroxyphenyl) n-pentane, 1,1-bis (4-hydroxyphenyl) n-hexane, 1,1-bis (4-hydroxyphenyl) n-heptane, 1,1-bis (4-hydroxyphenyl) n-octane, 1,1-bis (4-hydroxyphenyl) n-nonane, 1 , 1-bis (4-hydroxyphenyl) n-decane, 1,1-bis (4-hydroxyphenyl) n-dodecane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1- Bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) -3-methylpentane, 1,1-bis (4-hydroxyphenyl) -2,3-dimethylpentane, 1, 1-bis (4-hydroxyphenyl) -2-ethylbutane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 1,1-bis (4-hydroxyphenyl) -3,7-dimethyloctane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane , 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxyphenyl) n-pentane, 2,2-bis ( 4-Hydroxyphenyl) n-hexane, 2,2-bis (4-hydroxyphenyl) n-heptane, 2,2-bis (4-hydroxyphenyl) n-octane, 2,2-bis (4-hydroxyphenyl) ) N-nonan, 2,2-bis (4-hydroxyphenyl) n-decane, 2,2-bis (4-hydroxyphenyl) n-dodecane, 2,2-bis (4-hydroxyphenyl) Hydroxyphenyl) ethyl propionate, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) -4-methylhexane, 2,2-bis (4-) Hydroxyphenyl) Hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis [2- (2-( 4-Hydroxyphenyl) -2-propyl] benzene, bis (2-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 3,3-bis (3-methyl-4-hydroxyphenyl) )butane

A compound having a phenolic hydroxyl group can exhibit the most effective thermal discoloration property, but is an aromatic carboxylic acid and an aliphatic carboxylic acid having 2 to 5 carbon atoms, a carboxylic acid metal salt, an acidic phosphoric acid ester and a metal salt thereof. , 1, 2,3-Triazole and a compound selected from its derivatives may be used.

The component (c) of the reaction medium that reversibly causes the electron transfer reaction by the component (a) and the component (b) in a specific temperature range will be described.
Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When the above reversible thermochromic composition is applied to microencapsulation and secondary processing, low molecular weight ones evaporate to the outside of the capsule when subjected to high heat treatment, so carbon is used to stably retain the composition in the capsule. Several tens or more of compounds are preferably used.

As alcohols, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective. For example, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, etc. Examples thereof include heptadecyl alcohol, octadecyl alcohol, eikosyl alcohol, and docosyl alcohol.

As the esters, esters having 10 or more carbon atoms are effective, and any combination of a monovalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monovalent alcohol having an aliphatic and an alicyclic or aromatic ring is effective. Esters, aliphatics and alicyclics obtained from any combination of a polyvalent carboxylic acid having an aliphatic and alicyclic or aromatic ring and a monovalent alcohol having an alicyclic or alicyclic or aromatic ring. Alternatively, esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and an aliphatic and polyhydric alcohol having an alicyclic or aromatic ring can be mentioned, for example, ethyl caprylate, octyl caprylate, stearyl caprylate. , Myristyl caprate, docosyl caprice, 2-ethylhexyl laurate, n-decyl laurate, 3-methylbutyl myristate, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n stearate -Butyl, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, n-undecyl stearate, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate , Behenyl behenate, cetyl benzoate, 4-tert-butyl stearyl benzoate, dimyristyl phthalate, distearyl phthalate, dimyristyl oxalate, disetyl oxalate, disetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate , Dilauryl azelaate, Di- (n-nonyl) sebacate, Dineopentyl 1,18-octadecylmethylene dicarboxylate, Ethylene glycol dimyristate, Propropylene glycol dilaurate, Propropylene glycol distearate, Hexylene glycol dipalmitate, 1, 5-Pentanediol distearate, 1,2,6-hexanetriol trimilistate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprine, xylene glycol distea Examples of rates and the like can be given.

Further, an ester of a saturated fatty acid and a branched aliphatic alcohol, an ester of an unsaturated fatty acid or a saturated fatty acid having a branch or a substituent and an aliphatic alcohol having a branched or 16 or more carbon atoms, cetyl butyrate, Ester compounds selected from stearyl butyrate and behenyl butyrate are also effective.
Examples of the ester compound include 2-ethylhexyl buty acid, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl capricate, 3,5,5-trimethylhexyl lauric acid, and 3,5,5 palmitic acid. -Trimethylhexyl, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitic acid, 1-ethylpropyl stearate, 1 behenic acid -Ethylpropyl, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprice, 2-methylpentyl laurate, 2-Methylbutyl stearate, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate , Caproate 1-ethylpentyl, palmitic acid 1-ethylpentyl, stearate 1-methylpropyl, stearate 1-methyloctyl, stearate 1-methylhexyl, laurate 1,1-dimethylpropyl, capricate 1-methyl Pentyl, 2-methylhexyl palmitate, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl palmitate, 3,7-dimethyloctyl palmitate, 3,7-Dimethyloctyl stearate, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, iso-ercaate Stearyl, cetyl isostearate, stearyl isostearate, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, buty acid Examples thereof include stearyl and behenyl butyrate.

Further, in order to change the color by showing a large hysteresis characteristic with respect to the color density-temperature curve and to give color memory depending on the temperature change, it is described in Japanese Patent Publication No. 4-17154 and has a temperature of 5 ° C or higher and lower than 50 ° C. A carboxylic acid ester compound exhibiting a ΔT value (melting point-cloud point), for example, a carboxylic acid ester containing a substituted aromatic ring in the molecule, a carboxylic acid containing an unsubstituted aromatic ring, and an aliphatic alcohol having 10 or more carbon atoms. Esters, carboxylic acid esters containing cyclohexyl groups in molecules, esters of fatty acids with 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, esters of fatty acids with 8 or more carbon atoms and branched aliphatic alcohols, dicarboxylic acids and aromatics Esters with group alcohols or branched aliphatic alcohols, dibenzyl silicate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, disetyl adipate, distearyl adipate, trilaurin, trimyristin, tristea, di Examples thereof include myristin and distea.

Further, an odd aliphatic monohydric alcohol having 9 or more carbon atoms, a fatty acid ester compound obtained from an aliphatic carboxylic acid having an even number of carbon atoms, n-pentyl alcohol or n-heptyl alcohol, and an even number of 10 to 16 carbon atoms. A fatty acid ester compound having 17 to 23 total carbon atoms obtained from an aliphatic carboxylic acid is also effective.
Examples of the fatty acid ester compound include n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, and capryl. Acid n-undecyl, capricate n-tridecyl, caprylate n-pentadecyl, capricate n-heptyl, capricate n-nonyl, capricate n-undecyl, capricate n-tridecyl, capricate n-pentadecyl, laurate n -Pentyl, n-heptyl laurate, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate , N-undecyl myristate, n-tridecyl myristate, n-pentadecyl myristate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, palmitin N-pentadecyl acid, n-nonyl stearate, n-undecyl stearate, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eikosanoate, n-undecyl eikosanoate, n-tridecyl eikosanoate, n-eikosanoate -Pentadecyl, n-nonyl behenate, n-undecyl behenate, n-tridecyl behenate, n-pentadecyl behenate and the like can be exemplified.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, for example, 2-decanone, 3-decanone, 4-decanone, 2-undecanone, 3-undecanone, 4-undecanone, 5-undecanone. , 2-Dodecanone, 3-Dodecanone, 4-Dodecanone, 5-Dodecanone, 2-Tridecanone, 3-Tridecanone, 2-Tetradecanone, 2-Pentadecanone, 8-Pentadecanone, 2-Hexadecanone, 3-Hexadecanone, 9-Heptadecanone, 2 Examples thereof include pentadecanone, 2-octadecanone, 2-nonadecanone, 10-nonadecanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, lauron, and stearone.
Furthermore, arylalkylketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradeca. Nophenone, 4-n-dodecanoacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurofenone, 4-n-decanoacetophenone, n-undecanophenone, 4-n-nonylacetophenone, n-decanophenone, 4-n-octylacetophenone, n-nonanophenone, 4-n-heptylacetophenone, n-octanophenone, 4-n-hexylacetophenone, 4-n-cyclohexylacetophenone, 4-tert-butylpropiophenone , N-Heptaphenone, 4-n-pentylacetophenone, cyclohexylphenylketone, benzyl-n-butylketone, 4-n-butylacetophenone, n-hexanophenone, 4-isobutylacetophenone, 1-acetonaphthone, 2-acetonafton, cyclopentylphenyl Examples include ketones.

As the ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and for example, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, and didodecyl ether. , Ditridecyl ether, Ditetradecyl ether, Dipentadecyl ether, Dihexadecyl ether, Dioctadecyl ether, Decanediol dimethyl ether, Undecanediol dimethyl ether, Dodecanediol dimethyl ether, Tridecanediol dimethyl ether, Decanediol diethyl ether, Undecanediol diethyl ether Etc. can be exemplified.

Examples of acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, capric acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide and olein. Acid amides, erucic acid amides, benzamides, caproic acid anilides, capric acid anilides, capric acid anilides, lauric acid anilides, myristic acid anilides, palmitate anilides, stearate anilides, behenic acid anilides, oleic acid anilides, erucate anilides, caprones. Acid N-methylamide, capric acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearate N-methylamide, behenic acid N-methylamide, oleic acid N -Methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearate N-ethylamide, oleic acid N-ethylamide, lauric acid N-butylamide, myristic acid N-butylamide , Palmitic acid N-butylamide, stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, steaic acid N-octylamide, oleic acid N -Octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearate N-dodecylamide, oleic acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitin Acid amides, distearate amides, dioleic acid amides, trilauric acid amides, trimylistic acid amides, tripalmitic acid amides, tristearic acid amides, trioleic acid amides, succinic acid amides, adipic acid amides, glutarate amides, malonic acid amides. , Azelaic acid amide, maleic acid amide, succinic acid N-methylamide, adipic acid N-methylamide, glutaric acid N-methylamide, malonic acid N-methylamide, azelaic acid N-methylamide, succinic acid N-ethylamide, adipic acid N-ethylamide , Glutal acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipii Examples thereof include acid N-butyramide, glutaric acid N-butyramide, malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

〔式中、Ｒ_１は水素原子又はメチル基を示し、ｍは０～２の整数を示し、Ｘ_１及びＸ_２のいずれか一方は－（ＣＨ_２）_ｎＯＣＯＲ_２又は（ＣＨ_２）_ｎＣＯＯＲ_２、他方は水素原子を示し、ｎは０～２の整数を示し、Ｒ_２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ_１及びＹ_２はそれぞれ独立して、水素原子、炭素数１～４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｒ及びｐはそれぞれ独立して、１～３の整数を示す〕
式（１）で示される化合物のうち、Ｒ_１が水素原子の場合、より広いヒステリシス幅を有する可逆熱変色性組成物が得られるため好ましく、さらにＲ_１が水素原子であり、且つ、ｍが０の場合がより好ましい。
なお、式（１）で示される化合物のうち、より好ましくは下記式（２）で示される化合物である。

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、好ましくは炭素数１０～２４のアルキル基であり、より好ましくは炭素数１２～２２のアルキル基である）
式（２）で示される化合物としては、例えば、オクタン酸４－ベンジルオキシフェニルエチル、ノナン酸４－ベンジルオキシフェニルエチル、デカン酸４－ベンジルオキシフェニルエチル、ウンデカン酸４－ベンジルオキシフェニルエチル、ドデカン酸４－ベンジルオキシフェニルエチル、トリデカン酸４－ベンジルオキシフェニルエチル、テトラデカン酸４－ベンジルオキシフェニルエチル、ペンタデカン酸４－ベンジルオキシフェニルエチル、ヘキサデカン酸４－ベンジルオキシフェニルエチル、ヘプタデカン酸４－ベンジルオキシフェニルエチル、オクタデカン酸４－ベンジルオキシフェニルエチル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (1).

[In the formula, R ₁ represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either X ₁ or X ₂ is-(CH ₂ ) _n OCOR ₂ or (CH ₂ ) _n COOR. ₂ , the other indicates a hydrogen atom, n indicates an integer of 0 to 2, R ₂ indicates an alkyl group or an alkenyl group having 4 or more carbon atoms, and Y ₁ and Y ₂ independently indicate a hydrogen atom and carbon. Indicates any of an alkyl group, a methoxy group, or a halogen atom of the number 1 to 4, and r and p independently indicate an integer of 1 to 3].
Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and further, R ₁ is a hydrogen atom and m is The case of 0 is more preferable.
Of the compounds represented by the formula (1), the compound represented by the following formula (2) is more preferable.

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms).
Examples of the compound represented by the formula (2) include 4-benzyloxyphenylethyl octanate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, and dodecane. 4-benzyloxyphenylethyl acid, 4-benzyloxyphenylethyl tridecanoate, 4-benzyloxyphenylethyl tetradecanoate, 4-benzyloxyphenylethyl pentadecanoate, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxy heptadecanoate Examples thereof include phenylethyl and 4-benzyloxyphenylethyl octadecanoate.

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ独立して、１～３の整数を示し、Ｘ及びＹはそれぞれ独立して、水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示す）
式（３）で示される化合物としては、例えば、オクタン酸１，１－ジフェニルメチル、ノナン酸１，１－ジフェニルメチル、デカン酸１，１－ジフェニルメチル、ウンデカン酸１，１－ジフェニルメチル、ドデカン酸１，１－ジフェニルメチル、トリデカン酸１，１－ジフェニルメチル、テトラデカン酸１，１－ジフェニルメチル、ペンタデカン酸１，１－ジフェニルメチル、ヘキサデカン酸１，１－ジフェニルメチル、ヘプタデカン酸１，１－ジフェニルメチル、オクタデカン酸１，１－ジフェニルメチル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (3).

(In the formula, R represents an alkyl group or an alkenyl group having 8 or more carbon atoms, m and n independently represent integers of 1 to 3, and X and Y independently represent hydrogen atoms and carbon atoms. Indicates any of an alkyl group of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom)
Examples of the compound represented by the formula (3) include octanate 1,1-diphenylmethyl, nonanoic acid 1,1-diphenylmethyl, decanoic acid 1,1-diphenylmethyl, undecanoic acid 1,1-diphenylmethyl, and dodecane. Acid 1,1-diphenylmethyl, tridecanoic acid 1,1-diphenylmethyl, tetradecanoic acid 1,1-diphenylmethyl, pentadecanoic acid 1,1-diphenylmethyl, hexadecanoic acid 1,1-diphenylmethyl, heptadecanoic acid 1,1- Examples thereof include diphenylmethyl and 1,1-diphenylmethyl octadecanoic acid.

（式中、Ｘは水素原子、炭素数１～４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す）
式（４）で示される化合物としては、例えば、マロン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、こはく酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、こはく酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、グルタル酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、グルタル酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、アジピン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、ピメリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、スベリン酸と２－〔４－(３－メチルベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(４－クロロベンジルオキシ）フェニル〕エタノールとのジエステル、スベリン酸と２－〔４－(２，４－ジクロロベンジルオキシ）フェニル〕エタノールとのジエステル、アゼライン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、セバシン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１０－デカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－（４－ベンジルオキシフェニル）エタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－〔４－(２－メチルベンジルオキシ）フェニル〕エタノールとのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (4).

(In the formula, X indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m indicates an integer of 1 to 3, and n indicates an integer of 1 to 20).
Examples of the compound represented by the formula (4) include a diester of malonic acid and 2- [4- (4-chlorobenzyloxy) phenyl] ethanol, and succinic acid and 2- (4-benzyloxyphenyl) ethanol. Diester, diester of astringent acid and 2- [4- (3-methylbenzyloxy) phenyl] ethanol, diester of glutaric acid and 2- (4-benzyloxyphenyl) ethanol, diester of glutaric acid and 2- [4-( 4-Chlorobenzyloxy) phenyl] Diester with ethanol, diester with adipic acid and 2- (4-benzyloxyphenyl) ethanol, diester with pimelic acid and 2- (4-benzyloxyphenyl) ethanol, with suberic acid Diester with 2- (4-benzyloxyphenyl) ethanol, diester with suberic acid and 2- [4- (3-methylbenzyloxy) phenyl] ethanol, diester with suberic acid and 2- [4- (4-chlorobenzyloxy) oxy ) Diester with phenyl] ethanol, diester with suberic acid and 2- [4- (2,4-dichlorobenzyloxy) phenyl] ethanol, diester with azelaic acid and 2- (4-benzyloxyphenyl) ethanol, sebacin Diester of acid and 2- (4-benzyloxyphenyl) ethanol, diester of 1,10-decandicarboxylic acid and 2- (4-benzyloxyphenyl) ethanol, 1,18-octadecanedicarboxylic acid and 2- (4) Examples thereof include a diester with -benzyloxyphenyl) ethanol, a diester with 1,18-octadecanedicarboxylic acid and 2- [4- (2-methylbenzyloxy) phenyl] ethanol, and the like.

（式中、Ｒは炭素数１～２１のアルキル基又はアルケニル基を示し、ｎは１～３の整数を示す）
式（５）で示される化合物としては、例えば、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとウンデカン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンと酪酸とのジエステル、１，４－ビス（ヒドロキシメトキシ）ベンゼンとイソ吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと酢酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとプロピオン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンと吉草酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプロン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリル酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとカプリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとラウリン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとミリスチン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (5).

(In the formula, R represents an alkyl group or an alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound represented by the formula (5) include a diester of 1,3-bis (2-hydroxyethoxy) benzene and capric acid, and a diester of 1,3-bis (2-hydroxyethoxy) benzene and undecanoic acid. , Diester of 1,3-bis (2-hydroxyethoxy) benzene and lauric acid, Diester of 1,3-bis (2-hydroxyethoxy) benzene and myristic acid, 1,4-bis (hydroxymethoxy) benzene Diester with fatty acid, diester with 1,4-bis (hydroxymethoxy) benzene and isovaleric acid, diester with 1,4-bis (2-hydroxyethoxy) benzene and acetic acid, 1,4-bis (2-hydroxy) Diester of ethoxy) benzene and propionic acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and valerate, diester of 1,4-bis (2-hydroxyethoxy) benzene and caproic acid, 1, Diester of 4-bis (2-hydroxyethoxy) benzene and capric acid, diester of 1,4-bis (2-hydroxyethoxy) benzene and capric acid, 1,4-bis (2-hydroxyethoxy) benzene and laurin Examples thereof include a diester with an acid, a diester with 1,4-bis (2-hydroxyethoxy) benzene and myristic acid, and the like.

（式中、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１～３の整数を示し、ｎは１～２０の整数を示す）
式（６）で示される化合物としては、例えば、こはく酸と２－フェノキシエタノールとのジエステル、スベリン酸と２－フェノキシエタノールとのジエステル、セバシン酸と２－フェノキシエタノールとのジエステル、１，１０－デカンジカルボン酸と２－フェノキシエタノールとのジエステル、１，１８－オクタデカンジカルボン酸と２－フェノキシエタノールとのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (6).

(In the formula, X indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m indicates an integer of 1 to 3, and n indicates 1 to 20. Indicates an integer of)
Examples of the compound represented by the formula (6) include a diester of succinic acid and 2-phenoxyethanol, a diester of suberic acid and 2-phenoxyethanol, a diester of sebacic acid and 2-phenoxyethanol, and 1,10-decandycarboxylic acid. And 2-phenoxyethanol diester, 1,18-octadecanedicarboxylic acid and 2-phenoxyethanol diester and the like can be exemplified.

（式中、Ｒは炭素数４～２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４～２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す）
式（７）で示される化合物としては、例えば、４－フェニル安息香酸デシル、４－フェニル安息香酸ラウリル、４－フェニル安息香酸ミリスチル、４－フェニル安息香酸シクロヘキシルエチル、４－ビフェニル酢酸オクチル、４－ビフェニル酢酸ノニル、４－ビフェニル酢酸デシル、４－ビフェニル酢酸ラウリル、４－ビフェニル酢酸ミリスチル、４－ビフェニル酢酸トリデシル、４－ビフェニル酢酸ペンタデシル、４－ビフェニル酢酸セチル、４－ビフェニル酢酸シクロペンチル、４－ビフェニル酢酸シクロヘキシルメチル、４－ビフェニル酢酸ヘキシル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (7).

(In the formula, R indicates any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms, and X is a hydrogen atom and an alkyl having 1 to 4 carbon atoms. Indicates a group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n indicates 0 or 1).
Examples of the compound represented by the formula (7) include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, 4-. Nonyl biphenylacetate, decyl 4-biphenylacetate, lauryl 4-biphenylacetate, myristyl 4-biphenylacetate, tridecyl 4-biphenylacetate, pentadecyl 4-biphenylacetate, cetyl 4-biphenylacetate, cyclopentyl 4-biphenylacetate, 4-biphenylacetate Examples thereof include cyclohexylmethyl and hexyl 4-biphenylacetate.

（式中、Ｒは炭素数３～１８のアルキル基又は炭素数３～１８の脂肪族アシル基を示し、Ｘは水素原子、炭素数１～３のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子又はメチル基を示し、Ｚは水素原子、炭素数１～４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す）
式（８）で示される化合物としては、例えば、４－ブトキシ安息香酸フェノキシエチル、４－ペンチルオキシ安息香酸フェノキシエチル、４－テトラデシルオキシ安息香酸フェノキシエチル、４－ヒドロキシ安息香酸フェノキシエチルとドデカン酸とのエステル、バニリン酸フェノキシエチルのドデシルエーテル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (8).

(In the formula, R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms, and X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. , Y indicates a hydrogen atom or a methyl group, Z indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom).
Examples of the compound represented by the formula (8) include phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, phenoxyethyl 4-tetradecyloxybenzoate, phenoxyethyl 4-hydroxybenzoate and dodecanoic acid. Examples thereof include an ester with and a dodecyl ether of phenoxyethyl vanillate.

（式中、Ｒは炭素数４～２２のアルキル基、炭素数４～２２のアルケニル基、シクロアルキルアルキル基、シクロアルキル基のいずれかを示し、Ｘは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、アルキル基、アルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す）
式（９）で示される化合物としては、例えば、４－ヒドロキシ安息香酸オクチルの安息香酸エステル、４－ヒドロキシ安息香酸デシルの安息香酸エステル、４－ヒドロキシ安息香酸ヘプチルの４－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸ドデシルの２－メトキシ安息香酸エステル、４－ヒドロキシ安息香酸シクロヘキシルメチルの安息香酸エステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (9).

(In the formula, R indicates any of an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, and a cycloalkyl group, and X indicates a hydrogen atom, an alkyl group, an alkoxy group, and a halogen. Indicates any of the atoms, Y indicates any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, and n indicates 0 or 1).
Examples of the compound represented by the formula (9) include an benzoic acid ester of octyl 4-hydroxybenzoate, a benzoic acid ester of decyl 4-hydroxybenzoate, and a 4-methoxybenzoic acid ester of heptyl 4-hydroxybenzoate, 4 Examples thereof include 2-methoxybenzoic acid ester of dodecyl hydroxybenzoate and benzoic acid ester of cyclohexylmethyl 4-hydroxybenzoate.

（式中、Ｒは炭素数３～１８のアルキル基、炭素数６～１１のシクロアルキルアルキル基、炭素数５～７のシクロアルキル基、炭素数３～１８のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１～４のアルキル基、炭素数１～３のアルコキシ基、ハロゲン原子のいずれかを示し、Ｙは水素原子、炭素数１～４のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示す）
式（１０）で示される化合物としては、例えば、４－ヒドロキシ安息香酸ノニルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸デシルのフェノキシエチルエーテル、４－ヒドロキシ安息香酸ウンデシルのフェノキシエチルエーテル、バニリン酸ドデシルのフェノキシエチルエーテル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (10).

(In the formula, R indicates any of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms. X indicates any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom, and Y indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, and an ethoxy group. , Indicates one of the halogen atoms)
Examples of the compound represented by the formula (10) include phenoxyethyl ether of nonyl 4-hydroxybenzoate, phenoxyethyl ether of decyl 4-hydroxybenzoate, phenoxyethyl ether of undecyl 4-hydroxybenzoate, and dodecyl vanillate. Examples thereof include phenoxyethyl ether and the like.

（式中、Ｒは炭素数３～８のシクロアルキル基又は炭素数４～９のシクロアルキルアルキル基を示し、ｎは１～３の整数を示す）
式（１１）で示される化合物としては、例えば、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンカルボン酸とのジエステル、１，４－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル、１，３－ビス（２－ヒドロキシエトキシ）ベンゼンとシクロヘキサンプロピオン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (11).

(In the formula, R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3).
Examples of the compound represented by the formula (11) include a diester of 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanecarboxylic acid, and 1,4-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid. Diester, 1,3-bis (2-hydroxyethoxy) benzene and cyclohexanepropionic acid diester and the like can be exemplified.

（式中、Ｒは炭素数３～１７のアルキル基、炭素数３～８のシクロアルキル基、炭素数５～８のシクロアルキルアルキル基のいずれかを示し、Ｘは水素原子、炭素数１～５のアルキル基、メトキシ基、エトキシ基、ハロゲン原子のいずれかを示し、ｎは１～３の整数を示す）
式（１２）で示される化合物としては、例えば、４－フェニルフェノールエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールジエチレングリコールエーテルとラウリン酸とのジエステル、４－フェニルフェノールトリエチレングリコールエーテルとシクロヘキサンカルボン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとオクタン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとノナン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとデカン酸とのジエステル、４－フェニルフェノールエチレングリコールエーテルとミリスチン酸とのジエステル等を例示できる。 Further, the component (c) may be a compound represented by the following formula (12).

(In the formula, R indicates any of an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkylalkyl group having 5 to 8 carbon atoms, and X is a hydrogen atom and 1 to 1 carbon atoms. Indicates any of 5 alkyl group, methoxy group, ethoxy group, and halogen atom, and n indicates an integer of 1 to 3).
Examples of the compound represented by the formula (12) include a diester of 4-phenylphenol ethylene glycol ether and cyclohexanecarboxylic acid, a diester of 4-phenylphenol diethylene glycol ether and lauric acid, and 4-phenylphenol triethylene glycol ether. Diester with cyclohexanecarboxylic acid, diester with 4-phenylphenolethylene glycol ether and octanoic acid, diester with 4-phenylphenolethylene glycol ether and nonanoic acid, diester with 4-phenylphenolethylene glycol ether and decanoic acid, 4 -A diester of phenylphenol ethylene glycol ether and myristic acid can be exemplified.

In addition, a heat-coloring type (coloring by heating and decoloring by cooling) using a gallic acid ester (Japanese Patent Laid-Open No. 51-44706, JP-A-2003-253149) as an electron-accepting compound is used for reversible thermal discoloration. A reversible thermochromic microcapsule pigment containing a sex composition can also be applied (see FIG. 3).

The reversible thermochromic composition is a companion containing the above components (a), (b), and (c) as essential components, and the ratio of each component is the concentration, discoloration temperature, discoloration form and each. Although it depends on the type of the component, the component ratio at which the desired property is generally obtained is (a) component 1, (b) component 0.1 to 100, preferably 0.1 to 50, and more. The range is preferably 0.5 to 20, (c) component 5 to 200, preferably 5 to 100, and more preferably 10 to 100 (all of the above ratios are parts by mass).

The reversible thermochromic composition is encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment (hereinafter, may be referred to as "microcapsule pigment" or "pigment"), or is a thermoplastic resin or thermosetting. It can be used by dispersing it in a sex resin to form reversible thermochromic resin particles, but the reversible thermochromic composition should be encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment. Is preferable. By encapsulating it in microcapsules, it is possible to form a chemically and physically stable pigment, and further, under various conditions of use, the reversible thermochromic composition is kept in the same composition and is the same. This is because it is possible to exert the action and effect of.

Microencapsulation is a known isocyanate-based interfacial polymerization method, melamine-formalin-based in-Situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method. , Air suspension coating method, spray drying method, etc., which are appropriately selected according to the intended use. Further, the surface of the microcapsules can be further provided with a secondary resin film depending on the purpose to impart durability, or the surface characteristics can be modified for practical use.
It should be noted that, at the time of microencapsulation, by blending a non-thermochromic colorant such as a general dye or pigment, it is possible to bring about a reciprocal color change from colored (1) to colored (2).
The reversible thermochromic microcapsule pigment preferably has a mass ratio of inclusions: wall film of 7: 1 to 1: 1, and the mass ratio of inclusions and wall film is within the above range to develop color. It is possible to prevent a decrease in color density and sharpness at the time. More preferably, the mass ratio of inclusions: wall membrane is 6: 1 to 1: 1.

The reversible thermochromic layer is a liquid composition such as printing ink or paint prepared by dispersing a reversible thermochromic microcapsule pigment in a vehicle containing a binder resin, and screen printing, offset printing, gravure printing, or coater. , And a printing method such as transfer printing, or a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, and dip coating, the first or second transparent adhesive layer. It is a layer provided on top.
Reversible thermal discoloration layers include solid patterns, circles, ellipses, squares, rectangles, various characters, symbols, figures, patterns, as well as images of people, animals, plants, fruits, groceries, vehicles, buildings, celestial bodies, etc. There may be.

The vehicle that disperses the reversible heat-discoloring microcapsule pigment is composed of a solvent, a binder resin, and various additives to be blended as necessary, and affects the heat-discoloring function and sensitivity of the reversible heat-discoloring microcapsule pigment. If it does not reach, it is not particularly limited.
The reversible thermal discoloration layer is a layer formed of a binder resin by volatilizing a volatile component such as a solvent in the above liquid composition.
Further, by blending a non-thermochromic colorant such as a general dye or a pigment in the vehicle together with the reversible thermochromic microcapsule pigment, the reversible thermochromic layer is changed from colored (1) to colored (2). It can bring about a strange color change.

Examples of the solvent include water and various organic solvents.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3-methyl- Examples thereof include 3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Examples of the binder resin include ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylix styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-chlorinated polyethylene-. Styline copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin , Vinyl chloride-vinylidene chloride copolymer, chlorinated polyethylene, chlorinated polypropylene, polyamide resin, polycarbonate, polybutadiene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, high impact polystyrene, styrene-maleic acid copolymer resin, acrylic-styrene Copolymer resin, polypropylene, polymethylstyrene, acrylic acid ester resin, polymethylmethacrylate, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, rosin-modified alkido resin, phenol resin-modified alkido resin, styrene-modified alkido resin, epoxy resin-modified alkido Resin, acrylic modified alkyd resin, aminoalkido resin, butyral resin, urethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride -Acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicon resin, phenol resin, petroleum hydrocarbon resin, ketone resin, toluene resin, xylene resin, melamine resin, Urea resin, benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid salt, polymethacrylate, acrylic acid ester type emulsion, methacrylic acid ester type emulsion, Vinyl acetate-acrylic acid ester copolymer resin emulsion, ethylene-vinyl acetate copolymer resin emulsion, styrene-acrylic acid ester copolymer resin emulsion, vinyl chloride emulsion, vinylidene chloride emulsion, polyvinyl acetate emulsion, poly Olefin emulsion, rosin ester emulsion, epoxy resin emulsion, polyurethane emulsion, synthetic rubber latex, low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polystyrene, kumaron plastic, polybutene, phenoxy plastic, liquid polybutadiene, liquid rubber, petroleum Synthetic resins such as hydrocarbon resins and cyclopentadiene petroleum resins,
Examples thereof include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubbers, celacs, agar, casein, glue, gelatin, and polyterpene.

The twisted yarn of the present invention and products such as fabrics, headdresses, toys and the like using the twisted yarn can be easily discolored by a water adhering tool, a heat discoloring tool, a cold heat discoloring tool, etc., which will be described later, but a liquid such as hot water or cold water can be easily discolored. When the color is changed by using, the binder resin is preferably a water-insoluble resin. By using a water-insoluble resin as the binder resin, the binder resin does not dissolve when the twisted yarn and the product using the twisted yarn are discolored by the above-mentioned water adhering tool, heat discoloring tool, and cold heat discoloring tool, so that the reversible heat discoloring layer is deformed. It is difficult for the reversible thermal discoloration layer to be damaged or damaged, and the microcapsule pigment contained in the reversible thermal discoloration layer is suppressed from flowing, so that there are places where the reversible thermal discoloration layer does not discolor, or discoloration of the reversible thermal discoloration layer occurs. It is possible to suppress non-uniformity.

Additives include cross-linking agents, curing agents, desiccants, plasticizers, viscosity regulators, dispersants, UV absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, defoaming agents. , Matters, penetrants, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, fungicides, preservatives, rust preventives and the like.

In the present invention, the average particle size of the reversible thermochromic microcapsule pigment is in the range of 0.1 to 50 μm (preferably 0.5 to 30 μm, more preferably 1 to 20 μm), and the solid content of the binder resin is 100. It is preferable that the reversible thermochromic microcapsule pigment is blended in the range of 50 to 200 parts by mass (preferably 90 to 160 parts by mass) with respect to parts by mass. Most preferably, the average particle size of the reversible thermochromic microcapsule pigment is in the range of 1 to 20 μm, and the reversible thermochromic microcapsule pigment is 90 to 160 mass by mass with respect to 100 parts by mass of the solid content of the binder resin. It is to be blended in the range of parts.
When the average particle size of the microcapsule pigment is within the above range, the color change due to the temperature change of the reversible thermochromic layer can be easily visually recognized due to the high concentration of color development, and further, the vehicle of the microcapsule pigment can be used. It becomes easy to improve the dispersion stability of. Further, by blending the reversible thermochromic microcapsule pigment with respect to the solid content of the binder resin within the above range, the first and second transparent adhesive layers provided adjacent to the reversible thermochromic layer are provided. Adhesiveness is less likely to be impaired.
Therefore, when both the average particle size of the microcapsule pigment and the blending ratio of the microcapsule pigment to the solid content of the binder resin are within the above ranges, the visibility such as the color change due to the temperature change of the reversible thermal discoloration layer becomes better. It is good, and the adhesiveness between each layer is improved. The occurrence of delamination between the layer and the transparent resin layer is suppressed, and the reversible thermal discoloration layer is protected from external factors such as scratches by the plain yarn made of the transparent resin film and the transparent resin layer. A reversible thermochromic twisted yarn having gloss can be easily obtained.
The "solid content of the binder resin" includes not only the solid content of the binder resin itself but also the solid content of additives such as a cross-linking agent and a curing agent that act when the binder resin forms a reversible thermal discoloration layer. It's a waste.

For the measurement of the average particle size, the particle area is determined by the image analysis type particle size distribution measurement software [manufactured by Mountech Co., Ltd., product name: MacView], and the projected area circle equivalent diameter (Heywood diameter) is determined from the area of the particle area. ) Is calculated, and it is a value measured as the average particle diameter of particles corresponding to equal volume spheres based on the value.
If the particle size of all or most of the particles exceeds 0.2 μm, a particle size distribution measuring device [manufactured by Beckman Coulter Co., Ltd., product name: Multisizer 4e] is used by the Coulter method. It is also possible to measure as the average particle size of a considerable number of particles.
Furthermore, a laser diffraction / scattering type particle size distribution measuring device calibrated based on the numerical values measured using the above software or a measuring device by the Coulter method [manufactured by Horiba Seisakusho Co., Ltd., product name: LA- 300], the particle size based on the volume and the average particle size may be measured.

The reversible thermochromic layer has an average thickness (T) in the range of 1 to 50 μm (preferably 3 to 40 μm, more preferably 5 to 30 μm), and has an average particle size (D) of the reversible thermochromic microcapsule pigment. ) And the average thickness (T) of the reversible thermal discoloration layer preferably satisfy the following formula (I).
0.002 ≤ D / T <1 (I)
Most preferably, the average thickness (T) of the reversible thermochromic layer is in the range of 5 to 30 μm, and the average particle size (D) of the reversible thermochromic microcapsule pigment and the average thickness of the reversible thermochromic layer ( T) satisfies the above formula (I).
When the value (D / T) obtained by dividing the average particle size of the reversible thermochromic microcapsule pigment by the average thickness of the reversible thermochromic layer is within the above range, the reversible thermochromic twisted yarn has a flexible texture. At the same time, the visibility such as color change due to the temperature change of the reversible thermal discoloration layer is good, and the adhesiveness of the first and second transparent adhesive layers provided adjacent to the reversible thermal discoloration layer is not easily impaired. Become.
Therefore, the average thickness (T) of the reversible thermochromic layer is within the above range, and the average particle size (D) of the reversible thermochromic microcapsule pigment and the average thickness (T) of the reversible thermochromic layer are. By satisfying the above formula (I), it has a flexible texture, good visibility such as color change due to temperature change of the reversible thermal discoloration layer, and further improves the adhesiveness between each layer, so that reversible thermal discoloration is achieved. The occurrence of delamination between the reversible heat-discoloring layer and the transparent resin film, and the delamination between the reversible heat-discoloring layer and the transparent resin layer due to the stress when processing the sex flat yarn into twisted yarn is suppressed, and the material is transparent. It is possible to easily obtain a reversible heat-discoloring twisted yarn having a gloss, which is excellent in the effect that the reversible heat-discoloring layer is protected from external factors such as scratches by the plain yarn made of the sex resin film and the transparent resin layer.
The average thickness (T) of the reversible thermal discoloration layer is the maximum thickness (T) of the reversible thermal discoloration layer by visual measurement or image analysis software based on a cross-sectional photograph of the reversible thermal discoloration layer with an optical microscope or an electron microscope. It is a value obtained by calculating T ₁ ) and the minimum thickness (T ₂ ) and using the following formula (II).
T = (T ₁ + T ₂ ) / 2 (II)

The transparent resin layer is provided on the second transparent adhesive layer, and can impart luster to the reversible thermochromic twisted yarn, and further, stress when processing the reversible thermochromic twisted yarn into twisted yarn and the like. , Prevents damage to the second transparent adhesive layer and the reversible heat discoloration layer due to external factors such as scratches, and makes the reversible heat discoloration twisted yarn having excellent durability and glossiness of the reversible heat discoloration layer. be able to.

The transparent resin layer is a liquid composition such as a printing ink or a paint containing a transparent resin, which is printed by a printing method such as screen printing, offset printing, gravure printing, coater, and transfer printing, or brush coating or spraying. It is a layer provided on the second transparent adhesive layer by a coating method such as coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, and dip coating.

The above liquid composition is composed of a solvent, a transparent resin, and various additives to be blended as necessary, and the transparent resin is dissolved or dispersed in the solvent, or used in the form of an emulsion or the like. The liquid composition does not affect the adhesiveness of the adjacent second transparent adhesive layer, and is not particularly limited as long as the design, characters, and color change of the reversible thermal discoloration layer due to temperature change can be visually recognized.
The transparent resin layer is a layer formed of the transparent resin by volatilizing volatile components such as a solvent in the above liquid composition.

Examples of the solvent include water and various organic solvents.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3-methyl- Examples thereof include 3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Examples of the transparent resin include acrylic resin, epoxy resin, epoxy-acrylate copolymer resin, urethane resin, ethylene resin, urethane-acrylic copolymer resin, melamine resin, phenol resin, urea resin, urea resin, and urea-melamine. Thermal curable resins such as polymerized resins, diallyl phthalate resins, polyester resins, alkyd resins, rosin maleated, vinyl butyral resins, cellulose resins, polyamide resins, two-component curable resins, ultraviolet curable resins, electron beam curable resins, etc. However, a crosslinkable resin is suitable because it has excellent scratch resistance and can easily prevent damage to the second transparent adhesive layer and the reversible thermal discoloration layer.
The crosslinkable resin is a resin that has a reactive functional group in the resin molecule and can form a three-dimensional structure by a reaction with a crosslinking agent or a crosslinking reaction such as self-polymerization or self-condensation. A sex resin layer can be formed. Examples of the crosslinkable resin include an ultraviolet curable resin composed of a polymerization initiator and an acrylic acid ester resin, an isocyanate-based curing agent and a polyol resin, an amine-based curing agent and an epoxy resin, and a carbodiimide-based curing agent and a polyester-based resin. Can be exemplified by a heat-curable resin or the like.
The transparent resin may be used alone or in admixture of two or more.

Additives include cross-linking agents, hardeners, desiccants, plasticizers, viscosity regulators, dispersants, fungicides, smoothing agents, gelling agents, defoaming agents, matting agents, penetrants, pH regulators, foaming agents. Examples thereof include agents, coupling agents, moisturizing agents, lubricants, antifungal agents, preservatives, and rust preventives.

Further, it is preferable to use a transparent resin film as the transparent resin layer. The transparent resin film has the effect of preventing damage to the second transparent adhesive layer and the reversible heat discoloration layer due to stress when processing the reversible heat discoloration flat yarn into twisted yarn and external factors such as scratching. It is possible to obtain a reversible thermochromic twisted yarn which is more excellent and has further improved durability of the reversible thermochromic layer.
The transparent resin film is not particularly limited as long as the design, characters, and color change due to temperature change of the reversible thermal discoloration layer can be visually recognized, and is the same as the transparent resin film used for the plain yarn described above. Things can be used.

Further, the transparent resin layer may have a brilliant property in addition to the glossiness, and the transparent resin layer may contain a transparent metal glossy pigment or a transparent pearl glossy layer described later, or may be transparent. By using a transparent brilliant resin film as the resin layer, a brilliant transparent resin layer can be obtained.
Examples of the transparent brilliant resin film include a transparent metal glossy resin film having a single layer or a laminated structure using a transparent metal glossy pigment, and a single layer or a laminated structure using a transparent pearl glossy pigment, which will be described later. Examples thereof include a pearl glossy resin film, a transparent pearl glossy resin film composed of a transparent multilayer film, a transparent hologram resin film, a transparent iris resin film, and a transparent light-reflecting resin film.
Since the transparent resin layer has brilliance, in addition to the above-mentioned effect of preventing damage to the second transparent adhesive layer and the reversible thermal discoloration layer due to external factors such as stress and scratching, reversible thermal discoloration Since it is possible to impart brilliance to the sex twisted yarn and the brilliance can be visually recognized along with the color change due to the temperature change of the reversible heat discoloration layer, the reversible heat discoloration twisted yarn satisfies the variety of color change. be able to.
As the transparent resin layer having brilliance, it is preferable to use a transparent brilliant resin film, and the second is due to stress when processing a reversible thermochromic flat yarn into twisted yarn and external factors such as scratching. It is excellent in the effect of preventing damage to the transparent adhesive layer and the reversible thermal discoloration layer, and can improve the durability of the reversible thermal discoloration layer.

The thickness of the transparent resin layer is in the range of 3 to 50 μm, preferably 6 to 25 μm, more preferably 6 to 20 μm, which satisfies the practical use. When the thickness of the transparent resin layer exceeds 50 μm, it is difficult to process the reversible thermochromic flat yarn into twisted yarn, and the soft texture of the yarn is easily impaired. On the other hand, if the thickness is less than 3 μm, the thickness is too thin, so that the effect of protecting the second transparent adhesive layer and the reversible thermal discoloration layer from external factors such as stress and abrasion tends to be poor.

The transparency of the transparent resin layer is a property of transmitting light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079), and is a visible light region of the transparent resin layer. The light transmission rate (visible light transmission rate) in the above is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance is less than 5%, it becomes difficult to visually recognize the color change due to the design, characters, and temperature change of the reversible thermal discoloration layer.
For the above-mentioned visible light transmittance, a transparent resin layer is provided on a transparent base material that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210]. Was measured in the wavelength region from 380 nm to 780 nm, and was set as an intermediate value between the maximum value and the minimum value.

The first transparent adhesive layer constituting the twisted yarn of the present invention is provided between the plain yarn made of a transparent resin film and the reversible thermal discoloration layer, and provides the adhesiveness of the reversible thermal discoloration layer to the plain yarn made of a transparent resin film. It is something to improve. Further, the second transparent adhesive layer is provided between the reversible thermal discoloration layer and the transparent resin layer to improve the adhesiveness of the reversible thermal discoloration layer to the transparent resin layer. Therefore, due to the stress generated when the reversible heat-discoloring plain yarn is processed into a twisted yarn, delamination occurs between the reversible heat-discoloring layer and the transparent resin film, and between the reversible heat-discoloring layer and the transparent resin layer. The reversible thermal discoloration layer is protected from external factors such as stress and scratches by the plain thread made of the transparent resin film and the transparent resin layer, and the reversible thermal discoloration layer has excellent durability and is reversible. A heat-discolorable twisted yarn can be obtained.
Further, a light stabilizer can be contained in the first and second transparent adhesive layers, and the first transparent adhesive layer is provided on one surface of the reversible thermal discoloration layer to provide the second transparency. By providing the adhesive layer on the other surface of the reversible thermal discoloration layer, the light resistance of the reversible thermal discoloration layer can be improved. Therefore, by providing the first and second transparent adhesive layers containing a light stabilizer, the plain thread made of the reversible heat discoloration layer and the transparent resin film, and the reversible heat discoloration layer and the transparent resin layer can be provided. The reversible heat-discoloring layer and the transparent resin layer, and the reversible heat-discoloring layer and the transparent resin layer, due to the stress generated when the reversible heat-discoloring plain yarn is processed into twisted yarn. In addition to suppressing the occurrence of delamination between layers and protecting the reversible thermal discoloration layer from external factors such as stress and scratches by the plain yarn made of a transparent resin film and the transparent resin layer, reversible thermal discoloration due to light is achieved. It is possible to prevent deterioration and damage of the layer. That is, a reversible thermochromic twisted yarn having a gloss, which has an effect of protecting the reversible thermochromic layer from external factors such as stress, abrasion, and light, and has excellent durability and light resistance of the reversible thermochromic layer. Since it can be obtained, it is preferable to contain a light stabilizer in the first and second transparent adhesive layers.

The light stabilizer contained in the first and second transparent adhesive layers can prevent photodegradation of the reversible thermochromic composition composed of the component (a), the component (b), and the component (c). can.
Among the light stabilizers, the ultraviolet absorber effectively blocks ultraviolet rays contained in sunlight and the like, and prevents photodegradation caused by the excited state due to the optical reaction of the component (a). Further, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction by light.
The light stabilizer is preferably blended in a proportion of 0.3 to 24% by mass, more preferably 0.3 to 16% by mass, based on 1% by mass of the component (a).
As the light stabilizer, one kind or a mixture of two or more kinds can be used as appropriate.

As an ultraviolet absorption collector, for example,
2,4-Hydroxybenzophenone,
2-Hydroxy-4-methoxybenzophenone,
2,2'-Dihydroxy-4,4'-dimethoxybenzophenone,
2,2', 4,4'-tetrahydroxybenzophenone,
2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-Hydroxy-4-octyloxybenzophenone,
Bis- (5-benzoyl-4-hydroxy-2-methoxyphenyl) -methane,
2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzophenone,
4-Dodecyloxy-2-hydroxybenzophenone,
2-Hydroxy-4-octadecyloxybenzophenone,
2,2'-Dihydroxy-4-methoxybenzophenone,
4-Benzyloxy-2-hydroxybenzophenone,
2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) Benzophenone-based UV absorbers such as benzophenone,
Phenyl salicylate,
4-tert-Butylphenyl salicylate,
4-octylphenyl salicylate,
2,4-Di-tert-butylphenyl-4-hydroxybenzoate,
1-Hydroxybenzoate,
3-tert-Butyl-1-hydroxybenzoate,
1-Hydroxy-3-tert-octylbenzoate,
Salicylic acid-based UV absorbers such as resorcinol monobenzoate,
2-Ethyl-2-cyano-3,3'-diphenylacrylate,
2-Ethylhexyl-2-cyano-3,3'-diphenylacrylate,
Cyanoacrylate-based UV absorbers such as 2-ethylhexyl-2-cyano-3-phenylthinate,
2- (2-Hydroxy-5-tert-butylphenyl) benzotriazole,
2- (2-Hydroxy-5-methylphenyl) benzotriazole,
2- [3,5-bis (a, a-dimethylbenzyl) -2-hydroxyphenyl] -2H-benzotriazole,
2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole,
2- (3-tert-Butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole,
2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole,
β- [3- (2H-benzotriazole-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid-polyethylene glycol 300 ester,
2- (3-Dodecyl-2-hydroxy-5-methylphenyl) benzotriazole,
Bis {β- [3- (2H-benzotriazole-2-yl) -5-tert-butyl-4-hydroxyphenyl]} propionic acid-polyethylene glycol 300 ester,
2- (3-tert-Butyl-2-hydroxyphenyl-5-propyloctylate) -5-chlorobenzotriazole,
2- [2-Hydroxyphenyl-3,5-di- (1,1'-dimethylbenzyl) phenyl] -2H-benzotriazole,
2- (2-Hydroxy-5-tert-octylphenyl) -2H-benzotriazole,
2- (3-tert-Butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl) benzotriazole,
2- (2-Hydroxy-5-tetraoctylphenyl) benzotriazole,
2- (2-Hydroxy-4-octoxyphenyl) benzotriazole,
2- [2'-Hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotriazole,
Benzotriazole-based UV absorbers such as 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole,
Ethandiamid-N- (2-ethoxyphenyl) -N'-(4-isododecylphenyl),
2,2,4,4-Tetramethyl-20- (β-lauryl-oxycarbonyl) -ethyl-7-oxa-3,20-diazodispyro (5,1,11,2) heneic acid-21-one, etc. Oxalic acid anilide UV absorber,
2,4-Diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-pentoxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine,
2,4-Diphenyl-6- [2-Hydroxy-4- (2-butoxyethoxy) phenyl] -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine,
2,4-Di-p-Trail-6- (2-Hydroxy-4-propoxyphenyl) -1,3,5-triazine,
2,4-di-p-Trail-6- (2-Hydroxy-4-butoxyphenyl) -1,3,5-triazine,
2,4-Di-p-Trail-6- (2-Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine,
2,4-di-p-Trail-6- (2-Hydroxy-4-pentoxyphenyl) -1,3,5-triazine,
2,4-Di-p-Trail-6- (2-Hydroxy-4-octyloxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine,
2,4-di-p-Trail-6- [2-Hydroxy-4- (2-hexyloxyethoxy) phenyl] -1,3,5-triazine,
2- {4-[(2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- {4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [4-{[2-Hydroxy-3- (2'-ethyl) hexyl] oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine,
2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- [2,4-bis (butyloxyphenyl)]-1,3,5-triazine,
2- {2-Hydroxy-4-[(1-octyloxycarbonylethoxy) phenyl]} -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine-based UV absorbers It can be exemplified.

As an antioxidant (anti-aging agent), for example,
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, dimethyl-1- (2-hydroxyethyl) succinate,
Poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) ) Imine] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) Imine]} Hexamethylene,
2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentapetyl-4-piperidyl),
N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentapetyl-4-piperidyl) amino] -6-chloro- 1,3,5-triazine condensate,
Bis (1,2,2,6,6-pentamethyl-4-piperidylsebacic acid),
4-Benzoyloxy-2,2,6,6-tetramethylpiperidine,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Hinderedamine-based antioxidants such as 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione,
2,6-di-tert-butyl-4-methylphenol,
2-tert-Butyl-4-methoxyphenol,
2,6-di-tert-butyl-4-ethylphenol,
Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
2,2-Methylenebis (4-methyl-6-tert-butylphenol),
4,4-thiobis (2-methyl-6-tert-butylphenol),
2,2-thiobis (4-methyl-6-tert-butylphenol),
4,4-Butylidenebis (3-methyl-6-tert-butylphenol),
3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl},
2,4,8,10-Tetraoxaspiro [5,5] undecane,
1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,
Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane,
2,2-Ethylene bis (4,6-di-tert-butylphenol),
Bis [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) butyric acid] -glycol ester,
1,3,5-Tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- [1H, 3H, 5H] -trione,
Tocopherol,
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate,
Pentaerythritol tetrakis (3-laurylthiopropionate),
Triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate],
1,6-Hexadiol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
2,2-thioethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
N, N'-hexamethylenebis (3,5-tert-butyl-4-hydroxy-hydrocinnamamide),
Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate,
2,2,4-trimethyl-1,2-hydroquinone,
Stylate phenol,
2,5-di-tert-butyl hydroquinone,
Phenolic antioxidants such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate,
Girauril-3,3'-thiodipropionate,
Dimyristil-3,3'-thiodipropionate,
Distearyl-3,3'-thiodipropionate,
Sulfur-based antioxidants such as stearylthiopropylamide,
Tris (2,4-di-tert-butylphenyl) phosphite,
Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
3,5-Di-tert-butyl-4-hydroxy-benzylphosphanate-diethyl ester,
Triphenylphosphite,
Diphenylisodecylphosphite,
Phenylisodecylphosphite,
4,4'-Butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite,
Octadecylphosphite,
Tris (nonylphenyl) phosphite,
Diisodecylpentaerythritol diphosfite,
9,10-Dihydroxy-9-oxa-10-phosphaphenanthrene,
10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide,
10-decyloxy-9,10-dihydroxy-9-oxa-10-phosphaphenanthrene,
Cyclic Neopentane Tetraylbis (2,4-di-tert-butylphenyl) phosphite,
Cyclic Neopentane Tetraylbis (2,6-di-tert-butyl-4-methylphenyl) phosphite,
2,2-Methylenebis (4,6-di-tert-butylphenyl) octylphosphite,
2,4-Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine,
Examples thereof include phosphoric acid-based antioxidants such as octylated diphenylamine.

Examples of the single-term oxygen extinguishing agent include carotene, pigments, amines, phenols, nickel complexes, sulfides and the like, and examples thereof include 1,4-diazabicyclo [2,2,2] octane (DABCO). β-Carotene, 1,3-Cyclohexadiene, 2-diethylaminomethylfuran, 2-phenylaminomethylfuran, 9-diethylaminomethylanthracene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickel dimethyldithiocarbamate , Nickel 3,5-di-tert-butyl-4-hydroxybenzyl-O-ethylphosphonate, nickel 3,5-di-tert-butyl-4-hydroxybenzyl-O-butylphosphonate, nickel [2,2] ′ -Thiobis (4-tert-octylphenolate)] n-butylamine, nickel [2,2 ′-thiobis (4-tert-octylphenolate)] 2-ethylhexylamine, nickelbis [2,2′-thiobis (2,2′-thiobis) 4-tert-octylphenolate)], nickel bis [2,2'-sulfonbis (4-octylphenolate)], nickel bis (2-hydroxy-5-methoxyphenyl-Nn-butylaldoimin), nickel Examples thereof include bis (dithiobenzyl) and nickel bis (dithiobiacetyl).

Examples of the superoxide anion quencher include a complex of superoxide dismutase, cobalt, and nickel.

Examples of the ozone quenching agent include 4,4'-thiobis (6-tert-butyl-m-cresol), 2,4,6-tri-tert-butylphenol, 1,4-diazabicyclo [2,2,2]. Octane, N-Phenyl-β-naphthylamine, α-tocopherol, 4,4'-methylene-bis (2,6-di-tert-butylphenol), P, P'-diaminodiphenylmethane, 2,2'-methylene-bis (6-tert-butyl-p-cresol), N, N'-diphenyl-P-phenylenediamine, N, N'-diphenylethylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine and the like can be exemplified.

The first and second transparent adhesive layers are printing of liquid compositions such as printing inks and paints containing a transparent adhesive resin, such as screen printing, offset printing, gravure printing, coaters, and transfer printing. A plain yarn made of a transparent resin film, a reversible thermochromic layer, or a transparent resin by a method or a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, and dip coating. It is a layer provided on each layer.

The above liquid composition is composed of a solvent, a transparent adhesive resin, and various additives to be blended as necessary, but it is preferable to further contain a light stabilizer. The transparent adhesive resin is dissolved or dispersed in a solvent, or is used in the form of an emulsion or the like. The liquid composition is particularly limited as long as the design, characters, and color change of the adjacent reversible thermochromic layer are visually recognized and the heat discoloration function and sensitivity of the reversible thermochromic microcapsule pigment are not affected. It's not something.
The first and second transparent adhesive layers are layers formed by the transparent adhesive resin by volatilizing volatile components such as a solvent in the above liquid composition.

Examples of the solvent include water and various organic solvents.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3-methyl- Examples thereof include 3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Examples of the transparent adhesive resin include isocyanate resin, urea resin, acrylic resin, vinyl acetate resin, urethane resin, epoxy resin, diallyl phthalate resin, olefin resin, vinyl chloride resin, polyester resin, and vinyl chloride-vinyl acetate. Examples thereof include a polymer resin and an acrylic-urethane copolymer resin.
Although different types of transparent adhesive resins can be used for the first transparent adhesive layer and the second transparent adhesive layer, it is preferable to use the same transparent adhesive resin.
Among the above resins, flexible resins such as acrylic resin, vinyl acetate resin, urethane resin, epoxy resin, vinyl chloride resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, and acrylic-urethane copolymer resin are available. Preferably, the adhesive layer follows the bending of the flat yarn when the reversible heat-discoloring plain yarn is processed into a twisted yarn, and the reversible heat-discoloring layer and the transparent resin film, and the reversible heat-discoloring layer and the transparent resin layer Since the adhesiveness between the layers is easily maintained, the occurrence of delamination can be suppressed.
The transparent adhesive resin may be used alone or in admixture of two or more.

The twisted yarn of the present invention and products such as fabrics, headdresses, toys and the like using the twisted yarn can be easily discolored by a water adhering tool, a heating discoloring tool, a cold heat discoloring tool, etc., which will be described later, but a liquid such as hot water or cold water can be easily discolored. When the color is changed by using, the transparent adhesive resin is preferably a water-insoluble resin. By using a water-insoluble resin as the binder resin, the transparent adhesive resin does not dissolve when the twisted yarn and the product using the twisted yarn are discolored by the above-mentioned water adhering tool, heat discoloring tool, and cold heat discoloring tool. It is possible to prevent the second transparent adhesive layer from being deformed or chipped and the adhesiveness from being impaired.

Additives include cross-linking agents, hardeners, desiccants, plasticizers, viscosity regulators, dispersants, fungicides, smoothing agents, gelling agents, defoaming agents, matting agents, penetrants, pH regulators, foaming agents. Examples thereof include agents, coupling agents, moisturizing agents, lubricants, antifungal agents, preservatives, and rust preventives.

The thickness of the first and second transparent adhesive layers is in the range of 0.5 to 20 μm, preferably 1 to 10 μm, more preferably 2 to 5 μm, which satisfies the practical use. When the thickness of the first and second transparent adhesive layers exceeds 20 μm, it is difficult to process the reversible thermochromic flat yarn into twisted yarn, and the soft texture of the yarn is easily impaired. On the other hand, if the thickness is less than 0.5 μm, it becomes difficult to exhibit the effect of improving the adhesiveness between the plain thread made of the reversible thermal discoloration layer and the transparent resin film and the reversible thermal discoloration layer and the transparent resin layer. Further, when the light stabilizer is contained in the adhesive layer, the effect of improving the light resistance tends to be poor.

The transparency of the first and second transparent adhesive layers is the property of transmitting light having a wavelength in the visible light region (the wavelength region of 380 to 780 nm defined by JIS B 7079). The light transmission rate (visible light transmission rate) in the visible light region of the second transparent adhesive layer is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance is less than 5%, it becomes difficult to visually recognize the design, characters, color change due to temperature change, etc. of the adjacent reversible thermochromic layer.
For the above visible light transmittance, a first or second transparent adhesive layer is provided on a transparent substrate that transmits light with a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product. Name: U-3210] was used to measure in the wavelength region of 380 nm to 780 nm, and the value was set to an intermediate value between the maximum value and the minimum value.

As shown in FIG. 4, the reversible thermochromic twisted yarn (1) of the present invention is obtained by twisting the above reversible thermochromic flat yarn (2) with a right (S) twist or a left (Z) twist only in one direction. It is a twisted yarn in the form of a single twist.
Conventionally, the microcapsule pigment contained in the reversible thermal discoloration layer has a larger particle size than a general-purpose non-thermal discoloration colorant, and the thickness of the reversible thermal discoloration layer tends to increase. There was a problem that it tended to have a hard touch. However, by processing the reversible heat-discoloring plain yarn into a twisted yarn, the yarn can be bulged and has a soft tactile sensation. Therefore, it is preferable to use the reversible heat-discoloring flat yarn as a twisted yarn.
Further, in the reversible thermochromic flat yarn, since the reversible thermochromic layer is visible only from two directions of one wide surface or the other wide surface, the design, characters, and temperature of the reversible thermochromic layer may be recognized depending on the viewing direction. It was sometimes difficult to visually recognize the color change due to the change. However, when the reversible heat-discoloring plain yarn is processed into a twisted yarn, the reversible heat-discoloring layer becomes visible from the entire surface of the twisted yarn, and the color change due to the temperature change of the reversible heat-discoloring layer becomes easily visible. The heat-discolorable flat yarn is preferably twisted.
In the one-sided twisted yarn shown in FIG. 4, the number of times of twisting the reversible thermochromic flat yarn is preferably 100 to 1000 times per 1 m of the plain yarn. When the number of twists is within the above range, the color change due to the pattern, characters, and temperature change of the reversible thermal discoloration layer becomes more visible from the entire surface of the plyed yarn, and the twisted yarn has a soft touch.

Further, the reversible thermochromic twisted yarn of the present invention may be composed of the above-mentioned reversible thermochromic flat yarn and the yarn.
As shown in FIG. 5, the reversible thermochromic flat yarn (2) and the yarn (8) are aligned and twisted only in one side, which is obtained by right (S) twisting or left (Z) twisting. Examples thereof include a reversible thermochromic twisted yarn (1) in a single-twisted form. Further, a twisted yarn in the form of a twisted twist, in which two yarns are twisted into a core yarn using a reversible thermochromic flat yarn as a core yarn, can be mentioned.
Further, as shown in FIG. 6, the reversible thermochromic twisted yarn (1) may be formed by using the yarn (8) as the core yarn and providing the reversible thermochromic flat yarn (2) around the core yarn. Examples thereof include round twisting, bellows twisting, and hagoromo twisting.
The reversible thermochromic twisted yarn composed of the reversible thermochromic flat yarn and the yarn has a different texture and decorativeness from the single-twisted reversible thermochromic twisted yarn obtained by processing only the reversible thermochromic yarn. It is preferably used because it can improve the durability as a twisted yarn.
In the single-twisted twisted yarn shown in FIG. 5, the number of times of twisting the reversible heat-discoloring plain yarn and the yarn is preferably 100 to 1000 times per 1 m of the plain yarn. When the number of twists is within the above range, the color change due to the pattern, characters, and temperature change of the reversible thermal discoloration layer becomes easier to see from the entire surface of the plyed yarn, and it has a soft touch and is more durable. It becomes easier to make a better twisted yarn.

The yarn is not particularly limited and general-purpose yarns can be used. For example, chemical fibers such as polyester, rayon, nylon and cupra, natural fibers such as cotton yarn, silk yarn, hemp yarn and yarn, blended yarns and twisted yarns and lame Examples thereof include yarn and rayon. Further, plain yarn made of paper, synthetic paper, knitted cloth, woven cloth, cloth such as non-woven fabric, synthetic leather, leather, plastic, elastomer, resin film, rubber and the like can also be used.

When the reversible heat-discoloring plain yarn has curl property, it may be difficult to handle when applied to products, etc., but the curl property is suppressed by processing the reversible heat-discoloring plain yarn having curl property into twisted yarn. Since it can be easily handled when applied to products and the like, it is preferable to use twisted yarn as the reversible thermochromic flat yarn.

As shown in FIG. 7, the reversible thermochromic flat thread (2) applied to the present invention has a first transparent adhesive layer (4) on one surface of the reversible thermochromic layer (5) and a first on the other surface. A second transparent adhesive layer (6) is provided, and a transparent resin film (3) is provided on the outer surface of the first transparent adhesive layer (the opposite surface of the first transparent adhesive layer to which the reversible thermal discoloration layer is provided). ) Is provided, and the transparent resin layer (7) is provided on the outer surface of the second transparent adhesive layer (the opposite surface of the second transparent adhesive layer on which the reversible thermal discoloration layer is provided). However, as shown in FIG. 8, the transparent resin layer (7) is the same transparent resin film (3) as the transparent resin film constituting the plain yarn, and is the first transparent adhesive. The reversible thermochromic flat yarn in which the transparent adhesive resin contained in the layer and the transparent adhesive resin contained in the second transparent adhesive layer are the same resin is most preferable.
In the reversible thermochromic flat yarn having the above configuration, the reversible thermochromic layer is used as an intermediate layer, and the layers provided on one surface and the other surface of the reversible thermochromic layer are the same. Therefore, the shrinkage of the transparent adhesive resin that occurs in the process of forming the first and second transparent adhesive layers is likely to occur uniformly on one surface and the other surface of the reversible thermal discoloration layer, resulting in anisotropy. Since it is unlikely to occur, curling property is suppressed in the reversible thermochromic flat yarn, and the reversible thermochromic flat yarn can be easily handled when processing into a twisted yarn. Further, during the production of the reversible heat-discoloring twisted yarn, the strain due to the thermal expansion and stress of the transparent resin film tends to occur uniformly on each of one surface and the other surface of the reversible heat-discoloring layer, so that the curl property is suppressed. The reversible thermochromic twisted yarn can be obtained, and the reversible thermochromic twisted yarn is excellent in handleability when applied to a product or the like.

In the single-twisted twisted yarn of the present invention, the reversible heat-discoloring layer is visually recognized from the circumferential direction by twisting the reversible heat-discoloring flat yarn, so that the design, characters, and color change of the reversible heat-discoloring layer are twisted. It is visible uniformly and clearly on the entire surface of.
In a single-twisted twisted yarn consisting of a reversible heat-discoloring plain yarn and a yarn, a plain yarn is preferable as the yarn, and the wide surface of the reversible heat-discoloring plain yarn and the wide surface of the yarn (flat yarn) tend to adhere to each other. , The durability of the twisted yarn can be further improved. Further, as the yarn, a plain yarn having substantially the same width as the reversible thermochromic flat yarn is more preferable, and by setting the width to substantially the same width, the wide surface of the reversible thermochromic flat yarn and the wide surface of the yarn (flat yarn) can be used. It is preferable because the durability of the twisted yarn can be further improved because the adhesiveness can be improved and the reversible thermochromic flat yarn can be stably twisted when the twisted yarn is processed. Here, "substantially the same" means that the width (W ₁ ) of the reversible thermochromic flat yarn and the width (W ₂ ) of the yarn (flat yarn) twisted together with the reversible thermochromic flat yarn are exactly the same width. Further, in the present invention, the width (W ₁ ) of the reversible thermochromic flat yarn and the width (W ₂ ) of the yarn (flat yarn) twisted together with the reversible thermochromic flat yarn are 0.8 ≦ W ₂ / W ₁ . It also includes satisfying ≤1.2. If the ratio of the width of the thread (plain thread) to the width of the reversible heat-discoloring plain thread (W ₂ / W ₁ ) is within the above range, the width of the reversible heat-discoloring plain thread and the width of the thread (flat thread) are the same. Can be considered to be. It is preferably 0.85 ≦ W ₂ / W ₁ ≦ 1.15, and more preferably 0.9 ≦ W ₂ / W ₁ ≦ 1.1.
As the plain yarn, a plain yarn made of a transparent resin film is preferable, and while improving the durability and heat resistance of the twisted yarn, it is possible to improve the visibility such as color change due to the temperature change of the reversible thermal discoloration layer.

In the twisted yarn of the present invention in which the yarn is used as the core yarn and the reversible thermochromic flat yarn is provided around the core yarn, the design, characters, and temperature change of the reversible thermochromic layer can be seen only in the place where the reversible thermochromic layer can be visually recognized. The color change due to is visually recognized. Therefore, in the plying in which the reversible thermal discoloration layer is wound around the core yarn without gaps (for example, the twisted yarn in the round twisted form), the color change due to the temperature change of the reversible thermal discoloration layer is visually recognized on the entire surface of the twisted yarn. In the plying in which the reversible heat-discoloring flat yarn is loosely wound around the core yarn (for example, the twisted yarn in the bellows twisting form), the color of the core yarn is visually recognized alternately with the color change due to the temperature change of the reversible heat-discoloring layer. Will be done.
As the yarn, a yarn having a circular cross-sectional shape is preferable, and when a reversible heat-discoloring plain yarn is provided around the yarn, the outer surface of the yarn and the wide surface of the reversible heat-discoloring plain yarn tend to be in close contact with each other, so that the durability of the twisted yarn is high. The sex can be further improved. Examples of the circular shape include a perfect circular shape and an elliptical shape, but a perfect circular shape is preferable.
Further, as the yarn, a transparent yarn is preferable, and since the reversible thermal discoloration layer of the reversible thermal discoloration plain yarn is visually recognized through the core yarn, the color change due to the temperature change of the reversible thermal discoloration layer is uniform over the entire surface of the twisted yarn. Moreover, it is easy to see clearly and is suitable.

The above-mentioned thread is further preferably a brilliant thread having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, light interference property, and light reflection property. By using the brilliant yarn, it is possible to impart brilliance to the reversible thermochromic twisted yarn, and the color change due to the temperature change and the brilliance can be visually recognized at the same time, so that the variety of color change is satisfied. It can be a reversible thermochromic twisted yarn. When a bright yarn is used, the number of twists of the reversible thermochromic flat yarn is preferably 100 to 1000 times per 1 m of the plain yarn. When the number of twists is within the above range, the color change due to the pattern, characters, and temperature change of the reversible thermal discoloration layer and the brilliance can be more uniformly and clearly visually recognized from the entire surface of the plyed yarn. It has a soft touch and is easy to make into a twisted yarn with excellent durability.

When the reversible thermochromic plain yarn and the bright yarn do not have transparency and the bright yarn is not visible from the reversible thermochromic flat yarn side, or the reversible thermochromic yarn is not visible from the bright yarn side. Even so, in the single-twisted twisted yarn of the present invention, the reversible thermochromic flat yarn and the brilliant yarn are twisted together, and the brilliant yarn shows color change due to the temperature change of the reversible thermochromic layer. The brilliance is visually recognized at the same time, and the color change accompanied by the brilliance can be visually recognized uniformly on the entire surface of the twisted yarn.
In the one-sided twisted yarn composed of a reversible heat-discoloring plain yarn and a yarn, a brilliant yarn is preferable as the brilliant yarn, and the wide surface of the reversible heat-discoloring plain yarn and the wide width of the brilliant yarn (brilliant plain yarn). Since the surfaces are easily brought into close contact with each other, the durability of the plyed yarn can be further improved, and the color change accompanied by the brilliance developed by the reversible thermal discoloration layer and the brilliant plain yarn can be visually recognized more clearly. Further, as the brilliant yarn, a brilliant plain yarn having substantially the same width as the reversible thermochromic flat yarn is more preferable, and by setting the width substantially the same, the wide surface of the reversible thermochromic flat yarn and the brilliant yarn (brilliant yarn) are used. It enhances the adhesion on the wide surface of the (sexual plain yarn), makes it possible to visually recognize the color change accompanied by brilliance more clearly, and further stabilizes the form as a twisted yarn when processing a reversible heat-discoloring plain yarn into a twisted yarn. It is suitable because it is easy to do. Here, "substantially the same" means that the width of the reversible thermochromic flat yarn (W ₁ ) and the width of the bright yarn (brilliant plain yarn) twisted together with the reversible thermochromic flat yarn (W ₂ ) are exactly the same width. In addition, in the present invention, the width (W ₁ ) of the reversible thermochromic flat yarn and the width (W ₂ ) of the brilliant yarn twisted together with the reversible thermochromic flat yarn are 0. It also includes satisfying .8 ≤ W ₂ / W ₁ ≤ 1.2. If the ratio of the width of the brilliant yarn (brilliant plain yarn) to the width of the reversible thermochromic flat yarn (W ₂ / W ₁ ) is within the above range, the width of the reversible thermochromic flat yarn and the brilliant yarn (brilliant) The widths of the sex flat yarns) can be considered to be the same. It is preferably 0.85 ≦ W ₂ / W ₁ ≦ 1.15, and more preferably 0.9 ≦ W ₂ / W ₁ ≦ 1.1.

In the twisted yarn of the present invention in which the brilliant yarn is used as the core yarn and the reversible thermochromic flat yarn is provided around the core yarn, the design, characters, and temperature of the reversible thermochromic layer are only visible where the reversible thermochromic layer is visible. The color change due to the change is visually recognized. Therefore, in a twisted yarn in which a reversible thermochromic flat yarn is loosely wound around a core yarn (for example, a bellows twisted type of twisted yarn), the color change due to the temperature change of the reversible thermochromic layer and the brilliance of the core yarn alternate. It is visually recognized.
As the yarn, a brilliant yarn having a circular cross-sectional shape is preferable, and when a reversible heat-discoloring plain yarn is provided around the yarn, the outer surface of the yarn and the wide surface of the reversible heat-discoloring plain yarn tend to be in close contact with each other. Durability can be improved. Examples of the circular shape include a perfect circular shape and an elliptical shape, but a perfect circular shape is preferable.

Examples of the brilliant yarn having metallic luster include a yarn having a metallic luster layer provided on a general-purpose yarn, a plain yarn made of a brilliant laminate having a metallic luster layer provided on a support, and a brilliant yarn having a metallic luster. Examples thereof include flat yarn made of a resin film.
As the metal gloss layer, a layer formed by providing a metal plate or a metal foil, a layer formed by vapor deposition using a metal such as aluminum, chromium, zinc, gold, silver, or nickel, and a metal gloss pigment in the vehicle. Using a liquid composition such as printing ink or paint prepared by dispersing in, screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer printing, or other printing methods, brush coating, spray coating, etc. Examples thereof include a layer formed by a coating method such as electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc. By forming the above metal gloss layer on a thread or a support, the metal gloss is formed. It is possible to obtain a thread having a laminated structure provided with a layer or a brilliant laminated body.
The metallic luster layer formed by the liquid composition is a layer formed by a compound other than the volatile components such as a solvent in the liquid composition volatilized.

For a bright resin film having metallic luster, a metallic luster pigment is melt-blended into a transparent thermoplastic resin or a transparent thermosetting resin to prepare a resin composition for molding such as pellets, powders, or pastes. It is a single-layer resin film that can be obtained by molding into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding.
As the brilliant yarn having a metallic luster, a laminated yarn having a metallic luster layer, a plain yarn made of a brilliant laminate having a metallic luster layer, and a plain yarn made of a single-layer brilliant resin film can be used.
By cutting the above-mentioned brilliant laminate or brilliant resin film to an appropriate width with a slitter, a plain yarn having a metallic luster can be obtained.

As the metallic gloss pigment, a metal powder obtained by powdering fine aluminum, copper, brass, gold, silver, nickel, etc., a metal powder obtained by depositing a metal on a phenol resin, a vinyl chloride resin, etc. by a conventional method is made into a powder. A transparent metal bright pigment in which the surface of a core material such as powder or a piece of glass is coated with a metal oxide such as titanium oxide, zirconium oxide, chromium oxide, vanadium oxide, or iron oxide, or a transparent metal bright pigment having color flop properties. And so on.

As a transparent metal glossy pigment in which the surface of a core material such as a glass piece is coated with a metal oxide, for example, a flake-shaped glass piece is used as a core material and the surface thereof is coated with a metal oxide such as titanium oxide. Examples thereof include a metal gloss pigment and a two-layer coating type transparent metal gloss pigment in which a glass piece of borosilicate is used as a core material, the surface thereof is coated with silicon dioxide, and the surface thereof is coated with titanium oxide.
A transparent metallic luster pigment having a flake-shaped glass piece as a core material and whose surface is coated with a metal oxide such as titanium oxide has high metallic luster and transparency by using glass as the core material. Further, it exhibits a gold color, a silver color, a copper color, a metallic color, or the like depending on the coverage of the metal oxide.
The two-layer coating type transparent metallic glossy pigment, which uses a piece of borosilicate glass as a core material, whose surface is coated with silicon dioxide, and further coated with titanium oxide, is more resistant to borosilicate glass used as a core material than general glass. Since it has excellent impact resistance, heat resistance, chemical resistance, etc., it can maintain a state in which it is hard to crack even if the thickness of the core material is reduced. Therefore, the mass per reflection area can be reduced, and the light transmittance of the pigment can be improved. Further, it exhibits a gold color, a silver color, a copper color, a metallic color, or the like depending on the coverage of the metal oxide.

Examples of the transparent metallic luster pigment having a color flop property include a cholesteric liquid crystal type metallic luster pigment, a transparent metallic luster pigment in which silicon oxide is coated with one or more kinds of metal oxides, and the like.
A cholesteric liquid crystal type metallic luster pigment will be described. The liquid crystal polymer used as a cholesteric liquid crystal type metallic luster pigment has a property that only a part of the incident light is reflected in a wide spectral region due to the interference effect of light, and the light is transmitted in all the other regions. The region of the reflection spectrum is determined by the pitch width of the spiral polymer and the index of refraction of the material, and the region of the reflection spectrum is divided into left and right spirally polarized light components, depending on the direction of rotation of the helix. One can be reflected and the other can be transmitted. As a result, the cholesteric liquid crystal type metallic luster pigment has the property of transmitting and reflecting over the entire spectral region, that is, the excellent metallic luster and the color flop property in which the hue changes depending on the viewpoint. In addition, the cholesteric liquid crystal type metallic luster pigment has transparency as well as metallic luster.
A transparent metallic luster pigment in which silicon oxide is coated with one or more kinds of metal oxides has light transmission and is a color that can express various colors depending on the viewing angle and the angle of light hit by the interference effect of light. It has flop properties and excellent metallic luster. Further, when silicon oxide is coated in multiple layers with two or more kinds of metal oxides, color flop properties and metallic luster can be more effectively imparted by using metal oxides having different light reflectances. Examples of the metal oxide include tin oxide, titanium oxide, iron oxide and the like.

The brilliant yarn having pearl luster includes a yarn having a pearl luster layer provided on a general-purpose yarn, a plain yarn made of a brilliant laminate having a pearl luster layer provided on a support, and a brilliant yarn having pearl luster. Examples thereof include flat yarn made of a resin film.
The pearl luster layer is a printing method such as screen printing, offset printing, process printing, gravure printing, coater, tampo printing, transfer, etc., of a liquid composition such as printing ink or paint prepared by dispersing the pearl luster pigment in a vehicle. , Or a layer formed by a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, sink coating, roller coating, dip coating, etc., and the above-mentioned pearl luster layer is applied on a thread or a support. By forming the yarn, it is possible to obtain a thread having a laminated structure provided with a pearl gloss layer and a brilliant laminated body having a pearl gloss layer provided on a support.
The pearl gloss layer formed by the liquid composition is a layer formed by a compound other than the volatile components such as a solvent in the liquid composition volatilized.

For a brilliant resin film having pearl luster, a pearl luster pigment is melt-blended into a transparent thermoplastic resin or a transparent thermosetting resin to prepare a resin composition for molding such as pellets, powders, or pastes. It is a single-layer brilliant resin film that can be obtained by molding into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding.
As the brilliant yarn having pearl luster, a yarn having a laminated structure having pearl luster, a plain yarn made of a brilliant laminated body having pearl luster, and a plain yarn made of a single layer of brilliant resin film can be used.
By cutting the above-mentioned brilliant laminate or brilliant resin film to an appropriate width with a slitter, a plain yarn having pearl luster can be obtained.

As pearl luster pigments, in addition to fish scale foil composed of guanine, silk mica, basic lead carbonate, acid lead arsenide, bismuth oxychloride, etc., the surface of core materials such as natural mica, synthetic mica, and flaky aluminum oxide. Examples thereof include transparent pearl bright pigments coated with metal oxides such as titanium oxide, zirconium oxide, chromium oxide, vanadium oxide and iron oxide.

As the transparent pearl luster pigment having natural mica as a core material, for example, the surface of natural mica particles is coated with titanium oxide, the upper layer of titanium oxide is further coated with iron oxide or a non-discoloring colorant, and natural. Examples include those in which the surface of the mica particles is coated with iron oxide. The surface of the natural mica particles is coated with 41 to 44% by mass of titanium oxide, and the surface of the natural mica particles is a golden pearl bright pigment having a particle size of 5 to 50 μm. A golden pearl luster pigment with a particle size of 5 to 60 μm, which is coated with 30 to 38% by mass of iron oxide and the upper layer is coated with 0.5 to 10% by mass of a non-color-changing colored pigment, and the surface of natural mica particles is 16 to 16 to A silver pearl luster pigment with a particle size of 5 to 100 μm coated with 39% by mass of iron oxide, a metallic pearl luster pigment with a surface of natural mica particles coated with 45 to 58% by mass of titanium oxide, and a surface of natural mica particles of 45. Examples thereof include metallic pearl bright pigments coated with ~ 58% by mass of iron oxide and the upper layer thereof with 0.5 to 10% by mass of a non-discoloring colorant. Further, it exhibits a gold color, a silver color, a copper color, a metallic color, or the like depending on the coverage of the metal oxide.
The transparent pearl luster pigment whose core material is synthetic mica and whose surface is coated with a metal oxide has a higher content of metal ions such as impurities and iron as a coloring factor than a system using natural mica as a core material. It is less, has excellent brilliance, has a glittering appearance, and has high transparency. Further, depending on the coverage of the metal oxide, it exhibits a gold color, a silver color, a copper color, a metallic color, or the like. As the synthetic mica, for example, KMg3 (AlSi3O10) F2 can be exemplified.
The shape of the synthetic mica is not specified, but for example, a flat shape or a scale shape can be exemplified.
A transparent pearl luster pigment whose core material is flaky aluminum oxide and whose surface is coated with a metal oxide such as titanium oxide is excellent because the surface of the core material aluminum oxide has a high reflectance and a sharp particle size distribution. It has high brilliance and high transparency. Further, depending on the coverage of the metal oxide, it exhibits a gold color, a silver color, a copper color, a metallic color, or the like.

The support provided with the metallic gloss layer or the pearl gloss layer is not particularly limited, but is limited to paper, synthetic paper, knitted fabric, woven fabric, non-woven fabric and other fabrics, synthetic leather, leather, plastic, elastomer and rubber. Etc., and the form is preferably a flat shape, a sheet shape, or a film shape.
Further, a film made of a general-purpose resin is suitable as the support, and examples of the resin include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polyacrylate, polystyrene, polycarbonate, and ethylene-vinyl acetate. Polymerized resin, ethylene-acrylic acid ester copolymer resin, ionomer resin, ethylene-propylene copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, fluororesin, polyacetate, polyester resin, Examples thereof include polyamide resin, rubber hydrochloride, polyimide resin, urethane resin, and polypeptide resin.
Among the above resins, a resin film using a resin such as polyethylene, polypropylene, polyethylene terephthalate, or vinyl chloride resin is preferable because it is highly flexible and excellent in safety.

As the transparent thermoplastic resin or the transparent thermosetting resin to which the metal gloss pigment or the pearl gloss pigment is melt-blended, a colorless transparent resin or a colored transparent resin can be used.
Examples of the transparent thermoplastic resin or the transparent thermosetting resin include polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, and vinyl acetate resin. , Vinyl chloride resin, vinylidene chloride resin, acrylic acid ester resin, methacrylic acid ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin , Ethylene-vinyl alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, cycloolefin copolymer and other transparent thermoplastic resins.
Examples of transparent thermosetting resins such as epoxy resin, epoxy acrylate, phenol resin, unsaturated polyester resin, urea resin, aryl resin, and silicone resin can be exemplified.
The metallic luster pigment or the pearl luster pigment is blended in the resin in an proportion of 0.1 to 40% by mass, preferably 0.3 to 30% by mass, and more preferably 0.5 to 25% by mass. If the blending ratio of the metallic luster pigment or the pearl luster pigment exceeds 40% by mass, the dispersion stability and processing suitability are likely to be lacking when dispersed in the resin. On the other hand, if the blending ratio is less than 0.1% by mass, it becomes difficult to exhibit the desired brilliance.

The vehicle in which the metallic luster pigment or the pearl luster pigment is dispersed is composed of a solvent, a binder resin, and various additives to be blended as needed.
Examples of the solvent include water and various organic solvents.
Examples of the organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, and ethylene. Glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, n-octane, isooctane, n-heptane, methylcyclohexane, ethylcyclohexane, toluene, xylene, 3-methoxybutanol, 3-methyl- Examples thereof include 3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, and hexylene glycol.

Examples of the binder resin include ionomer resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylix styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-chlorinated polyethylene-. Styline copolymer resin, ethylene-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride graft copolymer resin, vinyl acetate resin, vinyl chloride resin, chloride Vinylidene resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, chlorinated polyethylene, chlorinated polypropylene, polyamide resin, polycarbonate, polybutadiene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, high impact polystyrene, styrene-maleic acid Copolymer resin, acrylic-styrene copolymer resin, polypropylene, polymethylstyrene, acrylic acid ester resin, polymethylmethacrylate, epoxy acrylate resin, alkylphenol resin, rosin-modified phenol resin, rosin-modified alkyd resin, phenol resin-modified alkyd resin, styrene Modified alkyd resin, epoxy resin modified alkido resin, acrylic modified alkyd resin, aminoalkido resin, butyral resin, urethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester Resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyisobutylene, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether, fluororesin, silicon resin, phenol resin, petroleum hydrocarbon resin, ketone resin, toluene Resin, xylene resin, melamine resin, urea resin, benzoguanamine resin, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer resin, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylate, polymethacrylate, acrylic acid ester type Emulsion, methacrylic acid ester-based emulsion, vinyl acetate-acrylic acid ester copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, styrene-acrylic acid ester copolymer emulsion, vinyl chloride-based emulsion, vinylidene chloride-based emulsion, polyacetic acid Vinyl-based emulsions, polyolefin-based emulsions, rosin ester-based emulsions, epoxy resin-based emulsions, polyurethane-based emulsions, synthetic rubber latex, low-molecular-weight polyethylene, low-molecular-weight polypropylene, low-molecular-weight polystyrene, kumaron plastic, polybutene, phenoxyplastic, liquid polybutadiene, Synthetic resins such as liquid rubber, petroleum hydrocarbon resin, cyclopentadiene petroleum resin, etc.
Examples thereof include natural or semi-synthetic resins such as cellulose derivatives, alginic acid derivatives, rosin derivatives, starches, polysaccharides, gums, natural rubbers, celacs, agar, casein, glue, gelatin, and polyterpene.
The metallic luster pigment or the pearl luster pigment is blended in the binder resin in an proportion of 0.1 to 40% by mass, preferably 0.2 to 30% by mass, and more preferably 0.5 to 20% by mass. If the blending ratio of the metallic luster pigment or the pearl luster pigment exceeds 40% by mass, the dispersion stability and processing suitability are likely to be lacking when dispersed in the binder resin. On the other hand, if the blending ratio is less than 0.1% by mass, it becomes difficult to exhibit the desired brilliance.

Additives include cross-linking agents, curing agents, desiccants, plasticizers, viscosity regulators, dispersants, UV absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, defoaming agents. , Matters, penetrants, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, fungicides, preservatives, rust preventives and the like.

Further, as the brilliant resin film having pearl luster, a transparent multilayer film exhibiting a light interference phenomenon in which 10 or more layers made of polymers having different refractive coefficients are provided in the intermediate layer, and the multilayer film is transparent to light. A resin film containing a sex dye can also be used. The transparent pearl glossy resin film is formed by laminating at least 10 layers of a film (thin film layer) made of an extremely thin translucent thermoplastic resin having a uniform thickness of about 30 to 500 nm, and adjacent to each other in contact with each other. The layers are translucent resins made of different materials, have different refractive indexs at least by a numerical value of 0.03, and contain a translucent dye in the layers. Therefore, the translucent dye enhances or changes at least one color tone of the reflected color and the transmitted color of the layer.
Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethylmethacrylate and polyacrylate, polyolefin resins such as polyethylene and polypropylene, polystyrenes and ethylene-vinyl acetate copolymer resins. It can be exemplified.
Examples of the translucent dye include azo dyes, anthraquinone dyes, pyridone dyes, pyrazolone derivative dyes and the like. The translucent dye is contained in one layer or two or more layers, and may be contained in all layers. The amount of the dye added is sufficient to enhance or change at least one of the transmitted colors of the thin film layer, at least one of the reflected light of the thin film layer, or both as compared with the non-added system. A large amount is added.
Specific examples of the transparent brilliant resin film having pearl luster include BASF's product name: AURORA FILM.
By cutting the above-mentioned brilliant resin film to an appropriate width with a slitter, a plain yarn having pearl luster can be obtained.

Examples of the holographically brilliant yarn include plain yarn made of a holographically brilliant resin film using a general-purpose hologram.
The hologram has a light reflecting layer provided on at least one surface of a fine uneven pattern, and is transparent formed from a metal compound or the like on a transparent hologram forming layer having an uneven pattern on a substrate such as a transparent resin film. Examples thereof include a relief type (embossed type) hologram provided with a sex reflective layer and a volume type hologram (Lipman hologram).
By cutting the above-mentioned glittering resin film to an appropriate width with a slitter, a plain yarn having a holographic property can be obtained.

Examples of the iris-like brilliant yarn include a plain yarn made of a iris-like brilliant resin film.
Examples of the iris-like brilliant resin film include transparent metal compounds (for example, titanium oxide, silicon oxide, zinc oxide, and cadmium sulfide) having a refractive index difference of 0.05 or more from the substrate on the surface of the substrate. , Magnesium fluoride, cerium fluoride, etc.), and a transparent resin layer with irregularities having a refractive index difference of 0.05 or more from the thin film is laminated in order, or a transparent plastic with a different refractive index. An example is a transparent iris resin film in which thin films are laminated in multiple layers.
Specifically, as the transparent iris resin film, ENGELHARD Co., Ltd., product name: IRIDESCENT FILM and the like can be exemplified.
By cutting the above-mentioned brilliant resin film to an appropriate width with a slitter, a plain yarn having an iris property can be obtained.

Examples of the brilliant yarn having light interference property include a plain yarn made of a brilliant laminated body having light interference property.
As a brilliant laminate having light interference, for example, a brilliant laminate in which a transparent film having a thickness thin enough to cause light interference is coated on the surface of a base material having a metallic mirror surface with a colored or colorless paint. I can exemplify the body.
By cutting the above-mentioned brilliant laminate with a slitter to an appropriate width, a plain yarn having light interference can be obtained.

The optical properties of light reflection include retroreflectiveness, and examples of the light-reflecting bright yarn include a plain yarn made of a light-reflecting bright laminate and a transparent bright resin having light-reflectivity. Examples thereof include a flat thread made of a film.
As the brilliant laminate having light reflectivity, for example, a brilliant laminate having retroreflective property in which a single layer of high-refractive index glass beads is provided on a light-reflecting layer such as an aluminum-deposited layer can be exemplified.
The brilliant resin film having light reflectivity has, for example, a structure in which a plurality of polyester thin films having light reflectivity are laminated while shifting the stretching axis, has a metallic luster like a mirror surface, and is visually recognized. An example is a transparent light-reflecting resin film which exhibits a metallic luster color change depending on an angle and further has transparency depending on a viewing angle.
Specific examples of the transparent light-reflecting resin film include Hologram Supply Co., Ltd., product name: Magical Film (Mirage Film), and the like.
By cutting the above-mentioned brilliant laminate or brilliant resin film to an appropriate width with a slitter, a plain yarn having light reflectivity can be obtained.

The thickness of the plain yarn made of the brilliant laminate or the brilliant resin film is in the range of 3 to 50 μm, preferably 5 to 40 μm, more preferably 10 to 30 μm, which satisfies the practical use. When the thickness of the brilliant laminate or the brilliant resin film exceeds 50 μm, it is difficult to process the reversible thermochromic flat yarn into twisted yarn, and the soft texture of the yarn is easily impaired. On the other hand, if the thickness is less than 3 μm, the thickness is too thin, so that the strength is poor, it is difficult to satisfy the durability as a thread, and it is difficult to exhibit the desired brilliance.

The above-mentioned brilliant yarn is preferably a transparent brilliant yarn having further transparency.
In a single-twisted plying composed of a reversible thermochromic flat yarn and a brilliant yarn, if the brilliant yarn is a transparent brilliant yarn, the reversible thermal discoloration layer of the reversible thermochromic flat yarn is visually recognized through the transparent brilliant yarn. Therefore, it is preferable because the color change accompanied by the brilliance developed by the reversible thermal discoloration layer and the transparent brilliant yarn can be easily and uniformly and clearly visually recognized on the entire surface of the plyed yarn.
Further, in a twisted yarn in which a brilliant yarn is used as a core yarn and a reversible thermochromic flat yarn is provided around the core yarn, if the brilliant yarn is a transparent brilliant yarn, the reversible thermochromic flat yarn is passed through the core yarn. Since the reversible thermal discoloration layer can be visually recognized, the color change accompanied by the brilliance developed by the reversible thermal discoloration layer and the transparent brilliant yarn can be easily visually recognized uniformly and clearly on the entire surface of the plyed yarn, which is preferable.

As the transparent brilliant thread, a thread having a metallic luster layer containing a transparent metallic luster pigment or a thread having a pearl luster layer containing a transparent pearl luster pigment is provided on a general-purpose thread having transparency. Examples thereof include flat yarn made of a transparent resin film.
As the brilliant resin film having transparency, the above-mentioned transparent metal bright pigment or transparent pearl bright pigment is melt-blended into a transparent thermoplastic resin or a transparent thermosetting resin to pellet, powder, or paste. Use a single-layer transparent brilliant resin film obtained by preparing a resin composition for molding such as, and molding it into a flat form such as a sheet or a film by various molding means such as extrusion molding, calendar molding, and inflation molding. be able to.
Further, using a liquid composition such as a printing ink or a paint prepared by dispersing a transparent metal gloss pigment or a transparent pearl gloss pigment in the vehicle described above, transparency is supported by the printing means or coating means described above. It is also possible to use a transparent bright resin film having a laminated structure in which a transparent bright layer (transparent metal gloss layer or transparent pearl gloss layer) is formed on the body.
In addition, a transparent brilliant resin film such as the above-mentioned transparent pearl glossy resin film, transparent hologram-like resin film, transparent iris resin film, and transparent light-reflecting resin film can also be used.
As the transparent brilliant resin film, a transparent brilliant resin film having a single layer or a laminated structure can be used.
In addition, a brilliant plain yarn obtained by cutting the above-mentioned transparent brilliant resin film with a slitter to an appropriate width can be used as the transparent brilliant yarn.

As the transparent thermoplastic resin or the transparent thermosetting resin, a colorless transparent resin or a colored transparent resin can be used, as long as the design, characters, and color change of the reversible thermosetting layer can be visually recognized. It is not particularly limited.
Examples of the transparent thermoplastic resin or the transparent thermosetting resin include polyethylene, polypropylene, polyisobutylene, polybutadiene, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycyclohexylene-dimethylene terephthalate, and vinyl acetate resin. , Vinyl chloride resin, vinylidene chloride resin, acrylic acid ester resin, methacrylic acid ester resin, polyvinyl butyral, polyarylate, polyetherimide, polycarbonate, polysulfone, ionomer resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin , Ethylene-vinyl alcohol copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid ester copolymer resin, acrylonitrile-styrene copolymer resin, thermoplastic resin such as cycloolefin copolymer,
Examples of thermosetting resins such as epoxy resin, epoxy acrylate, phenol resin, unsaturated polyester resin, urea resin, aryl resin, and silicone resin can be exemplified.
The transparent metallic luster pigment or the transparent pearl luster pigment is blended in a transparent thermoplastic resin or a transparent thermosetting resin in a proportion of 0.1 to 40% by mass, preferably 0.3 to 30% by mass. Will be done. If the blending ratio of the transparent metallic luster pigment or the transparent pearl luster pigment exceeds 40% by mass, the dispersion stability and processability tend to be poor when dispersed in the resin. On the other hand, if the blending ratio is less than 0.1% by mass, it becomes difficult to exhibit the desired brilliance.

As the transparency support, a colorless transparent one or a colored transparent one can be used, and is not particularly limited as long as the design, characters, and color change due to temperature change of the reversible thermal discoloration layer can be visually recognized.
As the transparent support, for example, general-purpose resins such as polyethylene, polypropylene, vinyl chloride resin, polyethylene terephthalate, polybutylene terephthalate, polymethylmethacrylate, polyacrylate, polystyrene, polycarbonate, cellulose acetate, polyvinyl alcohol, and polyamide resin are used. Examples thereof include a thermoplastic resin molded body having a planar shape such as a sheet-like shape and a film-like shape. A transparent plastic sheet using a resin such as polyethylene, polypropylene, polyethylene terephthalate, or vinyl chloride resin is preferable because it is highly flexible and excellent in safety.

The transparency of the brilliant yarn is the property of transmitting light having a wavelength in the visible light region (wavelength region of 380 to 780 nm defined by JIS B 7079), and the transparency of the brilliant yarn having transparency is visible. The light transmission rate (visible light transmission rate) in the light region is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more. When the visible light transmittance is less than 5%, it becomes difficult to visually recognize the color change due to the design, characters, and temperature change of the reversible thermal discoloration layer.
For the above-mentioned visible light transmittance, a transparent bright thread is provided on a transparent substrate that transmits light having a wavelength in the visible light region, and a spectrophotometer [manufactured by Hitachi, Ltd., product name: U-3210]. ] Was measured in the wavelength region from 380 nm to 780 nm, and the value was taken as an intermediate value between the maximum value and the minimum value.

As the twisted yarn of the present invention, a single-twisted twisted yarn composed of a reversible thermochromic flat yarn and a bright plain yarn made of a transparent pearl glossy resin film or a transparent iris resin film is most preferably used.
In the twisted yarn of the above form, the wide surface of the reversible thermochromic flat yarn and the wide surface of the bright flat yarn tend to adhere to each other, so that the durability of the twisted yarn can be improved, and the reversible thermochromic layer and the brilliant property can be improved. The color change accompanied by the brilliance developed by the plain yarn can be visually recognized more clearly.
Further, since the microcapsule pigment contained in the reversible thermal discoloration layer has a larger particle size than a general-purpose non-thermal discoloration colorant and the thickness of the reversible thermal discoloration layer tends to increase, the reversible thermal discoloration flat yarn is used. It tends to be hard to the touch. On the other hand, since the transparent pearl glossy resin film or the transparent iris resin film is formed by laminating thin films in multiple layers, the glittering plain yarn has a soft tactile sensation.
Therefore, the one-sided reversible thermochromic twisted yarn composed of the reversible thermochromic flat yarn and the brilliant plain yarn has excellent durability, and the color change accompanied by the brilliance developed by the reversible thermochromic layer and the brilliant plain yarn. Is most suitable because it can be visually recognized uniformly and clearly on the entire surface of the twisted yarn, and further, by twisting the brilliant plain yarn having a soft tactile sensation together with the reversible thermochromic twisted yarn, the reversible thermochromic twisted yarn can be given a soft tactile sensation. Used for.

Further, in the one-sided twisted yarn composed of the reversible heat-discoloring plain yarn and the brilliant yarn, the brilliant reversible heat-discoloring yarn having a transparent resin layer having a brilliant property is used as the reversible heat-discoloring yarn. You can also. Here, when the optical properties of the transparent resin layer and the optical properties of the brilliant yarn are the same, as compared with the case of using a reversible thermochromic flat yarn in which the transparent resin layer does not have brilliance. Color changes with strong brilliance are strongly visible. On the other hand, when the optical properties of the transparent resin layer and the optical properties of the brilliant yarn are different from each other, the brilliance in which the respective optical properties are mixed is visually recognized, and the transparent resin layer does not have the brilliant property. When a reversible thermochromic flat yarn is used, it is difficult to visually recognize it, and a color change accompanied by specific brilliance is visually recognized, which is preferable.
The above-mentioned brilliant yarn is preferably a transparent brilliant yarn. When the brilliant yarn has transparency, the brilliant reversible thermochromic flat yarn is visually recognized through the transparent brilliant yarn, and the color change with brilliance that is visually recognized on the entire surface of the plyed yarn is more clearly visible. Suitable.

The width (W') of the plain yarn applied to the present invention is 100 to 5000 μm, preferably 100 to 2000 μm, more preferably 150 to 1000 μm, and when it is within the above range, the temperature change of the reversible thermochromic flat yarn is changed. The color change due to the above and the brilliance of the brilliant plain yarn can be clearly seen, and the durability of the twisted yarn can be satisfied.
The thickness (T') of the plain yarn is 8 to 190 μm, preferably 10 to 100 μm, more preferably 10 to 50 μm, and when it is within the above range, the twisted yarn has a flexible texture and is used as a twisted yarn. The durability of the above can be satisfied, and the applicability to products and the like can be excellent.

The plain yarn applied to the present invention is, for example, reversible in which a first transparent adhesive layer, a reversible thermal discoloration layer, a second transparent adhesive layer, and a transparent resin layer are sequentially provided on one surface of a transparent resin film. The reversible thermochromic flat yarn shown in FIG. 7 can be obtained by cutting the thermochromic laminate to an appropriate width with a slitter.
In the reversible thermochromic laminate constituting the plain yarn applied to the present invention, for example, a first transparent adhesive layer is provided on one surface of a transparent resin film, and an outer surface (first) of the first transparent adhesive layer is provided. A laminate obtained by providing a reversible thermal discoloration layer on the side of one transparent adhesive layer opposite to the side on which the transparent resin film is provided, and a second transparent adhesive on one surface of the transparent resin film. The laminated body obtained by providing the layer can be produced by adhering the reversible thermal discoloration layer and the transparent resin film via the second transparent adhesive layer.
Further, the laminate obtained by providing the adhesive layer on one surface of the transparent resin film is cut in half with a slitter, and the adhesive layer (first transparency) of the one obtained by cutting is cut. A laminate obtained by providing a reversible thermal discoloration layer on the outer surface (the surface of the adhesive layer opposite to the side on which the transparent resin film is provided) and the other laminate obtained by cutting are provided. It is also possible to prepare a reversible thermochromic laminate by attaching a reversible thermochromic layer and a transparent resin film via an adhesive layer (second transparent adhesive layer) of the other laminate.
By cutting these reversible thermochromic laminates to an appropriate width with a slitter, the reversible thermochromic flat yarn shown in FIG. 7 can be obtained.

The above-mentioned laminate can also be produced by separately providing an adhesive layer. For example, the outer surface of the reversible thermal discoloration layer (the first transparency of the reversible thermal discoloration layer) of a laminate in which a first transparent adhesive layer and a reversible thermal discoloration layer are sequentially provided on one surface of a transparent resin film. A laminate having an adhesive layer further provided on the side opposite to the side on which the adhesive layer is provided) and the other laminate having a second transparent adhesive layer provided on one surface of the transparent resin film. A reversible thermochromic layer and a transparent resin film can be attached to each other via an adhesive layer and a second transparent adhesive layer to prepare a reversible thermochromic laminate, and the reversible thermochromic layer and the transparent resin film can be produced. Can be obtained as a reversible thermochromic laminate in which the above is more firmly adhered.
By cutting this laminate to an appropriate width with a slitter, the first transparent adhesive layer (4) is reversible on one wide surface of the plain yarn made of the transparent resin film (3) shown in FIG. A reversible thermochromic flat yarn (2) is obtained in which a thermochromic layer (5), an adhesive layer (9), a second transparent adhesive layer (6), and a transparent resin film (3) are sequentially provided.
The adhesive used for the adhesive layer does not affect the thermal discoloration function, sensitivity, etc. of the reversible thermal discoloration microcapsule pigment contained in the reversible thermal discoloration layer, and does not affect the design, characters, temperature, etc. of the reversible thermal discoloration layer. It is not particularly limited as long as the color change due to the change can be visually recognized.
Examples of the adhesive include acrylic resin, urethane resin, ethylene-vinyl acetate copolymer resin, rubber resin, silicone resin, epoxy resin and the like.

The twisted yarn of the present invention can be discolored by applying heat by hand, applying heat or cold heat by a water adhering tool, or using a heating tool or a cooling tool.
As the water adhering tool, a writing tool or a coating tool having a brush tip or a fiber pen body at the tip, and a writing tool or a coating tool provided with a fiber body or a brush that holds water in the container and draws out the water in the container. Examples thereof include tools, roller-shaped coating tools, and the like.
Examples of the heating tool include an energizing heating discoloring tool equipped with a resistance heating element such as a PTC element, a heating discoloring tool filled with a medium such as hot water, a heating discoloration tool using steam or laser light, and application of a hair dryer. Be done.
Examples of the cooling tool include a current-carrying cold-heat discoloring tool using a Pertier element, a cold-heat discoloring tool filled with a medium such as cold water or ice chips, a livestock cooling agent, and application of a refrigerator or a freezer.
Since the twisted yarn can be easily discolored, a method of applying heat by hand, a method of applying heat or cold heat with a water adhering tool, a heating discoloring tool filled with a medium such as hot water, and a medium such as cold water or ice pieces are filled. It is preferable to use a cold heat discoloring tool.

The twisted yarn of the present invention can be used for a fabric, the visibility of the color change due to a temperature change is good, and the fabric having excellent durability of the reversible thermal discoloration layer can be obtained. Further, when the light stabilizer is contained in the first and second transparent adhesive layers, it is possible to obtain a fabric having excellent durability and light resistance of the reversible thermal discoloration layer.
The fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, braids, non-woven fabrics, and pile fabrics. The fabric can be made by using reversible thermochromic plying for at least one of the warp and weft.

Further, the plyed yarn of the present invention can be used for a headdress, and a headdress having good visibility of color change due to a temperature change and excellent durability of a reversible thermal discoloration layer can be obtained. Further, when the light stabilizer is contained in the first and second transparent adhesive layers, a headdress product having excellent durability and light resistance of the reversible thermal discoloration layer can be obtained.
The headdress is not particularly limited, and examples thereof include hair wigs and hair extensions.

Further, the plyed yarn of the present invention can be used for a toy, the visibility of the color change due to the temperature change is good, and the toy having excellent durability of the reversible thermal discoloration layer can be obtained. Further, when the light stabilizer is contained in the first and second transparent adhesive layers, a toy having excellent durability and light resistance of the reversible thermal discoloration layer can be obtained.
The toy is not particularly limited, but for example, a doll or animal figurine toy with hair or body hair made of reversible heat-discoloring twisted yarn, a stuffed animal with body hair made of reversible heat-discoloring twisted yarn, or an attachment thereof. Examples of products can be given. Here, examples of the accessories include hair extensions for doll toys, clothing for doll toys, scarves, and the like.
The twisted yarn of the present invention is preferably used as hair or body hair provided in a toy such as a doll or an animal figurative toy, or as an accessory for a doll toy. The color of these hairs, body hairs, or accessories can be easily changed and enjoyed by a method of applying heat by hand or a method of applying heat or cold heat with a water adhering tool. Such a color change can be repeated.
Further, the above-mentioned toy using the reversible heat-discoloring plying and the water adhering tool can be combined to form a toy set.

Further, the following can be exemplified as a product using the twisted yarn of the present invention.
(1) Toys Accessory toys, drawing toys, picture books for toys, stacking toys, block toys, clay toys, fluid toys, frames, kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, and vehicles, animals , Plants, buildings, toys that imitate food, etc.
(2) Clothing T-shirts, sweatshirts, blouses, dresses, swimwear, raincoats, skiwear and other clothing, shoes and shoe straps and other clothing, handkerchiefs, towels, bathrobes and other cloth personal belongings, gloves, ties, hats, scarves. , Muffler, etc.
(3) Indoor decorations Carpets, curtains, curtain strings, table hangings, rugs, cushions, carpets, rugs, chair upholstery, sheets, mats, picture frames, artificial flowers, photo stands, etc.
(4) Furniture Duvets, pillows, mattresses, bedding such as beds, chairs, sofas, etc.
(5) Ornaments Rings, bangles, tiaras, earrings, hair clips, nails, ribbons, scarves, watches, glasses, eyebrows, beards, eyebrows, etc.
(6) Others Bags, packaging containers, embroidery threads, exercise equipment, fishing equipment, coasters, musical instruments, purses and other bags, umbrellas, training equipment, etc.

Examples are shown below, but the present invention is not limited thereto. In addition, the part in an Example shows a mass part.

Preparation of reversible thermochromic microcapsule pigment A (a) As a component, 2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro [5H- [1] benzopyrano [2,3-d] ] Pyrimidine-5,1'(3'H) -isobenzofuran] -3'-one 2 parts, (b) component 2,2-bis (4-hydroxyphenyl) hexafluoropropane 5 parts, and ( C) A reversible thermochromic composition consisting of 50 parts of cyclohexylmethyl stearate as a component is added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer and 50 parts of an auxiliary solvent as a wall film material, and then 8 After emulsifying and dispersing in a% polyvinyl alcohol aqueous solution and continuing stirring while heating, 2.5 parts of a water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A reversible thermochromic microcapsule pigment A having an average particle diameter ( _DA ) of 4.6 μm was obtained from the above microcapsule dispersion by centrifugation.
The reversible thermochromic microcapsule pigment A had a complete color development temperature t ₁ of 14 ° C. and a complete decolorization temperature t ₄ of 38 ° C., and changed reversibly from pink to colorless due to temperature changes.

Fabrication of reversible thermochromic flat yarn A (see FIG. 7)
30 parts of reversible heat-discoloring microcapsule pigment A, 60 parts of polyester resin emulsion (solid content: 50%), 1 part of leveling agent, 1 part of defoaming agent, 0.5 part of viscosity modifier, and 5 parts of water. And 2.5 parts of a carbodiimide-based curing agent (solid content: 40%) were uniformly mixed in a vehicle to prepare a reversible thermochromic liquid composition which is a printing ink used for screen printing.
A liquid composition, which is a printing ink used for gravure printing, was prepared by uniformly mixing in a vehicle consisting of 98 parts of urethane resin and 2 parts of an isocyanate-based curing agent.
As the transparent resin film (3), solid printing is performed on one surface of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm on a 200-mesh gravure roll plate using a liquid composition. Then, it was heat-cured at 80 ° C. to form a first transparent adhesive layer (4) (visible light transmittance: 98%) having a thickness of 2 μm.
Next, 120 using the reversible thermochromic liquid composition on the outer surface of the first transparent adhesive layer (4) (the surface of the first transparent adhesive layer opposite to the side on which the transparent resin film is provided). Solid printing was performed on a screen plate of the mesh, and the mixture was heated at 110 ° C. to form a reversible thermal discoloration layer (5) having an average thickness ( _TA ) of 15 μm.
Next, on the outer surface of the reversible thermal discoloration layer (5) (the surface of the reversible thermal discoloration layer opposite to the side on which the first transparent adhesive layer is provided), a 200-mesh gravure roll plate is used using a liquid composition. Solid printing was performed on the entire surface to form a second transparent adhesive layer (6) (visible light transmittance: 98%) having a thickness of 2 μm.
Next, on the outer surface of the second transparent adhesive layer (6) (the surface of the second transparent adhesive layer opposite to the side on which the reversible thermal discoloration layer is provided), the transparent resin layer (7) has a thickness of 12 μm. A transparent PET film (visible light transmittance: 99%) was placed and heat-cured at 80 ° C. in a pressure-welded state to prepare a reversible thermochromic laminate.
The above reversible thermochromic laminate was cut with a microslitter into a thread shape of 250 μm to prepare a reversible thermochromic flat yarn (2) (reversible thermochromic flat yarn A) having a thickness of 43 μm.
The above-mentioned reversible heat-discoloring laminate has excellent adhesion between the reversible heat-discoloring layer and the transparent resin film, and the reversible heat-discoloring layer and the transparent resin layer, and the outermost transparent resin film and the transparent layer. Since the reversible heat discoloration layer is protected by the sex resin layer, even if the teeth come into contact with each other when cutting with a microslitter, the reversible heat discoloration layer is less likely to be damaged or scratched.
The obtained reversible thermochromic flat yarn A reversibly changed to colorless at 38 ° C. or higher and pink at 14 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plain yarn, and the above change could be repeated.
Further, in the reversible heat-discoloring plain yarn, the curl property is suppressed because the layers provided on one surface and the other surface of the reversible heat-discoloring layer are the same with the reversible heat-discoloring layer as an intermediate layer, and the twisted yarn has. It was easy to handle when processing.

Fabrication of reversible thermochromic flat yarn A'(see FIG. 7)
30 parts of reversible heat-discoloring microcapsule pigment A, 60 parts of polyester resin emulsion (solid content: 50%), 1 part of leveling agent, 1 part of defoaming agent, 0.5 part of viscosity modifier, and 5 parts of water. And 2.5 parts of a carbodiimide-based curing agent (solid content: 40%) were uniformly mixed in a vehicle to prepare a reversible thermochromic liquid composition which is a printing ink used for screen printing.
As a light stabilizer, 5 parts of 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (manufactured by BASF, product name: Tinubin PS), 50 parts of acrylic resin, 43 parts of urethane resin, isocyanate. A liquid composition, which is a printing ink used for gravure printing, was prepared by uniformly mixing the mixture in a vehicle consisting of two parts of the system curing agent.
As the transparent resin film (3), solid printing is performed on one surface of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm on a 200-mesh gravure roll plate using a liquid composition. Then, it was heat-cured at 80 ° C. to form a first transparent adhesive layer (4) (visible light transmittance: 96%) having a thickness of 2 μm.
Next, 120 using the reversible thermochromic liquid composition on the outer surface of the first transparent adhesive layer (4) (the surface of the first transparent adhesive layer opposite to the side on which the transparent resin film is provided). Solid printing was performed on a screen plate of the mesh, and the mixture was heated at 110 ° C. to form a reversible thermal discoloration layer (5) having an average thickness (TA _′ ) of 15 μm.
Next, on the outer surface of the reversible thermal discoloration layer (5) (the surface of the reversible thermal discoloration layer opposite to the side on which the first transparent adhesive layer is provided), a 200-mesh gravure roll plate is used using a liquid composition. Solid printing was performed on the entire surface to form a second transparent adhesive layer (6) (visible light transmittance: 96%) having a thickness of 2 μm.
Next, on the outer surface of the second transparent adhesive layer (6) (the surface of the second transparent adhesive layer opposite to the side on which the reversible thermal discoloration layer is provided), the transparent resin layer (7) has a thickness of 12 μm. A transparent PET film (visible light transmittance: 99%) was placed and heat-cured at 80 ° C. in a pressure-welded state to prepare a reversible thermochromic laminate.
The above reversible thermochromic laminate was cut into a thread shape of 250 μm with a microslitter to prepare a reversible thermochromic flat yarn (2) (reversible thermochromic flat yarn A') having a thickness of 43 μm.
The above-mentioned reversible heat-discoloring laminate has excellent adhesion between the reversible heat-discoloring layer and the transparent resin film, and the reversible heat-discoloring layer and the transparent resin layer, and the outermost transparent resin film and the transparent layer. Since the reversible thermal discoloration layer is protected by the sex resin layer, it is difficult for the reversible thermal discoloration layer to be damaged or scratched even if the teeth come into contact with each other when cutting with a microslitter. Further, by containing a light stabilizer in the adhesive layer, the light resistance of the reversible thermal discoloration layer was excellent.
The obtained reversible thermochromic flat yarn A'reversibly changed to colorless at 38 ° C. or higher and pink at 14 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plain yarn, and the above change could be repeated.
Further, in the reversible thermochromic flat yarn, the curl property is suppressed because the layers provided on one surface and the other surface of the reversible thermochromic layer are the same with the reversible thermochromic layer as an intermediate layer, and the twisted yarn has. It was easy to handle when processing.

Preparation of Reversible Thermochromic Microcapsule Pigment B (a) As a component, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 1 A reversible thermochromic composition consisting of 5 parts, 5 parts of 2,2-bis (4-hydroxyphenyl) hexafluoropropane as the (b) component, and 50 parts of cyclohexylmethyl stearate as the (c) component. Was put into a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer and 50 parts of an auxiliary solvent as a wall film material, then emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution, and the mixture was continuously stirred while being heated. 2.5 parts of water-soluble aliphatic modified amine was added, and further stirring was continued to prepare a microcapsule dispersion. A reversible thermochromic microcapsule pigment _B having an average particle size (DB) of 10.0 μm was obtained from the above microcapsule dispersion by centrifugation.
The reversible thermochromic microcapsule pigment B had a complete color development temperature t ₁ of 13 ° C. and a complete decolorization temperature t ₄ of 38 ° C., and changed reversibly from blue to colorless due to temperature changes.

Fabrication of reversible thermochromic flat yarn B (see FIG. 7)
Viscosity adjustment of 40 parts of reversible heat-discoloring microcapsule pigment B, 0.5 part of pink general pigment, 50 parts of polyester resin emulsion (solid content: 50%), 1 part of leveling agent, 1 part of defoaming agent. A printing ink used for screen printing, which is uniformly mixed in a vehicle consisting of 0.5 parts of an agent, 4.5 parts of water, and 2.5 parts of a carbodiimide-based curing agent (solid content: 40%). A reversible thermochromic liquid composition was prepared.
As a light stabilizer, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- [2,4-bis (butyloxyphenyl)]-1,3,5-triazine (manufactured by BASF, product) Name: Chinubin 460) A liquid composition that is a printing ink used for gravure printing by uniformly mixing 3 parts in a vehicle consisting of 50 parts of acrylic resin, 45 parts of urethane resin, and 2 parts of isocyanate-based curing agent. Was prepared.
As the transparent resin film (3), solid printing is performed on one surface of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm with a 150-mesh gravure roll plate using a liquid composition. Then, it was heat-cured at 80 ° C. to form a first transparent adhesive layer (4) (visible light transmittance: 95%) having a thickness of 3 μm. Next, 100 using a reversible thermochromic liquid composition on the outer surface of the first transparent adhesive layer (4) (the surface of the first transparent adhesive layer opposite to the side on which the transparent resin film is provided). Solid printing is performed on a screen plate of a mesh and heat-cured at 100 ° C. to form a reversible thermal discoloration layer (5) having an average thickness ( _TB ) of 20 μm, and the first transparency is obtained on a transparent resin film. A laminated body in which an adhesive layer and a reversible thermal discoloration layer were sequentially provided was produced.
On one side of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm as the transparent resin layer (7), solid printing was performed on the entire surface with a 150 mesh gravure roll plate using a liquid composition. A second transparent adhesive layer (6) (visible light transmittance: 95%) having a thickness of 3 μm was formed, and a laminated body in which the second transparent adhesive layer was provided on the transparent resin layer was produced.
Next, the above two laminates are attached with a reversible thermal discoloration layer and a transparent PET film via a second transparent adhesive layer, and heat-cured at 80 ° C. to obtain a reversible thermal discoloration laminate. Made.
The above reversible thermochromic laminate was cut into a thread shape of 375 μm with a microslitter to prepare a reversible thermochromic flat yarn (2) (reversible thermochromic flat yarn B) having a thickness of 50 μm.
The above-mentioned reversible heat-discoloring laminate has excellent adhesion between the reversible heat-discoloring layer and the transparent resin film, and the reversible heat-discoloring layer and the transparent resin layer, and the outermost transparent resin film and the transparent layer. Since the reversible heat discoloration layer is protected by the sex resin layer, even if the teeth come into contact with each other when cutting with a microslitter, the reversible heat discoloration layer is less likely to be damaged or scratched. Further, by containing a light stabilizer in the adhesive layer, the light resistance of the reversible thermal discoloration layer was excellent.
The obtained reversible thermochromic flat yarn B reversibly changed to pink at 38 ° C. or higher and purple at 13 ° C. or lower, and maintained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plain yarn, and the above change could be repeated.
Further, in the reversible thermochromic flat yarn, the curl property is suppressed because the layers provided on one surface and the other surface of the reversible thermochromic layer are the same with the reversible thermochromic layer as an intermediate layer, and the twisted yarn has. It was easy to handle when processing.

Fabrication of reversible thermochromic flat yarn B'(see FIG. 7)
Viscosity adjustment of 40 parts of reversible heat-discoloring microcapsule pigment B, 0.5 part of pink general pigment, 50 parts of polyester resin emulsion (solid content: 50%), 1 part of leveling agent, 1 part of defoaming agent. A printing ink used for screen printing, which is uniformly mixed in a vehicle consisting of 0.5 parts of an agent, 4.5 parts of water, and 2.5 parts of a carbodiimide-based curing agent (solid content: 40%). A reversible thermochromic liquid composition was prepared.
As a light stabilizer, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- [2,4-bis (butyloxyphenyl)]-1,3,5-triazine (manufactured by BASF, product) Name: Chinubin 460) A liquid composition that is a printing ink used for gravure printing by uniformly mixing 3 parts in a vehicle consisting of 50 parts of acrylic resin, 45 parts of urethane resin, and 2 parts of isocyanate-based curing agent. Was prepared.
As the transparent resin film (3), solid printing is performed on one surface of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm with a 150-mesh gravure roll plate using a liquid composition. Then, it was heat-cured at 80 ° C. to form a first transparent adhesive layer (4) (visible light transmittance: 95%) having a thickness of 3 μm. Next, 100 using a reversible thermochromic liquid composition on the outer surface of the first transparent adhesive layer (4) (the surface of the first transparent adhesive layer opposite to the side on which the transparent resin film is provided). Solid printing is performed on a mesh screen plate and heat-cured at 100 ° C. to form a reversible thermal discoloration layer (5) having an average thickness (TB _' ) of 20 μm, and the first transparent layer is formed on a transparent resin film. A laminate in which a sex-adhesive layer and a reversible thermal discoloration layer were sequentially provided was produced.
As the transparent resin layer (7), on one surface of a transparent iris resin film (manufactured by ENGELHARD, product name: IRIDESCNT FILM IF-8181 R / G) (visible light transmission rate: 75%) having a thickness of 18 μm. A second transparent adhesive layer (6) (visible light transmission rate: 95%) having a thickness of 3 μm was formed by solid printing on the entire surface with a 150 mesh gravure roll plate using the liquid composition, and the transparency was obtained. A laminate having a second transparent adhesive layer on the resin layer was produced.
Next, the above two laminates were attached with a reversible thermal discoloration layer and a transparent iris resin film via a second transparent adhesive layer, and heat-cured at 80 ° C. to achieve brilliant reversible thermal discoloration. A sex laminate was produced.
The above-mentioned bright reversible thermochromic laminate was cut into a thread shape of 375 μm with a microslitter to prepare a reversible thermochromic flat yarn (2) (reversible thermochromic flat yarn B') having a thickness of 50 μm. ..
The above-mentioned bright reversible thermochromic laminate has excellent adhesion between the reversible thermochromic layer and the transparent resin film, and the reversible thermochromic layer and the transparent resin layer, and the outermost transparent resin film. Since the reversible heat-discoloring layer is protected by the transparent resin layer, the reversible heat-discoloring layer is less likely to be damaged or scratched even if the teeth come into contact with each other when cutting with a microslitter. Further, by containing a light stabilizer in the adhesive layer, the light resistance of the reversible thermal discoloration layer was excellent.
The obtained reversible thermochromic flat yarn B'reversibly changed to pink having iris at 38 ° C or higher and purple having iris at 13 ° C or lower, and in the temperature range of 20 to 33 ° C, any of the above. It retained that color and satisfied the variety of color changes. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plain yarn, and the above change could be repeated.

Example 1
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 4)
The reversible heat-discoloring plain yarn A (2) was set in a twisting machine and twisted 300 times per 1 m of the plain yarn to produce a one-sided heat-discoloring twisted yarn (1) twisted only in one direction. .. Since the curl property of the reversible thermochromic flat yarn A is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn has a soft tactile sensation, and since the curl property is suppressed, it is excellent in handleability when applied to products and the like.
The reversible thermochromic twisted yarn was colorless at 38 ° C. or higher, pink at 14 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent.
The twisted yarn has an average particle size ( _DA ) of 4.6 μm of the reversible thermochromic microcapsule pigment, and 96.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and the D / T ( _DA / _TA ) is 0.307, the color change due to the temperature change is more easily visible, has a flexible texture, and is outside the stress and scratches. It was superior in the durability of the reversible thermal discoloration layer to the target factor.

Example 2
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 4)
Reversible heat discoloration flat yarn A'(2) is set in a twisting machine and twisted 300 times per 1 m of plain yarn to produce a reversible heat discoloration twisted yarn (1) in a single-twisted form in which twisting is applied only in one direction. did. Since the curl property of the reversible thermochromic flat yarn A'is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn has a soft tactile sensation, and since the curl property is suppressed, it is excellent in handleability when applied to products and the like.
The reversible thermochromic twisted yarn was colorless at 38 ° C. or higher, pink at 14 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size ( _DA ) of 4.6 μm of the reversible thermochromic microcapsule pigment, and 96.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and the D / T ( _DA / TA _' ) is 0.307, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, and light. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors such as.

Example 3
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 4)
The reversible heat-discoloring plain yarn B (2) was set in a twisting machine and twisted 180 times per 1 m of the plain yarn to produce a one-sided heat-discoloring twisted yarn (1) twisted only in one direction. .. Since the curl property of the reversible thermochromic flat yarn B is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn has a soft tactile sensation, and since the curl property is suppressed, it is excellent in handleability when applied to products and the like.
The reversible thermochromic twisted yarn was pink at 38 ° C. or higher, purple at 13 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
In the above twisted yarn, the average particle size ( _DB ) of the reversible thermochromic microcapsule pigment is 10.0 μm, and the microcapsule pigment blended with 100 parts by mass of the solid content of the binder resin is 153.8. Since it is a mass part and has a _D / T (DB / _TB ) of 0.500, color changes due to temperature changes are more easily visible, have a flexible texture, and have stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 4
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 4)
The reversible heat-discoloring plain yarn B'(2) is set in a twisting machine and twisted 180 times per 1 m of the plain yarn to produce a one-sided heat-discoloring twisted yarn (1) twisted only in one direction. did.
The obtained plyed yarn had a soft tactile sensation. Further, since the curl property of the reversible thermochromic flat yarn B'is suppressed by processing it into a twisted yarn, the obtained twisted yarn is excellent in handleability when applied to a product or the like.
The reversible thermochromic twisted yarn is pink with iris at 38 ° C or higher, purple with iris at 13 ° C or lower, retains any of the above colors in the temperature range of 20 to 33 ° C, and has a color. It satisfied the variety of changes. The color change accompanied by the brilliance due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
In the above twisted yarn, the average particle size ( _DB ) of the reversible thermochromic microcapsule pigment is 10.0 μm, and the microcapsule pigment blended with 100 parts by mass of the solid content of the binder resin is 153.8. Since it is a mass part and the _D / T (DB / TB _' ) is 0.500, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, and light. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors such as.

Example 5
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 5)
As the thread (8), a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm is cut with a microslitter into a thread shape of 250 μm, and is referred to as a plain thread (hereinafter referred to as “transparent plain thread”). May) got.
Reversible thermal discoloration Reversible thermal discoloration in a single-twisted form in which the transparent plain yarn A'(2) and the transparent plain yarn (8) are set in a twisting machine and twisted 250 times per 1 m of the plain yarn, and twisted only in one side. A sex twisted yarn (1) was produced. Since the curl property of the reversible thermochromic flat yarn A is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability and heat resistance as a twisted yarn. Furthermore, by making the widths of the reversible heat-discoloring yarn and the transparent yarn the same, when the respective yarns are aligned and twisted, the wide surface of the reversible heat-discoloring yarn and the wide surface of the transparent yarn are used. Was in close contact with each other, and the durability as a twisted yarn could be further improved. Further, since the curl property of the twisted yarn is suppressed, it is excellent in handleability when applied to products and the like.
The reversible thermochromic twisted yarn was colorless at 38 ° C. or higher, pink at 14 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. Further, since the yarn twisted together with the reversible heat-discoloring yarn is made of a transparent resin film and the reversible heat-discoloring yarn is visible from the transparent yarn side, the visibility of the color change due to the temperature change is not impaired, and the entire surface of the twisted yarn is not impaired. It was visually recognized uniformly and clearly. The above changes could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size ( _DA ) of 4.6 μm of the reversible thermochromic microcapsule pigment, and 96.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and the D / T ( _DA / TA _' ) is 0.307, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, and light. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors such as.

Example 6
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 5)
As the thread (8), an opaque holographic resin film (visible light transmittance: 0%) having a thickness of 15 μm is cut with a microslitter into a thread shape of 250 μm, and an opaque holographic plain thread (hereinafter referred to as “brilliant property”) is cut. Sometimes referred to as "flat thread") was obtained.
Reversible heat-discoloring flat yarn A'(2) and bright flat yarn (8) are set in a twisting machine, twisted 250 times per 1 m of plain yarn, and twisted only in one direction. A sex twisted yarn (1) was produced. Since the curl property of the reversible thermochromic flat yarn A'is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, since the curl property of the twisted yarn is suppressed, it is excellent in handleability when applied to products and the like.
As for the reversible thermochromic twisted yarn, the reversible thermochromic plying was colorless at 38 ° C. or higher, and only the holographic property of the brilliant spatula was visually recognized. At 14 ° C or lower, the holographic pink color is visually recognized by the pink reversible thermochromic flat yarn and the bright flat yarn, and in the temperature range of 20 to 33 ° C, any of the above-mentioned aspects is maintained, and the diversity of color change is exhibited. It was satisfying. The above changes could be repeated. Further, by making the widths of the reversible heat-discoloring plain yarn and the brilliant plain yarn the same, when the respective plain yarns are aligned and twisted, the wide surface of the reversible thermochromic flat yarn and the wide surface of the brilliant flat yarn are used. In close contact with each other, the durability as a twisted yarn was improved, and the visibility of the color change accompanied by the brilliance due to the temperature change could be further improved.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size ( _DA ) of 4.6 μm of the reversible thermochromic microcapsule pigment, and 96.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and the D / T ( _DA / TA _' ) is 0.307, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, and light. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors such as.

Example 7
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 5)
As the thread (8), a transparent pearl glossy resin film (manufactured by BASF: product name: AURORA 8181RG) (visible light transmittance: 70%) having a thickness of 18 μm is cut into a thread shape of 250 μm by a microslitter. Then, a transparent pearl glossy plain yarn (hereinafter, may be referred to as "brilliant plain yarn") was obtained.
Reversible heat discoloration Reversible heat discoloration of a single twisted form in which the reversible heat discoloration flat yarn B (2) and the brilliant flat yarn (8) are set in a twisting machine and twisted 250 times per 1 m of the plain yarn, and twisted only in one direction. A twisted yarn (1) was produced. Since the curl property of the reversible thermochromic flat yarn B is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, since the curl property of the twisted yarn is suppressed, it is excellent in handleability when applied to products and the like.
In the reversible heat-discoloring twisted yarn, a pink color having pearly luster is visually recognized by the pink reversible heat-discoloring flat yarn and the bright flat yarn at 38 ° C or higher, and the purple reversible heat-discoloring flat yarn and the bright flat yarn are recognized at 13 ° C or lower. Purple with pearly luster was visually recognized, and kept any of the above-mentioned colors in the temperature range of 20 to 33 ° C., satisfying the variety of color changes. In addition, the yarn twisted together with the reversible heat-discoloring flat yarn is made of a transparent pearl glossy resin film, and the reversible heat-discoloring flat yarn can be visually recognized from the brilliant flat yarn side. Was not impaired and was visible uniformly and clearly on the entire surface of the twisted yarn. The above changes could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
In the above twisted yarn, the average particle size ( _DB ) of the reversible thermochromic microcapsule pigment is 10.0 μm, and the microcapsule pigment blended with 100 parts by mass of the solid content of the binder resin is 153.8. Since it is a mass part and has a _D / T (DB / _TB ) of 0.500, color changes due to temperature changes are more easily visible, have a flexible texture, and have stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 8
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 5)
As the thread (8), a transparent iris resin film (manufactured by ENGELHARD, product name: IRIDESCNT FILM IF-8181 R / G) (visible light transmittance: 75%) having a thickness of 18 μm is used as a thread of 375 μm with a microslitter. A transparent iris flat thread (hereinafter, may be referred to as a "brilliant flat thread") was obtained.
Reversible heat discoloration Reversible heat discoloration of a single twisted form in which the reversible heat discoloration flat yarn B (2) and the brilliant flat yarn (8) are set in a twisting machine and twisted 180 times per 1 m of the plain yarn, and twisted only in one direction. A twisted yarn (1) was produced. Since the curl property of the reversible thermochromic flat yarn B is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, since the curl property of the twisted yarn is suppressed, the obtained twisted yarn is excellent in handleability when applied to a product or the like.
In the reversible heat-discoloring twisted yarn, a pink color having iris is visually recognized by the pink reversible heat-discoloring flat yarn and the bright flat yarn at 38 ° C. or higher, and the iris by the purple reversible heat-discoloring layer and the bright flat yarn at 13 ° C or lower. Purple having a property was visually recognized, and one of the above-mentioned colors was retained in the temperature range of 20 to 33 ° C., satisfying the variety of color changes. In addition, the yarn twisted together with the reversible heat-discoloring plain yarn is made of a transparent iris resin film, and the reversible heat-discoloring flat yarn is visible from the brilliant plain yarn side. It was not impaired and was visible uniformly and clearly on the entire surface of the twisted yarn. The above changes could be repeated. Further, by making the widths of the reversible heat-discoloring plain yarn and the brilliant flat yarn the same, when the respective plain yarns are aligned and twisted, the wide surface of the reversible thermochromic flat yarn and the wide surface of the brilliant flat yarn are used. In close contact with each other, the durability as a twisted yarn was improved, and the visibility of the color change accompanied by the brilliance due to the temperature change could be further improved.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size (DB) of 10.0 μm as a reversible thermochromic microcapsule pigment, and _153.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and has a _D / T (DB / _TB ) of 0.500, color changes due to temperature changes are more easily visible, have a flexible texture, and have stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 9
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 5)
As the thread (8), a transparent iris resin film (manufactured by ENGELHARD, product name: IRIDESCNT FILM IF-8181 R / G) (visible light transmittance: 75%) having a thickness of 18 μm is used as a thread of 375 μm with a microslitter. A transparent iris flat thread (hereinafter, may be referred to as a "brilliant flat thread") was obtained.
A single-twisted form in which the reversible heat-discoloring plain yarn B'(2) and the yarn (brilliant plain yarn) (8) are set in a twisting machine and twisted 180 times per 1 m of the plain yarn, and twisted only in one side. A reversible thermochromic twisted yarn (1) was produced. The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, since the curl property of the reversible thermochromic flat yarn B'is suppressed by processing it into a twisted yarn, the twisted yarn is excellent in handleability when applied to a product or the like.
The reversible thermochromic twisted yarn is pink with iris at 38 ° C or higher, purple with iris at 13 ° C or lower, retains any of the above colors in the temperature range of 20 to 33 ° C, and has a color. It satisfied the variety of changes. In addition, the yarn twisted together with the reversible heat-discoloring plain yarn is made of a transparent iris resin film, and the reversible heat-discoloring flat yarn is visible from the brilliant plain yarn side. It was not impaired and was visible uniformly and clearly on the entire surface of the twisted yarn. Furthermore, since the transparent resin layer and the bright plain thread are made of the same transparent iris resin film and the optical properties of the reversible thermochromic flat thread and the bright plain thread are the same, the brilliance (pearl luster) is strongly visible. Was done. The above changes could be repeated. Further, by making the widths of the reversible heat-discoloring plain yarn and the brilliant flat yarn the same, when the respective plain yarns are aligned and twisted, the wide surface of the reversible thermochromic flat yarn and the wide surface of the brilliant flat yarn are used. In close contact with each other, the durability as a twisted yarn was improved, and the visibility of the color change accompanied by the brilliance due to the temperature change could be further improved.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size (DB) of 10.0 μm as a reversible thermochromic microcapsule pigment, and _153.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a part and the _D / T (DB / TB _' ) is 0.500, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 10
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 6)
Reversible heat discoloration flat yarn B (2) and transparent polyester fiber having a perfect circular cross section as the yarn (8) are set in a plying machine, and the above yarn is used as a core yarn to reversibly heat around the core yarn. Twisting was performed so that the discolorable flat yarn B was provided, and a reversible heat-discolorable twisted yarn (1) in a round twisted form was produced. Since the curl property of the reversible thermochromic flat yarn B is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, in the above-mentioned plying, a reversible heat-discoloring flat yarn is wound without a gap so that the core yarn is not visible from the surroundings, and the cross-sectional shape of the core yarn is a perfect circular shape, so that the reversible heat is reversible around the core yarn. When the discolorable plain yarn is provided, the outer surface of the core yarn and the wide surface of the reversible heat-discolorable plain yarn are in close contact with each other, so that the durability of the plyed yarn can be improved. Further, since the curl property of the twisted yarn is suppressed, it is excellent in handleability when applied to products and the like.
The reversible thermochromic twisted yarn was pink at 38 ° C. or higher, purple at 13 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size (DB) of 10.0 μm as a reversible thermochromic microcapsule pigment, and _153.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and has a _D / T (DB / _TB ) of 0.500, color changes due to temperature changes are more easily visible, have a flexible texture, and have stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 11
Manufacture of reversible thermochromic twisted yarn A two-layer coating type transparent metallic gloss pigment [Merck Co., Ltd., product name:] using borosilicate glass as a core material, its surface coated with silicon dioxide, and further coated with titanium oxide. Miraval 5423 Magic Lilac] 1 part is uniformly mixed in a vehicle consisting of 45 parts of a resin solution in which vinyl chloride-vinyl acetate resin is dissolved in 20% of methylisobutylketone, 20 parts of xylene, and 20 parts of methylisobutylketone. A metallic glossy liquid composition, which is a paint used for spray painting, was prepared.
As the thread, the entire surface of the transparent polyester fiber having a perfect circular cross-sectional shape is spray-painted with the above paint and dried to provide a metallic gloss layer (hereinafter, "brilliant thread"). May be expressed as).
A reversible heat-discoloring plain yarn B and a yarn (transparent polyester fiber provided with a metallic gloss layer) are set in a twisting machine, and the above-mentioned yarn is used as a core yarn, and a reversible heat-discoloring flat yarn B is provided around the core yarn. In this way, a reversible thermochromic twisted yarn in the form of bellows twist was produced. Since the curl property of the reversible thermochromic flat yarn B is suppressed, it can be easily handled when it is processed into a twisted yarn.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, in the above-mentioned plying, since the cross-sectional shape of the core yarn is a perfect circle, when the reversible thermochromic flat yarn is provided around the core yarn, the outer surface of the core yarn and the wide surface of the reversible thermochromic flat yarn are provided. Therefore, the durability of the twisted yarn could be improved. Further, since the curl property of the twisted yarn is suppressed, it is excellent in handleability when applied to products and the like.
In the reversible heat-discoloring twisted yarn, the reversible heat-discoloring plain yarn is pink at 38 ° C. or higher, the pink color is visually recognized at the place where the reversible heat-discoloring flat yarn is wound, and at the place where the reversible heat-discoloring flat yarn is not wound. A pink color with metallic luster was visually recognized. At 13 ° C or lower, the reversible thermochromic flat yarn is purple, purple is visually recognized in the place where the reversible thermochromic flat yarn is wound, and purple with metallic luster in the place where the reversible thermochromic yarn is not wound. Was visually recognized. This is because the reversible thermal discoloration flat yarn is visually recognized through the core yarn due to the transparency of the core yarn, and the color change due to the temperature change is uniformly and clearly visible on the entire surface of the twisted yarn, and the reversible thermal discoloration is visually recognized. In the place where the sex flat yarn was not wound, a pink color having a metallic luster, to which the metallic luster by the bright yarn was imparted, was visually recognized. In the temperature range of 20 to 33 ° C., any of the above-mentioned colors was maintained, and the variety of color changes was satisfied. The above changes could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size (DB) of 10.0 μm as a reversible thermochromic microcapsule pigment, and _153.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and has a _D / T (DB / _TB ) of 0.500, color changes due to temperature changes are more easily visible, have a flexible texture, and have stress, scratches, light, etc. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors.

Example 12
Fabrication of Reversible Thermal Discoloration Plying (See Fig. 6)
A transparent polyester fiber having a perfect circular cross-sectional shape is set in a twisting machine as a reversible thermochromic flat yarn B'(2) and a yarn (8), and the above yarn is used as a core yarn around the core yarn. The transparent resin layer (transparent iris resin film) of the reversible thermochromic flat yarn B was twisted so as to be the surface to prepare a reversible thermochromic twisted yarn (1) in a round twisted form.
The obtained twisted yarn had a soft touch and was excellent in durability as a twisted yarn. Further, in the above-mentioned twisted yarn, a reversible heat-discoloring flat yarn is wound without a gap so that the core yarn is not visible from the surroundings, and the cross-sectional shape of the core yarn is a perfect circular shape, so that the core yarn has a reversible heat on the outside of the core yarn. When the discolorable plain yarn is provided, the outer surface of the core yarn and the wide surface of the reversible heat-discolorable plain yarn are in close contact with each other, so that the durability of the plyed yarn can be improved. Further, since the curl property of the reversible thermochromic flat yarn B'is suppressed by processing it into a twisted yarn, the obtained twisted yarn is excellent in handleability when applied to a product or the like.
The reversible thermochromic twisted yarn is pink with iris at 38 ° C or higher, purple with iris at 13 ° C or lower, retains any of the above colors in the temperature range of 20 to 33 ° C, and has a color. It satisfied the variety of changes. The color change accompanied by the brilliance due to the temperature change was visually recognized uniformly and clearly on the entire surface of the plyed yarn, and the above change could be repeated.
In addition, the adhesiveness between the reversible thermal discoloration layer and the transparent resin film, and the reversible thermal discoloration layer and the transparent resin layer is excellent, and delamination does not occur due to stress during twisting, and the transparent resin film. In addition, since the transparent resin layer exerts the effect of protecting the reversible thermal discoloration layer from external factors such as scratching, the durability of the reversible thermal discoloration layer is excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.
The twisted yarn has an average particle size (DB) of 10.0 μm as a reversible thermochromic microcapsule pigment, and _153.8 microcapsule pigments are blended with respect to 100 parts by mass of the solid content of the binder resin. Since it is a mass part and the _D / T (DB / TB _' ) is 0.500, the color change due to the temperature change is more easily visible, has a flexible texture, and has stress, scratches, and light. It was superior in durability and light resistance of the reversible thermal discoloration layer against external factors such as.

Example 13
Fabrication of Fabric Using Reversible Thermal Discoloration Plying The reversible thermal discoloration plying of Example 10 is set in a loom using polyester fibers colored purple in the warp to produce a plain weave reversible thermal discoloration fabric. did. Since the curl property of the twisted yarn is suppressed, it is easy to handle when producing the fabric, and it can be easily woven. In addition, the obtained fabric had a flexible texture and was excellent in durability.
Since the reversible heat-discoloring plying is pink at 38 ° C or higher, a lattice pattern in which pink and purple are alternately arranged can be visually recognized, and the reversible heat-discoloring plying is purple at 13 ° C or lower, so that the entire surface is covered. It was visually recognized as purple and retained any of the above-mentioned aspects in the temperature range of 20 to 33 ° C. The above changes could be repeated.
Further, since the adhesiveness between the reversible heat discoloration layer and the transparent resin film and the reversible heat discoloration layer and the transparent resin layer is excellent, delamination does not occur due to the stress during weaving, and the transparent resin film and the transparent resin film and The transparent resin layer exhibited the effect of protecting the reversible thermal discoloration layer, and the durability of the reversible thermal discoloration layer was excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.

Example 14
Preparation of Hair Extension Using Reversible Heat Discoloration Twist The hair extension (hair extension) was prepared by planting hair on a fastener by a conventional method using the reversible heat discoloration twist of Example 5. Since the curl property of the plyed yarn was suppressed, it was easy to handle when producing the hair extension, and the hair could be easily transplanted to the fastener. In addition, the obtained hair extension had a flexible texture and was excellent in durability.
The hair extension was colorless above 38 ° C, pink below 14 ° C, and retained any of the above colors in the temperature range of 20-33 ° C. Further, the yarn twisted together with the reversible heat-discoloring plain yarn is a plain yarn made of a transparent resin film (transparent plain yarn), and since the reversible heat-discoloring plain yarn is visually recognized from the transparent yarn side, the color change due to the temperature change is visually recognized. The sex was not impaired and was visible uniformly and clearly throughout the hair extension. The above changes could be repeated.
Further, since the adhesiveness between the reversible thermal discoloration layer and the transparent resin film and the reversible thermal discoloration layer and the transparent resin layer is excellent, delamination does not occur due to the stress at the time of flocking, and the transparent resin. The film and the transparent resin layer exhibited the effect of protecting the reversible thermal discoloration layer, and the durability of the reversible thermal discoloration layer was excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.

Example 15
Fabrication of a doll toy with hair using reversible heat-discoloring twisted yarn The reversible heat-discoloring twisted yarn of Example 3 was planted on the head of a doll by a conventional method, and the hair using the reversible heat-discoloring twisted yarn was provided. I made a doll toy. Since the curl property of the twisted yarn is suppressed, it is easy to handle when producing a doll toy, and hair can be easily transplanted to the head of the doll toy. In addition, the obtained hair had a soft texture.
The hair of the doll toy was pink at 38 ° C. or higher, purple at 13 ° C. or lower, and retained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the temperature change was visually recognized uniformly and clearly throughout the hair, and the above change could be repeated.
Further, since the adhesiveness between the reversible thermal discoloration layer and the transparent resin film and the reversible thermal discoloration layer and the transparent resin layer is excellent, delamination does not occur due to the stress at the time of flocking, and the transparent resin film. In addition, the transparent resin layer exhibited the effect of protecting the reversible thermal discoloration layer, and the durability of the reversible thermal discoloration layer was excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.

Example 16
Manufacture of Hair Extension for Doll Toys Using Reversible Heat Discoloration Twisted Thread The reversible heat discoloring twisted yarn of Example 8 is transplanted to a fastener by a conventional method to prepare a hair extension for a doll toy, and hair provided for the doll toy. Attached to. Since the curl property of the plyed yarn was suppressed, it was easy to handle when producing the hair extension, and the hair could be easily transplanted to the fastener. In addition, the obtained hair extension had a flexible texture and was excellent in durability.
Hair extensions for doll toys are pink with iris at 38 ° C or higher, purple with iris at 13 ° C or lower, and retain any of the above colors in the temperature range of 20 to 33 ° C. It satisfied the variety of changes. In addition, the yarn twisted together with the reversible heat-discoloring plain yarn is a plain yarn made of a transparent iris resin film (brilliant plain yarn), and the reversible heat-discoloring plain yarn is visually recognized from the glittering plane yarn side, so that the yarn is brilliant due to temperature changes. The visibility of the color change accompanied by the above was not impaired, and the hair extension was uniformly and clearly visible throughout the hair extension. The above changes could be repeated.
Further, since the adhesiveness between the reversible thermal discoloration layer and the transparent resin film and the reversible thermal discoloration layer and the transparent resin layer is excellent, delamination does not occur due to the stress at the time of flocking, and the transparent resin film. In addition, the transparent resin layer exhibited the effect of protecting the reversible thermal discoloration layer, and the durability of the reversible thermal discoloration layer was excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.

Example 17
Production of Animal Shaped Toy with Hair Using Reversible Heat Discoloration Twist The reversible heat discoloration twisted yarn of Example 12 is planted on the tail of an animal shape toy in the shape of a horse by a conventional method, and the reversible heat discoloration twisted yarn is used. An animal figurative toy with hair was made using. Since the curl of the twisted yarn was suppressed, it was easy to handle when producing the animal-shaped toy, and the hair could be easily transplanted to the tail of the animal-shaped toy. In addition, the obtained hair had a soft texture and was excellent in durability.
The hair of an animal figurative toy is pink with iris at 38 ° C or higher, purple with iris at 13 ° C or lower, and retains any of the above colors in the temperature range of 20 to 33 ° C. It satisfied the variety of changes. The color change accompanied by the brilliance due to the temperature change was visually recognized uniformly and clearly throughout the hair, and the above change could be repeated.
Further, since the adhesiveness between the reversible thermal discoloration layer and the transparent resin film and the reversible thermal discoloration layer and the transparent resin layer is excellent, delamination does not occur due to the stress at the time of flocking, and the transparent resin film. In addition, the transparent resin layer exhibited the effect of protecting the reversible thermal discoloration layer, and the durability of the reversible thermal discoloration layer was excellent. Further, since the adhesive layer contains a light stabilizer to prevent deterioration and damage of the reversible thermal discoloration layer due to light, the reversible thermal discoloration layer is also excellent in light resistance.

Comparative Example 1
Preparation of reversible heat-discoloring flat yarn A "Reversible heat-discoloring microcapsule pigment A 30 parts, 60 parts of polyester resin emulsion (solid content: 50%), 1 part of leveling agent, 1 part of defoaming agent, viscosity adjuster Reversible heat, which is a printing ink used for screen printing, is uniformly mixed in a vehicle consisting of 0.5 part, 5 parts of water, and 2.5 parts of a carbodiimide-based curing agent (solid content: 40%). A discolorable liquid composition was prepared.
As a transparent resin film, solid printing was performed on one surface of a transparent PET film (visible light transmittance: 99%) having a thickness of 12 μm on a 120-mesh screen plate using a reversible thermochromic liquid composition. , A reversible thermal discoloration layer was formed so that the average thickness (TA _″ ) was 15 μm.
Next, on the outer surface of the reversible thermal discoloration layer (the surface of the reversible thermal discoloration layer opposite to the side on which the transparent resin film is provided), a transparent PET film having a thickness of 12 μm as a transparent resin layer (visible light transmission rate: 99). %) Was placed and heated at 110 ° C. in a pressure-welded state to prepare a reversible thermochromic laminate.
The above reversible thermochromic laminate was cut into a thread shape of 250 μm with a microslitter to prepare a reversible thermochromic flat yarn (reversible thermochromic flat yarn A ″) having a thickness of 39 μm.
The above-mentioned reversible thermochromic laminate did not cause any noticeable damage or scratches when cut with a microslitter.
The obtained reversible thermochromic flat yarn A "reversibly changed to colorless at 38 ° C. or higher and pink at 14 ° C. or lower, and maintained any of the above colors in the temperature range of 20 to 33 ° C. The color change due to the change was visually recognized on the entire surface of the plain thread, and the above change could be repeated.

The reversible heat-discoloring plain yarn A ″ has poor adhesion between the reversible heat-discoloring layer and the transparent resin film, and the reversible heat-discoloring layer and the transparent resin layer. When the twist was applied, delamination occurred due to the stress, and it was not possible to produce a reversible thermochromic twisted yarn in a single-twisted form in which the twist was applied only in one side. Further, the transparent resin film and the transparent resin. The effect of the layer to protect the reversible thermal discoloration layer from external factors such as scratching is insufficient, and the durability of the reversible thermal discoloration layer is inferior. Further, since the layer containing the light stabilizer is not provided. , Deterioration and damage of the reversible thermal discoloration layer due to light were not prevented, and the light resistance of the reversible thermal discoloration layer was also inferior.

Application example 1
Doll toy set A doll toy set was obtained by combining the doll toy of Example 15 with a coating tool in which cold water at 10 ° C. was stored in a container and a brush was provided to draw out the cold water in the container.
When the reversible heat discoloration layer is decolorized, the hair of the doll toy is pink, and when cold water is applied with the coating tool, the reversible heat discoloration layer becomes color development, the hair of the doll toy becomes purple, and under room temperature (20 ° C) environment. It was kept in a purple state. Further, when purple hair was sandwiched between both hands for a while and heat of 38 ° C. or higher was applied, the reversible heat-discoloring layer became decolorized, the hair became pink, and was maintained in a pink state in a room temperature (20 ° C.) environment. When cold water at 10 ° C. was applied again with the coating tool, the reversible thermochromic layer was in a colored state, and the hair could be made purple.

1 Reversible heat-discoloring twisted yarn 2 Reversible heat-discoloring flat yarn 3 Transparent resin film 4 First transparent adhesive layer 5 Reversible heat-discoloring layer 6 Second transparent adhesive layer 7 Transparent resin layer 8 Thread 9 Adhesive layer

Claims (14)

On one wide surface of the plain yarn made of a transparent resin film, a first transparent adhesive layer, (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) the above-mentioned (c) B) A reversible thermochromic microcapsule pigment containing at least a reversible thermochromic composition comprising a reaction medium for controlling the color reaction of (b) is fixed in a binder resin in a dispersed state. , A reversible thermochromic twisted yarn composed of a reversible thermochromic flat yarn in which a second transparent adhesive layer and a transparent resin layer are sequentially provided. The reversible thermochromic twisted yarn according to claim 1, wherein the first transparent adhesive layer and the second transparent adhesive layer contain a light stabilizer. The reversible thermochromic plying according to claim 1 or 2, wherein the transparent resin layer is a transparent resin film. The average particle size of the reversible thermochromic microcapsule pigment is 0.1 to 50 μm, and the reversible thermochromic microcapsule pigment is 50 to 200 parts by mass with respect to 100 parts by mass of the solid content of the binder resin. The reversible thermochromic twisted yarn according to any one of claims 1 to 3, which is blended in the range of. The average thickness of the reversible thermochromic layer is 1 to 50 μm, and the average particle size (D) of the reversible thermochromic microcapsule pigment and the average thickness (T) of the reversible thermochromic layer are as follows. The reversible thermochromic twisted yarn according to any one of claims 1 to 4, which satisfies (I).
0.002 ≤ D / T <1 (I) The reversible thermochromic twisted yarn comprising the reversible thermochromic flat yarn according to any one of claims 1 to 5 and the yarn. The reversible thermochromic twisted yarn according to claim 6, wherein the reversible thermochromic flat yarn is provided around the yarn. The reversible thermal discoloration according to claim 6 or 7, wherein the thread is a brilliant thread having an optical property selected from any of metallic luster, pearl luster, hologram property, iris property, light interference property, and light reflectivity. Sex twisted yarn. The reversible thermochromic plying according to claim 8, wherein the brilliant yarn is a transparent brilliant yarn having further transparency. A fabric using the reversible thermochromic plying according to any one of claims 1 to 9. A headdress provided with the reversible thermochromic plying according to any one of claims 1 to 9. The headdress according to claim 11, wherein the headdress is a hair wig or a hair extension. A toy comprising the reversible thermochromic plying according to any one of claims 1 to 9. 13. The toy according to claim 13, wherein the toy is a doll, a zoomorphic toy, a stuffed animal, or an accessory thereof.

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