CN113767159A - Reversible thermochromic microcapsule pigments - Google Patents

Reversible thermochromic microcapsule pigments Download PDF

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CN113767159A
CN113767159A CN202080025196.3A CN202080025196A CN113767159A CN 113767159 A CN113767159 A CN 113767159A CN 202080025196 A CN202080025196 A CN 202080025196A CN 113767159 A CN113767159 A CN 113767159A
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microcapsule pigment
compound
thermal discoloration
reversible thermal
reversible
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藤田胜幸
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Pilot Ink Co Ltd
Pilot Corp
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Pilot Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

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Abstract

The invention provides a color-changing indicator which is easy to display the color change from the decolored state to the colored state by heating at the temperature near the temperature of daily life in the temperature range of living environmentAnd a reversible thermochromic microcapsule pigment which is in a state of returning to a decolored state and has a high color density at the time of coloring. The solution is a reversible thermal discoloration microcapsule pigment, which contains a reversible thermal discoloration composition, wherein the reversible thermal discoloration composition comprises: (a) an electron-donating color-developing organic compound; (b) an electron-accepting compound which is a hydroxyphenyl acetate compound represented by the following general formula (1); (c) a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons as a reaction medium for reversibly causing an electron transfer reaction between the component (a) and the component (b); and (d) a styrene compound having a softening point of 5 ℃ or higher and a weight-average molecular weight of 200 to 10 ten thousand. (wherein R represents a linear or branched alkyl group having 12 to 22 carbon atoms, X, Y and Z are each independently hydrogen or a hydroxyl group, and two or three of them are hydroxyl groups.)

Description

Reversible thermochromic microcapsule pigments
Technical Field
The present invention relates to reversible thermochromic microcapsular pigments. More specifically, the present invention relates to a reversible thermochromic microcapsule pigment which develops color from a decolorized state by heating.
Background
Conventionally, among reversible thermochromic compositions containing (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium which reversibly causes an electron transfer reaction between the components (a) and (b), there have been disclosed a reversible thermochromic composition which exhibits a color change behavior that changes from a decolorized state to a colored state by heating and returns to the decolorized state by lowering the temperature by using a hydroxybenzoate ester as the component (b), and a microcapsule pigment containing the reversible thermochromic composition (for example, see patent document 1).
These reversible thermal discoloration compositions exhibit a color development state by heating, but the temperature of color development is high, and it is difficult to develop color easily at a temperature at or near the temperature of daily life. Further, even if a reversible thermochromic composition that develops color at a temperature at or near a temperature in daily life is obtained, the color density in the color developed state is low, and the practicability is not satisfactory.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-105732
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted intensive studies on a reversible thermal discoloration composition which develops color from a decolorized state by heating, and as a result, have found that a reversible thermal discoloration microcapsule pigment which contains a reversible thermal discoloration composition exhibiting a discoloration behavior that is easily changed from a decolorized state to a colored state by heating at a temperature in the living environment temperature range or in the vicinity of the daily living temperature and is restored to the decolorized state again, and having a high color density at the time of color development is obtained by using a specific hydroxyphenyl acetate compound as component (b) and adding a specific compound as component (d), and have completed the present invention.
Means for solving the problems
The reversible thermal discoloration microcapsule pigment according to the present invention contains a reversible thermal discoloration composition, the reversible thermal discoloration composition comprising:
(a) an electron-donating color-developing organic compound;
(b) an electron-accepting compound which is a hydroxyphenyl acetate compound represented by the following general formula (1);
(c) a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons as a reaction medium for reversibly causing an electron transfer reaction between the component (a) and the component (b); and
(d) a styrene compound having a softening point of 5 ℃ or higher and a weight average molecular weight of 200 to 10 ten thousand.
Figure BDA0003282589400000021
(in the formula, wherein,
r represents a linear or branched alkyl group having 12 to 22 carbon atoms,
x, Y, and Z are each independently hydrogen or hydroxy, two of which are hydroxy and the remainder are hydrogen, or three of which are hydroxy)
The present invention relates to a reversible thermal discoloration liquid composition comprising the above reversible thermal discoloration microcapsule pigment, and a carrier.
The laminate according to the present invention comprises: a support; and a reversible thermochromic layer comprising the microcapsule pigment.
The molded article of the present invention contains the above microcapsule pigment in a support.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a reversible thermochromic microcapsule pigment which exhibits a reversible discoloration behavior that is easily changed from a decolored state to a colored state by heating and then returns to the decolored state again at a temperature in the living environment temperature range or around the daily life temperature, has a high color density in color development, and can be used in various fields such as teaching elements, toys, and decorations.
Detailed Description
The following compounds are specifically exemplified for each component.
The component (a) of the present invention, that is, the electron-donating color former is a color-determining component, and is a compound that donates electrons to the component (b) as a developer to develop color.
Examples of the electron donating color developing organic compound include a phthalide compound, a fluoran compound, a styrylquinoline compound, a diazahydrorhodamine lactone compound, a pyridine compound, a quinazoline compound, and a bisquinazoline compound, and among them, a phthalide compound and a fluoran compound are preferable.
Examples of the phthalide compound include diphenylmethane phthalide compounds, phenylindolyl phthalide compounds, indolyl phthalide compounds, diphenylmethane azaphthalide compounds, phenylindolyl azaphthalide compounds, and derivatives thereof, and among them, phenylindolyl azaphthalide compounds and derivatives thereof are preferable.
Further, examples of the fluoran compound include an aminofluoran compound, an alkoxyfluoran compound, and derivatives thereof.
These compounds are exemplified below. There may be mentioned:
3, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide,
3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide,
3, 3-bis (1-n-butyl-2-methylindol-3-yl) phthalide,
3, 3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide,
3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (2-hexyloxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- [ 2-ethoxy-4- (N-ethylanilino) phenyl ] -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide,
3- (2-acetamide-4-diethylaminophenyl) -3- (1-propylindol-3-yl) -4-azaphthalide,
3, 6-bis (diphenylamino) fluorane,
3, 6-dimethoxy fluorane,
3, 6-di-n-butoxy fluorane,
2-methyl-6- (N-ethyl-N-p-tolylamino) fluorane,
3-chloro-6-cyclohexylaminofluoran,
2-methyl-6-cyclohexylaminofluoran,
2- (2-chloroamino) -6-dibutylaminofluoran,
2- (2-chloroanilino) -6-di-n-butylaminofluoran,
2- (3-trifluoromethylanilino) -6-diethylaminofluoran,
2- (3-trifluoromethylanilino) -6-dipentylaminofluoran,
2- (dibenzylamino) -6-diethylaminofluoran,
2- (N-methylanilino) -6- (N-ethyl-N-p-tolylamino) fluoran,
1, 3-dimethyl-6-diethylaminofluorane,
2-chloro-3-methyl-6-diethylaminofluorane,
2-anilino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methoxy-6-diethylaminofluoran,
2-anilino-3-methyl-6-di-n-butylaminofluoran,
2-anilino-3-methoxy-6-di-n-butylaminofluoran,
2-dimethylamino-3-methyl-6-diethylaminofluoran,
2-anilino-3-methyl-6- (N-ethyl-N-p-tolylamino) fluoran,
1, 2-benzo-6-diethylaminofluorane,
1, 2-benzo-6- (N-ethyl-N-isobutylamino) fluoran,
1, 2-benzo-6- (N-ethyl-N-isopentylamino) fluoran,
2- (3-methoxy-4-dodecyloxystyrene) quinoline,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (diethylamino) -8- (diethylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-n-butylamino) -8- (di-n-butylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-n-butylamino) -8- (diethylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (di-N-butylamino) -8- (N-ethyl-N-isopentylamino) -4-methyl,
Spiro [5H- (1) benzopyrano (2,3-d) pyrimidine-5, 1 ' (3 ' H) isobenzofuran ] -3 ' -one, 2- (dibutylamino) -8- (dipentylamino) -4-methyl,
4,5,6, 7-tetrachloro-3- [4- (dimethylamino) -2-methoxyphenyl ] -3- (1-butyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,
4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl ] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,
4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-ethoxyphenyl ] -3- (1-pentyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,
4,5,6, 7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl ] -3- (1-ethyl-2-methyl-1H-indol-3-yl) -1(3H) -isobenzofuranone,
3 ', 6 ' -bis [ phenyl (2-methylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -3-one,
3 ', 6 ' -bis [ phenyl (3-methylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -3-one,
3 ', 6 ' -bis [ phenyl (3-ethylphenyl) amino ] -spiro [ isobenzofuran-1 (3H),9 ' - [9H ] xanthen ] -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-methoxy-quinazoline,
4, 4' - (ethylenedioxy) -bis [2- (4-diethylaminophenyl) quinazoline ]
And so on.
In addition, the fluorans may be a compound having a substituent on the phenyl group forming the xanthene ring, and a substituent (for example, an alkyl group such as a methyl group, or a halogen atom such as a chlorine group) on the phenyl group forming the lactone ring, which is substituted on the phenyl group forming the xanthene ring, and which exhibits a blue or black color.
As the electron-accepting compound (b), a hydroxyphenyl acetate compound represented by the general formula (1) is used.
Figure BDA0003282589400000061
In the formula (I), the compound is shown in the specification,
r represents a linear or branched alkyl group having 12 to 22 carbon atoms,
x, Y and Z are each independently hydrogen or hydroxy, two or three of which are hydroxy,
preferably X, Y and Z are both hydroxy groups and one is hydrogen.
Further preferably, X and Y are hydroxyl groups and Z is hydrogen. Specifically, the 3, 4-dihydroxyphenyl acetate compound represented by the general formula (2) is preferable, and is suitable for use because it has a high color density when it develops color.
Figure BDA0003282589400000062
Wherein R is the same as R in the formula (1).
The alkyl group of the hydroxyphenyl acetate compound is a linear or branched alkyl group having 12 to 22 carbon atoms, and preferably a linear or branched alkyl group having 14 to 22 carbon atoms. The compound having an alkyl group having a carbon number of less than 12 or more than 22 is not practical because of low crystallinity. In addition, in consideration of practical performance such as discoloration characteristics and color development density, the linear alkyl group is preferably a linear alkyl group having 12 to 22 carbon atoms, more preferably a linear alkyl group having 16 to 22 carbon atoms, still more preferably a linear alkyl group having 16 to 20 carbon atoms, and still more preferably a linear alkyl group having 16 to 18 carbon atoms.
Examples of the hydroxyphenyl acetate compound include dodecyl 3, 4-dihydroxyphenyl acetate, tridecyl 3, 4-dihydroxyphenyl acetate, tetradecyl 3, 4-dihydroxyphenyl acetate, 2-methyltridecyl 3, 4-dihydroxyphenyl acetate, pentadecyl 3, 4-dihydroxyphenyl acetate, hexadecyl 3, 4-dihydroxyphenyl acetate, 2-ethyltetradecyl 3, 4-dihydroxyphenyl acetate, heptadecyl 3, 4-dihydroxyphenyl acetate, 2-methylhexadecyl 3, 4-dihydroxyphenyl acetate, octadecyl 3, 4-dihydroxyphenyl acetate, 2-methylheptadecyl 3, 4-dihydroxyphenyl acetate, 2-ethylhexadecyl 3, 4-dihydroxyphenyl acetate, and mixtures thereof, Nonadecyl 3, 4-dihydroxyphenylacetate, eicosyl 3, 4-dihydroxyphenylacetate, 2-methylnonadecyl 3, 4-dihydroxyphenylacetate, 2-ethyloctadecyl 3, 4-dihydroxyphenylacetate, heneicosyl 3, 4-dihydroxyphenylacetate, docosyl 3, 4-dihydroxyphenylacetate, dodecyl 3, 5-dihydroxyphenylacetate, tridecyl 3, 5-dihydroxyphenylacetate, tetradecyl 3, 5-dihydroxyphenylacetate, 2-methyltrodecyl 3, 5-dihydroxyphenylacetate, pentadecyl 3, 5-dihydroxyphenylacetate, hexadecyl 3, 5-dihydroxyphenylacetate, 2-ethyltetradecyl 3, 5-dihydroxyphenylacetate, eicosyl 3, 4-dihydroxyphenylacetate, eicosyl 3, 5-dihydroxyphenylacetate, and the like, Heptadecyl 3, 5-dihydroxyphenylacetate, 2-methylhexadecyl 3, 5-dihydroxyphenylacetate, octadecyl 3, 5-dihydroxyphenylacetate, 2-methylheptadecyl 3, 5-dihydroxyphenylacetate, 2-ethylhexadecyl 3, 5-dihydroxyphenylacetate, nonadecyl 3, 5-dihydroxyphenylacetate, eicosyl 3, 5-dihydroxyphenylacetate, 2-methylnonadecyl 3, 5-dihydroxyphenylacetate, 2-ethyloctadecyl 3, 5-dihydroxyphenylacetate, heneicosyl 3, 5-dihydroxyphenylacetate, docosyl 3, 5-dihydroxyphenylacetate. Further, X, Y examples of the substance in which all of Z and Z are hydroxyl groups include dodecyl 3,4, 5-trihydroxyphenyl acetate, tridecyl 3,4, 5-trihydroxyphenyl acetate, tetradecyl 3,4, 5-trihydroxyphenyl acetate, 2-methyltrodecyl 3,4, 5-trihydroxyphenyl acetate, pentadecyl 3,4, 5-trihydroxyphenyl acetate, hexadecyl 3,4, 5-trihydroxyphenyl acetate, 2-ethyltetradecyl 3,4, 5-trihydroxyphenyl acetate, heptadecyl 3,4, 5-trihydroxyphenyl acetate, 2-methylhexadecyl 3,4, 5-trihydroxyphenyl acetate, octadecyl 3,4, 5-trihydroxyphenyl acetate, and the like, 2-methylheptadecyl 3,4, 5-trihydroxyphenylacetate, 2-ethylhexadecyl 3,4, 5-trihydroxyphenylacetate, nonadecyl 3,4, 5-trihydroxyphenylacetate, eicosyl 3,4, 5-trihydroxyphenylacetate, 2-methylnonadecyl 3,4, 5-trihydroxyphenylacetate, 2-ethyloctadecyl 3,4, 5-trihydroxyphenylacetate, heneicosyl 3,4, 5-trihydroxyphenylacetate, etc. Generally, a compound having a high hydroxyl group tends to have a high color density when it develops color.
As a reaction medium for reversibly causing an electron transfer reaction between the component (a) and the component (b), a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons is used.
By using the compound of component (c), the sensitivity to color development by the reaction of component (a) and component (b) is small, and the color development behavior and color density due to heating can be effectively improved.
The higher the number of carbon atoms of the alkyl group in the hydroxybenzoate ester as the component (b) is, the higher the crystallinity tends to be, and thus, a hydroxybenzoate ester having high crystallinity can be used at a discoloration temperature in a low temperature range by adding the component (c).
Examples of the catenated hydrocarbon include saturated catenated hydrocarbons such as pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane and triacontane, unsaturated catenated hydrocarbons such as 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacocene, 1-hexacocene, 1-heptacosene, 1-octacosene, 1-nonacosene and 1-triacontene.
Examples of the alicyclic hydrocarbon include cyclooctane, cyclododecane, n-pentadecylcyclohexane, n-octadecylcyclohexane, n-nonadecylcyclohexane and decahydronaphthalene.
Examples of the halogenated hydrocarbon include 1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane, 1-bromotetradecane, 1-chlorotetradecane, 1-bromopentadecane, 1-bromohexadecane, 1-chlorohexadecane, 1-iodohexadecane, 1-bromoheptadecane, 1-bromooctadecane, 1-chlorooctadecane, 1-iodooctadecane, 1-bromoeicosane, 1-chloroeicosane, 1-bromodocosane, and 1-chlorodocosane.
The following are styrene compounds (d) having a softening point of 5 ℃ or higher and a weight average molecular weight of 200 to 10 ten thousand.
As the styrene compound, a compound having a weight average molecular weight of 200 to 6000 is suitably used.
The weight average molecular weight was measured by GPC (gel permeation chromatography).
Examples of the styrene-based compound include low-molecular-weight polystyrene, styrene- α -methylstyrene-based copolymers, α -methylstyrene polymers, and copolymers of α -methylstyrene and vinyltoluene.
As the low molecular weight polystyrene, those available under the trade name of sanyo chemical industries (ltd.): ハイマー SB-75 (weight average molecular weight 2000), ハイマー ST-95 (weight average molecular weight 4000) and the like.
As the styrene- α -methylstyrene-based copolymer, a product name manufactured by physico-chemical ハーキュレス (ltd.): ピコラスチック A5 (weight average molecular weight 317), ピコラスチック A75 (weight average molecular weight 917), trade name of physicochemical No. ハーキュレス (Strain): ピコラスチック D125 (weight average molecular weight 3000), etc.
The α -methylstyrene polymer may be used under the trade name of physiochemical ハーキュレス (co.): クリスタレックス 3085 (weight average molecular weight 664), クリスタレックス 3100 (weight average molecular weight 1020), クリスタレックス 1120 (weight average molecular weight 2420), and the like.
As the copolymer of α -methylstyrene and vinyltoluene, those having trade names of physiochemical ハーキュレス (strain): ピコテックス LC (weight average molecular weight 950), ピコテックス 100 (weight average molecular weight 1740), and the like.
The styrene-based compounds may be used alone or in combination of 2 or more.
The addition of the component (d) changes the polarity of the compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons as a reaction medium, so that the solubility of the component (b) in the reaction medium decreases and the crystallization of the component (b) proceeds slowly. Therefore, a reversible thermochromic microcapsule pigment (hereinafter, may be simply referred to as a microcapsule pigment) containing a reversible thermochromic composition, which is cooled from a color-developed state to a discoloration-inducing temperature in a temperature-lowering process, is decolorized by leaving it.
The microcapsule pigment of the present invention preferably further comprises (e) a compound having a melting point of 50 ℃ or higher and selected from the group consisting of alcohols, esters, ethers, ketones, acid amides and aromatic hydrocarbons (hereinafter, may be simply referred to as component (e)). The component (e) is exemplified below.
Examples of the alcohols include hexadecane 1-ol, heptadecane 1-ol, octadecane 1-ol, nonadecane 1-ol, eicosane 1-ol, heneicosane 1-ol, docosane 1-ol, tetracosane 1-ol, hexacosane 1-ol, octacosane 1-ol, and triacontane 1-ol.
Examples of the esters include eicosyl laurate, behenyl laurate, ditetradecyl laurate, hexacosanyl laurate, dioctadecyl laurate, cetyl myristate, stearyl myristate, eicosyl myristate, behenyl myristate, ditetradecyl myristate, hexacosanyl myristate, dioctadecyl myristate, myristyl palmitate, cetyl palmitate, stearyl palmitate, eicosyl palmitate, behenyl palmitate, ditetradecyl palmitate, hexacosanyl palmitate, dioctadecyl palmitate, cetyl stearate, stearyl stearate, eicosyl stearate, behenyl stearate, hexacosanyl stearate, distearyl stearate, stearyl stearate, behenyl stearate, docosanyl stearate, distearyl stearate, stearyl stearate, behenyl stearate, and the like, Decyl eicosanoate, undecyl eicosanoate, tridecyl eicosanoate, myristyl eicosanoate, cetyl eicosanoate, stearyl eicosanoate, behenyl eicosanoate, ditetradecyl eicosanoate, hexacosanoic eicosanoate, dioctadecyl eicosanoate, methyl behenate, hexyl behenate, octyl behenate, decyl behenate, undecyl behenate, lauryl behenate, tridecyl behenate, myristyl behenate, cetyl behenate, stearyl behenate, eicosanoyl behenate, behenyl behenate, ditetradecyl behenate, hexacosanoic behenyl behenate, dioctadecyl behenate, distearyl oxalate, behenyl succinate, eicosyl succinate, behenyl acetate, and behenyl acetate, Behenyl succinate, distearyl glutarate, dieicosyl glutarate, behenyl glutarate, dimyristyl adipate, dicetyl adipate, distearyl adipate, eicosyl adipate, behenyl adipate, dicetyl suberate, distearyl suberate, dieicosyl suberate, behenyl suberate, myristyl azelate, dicetyl azelate, distearyl azelate, eicosyl azelate, behenyl azelate, dimyristyl sebacate, dicetyl sebacate, distearyl sebacate, dieicosyl sebacate, behenyl sebacate, ditridecyl 1, 14-tetradecylidene dicarboxylate, dimyristyl 1, 14-tetradecylidene dicarboxylate, Dicetyl 1, 14-tetradecylidene dicarboxylate, dipalmityl 1, 14-tetradecylidene dicarboxylate, distearyl 1, 14-tetradecylidene dicarboxylate, dieicosyl 1, 14-tetradecylidene dicarboxylate, dibehenyl 1, 14-tetradecylidene dicarboxylate, dilauryl 1, 16-hexadecylidene dicarboxylate, ditridecyl 1, 16-hexadecylidene dicarboxylate, dimyristyl 1, 16-hexadecylidene dicarboxylate, dicetyl 1, 16-hexadecylidene dicarboxylate, dipalmityl 1, 16-hexadecylidene dicarboxylate, distearyl 1, 16-hexadecylidene dicarboxylate, dieicosyl 1, 16-hexadecylidene dicarboxylate, dibehenyl 1, 16-hexadecylidene dicarboxylate, Didecyl 1, 18-octadecylenedicarboxylate, dilauryl 1, 18-octadecylenedicarboxylate, ditridecyl 1, 18-octadecylenedicarboxylate, dimyristyl 1, 18-octadecylenedicarboxylate, dicetyl 1, 18-octadecylenedicarboxylate, dipalmityl 1, 18-octadecylenedicarboxylate, distearyl 1, 18-octadecylenedicarboxylate, dieicosyl 1, 18-octadecylenedicarboxylate, dibehenyl 1, 18-octadecylenedicarboxylate, didecyl 1, 20-eicosylenedicarboxylate, dilauryl 1, 20-eicosylenedicarboxylate, ditridecyl 1, 20-eicosylenedicarboxylate, dimyristyl 1, 20-eicosylenedicarboxylate, Dicetyl 1, 20-eicosanedicarboxylate, dipalmityl 1, 20-eicosanedicarboxylate, distearyl 1, 20-eicosanedicarboxylate, dieicosyl 1, 20-eicosanedicarboxylate, dibehenyl 1, 20-eicosanedicarboxylate, trimyristin glycerol, tripalmitate glycerol tristearate, triglyceride nonadecanoate, cholesterol caproate, cholesterol caprylate, cholesterol capriate, cholesterol undecanoate, cholesterol laurate, cholesterol myristate, cholesterol palmitate, cholesterol stearate, cholesterol eicosanoate, cholesterol behenate, and the like.
Examples of the ethers include pentadecyl ether, dihexadecyl ether, dioctadecyl ether, dieicosyl ether, and dieicosyl ether.
Examples of the ketones include dioctyl ketone, dinonyl ketone, diundecyl ketone, ditridecyl ketone, dipentadecyl ketone, diheptadecyl ketone, dinonadecyl ketone, phenyloctyl ketone, phenylundecyl ketone, phenyltridecyl ketone, phenylpentadecyl ketone, and phenylheptadecyl ketone.
Examples of the acid amide include hexyl amide, heptyl amide, octyl amide, nonyl amide, decyl amide, undecyl amide, lauryl amide, tridecyl amide, myristyl amide, palmityl amide, stearyl amide, eicosyl amide, behenyl amide, hexacosyl amide, and octacosyl amide.
Examples of the aromatic hydrocarbons include biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, and trithiophene.
As the component (e), compounds shown in the following tables can be used.
TABLE 1
Figure BDA0003282589400000121
(e) The component (C) is preferably a compound selected from esters, ethers, and aromatic hydrocarbons, and more preferably an aromatic hydrocarbon.
In the case where the component (d) is crystallized during the temperature reduction from the color-developed state to the component (b) and the color is reduced, it may take a long time to completely reduce the color, and the addition of the component (e) can further promote the crystallization and improve the color reduction sensitivity.
(a) The proportions of the components (b), (c) and (d) are dependent on the color density, color change temperature, color change form and the type of each component, but generally the proportions of the components for obtaining desired characteristics are in the following ranges, with respect to 1 part of the component (a), 0.1 to 50 parts, preferably 0.5 to 20 parts of the component (b), 1 to 200 parts, preferably 5 to 100 parts of the component (c), 0.1 to 10.0 parts, preferably 0.5 to 5.0 parts of the component (d), and 0.1 to 5.0 parts, preferably 0.1 to 3.0 parts of the component (e) (the proportions are parts by mass).
The reversible thermal discoloration composition is used in the form of encapsulated microcapsules. This is because the reversible thermal discoloration composition can exhibit the same effect and maintain the same composition under various use conditions because the function thereof is not deteriorated and the heat resistance stability can be maintained even when the reversible thermal discoloration composition is brought into contact with a chemically active substance such as an acidic substance, a basic substance, or a peroxide or other solvent component.
The microcapsule pigment containing the reversible thermal discoloration composition has a particle size of 0.1 to 100 μm, preferably 0.5 to 30 μm, and more preferably 1 to 20 μm, which satisfies the practical use.
The particle size and the average particle size were measured by determining the particle area using an image analysis type particle size distribution measurement software "Mac-view" manufactured by Mountech, calculating the projected area equivalent circle diameter (Heywood diameter) from the area of the particle area, and measuring the particle size and the average particle size of the equivalent particles of the isosphere obtained therefrom. When the particle size of all or most of the particles exceeds 0.2. mu.m, the particle size and the average particle size as equivoluminous equivalent particles can be measured by the Coulter method using a particle size distribution measuring apparatus (product name: Multisizer 4e, manufactured by Beckmann Coulter).
Further, the volume-based particle diameter and the average particle diameter (median particle diameter) can be measured using a laser diffraction/scattering type particle diameter distribution measuring apparatus (apparatus name: LA-300, manufactured by horiba, Ltd.) calibrated based on the value measured using a measuring apparatus using the Coulter method.
Further, each component may be a mixture of 2 or more compounds, and a light stabilizer may be further added in a range not impairing the function.
Examples of the light stabilizer include compounds for inhibiting oxidation reaction, such as ultraviolet absorbers, visible light absorbers, infrared absorbers, antioxidants, carotenes, pigments, amines, phenols, nickel complexes, singlet oxygen quenchers such as thioethers, superoxide anion quenchers such as complexes of oxidative dismutase and cobalt and complexes of oxidative dismutase and nickel, and ozone quenchers, which prevent photodegradation by light due to the excited state caused by photoreaction of the component (a), and the like, and the mixing ratio is 0.3 to 24% by mass, preferably 0.8 to 16% by mass. Among these, a system using an ultraviolet absorber and an antioxidant and/or singlet oxygen quencher in combination is particularly effective for improving light resistance.
Further, an antioxidant, an antistatic agent, a polarity-imparting agent, a thixotropy-imparting agent, a defoaming agent, or the like may be added as necessary to improve the functions.
Further, a dye pigment (non-thermal discoloration) may be generally blended.
The color change characteristics of a microcapsule pigment comprising a reversible thermal discoloration composition comprising components (a), (b), (c), and (d) or components (a), (b), (c), (d), and (e) will be described.
Reversible thermochromic composition exhibiting a decolored state starts from a color development start temperature (T) during heating1) If the temperature of (A) reaches the complete color development temperature (T)2) The reversible thermochromic composition is brought into a complete color-developed state and cooled to a color-fading inducing temperature in the course of temperature reduction, and undergoes color fading upon standing.
T1Preferably 15 to 35 ℃, and more preferably 15 to 27 ℃. T is2Preferably 25 to 50 ℃, and more preferably 25 to 40 ℃.
The reversibly thermochromic microcapsular pigment material is dispersed in a carrier containing an additive as needed to prepare a liquid composition, and thus can be used for (i) a printing ink used for screen printing, offset printing, chromatography printing, gravure printing, coater, pad printing, etc., (ii) a coating material used for brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roll coating, dip coating, etc., (iii) an ink for a writing instrument such as a marker pen, a ball pen, a brush pen, etc., (iv) an ink for a writing instrument, (v) a drawing pigment, (vi) a cosmetic material, or (vii) a reversibly thermochromic liquid composition such as a coloring liquid for fibers.
Examples of the additives include resins, crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, dissolution aids, anti-settling agents, smoothing agents, gelling agents, antifoaming agents, matting agents, penetrants, pH modifiers, foaming agents, coupling agents, humectants, antifungal agents, preservatives, and rust inhibitors.
Examples of the carrier of the liquid composition according to the present invention include an oily carrier containing an organic solvent, and an aqueous carrier containing water and, if necessary, an organic solvent.
Examples of the organic solvent that can be used in the present invention include ethanol, propanol, butanol, glycerol, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiglycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, and the like.
Examples of the liquid composition include a shear thinning liquid composition containing a shear thinning viscosity-imparting agent in a carrier, and an aggregating liquid composition containing a water-soluble polymer aggregating agent in a carrier and suspending a pigment in a slowly aggregated state.
By including the shear thinning agent in the liquid composition, for example, when the ink composition is used, the aggregation and sedimentation of the pigment can be suppressed, and the bleeding of the handwriting can be suppressed, so that a good handwriting can be formed.
Further, when the ink composition containing the shear thinning agent is filled in a ballpoint pen, it is possible to prevent leakage of ink from a gap between the ballpoint and a pen tip when not in use, or to prevent backflow of the ink composition when the writing tip portion is placed upward (upright state).
Examples of the shear thinning viscosity-imparting agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 100 to 800 ten thousand) constituting an organic acid-modified heteropolysaccharide in which monosaccharide is glucose and galactose, guar gum, locust bean gum and a derivative thereof, hydroxyethyl cellulose, alkyl alginate, a polymer having a molecular weight of 10 to 15 ten thousand and containing an alkyl methacrylate as a main component, a thickening polysaccharide having gelling ability extracted from seaweed such as glucomannan, agar, and carrageenan, a benzylidene sorbitol, a benzylidene xylitol, or a derivative thereof, a crosslinkable acrylic polymer, inorganic microparticles, a polyglycerol fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyethylene glycol fatty acid ester, a polyoxyethylene alkyl ether, a polyoxypropylene alkyl ether, a polyoxyethylene alkylphenyl ether, a nonionic surfactant having an HLB value of 8 to 12 such as a fatty acid amide, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene alkyl ether, a polyoxypropylene alkyl ether, a polyoxyethylene alkylphenyl ether, and the like, Salts of dialkyl or dialkenyl sulfosuccinic acid, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.
Examples of the water-soluble polymer coagulant which can be used in the present invention include polyvinylpyrrolidone, polyethylene oxide, and water-soluble polysaccharides.
Examples of the water-soluble polysaccharide include tragacanth gum, guar gum, pullulan, cyclodextrin, and a water-soluble cellulose derivative, and specific examples of the water-soluble cellulose derivative include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose.
When the liquid composition is used as an ink composition to be filled in a ball point pen, it is preferable to prevent abrasion of the ball holder by adding a lubricant such as a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphoric triester such as tris (alkoxycarbonylmethyl) thiophosphoric acid, tris (alkoxycarbonylethyl) thiophosphoric acid, a phosphoric monoester of a polyoxyethylene alkyl ether or a polyoxyethylene alkylaryl ether, a phosphoric diester of a polyoxyethylene alkyl ether or a polyoxyethylene alkylaryl ether, or a metal salt, ammonium salt, amine salt, or alkanolamine salt thereof.
Further, by containing 2, 5-dimercapto-1, 3, 4-thiadiazole and/or a salt thereof, even when the pH of the ink is in an acidic or basic region, dispersion failure and aggregation of the microcapsule pigment which occur after the ink which has been frozen first is thawed can be suppressed, increase in the viscosity of the ink and blurring and lightening of handwriting accompanying the increase can be prevented, and corrosion of the ball can be prevented when the ink is used in a ball-point pen.
In addition, preservatives or fungicides such as (i) acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinylpyrrolidone, polyvinyl alcohol, dextrin, etc., resins for imparting tackiness and tackiness to paper surface, (ii) inorganic salts such as sodium carbonate, sodium phosphate, sodium acetate, etc., and pH adjusters such as organic basic compounds such as water-soluble amine compounds, (iii) rust inhibitors such as benzotriazole, methylbenzotriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, etc., (iv) phenol, sodium salts of 1, 2-benzothiazolin 3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl p-hydroxybenzoate, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine, etc., (v) urea, nonionic surfactants, etc., can be added as necessary, Reduced or non-reduced starch hydrolysate, oligosaccharide such as trehalose, wetting agents such as sucrose, cyclodextrin, glucose, dextrin, sorbitol, mannitol, sodium pyrophosphate, etc., (vi) antifoaming agents, (vii) dispersing agents, (viii) fluorine-based surfactants and nonionic surfactants that improve the permeability of the ink composition.
The reversible thermal discoloration microcapsule pigment may be contained in an amount of preferably 5 to 40% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass, based on the total mass of the liquid composition. When the content of the microcapsule pigment is in the above range, a desired color development intensity can be achieved, and further, when the microcapsule pigment is used as an ink composition, the running property can be prevented from being lowered.
A writing instrument capable of containing the liquid composition according to the present invention will be described. In one embodiment, the writing instrument includes a barrel containing the ink composition and a pen body for guiding out the ink in the barrel. Examples of the pen body include a marker pen body, a ball-point pen body, and a writing pen body. The marker pen body may be a fiber pen tip, a felt pen tip, a plastic pen tip, or the like. The ballpoint pen body may be a ballpoint pen tip.
The microcapsule pigment of the present invention can be combined with a support to form a laminate, and includes a reversible thermochromic layer containing the microcapsule pigment and a support. Further, a molded body containing a microcapsule pigment in a support may be used.
Specifically, the microcapsule pigment can be dispersed in a medium containing a binder as a film-forming material, applied as a reversible thermochromic material such as ink or paint, and formed into a laminate by forming a reversible thermochromic layer on a support such as paper, synthetic paper, cloth, flocked or napped cloth, nonwoven fabric, synthetic leather, plastic, glass, ceramics, wood, stone, or the like, or dispersed in a support to obtain a molded article, by a conventionally known method such as printing means such as screen printing, offset printing, gravure printing, coater, pad printing, transfer printing, etc., brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roll coating, dip coating, etc.
Further, the molded article may be obtained as a material that is kneaded and integrated with a thermoplastic in a molten state.
Specific examples of the product to which the microcapsule pigment is applied include the following.
(1) Toy type
Doll and animal-shaped toys, hair for doll and animal-shaped toys, accessories for doll such as doll, clothes, hat, handbag, shoes, etc., ornamental toys, cloth toys, drawing toys, picture book for toys, puzzle-like educational toys, building block toys, clay toys, flowing toys, spinning tops, kites, musical instrument toys, cooking toys, gun toys, catching toys, background toys, toys imitating vehicles, animals, plants, buildings, foods, etc.,
(2) clothing articles
T-shirt, training clothes, blouse, lady dress, swimsuit, raincoat, ski suit, shoes, shoelace, etc., handkerchief, towel, cloth bag, etc,
(3) indoor decoration
Carpets, curtains, window curtain ropes, tablecloths, bedding fabrics, back cushions, decorative frames, artificial flowers, photo frames and the like,
(4) furniture
Bedding such as bedding, pillow, mattress, etc., lighting equipment, air conditioning and heating equipment, etc.,
(5) ornament (CN)
Finger rings, bracelets, headwear, earrings, hairpins, false nails, ribbons, bowties and the like, clocks, glasses and the like,
(6) stationery
Writing tools, stamping tools, erasers, backing plates, rulers, adhesive tapes and the like,
(7) daily necessities
Cosmetics such as lipstick, eye shadow, nail beauty, hair dye, artificial nail, paint for artificial nail, toothbrush, etc.,
(8) kitchen article
Cups, plates, chopsticks, spoons, forks, pots, frying pans and the like,
(9) others
Calendars, labels, cards, recording materials, various printed matters for forgery prevention, books such as picture books, handbags, packaging containers, embroidery threads, sporting goods, fishing gear, cup mats, musical instruments, pocket warmers, bags such as coolant and purses, umbrellas, transportation means, buildings, temperature detection indicators, teaching tools, and the like.
Examples
Examples 1 to 14
The compositions used for the reversible thermal discoloration compositions of the present invention are shown in the following table.
In addition, the numbers in () in the table represent parts by mass, and the numbers below representing the amounts to be mixed are all parts by mass.
TABLE 2
Figure BDA0003282589400000191
As for component (D) in the table, ピコラスチック A75 is a low molecular weight polystyrene resin having a softening point of 75 ℃ and ピコラスチック D125 is a low molecular weight polystyrene resin having a softening point of 125 ℃ and ピコラスチック A5 is a low molecular weight polystyrene resin having a softening point of 5 ℃.
The compounds 1,2 and 6 described in the component (e) in the table are each compound described in the table exemplifying the component (e).
Each of the reversible thermal discoloration compositions was heated and melted to prepare a compatible body, and then an interfacial polymerization reaction was performed using an epoxy resin and an amine curing agent to obtain a microcapsule pigment in the form of a microcapsule encapsulated in an epoxy resin film.
With respect to the microcapsule pigment, the following measurement samples were prepared, and then the discoloration temperature was measured by the following measurement method.
Measurement sample
As for the discoloration characteristics of the microcapsule pigment, a reversible thermal discoloration ink in which 40 parts of the microcapsule pigment was dispersed in 60 parts of an ethylene-vinyl acetate emulsion was used, and the resulting mixture was printed on high-quality paper by screen printing to obtain a test sample.
Measurement method
The measurement samples of examples 1 to 14 were placed at predetermined positions of a colorimeter [ TC-3600 type colorimeter, Tokyo electrochromatography ], and heated at a rate of 10 ℃/min in a temperature range of 0 ℃ to 40 ℃.
After heating to 40 ℃, the mixture was cooled to the discoloration-inducing temperature and left to be decolorized.
The color change and color development onset temperature (T) of each example were measured1) Complete color development temperature (T)2) The following table shows the color erasing induction temperature and the color density (lightness value) at the time of color development.
TABLE 3
Figure BDA0003282589400000211
Comparative examples 1 and 2
The compositions used for the reversible thermal discoloration compositions are shown in the following table.
In addition, the numbers in () in the table represent parts by mass, and the numbers below representing the amounts to be mixed are all parts by mass.
TABLE 4
Figure BDA0003282589400000212
Each of the reversible thermal discoloration compositions was heated and melted to prepare a compatible body, and then an interfacial polymerization reaction was performed using an epoxy resin and an amine curing agent to obtain a microcapsule pigment in the form of a microcapsule encapsulated in an epoxy resin film.
With respect to the microcapsule pigment, after the following measurement samples were prepared, the discoloration temperature was measured by the following measurement method.
Measurement sample
As for the discoloration characteristics of the microcapsule pigment, a reversible thermal discoloration ink in which 40 parts of the microcapsule pigment was dispersed in 60 parts of an ethylene-vinyl acetate emulsion was used, and the resulting mixture was printed on high-quality paper by screen printing to obtain a test sample.
Measurement method
The measurement samples of comparative examples 1 and 2 were placed at predetermined positions of a colorimeter [ TC-3600 type colorimeter, Tokyo electrochromatography ], and heated at a rate of 10 ℃/min in a temperature range of 0 ℃ to 40 ℃.
After heating to 40 ℃, the resultant was cooled to a discoloration-inducing temperature and left to decolorize.
The color change and color development onset temperature (T) of each example were measured1) Complete color development temperature (T)2) The following table shows the color erasing induction temperature and the color density (lightness value) at the time of color development.
In the table, the smaller the lightness value, the higher the concentration, and the larger the concentration.
TABLE 5
Figure BDA0003282589400000221
Application example 1
A reversible thermal discoloration screen ink was prepared which consisted of 30.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 1, 2.0 parts of a fluorescent pigment (pink color), 50.0 parts of an acrylic resin emulsion, 3.0 parts of an antifoaming agent, and 15.0 parts of a turpentine oil emulsion.
On polyester taffeta, printing was performed by screen printing using a reversible thermochromic screen ink to form a reversible thermochromic layer, and a reversible thermochromic sheet was obtained.
The reversible thermal discoloration sheet shows a purple color when heated to 26 ℃ or higher.
After the reversible thermal discoloration sheet was cooled to 18 ℃, the reversible thermal discoloration sheet appeared pink when it was left to stand.
Application example 2
50.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 2 was uniformly dispersed and mixed in 50.0 parts of a linseed oil based offset ink carrier to prepare a reversible thermal discoloration offset ink.
A reversible thermochromic sheet is obtained by forming a reversible thermochromic layer on high-quality paper by offset printing using the above-mentioned offset ink.
The sheet appeared blue if warmed above 38 ℃.
After cooling the reversible thermal discoloration sheet up to 26 ℃, the reversible thermal discoloration sheet appeared colorless if left to stand.
Application example 3
33.3 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 3, 66.4 parts of a hard liquid epoxy resin, and 0.3 part of a defoaming agent were uniformly dispersed and kneaded to obtain a reversible thermal discoloration epoxy ink, and 20.0 parts of an aliphatic polyamide curable at room temperature was added to the ink, followed by stirring and mixing to prepare a reversible thermal discoloration epoxy ink.
A reversible thermochromic cup was obtained by performing screen printing on the surface of a ceramic cup with a 100-mesh screen made of stainless steel using a reversible thermochromic epoxy ink on a curved surface, and heating and curing at 70 ℃ for 60 minutes to form a reversible thermochromic layer.
The reversible thermochromic cup shows a blue color when heated to 50 ℃ or higher.
After cooling the reversible thermal discoloration cup to 35 ℃, the reversible thermal discoloration cup appeared colorless upon standing.
Application example 4
A carrier composed of 10.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 4, 1.0 part of a fluorescent pigment (pink color), 45.0 parts of a 50% acrylic resin/xylene solution, 15.0 parts of xylene, 23.0 parts of methyl isobutyl ketone, and 6.0 parts of a polyisocyanate-based curing agent was stirred and mixed to prepare a reversible thermal discoloration spray coating.
And spraying and coating a reversible thermal discoloration spraying coating on the whole electric car model to form a reversible thermal discoloration layer, thereby obtaining the reversible thermal discoloration electric car model.
The reversible thermochromic electric car model showed a purple color when heated to 32 ℃ or higher.
After the reversible thermal discoloration electric car model was cooled to 24 ℃, the reversible thermal discoloration electric car model appeared pink after being left to stand.
Application example 5
A carrier composed of 10.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 7, 1.0 part of a blue pigment, 45.0 parts of a 50% acrylic resin/xylene solution, 15.0 parts of xylene, 23.0 parts of methyl isobutyl ketone, and 6.0 parts of a polyisocyanate-based curing agent was stirred and mixed to prepare a reversible thermal discoloration spray coating.
And spraying and coating a reversible thermal discoloration spraying coating on the whole electric car model to form a reversible thermal discoloration layer, thereby obtaining the reversible thermal discoloration car model.
The reversible thermal discoloration automobile model showed purple color when heated to 38 ℃ or higher.
After cooling the reversible thermal discoloration automobile model to 26 ℃, the reversible thermal discoloration automobile model appeared blue upon standing.
Application example 6
50.0 parts of the microcapsule pigment encapsulating the reversible thermal discoloration composition prepared in example 5, 0.04 parts of a yellow pigment, 1000.0 parts of a 12 nylon resin (melting point 178 ℃ C.), and 10.0 parts of an ultraviolet absorber were mixed and dispersed in a Henschel mixer, and then, a reversible thermal discoloration 12 nylon resin pellet (resin composition for reversible thermal discoloration molding) was obtained using an extrusion molding machine.
The reversible thermal discoloration-moldable resin composition was melt-spun to obtain a molded article, i.e., a reversible thermal discoloration-moldable filament.
Hair was planted on the doll head using filaments.
The filaments appear a blue-yellow mixed green color when heated to a temperature of 32 ℃ or higher.
After cooling the filaments to 10 ℃, the filaments appeared yellow upon standing.
Application example 7
30.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 6 was mixed with a carrier composed of 45.0 parts of an acrylic resin emulsion, 1.0 part of an antifoaming agent, and 23.0 parts of dilution water, and the mixture was filtered through a 180-mesh screen to obtain a reversible thermal discoloration spray coating.
A spray gun (bore diameter 0.6mm) was filled with the spray paint to coat the entire surface of the white fabric (support), and then the resultant was dried to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic fabric.
The swimsuit was produced by sewing a fabric.
Swimwear appears blue if warmed above 38 ℃.
After the swimsuit is cooled to 20 ℃, the swimsuit appears white upon standing.
Application example 8
50.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 8 was uniformly dispersed and mixed in 50.0 parts of a linseed oil based offset ink carrier to prepare a reversible thermal discoloration offset ink.
A reversible thermochromic sheet is obtained by forming a reversible thermochromic layer on high-quality paper by offset printing using the above-mentioned offset ink.
The sheet was rubbed with a rubbing tool made of SEBS to generate heat, and the sheet was blue when heated to 32 ℃ or higher.
After the reversible thermal discoloration sheet was cooled to 5 ℃, the reversible thermal discoloration sheet appeared white after being left to stand.
Application example 9
50.0 parts of the microcapsule pigment containing the reversible thermal discoloration composition prepared in example 9 was uniformly dispersed and mixed in 50.0 parts of a linseed oil based offset ink carrier to prepare a reversible thermal discoloration offset ink.
On high-quality paper, offset printing was performed using an offset ink to form a reversible thermochromic layer, thereby obtaining a reversible thermochromic sheet.
Blue in color if warmed above 32 c from the sheet using an electrical heating tool.
After the reversible thermal discoloration sheet was cooled to 24 ℃ and left to stand for a while, the reversible thermal discoloration sheet appeared white.

Claims (11)

1. A reversible thermal discoloration microcapsule pigment having encapsulated therein a reversible thermal discoloration composition comprising:
(a) an electron-donating color-developing organic compound;
(b) an electron-accepting compound which is a hydroxyphenyl acetate compound represented by the following general formula (1);
(c) a compound selected from the group consisting of chain hydrocarbons, alicyclic hydrocarbons and halogenated hydrocarbons as a reaction medium in which an electron transfer reaction between the component (a) and the component (b) reversibly occurs; and
(d) a styrene compound having a softening point of 5 ℃ or higher and a weight average molecular weight of 200 to 10 ten thousand,
and the reversible thermal discoloration composition changes from a decolorized state to a colored state by heating and changes from the colored state to the decolorized state by lowering the temperature,
Figure FDA0003282589390000011
in the formula (I), the compound is shown in the specification,
r represents a linear or branched alkyl group having 12 to 22 carbon atoms,
x, Y and Z are each independently hydrogen or hydroxy, two of them are hydroxy and the remainder are hydrogen, or three of them are hydroxy.
2. The microcapsule pigment of claim 1, both of X, Y and Z being hydroxyl groups, one being hydrogen.
3. The microcapsule pigment of claim 1, X and Y are hydroxyl groups, and Z is hydrogen.
4. The microcapsule pigment according to any one of claims 1 to 3, wherein R is a linear alkyl group having 12 to 22 carbon atoms.
5. The microcapsule pigment according to any one of claims 1 to 4, wherein R is a linear alkyl group having 16 to 20 carbon atoms.
6. The microcapsule pigment according to any one of claims 1 to 5, further comprising (e) a compound having a melting point of 50 ℃ or higher selected from alcohols, esters, ketones, ethers, acid amides, and aromatic hydrocarbons.
7. The microcapsule pigment according to claim 6, wherein the component (e) is a compound selected from the group consisting of esters, ethers and aromatic hydrocarbons.
8. A reversible thermal discoloration liquid composition comprising the microcapsule pigment according to any one of claims 1 to 7, and a carrier.
9. The composition according to claim 8, wherein the microcapsule pigment is contained in an amount of 5 to 40% by mass based on the total mass of the liquid composition.
10. A laminate comprising: a support; a reversible thermochromic layer comprising the microcapsule pigment of any one of claims 1 to 7.
11. A molded article comprising the microcapsule pigment according to any one of claims 1 to 7 in a support.
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