JP6008666B2 - How to avoid abnormal discoloration during temperature history management - Google Patents

Description

  The present invention relates to a method for avoiding abnormal discoloration caused by a plasticizer when the temperature history of a test object having a resin containing a plasticizer on its surface is managed by a temperature history management material displayed by discoloration. It is.

  As a method for managing the temperature history of a test object, a method for physically detecting the temperature history using a thermocouple, a non-contact thermometer or the like is known. In addition, a method of visually detecting a temperature history by using a temperature history management material that displays a temperature by direct or indirect color change of a chemical substance that melts, decomposes, or chemically changes at a predetermined temperature, Are known.

  If the temperature history management material is used, the temperature and abnormal heat generation of the object to be measured such as electric cables and distribution facilities can be detected, managed, and recorded by a visible color change. As a temperature history management material, Patent Document 1 discloses a temperature-sensitive insulating cap in which a temperature sensor made of a material that changes color due to a temperature rise is incorporated in a cap body made of synthetic resin that covers a connection portion of an electric wire.

  Patent Document 2 discloses a temperature-sensitive ink containing, as a temperature history management material, a granular or powdery hot-melt material having a melting point at a temperature to be detected, and a resin for fixing it on a non-absorbable printing substrate. An irreversible temperature control material is disclosed in which a temperature-sensitive color-changing layer is formed on the printing substrate, which is irreversibly discolored by heat melting of the heat-meltable substance.

  A resin insulator that covers a connection portion of an electric cable that is a test object is generally formed of a thermoplastic resin such as vinyl chloride, and contains a plasticizer to impart flexibility and elasticity to the resin insulator. As shown in FIG. 3, the conventional temperature history management material 2 includes a pressure-sensitive adhesive layer 32 in which the plasticizer 21 in the test object 20 is spread by a cutting blade when the temperature history management material 2 is cut. After a long period of time, the light is gradually diffused without passing through the protective sheet 33, and is contacted with the heat-meltable substance in the temperature-sensitive color changing layer 34 via the liquefied heat-meltable substance absorption layer 35 and is detected. Although the temperature has not passed, the color changes abnormally (Route A). In addition, the conventional temperature history management material 2 is formed through the adhesive layer 30 and the paper substrate 31 (Route B), or through attached water droplets or volatilized / sublimated (Route C), and the temperature-sensitive color changing layer 34. It contacts and dissolves in the hot-melt material, and discolors abnormally.

  This abnormal discoloration has caused a misconception that the temperature of the test object has passed through a temperature history to be detected.

Japanese Utility Model Publication No. 62-37173 JP 2005-291825 A

  The present invention has been made in order to solve the above-described problems. Even when a temperature history management material is pasted on a test object having a resin containing a plasticizer in its surface layer, the management material is plastic. It is an object of the present invention to provide a method for avoiding abnormal discoloration during temperature history management, which can accurately detect a temperature history without abnormal discoloration by an agent.

The method for avoiding discoloration at the time of temperature history management according to claim 1, which has been made to achieve the above object, is to heat a granular or powder hot-melt material having a melting point at a temperature to be detected. a thermochromic member which discoloration by an adhesive member, together with the cover from the given across a gap in the protective sheet on the top surface of the plasticizer-free substrate plasticizer in impermeable, of the substrate A non-releasable adhesive layer is attached to the lower surface, and the formed temperature history management material is attached to a test temperature object in which the plasticizer is contained in the resin surface layer via the adhesive layer. When managing the temperature history of the temperature measurement object, the temperature-sensitive color changing member and the plasticizer are separated from each other by the gap and the base material, so that the plasticizer is in contact with the temperature-sensitive color changing member. While avoiding causing abnormal discoloration that does not depend on the discoloration, Characterized in that it manages the serial temperature history.

  The method for avoiding abnormal discoloration at the time of temperature history management according to claim 2 is the method according to claim 1, wherein the gap between the temperature-sensitive discoloration member and the adhesive member is at least 0. It attaches so that it may be set to 5 mm.

  The method for avoiding abnormal discoloration during temperature history management according to claim 3 is the method according to claim 1 or 2, wherein the substrate is made of celluloses, polyolefins, polyesters, polystyrenes, hydrochloric acid. It is characterized by molding with at least one material selected from rubbers, polyamides, fluororesins, polybutenes, polyvinyl butyrals, polyethylene oxides, polyurethanes, and polyimides.

  The abnormal discoloration repelling method at the time of temperature history management described in claim 4 is described in any one of claims 1 to 3, wherein a plurality of the adhesive members are intermittently attached. .

  The method for avoiding abnormal discoloration during temperature history management according to claim 5 is the method according to any one of claims 1 to 4, wherein the temperature history management material is formed to a size of at least 5 mm. It is characterized by that.

  The method for avoiding abnormal discoloration at the time of temperature history management according to claim 6 is the method according to any one of claims 1 to 5, wherein the temperature history management material is molded to a size of 5 to 9 mm. And sticking to the curved object to be tested.

  The method for avoiding abnormal discoloration during temperature history management according to claim 7 is the method according to any one of claims 1 to 6, wherein the acrylic resin adhesive, rubber adhesive, and ethylene vinyl acetate are used. The pressure-sensitive adhesive member is formed by applying an ink for a pressure-sensitive adhesive member containing at least one selected from a resin-based resin pressure-sensitive adhesive.

  The method for avoiding abnormal discoloration at the time of temperature history management according to claim 8 is the method according to any one of claims 1 to 7, wherein the color change between the substrate and the temperature-sensitive discoloration member is constant. It is characterized by forming at least one layer of sexually colored layers.

  The method for avoiding abnormal discoloration during temperature history management according to claim 9 is the method according to any one of claims 1 to 8, wherein the fatty acid derivative, alcohol derivative, ether derivative, aldehyde derivative, ketone derivative, By applying an ink for a temperature-sensitive color-changing member containing at least one kind of the above-mentioned heat-meltable substance selected from amine derivatives, amide derivatives, nitrile derivatives, hydrocarbon derivatives, thiol derivatives, and sulfide derivatives, the temperature-sensitive color-changing member It is characterized by forming.

The abnormal color change repelling temperature history management material according to claim 10 is a temperature history management material for managing a temperature history of a plasticizer attached to a test object containing a resin surface layer through an adhesive layer. a is, plasticizing the to be detected temperature and the temperature-sensitive color change member for discoloration by granular or powdery heat-fusible substance and the melting point is thermally melted, and the adhesion member, the plasticizer in a non-permeable The upper surface of the non-agent-containing base material is attached with a gap and covered with a protective sheet, and the lower surface of the base material is provided with a non-peelable adhesive layer. Since the temperature-changing member and the plasticizer are separated from each other, the plasticizer is in contact with the temperature-sensitive color-changing member, thereby avoiding abnormal color change that does not depend on the color change during temperature management. It is characterized by that.

  According to the method for avoiding abnormal discoloration at the time of temperature history management of the present invention, the temperature history management material attached to the test temperature object having the resin containing the plasticizer on the surface layer is obtained after a long period of time or Keep away the plasticizer in high temperature and high humidity environment. Therefore, since the temperature history management material does not discolor abnormally and changes color only when exposed to the temperature to be detected, it can be easily and accurately managed by visual inspection whether or not the temperature history to be detected has passed the temperature history to be detected. .

  The abnormal discoloration repelling temperature history management material used in the abnormal discoloration repelling method at the time of temperature history management can be easily manufactured in large quantities because it has a small and simple structure. In addition, the abnormal color change repelling temperature history management material accurately determines whether or not a temperature history exceeding a predetermined temperature has passed, without causing erroneous color change even under high temperature and high humidity conditions or long term temperature management. Since it can be displayed, it can be used for a long time.

It is a schematic cross section which shows the middle of the implementation of the abnormal discoloration repellent method at the time of temperature history management of this invention. It is a top view which shows the example of the temperature history management material used for the abnormal discoloration repellent method at the time of the temperature history management of this invention. FIG. 6 is a schematic cross-sectional view showing a state in which abnormal color change repelling method at the time of temperature history management of the present invention is not applied and the color is abnormally changed at temperature history tube.

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

  The method for avoiding abnormal discoloration during temperature management according to the present invention will be described with reference to FIG. The method for avoiding abnormal discoloration at the time of temperature management is to manage the temperature history of the test object 20 having the resin containing the plasticizer 21 on the surface by the temperature history management material 1 that displays the change in color tone. And a step of avoiding abnormal discoloration of the temperature history management material 1 by the plasticizer 21.

  First, a non-peelable adhesive layer 13 is attached to the lower surface of the non-permeable base material 12 of the plasticizer 21 after being attached with strong adhesiveness and then covered with a release paper (not shown). deep. A temperature-sensitive color-changing member ink containing a granular or powder-like heat-meltable substance 15 having an melting point at a temperature to be detected by the test object 20 and an ink vehicle is applied in a layered manner on the upper surface of the substrate 12 by printing. . As a result, the temperature-sensitive color changing member 14 is formed which changes irreversibly when the hot melt material 15 changes from a solid color to a transparent color due to a solid-liquid state change during heat melting.

  On the upper surface of the non-permeable base material 12 of the plasticizer, the temperature-sensitive ink for the pressure-sensitive adhesive member containing the pressure-sensitive adhesive is sufficiently separated by the gap 16 without overlapping or contacting the temperature-sensitive color changing member 14. The adhesive member 11 is formed by applying a layer around the discoloring member 14 by printing.

  The temperature-sensitive color changing member 14 and the pressure-sensitive adhesive member 11 are covered with the protective sheet 10 together with the gap 16 and pressure-sensitive bonded. If necessary, the temperature history management material 1 is obtained by cutting into a size suitable for attachment to the test object 20.

  The test object 20 to be temperature-controlled is, for example, an electric cable composed of a metal wire and a coating material in which the metal wire is coated with an insulating thermoplastic resin, or a thermoplastic resin mark tube that is coated and displayed by color. is there. These coating materials and the thermoplastic resin of the mark tube contain a plasticizer 21 for easy molding. Since the test object 20 has a resin containing the plasticizer 21 on its surface layer, the molecules of the plasticizer 21 are partially exposed from the surface layer. The obtained temperature history management material 1 is used to manage the temperature of the test object 20.

  The release paper is peeled off from the temperature history management material 1 to expose the adhesive layer 13. When the temperature history management material 1 is pasted on the resin surface layer of the test object 20 via the pasting layer 13, the temperature history management becomes possible. At this time, the temperature-sensitive color changing member 14 and the plasticizer 21 are in a non-contact state and separated by the gap 16 and the base material 12. The plasticizer 21 and the temperature-sensitive color-changing member 14 do not come into contact with each other even if they are exposed for a long time or under high-temperature and high-humidity conditions due to the interposition of the gap 16 and the base material 12 therebetween. Thereby, abnormal discoloration of the temperature-sensitive discoloration member 14 due to the plasticizer 21 is avoided.

  That is, when the plasticizer 21 contacts or enters the temperature-sensitive color changing member 14 over time as in the conventional temperature history management material 1, the hot-melt material 15 in the temperature-sensitive color changing member 14 is unexpectedly plasticized. 21 or in the binder resin in the temperature-sensitive color changing member 14. Then, although the temperature history management material 1 is not heated to a predetermined temperature, abnormal discoloration occurs as if the temperature has passed the predetermined temperature. However, according to the method for avoiding abnormal discoloration during temperature management, the gap 16 and the substrate 12 prevent such abnormal discoloration.

  Therefore, even if the plasticizer 21 existing on the surface layer of the test object 20 permeates the adhesive layer 13 over time, it is shielded by the non-permeable base material 12 of the plasticizer 21 and does not reach the temperature-sensitive color changing member 14. . Even if the plasticizer 21 volatilizes or sublimates from the surface layer of the test object 20 due to overheating or the like over time or is absorbed and diffused to the adhesive member 11 through water droplets attached to the adhesive member 11 and the surface layer, It is shielded and does not reach the temperature-sensitive color changing member 14. Further, when the temperature history management material 1 is formed by cutting, the adhesive member 11 is extended from the base material 12 to the pasting layer 13 with a cutting blade, and as a result, the plasticizer existing on the surface layer of the test object 20 Even if 21 is absorbed into the adhesive layer 13 and diffuses into the adhesive member 11 over time, it is shielded by the gap 16 and does not reach the temperature-sensitive color changing member 14. Furthermore, even if the plasticizer 21 is present in a high concentration on the surface layer of the test object 20, the plasticizer 21 is shielded by the non-permeable base material 12 and the gap 16 of the plasticizer 21 and does not reach the temperature-sensitive color changing member 14.

  As described above, the method for avoiding abnormal discoloration at the time of temperature control is that the temperature history management material 1 is abnormally discolored by various types and concentrations of plasticizers at the time of temperature control of the test object containing the plasticizer in the resin surface layer. This is to prevent the occurrence.

  The resin surface layer of the test object 20 is formed of a thermoplastic resin containing a plasticizer 21. For example, the resin surface layer of the test object 20 is a resin coating material for an electric cable formed of a thermoplastic resin, a resin insulator, or a mark tube for identifying an electric cable. Examples of the thermoplastic resin include vinyl chloride, polyethylene, and crosslinked polyethylene. The plasticizer 21 is added to a thermoplastic resin to improve flexibility and weather resistance. The phthalate ester, adipic acid ester, trimellitic acid ester, phosphoric acid ester, citric acid ester, epoxidized vegetable oil, sebacic acid Examples include esters, azelaic acid esters, maleic acid esters, and benzoic acid esters. Such plasticizers are water-insoluble. The plasticizer 21 is contained in an amount of 1% by weight or more with respect to the thermoplastic resin. The plasticizer 21 contains 50 wt% at the maximum with respect to the thermoplastic resin.

  The method for avoiding abnormal discoloration during temperature control by the plasticizer is that plastic member is formed by attaching the adhesive member 11 and the temperature sensitive discoloration member 14 to the upper surface of the substrate 12 so that the width L of the gap 16 is 0.5 mm or more. The agent 21 is preferable because it is more difficult to reach the temperature-sensitive color changing member 14. If the width L is shorter than 0.5 mm, the plasticizer 21 that has penetrated into the adhesive member 11 reaches the temperature-sensitive color changing member 14 by volatilization or sublimation even if there is some gap 16. The temperature-sensitive color change member 14 is contacted by the pressure applied to the protective sheet 10 or the adhesive member 11 is pushed and expanded into the gap 16 due to the bending or bending of the temperature history management material 1, thereby causing abnormal color change.

  In order to avoid abnormal discoloration during temperature control, the substrate 12 is made of cellulose such as cellulose, cellulose acetate butyrate and hydroxyethyl cellulose; polyolefins such as polyethylene, polypropylene and polybutene; polyesters such as polyethylene terephthalate; polystyrene Polystyrenes such as polystyrene copolymers; Hydrochloric rubbers; Polyamides; Fluororesin; Polyvinyl butyrals; Polyethylene oxides; Polyurethanes; Polyimides, alone or in combination, or copolymerized It is preferable that the plasticizer 21 is made of a resin and is made of a plasticizer-impermeable resin film because the plasticizer 21 hardly reaches the temperature-sensitive color changing member 14. Such a substrate needs to be free of a plasticizer.

  Moreover, since the base material 12 is excellent in flexibility when these are resin films, the temperature history management material 1 is bent without being scratched or creased to follow the shape of the test object 20. Can be pasted. Furthermore, when the base material 12 is such a resin film, even if the temperature of the test object 20 is overheated and, for example, the paper is scorched at 150 to 180 ° C., the plasticizer is not burnt, burnt, shrunk, or cracked. 21 does not penetrate into the temperature-sensitive color changing member 14. Among these, it is more preferable that the base material 12 is formed of a chemical-resistant resin film such as polyethylene terephthalate or polyimide, because the plasticizer 21 becomes more difficult to reach the temperature-sensitive color changing member 14. Among these, it is still more preferable that the base material 12 is formed with the polyimide resin film excellent in the flame retardance. Furthermore, it is preferable that the thickness of this base material 12 is 10-30 micrometers. If it is less than this range, the plasticizer 21 penetrates and reaches the temperature-sensitive color changing member 14 easily. If this range is exceeded, the flexibility of the temperature history management material 1 will be poor, and it will be strongly biased and peeled off when it is attached to a rounded electric cable.

  As a method for avoiding abnormal discoloration during temperature management, it is preferable to form the temperature history management material 1 in a size of at least 5 mm. It is even more preferable to form a 5-9 mm square square or 5-9 mm diameter circle. If the temperature history management material 1 is smaller than 5 mm, it becomes difficult to form the width L of the gap 16 at least 0.5 mm, and abnormal discoloration cannot be avoided. On the other hand, if it is larger than 9 mm, the width L of the gap 16 can be formed sufficiently and reliably, but the temperature history management material 1 is bent and pasted on the surface of the test object 20 that is curved. Then, the restoring force that tries to return to the flat surface acts and it is easy to peel off. For example, when the test object 20 is a mark tube having a diameter of 12 mm, the temperature history management material 1 is preferably 6.5 mm square.

  The method for avoiding abnormal discoloration at the time of temperature control is an adhesive member ink containing an acrylic resin adhesive, a rubber adhesive, or an ethylene vinyl acetate resin adhesive, and is printed on the upper surface of the substrate 12 so as to adhere to the adhesive member 11. It is preferable to form. It is more preferable that the adhesive member ink is an acrylic resin water-based paste ink. With such printing, the adhesive member 11 does not overlap or contact the temperature-sensitive color changing member 14 and is sufficiently separated by the gap 16 so that it is at least 0.5 mm around the temperature-sensitive color changing member 14. It is possible to attach the gap 16 accurately and easily. Thereby, adjustment can be made so that the plasticizer 21 does not penetrate into the temperature-sensitive color changing member 14. The adhesive member 11 may be formed by uniformly printing on the surface of the base material 12 excluding the temperature-sensitive color changing member 14 and the gap 16. As shown in FIG. 2 (a), the adhesive member 11 may be printed in a dot pattern to form an intermittent gap 16. Alternatively, the adhesive member 11 may be printed in a square tile pattern, a polka dot pattern, a checkered pattern, etc. The gap 16 may be formed. As shown in FIG. 2B, the adhesive member 11 may be formed in a concentric circle around the temperature-sensitive color changing member 14 to form intermittent gaps 16. When such a plurality of intermittent gaps 16 are provided, the plasticizer 21 is more difficult to penetrate into the temperature-sensitive color changing member 14. The adhesive member 11 may be printed up to the periphery of the base material 12, but when the protective sheet 10 is pressed or the temperature history management material 1 is bent or bent, the temperature history management material 1 outside from the periphery. In order not to protrude, the inner side about 1 mm from the periphery may be unprinted.

  Abnormal discoloration repellent methods during temperature control include heat melting properties such as fatty acid derivatives, alcohol derivatives, ether derivatives, aldehyde derivatives, ketone derivatives, amine derivatives, amide derivatives, nitrile derivatives, hydrocarbon derivatives, thiol derivatives, and sulfide derivatives. The temperature-sensitive color changing member 14 is formed by printing on the upper surface of the base material 12 with the ink for the temperature-sensitive color changing member containing the substance 15 and, if necessary, an ink vehicle such as a binder resin or a solvent. Preferably there is. When these hot-melt materials 15 come into contact with the plasticizer 21, they are easily dissolved and cause abnormal discoloration over time. However, the gap 16 and the substrate 12 prevent the abnormal discoloration.

  In the temperature-sensitive color changing member ink, a circle, a square, a pattern, or a character having a size of, for example, about 0.5 to 2 mm in the center of the base material 12 so as to be smaller than the size of the desired temperature history management material 1. As a result, the temperature-sensitive color changing member 14 is formed.

  The mechanism in which the obtained temperature history management material 1 is discolored only when heated to a temperature to be detected without being influenced by the plasticizer over time is as follows. The temperature-sensitive color changing member 14 is observed to be opaque like white because the particles or powder of the hot-melt material 15 diffusely reflects light before heating. Once heated to the melting point temperature or higher, the hot-melt material 15 is melted by heat and becomes transparent. Accordingly, the temperature-sensitive color changing member 14 is observed transparently. Thereafter, when cooled to a temperature lower than the melting point, the hot-melt material 15 solidifies, but does not return to the original granular or particulate form. Solidify while still transparent. As a result, the temperature-sensitive color changing member 14 is difficult to diffusely reflect light, changes its color from the original opaque white color to transparent, and no longer returns to the original white color. At this time, the temperature history management material 1 is observed through the color tone of the base material 12 when the temperature-sensitive color changing member 14 becomes transparent, and can be visually observed as a change in the color tone. Such a change in color tone is observed as a change in the overall color tone of the temperature-sensitive color changing member 14, unlike an abnormal color change that gradually changes with time from around the temperature-sensitive color changing member 14 due to the influence of the plasticizer. .

  The temperature-sensitive color changing member 14 is formed by printing by containing a dye that can be dissolved or diffused into the heat-meltable material 15 in the form of powder or particles in the ink for the temperature-sensitive color changing member. Also good. In this case, at the initial low temperature, the dye is concealed by the heat-meltable substance 15 irregularly reflecting light. When the hot-melt material 15 is melted by heat, the dye is diffused and the temperature-sensitive color changing member 14 is colored. Therefore, the difference in color before and after the heat-melting becomes clear, and the temperature to be detected 20 has passed the temperature to be detected. This can be seen more accurately.

  The temperature-sensitive color changing member 14 contains a large amount of the hot-melt material 15 with respect to the ink vehicle such as a binder resin. In the temperature-sensitive color changing member 14, the heat-meltable substance 15 is preferably contained in an amount of 70 to 95% by weight with respect to the resin. If the hot-melt material 15 is within this range, it does not cause abnormal discoloration that gradually changes over time from around the temperature-sensitive discoloration member 14 due to the influence of the plasticizer, regardless of the type and concentration of the plasticizer. . If the hot melt material 15 is less than this range, the hot melt hot melt material 15 forms a gap with the ink vehicle, causes irregular reflection of light and returns to white, resulting in a reversible color change. End up. On the other hand, if the hot-melt material 15 is larger than this range, the ink vehicle will be relatively small relative to the hot-melt material 15, and the temperature-sensitive color changing member 14 cannot be sufficiently fixed to the substrate 12. End up.

  An invariant colored layer (not shown) may be provided between the base material 12, the adhesive member 11 and the temperature-sensitive color changing member 14, and characters and figures such as numbers of temperatures to be detected are printed on the colored layer. May be. Thereby, the color change of the temperature-sensitive color change member 14 can be easily recognized as a clear one, and the specific temperature that has passed can be easily recognized. Further, a plurality of invariant colored layers may be laminated and formed, and in this case, the color of each layer may be changed.

  Fatty acid derivatives used as the hot-melt material 15 are myristic acid, palmitic acid, adipic acid, octanoic acid, tricosanoic acid, tetratriacontanoic acid, 2,3-dimethylnonanoic acid, 23-methyltetracosanoic acid, and 2-hexenoic acid. , Brassic acid, 2-methyl-2-dodecenoic acid, β-eleostearic acid, behenolic acid, cis-9,10-methyleneoctadecanoic acid, sorghumulinic acid, 3,3′-thiodipropionic acid-n- Dodecyl, trilaurin, palmitic acid anilide, stearic acid amide, zinc stearate, salicylic acid anilide, N-acetyl-L-glutamic acid, caproic acid-β-naphthylamide, enanthic acid phenylhydrazide, arachidic acid-p-chlorophenacyl formate, cholesteryl formate, 1-aceto-2,3-distearin, thio Lauric acid-n-pentadecyl, stearic acid chloride, palmitic anhydride, stearic acid-acetic anhydride, succinic acid, benzylammonium sebacate, 2-bromovaleric acid, α-sulfostearic acid methyl sodium salt, 2-fur Orarachidic acid.

  Similarly, alcohol derivatives include octadecyl alcohol, cholesterol, D-mannitol, galactitol, heptatriacontanol, hexadecan-2-ol, 1-trans-2-octadecenol, β-eleostearyl alcohol, cycloeicosanol, Examples include d (+) cellobiose, p, p′-biphenol, riboflavin, 4-chloro-2-methylphenol, and 2-bromo-1-indanol.

  Similarly, ether derivatives include dihexadecyl ether, dioctadecyl ether, cytidine, adenosine, sodium phenoxyacetate, 1,3-bis (4-hydroxyphenoxy) benzene, and aluminum triethoxide.

  Similarly, examples of the aldehyde derivative include stearaldehyde, paralauryl aldehyde, para stearaldehyde, naphthaldehyde, p-chlorobenzaldehyde, phthalaldehyde, and 4-nitrobenzaldehyde.

  Similarly, ketone derivatives include stearone, docosan-2-one, phenylheptadecyl ketone, cyclononadecane, vinyl heptadecyl ketone, 4,4-bisdimethylaminobenzophenone, bis (2,4-pentanedionite) calcium, 1-chloroanthraquinone. Is mentioned.

  Similarly, amine derivatives include tricosylamine, dioctadecylamine, N, N-dimethyloctylamine, heptadecamethyleneimine, naphthylamine, ethyl p-aminobenzoate, o-trithiourea, sulfamethazine, guanidine nitrate, p-chloroaniline, propyl. Amine hydrochloride is mentioned.

  Similarly, amide derivatives include hexylamide, octacosylamide, N-methyldodecylamide, N-methylheptacosylamide, α-cyanoacetamide, salicylamide, dicyandiamide, 2-nitrobenzamide, and N-bromoacetamide.

  Similarly, examples of the nitrile derivative include pentadecane nitrile, margaronitrile, 2-naphthonitrile, o-nitrophenoxyacetic acid, 3-bromobenzonitrile, 3-cyanopyridine, and 4-cyanophenol.

  Similarly, hydrocarbon derivatives include hexadecane, 1-nonatriacontene, trans-n-2-octadecene, hexatriacontylbenzene, 2-methylnaphthalene, bicene, cyanuric chloride, 1-fluorononadecane, 1-chloroeicosane, Examples include 1-iodopentadecane, 1-bromoheptadecane, 1,2,4,5-tetrakis (bromomethyl) benzene.

  Similarly, examples of the thiol derivative include pentadecane thiol, eicosane thiol, 2-naphthalene thiol, 2-mercaptoethyl ether, and 2-nitrobenzenesulfenyl chloride.

  Similarly, sulfide derivatives include 1,3-diatine, 2,11-dithia [3,3] paracyclophane, bis (4-hydroxy-3-methylphenyl) sulfide, 4,4-dipyridyl sulfide, 4-methylmercaptophenol. Is mentioned.

  As the resin of the ink vehicle in the ink for the temperature-sensitive color changing member, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, acrylic resin, phenol resin, nylon, polyvinyl alcohol are used, and commercially available PAS 800 medium (manufactured by Jujo Kaiko), High A set mat medium (manufactured by Mino Group) may be used.

  Water, ethanol, butanol, ethyl acetate, isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, butyl cellosolve, diethylbenzene, ethyl cellosolve, minerals as solvents for ink vehicles in inks for temperature-sensitive color change materials and adhesive materials You may use spirit.

  The order of the formation of the temperature-sensitive color changing member 14 by printing the ink for the temperature-sensitive color changing member and the formation of the pressure-sensitive adhesive member 11 by printing the ink for the pressure-sensitive adhesive member may be first. Since both are based on printing, the gap 16 can be formed accurately.

  The formation of the temperature-sensitive color changing member 14 and the pressure-sensitive adhesive member 11 are performed as follows. In order to obtain ink for temperature-sensitive color changing members and ink for pressure-sensitive adhesive members, respectively, a heat-meltable substance 15, or an acrylic resin-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, an ethylene vinyl acetate-based resin pressure-sensitive adhesive, and an ink vehicle as required A binder resin and a solvent, and an additive such as a pigment are dispersed and kneaded by a ball mill, a three-roller, a stirrer, or a disperser. This is printed on the upper surface of the base material 12 having the adhesive layer 13 on the lower surface in an arbitrary shape and size as desired to form the temperature-sensitive color changing member 14 and the adhesive member 11.

  Examples of the printing method of each ink for forming the temperature-sensitive color changing member 14 and the adhesive member 11 include screen printing, flexographic printing, offset printing, and gravure printing.

  The method for avoiding abnormal discoloration at the time of temperature control is preferably covered with a protective sheet 10 made of only a transparent or translucent resin film capable of visually recognizing discoloration of the temperature-sensitive discoloration member 14. The protective sheet 10 is made of polyethylene terephthalate or polyimide and does not contain a plasticizer. The protective sheet 10 can protect the temperature-sensitive color changing member 14 and the pressure-sensitive adhesive member 11 from external moisture and oxygen, or can be protected from scratches and frictional heat due to abrasion. In addition, the protective sheet 10 prevents the adhesive member 11 from absorbing moisture from the outside and expands and crushes the gap 16, thereby maintaining the shape of the gap 16. As a result, the plasticizer 21 is temperature sensitive. The discoloration member 14 is not reached.

  Abnormal discoloration repellent method at the time of temperature control, the non-peelable adhesive layer 13 may be affixed to the lower surface of the substrate 12 an adhesive film containing a patch such as an acrylic adhesive, The adhesive for the adhesive layer containing the adhesive patch may be applied to the lower surface of the substrate 12. The non-peelable adhesive layer 13 prevents the temperature history management material 1 from being peeled even if it is urged by the hard base material 12 when it is attached to a test object 20 such as a rounded electric cable. Whether or not the test object has passed a temperature history to be detected can be easily and accurately managed visually.

  An example in which the temperature is controlled by the method for avoiding abnormal discoloration at the time of temperature history management of the present invention is shown as an example, and an example in which the present invention is not applied and the temperature is controlled by the method for avoiding an abnormal discoloration at the time of temperature history management is shown in a comparative example. .

Example 1
(1. Preparation of temperature history management material)
After blending 100 parts by weight of palmitic acid, which is a heat-melting substance, and 150 parts by weight of an ink vehicle in which 10% by weight of ethyl cellulose, which is a binder resin, is mixed with diethylbenzene, which is a solvent, the mixture is pulverized and mixed in a ball mill. An ink for a temperature-sensitive color changing member was obtained. On the upper surface of the base material, which is a black polyethylene terephthalate film in which the 465 adhesive material manufactured by Sumitomo 3M Co., Ltd. is bonded to the lower surface, the obtained temperature-sensitive color changing member ink is screen-printed in a circle with a diameter of 2 mm and dried. A temperature sensitive color changing member was formed. After that, water-based glue (1458B, manufactured by ThreeBond Co., Ltd.), which is an ink for adhesive members, is printed by screen printing with a gap of 0.5 mm between the temperature-sensitive color change members and dried to form an adhesive member. did. Next, an untreated transparent polyester film as a protective sheet was bonded to the temperature-sensitive color changing member and the adhesive member together with the gaps, and then cut into a 5 mm square shape and molded to obtain a temperature history management material.

(2. Abnormal discoloration avoidance test over time under constant temperature and humidity acceleration conditions)
In order to confirm that the temperature history management material does not cause abnormal discoloration, the temperature history management material was left at a temperature slightly lower than the temperature at which the temperature history could be detected, under high-temperature and constant-humidity acceleration conditions. The acceleration conditions were as follows: 10 temperature history management materials were attached to Mark Tube TIC-16 (green) (manufactured by Nichif Co., Ltd., respectively) and placed in a constant temperature and humidity chamber at 50 ° C. and 90% Rh (relative humidity). It is to put. After 3 days, 7 days, 28 days, 56 days, 84 days and 112 days, the presence or absence of abnormal discoloration of the temperature history management material was visually confirmed. It was evaluated in two stages. In addition, when the temperature history management material peels from the mark tube, the temperature history management cannot be performed. The results are summarized in Table 2. Incidentally, the aging conditions for 112 days at 50 ° C. and 90% Rh correspond to the aging conditions for 2.5 years at room temperature and normal humidity (20 ° C. and 60% Rh).

(3. Temperature history display confirmation test by heating to the temperature to be detected)
In order to confirm whether the temperature history management material before and after the constant temperature and humidity acceleration condition changes color at the temperature to be detected and displays a desired temperature history display, a test was performed under the following conditions. Ten samples of temperature history management material before the constant temperature and humidity acceleration conditions were attached to the mark tube TIC-16 (green), placed in a constant temperature bath, heated from 50 ° C. to 1 ° C. and left at each temperature for 1 hour. The temperature at which the temperature history could be displayed was measured by visually confirming the presence or absence of discoloration of the temperature history management material. On the other hand, the temperature at which the temperature history was displayed in the same manner for the temperature history management material after 112 days in the time-dependent abnormal discoloration repellent test was measured. The results are summarized in Table 2. It should be noted that the case where discoloration has already occurred after 112 days in the time-lapse abnormal discoloration avoidance test is “impossible to measure due to abnormal discoloration”, and the case where the temperature history management material is peeled off from the mark tube is “impossible to measure due to peeling” did.

(4. Combustion test)
In order to confirm the difficulty of combustion, flames were applied for 5 seconds with a gas burner to each of the 10 unused temperature history management materials of Examples 1 to 6 and Comparative Examples 1 to 11 controlled at room temperature, and the degree of combustion was determined. This was confirmed by visual inspection. Evaluation was made in three stages: ignited when it was not ignited or extinguished in less than 10 seconds after igniting, ◯ when extinguished in 10 seconds or more and less than 30 seconds, and x when continuing to burn for 30 seconds or more. The results are summarized in Table 2.

(Examples 2-6 and Comparative Examples 1-6)
Table 1 shows the types of heat-meltable substances, the size of the temperature history management material, the width L of the gap between the temperature-sensitive discoloration member and the adhesive member, and the types of the base material / adhesive member / sticking layer and protective sheet Except for the above, a temperature history management material was produced in the same manner as in Example 1, and various tests similar to those in Example 1 were performed. The results are summarized in Table 2.

(Example 7)
Of the preparation of the temperature history management material of Example 1, the black polyethylene terephthalate film was replaced with a polyimide film with a 465 adhesive material manufactured by Sumitomo 3M as a patch on the lower surface, and an invariant colored layer on the upper surface. A temperature history management material was prepared in the same manner as in Example 1 except that EGS black manufactured by Teikoku Ink Co., Ltd. was applied by screen printing, and various tests similar to those in Example 1 were performed. The results are summarized in Table 2.

(Comparative Example 7)
Of the preparation of the temperature history management material of Example 1, except that the black polyethylene terephthalate film was replaced with black fine paper with a 465 adhesive material manufactured by Sumitomo 3M as a patch on the lower surface. Similarly, a temperature history management material was produced, and various tests similar to Example 1 were performed. The results are summarized in Table 2.

(Comparative Example 8)
In the preparation of the temperature history management material of Example 1, as a protective sheet, instead of an untreated transparent polyester film, a paste-attached polyester film PET16PL thin (trade name, manufactured by Lintec Corporation) was bonded to the entire lower surface. Except for this, a temperature history management material was produced in the same manner as in Example 1, and various tests similar to those in Example 1 were performed. The results are summarized in Table 2.

(Comparative Example 9)
A temperature-sensitive ink was obtained in which 10 parts by weight of white crystals of palmitic acid were blended with 16 parts by weight of an 8% aqueous solution of methylcellulose as a hot-melt material. The obtained temperature-sensitive ink was applied onto black paper as a substrate, dried, and then cut into a circle having a diameter of 3 mm. After sticking this on the base material polyethylene terephthalate film where a double-sided pressure-sensitive adhesive (manufactured by Sumitomo 3M Co., Ltd., 465) was pasted, a transparent polyester film was pasted as a protective sheet. After sticking a double-sided adhesive material (manufactured by Sumitomo 3M Co., Ltd., 465) on the back surface of the polyethylene terephthalate film of the base material, the four sides were cut into a size of 5 mm to obtain a temperature history management material. About this, the same various tests as Example 1 were done. The results are summarized in Table 2.

(Comparative Example 10)
Example 1 except that in the preparation of the temperature history management material of Example 1, the adhesive layer on the lower surface of the base material was replaced with light-adhesive 5035K (trade name, manufactured by Nitto Denko Corporation) which is extremely easy to peel off. In the same manner as above, a temperature history management material was prepared, and various tests similar to those in Example 1 were performed. The results are summarized in Table 2.

  As is apparent from Table 2, according to Examples 1 to 7 to which the method for avoiding abnormal discoloration at the time of temperature history management of the present invention is applied, the temperature history management material abnormally discolors for a long time even in a high temperature and high humidity environment. No discoloration was observed and the color changed correctly at the temperature to be detected. Moreover, it was not peeled off from the temperature of the test object, and even after burning, the fire was extinguished quickly. On the other hand, according to Comparative Examples 1 to 11 in which the present invention is not applied and temperature management is performed without using the method for avoiding abnormal discoloration during temperature history management, the temperature history management material is abnormally discolored due to the influence of the plasticizer in a short period of time. Or peeled off from the test object, or continued to burn due to ignition.

  The method for avoiding abnormal discoloration at the time of temperature history management using the temperature history management material of the present invention has a predetermined temperature even when the temperature history management material is affixed to a test object containing a plasticizer in the resin surface layer. It is used to accurately display whether or not the temperature history exceeds, and to manage the temperature history visually.

  1 is a temperature history management material, 2 is a conventional temperature history management material, 10 is a protective sheet, 11 is an adhesive member, 12 is a base material, 13 is a sticking layer, 14 is a temperature-sensitive color change member, 15 is a heat-meltable substance, 16 is a gap, 20 is a test object, 21 is a plasticizer, 30 is an adhesive layer, 31 is a base material, 32 is an adhesive layer, 33 is a protective sheet, 34 is a temperature-sensitive discoloration layer, and 35 is a liquefied hot melt The absorbing layer 36 of the active substance is a water droplet.

Claims (10)

A thermochromic member which discoloration by granular or powdery heat-fusible substance to be sensed temperature and the melting point is thermally melted, and an adhesive member, plasticizer-free basis of the plasticizer in a non-permeable Cover the upper surface of the material with a gap and then cover it with a protective sheet, attach a non-peelable adhesive layer to the lower surface of the base material, and form the temperature history management material with the plasticizer on the resin surface layer. Affixed to the test temperature contained through the adhesive layer, when managing the temperature history of the test temperature by the discoloration,
The temperature-sensitive color-changing member and the plasticizer are separated from each other by the gap and the base material, so that the plasticizer contacts the temperature-sensitive color-changing member and causes an abnormal color change not based on the color change. An abnormal discoloration repelling method during temperature history management, characterized in that the temperature history is managed while avoiding this.   2. The method for avoiding abnormal discoloration during temperature history management according to claim 1, wherein the temperature-sensitive discoloration member and the adhesive member are attached so that a width of the gap is at least 0.5 mm.   The base material is at least one selected from celluloses, polyolefins, polyesters, polystyrenes, hydrochloric acid rubbers, polyamides, fluororesins, polybutenes, polyvinyl butyrals, polyethylene oxides, polyurethanes, and polyimides. 3. The method for avoiding abnormal discoloration at the time of temperature history management according to claim 1 or 2, wherein the material is molded with a kind of material.   The method for avoiding abnormal discoloration during temperature history management according to claim 1, wherein a plurality of the adhesive members are intermittently attached.   The method for avoiding abnormal discoloration during temperature history management according to any one of claims 1 to 4, wherein the temperature history management material is formed into a size of at least 5 mm.   The temperature history management material is molded to a size of 5 to 9 mm and attached to the curved object to be tested. Abnormal discoloration avoidance during temperature history management according to claim 1, Method.   The adhesive member is formed by applying an ink for an adhesive member containing at least one selected from an acrylic resin-based adhesive, a rubber-based adhesive, and an ethylene-vinyl acetate-based resin adhesive. The method for avoiding abnormal discoloration during temperature history management according to any one of 1 to 6.   The method for avoiding abnormal discoloration during temperature history management according to any one of claims 1 to 7, wherein at least one invariant color-changing colored layer is formed between the substrate and the temperature-sensitive discoloration member.   Sensitivity containing at least one kind of the above hot-melting substance selected from fatty acid derivatives, alcohol derivatives, ether derivatives, aldehyde derivatives, ketone derivatives, amine derivatives, amide derivatives, nitrile derivatives, hydrocarbon derivatives, thiol derivatives, and sulfide derivatives. The method for avoiding abnormal discoloration during temperature history management according to any one of claims 1 to 8, wherein the temperature-sensitive discoloration member is formed by applying ink for a temperature discoloration member. A temperature history management material for managing a temperature history of a plasticizer, which is attached to a test temperature object contained in a resin surface layer via an adhesive layer,
A temperature-sensitive color-changing member that changes color by heat melting a granular or powdery hot-melt material having a melting point as a temperature to be detected, and an adhesive member are non-permeable and non- plasticizer containing the plasticizer . The upper surface of the base material is attached with a gap and covered with a protective sheet, and the lower surface of the base material is provided with a non-peelable adhesive layer, and the temperature-sensitive color changing member is formed between the gap and the base material. Since the plasticizer is isolated, the plasticizer is in contact with the temperature-sensitive color change member, and an abnormal color change that does not depend on the color change is avoided during temperature management. Abnormal discoloration repelling temperature history management material.

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