JP2010256297A - Irreversible temperature control indicator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple irreversible temperature control indicator which is easily manufactured where the color tone does not change suddenly even if it is exposed to transient or long-time continuous heating at a relatively high temperature lower than a temperature to be detected, the color tone clearly and irreversibly changes only when it reaches the temperature to be detected, and the history of the temperature is visually recognized. <P>SOLUTION: In this irreversible temperature control indicator 1, a hot-melt material 11 that includes powder, particle or wax form thermally melted at the temperature to be detected and is made of amide compound containing a plurality of amide groups is included in an ink layer 8 attached to an observation surface or non-observing surface side on a hot-melt material absorptive substrate 7 which changes the color tone by irreversible permeation and diffusion of the hot-melt material 11 in its thermal molten state. Alternately, the hot-melt material 11 is included in the substrate 7. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an irreversible temperature management indicator that displays whether a specific temperature has been reached by irreversible color change.

  Machines, electronic devices, and products that are stored at a constant temperature will fail or deteriorate when overheated, so it is necessary to monitor the overheating temperature in order to prevent failure and deterioration. Electric power facilities cause abnormal heat generation due to poor resistance at transmission line joints, etc. as a precursor to transmission line accidents, and railway facilities such as trains have failed bearings and grease used in rotating bodies as precursors to axle disconnection accidents. Since an abnormal heat generation phenomenon of the rotating shaft due to deterioration or the like is caused, it is necessary to monitor the heat generation temperature in order to prevent such accidents. Furthermore, it is necessary to measure the heating temperature of the injection-molded product and the optical lens in order to confirm whether or not the annealing process is performed at a desired heating temperature. Therefore, in order to manage these temperatures, a temperature management indicator is widely used in which the color tone irreversibly changes when the heating temperature to be detected is reached and the heating can be visually confirmed.

  As such a temperature control indicator, in JP-A No. 2004-133260, a temperature melting agent such as a powdered wax and a heat-melting substance such as a powdery wax that becomes transparent when melted at a predetermined temperature is applied on a substrate. A temperature indicating seal is disclosed. Further, in Patent Document 2, a wax that melts at a set temperature is superimposed on the coloring surface side of the base material, and a layer of a masking material that changes from opaque to transparent when the wax melts and penetrates on the surface side of the wax is formed. A temperature label is disclosed. In these, as a result of the melting of a hot-melting substance such as wax at a predetermined temperature or higher and becoming transparent, the concealed colored substance and coloring surface appear and change color.

  Commercially available waxes such as paraffin wax used for temperature management indicators such as these temperature indicating labels and temperature indication labels are classified according to the melting point and can be freely selected according to the temperature to be detected. Since the temperature is set to ° C., an indicator using wax cannot detect heating at 120 ° C. or higher. Moreover, a heat-melting material such as wax is inherently translucent, and even if the colored material such as pigment and the coloring surface of the substrate are concealed by irregularly reflecting light by pulverization processing, Because of the partial coloration, such an indicator is small because the color difference before and after the color change is small, and there is a possibility that the temperature management operator may misidentify it.

  In addition, as a temperature management indicator, an ink layer containing a heat-fusible substance that is a single organic component such as long-chain fatty acids and a binder is applied on the absorbent substrate, and the melting point of the heat-fusible substance is higher than that. Those that melt by heating and are absorbed by the substrate to change color are also known. In general, the organic component is poor in thermal stability, and even when the melting point is 130 ° C. or higher, it may be partially decomposed and unexpectedly melted or colored when exposed to a relatively high temperature below that temperature. It is not compatible with and is dispersed inhomogeneously. For this reason, the indicator that uses organic components is unexpectedly melted or colored even though it did not reach the temperature that should be detected. There is a risk of misunderstanding.

  Even an indicator where an ink layer containing a heat-meltable material such as cholesterol powder that is relatively excellent in thermal stability even when heated to a melting point of 147-150 ° C. is applied to the absorbent substrate is 120 ° C. Not only will the color change when exposed to ~ 130 ° C for a long period of time, but the color difference before and after the heat melting of the indicator is small due to the transparency of the cholesterol powder itself, which may be mistaken by temperature management workers. . In addition, this indicator is difficult to apply ink for forming an ink layer because of the low slipperiness of the cholesterol powder, and the productivity is low so that it is not suitable for industrial mass production.

JP 2009-36525 A JP 2001-83020 A

  The present invention has been made in order to solve the above-described problems, and even when exposed to a transient or long-term continuous heating at a relatively high temperature below the temperature to be detected, the color does not change unexpectedly and is detected. It is an object to provide a simple irreversible temperature management indicator that can be easily manufactured because the color tone is irreversibly changed only when the temperature to be reached is reached, and the temperature history can be visually confirmed. .

  The irreversible temperature management indicator according to claim 1, which has been made to achieve the above object, is a powdery, granular, or waxy material that melts at a temperature to be detected and has a plurality of amide groups. The heat-meltable substance composed of an amide compound having an irreversible penetration and diffusion in the heat-melted state changes the color tone by changing the color tone on the observation surface side or the non-observation surface side. It is contained in the attached ink layer or contained in the substrate.

  The irreversible temperature control indicator according to claim 2 is the irreversible temperature management indicator according to claim 1, wherein the amide compound is a bisamide compound.

  The irreversible temperature control indicator according to claim 3 is the indicator according to claim 2, wherein the bisamide compound is selected from saturated fatty acid bisamide, unsaturated fatty acid bisamide, aromatic ring-containing fatty acid bisamide, and hydroxy fatty acid bisamide. It is characterized by being.

  An irreversible temperature management indicator according to a fourth aspect is the one according to the first aspect, wherein the amide compound has a plurality of different amide groups.

  The irreversible temperature management indicator according to claim 5 is the indicator according to claim 1, wherein the dye that is dissolved and / or dispersed in the hot-melt material in the hot-melt state changes the hot-melt material. It is contained in the absorbent substrate or the ink layer.

  The irreversible temperature management indicator according to the present invention uses an amide compound having a plurality of amide groups as a hot-melt material, thereby allowing the temperature to be detected to be set from a low temperature of about 30 ° C. to a relatively high temperature of about 280 ° C. Temperature. Moreover, this irreversible temperature control indicator is not melted or changed in color even when exposed to transient or long-term continuous heating at a relatively high temperature below the temperature to be detected, particularly about 10 ° C. The heat resistance is excellent. Furthermore, this irreversible temperature management indicator changes the color tone irreversibly only when it has passed a temperature history that it has reached the temperature that should be detected. There is no fear of misidentification.

  When producing this irreversible temperature control indicator, the use of an ink containing a high-sliding hot-melt material used to form the ink layer of the indicator, particularly a bisamide compound and a binder, is caused by its low viscosity. Since the ink is easy to prepare and apply, the indicator can be easily and efficiently manufactured and has high productivity.

  This irreversible temperature management indicator has a large color difference before and after the change in color tone at the temperature to be detected, so that the temperature management operator does not have a possibility of misrecognizing that the temperature to be detected has been reached.

It is the top view and schematic sectional drawing of the irreversible temperature management indicator to which this invention is applied. It is a schematic cross section of another irreversible temperature management indicator to which the present invention is applied. It is a schematic cross section of another irreversible temperature management indicator to which the present invention is applied.

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

  A preferred example of the irreversible temperature management indicator of the present invention will be described with reference to FIG.

  The irreversible temperature control indicator 1 has a rectangular label shape, and an irreversible temperature indicating material 9 comprising a paper-made heat-meltable substance-absorbing substrate 7 and an ink layer 8 formed on the upper surface thereof by printing is provided on the substrate. On the 7 side, it is pasted via the adhesive layer 6 on the upper surface of the support 4. The heat-meltable substance-absorbing substrate 7 is a paper in which paper is colored with a non-diffusible colorant, and has a porous property that can absorb a heat-melted liquid heat-meltable substance. The ink layer 8 contains a bisamide compound that is a heat-meltable substance 11 that is a powdery, granular, or waxy solid that has a high light scattering property and conceals the substrate 7. The irreversible temperature indicating material 9 has an observation surface on the ink layer 8 side. The upper surface side of the support 4 is covered with a protective film 10 together with the irreversible temperature indicating material 9. An adhesive layer 3 covered with a release paper 2 is attached to the lower surface of the support.

  A thin plastic layer (not shown) may be attached to the upper surface side of the support 4, or a printing layer 5 indicating information such as a detected temperature may be attached.

  This irreversible temperature management indicator 1 is produced as follows. First, an ink is prepared by kneading a bisamide compound, which is a hot-melt material, a binder, and a solvent. When this ink is printed on the hot-melt substance-absorbing substrate 7 to form the ink layer 8 and then cut into a desired size, an irreversible temperature indicating material 9 is obtained. The pressure-sensitive adhesive layer 6 is attached to the upper surface of the support 4 to which the release paper 2 is attached via the pressure-sensitive adhesive layer 3 on the lower surface. A hot-meltable substance-absorbing substrate 7 of the irreversible temperature indicating material 9 is attached to the support 4 through the adhesive layer 6. When the upper surface side of the support 4 is covered with the protective film 10 together with the irreversible temperature indicating material 9 and pasted together by the adhesive layer 6 of the unattached portion of the irreversible temperature indicating material 9, the irreversible temperature management indicator 1 is obtained. can get.

  This irreversible temperature management indicator 1 is used in the following manner when temperature management or temperature measurement is performed on a test object such as a machine, equipment, or a constant temperature storage product. First, the release paper 2 is peeled off, and the indicator 1 is affixed to the test object (not shown) through the adhesive layer 3 that has appeared. At this time, the bisamide compound, which is a solid heat-meltable substance 11 contained in the ink layer 8 of the irreversible temperature indicating material 9 of the indicator 1, conceals the color tone of the heat-meltable substance-absorbing substrate 7 by the diffused light reflection. Therefore, the irreversible temperature indicating material 9 appears white. When the temperature of the test body or its surroundings rises, heat is transmitted to the indicator 1. When heated to a temperature equal to or higher than the melting point of the heat-meltable substance 11, the bisamide compound, which is a heat-meltable substance, is melted by heat to change from a solid to a transparent liquid. Absorbed and no light diffusely reflected. As a result, the irreversible temperature indicating material 9 can visually check the color tone of the hot-melt material absorbent substrate 7. Thereby, the temperature management operator can confirm visually that the to-be-tested body has reached the detected temperature. Since the indicator that has reached the detected temperature does not fade in the irreversibly changed color tone even after a long period of time, it can be stored as evidence of the history of temperature management. These irreversible temperature management indicators are widely used for maintenance management of facilities that require periodic temperature management and records during temperature measurement.

  As shown in FIG. 2, another irreversible temperature management indicator 1 is formed by printing on an opaque heat-meltable substance absorbent substrate 7 made of paper colored with a non-diffusible colorant and its lower surface. An irreversible temperature indicating material 9 composed of the ink layer 8 containing the heat-meltable substance 11 as described above is attached on the ink layer 8 side via the adhesive layer 6 on the upper surface of the support 4. Also good. The irreversible temperature indicating material 9 has an observation surface on the heat-meltable substance-absorbing substrate 7 side, and the color tone of the colorant appears. The irreversible temperature management indicator 1 is absorbed into the porous material of the heat-meltable substance-absorbing substrate 7 as the temperature of the heat-meltable substance 11 in the ink layer 8 melts and becomes a transparent liquid. As a result, the light transmittance of the substrate 7 is improved, and it can be visually observed that the substrate 7 is translucent or smeared, which appears as a change in the color tone of the indicator. Thereby, the temperature management operator can confirm visually that the to-be-tested body has reached the detected temperature.

  In addition, the diffusible pigment | dye which melt | dissolves and disperse | distributes to the hot-meltable substance of a hot-melt state may be contained in the hot-meltable substance absorptive board | substrate 7 or the ink layer 8 (not shown).

  As shown in FIG. 3, another irreversible temperature management indicator 1 is a hot melt containing a diffusible pigment 12 such as a pigment or a dye and a hot melt material 11 as described above on a support 4. The active substance-absorbing substrate 7 may be attached. The irreversible temperature management indicator 1 is a diffusible material that is melted into a liquid state by hot melting of the hot-melting substance 11 in the hot-melting substance-absorbing substrate 7 as the temperature rises. As a result of the dye 12 being dissolved and diffusing into the heat-meltable substance-absorbing substrate 7 while being mixed, the color tone exhibited by the dye 12 is changed. Thereby, the temperature management operator can confirm visually that the to-be-tested body has reached the detected temperature.

  Although the example of the bisamide compound was shown as the heat-meltable substance 11 used for the indicator shown in FIGS. 1 to 3, an amide compound having a plurality of amide groups, for example, a melting point of about 30 ° C. to 280 ° C. There is no particular limitation. The reason why the indicator 1 using such a heat-meltable substance 11 is excellent in thermal stability is not necessarily clear, but hydrogen between amide groups having strong polarity in the molecule of an amide compound such as a bisamide compound. It is presumed that the bisamide compounds are associated with each other due to bonding, and do not dissociate while being associated even when heated to a temperature slightly lower than the melting point.

  Moreover, when the ink containing the heat-meltable substance 11 which is an amide compound is used for forming the ink layer 8 of the indicator shown in FIGS. 1-2, it is easy to apply or the heat-meltability of the indicator shown in FIG. The reason why such a heat-meltable substance 11 is easily contained in the substance-absorbing substrate 7 is not necessarily clear, but amide compounds having a plurality of amide groups such as bis-fatty acid amide compounds are hydrophilic in the molecule. Since it has a functional amide group and an alkyl group such as a hydrophobic fatty acid chain, it exhibits high slipperiness based on excellent surface activity, and the slipperiness of the heat-meltable substance-absorbing substrate 7 to the porosity is improved. It is inferred that it is expensive.

Examples of the bisamide compound include N, N′-methylenebisacetamide, N, N′-methylenebispropionic acid amide, N, N′-methylenebisbutyric acid amide, N, N′-methylenebisvaleric acid amide, N, N′— Methylenebiscaproic acid amide, N, N′-methylenebisenanthic acid amide, N, N′-methylenebiscaprylic acid amide, N, N′-methylenebisperargonic acid amide, N, N′-methylenebiscapric acid amide, N, N'-methylenebisundecylic acid amide, N, N'-methylenebislauric acid amide, N, N'-methylenebistridecylic acid amide, N, N'-methylenebismyristic acid amide, N, N'- Methylenebispentadecylamide, N, N′-methylenebispalmitic acid amide, N, N′-methylenebisheptadecylamide, N, N′-methylenebisstearic acid amide N, N′-methylenebisnonadecanoic acid amide, N, N′-methylenebisarachinic acid amide, N, N′-methylenebisbehenic acid amide, N, N′-methylenebislignoceric acid amide, N, N '-Methylenebisserotinamide, N, N'-methylenebisheptaconic acid amide, N, N'-methylenebismontanic acid amide, N, N'-methylenebismellitic acid amide, N, N'-methylene Bislacceric acid amide, N, N′-methylenebislinoleic acid amide, N, N′-methylenebiserucic acid amide, N, N′-ethylenebisacetic acid amide, N, N′-ethylenebispropionic acid amide, N, N'-ethylenebisbutyric acid amide, N, N'-ethylenebisvaleric acid amide, N, N'-ethylenebiscaproic acid amide, N, N'-ethylenebisenanthic acid amide, N, N'-ethylenebiscaprylic acid Amide, N, N'-ethylene bisperargonamide, N, N'-ethylenebiscapric acid amide, N, N'-ethylenebisundecylamide, N, N'-ethylenebislauric acid amide, N, N'-ethylenebistri Decylamide, N, N′-ethylenebismyristate amide, N, N′-ethylenebispentadecylamide, N, N′-ethylenebispalmitamide, N, N′-ethylenebisheptadecylamide, N, N'-ethylenebisstearic acid amide, N, N'-ethylenebisnonadecanoic acid amide, N, N'-ethylenebisarachinic acid amide, N, N'-ethylenebisbehenic acid amide, N, N'- Ethylenebislignoceramide, N, N′-ethylenebiscerotic acid amide, N, N′-ethylenebisheptaconic acid amide, N, N′-ethylenebismontanoic acid amide, N, N′— Tylene bismelicinamide, N, N'-ethylenebislaccelamide, N, N'-ethylenebislinoleamide, N, N'-ethylenebiserucamide, N, N'-trimethylenebisacetamide N, N′-trimethylenebispropionic acid amide, N, N′-trimethylenebisbutyric acid amide, N, N′-trimethylenebisvaleric acid amide, N, N′-trimethylenebiscaproic acid amide, N, N'-trimethylenebisenanthamide, N, N'-trimethylenebiscaprylic acid amide, N, N'-trimethylenebisperargonic acid amide, N, N'-trimethylenebiscapric acid amide, N, N ' -Trimethylenebisundecylamide, N, N'-trimethylenebislauric acid amide, N, N'-trimethylenebistridecylamide, N, N'-trimethylenebismyristic acid N, N'-trimethylenebispentadecylamide, N, N'-trimethylenebispalmitic acid amide, N, N'-trimethylenebisheptadecylamide, N, N'-trimethylenebisstearic acid amide N, N'-trimethylenebisnonadecanoic acid amide, N, N'-trimethylenebisarachinic acid amide, N, N'-trimethylenebisbehenic acid amide, N, N'-trimethylenebislignoceric acid amide N, N'-trimethylenebiscellotic acid amide, N, N'-trimethylenebisheptaconic acid amide, N, N'-trimethylenebismontanic acid amide, N, N'-trimethylenebismellitic acid Amide, N, N'-trimethylenebislaccelamide, N, N'-trimethylenebislinoleic acid amide, N, N'-trimethylenebiserucamide, N, N'-tetramethylenebisvinegar Acid amide, N, N′-tetramethylenebispropionic acid amide, N, N′-tetramethylenebisbutyric acid amide, N, N′-tetramethylenebisvaleric acid amide, N, N′-tetramethylenebiscaproic acid amide, N, N′-tetramethylene bisenanthic acid amide, N, N′-tetramethylene biscaprylic acid amide, N, N′-tetramethylene bisperargonic acid amide, N, N′-tetramethylene biscapric acid amide, N, N'-tetramethylenebisundecylic acid amide, N, N'-tetramethylenebislauric acid amide, N, N'-tetramethylenebistridecylic acid amide, N, N'-tetramethylenebismyristic acid amide, N, N '-Tetramethylenebispentadecylamide, N, N'-tetramethylenebispalmitic acid amide, N, N'-tetramethylenebisheptadecylamide N, N′-tetramethylenebisstearic acid amide, N, N′-tetramethylenebisnonadecanoic acid amide, N, N′-tetramethylenebisarachinic acid amide, N, N′-tetramethylenebisbehenic acid amide, N, N′-tetramethylenebislignoceramide, N, N′-tetramethylenebisserocinamide, N, N′-tetramethylenebisheptaconic acid amide, N, N′-tetramethylenebismontanoic acid amide N, N′-tetramethylene bismelicinamide, N, N′-tetramethylene bislaccelic acid amide, N, N′-tetramethylene bislinoleic acid amide, N, N′-tetramethylene biserucic acid amide, N, N′-pentamethylenebisacetamide, N, N′-pentamethylenebispropionic acid amide, N, N′-pentamethylenebisbutyric acid amide, N, N′-pentamethy Renbisvaleric acid amide, N, N′-pentamethylenebiscaproic acid amide, N, N′-pentamethylenebisenanthic acid amide, N, N′-pentamethylenebiscaprylic acid amide, N, N′-pentamethylenebisperargon Acid amide, N, N′-pentamethylenebiscapric acid amide, N, N′-pentamethylenebisundecylamide, N, N′-pentamethylenebislauric acid amide, N, N′-pentamethylenebistridecyl acid Amide, N, N′-pentamethylenebismyristic acid amide, N, N′-pentamethylenebispentadecylic acid amide, N, N′-pentamethylenebispalmitic acid amide, N, N′-pentamethylenebisheptadecylic acid Amide, N, N′-pentamethylenebisstearic acid amide, N, N′-pentamethylenebisnonadecanoic acid amide, N, N′-pentamene Renbis arachidic acid amide, N, N′-pentamethylene bisbehenic acid amide, N, N′-pentamethylene bislignoceric acid amide, N, N′-pentamethylene biscerotic acid amide, N, N′-penta Methylene bisheptaconic acid amide, N, N′-pentamethylene bismontanic acid amide, N, N′-pentamethylene bismericinic acid amide, N, N′-pentamethylene bislaccelic acid amide, N, N′-penta Methylenebislinoleic acid amide, N, N′-pentamethylenebiserucic acid amide, N, N′-hexamethylenebisacetic acid amide, N, N′-hexamethylenebispropionic acid amide, N, N′-hexamethylenebisbutyric acid Amide, N, N′-hexamethylenebisvaleric acid amide, N, N′-hexamethylenebiscaproic acid amide, N, N′-hexamethylenebisenanthic acid amide, , N′-hexamethylene biscaprylic acid amide, N, N′-hexamethylene bisperargonic acid amide, N, N′-hexamethylene biscapric acid amide, N, N′-hexamethylene bisundecylic acid amide, N, N'-hexamethylenebislauric acid amide, N, N'-hexamethylenebistridecylamide, N, N'-hexamethylenebismyristic acid amide, N, N'-hexamethylenebispentadecylamide, N, N '-Hexamethylenebispalmitic acid amide, N, N'-hexamethylenebisheptadecylamide, N, N'-hexamethylenebisstearic acid amide, N, N'-hexamethylenebisnonadecanoic acid amide, N, N '-Hexamethylene bisarachinic acid amide, N, N'-hexamethylene bisbehenic acid amide, N, N'-hexamethylene bislignoceric acid amide N, N'-hexamethylenebisheptaconic acid amide, N, N'-hexamethylenebisheptaconic acid amide, N, N'-hexamethylenebismontanoic acid amide, N, N'-hexamethylenebismericin Acid amide, N, N'-hexamethylene bislaccelic acid amide, N, N'-hexamethylene bislinoleic acid amide, N, N'-hexamethylene biserucic acid amide, N, N'-methylene bishydroxystearic acid amide N, N′-ethylenebishydroxystearic acid amide, N, N′-trimethylene bishydroxystearic acid amide, N, N′-tetramethylene bishydroxystearic acid amide, N, N′-pentanemethylene bishydroxystearic acid Bisamide compounds such as amides, N, N'-hexamethylenebishydroxystearic acid amides and derivatives thereof ^{(R 1 -CO-NH) -} (C p H q) r - (NH-CO-R 2) (R 1, R 2 is a hydrocarbon group and / or an aromatic group, saturated or unsaturated group, p, q, and r are positive numbers);
Oxamide, malonamide, succinamide, glutaric acid diamide, adipic acid diamide, pimelic acid diamide, suberic acid diamide, azelaic acid diamide, sebacic acid diamide, maleic acid amide, fumaric acid amide, phthalic acid amide, isophthalic acid amide, terephthalic acid amide, N, N′-dimethyloxamide, N, N′-diethyloxamide, N, N′-dibutyloxamide, oxalic acid dianilide, N, N′-dimethylmalonamide, N, N′-diethylmalonamide, N , N′-dibutylmalonamide, malonic acid dianilide, N, N′-dimethylsuccinamide, N, N′-diethylsuccinamide, N, N′-dibutylsuccinamide, succinic acid dianilide, N, N ′ -Dimethyl glutaric acid diamide, N, N'-diethyl glutaric acid diamide, N, N'-dibutyl Tartric acid diamide, glutaric acid dianilide, N, N′-dimethyladipic acid diamide, N, N′-diethyladipic acid diamide, N, N′-dibutyladipic acid diamide, adipic acid dianilide, N, N′-dimethylpimerin Acid diamide, N, N′-diethylpimelic acid diamide, N, N′-dibutylpimelic acid diamide, pimelic acid dianilide, N, N′-dimethylsuberic acid diamide, N, N′-diethylsuberic acid diamide, N, N′- Dibutylsuberic acid diamide, suberic acid dianilide, N, N′-dimethylazelineic acid diamide, N, N′-diethylazelineic acid diamide, N, N′-dibutylazelineic acid diamide, azelaic acid dianilide, N, N′-dimethylsebacin Acid diamide, N, N′-diethyl sebacic acid diamide, N, N′-dibutyl sebacic acid diamide, Vasic acid dianilide, N, N′-dimethylmaleic acid amide, N, N′-diethylmaleic acid amide, N, N′-dibutylmaleic acid amide, maleic acid dianilide, N, N′-dimethylfumaric acid amide, N, N'-diethyl fumaric acid amide, N, N'-dibutyl fumaric acid amide, fumaric acid dianilide, N, N'-dimethylphthalic acid amide, N, N'-diethylphthalic acid amide, N, N'-dibutylphthalic acid Amide, phthalic acid dianilide, N, N′-dimethylisophthalic acid amide, N, N′-diethylisophthalic acid amide, N, N′-dibutylisophthalic acid amide, isophthalic acid dianilide, N, N′-dimethylterephthalic acid amide, N, N'-diethylterephthalic acid amide, N, N'-dibutylterephthalic acid amide, terephthalic acid dianilide, N-methyl-N'-phenyloxamide N-ethyl-N′-phenyloxamide, N-butyl-N′-phenyloxamide, N-methyl-N′-phenylmalonamide, N-ethyl-N′-phenylmalonamide, N-butyl-N ′ -Phenylmalonamide, N-methyl-N'-phenylsuccinamide, N-ethyl-N'-phenylsuccinamide, N-butyl-N'-phenylsuccinamide, N-methyl-N'-phenylglutar Acid diamide, N-ethyl-N′-phenylglutaric acid diamide, N-butyl-N′-phenylglutaric acid diamide, N-methyl-N′-phenyladipic acid diamide, N-ethyl-N′-phenyladipic acid diamide N-butyl-N′-phenyladipic acid diamide, N-methyl-N′-phenylpimelic acid diamide, N-ethyl-N′-phenylpimelic acid diamide N-butyl-N′-phenylpimelic acid diamide, N-methyl-N′-phenylsuberic acid diamide, N-ethyl-N′-phenylsuberic acid diamide, N-butyl-N′-phenylsuberic acid diamide, N-methyl-N′-phenyl azelaic acid diamide, N-ethyl-N′-phenyl azelaic acid diamide, N-butyl-N′-phenyl azelaic acid diamide, N-methyl-N′-phenyl sebacic acid diamide, N— Ethyl-N′-phenyl sebacic acid diamide, N-butyl-N′-phenyl sebacic acid diamide, N-methyl-N′-phenylmaleic acid amide, N-ethyl-N′-phenylmaleic acid amide, N-butyl- N′-phenylmaleic acid amide, N-methyl-N′-phenylfumaric acid amide, N-ethyl-N′-phenylfumaric acid amide, N -Butyl-N'-phenyl fumaric acid amide, N-methyl-N'-phenylphthalic acid amide, N-ethyl-N'-phenylphthalic acid amide, N-butyl-N'-phenylphthalic acid amide, N-methyl -N'-phenylisophthalic acid amide, N-ethyl-N'-phenylisophthalic acid amide, N-butyl-N'-phenylisophthalic acid amide, N-methyl-N'-phenylterephthalic acid amide, N-ethyl-N Dicarboxylic acid amide compounds such as' -phenylterephthalic acid amide, N-butyl-N'-phenylterephthalic acid amide, and derivatives thereof: (R ¹ -NH-CO)-(C _s H _t ) _u- (CO- NH-R ² ) (R ¹ and R ² are molecular groups centering on saturated and unsaturated hydrocarbons, and s, t, and u are positive numbers).
Bisamide compounds are Alflow H-50 series (trade name of NOF Corporation; Alfro is a registered trademark) and Alflow AD-281 series (of NOF Corporation) used as industrial raw materials as dispersants and lubricants. Product name), Alflow AD-221 series (product name manufactured by NOF Corporation), Bisamide series (product name of Nippon Kasei Co., Ltd.), SLIPAX series (product name of Nippon Kasei Corporation; SLIPAX is a registered trademark) , Trinoon series (trade name of Nippon Kasei Co., Ltd .; Trinoon is a registered trademark) may be used.

  Examples of the amide compound having three or more amide groups include polyamide compounds such as a co-condensation polymerization compound of hexamethylene diamine and adipic acid and a co-condensation polymerization compound of hexamethylene diamine and terephthalic acid.

The amide compound having a plurality of amide groups, particularly the bisamide compound, is preferably a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, an aromatic ring-containing fatty acid bisamide, or a hydroxy fatty acid bisamide. The bisamide compound is, for example, (C _v H _{2v + 1} CONH) ₂ (CH ₂ ) _w or (C _x H _{2x + 1} NHCO) ₂ (CH ₂ ) _y (where v and x are 1 to 35, w and y are 1 to 10) It is still more preferable that it is shown by.

  One kind of amide compound as the hot-melt material may be used, or a plurality of amide compounds may be used for temperature adjustment.

  The ink for forming the ink layer of the irreversible temperature control indicator is prepared by kneading a bisamide compound, a binder, and a solvent in a weight ratio of 0.1 to 100: 0.1 to 50: 1 to 500. Is preferred. Additives may be added to the ink as necessary.

  As a binder 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, vinegar Acid cellulose 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 It is done. 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 and Chemicals), Hy.
Unity Soy Medium (trade name of Toyo Ink Manufacturing Co., Ltd.), Nouvel Maxi Medium (trade name of Dainichi Seika Kogyo Co., Ltd.), Nouvel Senior Soy Medium (trade name of Dainichi Seika Kogyo Co., Ltd.), Q Set 200 Medium ( (Product name of Jujo Chemical Co., Ltd.), No. 900 Medium (Product name of Jujo Chemical Co., Ltd.), High Set Matte Medium (Product Name of Mino Group), JRP Medium (Product 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.), NEW
LP Super R medium (trade name of Toyo Ink Manufacturing Co., Ltd.).

  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.

  As other additives, 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, Ultra Blue, 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 may be used, or a plurality may be used in combination.

  Such an ink is prepared by mixing a bisamide compound, a binder, a solvent, and additives with a kneader such as a ball mill, a roll mill, or a sand mill.

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

  A porous material is suitable for the heat-meltable substance-absorbing substrate, and examples thereof include filter paper, nonwoven fabric, fabric, high-quality paper, and imitation paper. The substrate color is preferably red, black, amber, blue, orange, green, dark red or the like.

  Hereinafter, embodiments of the irreversible temperature management indicator of the present invention will be specifically described.

Example 1
100 g of N, N′-ethylenebisstearic acid amide (manufactured by Wako Pure Chemical Industries, Ltd.), 10 g of ethyl cellulose as a binder, and 400 g of ethanol as a solvent are placed in a 120 mm ball pot mill for 3 days and nights. The ink was prepared by pulverization and kneading. The obtained ink was printed by screen printing (150 mesh) on black fine paper which is a heat-meltable substance-absorbing substrate. It was naturally dried to obtain a white temperature indicating material having a bisamide compound-containing ink layer on the surface. This temperature indicating material was punched out to 10 mmφ. After attaching it to a plastic plate support at intervals of 30 mm, and covering the temperature indicating material with a protective film, it is cut into a size of 30 mm × 30 mm to obtain an irreversible temperature control indicator as shown in FIG. It was. When the temperature of this indicator was raised at a temperature heating rate of 2 to 3 ° C./min, the temperature indicator of the indicator irreversibly changed from white to black at 140 ° C.

(Example 2)
An irreversible temperature control indicator similar to that in Example 1 was prepared, and a long-term heating test at 130 ° C. was performed for 1,000 hours. This indicator remained the same color tone as before the test even after the long-term heating test. When the temperature of the indicator after the long-term heating test was increased at a temperature heating rate of 2 to 3 ° C./min, the color tone changed at 140 ° C. as in Example 1.

(Comparative Example 1)
An irreversible temperature control indicator was prepared in the same manner as in Example 1 except that cholesterol was used as a heat-meltable substance (manufactured by Tokyo Chemical Industry Co., Ltd.), and at the same temperature heating rate as in Example 1. When heated, the color changed from white to black at 140 ° C.

(Comparative Example 2)
An irreversible temperature control indicator was prepared using the same cholesterol as in Example 1, and a long-term heating test at 130 ° C. was performed. This indicator clearly changed color after 24 hours from the start of the long-term heating test at 130 ° C.

  The irreversible temperature management indicator of the present invention is used for temperature management of mechanical equipment, prevention of overheating accidents of power distribution equipment, and confirmation of temperature history of products kept at a constant temperature.

  1 is an irreversible temperature control indicator, 2 is a release paper, 3 is a pressure-sensitive adhesive layer, 4 is a support, 5 is a printing layer, 6 is a pressure-sensitive adhesive layer, 7 is a heat-meltable substance absorbent substrate, 8 is an ink layer, 9 is an irreversible temperature indicating material, 10 is a protective film, 11 is a hot-melt material, and 12 is a diffusible dye.

Claims (5)

  A heat-meltable substance consisting of an amide compound having a plurality of amide groups that melts and melts at the temperature to be detected irreversibly penetrates and diffuses in its hot-melt state. An irreversible temperature control indicator, which is contained in or contained in an ink layer attached to an observation surface side or a non-observation surface side on a heat-meltable substance-absorbing substrate that changes color tone .   The irreversible temperature management indicator according to claim 1, wherein the amide compound is a bisamide compound.   The irreversible temperature control indicator according to claim 2, wherein the bisamide compound is a fatty acid bisamide selected from a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, an aromatic ring-containing fatty acid bisamide, and a hydroxy fatty acid bisamide.   The irreversible temperature management indicator according to claim 1, wherein the amide compound has a plurality of different amide groups.   2. The dye that is dissolved and / or dispersed in the hot-melt material in a hot-melt state to be changed is contained in the hot-melt material-absorbing substrate or the ink layer. An irreversible temperature management indicator as described in.

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