JP5990364B2 - Indicating ink composition - Google Patents

Description

  The present invention relates to a temperature indicating ink composition that indicates whether a specific temperature has been reached by a reversible color change.

  In order to control the temperature of machines, equipment, and temperature-preserved products, temperature indicating materials such as temperature indicating paints and temperature indicating inks that are reversibly discolored according to temperature by including temperature indicating pigments and temperature indicating materials are widely used. This temperature indicating material is applied directly to the test object, sprayed with a spray or the like, or contained as an ink for an indicator discoloring member attached to the test object. By using a temperature indicating pigment that shows a hue according to temperature and reversibly changes color, the current temperature can be easily known by observing a reversible change in hue.

A typical thermochromic pigment conventionally used is a mercury (iodide) iodide complex. Among them, a silver tetraiodide (II) acid silver salt complex represented by Ag ₂ [HgI ₄ ] is used as a temperature indicating pigment for a temperature control indicator that is mainly used outdoors and changes color reversibly around 45 to 50 ° C. However, it is widely used. Patent Document 1 discloses a reversible temperature indicating material containing a mercury (II) iodide complex salt having silver (I) and copper (I) as a cation metal, a binder and / or a solvent. . This reversible temperature indicating material has a simple composition, is excellent in durability and light resistance, is capable of clear display in a temperature range around 50 ° C. by reversible discoloration, and has excellent visibility.

  In general, mercury tetraiodide (II) silver complexes with low light resistance are temporarily deteriorated due to light, particularly sunlight including ultraviolet rays, and exhibit abnormal discoloration, such as aluminum and copper attached thereto. Such thermochromic pigments have problems with their stability because they react with metal substrates and corrode those metals. In addition, since such a temperature indicating pigment contains mercury, waste liquid treatment is necessary in the production process, and a large-scale production facility is inevitably required. Furthermore, the temperature-increasing pigments are soared because of the soaring of the raw material, that is, the silver-containing reagent, accompanying the increase in the metal price of silver, which is a noble metal. Thus, there is a problem that productivity is poor due to an increase in raw material costs and manufacturing costs. At present, in addition to these causes, the use of mercury is avoided from the viewpoint of human safety measures and environmental protection measures against mercury.

  On the other hand, as a temperature-indicating material that does not contain mercury, for example, Patent Document 2 discloses one that includes a cobalt complex compound that reversibly colors depending on temperature. Compared to the mercury tetraiodide (II) complex, the human body and the environment are taken into consideration, and the color is freely changed at a desired specific temperature in a relatively wide temperature range of 40 to 100 ° C. However, in the REACH regulations of the European Union, cobalt compounds are concerned as an environmentally hazardous substance, so they are useful up to a certain level. Similarly, cobalt complex compounds containing cobalt metal may be subject to some restrictions in the future. And is being repelled.

JP 2010-24322 A JP 2009-36520 A

  The present invention has been made in order to solve the above-described problems, and has high functionality that freely changes color at a desired specific temperature in a wide temperature range, and is stable in storage and use. An object of the present invention is to provide a temperature indicating ink composition that is excellent, has high productivity with reduced raw material costs and manufacturing costs, and does not contain harmful metals such as mercury in consideration of the human body and the environment.

In order to achieve the above-mentioned object, the liquid temperature ink composition described in claim 1 of the claims is SO ₄ ²⁻ , SO ₃ ²⁻ , HSO ₄ ²⁻ , HSO ₃ ^2−. , S ₂ O ₃ ²⁻ , OH ⁻ , CH ₃ COO ⁻ , HCOO ⁻ , C ₂ O ₄ ²⁻ , CO ₃ ²⁻ , HPO ₄ ⁻ , PF ₆ ²⁻ , SiF ₆ ²⁻ , B (C ₆ H ₅₎ 4 ^_-, and ^R-SO 3 - _(R has at least counter anion consisting of one selected from the group) to the hydrocarbon group and / or an aromatic group, saturated or unsaturated, thermochromism a granular or powdered iron triazole complex compounds you reversibly change color at a temperature to be detected during the rise or fall in temperature by showing,
An adhesive binder covering the particle surface of the granular or powdered iron triazole complex ,
A solvent ,
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, Brilliantamine 6B, Pigment Scarlet 3B Lake, Rhodamine 6G PTMA Toner, Bengala, Naphthol Red FGR, Quinacridone Maze , Rhodamine B PTMA Toner, Methyl Violet PTMA Toner, Quinacridone Red, Dioxazine Violet, Victoria Pure Blue PTMA Toner, Phthalocyanine Blue, Alkali Blue Toner, Bitumen, Ultramarine Blue, Brilliant Green PTMA Toner, Diamond Green PTMA Toner, Phthalocyanine Green, Carbon An additive containing a material that adjusts the discoloration color tone, at least any one selected from black, zinc white, aluminum powder, extender pigment, bronze powder, fluorescent pigment, phosphorescent pigment, and pearl pigment,
In a weight ratio of 0.1-100: 0.1-50: 1-500: 0.001-10
Wherein in sticky binder, while dispersion remains the granular or powdered iron triazole complex compound, it characterized that you have been contained.

The temperature indicating ink composition according to claim 2 is the ink composition according to claim 1, which is a printing ink composition or a coating ink composition.

  The temperature indicating ink composition of the present invention contains an iron triazole complex as the temperature indicating pigment component, and the color change is reversibly reversible at a desired specific temperature in a wide temperature range from about -130 ° C to 130 ° C. Can show. This temperature indicating ink composition can be applied to substrates made of various materials such as paper, plastic and metal. This iron triazole complex does not react with a metal substrate such as aluminum or copper to corrode the metal like conventional temperature pigments, and is stable without deterioration in the temperature ink composition. And evenly distributed. Since the temperature indicating pigment is uniformly dispersed, the temperature indicating ink composition can exhibit uniform discoloration. Furthermore, the temperature indicating ink composition in which the temperature indicating pigment is stable can stably maintain its color changing function for a long period of time during storage and use.

  In addition, the temperature indicating ink composition of the present invention does not contain harmful metals such as mercury and cobalt that adversely affect the environment and the human body, and is highly safe for users and manufacturers. It is. Because it does not contain mercury or other harmful metals, waste liquids such as wastewater discharged during the production of temperature pigments and temperature ink compositions do not contain environmentally hazardous substances, eliminating the need for large-scale production equipment such as purification equipment. Manufacturing costs can be reduced. In addition, the temperature ink composition does not contain an expensive noble metal such as silver, and the use of an iron triazole complex compound with high versatility and low cost and safe iron as the central metal can reduce manufacturing costs. it can.

  According to the temperature indicating ink composition of the present invention, it is possible to prepare a printing ink having high functionality and a paint such as paint by containing various additives as required.

  The temperature indicating ink composition of the present invention is used as a printing ink and exhibits high printing function characteristics. For gravure printing, screen printing, flexographic printing, coater printing, offset printing, letterpress printing, lithographic printing It can be used as an ink for use in ink jet printers.

  The temperature indicating ink composition of the present invention is also used as an ink composition for paint coating such as a temperature indicating paint, and can be used by brushing directly on the test object to be temperature-controlled. Regardless of the shape of a specific location to be managed, it can be applied to a wide or narrow area or a portion with unevenness.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The temperature indicating ink composition of the present invention contains an iron triazole complex compound that is a temperature indicating pigment component that reversibly changes color at a desired temperature, a binder and a solvent that are ink components, and an additive as necessary. It is liquid.

  This temperature ink composition comprises 0.1 to 100 parts by weight of an iron triazole complex compound, 0.1 to 50 parts by weight of a binder, 1 to 500 parts by weight of a solvent, and optionally 0.001 to 10 parts by weight of an additive. Are prepared by kneading.

  In the temperature ink composition, the iron triazole complex compound as the temperature pigment component is dispersed in the medium as the ink component, and the particle surface of the iron triazole complex compound is coated with a binder and is in a stable state. This coated state prevents alteration of the iron triazole complex compound due to oxidation or the like. The iron triazole complex is preferably 0.1 to 500 μm in granular or powdery particles.

  The discoloration mechanism of the temperature indicating ink composition by the iron triazole complex compound, which is the temperature indicating pigment component, indicates whether or not a specific temperature has been reached by reversible color tone change due to the thermochromism of the iron triazole complex compound. When the iron triazole complex is heated from the original low temperature to a temperature higher than the characteristic discoloration temperature of the iron triazole complex, a spin crossover phenomenon occurs, and the color tone changes from colored (mainly pink) to white. When returning from high temperature to low temperature again, the color changes from white to colored (mainly pink), reversibly returns to the original spin state, and is restored to the original color. Therefore, by visually observing the color tone of the temperature indicating ink composition containing the iron triazole complex compound, it is accurate and easy to determine whether the current temperature is lower than or higher than the color change temperature of the iron triazole complex compound. Can be judged.

This iron triazole complex is a transition metal complex in which a central metal is a divalent iron ion and a ligand coordinated with the central metal is composed of triazole, a derivative thereof, and a counter anion. With respect to the iron triazole complex, hydrates and anhydrides exist, either of which may be used. The ligand triazole and its derivatives are 1,2,4-triazole, 4-methyl-1,2,4-triazole, 4-ethyl-1,2,4-triazole, 4-propyl-1,2 , 4-triazole, 4-butyl-1,2,4-triazole, 4-pentyl-1,2,4-triazole, 4-hexyl-1,2,4-triazole, 4-amino-1,2,4 -Triazole, 4-amino derivative-1,2,4-triazole, etc. are mentioned. A ligand that coordinates to an iron (II) cation and causes a spin crossover phenomenon is preferable. These ligands may be used alone or may be a complex compound formed from a plurality of ligands. The counter anion of the complex compound is F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , At ⁻ , SO ₄ ²⁻ , SO ₃ ²⁻ , HSO ₄ ²⁻ , HSO ₃ ²⁻ , S ₂ O ₃ ²⁻ , OH ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , NCS ⁻ , CN ⁻ , SCN ⁻ , CH ₃ COO ⁻ , HCOO ⁻ , C ₂ O ₄ ²⁻ , CO ₃ ²⁻ , HPO ₄ ⁻ , PF ₆ ^{2 _{-, SiF 6 2-, B (}} C 6 H 5) 4 -, or _{^{C 6 H 5 -SO 3 -,}} CH 3 -C 6 H 4 -SO 3 -, C 2 H 5 -C 6 H 4 -SO _{^{3 -, C 10 H 7 -SO}} 3 -, NH 2 -C 10 H 6 -SO 3 -, HO-C 10 H 6 -SO 3 -, SF 3 -SO 3 -, CH 3 -SO 3 -, C _{^{2 H 5 -SO 3 -, C}} 3 H 7 -SO 3 -, C 4 H 9 -SO 3 - ^{_{C 5 H 11 -SO 3 -,}} C 6 H 13 -SO 3 - R-SO 3 , such as ^- (R is a group of the hydrocarbon group and / or an aromatic group, saturated or unsaturated) of iron, such as ( II) Anions that are paired with triazole complex cations. These may be used alone or may be a complex compound having a plurality of counter ions.

  Specific examples of the iron triazole complex include tri (1,2,4-triazole) iron sulfate complex, tri (1,2,4-triazole) iron nitrate complex, and tri (1,2,4-triazole). ) Iron hydrochloride complex, tri (1,2,4-triazole) iron tetrafluoroborate complex, tri (1,2,4-triazole) iron fluorate complex, tri (1,2,4-triazole) ) Iron bromate complex, tri (4-amino-1,2,4-triazole) iron sulfate complex, tri (4-amino-1,2,4-triazole) iron nitrate complex, tri (4-amino-) 1,2,4-triazole) iron hydrochloride complex, tri (4-amino-1,2,4-triazole) iron tetrafluoroborate complex, tri (4-amino-1,2,4-triazole) Iron fluorate complex, tri (4-amino-1,2,4-triazole) iron bromate Complex, tri (4-methyl-1,2,4-triazole) iron sulfate complex, tri (4-methyl-1,2,4-triazole) iron nitrate complex, tri (4-methyl-1,2,4) -Triazole) iron hydrochloride complex, tri (4-methyl-1,2,4-triazole) iron tetrafluoroborate complex, tri (4-methyl-1,2,4-triazole) iron fluoride complex Tri (4-methyl-1,2,4-triazole) iron bromate complex, tri (4-ethyl-1,2,4-triazole) iron sulfate complex, tri (4-ethyl-1,2, 4-triazole) iron nitrate complex, tri (4-ethyl-1,2,4-triazole) iron hydrochloride complex, tri (4-ethyl-1,2,4-triazole) iron tetrafluoroborate complex, Tri (4-ethyl-1,2,4-triazole) iron fluorate complex, tri (4-ethyl- 1,2,4-triazole) iron bromate complex, tri (4-propyl-1,2,4-triazole) iron sulfate complex, tri (4-propyl-1,2,4-triazole) iron nitrate complex Tri (4-propyl-1,2,4-triazole) iron hydrochloride complex, tri (4-propyl-1,2,4-triazole) iron tetrafluoroborate complex, tri (4-propyl-1 , 2,4-triazole) iron fluoride salt complex, tri (4-propyl-1,2,4-triazole) iron bromate complex, tri (4-butyl-1,2,4-triazole) iron sulfate Complex, tri (4-butyl-1,2,4-triazole) iron nitrate complex, tri (4-butyl-1,2,4-triazole) iron hydrochloride complex, tri (4-butyl-1,2,4) -Triazole) iron tetrafluoroborate complex, tri (4-butyl-1,2,4-to Riazole) iron fluorate complex, tri (4-butyl-1,2,4-triazole) iron bromate complex, and the like.

  The binder which is an ink component covering the particle surface of the iron triazole complex compound has adhesiveness and has an effect of preventing oxidation of the iron triazole complex compound particles.

  Specific examples of binders include vinyl resins, silicone resins, rosin resins, terpene resins, phenol resins, alkyd resins, polyester resins, polyether resins, acrylic resins, polyurethane resins, epoxy resins, ketone resins, maleic resins, and coumarin resins. , Polyvinyl alcohol resin, polyvinyl butyral resin, polyethylene resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl formal resin , Polystyrene resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene-styrene resin (ABS resin), polymethyl methacrylate resin, methyl methacrylate (MMA) -styrene Polymer resin, polycarbonate resin, ethyl cellulose resin, cellulose acetate 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, methyl cellulose, ethyl cellulose, natural Examples include rubber, synthetic rubber, butyl rubber, petroleum resin, and oil. These binders may be used alone or in combination. Here, nylon is a registered trademark.

  Solvents that are stable with iron triazole complex as an ink component together with a binder include, for example, 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, vinegar Butyl, isoamyl 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, Examples thereof include carbon tetrachloride, cellosolve, methyl cellosolve, ethyl cellosolve, butyl cellosolve, carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylbenzene, and water. These solvents may be used alone or in combination.

  The temperature indicating ink composition prepared with these essential components may contain additives as necessary in order to improve performance such as storage stability, productivity, and functionality.

Examples of the additive include a material that improves the printability of the temperature indicating ink composition, a material that improves durability, and a material that adjusts the discoloration color tone. Specific examples of materials for improving the printability of the temperature indicating ink composition include wax, wax, dryer, dispersant, wetting agent, cross-linking agent, gelling agent, thickener, stabilizer, delustering agent, and defoaming agent. , Color separation inhibitor, photopolymerization initiator, mold inhibitor, plasticizer, thixotropy imparting agent, and the like. Specific examples of the material for improving durability include an ultraviolet absorber. Further, as materials for adjusting the discoloration color tone, 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 Parared, Villiant Fast Scarlet, Pyrazolone Red B, Barium Red 2B, Calcium Red 2B, Barium Resol Red, Lake Red C, Brilliantamine 6B, Pigment Scarlet 3B Lake, Rhodamine 6G PTMA Toner Ngara, Naphthol Red FGR, Quinacridone Magenta, Rhodamine B PTMA Toner, Methyl Violet PTMA Toner, Quinacridone Red, Dioxazine Violet, Victoria Pure Blue PTMA Toner, Phthalocyanine Blue, Alkali Blue Toner, Bituminous Blue, Ultramarine Blue, Brilliant Green PTMA Toner, Diamond Examples include green PTMA toner, phthalocyanine green, carbon black, zinc white, aluminum powder, extender pigment, bronze powder, fluorescent pigment, phosphorescent pigment, and pearl pigment. These additives are appropriately used according to the suitability of the temperature indicating ink composition and the printability, and may be used singly or in combination.

Such additives can facilitate the adjustment of the discoloration color tone of the temperature indicating ink composition. The temperature indicating ink composition comprises a mercury-containing temperature indicating pigment such as mercury (II) iodide complex compound (Cu ₂ [HgI ₄ ]) which is red at a low temperature and dark brownish purple at a high temperature and is difficult to adjust the color change. In contrast, it is pink at low temperatures and white at high temperatures, making it easy to adjust discoloration. For example, by adding an additive which is a pigment that does not change or discolor due to temperature, the discoloration color tone can be easily adjusted such that the color of the same system is shaded or the complementary color relationship before and after the discoloration. Specifically, by adding an appropriate amount of phthalocyanine blue to the iron triazole complex compound, a temperature indicating ink composition that turns purple at a low temperature and blue at a high temperature can be obtained. On the other hand, by adding an appropriate amount of fast yellow to the iron triazole complex compound, a temperature indicating ink composition that turns dark pink at low temperatures and yellow at high temperatures can be obtained.

  By containing the additive which shows these various performances, or selecting an ink component according to a use, the thermostatic ink composition of this invention turns into coating materials, such as printing ink and paint.

  The printing ink of the present invention can be used, for example, as an ink constituting a discolored portion of a temperature management indicator that is attached to a test object.

  The printing ink of the present invention can be used, for example, as an ink that changes color when the temperature of a printed material changes, and can be used as an anti-tampering ink.

  The paint of the present invention is, for example, in the form of paint and can be directly applied to an object to be used as a thermo paint.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  The preparation and discoloration test of the temperature indicating ink composition to which the present invention is applied are shown in Examples 1 to 4.

Example 1
10 g of iron sulfate heptahydrate (FeSO ₄ · 7H ₂ O) is dissolved in 100 ml of distilled water, and 1 g of ascorbic acid is added. 2 to 3 drops of concentrated sulfuric acid was added to the solution and heated to dissolve all the solutes to obtain a solution (1). In a separate container, 25 g of 4-amino-1,2,4-triazole was dissolved in 100 ml of ethanol and heated in a water bath to obtain a solution (2). Next, while warming the solution (1), the solution (2) was added and stirred for 1 to 2 hours. Upon cooling to room temperature, a pink precipitate was obtained. The precipitate was filtered while being washed with ethanol, and then allowed to stand for 2 to 3 days by natural drying to obtain 12 g of a pink powder. The pink powder was an iron (4-amino-1,2,4-triazole) sulfate complex.

  10 g of the obtained iron triazole complex compound, 30 g of commercially available medium (product name: Utack A undercoat clear; manufactured by Nippon Special Paint Co., Ltd.), 30 g of toluene and 3 g of ethyl acetate as a solvent, 3 g of barium sulfate (manufactured by Kanto Chemical Co., Ltd.) Then, Hi-Filler # 12 (manufactured by Matsumura Sangyo Co., Ltd.) was kneaded as talc to prepare a reversible temperature indicating paint as a temperature indicating ink composition. The reversible thermogenic paint obtained by the preparation was pink. The obtained reversible temperature indicating paint was spray-coated on a standard test plate A1050P (1.5 mm × 70 mm × 150 mm; manufactured by Nippon Test Panel Co., Ltd.) with an air spray, and the reversible temperature indicating paint was dried. After drying, a pink coating layer was obtained on the upper surface of the standard test plate. When these standard test plates were placed in a constant temperature bath at 70 ° C., the pink coating layer turned white. When it was taken out from the thermostat and cooled to near room temperature, the discolored white coating layer returned to pink. Furthermore, it was confirmed that the pink coating layer changed to white again when it was heated in a thermostat, and repeatedly changed color. Further, even when the standard test plate was placed in a constant temperature bath at 60 ° C., the pink color maintained the same color tone and did not change color. From this, it was confirmed that these reversible temperature indicating paints have a temperature detection capability.

(Example 2)
For the thermochromic pigment exhibiting thermochromism, the iron (4-amino-1,2,4-triazole) sulfate complex compound of Example 1 is used.

  10 g of iron triazole complex, 90 g of commercially available medium (product name: New LP Super R medium; manufactured by Toyo Ink Manufacturing Co., Ltd.), 18 g of SL-302 solvent C (manufactured by Toyo Ink Manufacturing Co., Ltd.) as solvent, R820 as titanium oxide 8 g (Ishihara Sangyo Co., Ltd.) and 2 g of Hi-Filler # 12 (Matsumura Sangyo Co., Ltd.) as talc were kneaded to prepare gravure printing ink as a temperature indicating ink composition. The ink for gravure printing obtained by the preparation was pink. The obtained gravure printing ink was printed on a polyethylene terephthalate (PET) film having a thickness of 12 μm using GRAVO-PROOF MINI (manufactured by Nissho Gravure Co., Ltd.) and dried. After drying, a light pink coating layer was obtained on the upper surface of the PET film. When these PET films were placed in a thermostat at 70 ° C., the light pink coating layer turned white. When it was taken out from the thermostat and cooled to near room temperature, the discolored white coating layer returned to a light pink color. Further, it was confirmed that the light pink coating layer turned white again when heated in a constant temperature bath in the same manner and repeatedly changed color.

(Example 3)
10 g of iron sulfate heptahydrate (FeSO ₄ · 7H ₂ O) was dissolved in 150 ml of 0.1N nitric acid. To the solution, 9.3 g of barium nitrate was added and stirred while heating to obtain a solution (3). When this solution (3) was stirred for 2 hours and then allowed to stand naturally, a white precipitate (barium sulfate) was formed. The precipitate was filtered to obtain a solution (4) as a filtrate. In a separate container, 10 g of 4-amino-1,2,4-triazole was dissolved in 100 ml of ethanol and heated in a water bath to obtain a solution (5). Next, while warming the solution (4), the solution (5) was added and stirred for 1 to 2 hours. Upon cooling to room temperature, a pink precipitate was obtained. This precipitate was filtered while being washed with ethanol, and then allowed to stand for 2 to 3 days by natural drying to obtain 6 g of a pink powder. The pink powder was an iron (4-amino-1,2,4-triazole) nitrate complex.

  10 g of the obtained iron triazole complex compound, 20 g of a commercially available medium (product name: No. 5 L Carton Medium GW; manufactured by T & K Tohka Co., Ltd.), 15 g of ethyl acetate as a solvent, calcium carbonate (manufactured by Iwai Chemical Co., Ltd.) 1 g was kneaded to prepare a reversible ultraviolet (UV) curable flexographic ink which is a temperature indicating ink composition. The UV curable flexographic ink obtained by the preparation was pink. The obtained UV curable flexographic printing ink was printed on a high-quality tack paper with a letterpress, and UV curable flexographic ink was UV cured using TOSCURE 401 (manufactured by Toshiba Corporation) as a UV irradiation device. . After curing, a pink coating layer was obtained on the upper surface of the high-quality tack paper. A high-quality tack paper coated with UV curable flexographic ink was cut into a size of 10 mm × 10 mm to obtain a temperature control indicator. When this temperature control indicator was placed in a constant temperature bath at 65 ° C., the pink temperature control indicator turned white. When the temperature was taken out from the thermostatic bath and cooled to near room temperature, the white temperature control indicator that had changed color returned to pink. Furthermore, when it heated similarly in the thermostat, it confirmed that the pink temperature control indicator changed to white again and changed color repeatedly.

Example 4
10 g of iron sulfate heptahydrate (FeSO ₄ · 7H ₂ O) and ₂ g of ascorbic acid were dissolved in 100 ml of distilled water to obtain a solution (6). 10 g of barium nitrate was dissolved in 100 ml of distilled water to obtain a solution (7). Solution (7) was added to solution (6) and stirred with heating to obtain solution (8). When this solution (8) was stirred for 4 hours and then allowed to stand naturally, a white precipitate (barium sulfate) was formed. The precipitate was filtered to obtain a solution (9) as a filtrate. To the solution (9), 20 g of potassium tetrafluoroborate was added, stirred for 2 hours with heating, and left to stand to form a white precipitate (potassium nitrate). The precipitate was filtered to obtain a solution (10) as a filtrate. In a separate container, 10 g of 4-amino-1,2,4-triazole was dissolved in 100 ml of ethanol and heated in a water bath to obtain a solution (11). Next, while warming the solution (10), the solution (11) was added and stirred for 4 hours. Upon cooling to room temperature, a pink precipitate was obtained. This precipitate was filtered while being washed with ethanol, and then allowed to stand for 2 to 3 days by natural drying to obtain 10 g of a pink powder. The pink powder was an iron (4-amino-1,2,4-triazole) tetrafluoroborate complex compound.

  A reversible screen printing ink as a temperature indicating ink composition was prepared by kneading 10 g of the obtained iron triazole complex compound, 1 g of butyl rubber, and 20 g of mineral spirit as a solvent. The ink for screen printing obtained by the preparation was pink. The obtained screen printing ink was printed on high-quality paper with a screen plate (150 mesh), and the screen printing ink was naturally dried. After drying, a pink coating layer was obtained on the top surface of the fine paper. Securities (for example, admission tickets) were prepared using high-quality paper coated with screen printing ink. When this ticket was heated to 50 ° C., the pink coating layer turned white. When the heating was stopped and the system was cooled, the discolored white coating layer returned to pink. As a result, it was confirmed that this ticket is not a forgery.

  The temperature indicating ink composition of the present invention is in a liquid state, and is applied to a paint to be directly applied to or sprayed on a test object whose temperature is to be detected, an indicator attached to the test object, or an anti-counterfeit ink. Used for available inks. The temperature indicating ink composition can be applied to these specimens for temperature management of mechanical equipment, prevention of overheating accidents of power distribution equipment, temperature management of constant temperature storage products, counterfeiting of securities, and the like.

Claims (2)

SO ₄ ²⁻ , SO ₃ ²⁻ , HSO ₄ ²⁻ , HSO ₃ ²⁻ , S ₂ O ₃ ²⁻ , OH ⁻ , CH ₃ COO ⁻ , HCOO ⁻ , C ₂ O ₄ ²⁻ , CO ₃ ²⁻ , HPO ₄ ⁻ , PF ₆ ²⁻ , SiF ₆ ²⁻ , B (C ₆ H ₅ ) ₄ ⁻ , and R—SO ₃ ⁻ (where R is a saturated or unsaturated hydrocarbon group and / or aromatic group) at least it has a counter anion consisting of one reversibly color change to that granular or powdered iron triazole complex at a temperature to be detected during the rise or fall in temperature by indicating the thermochromism selected from) A compound ,
An adhesive binder covering the particle surface of the granular or powdered iron triazole complex ,
A solvent ,
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, Brilliantamine 6B, Pigment Scarlet 3B Lake, Rhodamine 6G PTMA Toner, Bengala, Naphthol Red FGR, Quinacridone Maze , Rhodamine B PTMA Toner, Methyl Violet PTMA Toner, Quinacridone Red, Dioxazine Violet, Victoria Pure Blue PTMA Toner, Phthalocyanine Blue, Alkali Blue Toner, Bitumen, Ultramarine Blue, Brilliant Green PTMA Toner, Diamond Green PTMA Toner, Phthalocyanine Green, Carbon An additive containing a material that adjusts the discoloration color tone, at least any one selected from black, zinc white, aluminum powder, extender pigment, bronze powder, fluorescent pigment, phosphorescent pigment, and pearl pigment,
In a weight ratio of 0.1-100: 0.1-50: 1-500: 0.001-10
Wherein in sticky binder, while dispersion remains the granular or powdered iron triazole complex compound, thermochromic ink composition of the liquid, it characterized that you have been contained.   2. The temperature indicating ink composition according to claim 1, which is a printing ink composition or a coating ink composition.