JP2013090882A - Temperature controllable cooking utensil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a richly designed colorful variously shaped temperature controllable cooking utensil which is safe, excellent in heat resistance to a temperature change in a broad area and light resistance to sunlight, ultraviolet and the like, and durability to repeated operational reproductions of a heating-cooling cycle, and capable of sensitively and reversibly discoloring, visually displaying in a clear color tone change, and correctly and easily recognizing a temperature control status with a desired specific temperature inside a detected object being a food like foodstuff, a degree to transfer heat into the inside, and the holding time at the temperature.SOLUTION: A reversible temperature indicating material containing a binder, and an iron-triazole iron complex compound reversibly changing its color at a predetermined temperature by indicating a thermochromism when the temperature rises or drops, is embedded and/or enclosed in a three-dimensional or a sheet-like resin mold material propagating heat inside to the predetermined temperature with time passage.

Description

  The present invention relates to a temperature-controlled cooking utensil that visually displays a heating condition inside a food by a change in color tone.

  When cooking foods such as eggs, noodles, vegetables, seafood, meat, etc. that are boiled or boiled, it is reversible depending on the heating temperature and heating time in order to visually check the boiled condition and boiled condition. A temperature management indicator having a temperature indicator that changes color is used.

  Currently, thermochromic mercury-containing halogen complex compounds are mainly used as temperature-indicating components in temperature-indicating materials for temperature management indicators sold in and outside of Japan. This temperature management indicator reversibly changes its color tone from a relatively dark color tone such as red to black-red or yellow to orange by heating. Due to the limited dark color, the color and design of the temperature indicating material and the temperature management indicator are restricted, and the variety of designs as products is lacking. Further, there is only an indicator having a color change temperature by heating of about 40 ° C. to 70 ° C., and the management temperature range is narrow. Furthermore, since harmful mercury, which is an environmentally hazardous substance, is contained, waste liquid treatment is necessary in the production process, and a large-scale production facility is inevitably required, resulting in poor productivity due to an increase in production cost. Other than these problems, the use of mercury is being avoided from the viewpoint of human safety measures and environmental protection measures against mercury.

  As a temperature control indicator that reversibly changes color without containing mercury, Patent Document 1 discloses an electron-accepting compound, an electron-donating compound that changes color by reversibly donating electrons upon contact with the compound, A temperature control indicator for cooking is disclosed in which a microcapsule enclosing a hot-melt substance that is melted at a heating temperature to be detected and brought into contact with the resin is molded in a resin molding material. In general, these organic compounds such as electron accepting compounds and electron donating compounds are easily decomposed over time by light or heat even if they are not used, and the degree of discoloration gradually increases when they are discolored repeatedly during temperature control. Therefore, an indicator using a temperature indicating material of an organic compound or a microcapsule enclosing the organic compound tends to have insufficient durability, particularly light resistance, heat resistance, and repetitive operation reproducibility.

  There is a demand for a temperature management indicator that is safe enough to be used for foods such as foods during cooking, and has excellent durability that discolors with high sensitivity even after repeated use.

JP 2008-203055 A

  The present invention has been made to solve the above-mentioned problems, does not contain harmful metals such as mercury, which is an environmentally hazardous substance, is safe, has heat resistance against a wide range of temperature changes, and is resistant to sunlight, ultraviolet rays, etc. Excellent in durability such as reproducibility and repetitive operation repeatability of heating-cooling cycle, specific desired temperature inside the object to be detected which is food such as food, the degree of heat transfer to the inside, and the temperature The temperature control status with the retention time in the sensor can be reversibly discolored with high sensitivity and visually displayed with clear color change, and can be accurately and easily distinguished, and various shapes and colors provide rich design An object is to provide a temperature control cooking utensil.

  The temperature controlled cooking utensil according to claim 1 made to achieve the above object is reversibly discolored at a predetermined temperature when the temperature rises or falls by showing thermochromism. A reversible temperature indicating material containing an iron triazole complex compound and a binder is embedded and / or enclosed in a three-dimensional or sheet-shaped resin molding material that propagates heat to the inside over time to reach the predetermined temperature. It is characterized by that.

  A temperature-controlled cookware according to a second aspect is the one according to the first aspect, wherein the reversible temperature indicating material is in a layered form attached to a base material.

  The temperature-controlled cooking utensil according to claim 3 is the one described in claim 1, wherein the reversible temperature indication is less than or above the color change temperature of the reversible temperature indication material and the reversible temperature indication material. The invariant color-dye-containing layer having a color different from the hue exhibited by the material is arranged side by side or at least partially overlapped on the substrate.

  The temperature control cooking appliance according to claim 4 is the one described in claim 1, wherein the resin molding material is oval, semi-oval, elliptical, semi-elliptical, spherical, hemispherical. Further, the solid shape is any one of a columnar shape and a weight shape.

  The temperature-controlled cooking utensil of the present invention has a specific desired temperature inside the object to be detected such as foods such as ingredients and processed foods, the degree of heat transfer to the inside, and the holding at that temperature. The temperature management status with respect to time can be easily and accurately displayed with visible color change. For this reason, even if the object to be detected is not loosened or cut off, it is possible to confirm the specific boiled state with a subtle boiled rice cake such as half-boiled or raw-boiled by clear color change that can be visually discerned.

  This temperature-controlled cooking utensil is a reversible that contains an iron triazole complex compound that can be freely and reversibly displayed at a desired specific temperature in a wide temperature range from about -120 ° C to 120 ° C. The temperature-indicating material makes it possible to control the temperature according to the intended use without causing denaturation or deterioration over a wide range of temperature changes. In addition, for example, by adding an invariant colorant that does not change color due to a temperature change to an iron triazole complex compound whose color change color tone reversibly changes from pink to white, the color change color tone can be freely adjusted, The color difference before and after the color change can be increased. Since the temperature-controlled cooking utensil can freely adjust the discolored color tone, it can have a desired shape and color and is rich in design. Furthermore, this temperature-controlled cooking utensil makes it easy to discriminate it by resembling the shape of the object to be detected, for example, the shape of a boiled egg, or the specific temperature inside the object or the heat transfer to the inside depending on the shape and physical properties of the object to be detected It can be expressed in a pseudo manner according to the degree.

  In addition, temperature controlled cooking utensils are physically and chemically more stable against heat, light, and changes over time than simple organic compounds because the iron triazole complex is a complex of organic and inorganic substances. It is uniformly dispersed with no change in quality. And it is excellent in the repetition durability of the heating-cooling cycle, and can be used stably. Therefore, the temperature management cooking utensil can visually and accurately confirm the state of heat propagation over time in the heating-cooling of the detected object.

  Furthermore, this temperature-controlled cookware does not contain harmful metals such as mercury that adversely affect the environment and the human body in the reversible temperature indicating material, and is highly safe for users and manufacturers. Because it does not contain mercury or other harmful metals, waste liquids such as wastewater discharged during the manufacture of temperature-controlled cooking utensils do not contain environmentally hazardous substances, and large-scale production equipment such as purification equipment is not required, resulting in production costs. Can be suppressed. Furthermore, the production cost can be reduced by using an iron triazole complex compound having high versatility and inexpensive and safe iron as a central metal as a temperature indicating pigment.

It is the schematic cross section of the temperature control cooking utensil to which this invention is applied, and a partially expanded schematic cross section. It is a top view which shows the middle of use of the temperature control cooking utensil to which this invention is applied. It is a schematic cross section of the indicator in the temperature management cooking appliance to which the present invention is applied. It is a schematic cross section of another temperature control cooking utensil to which the present invention is applied. It is the model top view and schematic cross section of another temperature management cooking appliance to which this invention is applied. It is a perspective schematic diagram which shows the use condition of another temperature management cooking appliance to which this invention is applied.

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

  The temperature control cooking utensil of the present invention will be described with reference to FIG. 1 corresponding to the embodiment.

  As shown in the schematic cross-sectional view of FIG. 1A, the temperature-controlled cooking utensil 1 is a three-dimensional resin molding material 6 in which a thin sheet-like indicator 5 is hemispherical, colorless, or colored, transparent or translucent. It is embedded and enclosed inside. As shown in the partially enlarged schematic cross-sectional view of FIG. 1B, the indicator 5 has an iron triazole complex compound 7 which is a temperature indicating pigment component reversibly discolored at a desired temperature on the observation surface side of the substrate 3. A reversible temperature indicating material 2 dispersed in a binder, which is a resin, is formed into a layer, and a part of the reversible temperature indicating material 2 is provided with an invariant color-dye-containing layer 4 made of an invariant colorant 8 that does not change color due to a temperature change. It is formed by overlapping.

  When the reversible temperature indicating material 2 containing the iron triazole complex compound 7 is heated from a temperature lower than the temperature at which the iron triazole complex compound 7 changes color to a temperature higher than the color change temperature, the color tone of the reversible temperature indicating material 2 is increased. Changes. When the reversible temperature indicating material 2 is lowered from a temperature higher than the color change temperature of the iron triazole complex compound 7 to a temperature lower than the color change temperature again, the color tone of the color change is restored again. Therefore, by visually observing the color tone of the reversible temperature indicating material 2, it can be easily visually discriminated whether the current temperature at the site of the indicator 5 is lower than or higher than the color change temperature of the iron triazole complex compound 7.

  The reversible temperature indicating material 2 and the invariant color pigment-containing layer 4 may be colored and transparent and visible light transmissive, or colored and opaque and visible light non-transmissive.

  For example, when the invariant color dye-containing layer 4 is visible light transmissive, the color tone of the invariant color dye 8 contained in the invariant color dye-containing layer 4 overlaps with the lower layer on the exposed invariant color dye-containing layer 4. Another color tone in which the color tone of the reversible temperature indicating material 2 is mixed is visually recognized, and only the color tone of the reversible temperature indicating material 2 itself is visually recognized on the exposed reversible temperature indicating material 2.

  On the other hand, when the invariant color dye-containing layer 4 is visible light non-transmissive, only the color tone of the invariant color dye 8 contained in the invariant color dye-containing layer 4 is visually recognized on the exposed invariant color dye-containing layer 4. On the exposed reversible temperature indicating material 2, only the color tone of the reversible temperature indicating material 2 itself is visually recognized.

  This temperature control cooking utensil 1 shown in FIG. 1 is manufactured as follows.

  First, 0.1 to 100 parts by weight of iron triazole complex 7 which is a thermochromic pigment component reversibly discolored at a desired temperature, 0.1 to 50 parts by weight of a binder which is an ink component, and 1 to 500 parts by weight of a solvent. Then, if necessary, 0.001 to 10 parts by weight of an additive is kneaded to prepare a reversible temperature indicating ink. The reversible temperature indicating ink 2 is formed by applying the reversible temperature indicating ink to the observation surface side of the opaque white substrate 3 by printing. Further, on the reversible temperature indicating material 2, an invariant color ink containing an invariant colorant 8 which is different in color before and after the color change exhibited by the reversible temperature indicating material 2 and does not change color due to a temperature change is overlaid and printed. By forming the colored transparent invariant color pigment-containing layer 4 having transparency, a sheet-like indicator 5 as shown in FIG. 1B is obtained.

  Next, a colorless or colored transparent or translucent curable resin raw material is applied to the mold recess 8 in a metal or glass mold having a desired recess such as a semi-elliptical sphere and coated with a release material. Pour to about the minute and cure by heating or light irradiation. There, the indicator 5 is placed with the observation surface side of the indicator 5 on which the reversible temperature indicating material 2 and the invariant color pigment-containing layer 4 are formed facing the mold side. Further, after pouring a resin material and completely immersing the indicator 5 in the resin material, the resin material is cured by heating or light irradiation. Thereafter, when the hemispherical cured resin molding material is taken out from the mold, the temperature control cooking utensil 1 is obtained.

  This temperature control cooking utensil 1 shown in FIG. 1 is used as follows.

  This temperature-controlled cooking utensil 1 is heated by being exposed to the same environment as the object to be detected. A specific mode of use and a mechanism for reversibly discoloring the temperature-controlled cooking utensil 1 at that time will be described below with reference to FIGS. 1 and 2. At this time, the discoloration color tone of the iron triazole complex compound 7 as a temperature indicating pigment changes from pink to white before and after heating at the specific temperature. Furthermore, the invariant color dye-containing layer 4 uses an invariant color dye 8 that exhibits yellow.

  Put this temperature-controlled cookware 1 together with raw eggs in a pot filled with water. In a low-temperature state before heating the pan, the temperature-controlled cooking utensil 1 is an indicator in which a visible light transmissive invariant color pigment-containing layer 4 is attached on the reversible temperature indicating material 2 attached to the base material 3. 2, the small elliptical invariant color-dye-containing layer 4 located in the center of the iron triazole complex contained in the reversible temperature-indicating material 2 in yellow and the lower layer of the invariant color dye 8 as shown in FIG. A dull yellow peach color which is a color mixed with the pink color of the compound 7 is shown, and the large elliptical reversible temperature indicating material 2a surrounding the pink color of the iron triazole complex compound 7 is shown. In (a) to (c) of FIG. 2, the range of the reversible temperature indicating material 2 a that is colored pink is illustrated by a diagonal line that rises to the right, and the invariant color pigment-containing layer 4 that is colored yellow is shown. It is illustrated by a diagonal line rising to the left, and a mixed color of both colors is illustrated by a cross diagonal line.

  In the initial state where the pan is started to be heated, the heat accompanying the heating propagates over time from the surface of the resin molding material 6 of the temperature-controlled cooking utensil 1 to the inside. The temperature is getting lower. Along with this, this heat also propagates over time to the reversible temperature indicating material 2a. When the propagated heat exceeds the characteristic discoloration temperature of the iron triazole complex 7, a spin crossover phenomenon occurs in the iron triazole complex 7, and the color tone of the reversible temperature indicating material 2 changes from pink to white. To do. In accordance with the propagation of heat over time from the vicinity of the surface of the resin molding material 6 to the inside thereof, this discoloration is earlier in the vicinity of the surface of the resin molding material 6 and slower in the deeper portion. Therefore, it shows that the temperature management cooking appliance 1 is fully heated to the deep part of the resin molding material 6, so that the discoloration range is wide.

  As a result, as shown in FIG. 2 (b), the reversible temperature indicating material 2 of the temperature-controlled cooking utensil 1 starts to gradually discolor from its peripheral portion, and shows the heat propagation state. At this time, if the eggs boiled together are taken out, they are obtained as soft soft-boiled eggs. When the heating is continued, as shown in FIG. 2 (b), the boundary line between the pink color and the white color of the reversible temperature indicating material 2, 2a approaches the invariant color pigment-containing layer 4 in the center, and the white color change range is Become a wide range. The invariant color pigment-containing layer 4 exhibits a yellow pink color, which is a color in which the yellow color of the invariant color pigment 8 and the pink color of the iron triazole complex compound 7 are mixed, as in the low temperature state. If the egg is taken out at this time, a hard soft-boiled egg can be obtained. In these FIGS. 2 (a) and 2 (b), the yolk is semi-ripe and dull yellow peach to orange, so it has a color approximate to the dull yellow peach color as the invariant color pigment-containing layer 4. ing. If the heating is continued further, as shown in FIG. 2 (c), the reversible temperature indicating material 2 changes its color to white on the entire surface, and the invariant color pigment-containing layer 4 which is yellow peach color has its original color. Shows a bright yellow color. Therefore, the invariant color-dye-containing layer 4 is visually recognized as if it changed from yellow peach color to yellow color due to the discoloration of the lower reversible temperature indicating material 2. At this time, if the egg is taken out, the egg can be obtained in a solid cake. In FIG. 2C, the yolk is sufficiently solid and has a bright yellow color, and thus has a bright yellow color or an approximate color to yellow that is visually observed as the invariant color pigment-containing layer 4.

  When the temperature control cooking utensil 1 returns to a low temperature again, the iron triazole complex compound 7 reversibly returns to the original spin state, whereby the reversible temperature indicating material 2 is restored from white to pink which is the original color tone. Therefore, in the heating-cooling cycle, such a color change from pink to white or from white to pink is repeated.

  The temperature-controlled cooking utensil 1 shown in FIG. 2, which is designed in such a way that the egg yolk and the reversible temperature indicating material 2 represent the egg yolk and the reversible temperature indicating material 2 and the egg cross-section is imaged, covers the shell. The color changes as if you were looking at the contents of the broken egg. Such a temperature-controlled cooking utensil 1 visually displays the state of heat propagation to the object to be detected, and visually and easily discriminates the state of the object to be detected, such as the degree of boiled or boiled can do.

  The temperature controlled cooking utensil 1 of the present invention is obtained by appropriately adjusting the reversible temperature indicating ink, the thickness of the resin molded material 6 from the surface of the temperature controlled cooking utensil to the reversible temperature indicating material 2, the resin composition of the resin molded material 6, and the like. The time from the start of heating to the color change or the temperature at which the color changes can be adjusted. In adjusting the discoloration temperature and the discoloration time, for example, when managing the temperature range of 70 to 100 ° C., the thickness of the resin molding material 6 from the temperature control cookware surface to the reversible temperature indicating material 2 is 1 to 1. It is preferable that it is 3 cm.

  In the temperature management cooking utensil 1, an example in which the observation surface side of the indicator 5 is directed to the curved surface side of the semi-elliptical spherical resin molding material 6 is illustrated, but is directed to the flat surface side of the hemispherical resin molding material 6. May be. The indicator 5 may be formed with an adhesive layer on the reversible temperature indicating material 2 and the invariant color pigment-containing layer 4 to form an adhesive layer, or may be provided with a protective film.

  As shown in FIG. 3A, the indicator 5 is covered with the reversible temperature-indicating material 2 from above the base 3 together with the invariant color pigment-containing layer 4 attached to a part of the observation surface side on the base 3. As shown in FIG. 3B, the reversible temperature indicating material 2 and the invariant color dye-containing layer 4 are arranged side by side on the observation surface side of the substrate 3 and formed. It may be. Further, as shown in FIG. 3C, only the reversible temperature indicating material 2 is formed on the observation surface side on the substrate 3, and it is not necessary to have the invariant color dye-containing layer 4.

  Moreover, although the shape of the temperature control cooking appliance 1 illustrated the semi-elliptical sphere according to the boiled egg, the solid shape is not specifically limited, It can select suitably according to shapes of test objects, such as a foodstuff. For example, it may be a spherical shape such as a true sphere or an elliptical sphere matched with a boiled egg or a hemispherical shape thereof, or a thin and long cylindrical shape that is suitable for noodles such as udon and pasta. It may be prismatic or spindle-shaped.

  When the temperature control cooking utensil 1 has a cylindrical shape, as shown in FIG. 4, the reversible temperature indicating material 2 that is slightly thinner and smaller than the resin molding material 6 and contains the iron triazole complex compound 7 is cylindrical. The resin molding material 6 may be embedded or covered with a film-shaped resin molding material 6 and enclosed. The temperature management cooking utensil 1 can be used as an indicator for managing the rise of noodles or pasta when it is thin and long cylindrical with a thickness of about pasta. When the temperature control cooking utensil 1 is put in a pan together with pasta and heated to a temperature higher than the desired temperature, the color gradually changes from the surface of the reversible temperature indicating material 2. If the boiled pasta is taken out during the discoloration, aldente pasta is obtained. Furthermore, when the temperature inside the indicator reaches a desired temperature, the entire surface of the reversible temperature indicating material 2 is discolored. If you take out the boiled pasta after completely discoloring, you can get a boiled pasta. Similarly, by adjusting the time until discoloration or the discoloration temperature according to the object to be detected and visually displaying the propagation of heat, it is possible to determine the degree of boil of other ingredients such as vegetables.

  When the temperature control cooking utensil 1 is in the form of a sheet, as shown in FIG. 5 (a) schematic plan view and (a ′) schematic cross-sectional view, an iron triazole complex compound 7 is formed on one side of the substrate 3 which is a resin film. The rectangular indicator 5 in which the reversible temperature indicating material 2 containing s is formed may be inserted with a film-shaped or sheet-shaped resin forming material 6 and heat-laminated to be enclosed. The resin molding material 6 covering the indicator 5 is colorless and transparent, colored and transparent, or translucent, and it is possible to clearly confirm the discoloration of only the portion that has been heated to reach a predetermined temperature. Here, (b) of FIG. 5 is a figure which shows the middle of a color change when a part of temperature management cooking appliance 1 reaches the color change temperature. (A) and (b) of FIG. 5 show the unchanging color range X, which is a range showing the color when heated to the color before the heating and the color change temperature or higher and then cooled to a temperature lower than the color change temperature, with diagonal lines rising to the left. A discoloration range Y, which is a range indicating the color when heated to the discoloration temperature or higher, is indicated by a diagonal line rising to the left.

  For example, as shown in FIG. 6, a part of the temperature management cooking utensil 1 shown in FIG. 5 may be used in contact with a measurement object or an observation object. Only the portion that has reached the discoloration temperature is discolored with high sensitivity, so the temperature change and heat transfer process can be visually observed.

  The reversible temperature indicating material 2 of the temperature control cooking utensil 1 is a reversible temperature indicating ink in which the particle surface of the iron triazole complex compound 7 which is a temperature indicating pigment is coated with a binder which is a resin and is uniformly dispersed in a medium which is an ink component. Is formed. In the reversible temperature indicating material 2, the iron triazole complex compound 7 is uniformly dispersed in the binder while the particle surface is coated. This coated state prevents alteration of the iron triazole complex 7 due to oxidation or the like. The iron triazole complex 7 is preferably 0.1 to 500 μm particles or powder particles. Even the iron triazole complex 7 which is considered to have poor durability in a powder form can exist stably.

This iron triazole complex 7 is a transition metal complex in which the central metal is a divalent iron ion and the ligand coordinated with the central metal is composed of triazole, a derivative thereof, and a counter anion. . Regarding the iron triazole complex 7, there are hydrates and anhydrides, 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 7 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 bromine Salt 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 Salt 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- Triazole) iron fluorate complex, tri (4-butyl-1,2,4-triazole) iron bromate complex, and the like. These may be used alone or in a complex.

Particularly preferred are tri (4-amino-1,2,4-triazole) iron sulfate complex, tri (4-amino-1,2,4-triazole) iron tetrafluoroborate complex, and (1 , 2,4-triazole) and (4-amino-1,2,4-triazole) ligands and the like, and iron nitrate complexes.
These iron triazole complex compounds 7 show pink to reddish purple at low temperatures and show white to pale yellow at high temperatures due to thermochromism.

  The binder which is an ink component covering the particle surface of the iron triazole complex compound 7 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, 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 thereof include rubber, synthetic rubber, petroleum resin, and oil. Moreover, these binders may be used individually by 1 type, and may be used in mixture of multiple. Nylon is a registered trademark.

  Solvents that are stable with the iron triazole complex 7 as an ink component together with the 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, Butyl acid, 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 , Carbon tetrachloride, cellosolve, methyl cellosolve, ethyl cellosolve, butyl cellosolve, carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, diethylbenzene, water and the like. These solvents may be used alone or in combination.

  The reversible temperature indicating material 2 containing these essential components may contain additives as necessary in order to improve performance such as storage stability, productivity, and functionality.

  Additives used in combination with these binders and solvents include materials that improve the printability of ink, materials that improve durability, and materials that adjust the discoloration color tone.

  Materials that improve the printability of ink include wax, wax, dryer, dispersant, wetting agent, cross-linking agent, gelling agent, thickener, stabilizer, matting agent, defoaming agent, anti-coloring agent, light Examples thereof include a polymerization initiator, an antifungal agent, a plasticizer, and a thixotropy imparting agent. Specific examples of materials that improve durability include ultraviolet absorbers. 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.

Examples of coloring materials for adjusting the discoloration color tone include titanium oxide, calcium carbonate, silicon dioxide, alumina white (Al ₂ O ₃ .xH ₂ O), clay, precipitated barium sulfate, gloss white, fast yellow G, and 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 Risol Red, Lake Red C, Brilliantamine 6B, Pigment Scarlet 3B Lake, Rhodamine 6G PTMA Toner, Bengga 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, bitumen, ultramarine, brilliant green PTMA toner, diamond green Examples thereof include 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 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 reversible temperature indicating material 2 can easily adjust the discoloration color tone by the material that adjusts the discoloration color tone. The reversible temperature indicating material 2 is a mercury-containing temperature indicating a red color at a low temperature such as mercury (II) copper complex compound (Cu ₂ [HgI ₄ ]), a dark brown color at a high temperature, and the color tone before and after the color change is difficult to adjust. Unlike pigments, they exhibit a relatively light color such as pink at low temperatures and white at high temperatures, making it easy to adjust the color tone before and after the color change. For example, by adding an additive that is a pigment that does not change or discolor with temperature, it is possible to easily and clearly adjust the discoloration color tone, such as those that show shades of the same color in shades or those that show complementary colors before and after discoloration. it can. Specifically, by mixing an appropriate amount of the iron triazole complex compound 7 and phthalocyanine blue, the reversible temperature indicating material 2 that turns purple at a low temperature and blue at a high temperature can be obtained. On the other hand, by mixing an appropriate amount of iron triazole complex compound 7 and fast yellow, the reversible temperature indicating material 2 that turns dark pink at low temperatures and yellow at high temperatures can be obtained.
Depending on the material that adjusts the discoloration color tone, before and after the discoloration of the reversible temperature indicating material 2, the change in color tone is clarified or the complementary color is emphasized, and the displayed color is temperature-controlled. The effect of making it easy to visually recognize according to an environment or a state arises.

  The material for adjusting the discoloration color tone is preferably 0.1 to 1 part by weight with respect to 1 to 10 parts by weight of the iron triazole complex 7 contained in the reversible temperature indicating material 2. Moreover, it is preferable that the particle diameter of the material which adjusts a discoloration color tone is 0.001-1 micrometer.

  The reversible temperature indicating ink prepared by mixing and adjusting these is printed on the substrate 3 by, for example, gravure printing, screen printing, flexographic printing, coater printing, offset printing, letterpress printing, planographic printing, ink jet printing, indicator 5 can be formed.

  The base material 3 is a polymer film, polymer plate, glass plate, glass cloth, metal foil, metal plate, paper, synthetic paper, cloth, fibrous sheet, non-woven fabric, cellulose, etc. As long as the substrate can be confirmed from the above, a transparent or translucent polymer film is particularly preferable. For example, polyester, polypropylene, polyethylene, polystyrene, polyethylene terephthalate (PET), polycarbonate, polystyrene, cellulose triacetate, polyvinyl alcohol, polypropylene, polyvinyl chloride, cellophane, nylon, polymethyl (meth) acrylate, polyolefin, polyimide, or polyvinyl acetate Examples thereof include those formed in a film shape. The polymer film may be formed by combining these alone or in combination, or may be formed by copolymerization. The substrate 3 may be transparent, translucent, or opaque.

  The invariant color pigment-containing layer 4 is formed of an invariant color ink containing the invariant color pigment 8, a binder and a solvent, and, if necessary, an additive. The invariant colorant 8 contained in the invariant colorant-containing layer 4 does not discolor due to a temperature change, and includes, for example, a coloring material that adjusts the discoloration color to be contained in the reversible temperature indicating material 2 as described above. It is done. One kind of these invariant colorants 8 may be used, or a plurality of them may be used in combination. The invariant colorant 8 is preferably contained in an amount of 0.001 to 10 parts by weight in the invariant color ink. Further, the particle size of the invariant colorant 8 is preferably 0.001 to 1 μm.

  What was illustrated above can be used for the binder, solvent, and additive which are contained in the invariant color ink which forms the invariant color pigment-containing layer 4. Further, the invariant color ink uses the color exemplified in the invariant color pigment 8 and may be a commercially available ink such as a lithographic ink, gravure ink, letterpress ink, or screen ink. Moreover, the ink manufactured using the illustrated invariant color pigment | dye 8 and a commercially available vehicle may be sufficient.

  For the protective film, the same material as that used for the substrate 3 can be used. Moreover, it may be a colored film depending on the design of the indicator, not limited to transparent and translucent, and may be an opaque film that sharpens the color change of the reversible temperature indicating material 2 such as white PET or YUPO synthetic paper.

  The pressure-sensitive adhesive material used for the pressure-sensitive adhesive layer is preferably acrylic, rubber-based, vinyl ether-based, silicone-based, epoxy-based, or a composite or copolymer thereof. An adhesive material such as a commercially available pressure-sensitive adhesive (manufactured by Sumitomo 3M Limited) may be used.

  The resin raw material for forming the resin molding material 6 is phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicon resin, alkyd resin, polyimide, polyaminobismaleimide, silicone resin, vinyl chloride resin , Vinyl acetate resin, polyvinyl alcohol, polyvinyl butyral, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), polymethyl methacrylate, polyphenylene oxide, polyurethane, ionomer resin, cellulosic plastic, polyethylene, polypropylene, polyamide, polycarbonate, polyacetal Polyphenylene sulfide, vinylidene chloride resin, polyethylene terephthalate, fluorine resin can be used, these resins May be used alone, it is possible to use a composite material. These resin materials may be colored by adding pigments or dyes to the extent that they do not interfere with the colors of the reversible temperature indicating material 2 and the invariant color pigment-containing layer 4.

  Hereinafter, the Example which produced the temperature control cooking utensil of this invention as a prototype is described in detail.

Example 1
In a reaction vessel, 10 g of iron sulfate heptahydrate (FeSO ₄ · 7H ₂ O) was dissolved in 100 ml of distilled water, and 1 g of ascorbic acid was added. 2 to 3 drops of concentrated sulfuric acid was added to the solution and heated to dissolve all solutes, and Solution 1 was obtained. In a separate reaction vessel, 25 g of 4-amino-1,2,4-triazole was dissolved in 100 ml of ethanol and warmed in a water bath to obtain Solution 2. Next, while warming solution 1, solution 2 was added and stirred for 1-2 hours and cooled to room temperature, resulting in a pink precipitate. 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 a tri (4-amino-1,2,4-triazole) iron sulfate complex. A reversible temperature indicating ink was prepared by kneading 10 g of the obtained iron triazole complex compound, 1 g of butyl rubber as a binder, and 10 g of mineral spirit as a solvent. The obtained reversible temperature indicating ink is applied to one side of the base material 3 made of a polyester film, and the solvent is dried, so that the reversible temperature indicating material 2 is formed on the base material 3 as shown in FIG. A circular indicator 5 having a diameter of 50 mm was obtained.

  3 g of Parmek (Nippon Yushi Co., Ltd .: trade name) was mixed well with 200 g of unsaturated polyester-upica (manufactured by Nippon Yupica Co., Ltd .: trade name), and poured into a hemispherical concave mold made of glass. The indicator 5 obtained above was placed in this resin solution so as to be completely immersed in the resin solution. The mold was heated at 60 ° C. for 8 hours to cure the resin. After curing, the resin was taken out of the mold and shaped to obtain a hemispherical temperature-controlled cooking utensil 1 having a diameter of 80 mm. This temperature control cooking utensil 1 was pink.

  When the prepared temperature control cooking utensil 1, several raw eggs and water are put in a cooking pan and heated, as the water temperature rises, as shown in FIG. It started to turn white. When the white color was changed from the surface part to the inside to about half of the position, when the egg was taken out, a soft-boiled egg was obtained. When heating was continued and the egg was taken out when the entire indicator turned white, the egg was obtained in a solid cake.

  Then, when this temperature control cooking utensil 1 was cooled to room temperature, the color tone returned from white to pink. When this temperature-controlled cooking utensil 1 was reused and the test of cooking with raw eggs was conducted 10 times, the same result was obtained 10 times.

(Example 2)
A reversible temperature indicating ink was prepared by kneading 10 g of the iron triazole complex compound obtained in the same manner as in Example 1, 1 g of fast yellow as the invariant colorant, 1 g of butyl rubber as the binder, and 10 g of mineral spirit as the solvent. The obtained reversible temperature indicating ink was applied to one side of the substrate 3 made of a polyester film, and the solvent was dried to form a circular indicator 5 having a diameter of 25 mm. The central portion of the circular indicator 5 having a diameter of 50 mm obtained in Example 1 is cut out into a circular shape having a diameter of 25 mm to form a donut-shaped indicator 5. Built-in indicator 5 was obtained.

  As in Example 1, 200 g of unsaturated polyester-upica (manufactured by Nippon Iupika Co., Ltd .: trade name) and 3 g of Parmec (manufactured by Nippon Oil & Fats Co., Ltd .: trade name) are mixed well, and glass hemispherical concave molding Poured into the mold. The indicator 5 obtained above was placed in this resin solution so as to be completely immersed in the resin solution. The mold was heated at 60 ° C. for 8 hours to cure the resin. After curing, the resin was taken out of the mold and shaped to obtain a hemispherical temperature-controlled cooking utensil 1 having a diameter of 80 mm. This temperature-controlled cooking utensil 1 was pink on the outside by a donut-shaped indicator 5 having a diameter of 50 mm, and dark pink on the inside by a circular indicator 5 having a diameter of 25 mm.

  As in Example 1, when the prepared temperature-controlled cooking utensil 1, several raw eggs and water are put into a cooking pan and heated, the donut-shaped indicator 5 is pink from its surface toward the inside as the water temperature rises. The color started to change from white to white. When the white color was changed from the surface part to the inside to about half of the position, when the egg was taken out, a soft-boiled egg was obtained. When the egg was removed when the donut-shaped indicator 5 on the outside turned white and the circular indicator 5 on the inside turned yellow, heating was continued and an egg was obtained in a solid cake.

  Then, when this temperature control cooking utensil 1 was cooled to room temperature, the color tone returned from white to pink and the inside from yellow to dark pink. When this temperature-controlled cooking utensil 1 was reused and the test of cooking with raw eggs was conducted 10 times, the same result was obtained 10 times.

(Example 3)
FIG. 4 shows an indicator using the tri (4-amino-1,2,4-triazole) iron sulfate complex obtained in Example 1, in which the reversible temperature indicating material 2 is embedded with a resin as in Example 1. It was possible to know the heating state of a bar-shaped food such as pasta by making a bar-shaped temperature control cooking utensil 1 as shown in FIG. Thus, it was possible to know different types of heating states by changing the shape of the indicator.

Example 4
In a reaction vessel, 14 g of iron sulfate heptahydrate (FeSO ₄ .7H ₂ O) was dissolved in 200 ml of 0.1 mol / l nitric acid to obtain a solution 3. To this solution 3, 13 g of barium nitrate was added and stirred for 3 to 4 hours while warming to about 40 to 50 ° C. with a water bath. After stirring, the precipitated white barium sulfate was removed by filtration to obtain a filtrate solution 4. Furthermore, 10.4 g of 1,2,4-triazole was added to another reaction vessel and dissolved with 200 ml of ethanol while warming in a water bath, and this solution was stirred while warming at about 50-60 ° C. with a water bath. Added to Solution 4 and stirred for 1-2 hours. After stirring, the solvent was distilled off with a rotary evaporator, and when cooled, a pink powder was obtained. This pink powder was a tri (1,2,4-triazole) iron nitrate complex.

  Next, another solution 4 is obtained by the same method as described above. Further, 12.6 g of 4-amino-1,2,4-triazole was added to another reaction vessel and dissolved with 200 ml of ethanol while warming in a water bath, and this solution was warmed at about 50-60 ° C. with a water bath. Added to stirring solution 4 and stirred for 1-2 hours. After stirring, the solvent was distilled off with a rotary evaporator, and when cooled, a pink powder was obtained. This pink powder was a tri (4-amino-1,2,4-triazole) iron nitrate complex.

  Ten grams of the tri (1,2,4-triazole) iron nitrate complex and tri (4-amino-1,2,4-triazole) iron nitrate complex powder obtained by the above method were put in a reaction vessel, and distilled water was added. 100 g was added and stirred for about 1 hour while warming to about 60 ° C. in a water bath. Thereafter, water was evaporated by evaporation in a 105 ° C. constant temperature bath and dried to obtain a dark pink powder. This dark pink powder is considered to be an iron triazole nitrate complex compound in which a plurality of ligands whose ligands are 1,2,4-triazole and 4-amino-1,2,4-triazole are mixed. .

10 g of the obtained iron triazole complex compound and commercially available PAS as a medium
A reversible temperature indicating ink was prepared by kneading 10 g of No. 800 medium and 10 g of butyl cellosolve as a solvent with a lykai machine. The obtained reversible temperature indicating ink was applied to one side of the base material 3 made of a polyester film, and the solvent was dried to form the reversible temperature indicating material 2 to obtain a rectangular indicator 5 of 20 mm × 200 mm.

  The obtained indicator 5 is inserted into a commercially available film for exclusive use of a laminator which is a resin molding material 6 (manufactured by Asuka Co., Ltd.), and is laminated by heating with Lami-α800 (manufactured by Nippon GC Corporation). Was cut into 25 mm × 205 mm to prepare a temperature-controlled cooking utensil 1 for learning. This temperature control cooking utensil 1 is shown in FIG. FIG. 5A is a schematic front view, and a cross-sectional view taken along line AA is shown in FIG. FIG. 5B is a diagram showing a state in use during heating, in which the unchanging color range X is indicated by a diagonal line that rises to the left, and the color change range Y caused by heating is indicated by a diagonal line that rises to the left. The temperature control cooking utensil 1 before heating was pink in the indicator 5 portion.

  As shown in FIG. 6, water and a temperature-controlled cooking utensil 1 for learning were placed in a beaker 15 and heated using a heating utensil 16 from below. The temperature management cooking utensil 1 changed from the pink color of the indicator 5 to white from the water surface grounding position of the temperature management cooking utensil 1 downward due to the convection. The pink unchanging color range X is illustrated by a left-upward diagonal line, and the white color changing range Y is illustrated by a left-upward diagonal line. The invisible convection could be learned by the discoloration that progressed downward from the water surface installation position.

  The temperature-controlled cooking utensil of the present invention is used for grasping temperature management and heat propagation conditions during cooking of food such as eggs, noodles, vegetables, seafood, meat, and processed foods. This temperature control cooking utensil is used as a cooking utensil for home use, teaching materials, and business use.

  1 is a temperature-controlled cookware, 2 and 2a are reversible temperature indicating materials, 3 is a base material, 4 is an invariant color pigment-containing layer, 5 is an indicator, 6 is a resin molding material, 7 is an iron triazole complex, and 8 is invariant color A dye, 15 is a beaker, 16 is a heating device, X is an unchanging color range, and Y is a discoloring range.

Claims (4)

  A reversible temperature indicating material containing an iron triazole complex compound and a binder that reversibly discolors at a predetermined temperature when the temperature is increased or decreased by exhibiting thermochromism, the heat is transmitted to the inside over time, the predetermined temperature A temperature-controlled cooking utensil embedded and / or enclosed in a three-dimensional or sheet-shaped resin molding material that reaches   The temperature-controlled cooking utensil according to claim 1, wherein the reversible temperature indicating material is a layer attached to a base material.   The reversible temperature indicating material and the invariant color-dye-containing layer having a color different from the hue exhibited by the reversible temperature indicating material at a temperature lower than or above the color change temperature of the reversible temperature indicating material are arranged side by side or at least one. The temperature-controlled cooking utensil according to claim 1, wherein the temperature-controlled cooking utensil is attached in duplicate.   2. The resin molding material according to claim 1, wherein the resin molding material has an oval shape, a semi-oval shape, an elliptical sphere, a semi-elliptical sphere, a spherical shape, a hemispherical shape, a columnar shape, or a pyramid shape. Temperature control cookware.

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