JP785H - Temperature indicating material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electron-donating color-forming organic compound, a compound having a phenolic hydroxyl group, amyl acetate, isoamyl acetate, octyl acetate, butyl propionate, octyl propionate, ethyl caproate, and caproic acid n. -Amyl, ethyl caprylate, n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, ethyl stearate, n-butyl stearate. The present invention relates to a reversible temperature indicating material which has one or two or more of three components selected from the above as essential components and is decolored by heating at -70 ° C to + 40 ° C and developed by cooling. The present inventor investigated coloration due to a reaction between an electron-donating color-forming organic compound and a compound having a phenolic hydroxyl group, and using both of them, amyl acetate, isoamyl acetate, octyl acetate,
Butyl propionate, octyl propionate, ethyl caproate, n-amyl caproate, ethyl caprylate,
Add a compound selected from n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, ethyl stearate, n-butyl stearate. We obtained new knowledge that the coloration phenomenon changes with temperature when reacted. As a result of further research based on this new finding, the present invention has been completed. Conventionally, metal complex crystals have been used as a temperature indicating material, and they have been used for temperature detection of temperature indicating paints. However, these metal complex crystals have a discoloration temperature range of substantially 50 ° C. to several hundred degrees (° C.) and most of them are 100 ° C. or higher. Moreover, the color and discoloration temperature cannot be freely selected, and it is inevitable to depend on the properties of the complex salt substance itself. That is, the types of substances that change color at 100 ° C or lower are limited to a few types, and the color changes are Ag ₂ HgI ₄ , yellow to orange at 50 ° C, Cu ₂ HgI ₄ , 7
It changes from red to brown at 0 ° C, and it is of course impossible to choose the type of color, and the discoloration is very similar. In addition, since a metal complex salt crystal is used, this kind of temperature indicating material has no light permeability and is limited in its use. Further, this kind of temperature indicating material contains many compounds containing heavy metals, and especially discolors at 100 ° C or less. As mentioned above, since the substance containing Hg contains the above-mentioned Hg, it is necessary to pay attention to the danger at the time of use, and at the same time, it can become a source of pollution. The liquid crystal as the other temperature indicating material has a color change temperature range of approximately -20 ° C to + 200 ° C, and very few liquid crystals change color particularly at 0 ° C or less. Further, the color and the discoloring temperature cannot be freely selected as in the above, and it is unavoidable to depend on the property of the liquid crystal substance itself. That is, in order to obtain a substance having the required color and discoloration temperature, there is no other way than selecting one from the substances synthesized so far or waiting for a substance to be synthesized in the future. On the other hand, this kind of substance has the drawback that it is chemically extremely sensitive and its action and effect are deteriorated by contact with other substances. Also, it should only work in liquid form,
Considering that cholesteric liquid crystal requires a black base and that this kind of compound is extremely expensive, its use as a temperature-indicating material is a major constraint, which is extremely inconvenient for application development. It was Therefore, in order to solve such a problem, the inventor has
First, we have invented a new type of temperature indicating material called a temperature indicating material which contains three components of an electron-donating color-developing organic compound, a compound having a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group as essential components. The present invention has a great feature not seen in conventional thermosensitive materials that the discoloration temperature region is lower than that of the invention using the compound having an alcoholic hydroxyl group, and that the thermosensitive material can be expanded to the low temperature industry. Is considered to be an extremely large contribution to industrial safety and convenience. Further, the most characteristic feature of the reversible temperature indicating material which is decolored by heating at −70 ° C. to + 40 ° C. and develops color upon cooling according to the present invention is that the temperature at which the color changes and the combination of color types can be freely adjusted. That is, a color is selected with an electron-donating color-developing organic compound, and the compound is colored with a phenolic hydroxyl group to determine the concentration, and then amyl acetate, isoamyl acetate, octyl acetate,
Butyl propionate, octyl propionate, ethyl caproate, n-amyl caproate, ethyl caprylate,
Kind of compound selected from n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, ethyl stearate, n-butyl stearate or The color change temperature can be determined by the amount added. In other words, roughly -70 ° C to + 40 ° C
It is possible to change red, blue, yellow, green, orange, purple, and other subtle colors from colored to colorless and from colorless to colored by appropriately combining the three substances at temperatures between So, like the conventional temperature indicator,
In the case of searching for a substance having the required color and discoloration temperature, there is no other method than selecting from the substances synthesized so far or waiting for the substance to be synthesized in the future, but the present invention is completely unmatched in the past. There is a great degree of freedom in selection -70
It is a reversible temperature indicating material that is decolored by heating at 0 ° C to + 40 ° C and develops color by cooling. Also, the change in color changes from colored to colorless,
A very remarkable change from colorless to colored is also a point different from the conventional temperature indicating materials. However, it is also possible to change from colored (I) to colored (II) like the discoloration of conventional temperature indicating materials by adding colorants such as general dyes and pigments to the three essential components. In addition, the temperature indicating material according to the present invention can also transmit light, is effective for display and other applications, and has a feature not used in conventional temperature indicating materials in that it can be used in a solid or liquid form. In addition, considering that it does not contain substances that cause pollution and is inexpensive, it can be said that it is an extremely excellent temperature indicating material when applied to various industrial materials and other uses. As the electron-donating color-forming organic compound used in the present invention,
Diarylphthalides, polyarylcarbinols,
Leuco auramines, acyl auramines, aryl auramines, rhodamine B lactams, indolines,
Examples include spiropyrans and fluorans. These compounds are exemplified below. Crystal Violet Lactone, Malachite Green Lactone, Michler Hydrol, Crystal Violet Carbinol, Malachite Green Carbinol, N- (2,3-Dichlorophenyl) Leukoauramine, N
-Benzoyl auramine, N-acetyl auramine, N-phenyl auramine, rhodamine B lactam, 2- (phenyl imino ethanedilidene) 3,3-dimethyl indoline, N.3,3-trimethylindolinobenzospiropyran , 8'-Methoxy-N.3,3-trimethylindolinobenzospiropyran, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-6-benzyloxyfluor Oran, 1.2-benz-6-diethylaminofluorane, and the like. Examples of the compound having a phenolic hydroxyl group include monophenols to polyphenols, and further substituents thereof include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group and halogen. These compounds are exemplified below. Phenol, O-cresol, P-cresol, P-ethylphenol, tert-butylphenol, 2,6
-Ditertiary butyl-4-methylphenol, nonylphenol, dodecylphenol, styrenated dophenol, 2,2'methylenebis (4-methyl-6-tertiarybutylphenol), α-naphthol, β-
Naphthol, hydroquinone monomethyl ether, guaiacol, eugenol, P-chlorophenol, P-
Bromophenol, O-bromophenol, O-chlorophenol, 2,4,6-trichlorophenol, O-phenylphenol, P-phenylphenol, P- (P-
Chlorophenyl) phenol, O- (O-chlorophenyl) phenol, salicylic acid, methyl P-oxybenzoate, ethyl P-oxybenzoate, propyl P-oxybenzoate, butyl P-oxybenzoate, octyl P-oxybenzoate, Dodecyl P-oxybenzoate, catechol, hydroquinone, resorcin, 3-methylcatechol, 3-isopropylcatechol, P-tertiarybutylcatechol, 2,5-ditertiarybutylhydroquinone, 4,4'-methylenediphenol, bis Phenol A, 1,2-dioxynaphthalene, 2,3-dioxynaphthalene, chlorcatechol, bromocatechol, 2,4-dihydroxybenzophenone, phenolphthalein, O-
Cresolphthalein, methyl protocatechuate, ethyl protocatechuate, propyl protocatechuate, octyl protocatechuate, dodecyl protocatechuate, pyrogallol, oxyhydroquinone, phloroglucin, 2,4,6-trioxymethyl Benzene, 2,3,4-
Trioxyethylbenzene, gallic acid, methyl gallate, ethyl gallate, propyl gallate, butyl gallate, hexyl gallate, octyl gallate, dodecyl gallate, cetyl gallate, stearyl gallate, 2,3,5
-Trioxynaphthalene, tannic acid, phenol resin, etc. The ester used is exemplified below. Amyl acetate, octyl acetate, butyl propionate, octyl propionate, ethyl caproate, amyl caproate, ethyl caprylate, amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, There are butyl myristate, methyl stearate, ethyl stearate, butyl stearate. Electron-donating color-forming organic compound, compound having phenolic hydroxyl group, amyl acetate, isoamyl acetate, octyl acetate, butyl propionate, octyl propionate, ethyl caproate, n-amyl caproate, ethyl caprylate, capryl. Three components of a compound selected from n-amyl acid ester, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, ethyl stearate, and n-butyl stearate. Although they are appropriately combined and melted or melted at an appropriate temperature to make them uniform to obtain a temperature indicating material, two or more of each of these components may be mixed. For example, 1 g of crystal violet lettactone is mixed with 1 g of octyl ester of P-oxybenzoic acid and 5 g of methyl stearate, and the mixture is heated to 100 ° C. and melted to homogenize. The mixture thus obtained is at 35 ° C.
The following are blue and colorless at 35 ° C. or higher, and can be used as a reversible temperature indicating material. Here, rhodamine lactone as an electron-donating color-forming organic compound, octyl gallate as a compound having a phenolic hydroxyl group, and methyl myristate as an ester are further added to the above composition to change the color tone and discoloration temperature. be able to. The temperature indicating material according to the present invention is a reversible temperature indicating material that is decolored by heating at −70 ° C. to + 40 ° C. and develops color by cooling. on the other hand,
In the present invention, the properties of the temperature indicating material can be changed by adding substances other than the above-mentioned three components, and the temperature indicating material can be transformed into a more convenient shape for use. Examples of substances other than the three components are n-paraffin, isoparaffin, dibenzylbenzene, dipropylbenzylbenzene, diethylbenzylbenzene, diphenylpropyldiphenyl, cyclohexyldiphenyl,
Octylnaphthalene, dodecylbenzene, xylene, n
-Hexane, n-pentane, fluid paraffin, etc. For example, if dibenzylbenzene or diphenyl is slightly added to the above-mentioned three essential components, the transparency of the temperature indicating material can be remarkably improved with almost no change in color tone. In addition, if high melting point isoparaffin is added to the above three essential components,
It is effective for solidifying the temperature indicator with almost no change in color tone and discoloration temperature. The present invention, as described above, includes amyl acetate, isoamyl acetate,
Octyl acetate, butyl propionate, octyl propionate, ethyl caproate, n-amyl caproate, ethyl caprylate, n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate. , Butyl myristate, methyl stearate, ethyl stearate, and n-butyl stearate are used in combination to make the color-developing material that reacts and colors when contacted with each other in advance to be mixed and mixed. It is a successful product, and it has an excellent effect with no unevenness in coloring. Therefore, this technology is completely different from the method in which the color-forming substance is separated and mixed only at the time of coloring. As described above, the reversible temperature-indicating material according to the present invention, which is decolored by heating at -70 ° C to + 40 ° C and developed by cooling, is an electron-donating color-forming organic compound, a compound having a phenolic hydroxyl group, amyl acetate, acetic acid. Isoamyl, octyl acetate, butyl propionate, octyl propionate, ethyl caproate, n-amyl caproate, ethyl caprylate, n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, myristin Ethyl acid, butyl myristate, methyl stearate, ethyl stearate, n-stearate
By combining three components of compounds selected from butyl as appropriate, the color disappears by heating at -70 ° C to + 40 ° C and develops by cooling, which is not possible with conventional thermochromic materials that can freely control the color and discoloration temperature. However, the present invention is not limited to this. The methods for manufacturing the temperature indicating material shown in the examples are as follows. Electron-donating color organic compounds, compounds having phenolic hydroxyl groups and amyl acetate, isoamyl acetate, octyl acetate, butyl propionate, octyl propionate,
Ethyl caproate, n-amyl caproate, ethyl caprylate, n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, stearic acid Ethyl, stearic acid n
-A compound selected from butyl is mixed, and in some of the examples, an additive is further added, and this is heated to about 100 ° C, dissolved or melted to homogenize it, and cooled to room temperature-
A reversible temperature indicating material that is decolored by heating at 70 ° C to + 40 ° C and develops color by cooling. The meanings of the abbreviations used in the examples are as follows. CVL: Crystal Violet Lactone BS-P: Leuco auramine-based compound PSD-G manufactured by Yamamoto Chemical Synthesis Co., Ltd. Fluoran-based compound manufactured by Nisso Kako Co., Ltd. PSD-P: Fluoran-based compound manufactured by Nisso Kako Co., Ltd. Orient B: Leuco auramine compound Zu-P manufactured by Orient Chemical Industry Co., Ltd. Leuco compound Y-1 manufactured by Yamamoto Chemical Synthesis Co., Ltd. Leuco compound Pink 98 manufactured by Yamamoto Chemical Synthesis Co., Ltd .: Iwaki Pharmaceutical Co., Ltd. Fluoran compound LD-S: 3,4,5,6 tetrahydrophthalimide methyl-1,3,3 trimethylindolino-β-
Naphtospiropyran LD-M: Malachite Green Lactone VFY-3107: Vali Fast Y manufactured by Orient Chemical Industry Co., Ltd.
ellow # 3107 Spirit dye ASY-GRH: Hozengaya Chemical Co., Ltd. Aizen Spilon Yello
w GRH Spirit Dye (S): Solid (P): Paste (L): Number in liquid (): Shows compounding amount g Next, the test results of the temperature indicating material shown in the examples are described. In the test method, the sample was enclosed in a capillary tube with an inner diameter of 1 mm, and this was cooled or heated to measure the color tone and discoloration temperature. The description of the test results is as follows. () () Indicates the color tone and discoloration temperature (℃) in that order. Indicates a colored area, and a portion without description indicates a non-colored area. For example, in the above example, it means that it is colored blue below 51 ° C and is colorless above 51 ° C. In addition, the performance comparison with the temperature indicating material according to the present invention will be described after the test results. As described above, various combinations are shown in the embodiment, but the number is not limited to the number in the embodiment. However, there is a difference in the sensitivity of discoloration, and it is necessary to use them properly according to the application. Further, as shown in the test results, the discoloration temperature sufficiently includes the temperature range of our daily life, and many discolorations below 0 ° C., which are unparalleled, are also seen. On the other hand, there are many kinds of colors, and the change of color is possible from colored to colorless, from colorless to colored, and from colored (I) to colored (II). In addition to the conventional use of temperature-indicating materials, the use of characteristics has made it possible to apply to new fields. For example, temperature detection in various industries, especially temperature detection in low temperature industry, monitoring of temperature rise and fall in chemical reactions, prevention of disasters by indicating temperature of dangerous goods container or storage, early detection of heat generation due to overload of electric circuit and electric equipment There are applications such as temperature indicators for refrigerators, refrigerators, temperature indicators for coolers, bath temperature indicators, display devices, advertising paper, teaching materials, toys, etc.

Claims (1)

[Corrected description] [Claims] [Claim 1] (a) an electron-donating color-forming organic compound, (b) a compound having a phenolic hydroxyl group, and (c) amyl acetate, isoamyl acetate, octyl acetate, Butyl propionate, octyl propionate, ethyl caproate, n-caproate
From amyl, ethyl caprylate, n-amyl caprylate, ethyl caprate, amyl caprate, octyl caprate, methyl myristate, ethyl myristate, butyl myristate, methyl stearate, ethyl stearate, n-butyl stearate 1 or 2 or more selected
A reversible temperature indicating material that decolorizes by heating at -70 ° C to + 40 ° C and develops color by cooling, which has the three components as essential components.