JP4175519B1 - Indicating material and temperature control indicator using the same - Google Patents

Abstract

[PROBLEMS] A simple material including a temperature indicating material made of a compound that does not contain the harmful metal mercury and is safe and has a hue corresponding to the temperature. A specific temperature range is clearly and accurately determined by reversible color change. In addition, an inexpensive temperature indicating material that can be freely adjusted by a simple method and a temperature management indicator using the temperature indicating material can be provided.
A temperature indicating material includes a metal complex compound that changes color by changing a complex structure in accordance with a temperature change, and an alkylammonium salt compound. The temperature management indicator is enclosed in a glass tube, a glass bottle, a resin case or a resin capsule, or sandwiched between resin film sheets. Another temperature management indicator is one in which an indicator ink composition containing a temperature indicating material is adsorbed, absorbed and / or applied to at least a portion of a substrate.
[Selection figure] None

Description

  The present invention relates to a temperature indicating material that displays a specific temperature range by a reversible hue change when the temperature rises or falls, and a temperature management indicator using the temperature indicating material.

  A reversible temperature indicator is known that displays a specific temperature range without using a temperature measuring machine or a mercury thermometer, and shows a hue corresponding to the temperature by a temperature indicating material. Such an indicator can easily know the current temperature by observing a reversible change in hue. Machine equipment that should be temperature controlled, products in circulation, and equipment that should prevent burns. It is attached to and used.

  As this reversible temperature indicator, one containing a mercury-containing halogen complex compound as a temperature indicating material has been widely used. However, temperature indicating materials containing harmful mercury are being avoided from the viewpoint of safety to the human body and environmental protection.

  As a mercury-free reversible temperature indicator, for example, Patent Document 1 discloses a temperature indicating material comprising an electron-donating color-forming organic compound, a phenolic hydroxyl group-containing compound, and an alcoholic hydroxyl group-containing compound. Discloses a reversible thermostat containing a fusible substance, a leuco dye and a 4-hydroxycoumarin derivative, and Patent Document 3 discloses an electron-donating color-forming organic compound and an electron-accepting organic compound in microcapsules. An enclosed indicator is disclosed. Furthermore, an indicator containing a thermochromic substance that is a complex salt compound of a transition metal such as copper is also known.

  In general, indicators using organic compounds such as organic dyes and organic pigments as a temperature indicating material that shows a hue according to temperature lack long-term stability due to poor durability of organic compounds, and are versatile There is no. On the other hand, the indicator using a metal complex compound as a temperature indicating material has good durability of the metal complex compound and can be discolored only at a specific temperature specific to each, but cannot be discolored at other than that temperature, It is not versatile.

  Indicators that are not durable or long-term stable have a short life. In addition, because a wide range of temperature management is required during the manufacturing and distribution processes of products, indicators that change colors in specific temperature ranges by selecting different organic compounds and metal complex compounds are used in a wide range of temperatures. It is cumbersome and costly to develop and manufacture several types in combination.

Japanese Patent Publication No. 51-44706 Japanese Patent Publication No. 2-19155 Japanese Patent Laid-Open No. 5-32045

  The present invention has been made in order to solve the above-mentioned problems, and is a simple one including a temperature indicating material composed of a compound which does not contain harmful metal mercury and is safe and has a hue corresponding to temperature. An object of the present invention is to provide an inexpensive temperature indicator that can clearly and accurately display a temperature range by a reversible color change and can freely adjust the temperature range by a simple method, and a temperature management indicator using the temperature indicator. And

The temperature indicating material according to claim 1, which has been made to achieve the above object, comprises a hexaaqua- cobalt (II) complex ion and a counter ion thereof, a halogen ion, a thiocyanate ion, and a cyanate. A metal complex compound comprising a cobalt (II) salt having at least one of an ion and an azide ion, and changing its complex structure and changing color according to a temperature change;
CH _3- (CR ¹ ₂ ) _m1 -N + H _m2 (CH ₃ ) _(3-m2) (1)
(In formula (1), m1 = 10-20, m2 = 0-3, R ¹ = H, CH ₃ or C ₂ H ₅ )
And an alkylammonium salt compound containing a cation represented by the above formula.

  The temperature indicating material according to claim 2 is the temperature indicating material according to claim 1, wherein the complex structure is changed by substituting the ligand in the metal complex compound with another ligand. And

The temperature indicating material described in claim 3 is the temperature indicating material described in claim 1, characterized in that the metal complex compound is cobalt (II) bromide hexahydrate .

  The temperature indicating material according to claim 4 is the temperature indicating material according to claim 1, characterized in that the alkylammonium salt compound is 0.1 to 100 parts by weight and the metal complex compound is 1 part by weight.

  The temperature indicating material described in claim 5 is the temperature indicating material described in claim 4 and includes alcohols and / or water.

  The temperature indicating material according to claim 6 is the temperature indicating material according to claim 5, characterized in that the alcohols and / or the water are 500 parts by weight at the maximum.

  The temperature indicating material described in claim 7 is the temperature indicating material described in claim 5, wherein the alcohol is an alkyl monoalcohol compound and / or a dialcohol compound.

  The temperature indicating material according to an eighth aspect is the one according to the first aspect, wherein the alkylammonium salt compound has a lamellar structure.

The temperature indicating material according to claim 9 is the temperature indicating material according to claim 3, which is the hexaaqua- cobalt (II) complex ion in the cobalt bromide (II) hexahydrate [Co (OH _{2) 6]} ^2+, by the temperature change due to heat, and wherein a halogenated cobalt complex ion [CoBr _4] ^2-on becomes possible.

  In the temperature management indicator according to claim 10, the temperature indicating material according to any one of claims 1 to 9 is enclosed in a glass tube, a glass bottle, a resin case or a resin capsule, or sandwiched between resin film sheets. It is characterized by.

  In the temperature management indicator according to claim 11, the indicator ink composition containing the temperature indicating material according to any one of claims 1 to 9 is adsorbed, absorbed and / or applied to at least a part of the substrate. It is characterized by.

  Since the temperature indicating material of the present invention does not contain mercury, it is safe for the human body and the environment. Moreover, it can be easily and efficiently manufactured with a simple structure, and is excellent in durability and long-term storage stability. Further, the temperature indicating material can be freely changed in color at a desired specific temperature in a wide temperature range of about 40 to 100 ° C. only by changing the blending ratio of the composition components. Therefore, the temperature management indicator using the temperature indicating material is excellent in productivity and inexpensive, and can be used for temperature management in a wide temperature range, so that it has high versatility. Moreover, since the discoloration is clear, there is no fear of misidentification.

Preferred form for carrying out the invention

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

  The temperature indicating material of the present invention is manufactured as follows.

  First, 1 part by weight of a cobalt complex compound such as cobalt (II) salt hexahydrate as a metal complex compound and 0.1 to 100 parts by weight of an alkylammonium salt compound such as hexadecyltrimethylammonium bromide (CTMBr). Is dissolved in a solvent such as ethanol, and the solvent is distilled off to dryness. If necessary, a maximum of 500 parts by weight of an alcohol such as an alkyl monoalcohol compound or a dialcohol compound and / or a water medium. A temperature indicating material is obtained when dissolved or suspended in. The temperature indicator is then obtained by placing the temperature indicator in a glass bottle, covering with a lid inert to the solvent and enclosing.

  The metal complex compound is a compound in which a ligand is coordinated to the central metal, and is preferably a cobalt complex compound, and more preferably a cobalt complex salt compound having a counter ion. The ligand or counter ion is one of aqua, which is a ligand of water molecule; halogen ion, thiocyanate ion, cyanate ion or azide ion which is a ligand or counter anion. There may be a plurality of types.

  Specific examples of the metal complex compound include hexaaqua-cobalt (II) complex ions, tetrachloro-cobalt (II) complex ions in which ligands thereof are displaced by equilibrium migration with counter anions, tetrabromo-cobalt ( II) complex ion, tetraiodo-cobalt (II) complex ion, tetrathiocyanate ion-cobalt (II) complex ion, tetracyanate ion-cobalt (II) complex ion, tetraazide ion-cobalt (II) complex ion, etc. And those contained as complex salt ions.

  The alkylammonium salt compound forms an amphiphilic cation.

Specifically, the alkylammonium salt compound has the following chemical formula (1):
CH _3- (CR ¹ ₂ ) _m1 -N ⁺ H _m2 (CH ₃ ) _(3-m2) (1)
(In formula (1), m1 = 10-20, m2 = 0-3, R ¹ = H, CH ₃ or C ₂ H ₅ and preferably H.)
The compound containing the cation shown by these is mentioned. Of these, an n-alkylammonium salt compound having an alkyl group of 10 to 20 carbon atoms is preferred.

  The alkylammonium salt compound may contain alcohols such as alkyl monoalcohol compounds and dialcohol compounds, and water.

  The alkyl ammonium salt compound forms a lamellar structure, for example, alone or together with a long-chain alkyl monoalcohol compound. The alkyl monoalcohol compound is more preferably 0 to 5 parts by weight with respect to 1 part by weight of the alkylammonium salt compound.

Specific examples of the long-chain alkyl monoalcohol compound include the following chemical formula (2):
CH _3- (CR ² ₂ ) _n1 -OH (2)
(In formula (2), n1 = 10 to 20, preferably the same as m1 of the alkyl ammonium salt compound, R ² = H, CH ₃ or C ₂ H ₅ and preferably H.)
The higher aliphatic monoalcohol shown by these is mentioned. Of these, n-alkyl monoalcohols having an alkyl group of 10 to 20 carbon atoms are preferred.

  A temperature indicating material comprising a mixture of an amphiphilic cation derived from an alkylammonium salt compound and a metal complex compound in a lamellar state exhibits a specific temperature range when the temperature rises or falls in the presence of the medium. Causes a reversible color change. In particular, when a long-chain alkyl monoalcohol compound coexists, this compound enters the inside of the lamellar structure, lowers the electron density between layers of the lamellar structure, and adjusts the temperature range in which the color tone changes.

  As a medium, water; a lower aliphatic alkyl monoalcohol compound having 1 to 5 carbon atoms such as methanol, ethanol, 1-butanol and 1-propanol; 2 to 5 carbon atoms such as glycol exemplified by ethylene glycol A dialcohol compound is mentioned. Of these, water or ethylene glycol is preferred. Water or a lower aliphatic alkyl monoalcohol compound acts as a color change aid. Moreover, the dialcohol compound adjusts the temperature range which causes a change in color tone by adjusting the addition amount thereof.

  In order to improve stability, the temperature indicating material may be subjected to a pretreatment in which the powder of the metal complex compound is microencapsulated or resin-coated.

  The temperature control indicator is shown as an example enclosed in a glass bottle, but it is enclosed in a glass tube, filled in a transparent resin case or resin capsule, or sandwiched between polymer film sheets. You may do it.

  The temperature management indicator may be provided with a temperature indicating material layer by preparing an indicator ink composition containing the temperature indicating material and printing it on a substrate to cause adsorption, absorption, or application. . Such an indicator ink composition is prepared by adding a vehicle comprising an ink resin and an ink solvent and an additive to a temperature indicating material. The components and amounts of the vehicle and additives are appropriately adjusted in consideration of the printing method and the physical properties of the ink composition.

  Examples of the printing method include gravure printing, offset printing, silk screen printing, flexographic printing, planographic printing, and relief printing.

  As resins for ink constituting the vehicle, vinyl resin, silicone resin, rosin resin, terpene resin, phenol resin, alkyd resin, polyester resin, polyether resin, acrylic resin, polyurethane resin, epoxy resin, ketone resin, maleic acid resin, Coumarin resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyethylene resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, Polyvinyl formal resin, polystyrene resin, styrene-acrylonitrile copolymer resin, ABS resin, polymethyl methacrylate resin, MMA-styrene copolymer resin, polycarbonate resin, ethyl cellulose resin, cellulose acetate Rulose resin, propyl cellulose resin, cellulose acetate / butyrate resin, cellulose nitrate resin, polychlorofluoroethylene resin, polytetrafluoroethylene resin, tetrafluoroethylene-hexafluoroethylene copolymer resin, polyvinylidene fluoride resin, polyurethane resin, nylon 6 resin, nylon 66 resin, nylon 610 resin, nylon 11 resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycyclohexane terephthalate resin, urea resin, melamine resin, ethyl cellulose, natural rubber and synthetic rubber, petroleum resin, oil and fat . These may be one kind or a mixture of two or more.

  As a solvent for ink constituting the vehicle, n-hexane, n-heptane, mineral spirit, ink oil, solvent naphtha, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, Isobutyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, tridecyl alcohol, benzene, toluene, xylene, tetralin, dipentene, heptane, methyl isobutyl carbinol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetrahydrofuran , Methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl Isobutyl ketone, diacetone alcohol, diethyl ketone, ethyl amyl ketone, methylcyclohexane, isobutyl ketone, diacetone alcohol, isophorone, dimethylformamide, cyclohexane, cyclohexanone, methylcyclohexanone, dichloromethane, chloroform, carbon tetrachloride, cellosolve, methyl cellosolve, ethyl Examples include cellosolve, butyl cellosolve, carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, and water. These may be one kind or a mixture of two or more.

  It may be a commercially available printing vehicle. Examples of such vehicles include F-Gloss medium (trade name of Dainippon Ink & Chemicals, Inc.), Hy Unity Soy medium (trade name of Toyo Ink Manufacturing Co., Ltd.), and Nouvel Maxi media (commercial product of Daiichi Seika Kogyo Co., Ltd.). Name), Novel Senior Soy Medium (trade name of Dainichi Seika Kogyo Co., Ltd.), Q Set 200 Medium (trade name of Jujo Chemical Co., Ltd.), No. 900 Medium (trade name of Jujo Chemical Co., Ltd.), High Set Mat Medium (trade name of Mino Group), JRP medium (trade name of Seiko Advance), PAS No. 800 medium (trade name of Jujo Chemical Co., Ltd.), FBHD medium (trade name of Toyo Ink Manufacturing Co., Ltd.), Styrene B Medium (Trade name of Toyo Ink Manufacturing Co., Ltd.), EW LP Super R Mejiumu (Toyo Ink Mfg. Co., Ltd. trade name) and the like.

  As additives, for example, wax, more specifically carnauba wax, wood wax, beeswax, anhydrous lanolin, paraffin wax, microcrystalline wax, montan wax, ozokerite, petrolatum, petrolatum, polyethylene wax, polytetrafluoroethylene, chlorinated paraffin, And fatty acid amides.

  As other additives, liquid dryers and paste dryers can be mentioned.

  Other additives include dispersants, more specifically lecithin, sorbitan fatty acid esters, partial fatty acid esters of polyacrylic acid, alkylamine fatty acid salts, alkyldiamines, alkyltriamines, formalin condensates of sodium naphthalenesulfonate, lignin Sodium sulfonate, sodium alkyl sulfate ester, sodium alkylaryl sulfonate, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, styrene maleic acid resin, polyacrylic acid derivative, hydrogenated castor oil, aluminum soap, aluminum chelate, aluminum alcohol Rate, organic bentonite, polyethylene oxide, linear polyaminoamide, polycarboxylic acid alkylamine, sodium alginate, casein, methylcellulose , Hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylate, polyethylene oxide, silicone, nonionic activator, butylated hydroxytoluene, butylated hydroxyanisole, eugenol, fernol fungicides, colloidal silica, low molecular weight polyethylene, vanillin, Examples include coumarin, bran oil, lavender oil, acetophenone, barium, calcium metal soap, polyamide, isocyanate, nitrified cotton, aqueous ammonia, alcohol amines, and morpholine.

  As another additive, a polymerizable monomer, a polymerization initiator, more specifically, a benzoin ether photopolymerization initiator, a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, and the like can be given.

Further, as an additional additive, an adjustment pigment that highlights a change in color tone of the temperature indicating material according to temperature or adjusts to a color tone that is easy to see, more specifically, titanium oxide, calcium carbonate, silicon dioxide, alumina white ( Al ₂ O ₃ .xH ₂ O), clay, precipitated barium sulfate, gloss white, fast yellow G, fast yellow 10G, disazo yellow AAA, disazo yellow AAMX, disazo yellow AAOT, yellow iron oxide, disazo yellow HR, dinitroaniline Orange, disazo orange PMP, disnicidin orange, toluidine red, chlorinated para red, virilliant fast scarlet, pyrazolone red B, barium red 2B, calcium red 2B, barium resol red, lake red C, brillianthamine B, Pigment Scarlet 3B Lake, Rhodamine 6G PTMA Toner, Bengala, Naphthol Red FGR, Quinacridone Magenta, Rhodamine B PTMA Toner, Methyl Violet PTMA Toner, Quinacridone Red, Dioxazine Violet, Victoria Pure Blue PTMA Toner, Phthalocyanine Blue, Alkaline Blue Toner , Bitumen, ultramarine, brilliant green PTMA toner, diamond green PTMA toner, phthalocyanine green, carbon black, zinc white, aluminum powder, bronze powder, daylight fluorescent pigment, pearl pigment, and the like.

  These additives are appropriately used as necessary according to printability and ink suitability, and one kind thereof may be used or a plurality thereof may be used in combination.

  The temperature control indicator is a temperature indicating material or an indicator ink composition containing the temperature indicating material, a substrate having a planar structure such as paper, cloth, film, leather, resin lump, glass lump, metal lump, mineral, cement and the like. It may be adsorbed, absorbed, or applied to a part or all of the three-dimensional base material.

  The temperature management indicator is used as follows.

  A temperature control indicator is affixed to the test object to be temperature controlled. When the test object is heated together with the temperature management indicator, the color tone of the indicator changes when the intended temperature is reached, and the color tone is maintained even when heated. Thereafter, when the test object is allowed to cool together with the temperature management indicator, the color tone of the indicator changes when the desired temperature is reached, and the color tone is restored.

  Although the details of the mechanism of discoloration of the temperature indicating material in the indicator according to the temperature change are not necessarily clear, it is assumed as follows. An example in which cobalt (II) bromide hexahydrate, which is a cobalt complex compound, is used as a metal complex compound, n-hexadecyltrimethylammonium bromide is used as an alkylammonium salt compound, and dissolved in water-ethanol. This will be described with reference to FIG.

  This temperature indicating material has a lamellar structure in which the n-hexadecyltrimethylammonium ions are regularly arranged and formed in layers.

When the temperature indicating material is exposed to a relatively low temperature, cobalt (II) hexahydrate is aqua cobalt in which aqua, which is a water molecule of the neutral ligand, is coordinated to the cobalt atom of the central metal. A complex compound ([Co (OH ₂ ) ₆ ] ₂ ⁺ · 2Br ⁻ ) is formed. This aqua cobalt complex compound has a regular octahedral structure exhibiting a pink color and is bulky. The aquacobalt complex ion and the n-hexadecyltrimethylammonium ion in the lamellar structure are positively charged and are isolated while being electrostatically repelled from each other. At this time, the temperature indicating material is pink as a whole.

When the temperature indicating material is gradually heated, the intramolecular hydrogen bond of the aqua cobalt complex compound is weakened and dissociated, or the ligand thereof is easily replaced with another ligand such as a bromide ion. The aquacobalt complex compound has a halogenated cobalt complex ion ([CoBr ₄ ] ²⁻ ) and exhibits a blue color when it exceeds the boundary temperature at which the aqua ligand is converted to an active state where it is substituted with bromide ions. It becomes a cobalt complex compound. The cobalt halide complex ion is an anion and is a tetrahedral structure having a smaller steric hindrance than the regular octahedral structure, and therefore, n-hexadecyltrimethylammonium ion that enters between layers of the lamellar structure and faces the layer. Interacts with the positive charge. As a result, the aquacobalt complex ion and the n-hexadecyltrimethylammonium ion in the lamellar structure are more electrostatically stabilized than the low temperature state in which electrostatic repulsion occurs. At this time, the temperature indicating material is blue as a whole.

  The details of the mechanism by which the temperature at which the color changes varies depending on the blending ratio of the alkylammonium salt compound, the metal complex compound, and the solvent are not necessarily clear, but are presumed as follows.

  The charge density between the layers of the lamella structure depends on the carbon number of the alkyl group of the alkylammonium salt compound, the bonding position of the ammonium group, the amount of the alkylammonium salt compound, or the coexisting long chain alkyl monoalcohol compound or dialcohol It depends on the type and amount of alcohol such as a compound and water.

  When the electron density is high between the layers of the lamellar structure, the aqua cobalt complex ion easily replaces the ligand aqua with bromide ions even at low temperatures. It becomes easy to be taken in. As a result, the temperature indicating material changes color at a relatively low heating temperature.

  On the other hand, when the electron density is low between the layers of the lamellar structure, the aqua of the ligand is difficult to desorb from the aquacobalt complex ion at a low temperature, and the aqua of the ligand cannot be desorbed at a higher temperature. At high temperatures, the ligand aqua finally replaces bromide ions, and the resulting cobalt halide complex ions are incorporated between layers of the lamellar structure. As a result, the temperature indicating material changes color at a relatively high heating temperature.

  By changing the composition ratio in this way, the temperature indicating material can be discolored at an arbitrary temperature from 40 ° C. to 100 ° C.

  Conversely, when cooling after heating, if the boundary temperature is similarly exceeded, the temperature indicating material changes color and recovers. As a result, the color of the temperature indicating material changes reversibly over and over in response to a temperature change.

  Hereinafter, an example in which a temperature indicating material and a temperature management indicator using the temperature indicating material are made as a prototype will be described.

(Example 1)
20 g of cobalt (II) bromide hexahydrate and 100 g of n-hexadecyltrimethylammonium bromide were dissolved in ethanol and then dried. When 10 ml of water was added and mixed well, a pink temperature indicating material was obtained. When 1 g of the temperature indicating material was put in a glass tube and sealed with a lid, a temperature control indicator was obtained.

  When this temperature control indicator was heated by a temperature heater, it showed a pink color at about 30 ° C., but when the heating was further continued, it turned blue at about 60 ° C. When the temperature control indicator that had turned blue was cooled to about 20 ° C., it returned to pink again, indicating reversible color change. As is apparent from this result, the temperature management indicator changes color specifically at a specific temperature.

(Examples 2a to 2b)
The amounts of cobalt (II) bromide hexahydrate, n-hexadecyltrimethylammonium bromide, and 1-n-hexadecanol shown in Table 1 were dissolved in ethanol and then dried. When 1 ml of water was added and mixed well, two kinds of temperature indicating materials were obtained. The color tone was observed when they were sequentially exposed to 30 ° C., 40 ° C., 60 ° C. and 80 ° C. The results are shown in Table 1.

  As can be seen from Table 1, it was possible to change the color at a specific temperature simply by changing the composition ratio of the components.

(Examples 3a to 3e)
The amount of cobalt (II) bromide hexahydrate, n-hexadecyltrimethylammonium bromide, 1-n-hexadecanol, and ethylene glycol in the amounts shown in Table 2 were dissolved in ethanol, and then dried. Solidified. When 1 ml of water was added and mixed well, 5 types of temperature indicating materials were obtained. The color tone was observed when they were sequentially exposed to 30 ° C., 50 ° C., 60 ° C., 80 ° C., 90 ° C. and 100 ° C. The results are shown in Table 2.

  As is clear from Table 2, it was possible to freely change the color at a desired specific temperature in a wide temperature range up to 100 ° C. only by changing the composition ratio of the composition components.

Example 4
20 g of cobalt (II) bromide hexahydrate, 100 g of n-hexadecyltrimethylammonium bromide, and 50 g of 1-n-hexadecanol were dissolved in ethanol and then dried. 1 ml of water was added to it and mixed well. About the temperature indicating material obtained by gelling, an X-ray diffraction measuring device (manufactured by Rigaku Corporation) at a low temperature of 25 ° C. showing a pink color and at a high temperature of 60 ° C. showing a blue color. : Trade name RINT2100S). The result is shown in FIG. As is clear from FIG. 2, the lamellar structure has a layer thickness of 1.75 nm at a low temperature and is pink, while the lamellar structure has a thickness of 1.68 nm and 2.54 nm at a high temperature. It was confirmed that the crystal was discolored while maintaining the lamellar structure as shown in FIG.

(Example 5)
20 g of cobalt (II) bromide hexahydrate, 100 g of n-hexadecyltrimethylammonium bromide, and 50 g of 1-n-hexadecanol were dissolved in ethanol and then dried. When 100 ml of ethylene glycol was added thereto and mixed well, a pink temperature indicating material was obtained. When 1 g of the temperature indicating material was put in a glass tube and sealed with a lid, a temperature control indicator was obtained.

  When this temperature control indicator was heated with a temperature heater, it showed a pink color at about 50 ° C., but when the heating was further continued, it turned blue at about 80 ° C. As is apparent from this result, the temperature management indicator is one that changes color specifically at a specific different temperature.

(Example 6)
20 g of cobalt (II) bromide hexahydrate, 100 g of n-hexadecyltrimethylammonium bromide, and 200 g of 1-n-hexadecanol were dissolved in ethanol and then dried. When 100 ml of ethylene glycol was added thereto and mixed well, a pink temperature indicating material was obtained. When 1 g of the temperature indicating material was put in a glass tube and sealed with a lid, a temperature control indicator was obtained.

  When this temperature control indicator was heated by a temperature heater, it showed a pink color at about 80 ° C., but when the heating was further continued, it turned blue at about 120 ° C. As is apparent from this result, the temperature management indicator is one that changes color specifically at a specific different temperature.

  Since the temperature control indicator using the temperature indicating material of the present invention causes a color change depending on a specific temperature range, it is possible to prevent damage by detecting overheating of machines and instruments, and to prevent burns by displaying the temperature of heated daily necessities. It is used for various temperature management in the manufacturing process of industrial products and daily life, such as prevention and adjustment of bath water temperature.

It is a schematic diagram which shows the mechanism of the change of the color tone of the temperature indicating material to which this invention is applied. It is a figure which shows the spectrum of an X-ray diffraction when the temperature indicator to which this invention is applied is changed in temperature.

Claims (11)

A cobalt (II) salt having a hexaaqua-cobalt (II) complex ion and at least one of a halogen ion, a thiocyanate ion, a cyanate ion, and an azide ion as a counter ion thereof . A metal complex compound that changes color by changing its complex structure;
CH _3- (CR ¹ ₂ ) _m1 -N + H _m2 (CH ₃ ) _(3-m2) (1)
(In formula (1), m1 = 10-20, m2 = 0-3, R ¹ = H, CH ₃ or C ₂ H ₅ )
A temperature indicating material comprising an alkylammonium salt compound containing a cation represented by the formula:   The temperature indicating material according to claim 1, wherein the complex structure is changed by substituting a ligand in the metal complex compound with another ligand. The temperature indicating material according to claim 1, wherein the metal complex compound is cobalt bromide (II) hexahydrate .   The temperature indicating material according to claim 1, wherein the alkylammonium salt compound is 0.1 to 100 parts by weight and the metal complex compound is 1 part by weight.   The temperature indicating material according to claim 4, comprising alcohols and / or water.   The temperature indicating material according to claim 5, wherein the alcohols and / or the water are 500 parts by weight at the maximum.   The temperature indicating material according to claim 5, wherein the alcohol is an alkyl monoalcohol compound and / or a dialcohol compound.   The temperature indicating material according to claim 1, wherein the alkylammonium salt compound has a lamellar structure. The [Co (OH ₂ ) ₆ ] ²⁺ , which is the hexaaqua-cobalt (II) complex ion in the cobalt (II) bromide hexahydrate, is converted into a cobalt halide complex ion by the temperature change due to heating. there [CoBr _4] thermochromic material according to claim 3, characterized in that ^2- to.   A temperature management indicator, wherein the temperature indicating material according to any one of claims 1 to 9 is enclosed in a glass tube, a glass bottle, a resin case or a resin capsule, or sandwiched between resin films.   A temperature management indicator, wherein the indicator ink composition containing the temperature indicating material according to claim 1 is adsorbed, absorbed and / or applied to at least a part of a substrate.

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