JPS612786A - Thermochromic material - Google Patents

Abstract

PURPOSE:A thermochromic material useful as printing ink, coating compound, etc., coloring and decoloring reversibly in a specific temperature range, consisting of a compatible material comprising a coloring organic compound of electron donor, a heterocyclic compound as a developer and an organic solvent as essential components. CONSTITUTION:The aimed thermochromic material consisting of a compatible material comprising (A) a colorless coloring organic compound of electron donor, (B) a compound shown by the formula I and/or formula II [X is NH, S, O; Y is SO2, SO, S, or CO; Z is R, RCO, NRR', halogen, OR, COOR, or NO2 (R and R' are H, or alkyl)] as a developer for the component A, and (C) one or more compounds selected from alcohols, esters, ketones, ethers, acid amides, and >=6C aliphatic carboxylic acids, having an action to cause reversibly the coloring reactions of the components A and B in a specific temperature range, as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermochromic material that reversibly develops and discolors in a specific temperature range. These thermochromic materials can be used as printing inks or paints by being dispersed in a vehicle, or as molded objects, filaments, or filaments by being kneaded into a polymer, as temperature indicating materials that change color due to temperature changes, or as indicating materials for appropriate and dangerous temperatures. It is also used to enjoy the surface color, design, etc. that changes with temperature changes.

The applicant hereby acknowledges that the prior art is a) electron-donating color-forming organic compound, (
B) A reversible thermochromic material consisting of three components: a phenol compound and (c) a compound selected from alcohols, esters, ketones, ethers, acid amides, and carboxylic acids (Japanese Patent Publication No. 51-44707.44709.4490)
8, Japanese Patent Publication No. 51-31682.54-58727, etc.)
proposed.

Problems to be Solved by the Invention The present invention further increases the degree of freedom regarding the color developer of the thermochromic material, that is, the component (b).

Means for Solving the Problems The thermochromic material of the present invention includes (a) a substantially colorless electron-donating color-forming organic compound, (b) a heterocyclic compound as described below, and (c) an alcohol. , esters, ketones, ethers, acid amides, and aliphatic carboxylic acids having 6 or more carbon atoms.

The electron-donating color-forming organic compounds of component (a) include diarylphthalides, polyarylcarbinols, leucouramines, acylouramines, arylauramines, rhodamine B-lactams, indolines, and spiropyrans. There are fluorans, fluorans, etc.

Examples of these compounds are shown below.

Crystal violet lactone, malachite green lactone, Michler hitrol, crystal violet carpinol, malachite green carpinol, N
-(2,3-dichlorobuenyl)leucoauramine, N
- Hendiyl auramine, rhodamine B lactam, N-
Acetyl auramine, N-phenyl auramine, 2-(
Phenyliminoethylidene 13,3-dimethylindoline, N-3,3-trimethylindolinohensis spiropyran, 8-methoxy-N-3,3-)limethylindolinohenzospirobilane, 3-diethylamino-6-methyl-7 -Chlorfluorane 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-besozyloxyfluorane, 1,2-benz-6-diethylaminofluorane, 3,6-di-p-toluidino-4,5-
Dimethylfluoran-phenylhydrazide-γ-lactam, 3-amino-5-methylfluoran, 2-methyl-
3-Amino-6,7-dimethylfluorane, 2.3-butylene-6-di-n-butylaminofluorane, 3-diethylamino-7-anilinofluorane, 3-diethylamino-7-(p-)luidino ) fluoran, 7-acetamino-3-diethylaminofluoran, 2-promo-6-cyclohexylaminofluoran, 2,7-dichloro-3-methyl-6-n-butylaminofluoran, and the like.

Component (b) is selected from heterocyclic compounds represented by the following general formulas (1) and (2).

general formula %formula% Halogen atom, OR, COOR or NO2,R.

R' represents an H atom or an alkyl group, respectively.

Specific examples of these heterocyclic compounds are shown below.

2-mercaptohendioxazole, 2-mercapto-
5-Methylbenzoxazole. 2-Mercapto-5-
n-Butylbenzoxazole.

2-mercapto-6-chlorobenzoxazole, 2-
Mercapto-6-medoxybenzoxazole, 2-mercaptohenzothiazole, 2-mercapto-5-ethylhenzothiazole, 2-mercapto-5-promohenzothiazole, 2-mercapto-6-acetylbenzothiazole, 2-mercapto-6 - Hydroxyhenzothiazole.

2-mercaptobenzimidazole, 2-mercapto-
5-nitrobenzimidazole, 2-mercapto-4,
5,6,7-titrachloropenzimidazole, benzisothiazol-3(2H)-one, 1,1-dioxide, 5-aminobenzisothiazol-3(2H)-
on, 1,1 dioxide, 5-chlorobenziisothiazol-3(2H)-on, 1. l-dioxide, 5
-methoxybenziisothiazol-3(2H)-one,
1. l-dioxide, benzisothiazole-3 (2
H)-one, 1-oxide, 4,5゜6.7-titrabromobenziisothiazole-3(2old-one, 1-oxide, 5-nitrobenzisothiazole-3(2H)
-one, 1-oxide, 5-hydroxybenziisothiazol-3<2H)-one, 1-oxide, benzisothiazole JLz-3(2H)-one, 5-nitrobenzisothiazol-3(2H)-one , 4,5°6.
7-Titrachlorohenzoisothiazole-3(2H)-
on, 6-methoxybenziisothiazole-3 (2H
)-one, 1,3-isoindoledione, 4.5.6
．． 7-titrachloro1゜3-isoindoledione,
5-Nitro-1,3-isoindoledione, 5-trifluoromethyl-1,3-isoindoledione, 5-
Examples include acetyl-1,3-isoindoledione, 5-hydroxy-1,3-isoindoledione, and 5-carboxyethyl-1,3-isoindoledione.

Next, component (c) will be described.

Alcohols include monohydric alcohols, polyhydric alcohols, and derivatives thereof. 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-tocosyl alcohol.

n-mericyl alcohol, isocetyl alcohol, isostearyl alcohol, isotococyl alcohol, oleyl alcohol, cyclohexanol, cyclopenknol, benzyl alcohol.

Cinnamyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol.

Polyethylene glycol, propylene glycol, butylene glycol, hexylene glycol.

Cyclohexane-1,4-diol 5 Trimethylolpropane, 1. 2. 6-hexandriol,
There are pentaerythritol, sorbitol, mannitol, etc.

Examples of ester compounds are shown below.

Amyl acetate, octyl acetate, butyl propionate, phenyl propionate, ethyl caproate.

Amyl caproate, ethyl caprylate, amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl laurate, catyl laurate, butyl laurate, hexyl laurate, octyl laurate, dodecyl laurate, lauric acid Myristyl, 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, palmitic acid Butyl, hexyl palmitate, octyl palmitate, lauryl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, methyl stearate, ethyl stearate,
Butyl stearate, hexyl stearate, octyl stearate, lauryl stearate, myristyl stearate, cetyl stearate, stearyl stearate, methyl behenate, ethyl behenate, propyl behenate.

Butyl behenate, edyl benzoate, butyl benzoate,
Amyl benzoate, phenyl benzoate, ethyl acetoacetate, methyl tholeate, butyl oleate, butyl acrylate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dibutyl malonate, dibutyl tartrate, dimethyl sepatate.

Dibutyl sepatate, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibutyl fumarate, diethyl maleate, dibutyl maleate, triethyl citrate, 12-hydroxystearic acid triglyceride, castor oil, dioxystearic acid methyl ester, 1
Examples include 2-hydroxystearic acid methyl ester.

Examples of ketone compounds are shown below.

Diethyl ketone, ethyl butyl ketone 1 Methyl hexyl ketone, medityl toxide, cyclohexanone, methyl cyclohexanone, acetophenone, propiophenone, benzophenone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, ketone sol, etc.

Examples of ether compounds are shown below.

Butyl ether, hexyl ether, diisopropylbenzyl ether, diphenyl ether.

Examples include dioxane, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol diphenyl ether, and ethylene glycol monophenyl ether.

Examples of acid amide compounds are shown below.

Acedoamide, propionic acid amide, butyric acid amide, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, valmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide , benzamide, caproic anilide, caprylic anilide, capric anilide, lauric anilide, myristic anilide, balmitic anilide, stearic anilide, behenic anilide, oleic anilide, erucic anilide,
Caproic acid N-methylamide, Caprylic acid N-methylamide, Capric acid N-methylamide, Lauric acid N-methylamide, Myristic acid N-methylamide, Valmitic acid N-methylamide, Stearic acid N-methylamide, Behenic acid N-methylamide, Oleic acid N-methylamide, erucic acid N-methylamide, lauric acid N-ethylamide, myristic acid N-ethylamide.

Valmitic acid N-ethylamide, stearic acid N-ethylamide, oleic acid N-ethylamide.

Lauric acid N-butyramide, myristic acid N-butyramide, valmitic acid N-butyramide.

Stearic acid N-butylamide, oleic acid N-butylamide, lauric acid N-octylamide.

Myristic acid N-octylamide 5 Valmitic acid N-octylamide, stearic acid N-octylamide, oleic acid N-octylamide, lauric acid N-dodecylamide, myristic acid N-dodecylamide, valmitic acid N-dodecylamide.

Stearic acid N-dodecylamide, oleic acid N-dodecylamide, distearic acid amide, cibalmitic acid amide 2, cimiristic acid amide, dioleic acid amide,
Dioleic acid amide, tristearic acid amide, tribalmitic acid amide, olimyristic acid amide, trilauric acid amide, orioleic 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-methicamide 1 Azelaic acid N-methylamide.

Succinic acid N-ethylamide, adipic acid N-ethylamide, glutaric acid N-ethylamide, malonic acid N-ethylamide, azelaic acid N-ethylamide, amber #i,
N-Butyramide 5 Adipic acid N-butyramide, Glutaric acid N-butyramide.

Examples include malonic acid N-butylamide, adipic acid N-octylamide, and adipic acid N-dodecylamide.

Examples of aliphatic carboxylic acids having 6 or more carbon atoms include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, valmitic acid, and stearic acid.

Arachic acid, behenic acid, lignoceric acid, cerotic acid,
Montanic acid, melisic acid, isomyristic acid, isopalmitic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, lylunic acid, eleostearic acid, arachidonic acid, 2-oxylauric acid, 2-oxymyristic acid, 2 -Oxypalmitic acid, 2-oxystearic acid, 3-oxystearic acid, 12-hydroxystearic acid, ricinoleic acid, 2-bromurauric acid.

2-Bromyristic acid, 2-Brombalmitic acid, 2
-Bromstearic acid, 2-chlorostearic acid, 18
-Bromstearic acid, 18-chlorostearic acid, dioxypalmitic acid, dioxystearic acid, 3-ethyl-3-lauryl-3-oxypropionic acid, 52-methyl-3-oxystearic acid, 2-ketostearic acid,
2-ketobalmitic acid, schizelaic acid monoethyl ester, azelaic acid monobutyl ester, azelaic acid monooctyl ester, sepatic acid monoethyl ester,
Sepatic acid monobutyl ester, Sepatic acid monooctyl ester, Sepatic acid monolauryl ester, 1.1
Examples include 2-dodecamethylene dicarboxylic acid, L14-tetradecamethylene dicarboxylic acid, 1,16-hexadecamethylene dicarboxylic acid, and dimer acid.

Effect The above three components are component (a) :component (b) :component (c) are mixed at a weight ratio of 1:0.1 to 10:1 to 100 and melted at 80 to 100°C to form a homogeneous compatible solution. By doing so, it becomes a thermochromic material that reversibly develops and fades in color within a specific temperature range.

Here, component (A) is a component that determines the color when coloring, component (B) is a color developer for component (A), and component (C) is a component that determines the color at the time of coloring. A reaction medium that causes a color reaction to occur reversibly within a specific temperature range.

These thermochromic materials may be solid or liquid at room temperature, but all of them are liquid at temperatures sufficiently higher than their respective color change temperatures, such as strong acidic substances or components that irreversibly color the component (a). If it comes into contact with other substances, such as those that interfere with the reaction between (a) and (b), its properties may be impaired. By forming the thermochromic material into microcapsules having a particle size of a few to about 30 μm using a well-known microencapsulation method, the above problem can be solved.
It is also possible to coexist two or more types of thermochromic materials exhibiting different color change temperatures in the same system, expanding its uses.

Effects of Examples and Invention Table 1 shows the composition, color change temperature, and color change of the thermochromic material of each example. The numbers in parentheses are the composition ratios expressed in parts by weight, and the discoloration temperature is expressed in °C.The color change is shown on the left side of the arrow when it is lower than the discoloration temperature, and on the right side is the color when it is higher than the discoloration temperature. .

Examples 9 and 10 are examples of thermochromic materials encapsulated in microcapsules.

The contents of the components represented by symbols in the table are as follows.

CVL: Crystal Violeno Traftone Leuco Dye A Nispiro (12-H-henzo[α]xanthine-1
2,1° (3'H)-isobezofuran]-3゛-
on, 9-(diethylamino)-leuco dye B Nispiro[isobenzofuran-1(3H)
, 9'-(9H)xanthine-3-one, chloro-
6'-(diethylamino)-3'-methyl-leuco dye C Nispiro [isobenzofuran-1 (3H)
, 9′-(9H)xanthec-3-one, 6″-diethylamino-3°-methyl-2′-(phenylamino)-leuco dye D Nispiro[isobenzofuran-1(3H)
, 9'-(9H)xanthinetwo-3-one, 6°-(
diethylamino)-2'-(cyclohexyl(phenylmethyl)amino)- Into 80 g of a 5% gelatin aqueous solution, 80 g of the thermochromic material of Example 1 heated to 80°C was added dropwise and stirred to form minute droplets. Further, 80 g of a 5% aqueous gum arabic solution is added, acetic acid is added under constant stirring to adjust the pH of the system to 5, and 200 g of water is added to cause coacervation. 4 and then add 1 g of 87% formalin.In the previous operations, the temperature of the system was kept at 50°C, and in order to gel the thick liquid film formed, the system was cooled to 10°C. After adjusting the pH to 9, a microcapsule suspension containing a thermochromic material was obtained by leaving it for several hours.The centrifuged thermochromic material in the form of microcapsules was the same as the thermochromic material of Example 1. It showed the same thermochromic properties.

Example 10

Claims (1)

[Scope of Claims] 1 (a) a substantially colorless electron-donating color-forming organic compound;
(b) The following general formula (1) is a color developer for the organic compound.
and (2) one or more heterocyclic compounds selected from the compounds represented by (2), and (c) the above (a) and (b).
A reaction medium that reversibly causes the coloring reaction of the components in a specific temperature range, selected from alcohols, esters, ketones, ethers, acid amides, and aliphatic carboxylic acids having 6 or more carbon atoms. A thermochromic material consisting of a compatible material containing one or more compounds as essential components. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) Here, X is NH, S or O, Y is SO2, SO, S or CO, and Z is R, RCO, NRR', halogen atom,
OR, COOR or NO2, R and R' each represent an H atom or an alkyl group. 2 Claim 1 encapsulated in microcapsules
Thermochromic materials described in Section 1.