JP2011162791A - Reversible thermochromic coating material or ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reversible thermochromic coating material or an ink composition preventing the browning degradation in color fading which is caused by exposure to light, exhibiting color tone of black or green in coloring and small residual color in color fading. <P>SOLUTION: The reversible thermochromic coating material or the ink composition includes (i) a specific fluoran derivative as an electron donating color development organic compound, (ii) an electron accepting compound and (iii) a microcapsule pigment capsulating a reversible thermochromic composition comprising a reaction medium reversibly causing electron donating-accepting reaction by the components in a specific temperature region and a vehicle. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a reversible thermochromic paint or ink composition. More specifically, a reversible thermochromic paint or ink composition that exhibits a black to green color tone during color development, becomes colorless when decolored, and does not undergo browning (coloring) in a decolored state caused by exposure to light. Related to things.

  Conventionally, a reversible thermochromic composition composed of a compatible solution containing as an essential component a reaction medium that reversibly causes an electron-donating reaction between an electron-donating color-forming organic compound and an electron-accepting compound in a specific temperature range. Several proposals have been disclosed (see, for example, Patent Documents 1 to 5).

Japanese Patent Publication No. 51-44706 Japanese Patent Publication No. 51-44707 Japanese Patent Publication No. 51-44708 Japanese Patent Publication No. 1-29398 Japanese Patent Publication No. 4-17154

In the conventional reversible thermochromic composition described above, the color tone in the colored state is determined by the structure of the electron donating color-forming organic compound used as component (a).
Among them, fluorane derivatives having substituted amino groups at the 2- and 6-positions are widely used as electron-donating color-forming organic compounds capable of exhibiting a black to green color tone.
The reversible thermochromic composition using the above-described conventional fluorane derivative exhibits a sufficient black to green color tone in a colored state, but is susceptible to browning (coloring) when exposed to light in a decolored state, The reversible thermochromic function was impaired.
In particular, when a reversible thermochromic layer is provided on a white or light support using the reversible thermochromic composition, the color-changed aspect is visually recognized by browning (coloring) in the decolored state described above. The change is not surprising and the merchantability is impaired.
The present invention prevents browning (coloring) caused by exposure to light, which could not be achieved with the conventional reversible thermochromic composition described above, and exhibits a good black to green color tone during color development. An attempt is made to provide a reversible thermochromic paint or ink composition using a reversible thermochromic composition that sometimes has little residual color, maintains color density during color development, and prevents browning (coloring) deterioration during decoloring. Is.

（式中、Ｒ_１は水素原子又は炭素数１〜８のアルキル基、Ｒ_２は炭素数１〜８のアルキル基、フェニル基、シクロヘキシル基、テトラヒドロフルフリル基、炭素数１〜８のアルキル基又は炭素数１〜８のアルコキシ基で置換されたフェニル基のいずれかを示す、或いは、Ｒ_１とＲ_２はそれらが結合している窒素原子と共にピロリジノ環、ピペリジノ環、モルホリノ環を形成してもよい）
更には、（ニ）成分として、紫外線吸収剤、酸化防止剤、一重項酸素消光剤、スーパーオキシドアニオン消光剤、オゾン消光剤、赤外線吸収剤から選ばれる一種又は二種以上の光安定剤を添加してなることを要件とする。 As described above, as a result of studying a reversible thermochromic composition that prevents browning (coloring) caused by exposure to light, exhibits black to green color tone at the time of color development, and has little residual color at the time of decolorization, as a result of electron transfer reaction In the coloring system according to (ii), (b) a specific fluorane derivative having a trifluoromethyl group represented by the general formula (1) is applied as an electron-donating color-forming organic compound, and functions as a developer (b) The inventors have found that a system in which an electron-accepting compound and (c) a reaction medium that causes the former color development and decoloration to occur in a specific temperature range satisfy the above requirements, and the present invention has been completed.
That is, the present invention provides (a) an electron donating color-forming organic compound represented by the following general formula (1), (b) an electron-accepting compound, (c) the components (a) and (b). A reversible thermochromic paint or ink composition comprising a microcapsule pigment encapsulating a reversible thermochromic composition composed of a reaction medium that reversibly causes an electron transfer reaction in a specific temperature range and a vehicle is required.

(Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a cyclohexyl group, a tetrahydrofurfuryl group, or an alkyl group having 1 to 8 carbon atoms. Or a phenyl group substituted with an alkoxy group having 1 to 8 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded form a pyrrolidino ring, piperidino ring, morpholino ring Also good)
Furthermore, as the component (d), one or more light stabilizers selected from ultraviolet absorbers, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and infrared absorbers are added. It is a requirement that

In the present invention, a specific fluorane derivative having a trifluoromethyl group is used as an electron-donating color-forming organic compound, which is difficult to prevent with a conventional reversible thermochromic composition and is exposed to light. A microcapsule pigment containing a reversible color-changing composition that exhibits a black to green color tone at the time of color development and little residual color at the time of color removal, and a vehicle A reversible thermochromic paint or ink composition can be obtained.
In addition, by adding a light stabilizer, it is possible to further prevent browning (coloring) deterioration at the time of decoloration caused by exposure to light, maintenance of color density at the time of light irradiation, and at the time of decoloration Prevention of browning (coloring) deterioration can be made permanent.

The components (A), (B), and (C) will be specifically described below.
Specific examples of the (i) fluorane derivative represented by the general formula (1) are as follows:
2-[(3-trifluoromethylphenyl) amino] -6-dimethylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-diethylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-propylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-butylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-amylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-hexylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-heptylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-di-n-octylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-Nn-butylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-Nn-hexylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Nn-butylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Ni-butylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Nn-amylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Ni-amylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Nn-hexylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-Nn-octylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-methylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-N- (4-methylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-Nn-butyl-N- (4-methylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-Nn-hexyl-N- (4-methylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-n-propylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-n-hexylphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-methoxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-N- (4-methoxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-Nn-butyl-N- (4-methoxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-Nn-hexyl-N- (4-methoxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-butoxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-hexyloxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N- (4-octyloxyphenyl) aminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-cyclohexylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-methyl-N-cyclohexylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-pyrrolidinofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-piperidinofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-morpholinofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-N-ethyl-N-tetrahydrofurfurylaminofluorane,
2-[(3-trifluoromethylphenyl) amino] -6-Nn-butyl-N-tetrahydrofurfurylaminofluorane,
2-[(2-trifluoromethylphenyl) amino] -6-diethylaminofluorane,
2-[(2-trifluoromethylphenyl) amino] -6-di-n-butylaminofluorane,
2-[(2-trifluoromethylphenyl) amino] -6-N-ethyl-Ni-amylaminofluorane,
2-[(2-trifluoromethylphenyl) amino] -6-N-ethyl-N- (4-methoxyphenyl) aminofluorane,
2-[(2-trifluoromethylphenyl) amino] -6-N-ethyl-N- (4-methylphenyl) aminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-diethylaminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-di-n-butylaminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-N-ethyl-Ni-amylaminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-N-ethyl-N- (4-methoxyphenyl) aminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-N-methyl-N-cyclohexylaminofluorane,
2-[(4-trifluoromethylphenyl) amino] -6-N-ethyl-N-tetrahydrofurfurylaminofluorane and the like can be mentioned.

As the electron-accepting compound of the component (b), a group of compounds having active protons, a pseudo-acidic compound group (not an acid, but a group of compounds that act as an acid in the composition and cause the component (I) to develop color), There is a group of compounds having electron vacancies.
Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Specific examples are given below.
Phenol, o-cresol, tertiary butyl catechol, nonylphenol, n-octylphenol, n-dodecylphenol, n-stearylphenol, p-chlorophenol, p-bromophenol, o-phenylphenol, 4- (4- (1- Methylethoxyphenyl) sulfonylphenol, 4- (4-butyloxyphenyl) sulfonylphenol, 4- (4-pentyloxyphenyl) sulfonylphenol, 4- (4-hexyloxyphenyl) sulfonylphenol, 4- (4-heptyloxy) Phenyl) sulfonylphenol, 4- (4-octyloxyphenyl) sulfonylphenol, n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate, resorcin, dodecyl gallate,
2,2-bis (4′-hydroxyphenyl) propane,
4,4-dihydroxydiphenyl sulfone,
1,1-bis (4′-hydroxyphenyl) ethane,
2,2-bis (4′-hydroxy-3-methylphenyl) propane,
Bis (4-hydroxyphenyl) sulfide,
1-phenyl-1,1-bis (4′-hydroxyphenyl) ethane,
1,1-bis (4′-hydroxyphenyl) -3-methylbutane,
1,1-bis (4′-hydroxyphenyl) -2-methylpropane,
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,
2,2-bis (4′-hydroxyphenyl) butane,
2,2-bis (4′-hydroxyphenyl) ethyl propionate,
2,2-bis (4′-hydroxyphenyl) -4-methylpentane,
2,2-bis (4′-hydroxyphenyl) hexafluoropropane,
2,2-bis (4′-hydroxyphenyl) n-heptane,
2,2-bis (4′-hydroxyphenyl) n-nonane, and the like.
The compounds having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but their metal salts, aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms and their metal salts, carboxylic acids It may be a compound selected from acid metal salts, acidic phosphate esters and their metal salts, 1,2,3-triazole and derivatives thereof.
Furthermore, a fluoroalcohol compound can also be used, and is exemplified below.
2-hydroxyhexafluoroisopropylbenzene,
1,3-bis (2-hydroxyhexafluoroisopropyl) benzene,
1,4-bis (2-hydroxyhexafluoroisopropyl) benzene,
1,3-bis (2-hydroxymethyl-hexafluoroisopropyl) benzene,
1,3-bis (3-hydroxy-1,1-bistrifluoromethylpropyl) benzene,
1,4-bis (2-hydroxymethyl-hexafluoroisopropyl) benzene,
1,4-bis (3-hydroxy-1,1-bistrifluoromethylpropyl) benzene,
2-hydroxymethyl-hexafluoroisopropylbenzene,
Examples include 3-hydroxy-1,1-bistrifluoromethylpropylbenzene.

The component (c) of the reaction medium that causes the electron transfer reaction by the components (a) and (b) to occur reversibly in a specific temperature range will be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides.
When the above compounds are used for microencapsulation and secondary processing, those having a low molecular weight evaporate out of the capsule system when subjected to a high heat treatment. The above compounds are preferably used.
As the alcohols, aliphatic monovalent saturated alcohols having 10 or more carbon atoms are effective. Specifically, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl Alcohol, heptadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, etc. are mentioned.

  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 monohydric alcohol having an aliphatic and alicyclic or aromatic ring. Esters, aliphatic and alicyclic rings obtained from any combination of esters, aliphatic and alicyclic or aromatic polyvalent carboxylic acids obtained from the above and monohydric alcohols having aliphatic and alicyclic or aromatic rings Or esters obtained from any combination of monovalent carboxylic acid having an aromatic ring and aliphatic and alicyclic or polyhydric alcohol having an aromatic ring, specifically, ethyl caprylate, octyl caprylate, capryl Stearyl acid, myristyl caprate, docosyl caprate, 2-ethylhexyl laurate, n-decyl laurate, myris 3-methylbutyl acid, cetyl myristate, isopropyl palmitate, neopentyl palmitate, nonyl palmitate, cyclohexyl palmitate, n-butyl stearate, 2-methylbutyl stearate, 3,5,5-trimethylhexyl stearate, stearin N-undecyl acid, pentadecyl stearate, stearyl stearate, cyclohexylmethyl stearate, isopropyl behenate, hexyl behenate, lauryl behenate, behenyl behenate, cetyl benzoate, stearyl p-tert-butylbenzoate, dimyristyl phthalate , Distearyl phthalate, dimyristyl oxalate, dicetyl oxalate, dicetyl malonate, dilauryl succinate, dilauryl glutarate, diundecyl adipate, azelaic acid Lauryl, di- (n-nonyl) sebacate, dineopentyl 1,18-octadecylmethylenedicarboxylate, ethylene glycol dimyristate, propylene glycol dilaurate, propylene glycol distearate, hexylene glycol dipalmitate, 1,5-pentane Diol distearate, 1,2,6-hexanetriol trimyristate, 1,4-cyclohexanediol didecyl, 1,4-cyclohexanedimethanol dimyristate, xylene glycol dicaprate, xylene glycol distearate, etc. Can be mentioned.

In addition, esters of saturated fatty acids and branched fatty alcohols, unsaturated fatty acids or branched or substituted saturated fatty acids and esters of fatty alcohols having 16 or more carbon atoms, cetyl butyrate, stearyl butyrate and Ester compounds selected from behenyl butyrate are also effective.
Specifically, 2-ethylhexyl butyrate, 2-ethylhexyl behenate, 2-ethylhexyl myristate, 2-ethylhexyl caprate, 3,5,5-trimethylhexyl laurate, 3,5,5-trimethylhexyl palmitate, 3,5,5-trimethylhexyl stearate, 2-methylbutyl caproate, 2-methylbutyl caprylate, 2-methylbutyl caprate, 1-ethylpropyl palmitate, 1-ethylpropyl stearate, 1-ethylpropyl behenate, 1-ethylhexyl laurate, 1-ethylhexyl myristate, 1-ethylhexyl palmitate, 2-methylpentyl caproate, 2-methylpentyl caprylate, 2-methylpentyl caprate, 2-methylpentyl laurate, 2-stearate Mechi Butyl, 2-methylbutyl stearate, 3-methylbutyl stearate, 1-methylheptyl stearate, 2-methylbutyl behenate, 3-methylbutyl behenate, 1-methylheptyl stearate, 1-methylheptyl behenate, caproic acid 1 -Ethylpentyl, 1-ethylpentyl palmitate, 1-methylpropyl stearate, 1-methyloctyl stearate, 1-methylhexyl stearate, 1,1-dimethylpropyl laurate, 1-methylpentyl caprate, palmitic acid 2-methylhexyl, 2-methylhexyl stearate, 2-methylhexyl behenate, 3,7-dimethyloctyl laurate, 3,7-dimethyloctyl myristate, 3,7-dimethyloctyl palmitate, 3, stearate 7-Jime Luoctyl, 3,7-dimethyloctyl behenate, stearyl oleate, behenyl oleate, stearyl linoleate, behenyl linoleate, 3,7-dimethyloctyl erucate, stearyl erucate, isostearyl erucate, cetyl isostearate, isostearic acid Examples include stearyl acid, 2-methylpentyl 12-hydroxystearate, 2-ethylhexyl 18-bromostearate, isostearyl 2-ketomyristate, 2-ethylhexyl 2-fluoromyristate, cetyl butyrate, stearyl butyrate, and behenyl butyrate. It is done.

  Furthermore, with regard to the color density-temperature curve, there is a large hysteresis characteristic (the shape of the curve plotting the change in color density due to temperature change differs from the case where the temperature is changed from the low temperature side to the high temperature side from the discoloration temperature range. In order to give a color memory and thermal discoloration depending on the temperature change, it is disclosed in Japanese Patent Publication No. 4-17154 previously proposed by the present applicant. Carboxylic acid ester compounds exhibiting a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., for example, carboxylic acid ester containing a substituted aromatic ring in the molecule, carboxylic acid and carbon containing an unsubstituted aromatic ring Esters of aliphatic alcohols of several tens or more, carboxylic acid esters having a cyclohexyl group in the molecule, esters of fatty acids having 6 or more carbon atoms and unsubstituted aromatic alcohols or phenols, 8 or more fatty acids and branched fatty alcohols or esters, dicarboxylic acids and aromatic or branched fatty alcohol esters, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, adipic acid Examples include dicetyl, distearyl adipate, trilaurin, trimyristin, tristearin, dimyristin, and distearin.

Fatty acid ester compound obtained from an odd aliphatic monohydric alcohol having 9 or more carbon atoms and an aliphatic carboxylic acid having an even carbon number, n-pentyl alcohol or n-heptyl alcohol and an even aliphatic carboxylic acid having 10 to 16 carbon atoms A fatty acid ester compound having a total carbon number of 17 to 23 obtained from an acid is also effective.
Specifically, n-pentadecyl acetate, n-tridecyl butyrate, n-pentadecyl butyrate, n-undecyl caproate, n-tridecyl caproate, n-pentadecyl caproate, n-nonyl caprylate, n-undecyl caprylate, N-tridecyl caprylate, n-pentadecyl caprylate, n-heptyl caprate, n-nonyl caprate, n-undecyl caprate, n-tridecyl caprate, n-pentadecyl caprate, n-pentyl laurate, lauric acid n-heptyl, n-nonyl laurate, n-undecyl laurate, n-tridecyl laurate, n-pentadecyl laurate, n-pentyl myristate, n-heptyl myristate, n-nonyl myristate, n-myristate Undecyl, n-tridecyl myristate, N-pentadecyl ristinate, n-pentyl palmitate, n-heptyl palmitate, n-nonyl palmitate, n-undecyl palmitate, n-tridecyl palmitate, n-pentadecyl palmitate, n-nonyl stearate, stearic acid n-undecyl, n-tridecyl stearate, n-pentadecyl stearate, n-nonyl eicosanoate, n-undecyl eicosanoate, n-tridecyl eicosanoate, n-pentadecyl eicosanoate, n-nonyl behenate, n-behenate Examples include undecyl, n-tridecyl behenate, and n-pentadecyl behenate.

As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and 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-pentadecanone 2-octadecanone, 2-nonadecanone, 10-nonadacanone, 2-eicosanone, 11-eicosanone, 2-heneicosanone, 2-docosanone, laurone, stearone and the like.
Further, arylalkyl ketones having a total carbon number of 12 to 24, such as n-octadecanophenone, n-heptadecanophenone, n-hexadecanophenone, n-pentadecanophenone, n-tetradecane. Nophenone, 4-n-dodecanacetophenone, n-tridecanophenone, 4-n-undecanoacetophenone, n-laurophenone, 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-pentylacetofu Non, cyclohexyl phenyl ketone, benzyl -n- butyl ketone, 4-n-butyl acetophenone, n- hexanophenone, 4-isobutyl acetophenone, 1-acetonaphthone, 2-acetonaphthone, cyclopentyl phenyl ketone.

  As ethers, aliphatic ethers having a total carbon number of 10 or more are effective, and include dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, diundecyl ether, didodecyl ether, ditrityl ether. Decyl ether, ditetradecyl ether, dipentadecyl ether, dihexadecyl ether, dioctadecyl ether, decane diol dimethyl ether, undecane diol dimethyl ether, dodecane diol dimethyl ether, tridecane diol dimethyl ether, decane diol diethyl ether, undecane diol diethyl ether, etc. Can be mentioned.

  Acid amides include acetamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide , Erucic acid amide, benzamide, caproic acid anilide, caprylic acid anilide, capric acid anilide, lauric acid anilide, myristic acid anilide, palmitic acid anilide, stearic acid anilide, behenic acid anilide, oleic acid anilide, erucic acid anilide, caproic acid N -Methylamide, caprylic acid N-methylamide, capric acid N-methylamide, lauric acid N-methylamide, myristic acid N-methylamide, palmitic acid N-methylamide, stearic acid N-methylamido , Behenic acid N-methylamide, oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide, palmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide, laurin Acid N-butyramide, myristic acid N-butyramide, palmitic acid N-butyramide, stearic acid N-butyramide, oleic acid N-butyramide, lauric acid N-octylamide, myristic acid N-octylamide, palmitic acid N-octylamide, Stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, palmitic acid N-dodecylamide, stearic acid N-dodecylamide, olei Acid N-dodecylamide, dilauric acid amide, dimyristic acid amide, dipalmitic acid amide, distearic acid amide, dioleic acid amide, trilauric acid amide, trimyristic acid amide, tripalmitic acid amide, tristearic acid amide, trioleic acid Amide, succinic acid amide, adipic acid amide, glutaric acid amide, malonic acid amide, 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, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, succinic acid N-butylamide, adipic acid N- Examples include butyramide, glutaric acid N-butyramide, malonic acid N-butyramide, adipic acid N-octylamide, adipic acid N-dodecylamide, and the like.

  The reversible thermochromic composition of the present invention is a compatible solution containing the components (a), (b) and (c) as essential components, and the ratio of each component is the concentration, color change temperature, color change form and each component. In general, the component ratio for obtaining desired characteristics is (b) component 1 to (b) component 0.1 to 100, preferably 0.1 to 50, (c) ) In the range of components 5 to 100 (all the parts are parts by weight).

If necessary, various light stabilizers can be added to the reversible thermochromic composition of the present invention.
The light stabilizer is contained to prevent photodegradation of the reversible thermochromic composition comprising the components (A), (B), and (C), and is 0.3% relative to 1% by weight of the component (A). It is contained in a proportion of ˜24% by weight, preferably 0.3 to 16% by weight. Of the light stabilizers, the ultraviolet absorber effectively cuts ultraviolet rays contained in sunlight and the like, and prevents light degradation caused by the excited state due to the photoreaction of component (a). Antioxidants, singlet oxygen quenchers, superoxide anion quenchers, ozone quenchers and the like suppress the oxidation reaction caused by light.
The said light stabilizer may be used independently and may be used in combination of 2 or more type.

Next, the light stabilizer [(d) component] applied to the present invention will be specifically exemplified.
As an ultraviolet absorption collector,
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-octoxybenzophenone bis- (2-methoxy-4-hydroxy-5-benzoylphenyl) -methane 2- [2'-hydroxy-3'-5'-di-t-amyl Phenyl] -benzophenone 2-hydroxy-4-dodecyloxy-benzophenone [trade name: Seasorb 103, manufactured by Cypro Kasei Co., Ltd.]
2-hydroxy-4-octadecyloxybenzophenone 2,2′-dihydroxy-4-methoxybenzophenone 2-hydroxy-4-benzyloxybenzophenone 2- [2′-hydroxy-3′-5′-di-t-amylphenyl] -Benzophenone ultraviolet absorbers such as benzophenone.

Phenyl salicylate para-t-butylphenyl salicylate paraoctylphenyl salicylate 2-4-di-t-butylphenyl-4-hydroxybenzoate 1-hydroxybenzoate 1-hydroxy-3-t-butyl-benzoate 1-hydroxy-3-t -Octyl benzoate Salicylic acid ultraviolet absorbers such as resorcinol monobenzoate.

Cyanoacrylate ultraviolet absorbers such as ethyl-2-cyano-3,3′-diphenyl acrylate 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate 2-ethylhexyl-2-cyano-3-phenylcinnamate.

2- [5-t-butyl-2-hydroxyphenyl] -benzotriazole [trade name: Tinuvin-PS, manufactured by Ciba-Geigy Corporation]
2- [5-Methyl-2-hydroxyphenyl] -benzotriazole 2- [2, hydroxy-3,5-bis (a, a-dimethylbenzyl) phenyl] -2Hbenzotriazole 2- [3,5-di- t-butyl-2-hydroxyphenyl] -benzotriazole 2- [3-t-butyl-5-methyl-2-hydroxyphenyl] -5-chlorobenzotriazole 2- [3,5-di-t-butyl-2 -Hydroxyphenyl] -5-chlorobenzotriazole 2- [3,5-di-t-amyl-2-hydroxyphenyl] -benzotriazole [trade name: Tinuvin 328, manufactured by Ciba Geigy Corporation]
Methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol molecular weight 300 [trade name: Tinuvin 1130, manufactured by Ciba-Geigy Corporation]
2- [3-Dodecyl-5-methyl-2-hydroxyphenyl] benzotriazole Methyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate-polyethylene Glycol molecular weight 300
2- [3-tert-butyl-5-propyloctylate-2-hydroxyphenyl] -5-chlorobenzotriazole 2- [2-hydroxyphenyl-3,5-di- (1,1′-dimethylbenzyl) phenyl ] -2H-benzotriazole 2- [2-hydroxy-5-t-octylphenyl] -2H-benzotriazole 2- [3-t-butyl-5-octyloxycarbonylethyl-2-hydroxyphenyl] -benzotriazole [ (Product name: Tinuvin 384, manufactured by Ciba Geigy)
2- [2-hydroxy-5-tetraoctylphenyl] -benzotriazole 2- [2-hydroxy-4-octoxy-phenyl] -benzotriazole 2- [2'-hydroxy-3 '-(3 "4" 5 " 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl] -benzotriazole Benzotriazole-based UV absorbers such as 2- (2-hydroxy-5-t-butylphenyl) -benzotriazole.

Ethanediamide-N- (2-ethoxyphenyl) -N ′-(4-isododecylphenyl)
2,2,4,4-tetramethyl-20- (β-lauryl-oxycarbonyl) -ethyl-7-oxa-3,20-diazodispiro (5,1,11,2) heneic acid-21-one, etc. Examples include oxalic anilide-based ultraviolet absorbers.

As an antioxidant (anti-aging agent)
Dimethyl-1- (2, hydroxyethyl) -4-hydroxy-2,2,6,6, tetramethylpiperidine polycondensate poly [[6- (1,1,3,3-tetramethylbutyl) imino succinate -1,3,5-triazine-2-4-cyyl "" (2,2,6,6-tetramethyl-4-piperidyl) imino "]
2- (3,5-di-t-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-piperidyl sebacic acid]
4-Benzoyloxy-2,2,6,6-tetramethylpiperidine bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate 8-acetyl-3-dodecyl-7,7,9,9- Hindered amine antioxidants such as tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione.

2,6, di-t-butyl-4-methylphenol 2-t-butyl-4-methoxyphenol 2,6-di-t-butyl-4-ethylphenol octadecyl-3- (3,5-di-t -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-t-butyl-4-hydroxybenzyl) benzene tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] -methane 2,2-ethylenebis (4,6-di -T-butylphenol)
Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] -glycol ester 1,3,5-tris (3′5′-di-t-butyl-4 '-Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) -trione Tocophenol 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl Benzyl) isocyanurate 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-t-butyl-4-hydroxy-hydrocinnamamide)
Tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate 2,2,4-trimethyl-1,2-hydroquinone styratephenol 2,5-di-t-butyl-hydroquinone bis ( 2,2,6,6-tetramethyl-4, piperidyl) phenolic antioxidants such as sebacate.

Dilauryl-3,3′-thiodipropionate Dimyristyl-3,3′-thiodipropionate Sulfur-based antioxidants such as distearyl-3,3′-thiodipropionate stearylthiopropylamide.

Tris (2,4-di-t-butylphenyl) phosphite bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite 3,5-di-t-butyl-4-hydroxy-benzylphospha Nate-diethyl ester Triphenyl phosphite Diphenyl isodecyl phosphite Phenyl isodecyl phosphite 4,4'-Butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite Octadecyl phosphite Tris (nonylphenyl) Phosphite diisodecylpentaerythritol diphosphite 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9- Oxa-10-phosphafena Tren-10-oxide 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene cyclic neopentatetraylbis (2,4-di-t-butylphenyl) phosphite cyclic neopentanetetra Irbis (2,6, -di-t-butyl-4-methylphenyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite 2,4-bis- (n-octylthio) ) -6- (4-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Phosphate antioxidants such as octylated diphenylamine and the like.

As a singlet oxygen quencher,
Examples include carotenes, pigments, amines, phenols, nickel complexes, sulfides and the like, such as 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- t-butyl-4-hydroxybenzyl O-ethylphosphonate, nickel 3,5-di-t-butyl-4-hydroxybenzyl O-butylphosphonate, nickel [2 · 2′-thiobis (4-t-octylphenol) Lat)]] (n-butylamine), nickel [2,2'-thio-bi (4-t-octylphenolate)] (2-ethylhexylamine), nickel bis [2,2′-thio-bis (4-t-octylphenolate)], nickel bis [2,2′-sulfone- Bis (4-octylphenolate)], nickel bis [2-hydroxy-5-methoxyphenyl-Nn-butylaldoimine), nickel bis (dithiobenzyl), nickel bis (dithiobiacetyl), and the like.

As a superoxide anion quencher,
Examples include complexes of superoxide dismutase, cobalt, and nickel.

  As the ozone quencher, 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-t-butylphenol), P, P′-diaminodiphenylmethane, 2,2′-methylene-bis (6 -T-butyl-P-cresol), N, N'-diphenyl-P-phenylenediamine, N, N'-diphenylethylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine and the like.

但し、式中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４はアルキル基、Ｘはハロゲン又は水素原子のいずれか、Ｍｅはニッケル、パラジウム、白金のいずれかを示す。

但し、式中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４はアルキル基、Ｘはハロゲン又は水素原子のいずれか、Ｍｅはニッケル、パラジウム、白金のいずれか、Ｘは炭素、酸素、硫黄原子のいずれかを示す。

但し、式中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４はアルキル基、Ｘはハロゲン又は水素原子のいずれか、Ｍｅはニッケル、パラジウム、白金のいずれか、Ｘはハロゲン、又は水素原子を示す。

但し、Ｒは水素原子、アルキル基、フェニル基、アルキル又はアルコキシ置換フェニル基、チエニル基のいずれか、Ｍｅはニッケル、パラジウム、白金のいずれかを示す。

但し、Ｒはアルキル基、Ｘは陰イオンとして過塩素酸塩（ＣｌＯ_４ ⁻）、フッ化ホウ素酸塩（ＢＦ_４ ⁻）、トリクロロ酢酸塩（Ｃｌ_３ＣＯＯ⁻）、トリフルオロ酢酸塩（ＣＦ_３ＣＯＯ⁻）、ピクリン酸塩〔（ＮＯ_３）_３Ｃ_６Ｈ_２Ｏ⁻〕、ヘキサフルオロ砒酸塩（ＡｓＦ_６ ⁻）、ヘキサクロロアンチモン酸塩、（ＳｂＣｌ_６ ⁻）、ヘキサフルオロアンチモン酸塩（ＳｂＦ_６ ⁻）、ベンゼンスルホン酸塩（Ｃ_６Ｈ_５ＳＯ_３ ⁻）、アルキルスルホン酸塩（ＲＳＯ_３ ⁻）、リン酸塩（ＰＯ_４ ^３−）、硫酸塩（ＳＯ_４ ^２−）、塩化物（Ｃｌ⁻）、臭化物（Ｂｒ⁻）のいずれかを示す。
等が挙げられる。 The infrared absorber is a compound having the property of having a maximum absorption in the near-infrared region of 700 to 2000 nm and not having much absorption in the visible region of 400 to 700 nm.

However, R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > in a formula shows an alkyl group, X is either a halogen or a hydrogen atom, Me shows either nickel, palladium, or platinum.

However, in the formula, R ₁ , R ₂ , R ₃ , R ₄ are alkyl groups, X is either halogen or hydrogen atom, Me is nickel, palladium, platinum, X is carbon, oxygen, sulfur atom Indicates either.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups, X is either a halogen or a hydrogen atom, Me is any of nickel, palladium or platinum, and X is a halogen or a hydrogen atom. .

However, R represents a hydrogen atom, an alkyl group, a phenyl group, an alkyl or alkoxy-substituted phenyl group, or a thienyl group, and Me represents any of nickel, palladium, or platinum.

However, R is an alkyl group, X is an anion as a perchlorate (ClO ₄ ⁻ ), a fluoborate (BF ₄ ⁻ ), a trichloroacetate (Cl ₃ COO ⁻ ), a trifluoroacetate (CF ₃ COO ⁻ ), picrate ([NO ₃ ) ₃ C ₆ H ₂ O ⁻ ], hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate, (SbCl ₆ ⁻ ), hexafluoroantimonate (SbF ₆₎ ⁻ ), Benzenesulfonate (C ₆ H ₅ SO ₃ ⁻ ), alkylsulfonate (RSO ₃ ⁻ ), phosphate (PO ₄ ³⁻ ), sulfate (SO ₄ ²⁻ ), chloride (Cl ⁻ ) Or bromide (Br ⁻ ).
Etc.

The reversible thermochromic composition described above is used as a microcapsule pigment encapsulated in microcapsules. This is because the reversible thermochromic composition can be kept in the same composition under the various use conditions and can exhibit the same effects.
By encapsulating in the microcapsule, a chemically and physically stable pigment can be constituted, and the particle diameter of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 30 μm satisfies the practicality.
Microencapsulation includes conventionally known interfacial polymerization methods, in situ polymerization methods, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melt dispersion cooling methods, air suspensions. There are a coating method, a spray drying method, and the like, which are appropriately selected according to the application. Further, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
The light stabilizer may be encapsulated in a microcapsule together with the reversible thermochromic composition, or in the case where it is not encapsulated in the microcapsule, it is added to a vehicle used when applied as a coloring material.
In addition, the light stabilizer can be encapsulated in a microcapsule and added to the vehicle.

The microcapsule pigment encapsulating the reversible thermochromic composition is dispersed in a vehicle containing a resin binder to form a colored layer.
In addition, the color change of a colored layer can also be comprised variously by mixing the appropriate quantity of a non-thermochromic colored dye or pigment.

The microcapsule pigment encapsulating the reversible thermochromic composition is dispersed in various vehicles and printed or coated on a support such as paper, fabric, leather, plastic, etc. in the form of printing ink or paint. You can get things. In addition, as a form of writing ink, characters and figures can be drawn on the support.
Thus, toys (hair for dolls or animal toys, costumes for dolls and stuffed animals), decorations, teaching materials such as writing boards, stationery, textile products, household goods, sports equipment, indoor / outdoor equipment, clothing, various printed materials, etc. , Used in various fields.

The following table shows the composition, color change, and color change temperature of the components (A), (B), and (C) as Examples 1 to 10.
Examples 11 to 14 show the composition, color change, and discoloration temperature of the components (A), (B), (C), and (D).
In addition, the number in () in a table | surface shows a weight part.

Comparative Example As Comparative Examples 1 and 2, the composition, color change, and discoloration temperature using a fluorane derivative having a substituted amino group at the 2-position and 6-position not substituted with a trifluoromethyl group as the component (a) Indicates.

Preparation of reversible thermochromic composition encapsulated in microcapsules In 70 parts of the composition of Example 4, 10 parts of Epon 828 [epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.] was heated and dissolved at 100 ° C. Is dripped into 100 parts of a 10% gelatin aqueous solution and stirred to form fine droplets. A solution prepared by dissolving 5 parts of a curing agent U (an amine adduct of an epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) in 45 parts of water was gradually added to the stirring solution, and the liquid temperature was adjusted. While maintaining at 80 ° C., stirring was continued for about 5 hours to obtain a microcapsule suspension. The microcapsule pigment obtained by centrifuging the microcapsule suspension exhibited a black color at a temperature lower than 15 ° C. and colorless at a temperature higher than 15 ° C., as in the composition of Example 4, and had reversibility.
The compositions of Examples 5 to 14 were also made into microcapsule pigments by the same method as described above.
The obtained microcapsule pigment showed the same color change temperature and color change as the composition, and this aspect change could be repeated.

Production of Reversible Thermochromic Composition Encapsulated in Microcapsules The composition of Comparative Example 2 was made into a microcapsule pigment by the same method as described above. Like the composition of Comparative Example 2, the obtained microcapsule pigment exhibited a black color at less than 15 ° C., became colorless at 15 ° C. or more, and had reversibility.

Light Resistance Test Preparation of Light Resistance Test Sample 10 parts of the reversible thermochromic compositions of Examples 1 to 3 and Comparative Example 1 were accommodated in a bottomed cylindrical glass tube to obtain a test sample.
The reversible thermochromic compositions of Examples 4 to 14 and Comparative Example 2 were synthesized by adding 20 parts of microcapsule pigments containing each composition as a colorant and adding them to 80 parts of a vehicle as an ink. Test samples were obtained by printing on paper.

The test samples were measured with a color difference meter (TC-3600, manufactured by Tokyo Denshoku Co., Ltd.), with the color density before coloring and the whiteness when decoloring before and after light irradiation as lightness values. For Examples 1 to 10 and Comparative Examples 1 and 2, changes in lightness values were measured when irradiated with light for 0, 5, and 10 hours, and Examples 11 to 14 were irradiated for 0, 5, 10, and 20 hours. The change in brightness value over time was measured. In this test, a carbon arc fade meter was used.
The light resistance test results are shown in the following table.

  From the above results, the reversible thermochromic composition used in the present invention and the microcapsule pigment encapsulating the composition not only maintain the color density at the time of light irradiation but also browning (coloring) degradation at the time of decoloration. Excellent light resistance that hardly occurs. On the other hand, all of the comparative examples caused browning (coloring) degradation during decoloring even though the color density at the time of light irradiation was maintained.

Example 15
43.0 parts by weight of microcapsule pigment containing the reversible thermochromic composition prepared in Example 7, 50.0 parts by weight of ethylene-vinyl acetate copolymer resin emulsion, 3.0 parts by weight of antifoaming agent, thickener A reversible thermochromic screen ink was obtained by uniformly stirring and mixing in a vehicle comprising 1.0 part by weight of (sodium alginate), 3.0 parts by weight of a leveling agent and 1.0 part by weight of a preservative.
The screen ink is printed using a 150 mesh screen plate made of polyester to form a reversible thermochromic layer on an 80 μm thick white synthetic paper coated with an adhesive and a 1 mm thick polyethylene foam. A reversible thermochromic writing board was obtained.
When the reversible thermochromic writing board was written with a cold-heat pen filled with cold water, a black handwriting appeared, and the state was maintained at a temperature of less than 32 ° C. When the temperature was raised to 32 ° C. or higher, the black handwriting disappeared and turned white, and this state was maintained at a temperature exceeding 15 ° C. The aspect change could be repeated.
In the writing board, the reversible thermochromic layer of the writing surface did not brown even after lapse of time, and the white reversible surface was maintained when the reversible thermochromic layer was decolored.
In addition, when a reversible thermochromic writing board similar to the above was prepared using the microcapsule pigment encapsulating the reversible thermochromic composition of Comparative Example 2, the initial appearance showed the same change in appearance, but the writing surface over time changed. Since the reversible thermochromic layer was browned and the layer was colored in a decolored state, a clear color change from white to black could not be exhibited, impairing commercial properties.

Example 16
30.0 parts by weight of a microcapsule pigment encapsulating the reversible thermochromic composition prepared in Example 12 was added to 45.0 parts by weight of an acrylate resin emulsion, a water-dispersed light stabilizer (trade name: Cibatex LFN, Nippon Ciba-Geigy) A reversible thermochromic aqueous spray that is uniformly dispersed in a vehicle consisting of 1.5 parts by weight, 1.0 part by weight of an antifoaming agent, and 22.5 parts by weight of diluting water, filtered through a 180 mesh stainless steel screen. A paint was obtained.
Next, the water-based spray paint was partially applied to a polyester white brushed fabric, and then dried to form a reversible thermochromic layer to obtain a reversible thermochromic fabric.
The fabric was sewed to produce a reversible thermochromic stuffed toy in the form of a dog.
When the stuffed animal was brought into contact with a color changing tool filled with cold water at 5 ° C., a black pattern appeared partially, and when left alone, it returned to white again.
In the stuffed toy, the reversible thermochromic layer did not brown after the lapse of time, and the reversible thermochromic layer maintained a white stuffed animal in the decolored state.
Further, when the same reversible thermochromic stuffed toy as described above was prepared using the microcapsule pigment encapsulating the reversible thermochromic composition of Comparative Example 2, the reversible thermochromic layer gradually changed over time, although the same appearance change was initially observed. Was browned, and the layer was colored in a decolored state, so that it was not possible to show a clear color change from a white stuffed animal to a stuffed animal with a black pattern on a white background, which impaired commerciality. .

Example 17
30.0 parts by weight of the microcapsule pigment encapsulating the reversible thermochromic composition prepared in Example 14 was added to 40.0 parts by weight of an acrylic resin / xylene solution, 20.0 parts by weight of xylene, and 20.0 parts of methyl isobutyl ketone. A reversible thermochromic oil-based spray coating was obtained by stirring and mixing in a vehicle consisting of 10.0 parts by weight of an isocyanate-based curing agent.
The reversible thermochromic oil spray paint was partially applied to a bear-shaped molding and then dried to form a reversible thermochromic layer to obtain a reversible thermochromic animal toy.
When cold air was blown onto the toy, a black pattern appeared partially and the appearance of the panda was visually recognized, and the state was maintained at a temperature of less than 32 ° C. Moreover, when warm air was blown and heated to 32 ° C. or higher, the black handwriting disappeared and turned white, and the appearance of a white bear was visually recognized. This state was maintained at a temperature exceeding 15 ° C. The aspect change could be repeated.
In the animal toy, the reversible thermochromic layer did not brown even after lapse of time, and the appearance of a white bear was maintained when the reversible thermochromic layer was decolored.
In addition, when a reversible thermochromic animal toy similar to that described above was prepared using the microcapsule pigment encapsulating the reversible thermochromic composition of Comparative Example 2, the reversible thermochromic color changes with time, although initially the same change in appearance was exhibited. Since the layer was browned and the layer was colored in a decolored state, it was not possible to show a clear color change from white bear to panda, which impaired commercial properties.

Claims (2)

(A) As an electron-donating color-forming organic compound, a fluorane derivative represented by the following general formula (1), (b) an electron-accepting compound, (c) an electron transfer reaction by the components (a) and (b) above is specified. A reversible thermochromic paint or ink composition comprising a microcapsule pigment containing a reversible thermochromic composition comprising a reaction medium reversibly occurring in a temperature range and a vehicle.

(Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₂ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a cyclohexyl group, a tetrahydrofurfuryl group, or an alkyl group having 1 to 8 carbon atoms. Or a phenyl group substituted with an alkoxy group having 1 to 8 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom to which they are bonded form a pyrrolidino ring, piperidino ring, morpholino ring Also good) (D) As a component, an ultraviolet absorber, an antioxidant, a singlet oxygen quencher, a superoxide anion quencher, an ozone quencher, or an infrared absorber is added, or two or more light stabilizers are added. The reversible thermochromic paint or ink composition according to claim 1.