JPS6031235B2 - thermochromic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermochromic material having the composition as described in the claims.

The present inventor studied the star color caused by the reaction between an electron-donating pyrophic organic compound and a compound having a phenolic hydroxyl group, and by adding an aromatic hydrocarbon solvent to these and mixing them homogeneously, Any color can be changed at any temperature by adding and homogeneously mixing a compound selected from alcohols, esters, ketones, ether thiols, sulfides, disulfides, sulfoxides, and sulfones. I gained new knowledge that it is possible.

Furthermore, this change is a marked change from reversibly colored to colorless, from colorless to colored, and from reversibly colored (1) to colored (0), while reversibly changing the base as desired. As it has the characteristic of being able to hide and reveal things, we discovered that by combining it with other materials and techniques, it could become an extremely superior and useful thermochromic material.As a result of further research, we discovered that , has completed the present invention.

Conventionally, metal salt crystals having special thermochromic properties have been used as thermochromic materials.

However, this metal salt crystal has a discoloration temperature range of substantially 5.
000 to several hundred degrees (00), and most of them are over 10,000 degrees, and there are no discoloration substances in the daily life temperature range, so there are restrictions on the uses. In addition, the color and color change temperature of this type of tsuba salt cannot be freely selected, and must depend on the properties of the salt material itself. In other words, the types of substances that change color at 10,000 or less are limited to 2 to 3, and the color change is from yellow to deep blue at 50°C with the compound Ag2Hg14, and from red at 7000 with the compound CrHg14. It changes to brown, and of course it is not possible to choose the type of color, and the discoloration is very similar and not clear.

Furthermore, metal salt crystals have no light transmittance and cannot hide or reveal the underlying layer. Furthermore, many of the complex salts with this kind of properties contain heavy metals, and in particular, substances that change color at 100 qo or less contain mercury, as mentioned above, so when using them, it is necessary to be careful about the dangers of mercury, and at the same time, it is a source of pollution. Therefore, the use of large amounts of this substance was extremely inconvenient. The other thermochromic material, liquid crystal, has a color change temperature range of approximately -10°C to 120°C.
There are only one or two types of liquid crystals that change color, especially at temperatures below 0°C. Furthermore, the color and color change temperature cannot be freely selected and must depend on the properties of the liquid crystal material itself.
That is, if you want to find a substance that has the required color and color change temperature, there is no other way than to select it from among the substances that have been synthesized in the past or to obtain a substance that will be synthesized in the future. On the other hand, this kind of material has the disadvantage that it is chemically extremely sensitive and its effectiveness deteriorates when it comes into contact with other substances.Furthermore, cholesteric liquid crystal requires a black base, so it is only possible to obtain a material with a dark tone. Considering this fact and the fact that this type of compound is extremely expensive, the use of this type of compound as a thermochromic dye is a major constraint, and is extremely inconvenient in terms of application development. A large number of applications have been considered in the past that utilize the phenomenon of color change due to temperature, but there has been a lack of suitable materials, and the development of a material with excellent thermochromic properties has been awaited.

Therefore, the present invention provides a completely new type of thermochromic material that solves the various drawbacks mentioned above.

That is, the basic thermochromic material constituting the present invention consists of a compound selected from (a) an electron-donating color-forming organic compound, a compound having a low phenolic hydroxyl group, and an aromatic hydrocarbon solvent. Alternatively, the composition comprising a compound selected from alcohols, esters, ketones, ether thiols, sulfides, disulfides, sulfoxides, and sulfones has a discoloration temperature range of approximately 10,000 to 10,000. At 1200 qo, it sufficiently covers the daily life temperature range.

In addition, the ability to change color at temperatures below 0°C, especially minus several tens of degrees (°C), is a major feature not seen in conventional thermochromic pigments, allowing thermochromic pigments to be expanded to low-temperature industries. The contribution to industrial safety and convenience is extremely large. Furthermore, the greatest feature of the thermochromic material according to the present invention is that the combination of the temperature at which it changes color and the type of color can be freely selected. In other words, the above
It is possible to select a color based on the ingredients, determine the color development and concentration using the raw ingredient, and then determine the discoloration temperature point based on the type or amount of the compound selected from the white ingredient or the black ingredient.

In other words, it is possible for the substance to change from colored to colorless, and from colorless to colored, to red, blue, yellow, green, light, purple, black, and other subtle colors depending on the color scheme at a temperature of about 100q0 to 200q0. This is possible by appropriately combining the following. Specifically, for example, electron-donating star-colored organic compounds 1. Part by weight of bisphenol A 2. Parts by weight of aromatic hydrocarbon solvent 500. When the type of aromatic hydrocarbon solvent is changed in the weight part of the formulation, the discoloration temperature changes as follows.

In this case, there is no change in the discoloration temperature depending on the type of electron-donating organic compound. Furthermore, a desired color change temperature can be selected by using two or more aromatic hydrocarbon solvents in combination.

The physical properties of the isomer mixtures in the table are listed on the next page.

Dibenzyltoluene isomer mixture specific gravity
1.03k9′〆(20qo) pour point
-3y0 viscosity 3 mother st(
2000) Vapor pressure side Hg/200
q010 Specific Hg/305℃76°Hg/390% Inpropyl diphenyl isomer mixture specific gravity 0.979 (25o0) Pour point -5?0 Viscosity
4. &st(38qo)1.4CSt(9 tsubo○
) Vapor pressure 3.1 skin Hg/121008
2,8 rib Hg/204q.

76 Hg/294~301℃ Hydrogenated triphenyl isomer compound specific gravity 1.001~1.007 (25qo
/15.5℃) Pour point
-2 is 0 viscosity 7 ratio st (000) 2 $st (3800) vapor pressure
2.6 side Hg/150pm C22 side Hg/
2000095 side Hg/250℃ Refractive index n customer 1.560-1.5
75-propylnaphthalene isomer mixture specific gravity
0.96 (1500/4℃) pour point
-30qo or less Viscosity 6.0~6
．． &st (40℃) Vapor pressure 2.8 skin Hg/60q060 arm Hg/2000076Q cape Hg/
30,000 Here, by selecting the electron-donating color-forming organic compounds as follows, for example, crystal violet lactone (blue), rhodamine B lactam (red), 3-diethylamino-6-methyl-7-chlorofluoran (vermilion),
3-jethylamino-5-methyl-7-dibenzylaminofluorane (green), 6-bismethoxyfluorane (yellow), 3-jethylamino-6-methyl-7-p-n-octylanilinofluorane (black) ), etc., each color can be obtained.

As described above, the present invention allows the color and color change temperature point to be freely selected in the thermochromic material. Therefore, when looking for a substance with the required color and color change temperature, such as conventional thermochromic materials, there is no choice but to select it from among substances synthesized in the past or wait for substances to be synthesized in the future. Compared to the above, the present invention is a thermochromic material with a great degree of freedom in material selection, which has not been seen in the past.

Further, the color change is reversible and very noticeable from colored to colorless and from colorless to colored, which is different from conventional thermochromic pigments.

However, it is also possible to reversibly change from colored (1) to colored (b) by adding general dyes, pigments, etc. to the thermochromic material. On the other hand, the ability to transmit or hide light is also a major feature of the present invention. These features are shown in the performance comparison table. The composition of the present invention depends on the concentration, temperature of discoloration, form of discoloration, and type of each compound, but the composition of the present invention is based on the composition of the ingredients.

~10 state components and occupations' each approximately 10~1000 (
A range of weight ratios) is usually sufficient to obtain the desired properties. Both the first component and the circular component have the effect of determining the color change temperature of the thermochromic material as described above, but the second component, that is, the aromatic hydrocarbon solvent brushing component, alcohols, esters, etc. , ketones, ethers, thiols, sulfides, disulfides, sulfoxides, and sulfones.

That is, since many aromatic hydrocarbon solvents are liquid even at room temperature, it is possible to obtain a liquid thermochromic material that can have any color selected at any temperature, unlike any other solvent. We also provide a wide variety of materials that change color at low temperatures ranging from 0°C to several tens of degrees below zero in terms of thermochromic properties.

On the other hand, aromatic hydrocarbon solvents generally have no 'I' component and have an extremely excellent ability to dissolve electron-donating, color-forming organic compounds, so they are very convenient in terms of performance and production.
However, although aromatic hydrocarbon solvents have the above-mentioned properties when used as a component of thermochromic materials, they actually have fewer types and number of compounds compared to the compounds used as ingredients, so the discoloration temperature may be slightly affected. When it is desired to adjust the temperature to or even more broadly, it may be effective to coexist the first and eighth components.

In addition, many of the components [〇}, that is, compounds having a phenolic hydroxyl group, have relatively high polarity, and the aromatic hydrocarbon solvent alone may not have sufficient dissolving power. By taking advantage of the characteristics of the dissolving power of both, it is possible to dissolve the [i' and 'ol components very well, which is extremely convenient in terms of performance and production, and it is possible to obtain an even better thermochromic material. . On the other hand, t is also small to improve performance. ) Of course, two or more types of each component can be mixed together. As described above, the thermochromic material of the present invention has excellent characteristics not seen before, and furthermore, considering that it does not contain substances harmful to humans and animals and is inexpensive, it is suitable for use in various daily life materials, industrial applications, etc. It can be said to be an extremely excellent and useful thermochromic material when applied to industrial materials and other uses.

Next, the electron-donating color-forming organic compound used in the present invention is substantially colorless, and becomes star-colored when it reacts with an electron acceptor (Lewis acid) such as acidic clays or phenyls. These include diarylphthalides, polyarylcarbinols, leucouramines, acylouramines, arylauramines, rhodamine B lactams, indolines, spiropyrans, fluorans, and the like.

Examples of these compounds are shown below.

Crystal Violet Lactone, Malachite Green Raccoon, Michler Hydrol, Crystal Violet Carbinol, Malachite Green Carbinol, N
-(2,3-dichlorophenyl)leucoauramine, N
-Penzoyluramine, Rhodamine B-lactam, N-
Acetyl auramine, N-phenyl auramine, 21 (
(phenyliminoethanezylidene)-13,3-dimethylindoline, N-3,3-trimethylindolinobenzospiropyran, 8-methoxyN-3,3-trimethylindolinobenzospiropyran, 3-diethylamino-6
-Methyl-7-chlorofluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-
Penzyloxyfluorane, 1,2-bento-6-diethylaminofluorane, 3,6-di-P-toluidino 4,5-dimethylfluoran-phenylhydrazide-y
-lactam, 3-amino-5-methylfluorane, 2-methyl-3-amino-6-methyl-7-methylfluorane, 2,3-butylene-6-d-n-butylaminofluorane, 3-diethylamino-7- Anilinofluorane, 3-diethylamino-7-(para-toluidino)-fluorane, 7-acetamino-3-diethylaminofluorane, 2-from-6-cyclohexylaminofluorane, 2,7-dichloro-3-methyl-6-n- Butylaminofluorane, 3-diethylamino-6-methyl-7
-n-butylanilinofluorane, etc.

Examples of compounds having a phenolic hydroxyl group that can be used as electron acceptors for the electron-donating color-forming organic compound include "
There are monophenols to polyphenols, and their substituents include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, and halogens.

Examples of these compounds are shown below. Tertiary butylphenol, nonylphenol, dodecylphenol, styrene phenol, 2,2-methylenebis-
(4-methyl-6-tert-butylphenol),
Q-naphthol, 8-naphthol, hydroquinone monomethyl ether, guaiacol, eugenol, p-chlorophenol, p-bromophenol, o-chlorophenol, o-bromophenol/shi, ○-phenylinolephenol, p-phenylene 'Lephenol, p-cp-chlorophenyl)-phenol, o-(o-chlorophenyl)-phenol, methyl p-oxybenzoate, ethyl p-oxybenzoate, propyl p-oxybenzoate, p
-butyl oxybenzoate, octyl p-oxybenzoate, dodecyl p-oxybenzoate, 3-isopropylcatechol, p-tertiarybutylcatechol, 4,4-
Methylene diphenol, 4,4-thiobis-(6-tert-butyl-3-methylphenol), 111-bis-(4-hydroxyphenyl)-cyclohexane,
4,4-butylidene-bis-(6-tert-butyl-3-methylphenol), bisphenol A, bisphenol S, 1,2-dioxynaphthalene, 2,3-dioxynaphthalene.

Lucatechol, furomocatechol, 2,4-dihydroxybenzophenone, phenolphthalein, o-cresol phthalein, methyl protocatechuate, ethyl protocatechuate, propyl protocatechuate, octyl protocatechuate , dodecyl protocatechuate, 2,4,6-trioxymethylbenzene, 2,3,4
-trioxyethylbenzene, methyl gallate, ethyl gallate, propyl gallate, butyl gallate, hexyl gallate, octyl gallate, dodecyl gallate, cetyl gallate, stearyl gallate, 2, 3, 5- These include trioxynaphthalene, tannic acid, phenolic resin, etc. As the aromatic hydrocarbon solvent, the following [A] or [B]
] There are compounds represented by the general formula.

[A] [R: hydrogen, cyclohexyl group, or carbon number 1
-18 alkyl group R': Alkylene having 1 to 18 carbon atoms with or without an aralkyl group or aryl group as a substituent R'', R river: hydrogen, cyclohexyl group, alkyl group having 1 to 18 carbon atoms, respectively , aralkyl group or aryl group k, 1, m, n: 0, 1, 2, 3] [B] [R: hydrogen, alkyl group having 1 to 18 carbon atoms, aralkyl group, aryl group R: hydrogen, Alkyl group, aralkyl group, aryl group having 1 to 18 carbon atoms ×: benzene ring, cyclohexyl ring, or cyclobentyl ring m, n: 0, 1,
2, 3, 4] Examples of these compounds are shown below.

Isopropylbenzene, amylbenzene, mesitylene,
Cymene, 5-methyl-3-isobutyltoluene, dodecylbenzene, cyclohexylbenzene, piphenyl, methylbiphenyl, ethylbiphenyl, inpropylbiphenyl, diethylbiphenyl, trimethylbiphenyl,
Dimethylpropylbiphenyl, cyclohexylbiphenyl, benzylbenzene, phenyltolylmethane, xylyl phenylmethane, ditolylmethane, dicumenylmethane, trioctyldiphenylmethane, tribentyldiphenylmethane, tolylxylmethane, dixyllymethane, diphenylethane, tolylph enylethane, xylyl phenylethane, ditolylethane, dixylylethane,
Ethylxylyl phenylethaso, phenyl isopropylphenylethane, ethyl phenyl dimethyl phenylethane, tolyldiisopropylphenylethane, trimethylisopropylphenylethane, diphenylpropane, ditolylpropane, dixylylpropane, phenyltolyl Propane, phenylxylylpropane, tolylxylylpropane, dibenzylbenzene, dioctylbenzylbenzene, dioctylbenzylethylbenzene, dibenzyltoluene, bis-(dimethylbenzyl)-benzene,
Dibenzyloctylbenzene, Pis(dimethylbenzyl)-octylbenzene, Bis(o-methylbenzyl)-benzene, Bis(Q-methylbenzyl)-toluene, Bis(Q-methylbenzyl)-ethylbenzene,
Bis(o-methylbenzyl)-isopropylbenzene, bis(2-Q-dimethylbenzyl)-benzene, bis(2-Q-dimethylbenzyl)-toluene, bis→
(2.4.Q-trimethylbenzyl)-benzene, methylnaphthalene, dimethylnaphthalene, propylnaphthaliso, allylnaphthalene, butylnaphthalene, methyltetraline, inpropyltetraline, butyltetraline,
Tetrahydronaphthylphenylmethane, tetrahydromethylnaphthylphenylethane, tetrahydronaphthylphenylethane, naphthylphenylmethane, methylnaphthylphenyl ethane, 1,1,3-trimethyl-3-phenylindane, 1,1,3-trimethyl-3-tolylindane , etc.

However, the above compound includes a mixture with isomers. Alcohols include monohydric alcohols, polyhydric alcohols, and their derivatives.

Examples of these compounds are shown below. n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n
-Lauryl alcohol, n-myristyl alcohol, n
- Cetyl alcohol, n-stearyl alcohol, n-icosyl alcohol, n-docosyl alcohol, n-
Mericyl alcohol, isocetyl alcohol, isostearyl alcohol, indococyl alcohol, oleyl alcohol, cyclohexanol, cyclobentanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol , butylene glycol, hexylene glycol, cyclohexane-1,4-diol, trimethylolpropane, 1,2,6-hexanetriol, bentaerythritol, sorbitol, mannitol, and the like.

Examples of esters include the following compounds.

Amyl acetate, octyl acetate, butyl propionate, octyl propionate, phenyl propionate, ethyl caproate, amyl caproate, ethyl caprylate, amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl laurate, Ethyl laurate, butyl laurate, hexyl laurate, octyl laurate, dodecyl laurate, myristyl laurate, cetyl laurate, stearyl laurate, methyl myristate, ethyl myristate, butyl myristate, hexyl myristate, Octyl myristate, lauryl myristate, myristyl myristate, cetyl myristate, stearyl myristate, methyl palmitate, ethyl palmitate, butyl palmitate, hexyl palmitate, octyl palmitate, lauryl palmitate, myristic palmitate, palmitate Cetyl acid, stearyl palmitate, methyl stearate, ethyl stearate, butyl stearate, hexyl stearate, octyl stearate, lauryl stearate, myristic stearate, cetyl stearate, stearyl stearate, methyl behenate, Ethyl behenylate, propyl behenylate, butyl behenylate,
Ethyl benzoate, butyl benzoate, amyl benzoate, phenyl benzoate, ethyl acetoacetate, methyl oleate, butyl oleate, butyl acrylate, jetyl oxalate, dibutyl oxalate, jetyl malonate, dibutyl malonate, diptyl tartrate , dibutyl sebatate, dimethyl sebatate, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibutyl fumarate, jetyl maleate, dibutyl maleate, triethyl citrate, 12-hydroxystearic acid triglyceride, castor oil, dioxystearin Examples include methyl ethyl acid, methyl 12-hydroxystearate, and the like.

The following compounds are exemplified as ketones.

Diethyl ketone, ethyl butyl ketone, methylhexyl ketone, diacetone alcohol, medityl oxide, cyclohexanone, methylcyclohexanone, acetophenone, fluorine.

Examples include lopiophenone, penzophenone, 2,4-bentanedione, acetonylacetone, ketone wax, and the like. The following compounds are exemplified as ethers. Butyl ether, hexyl ether, diisopropyl benzyl ether, diphenyl ether, dioxane, ethylene glycol diptylene ether, diethylene glycol dibutyl ether, ethylene glycol diethyl ether,
Examples include diethylene glycol diethyl ether, ethylene glycol diphenyl ether, and ethylene glycol monophenyl ether. Examples of thiol compounds are shown below.

n-decyl mercaptan, n-dodecyl mercaptan,
n-myristyl mercaptan, n-cetyl mercaptan, n-stearyl mercaptan, indodecyl mercaptan, isomyristyl mercaptan, isocetyl mercaptan.

mercaptan, dodecylbenzyl mercaptan, etc. Examples of sulfide compounds are shown below. G-n-octyl sulfide, G-n-nonyl sulfide, G-n-decyl sulfide, G-n-dodecyl sulfide, G-n-myristyl sulfide, G-n-cetyl sulfide, G-n-stearyl sulfide hydrodehyde, decyl sulfide, octyldodecyl sulfide, diphenyl sulfide, dibenzyl sulfide, ditolyl sulfide, diethyl phenyl sulfide, 4,4-dichlorodiphenyl sulfide , dilaurylthiodip.

pionate, distearylthiodipropionate, etc. Examples of disulfide compounds are shown below.

G-n-decyl disulfide, G-n-dode, sil disulfide, G-n-myristyl disulfide, G-n-cetyl disulfide, G-n-stearyl disulfide, diphenyl disulfide, dibenzyl disulfide,
Ditolyl disulfide, dinaphthyl disulfide, 4.
4-dichlorodiphenyl disulfide, etc.

Examples of sulfoxide compounds are shown below.

Examples include dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide, and the like.

Examples of sulfone compounds are shown below.

Diethyl sulfone, dibutyl sulfone, methylphenylsulfone, diphenyl sulfone, ditolyl sulfone, dibutyl phenyl sulfone, dibenzyl sulfone, 4.4
'-dichlorodiphenyl sulfone, etc.

On the other hand, as described above, the thermochromic material of the present invention has a liquid composition at room temperature, and this characteristic can be utilized for various purposes.

However, in order to further expand its uses, the present invention can be made even more useful by encapsulating the composition using known microencapsulation techniques. That is, thermochromic materials that change to various colors at various temperatures can be placed close to each other and yet maintain their effects independently. To be more specific, for example, {1} Thermochromic material that changes from yellow to colorless at 1,000 2) Thermochromic material that changes from blue to colorless at 2,000 Thermochromic material '3' Changes from red to colorless at 3,000 When using three types of thermochromic materials, '1}'
When 2'{3} is simply mixed, it becomes a thermochromic material that changes color from black to colorless in the vicinity of 10 to 2000 with no sharpness.

Because there is no isolation layer, the thermochromic materials in the two legs interact with each other, resulting in only one mixed color and lack of sensitivity in color change. Here, add 30 m(2}(3} of thermochromic material)
When mixing a thermochromic material encapsulated in microcapsules smaller than 10 mm, the thermochromic properties are black at 10 mm or lower, black at 1000 mm or lower.
Purple at ~2000, red at 20oC ~3000, 3000
At above, it changes to colorless, and when it is cooled from 3000 or higher, it changes from colorless to red to purple to black, and even more various changes are possible based on the above principle.

Moreover, the change is also very sharp. This is one of the useful characteristics of the present invention because each thermochromic material operates independently by being encapsulated in microcapsules. moreover,
Since it is protected by the capsule wall, its thermochromic performance does not deteriorate even when it comes into contact with highly reactive substances as well as with each other, and therefore has an extremely wide range of applications. For example, even if it comes into contact with chemically active substances such as acidic substances, alkaline substances, and peroxides, the thermochromic performance will not deteriorate.

Known microencapsulation techniques used in the present invention include interfacial polymerization, insi polymerization, submerged coating, phase separation from an aqueous solution, phase separation from an organic solution, and melt-dispersion cooling. method, air suspension coating method, spray drying method, etc., and can be appropriately selected and used depending on the purpose.

On the other hand, if desired, substances such as antioxidants, anti-aging agents, and ultraviolet absorbers can be used in combination with the thermochromic material. Examples of antioxidants and anti-aging agents include 2.6-
Ditertiarybutyl-4-methylphenol, 2.4
・6-Tritertiarybutylphenol, styrenated phenol, 2,2-methylenebis(4-methyl-6
-tertiarybutylphenol), 4,4-isopropylidene-bis-phenol, 2,6-bis(2'-hydroxy-3'-tertiarybutyl-5-methylbenzyl)-4-methylphenol, 4,4-thiobis-phenol (3-methyl-6-tert-butylphenol),
Tetrakis[methylene-(3,5-ditertiarybutyl-4-hydroxyhydrocinnamate)]methane, p-hydroxyphenyl-8naphthylamine, 2.
Examples include 2,4-trimethyl-1,2-dihydroquinoline, thiobis-(B naphthol), mercaptobenzothiazole, mercaptobenzimidazole, aldol-Q naphthylamine, and the like.

Examples of ultraviolet absorbers include benzophenone, salicylate, benzotriazole, and substituted acrylonitrile. For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-toxybenzophenone, 2-hydroxy -4-octoxybenzophenone,
2-hydroxy-4dodecyloxybenzophenone,
2-Hydroxy-4-octadecyloxybenzophenone, phenyl salicylate, paratertiary phenyl salicylate, paraoctylphenyl salicylate, 2
-(2'-Hydroxy-5-methyl-phenylphenyl)penzotriazole, 2-(2'-hydroxy-3,5-dithyalyphenyl)penzotriazole, 2-
(2'-hydroxy-3-tert-butyl-1,6
-methylphenyl)-5-chlorobenzotriazol,
2-(2'-Hydroxy-3',5'-ditertiarybutylphenyl)-5-chlorobenzotriazole, 2
-(2-hydroxy-4'-octaoxy-phenyl)
Examples include penzotriazole, 2'-ethylhexy-2-cya/-3-phenyl cinnamate, resorcinol monobenzoate, and the like.

Next, by homogeneously containing the thermochromic material of the present invention and the thermochromic material encapsulated in microcapsules in a polymer, it is possible to obtain a thermochromic polymer that is extremely useful for practical applications.

Furthermore, using the above-mentioned three types of materials and using conventionally known methods, we have applied them to thermochromic printing inks, thermochromic writing instruments, thermochromic paints, thermochromic sheets, thermochromic packaging, etc. can do.

Next, specific examples will be shown, but the present invention is not limited thereto. In addition, all the manufacturing methods of the thermochromic materials shown in the examples are as follows.

'I' Electron-donating color-forming organic compounds, 'Compounds having low phenolic hydroxyl groups, aromatic hydrocarbon solvents, or 6-alcohols, esters, ketones, ethers, thiols, sulfides, disulfides Mix one or more compounds selected from sulfoxides, sulfoxides, and sulfones, add additives in some examples, and heat, dissolve or melt the mixture to approximately 80 qo to 10 oz. The material is homogenized by heating and cooled to room temperature to obtain a thermochromic material. The following table describes the composition and properties of the thermochromic materials of Examples.

The numbers in parentheses in the table are parts by weight representing the composition ratio.
Example 97 80 oz of Epicoat 828 (epoxy resin manufactured by Shell Oil Co., Ltd.) was added to the thermochromic material 309 obtained in Example 3.
Dissolve by heating, add 150 g of a 5% aqueous gelatin solution dropwise, and stir to form a microbridge.

To this, dissolve the hardening agent U (amine adduct of epoxy resin manufactured by Shell Oil Co., Ltd.) in 20 days of water, and gradually add this to the solution in which Takaazusa was added first, and let the liquid temperature rise. When the temperature is maintained at 80 qo and the toozasa is continued for about 4 hours, Epicote 828 reacts with the curing agent U at the interface between the thermochromic material microdroplets and water, forming a solid polymer that is insoluble in water and the thermochromic material. This is coated with a thermochromic material to obtain a thermochromic material-containing capsule. The capsules produced as described above are used as they are, with or without post-treatment such as filtration, centrifugal concentration, and drying. The same applies to the following examples. Example 98 The thermochromic material obtained in Example 41 was subjected to the microcapsule production method shown in Example 97 to obtain thermochromic material-containing microcapsules.

Example 99 The thermochromic material obtained in Example 53 was subjected to the microcapsule manufacturing method shown in Example 97 to obtain thermochromic material-containing microcapsules.

Example 100 The thermochromic material obtained in Example 68 was subjected to the microcapsule manufacturing method shown in Example 97 to obtain thermochromic material-containing microcapsules.

Example 101 1.0 minutes of Desmodur N-75 (manufactured by Bayer, a polyvalent isocyanate) was dissolved with salt in the thermochromic material obtained in Example 7 of 30 minutes, and this was dissolved in 3% Gohsenol G.
M-14 (manufactured by Nippon Gosei Kagaku Co., Ltd., polyvinyl alcohol)
Drop it into 150 liters of aqueous solution and stir to form fine droplets.

To this, dissolve the hardening agent U of 20 ml in 20 ml of water, and gradually add this to the solution that was continuing to cross the ocean, and bring the temperature of the liquid to 50 ml.
If you keep it at 00 and continue playing Azusa for about 5 hours, you will get Death Module N.
-75 reacts with the curing agent U at the interface between the thermochromic material and water, producing solid polyuria that is insoluble in water and the thermochromic material, which coats the thermochromic material. A thermochromic material-containing capsule is obtained. Example 102 15 Yuramin P-1500 (manufactured by Mitsui Toatsu Chemical Co., Ltd.,
Into a solution of urea-formalin initial condensate) dissolved in 135 g of water, 30 g of the thermochromic material obtained in Example 60, which had been overflowed to 8 g, was added dropwise, and the mixture was poured into a microbottle.

Adding citric acid and lowering the airflow to 4, and continuing to use the rope for 5 hours while keeping it at 45-5000, a thermochromic material and a polymer that does not fall off in water are produced, which coats the thermochromic material, Microcapsules containing a thermochromic material are obtained. Example 103 30 g of the thermochromic material obtained in Example 21, which had been heated to 80° C., was dropped into 80 g of a 5% aqueous gelatin solution and stirred to form fine droplets.

Furthermore, 80 g of 5% gum arabic was added, acetic acid was added under constant heating to lower the pH to 5, 200 g of water was added to cause coacervation, and the pH was further lowered to 4.4. Add 37% formalin overnight for dura mater. In the previous operations, the temperature was kept at 50 q0, then cooled to 1000 q to gel the thick liquid film, and further p
By increasing H to 9 and leaving it for several hours, microcapsules containing a thermochromic material are obtained. Example 104 The thermochromic material obtained in Example 46 was subjected to the same microcapsule manufacturing method as in Example 103 to obtain thermochromic material-containing microcapsules.

Other thermochromic materials listed in the preceding table can be similarly encapsulated in microcapsules.

The meanings of abbreviations used in the examples are as follows.

Component [A]: Electron-donating color-forming organic compound component {o}:
Compound having a phenolic hydroxyl group Component 1: Aromatic hydrocarbon Solvent Component 6: One or two selected from alcohols, esters, ketones, ethers, thiols, sulfides, disulfides, sulfoxides, and sulfones. More than one species of compounds CVL: Crystal violet lactone PSD-V: 2-diethylamino-6-methylfluoran PSD-○: 2-cyclohexylaminofluoran PSD-P: 2-diethylaminobenzfluoran PSD daily R: 2- Diethylamino-5-methylfluorane PSD-T121:2-diethylamino-6-methyl-7-p-octylanilinofluorane PSD-T
126: 2-diethylamino-7-dibenzylaminofluoran 1014: 2-diethylamino-6,7-dibutylfluoran 1017: Halogenated triphenylmethanephthalide Shigeru-P:N-(2,3-dichlorophenyl)
Icoauramine Zu-P: Di-8-naphthospiropyran Y-1: 3,6-diethoxyfluoran orient B: Phenyl.

Ikoolamine-n-bis(dimethylaminophenyl)
-2-amino-6-methylbenzothiazole antigen W: 1,1-bis(4-hydroxyphenyl)cyclohexane antigen WX: 4,4'-thiobis(6-t-
phthyl-3-methylphenol) phenol resin PP
1810: Phenylphenol-formfuldehyde condensation resin Allocizer 202: Ethylpiphenyl isomer mixture Marosam S: Dibenzyltoluene isomer mixture HB
-40: Hydrogenated triphenyl isomer compound MCO-P:
Inpropyl diphenyl isomer compound Hi-D850:
1,1,3-tetramethyl-3-tolylindane isomer mixture Nisseki Hysol SAS-295: 1,1-phenylxylylethane isomer mixture Nisseki Hysol SA
S-SH: Bis(1-phenylethyl)xylene isomer mixture KMC-A: Inpropylnaphthalene isomer mixture Alcohol 20: Lauryl alcohol carol 40: Myristyl alcohol carol 60: Cetyl alcohol carol 80: Stearyl alcohol SEENOX 41$ : Tetra(laurylthiopropionic acid) pentaerythritol ester SEENOXDS:
Distearylthiodipropionate Tinuvin 326:
2-(2'-hydroxy-3-t-butyl5'-methylphenyl)penzotrizoa-/tinuvin 327:
2-(3',5-di-t-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazol-tinuvin P
:2-(2-hydroxy-5'-methylphenyl)penzotriazole sea soap 103:2-hydroxy-4dodecyloxybenzophenone sea soap 104
:2-Hydroxy-4-octadecyloxybenzophenone VFY#3107: Yellow dye (C.1.Soluv
ent Yellow25) BOS: Blue dye (C.1
．． SoiuventBlue25) Performance comparison table between thermochromic material according to the present invention and conventional thermochromic material As described above, the present invention has excellent characteristics, and therefore, in addition to the applications of conventional thermochromic materials, Utilizing the above-mentioned novel thermochromic properties, new fields or applications have become possible.

For example, temperature detection by color in various industries, temperature detection especially in low-temperature industries, monitoring by color change of temperature rise and fall in chemical reactions, etc., prevention of flames by color change temperature indication of dangerous goods containers or storage, temperature of chemical machinery, etc. Distribution measurement, temperature indicators for early detection of heat generation due to overloading of electric circuits and electrical equipment, temperature indicators for household refrigerators, frozen foods, air conditioners, various heaters, baths, etc., and other interesting and fun changes. It is used for displays, advertisements, educational materials, toys, etc. by taking advantage of its magic properties and ability to hide or reveal the base.

Claims (1)

[Scope of Claims] 1. Contains (a) a substantially colorless electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) an aromatic hydrocarbon solvent as essential components. Reversible thermochromic material. 2. (a) a substantially colorless electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, (c) an aromatic hydrocarbon solvent, and (d) alcohols, esters,
A reversible thermochromic material containing as an essential component one or more compounds selected from ketones, ethers, thiols, sulfides, disulfides, sulfoxides, and sulfones.