JPH07286914A - Temperature control label - Google Patents

Abstract

PURPOSE:To easily and surely determine whether or not the storage temperature of an article has risen above a predetermined temperature by bonding first and second labeling sheets together using a porous sheet, and containing a temperature controlling agent in one or more of the sheets. CONSTITUTION:A first labeling sheet has an adhesive layer which is provided on one side of a base sheet made preferably of a vinyl chloride resin and the like and which contains an organic chelate coupler. A second labeling sheet has an adhesive layer which is provided on one side of a base sheet and which contains a metallic compound that is colored when reacted with the organic chelate coupler, and both adhesive layers are bonded together by a porous sheet and at least one of the sheets contains a temperature controlling agent such as n-paraffin. As the temperature controlling agent flows within the porous sheet in a melting temperature range, either the metallic compound or the organic chelate coupler migrates within the porous sheet and is colored by reaction between them on contact. The color does not disappear even with the sheet kept below the melting point, and is detected to easily and surely determine whether or not the storage temperature of an article has risen above a predetermined temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a temperature control label, and more specifically, it develops color irreversibly after reaching a desired temperature or higher for a predetermined time, and whether or not the labeled article is controlled at a predetermined temperature. The present invention relates to a temperature management label that can be easily and surely detected by its color development.

[0002]

2. Description of the Related Art Recently, a courier service for delivering frozen products to a delivery destination while keeping them frozen has become popular. Most refrigeration vehicles used for this courier are small refrigeration vehicles, and often have a structure in which the refrigeration equipment is stopped when the engine is turned off. In such a refrigeration vehicle, if the engine is stopped for a long time, the temperature in the freezer may rise and the frozen product may thaw, causing the frozen product to rot or deteriorate. Without noticing this, if the engine is restarted and the refrigeration equipment is driven to refrigerate the inside of the freezer, the deteriorated frozen material is delivered to the delivery destination without noticing it. Also, even if the frozen product is stored in another refrigeration facility, whether the frozen product is thawed or has reached a predetermined temperature or more when the refrigeration facility is temporarily stopped due to a failure or the like. Can be difficult to detect reliably.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation of the prior art, and it is attached to various articles such as frozen articles and the storage temperature of the article is equal to or higher than a predetermined temperature. An object of the present invention is to provide a temperature management label capable of easily and surely detecting the temperature history of whether or not the temperature has been reached, and reliably knowing the storage management state of the article.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a metal compound capable of reacting with an organic chelate color-developing agent to form a color, and the organic chelate color-developing agent, By arranging the pressure-sensitive adhesive layers on opposite sides through the porous sheet, and by containing a temperature control agent that flows at a desired temperature in at least one of the pressure-sensitive adhesive layer and the porous sheet, the temperature can be adjusted to that temperature. If so, the temperature control agent flows, and along with the flow, the organic chelate coloring agent or the metal compound is moved in the porous sheet to be brought into contact with each other, react to cause irreversible color development, and the color development is detected. The inventors have found that the above problems can be achieved, and have completed the present invention based on this finding.

That is, the present invention provides a first label sheet in which a pressure-sensitive adhesive layer having an organic chelate coloring agent is provided on one side of a base sheet, and a color is developed by reacting with the organic chelate coloring agent on one side of the base sheet. A second label sheet provided with a pressure-sensitive adhesive layer having a metal compound capable of, of a pressure-sensitive adhesive layer having an organic chelate coloring agent of the first label sheet and a pressure-sensitive adhesive layer having a metal compound of the second label sheet. And a pressure-sensitive adhesive layer having an organic chelate coloring agent of the first label sheet, a pressure-sensitive adhesive layer having a metal compound of the second label sheet, and a temperature of at least one of the porous sheets. It is intended to provide a temperature management label characterized by containing a control agent. Hereinafter, the present invention will be described in detail.

The first label sheet according to the present invention comprises a substrate sheet and an adhesive layer having an organic chelate coloring agent provided on one surface thereof. The substrate sheet is not particularly limited, and a sheet made of any material can be used. Examples of such a sheet include polyethylene,
Polyolefin resin such as polypropylene, vinyl chloride resin, styrene resin, ABS resin, polyvinyl alcohol, acrylic resin, acrylonitrile-styrene resin, vinylidene chloride resin, AAS resin, AES resin, polyurethane resin, polyvinyl butyral resin, poly-4
-Methylpentene-1 resin, polybutene-1 resin, vinylidene fluoride resin, vinyl fluoride resin, fluororesin, polycarbonate resin, polyamide resin, acetal resin, polyphenylene oxide resin, polyester resin such as polybutylene terephthalate, polyethylene terephthalate, polyphenylene Various resins such as sulfide resin, polyimide resin, polysulfone resin, polyethersulfone resin, aromatic polyester resin, polyarylate resin, various rubbers such as thermoplastic elastomer, synthetic rubber, metal foil such as aluminum foil, impregnated paper, cellophane paper Examples include sheets of various types of paper such as high-quality paper, art paper, kraft paper, coated paper, lightweight coated paper, and synthetic paper, and laminated sheets of these sheets. Among these sheets, a sheet made of a polyester resin such as polyethylene terephthalate or polybutylene terephthalate or a vinyl chloride resin is preferable.

The thickness of the base sheet is usually 6 to 250 μm.
The range is 12 to 100 μm. Of the base sheet of the first label sheet and the base sheet of the second label sheet, the base sheet located on the label surface needs to be made of a material capable of detecting color development from the label surface. Therefore, it is preferable to make it transparent or semi-transparent so that the color development can be easily detected.

The pressure-sensitive adhesive layer is made of various pressure-sensitive adhesives, for example, natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic resin-based pressure-sensitive adhesives, polyvinyl ether resin-based pressure-sensitive adhesives, urethane resin-based pressure-sensitive adhesives, Examples thereof include silicone resin-based adhesives. Specific examples of the synthetic rubber adhesive include:
Styrene-butadiene rubber, polyisobutylene rubber, isobutylene-isoprene rubber, isoprene rubber, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block copolymer, ethylene-vinyl acetate thermoplastic elastomer And so on. Specific examples of the acrylic resin adhesive include homopolymers of acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile and the like. Or a copolymer etc. are mentioned. Specific examples of the polyvinyl ether resin-based adhesive include polyvinyl ether and polyvinyl isobutyl ether.
Specific examples of the silicone resin-based adhesive include dimethylpolysiloxane. Among these adhesives, acrylic resin-based adhesives are preferable, and acrylic resin-based adhesives in which polar monomers such as acrylic acid and methacrylic acid are 10% by weight or less are particularly preferable. . These adhesives can be used alone or in combination of two or more.

If necessary, a tackifier, a filler, a softening agent, a heat-light stabilizer, an antioxidant, a cross-linking agent and the like can be added to the above-mentioned pressure-sensitive adhesive. Examples of the tackifier include rosin resins, terpene phenol resins, terpene resins, aromatic hydrocarbon-modified terpene resins, petroleum resins, coumarone-indene resins, styrene resins, phenol resins, and xylene resins. Examples of the filler include zinc white, titanium oxide, silica, calcium carbonate, barium sulfate and the like. Examples of the softening agent include process oil, liquid rubber and plasticizer. Examples of the heat-light stabilizer include benzophenone-based, benzotriazole-based, hindered amine-based and the like, and antioxidants include anilide-based, phenol-based, phosphite-based,
Examples thereof include thioester type.

When the anchorage of the base material sheet and the adhesive is insufficient, the surface of the base material coated with the adhesive is subjected to corona discharge treatment, or polyester resin, urethane resin, chlorinated polyolefin or the like is used as a main component. It is preferable to provide a primer layer by coating a primer containing a filler if necessary. As the filler, various fillers such as silica, calcium carbonate, magnesium carbonate, kaolin, calcined clay, bentonite, zeolite, talc and diatomaceous earth can be used.

The pressure-sensitive adhesive layer may be provided on one side of the substrate sheet by various methods. For example, the above-mentioned pressure-sensitive adhesive may be dissolved in a suitable solvent and applied, or dispersed in a suitable medium. Examples thereof include a method of emulsifying and coating, a method of coating without solvent or a method of coating with a calendar roll. Of these methods, the preferred method is the solvent dissolution method in which the solvent is dissolved and applied. The thickness of the pressure-sensitive adhesive layer is not particularly limited and is usually 5 to 100 μm.
The range is m, preferably 10 to 50 μm.

The organic chelate color-developing agent may be applied to the surface of the pressure-sensitive adhesive layer, may be impregnated into the surface layer portion of the pressure-sensitive adhesive layer in contact with the porous sheet, or may be mixed in the pressure-sensitive adhesive layer. May be. When the organic chelate coloring agent is present at the interface between the pressure-sensitive adhesive layer and the porous sheet, it is preferable to provide a part where the organic chelate coloring agent does not exist in order to facilitate adhesion between the pressure-sensitive adhesive layer and the porous sheet. . When the organic chelate coloring agent is mixed in the pressure-sensitive adhesive layer, the mixing amount of the organic chelate coloring agent is 0.
It is preferable that the amount is from 01 to 10 parts by weight, and particularly 0.01
It is preferable that the amount is ˜1 part by weight. When the amount of the organic chelate color developing agent is less than 0.01 part by weight, the coloring ability is lowered, and the coloration tends to be thin, making it difficult to identify. When the amount exceeds 10 parts by weight, the color in the initial state before coloring is dark, Identification after color change becomes difficult, and the adhesive strength of the adhesive tends to decrease. The organic chelate coloring agent may be arranged, for example, in a letter shape indicating the control temperature so that the lower limit temperature for coloring can be recognized as a letter.

Examples of the organic chelate coloring agent used in the temperature control label of the present invention include O, O'-hydroxyazo compounds, O-hydroxyazo compounds, phthalein, sulfophthalein and triphenylmethane compounds, Examples thereof include phenolic compounds. O, O'-
Examples of the hydroxyazo compound include 1- (1-hydroxy-2-naphthylazo) -6-nitro-2-naphthol-4-sulfonic acid sodium salt and 1- (2-hydroxy-1-naphthylazo) -2-naphthol. -4-sulfonic acid sodium salt, 1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3-naphthoic acid, 3- (5-chloro-2-hydroxyphenylazo) -4,5 -Dihydroxynaphthalene-2,7-disulfonic acid disodium salt, 4- (2-hydroxy-4-)
Sulfonaphthylazo) -3-methyl-1-phenyl-2
-Sodium salt of pyrazolin-5-one, 3- (2-hydroxyphenylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid disodium salt, 3- (2
-Hydroxy-4-sulfophenylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid disodium salt, 7-amino-2- (2-hydroxy-8-sulfo-1-naphthylazo) -1-naphthol -3-sulfonic acid, 2- (2-hydroxyphenylazo) -1,5-
Naphthalenediol, 2- (2-hydroxy-5-sulfophenylazo) -1,5-naphthalenediol, 1-
(2-Hydroxy-4-nitrophenylazo) -2-naphthol, 1- (2-hydroxyphenylazo) -2-
Naphthol, 1- (2-hydroxy-5-sulfophenylazo) -2-naphthol, 1-hydroxy-8- (2
-Hydroxynaphthylazo) -2- (4-sulfonaphthylazo) -3,6-naphthalene disulfonic acid, 1- [1
-Hydroxy-6- (2-hydroxynaphthylazo)-
4-Sulfo-2-phenylazo] -2-naphthol-6
-Sodium salt of sulfonic acid, 4-hydroxy-3,5
-Sodium salt of bis (2-hydroxynaphthylazo) benzenesulfonic acid, sodium salt of 5- [1- (1,8-dihydroxy-4-sulfo-2-naphthylazo) -4-naphthylazo] salicylic acid, 1- (1 -Hydroxy-3,4,6-trichloro-2-phenylazo) -3-
Acetamide-2-naphthol-6-sulfonic acid sodium salt, 3-phenylazo-4,5-disulfonic acid disodium salt, 2- (2-hydroxy-3,6-disulfo-1-naphthylazo) -benzoic acid sodium salt Salt, 1
-(4,7-Disulfo-1-naphthylazo) -4- (1
-Hydroxy-3-sulfo-6-amino-2-naphthylazo) naphthalene, sodium salt of 2- (5-chloro-2-hydroxy-3-nitrophenylazo) -1-naphthol-4-sulfonic acid, 2- ( 5-chloro-2-hydroxy-3-sulfophenylazo) -1-naphthol-
5-sulfonic acid, 3- (3,6-disulfo-8-hydroxynaphthylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid, 1- (2-hydroxy-3-
Nitro-5-sulfophenylazo) -2-naphthol,
4- (4-nitrophenylazo) pyrocatechol, 4-
(3,4-Dihydroxyphenylazo) benzenesulfonic acid, 5-chloro-3- (2,4-dihydroxyphenylazo) -2-hydroxybenzenesulfonic acid sodium salt, 5-chloro-2-hydroxy-3- ( 1-Hydroxy-2-naphthylazo) benzenesulfonic acid sodium salt, 5-chloro-2-hydroxy-3- (2-hydroxynaphthylazo) benzenesulfonic acid, 3- (8
-Acetamido-2-hydroxynaphthylazo) -2-
Hydroxybenzenesulfonic acid sodium salt, azo-
Examples thereof include metahydroxynaphthyl-2-hydroxy-3-nitrobenzene-5-sulfonic acid.

Examples of O-hydroxyazo compounds include 1-pyridylazo-2-naphthol, 4- (2-pyridylazo) resorcinol, 2- (2-hydroxy-3,
6-Disulfo-1-naphthylazo) benzenearsonic acid sodium salt, 3- (2-arsonophenylazo)-
4,5-Dihydroxynaphthalene-2,7-disulfonic acid sodium salt, 3- (4-sulfophenylazo)-
Sodium salt of 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 7- (1-naphthylazo) -8-quinolinol-5-sulfonic acid, 4- (nitrophenylazo) -2-glycylmethyl-1-naphthol, 4- (nitrophenylazo) -2- [N, N-di (carboxymethyl) aminomethyl] naphthol and the like can be mentioned.

Examples of the phthalein, sulfophthalein and triphenylmethane compounds include 3,3-bis [N, N-di (carboxymethyl) -aminomethyl]-
O-cresolphthalein, pyrocatecholsulfophthalein, pyrogallolsulfophthalein, dibromopyrogallolsulfophthalein, fluorescein bismethyliminodiacetic acid, 3,3-bis [N, N-di (carboxymethyl) aminomethyl] -O-cresolsulfophthalein, 3,3'-bis [N, N-di (carboxymethyl) aminomethyl] thymolsulfophthalein, 2'-
Examples thereof include sulfo-3,3′-dimethyl-4-hydroxyfuchsin-5,5′-dicarboxylic acid sodium salt, glycine thymol blue, glycine cresol red, and parafuchsin complexone.

Examples of phenol compounds include 3,
4-dioxybutylphenol, α-chloro-3,4-
Dioxyacetophenone, 4,5-dichlorocatechol, catechol-3,5-disulfonic acid disodium salt, 3-methylcatechol, 4-methylcatechol, 3
-Isopropylcatechol, 4-isopropylcatechol, pt-butylcatechol, 4-t-octylcatechol, 3-t-butyl-5-methylcatechol, 5-
t-butyl-3-methylcatechol, 6-t-butyl-
3-methylcatechol, 3-t-octyl-5-methylcatechol, 3-methyl-5-t-octylcatechol, 3,5-diisopropylcatechol, 3,6-diisopropylcatechol, 3,5-di-t-butyl Catechol, 3,4-dioxyphenylacetic acid, gallic acid octyl ester, gallic acid dodecyl ester, gallic acid cesyl ester, gallic acid stearyl ester, trioxyacetophenone, tannic acid, 1,2-dioxynaphthalene, 2,3- Dioxynaphthalene, 2,3-dioxynaphthalene-6-sulfonic acid sodium salt, 6,7-dioxynaphthalene-2-sulfonic acid sodium salt, 1,
2-dioxynaphthalene-3,6-disulfonic acid sodium salt and the like can be mentioned.

Examples of other organic chelate color formers include diphenylcarbazone, diphenylcarbazide, N, N'-diphenylguanidine, diphenylthiocarbazone, and 1,3-diphenylurea. Of these organic chelate color formers, phenol compounds and diphenylcarbazone, diphenylcarbazide, N, N'-diphenylguanidine, diphenylthiocarbazone, 1,3-diphenylurea and the like are preferably used.

The second label sheet according to the present invention comprises a substrate sheet provided with an adhesive layer having a metal compound capable of reacting with the organic chelate color-developing agent to form a color on one surface thereof. As the base sheet, a sheet similar to the base sheet of the first label sheet can be used. The metal compound used in the temperature control label of the present invention is a metal compound capable of reacting with an organic chelate color-forming agent to form a color. Examples of this metal compound include various inorganic metal compounds and organic metal compounds. Examples of this metal compound include Cu, Ag, and A.
u, Mg, Cr, Sr, Ba, Zn, Cd, Hg, A
l, Tl, Ti, Sn, Pb, Sb, Bi, V, Ca,
Examples thereof include salts of metals such as Mo, W, Mn, Fe, Ni and Co, and preferably salts of Cu, Zn, Al and Sn. Examples of the inorganic metal salts include sulfates, hydrochlorides and phosphates of the above metals. As the organic metal salt, benzoate, octanoate, oleate, citrate, succinate, acetate, salicylate, cyclohexanebutyrate, tetraborate, oxalate of the above metal,
Stearate, thiocyanate, trifluoro acid salt,
Examples thereof include naphthenate, palmitate, picrate, maleate, malonate and laurate.
These metal compounds may be used alone or in combination of 2
You may use it in combination of 2 or more types.

As the pressure-sensitive adhesive layer, the same pressure-sensitive adhesive layer as the pressure-sensitive adhesive layer of the first label sheet can be used. The metal compound may be applied to the surface of the pressure-sensitive adhesive layer, may be impregnated into the surface layer portion of the pressure-sensitive adhesive layer in contact with the porous sheet, or may be mixed in the pressure-sensitive adhesive layer. When the metal compound exists at the interface between the pressure-sensitive adhesive layer and the porous sheet, it is preferable to provide a part where the metal compound does not exist in order to facilitate adhesion between the pressure-sensitive adhesive layer and the porous sheet. When the metal compound is mixed in the pressure-sensitive adhesive layer, the mixing amount of the metal compound is preferably 0.01 to 20 parts by weight, particularly 0.1 to 5 parts by weight, relative to 100 parts by weight of the pressure-sensitive adhesive. Preferably. The metal compound may be arranged, for example, in a character shape indicating the control temperature so that the lower limit temperature for color development can be recognized as a character.

The temperature control label of the present invention is adhered via a porous sheet between the pressure-sensitive adhesive layer having the organic chelate coloring agent of the first label sheet and the pressure-sensitive adhesive layer having the metal compound of the second label sheet. It is a combination. The porous sheet is not particularly limited as long as it can pass an organic chelate coloring agent or a metal compound, and for example, a polypropylene-based porous sheet, a polyethylene-based porous sheet, a Teflon-based porous sheet, Cellulose-based porous sheets, polycarbonate-based porous sheets, polysulfone-based porous sheets, paper, non-woven fabrics and the like can be mentioned, and polypropylene-based porous sheets and polyethylene-based porous sheets are preferably used.

In the present invention, the pore size of the porous sheet,
The color development time at the controlled temperature can be adjusted by adjusting the thickness. Specifically, if the pore size of the porous sheet is increased or the thickness is reduced, the color development speed is increased, and if the aperture size is decreased or the thickness is increased, the color development speed is reduced. The pore size of the porous sheet may be in various ranges, but usually the diameter may be in the range of 0.01 to 10 μm, preferably 0.1 to 5 μm.
The thickness of the porous sheet is not particularly limited,
Usually, it may be in the range of 5 to 200 μm, preferably 1
It is in the range of 0 to 100 μm. In addition, the porous sheet,
Although it may be a single layer, it may have a multilayer structure of two or more layers. The surface layer of the porous sheet may be impregnated with an organic chelate coloring agent or a metal compound. It is preferable to stack the impregnated material and the non-impregnated material to form a porous sheet because a porous portion that does not bring the organic chelate color developing agent into contact with the metal compound is easily formed.

Further, the temperature control label of the present invention comprises at least one of a pressure-sensitive adhesive layer having an organic chelate coloring agent for the first label sheet, a pressure-sensitive adhesive layer having a metal compound for the second label sheet, and a porous sheet. It contains a temperature control agent. The temperature control agent is a substance that starts to flow at a desired temperature, and preferably has a relatively small melting point range at each temperature. Examples of the temperature control agent include n-paraffins, alcohols, higher fatty acids (carboxylic acids) and their derivatives, higher fatty acid esters and their derivatives, aliphatic sulfonic acids or aromatic sulfonic acids and their derivatives, sulfones. Acid ester and its derivative, ketone compound, ether compound, thiol compound, sulfide compound and disulfide compound, sulfoxide compound, sulfone compound, acidic phosphoric acid ester compound and phosphoric acid ester compound, synthetic wax And the like.

Examples of paraffins include decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, thoriacosane. Examples include contane, entriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, tetracontane, dotetracontane, pentacontane, hexacontane, heptacontane, and the like.

Alcohols include monohydric alcohols to polyhydric alcohols and their derivatives.
For example, butyl alcohol, butanediol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-lauryl alcohol, n-myristyl alcohol, n-cetyl alcohol, n-stearyl alcohol, n-eicosyl alcohol, n- Docosyl alcohol, n-melisyl alcohol, isocetyl alcohol, isostearyl alcohol, isodocosyl alcohol, oleyl alcohol, cyclohexanol, cyclopentanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene Glycol, propylene glycol, butylene glycol, hexylene glycol, cyclohexane-1,4-diol, trimethylolpropane, , 2,6-hexane triol,
Examples include pentaerythrit, sorbit, and mannite.

The higher fatty acids (carboxylic acids) include
For example, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, crotonic acid, oleic acid, elaidic acid, linolenic acid, linoleic acid, monochloroacetic acid, Monobromoacetic acid, monofluoroacetic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, ricinoleic acid, 1,2-hydroxystearic acid, lactic acid, parbic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, malic acid, Tartaric acid, kikkoric acid, maleic acid, fumaric acid, naphthenic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, cinnamic acid, chlorobenzoic acid, bromobenzoic acid,
Ethoxybenzoic acid, mandelic acid, vanillic acid, resorcinic acid, dioxybenzoic acid, dioxychlorobenzoic acid, gallic acid, naphthoic acid, hydroxynaphthoic acid, phthalic acid, phthalic acid monoethyl ester, naphthalenedicarboxylic acid, naphthalenedicarboxylic acid monomethyl ester, Examples thereof include trimellitic acid and pyromellitic acid. Examples of metal salts of higher fatty acids include sodium, potassium, lithium, calcium, zinc, zirconium, aluminum, magnesium, nickel, of the above-mentioned carboxylic acids.
Examples thereof include metal salts such as cobalt, tin, copper, iron, vanadium, titanium, lead and molybdenum.

Examples of higher fatty acid esters include amyl acetate, octyl acetate, butyl propionate, octyl propionate, phenyl propionate, ethyl caproate, amyl caproate, amyl caprylate, ethyl caprylate, amyl caprate, Octyl caprate,
Methyl laurate, ethyl laurate, butyl laurate, hexyl laurate, octyl laurate, dodecyl laurate, myristyl laurate, cetyl laurate, stearyl laurate, methyl myristate, ethyl myristate, butyl myristate, myristate Hexyl, octyl myristate, lauryl myristate, myristyl myristate, cetyl myristate, stearyl myristate, methyl palmitate, ethyl palmitate, butyl palmitate, hexyl palmitate, octyl palmitate, dodecyl palmitate, myristyl palmitate, Cetyl palmitate, stearyl palmitate, methyl stearate, ethyl stearate, butyl stearate, hexyl stearate, octyl stearate. Lauryl stearate, myristyl stearate, cetyl stearate, stearyl stearate, methyl behenate, ethyl behenate, behenic acid propyl, butyl behenate, ethyl benzoate,
Butyl benzoate, amyl benzoate, phenyl benzoate,
Ethyl acetoacetate, methyl oleate, butyl oleate, butyl acrylate, diethyl oxalate, dibutyl oxalate, diethyl malonate, dibutyl malonate, dibutyl tartrate, dimethyl sebacate, dibutyl sebacate,
Dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibutyl fumarate, diethyl maleate, dibutyl maleate, triethyl citrate, tristearyl citrate, 12-hydroxystearic acid triglyceride, castor oil, dioxystearic acid methyl ester, 12-hydroxystearic acid methyl ester and the like can be mentioned.

Synthetic waxes include coal-based synthetic waxes (Montan wax: mp 85 ° C.), among which acid waxes (C _{23 to} C ₃₂ ), ester waxes (C _{23 to} C ₃₂ ), Examples thereof include emulsifier-containing ester wax and partially saponified ester wax (C _{23 to} C ₃₂ ). In addition, as a petroleum-based synthetic wax of synthetic wax,
There are polyethylene waxes, including high-density type, medium-density type, and low-density type. Further, as a fat-based synthetic wax of synthetic wax, hydrogenated castor oil and 12
-Hydroxystearic acid derivatives. Examples of hydrogenated castor oil include coconut oil, palm kernel oil, herring oil, cod liver oil, whale oil, palm oil, cottonseed oil, olive oil, peanut oil, soybean oil, linseed oil, castor oil and the like. As hydroxystearic acid derivatives, 12-hydroxystearic acid amide, N- (2-hydroxyethyl)
-12-hydroxystearic acid amide, N, N'-ethylenebis-12-hydroxystearic acid amide,
N, N'-hexamethylenebis-12-hydroxystearic acid amide, N, N'-xylenebis-12-hydroxystearic acid amide, methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol-mono- 12-hydroxystearate, glycerin-mono-12-hydroxystearate, ethylene glycol-mono-12-hydroxystearate, glycerin-tri-12-acetoxystearate, 12-hydroxylithium stearate, 12
-Calcium hydroxystearate and the like.

The temperature control agent to be used has a function of flowing at a desired temperature, moving one or both of the organic chelate color-developing agent and the metal compound, and bringing them into contact with each other to react with each other to develop a color. The temperature control agent may be selected according to the desired color development temperature. However, due to the properties of each temperature control agent, there are some that show fluidity before the melting point, so the temperature of the color development temperature is ± 3 to 5 ° C. It is good to choose one. For example, in the case of applying to a frozen product that is putrefaction when left to stand at 20 ° C. for several tens of minutes, it is preferable to use a temperature control agent having a melting point of 15 to 25 ° C.

The temperature control agent may be contained in at least one of the pressure-sensitive adhesive layer having the organic chelate coloring agent of the first label sheet, the pressure-sensitive adhesive layer having the metal compound of the second label sheet, and the porous sheet. . As a specific example of the mode in which the temperature control agent is contained, any one of a pressure-sensitive adhesive layer having an organic chelate coloring agent of the first label sheet, a pressure-sensitive adhesive layer having a metal compound of the second label sheet, or a porous sheet is used. Contained in the first label sheet, the adhesive layer having the organic chelate colorant of the first label sheet and the adhesive layer having the metal compound of the second label sheet, the organic chelate colorant of the first label sheet What is contained in a porous sheet and a pressure-sensitive adhesive layer having, a pressure-sensitive adhesive layer having a metal compound of a second label sheet and one contained in a porous sheet, a pressure-sensitive adhesive having an organic chelate coloring agent in a first label sheet The layer, the pressure-sensitive adhesive layer having the metal compound of the second label sheet, and the porous sheet may be contained in all of them. Of these embodiments, the temperature control agent is preferably contained in both the pressure-sensitive adhesive layer having the organic chelate coloring agent of the first label sheet and the pressure-sensitive adhesive layer having the metal compound of the second label sheet. The temperature control agent may be provided on the surface of each pressure-sensitive adhesive layer or the porous sheet, or may be mixed in them. When the temperature control agent is mixed in the pressure-sensitive adhesive layer, the mixing amount of the temperature control agent should be 1
The amount is preferably 0.1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 00 parts by weight.

The pressure-sensitive adhesive layer of the first label sheet or the second label sheet may have a multi-layer structure, and a pressure-sensitive adhesive layer may be provided on both sides of a porous sheet impregnated with an organic chelate coloring agent or a metal compound. The structure may be provided. The temperature control label of the present invention can have any planar shape, for example, various planar shapes such as a circle, an ellipse, a triangle, a quadrangle, a pentagon, a hexagon, and the like, and indicates the control temperature. Various patterns such as letters can be used.

The temperature control label of the present invention is used by being attached to an article for temperature control, and the surface of the base sheet of the first label sheet or the second label sheet is provided with an adhesive layer for attaching to the article. It is preferable to provide it. Further, release paper or release sheet may be attached to the surface of the adhesive layer. The thickness of the adhesive layer is not particularly limited,
Usually, it may be in the range of 5 to 100 μm, preferably 1
It is in the range of 0 to 50 μm.

[0032]

In the temperature control label of the present invention, the metal compound capable of reacting with the organic chelate color-developing agent and the organic chelate color-developing agent and the organic chelate color-developing agent are arranged on the opposite sides through the porous sheet. The organic chelate coloring agent does not develop color unless it moves inside the porous sheet and comes into contact with each other. In the temperature control label of the present invention, at least one of the pressure-sensitive adhesive layer provided on both sides of the porous sheet and the porous sheet contains a temperature control agent that flows at a desired temperature. The movement of the metal compound or the organic chelate coloring agent in the porous sheet is caused by the temperature control agent flowing in the melting temperature range. That is, when the temperature control agent flows in the porous sheet, the metal compound or the organic chelate coloring agent moves in the porous sheet along with the flow. As a result, the organic chelate color former or the metal compound comes into contact with each other and reacts with each other to irreversibly develop color. Since the color development is irreversible, once the color is developed, it will not disappear even if it is stored below the melting point of the temperature control agent. Therefore, by detecting the color development, it is possible to easily and surely detect the temperature history of whether or not the storage temperature of the article is equal to or higher than the predetermined temperature.

A preferred method for producing the temperature control label of the present invention will be described below. (1) A first label sheet is prepared by applying an adhesive containing an organic chelate coloring agent and a temperature control agent to a base sheet. (2) On the other hand, a pressure-sensitive adhesive containing a metal compound and a temperature control agent is applied to the base sheet to prepare a second label sheet. (3) Next, a porous sheet is attached to the surface of either the adhesive layer of the first label sheet or the adhesive layer of the second label sheet. (4) Of the first label sheet and the second label sheet, the one to which the porous sheet is attached is coated with an adhesive on the other surface of the base material to provide an adhesive layer. (5) Next, if necessary, this porous sheet is impregnated with a temperature control agent. In addition, the impregnation of the temperature control agent into the porous sheet is carried out by applying the porous sheet to the surface of either the pressure-sensitive adhesive layer of the first label sheet or the pressure-sensitive adhesive layer of the second label sheet in the step (3). You may go before laminating. By the above method, the first label sheet and the second label sheet are separately manufactured. A release paper or release sheet may be attached to the exposed pressure-sensitive adhesive layers of the first label sheet and the second label sheet at any stage of the above steps. These release papers and release sheets may be released when the first label sheet and the second label sheet are attached to each other, or when they are attached to various articles whose temperature is to be controlled.

The first label sheet and the second label sheet produced by the above method are laminated together when applied to various articles for which temperature control is desired to produce the temperature control label of the present invention, and the temperature of the article is optimized. It is possible to provide a temperature preservation management method. Specifically, the temperature of the first label sheet and the second label sheet is lower than the melting point of the temperature control agent, and a temperature control label is prepared by pasting them together, and the first label is attached to the target article, or the first label. Method to create a temperature control label by pasting either the label sheet or the second label sheet to the target article in advance, and bringing this and another label sheet to a temperature below the melting point of the temperature control agent and then pasting them together. And so on. The temperature management label of the present invention can be used for various articles, but is particularly effective for use in frozen articles and refrigerated articles and for heat generation inspection related to electric power heating equipment (prevention of accidents, etc.).

[0035]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The present invention is not limited to these examples.

Example 1 In FIG. 1, a polymerization of an acrylic resin-based adhesive (90 parts by weight of butyl acrylate and 10 parts by weight of 2-hydroxyethyl methacrylate) on a substrate sheet 1 (thickness: 25 μm) of polyethylene terephthalate resin. Of 100 parts by weight of the unsaturated monomer mixture and 200 parts by weight of ethyl acetate,
Acrylic resin adhesive obtained by charging a four-necked flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a dropping funnel, adding an appropriate amount of azoisobutyronitrile, and reacting at 80 ° C for 4 hours ) A mixture obtained by adding 0.1 part by weight of an organic chelate coloring agent (diphenylcarbazone) and 5 parts by weight of a temperature control agent (t-butyl alcohol, melting point: 25 ° C.) to 100 parts by weight so that the thickness becomes about 20 μm. Then, the pressure-sensitive adhesive layer 2 was formed by casting into a first label sheet to prepare a polyethylene terephthalate resin release film 3 (thickness: 38 μm). Figure 2
In the above, on the base material sheet 6 of polyethylene terephthalate resin (thickness: 25 μm), 1 part by weight of an acrylic resin adhesive (manufactured by Lintec Co., Ltd., product name: PK) with an organometallic compound (zinc stearate) and a temperature control agent (T-butyl alcohol, melting point: 25 ° C.) 5 parts by weight of a mixture was cast to a thickness of about 20 μm to form a pressure-sensitive adhesive layer 5, and a thickness of 25 μm and an average pore diameter of 0.15 μm were formed on the pressure-sensitive adhesive layer 5. The polypropylene porous membrane 4 (manufactured by Daicel Chemical Industries, Ltd., trade name: Celgard) was adhered. Next, a pressure-sensitive adhesive for refrigeration (manufactured by Lintec Co., Ltd., product name: PC) was cast on the release surface of the polyethylene terephthalate resin release film 8 (thickness: 38 μm) to a thickness of about 30 μm, and the adhesive layer 7 was formed. Was formed, and it was attached to the base material sheet 6 to prepare a second label sheet. Under freezing (−20 ° C.), the adhesive surface of the first label sheet and the porous film of the second label sheet were attached to each other to prepare a temperature control label having the configuration of FIG. This temperature control label was attached to a frozen product under freezing (-20 ° C), and the state of discoloration was visually observed. Furthermore, the frozen product with the temperature control label was left at 5 ° C. and 23 ° C., respectively, and the state of discoloration was visually observed. The results are shown in Table 1.
It was shown to.

Example 2 Example 2 was repeated except that the temperature control agent used in the first label sheet and the second label sheet was changed to 1,4-butanediol (melting point: 20 ° C.). A temperature control label was prepared in the same manner as in Example 1, and the discolored state of the temperature control label was visually observed. The results are shown in Table 1.

Example 3 In Example 1, the porous membrane was made of Tokuyama Soda Co., Ltd. under the trade name NF sheet (made of polypropylene, pore size 2.5 μm,
A temperature control label was prepared in the same manner as in Example 1 except that the thickness was changed to 120 μm), and the discolored state of the temperature control label was visually observed. The results are shown in Table 1.

Example 4 In Example 1, the amount of the temperature control agent used in the first label sheet and the second label sheet was changed from 5 parts by weight to 1 part.
A temperature control label was prepared in the same manner as in Example 1 except that the temperature control label was changed to 0 part by weight, and the discolored state of the temperature control label was visually observed. The results are shown in Table 1.

Example 5 A temperature control label was prepared in the same manner as in Example 1 except that copper stearate was used as the organometallic compound, and the discoloration of the temperature control label was visually observed. I observed. The results are shown in Table 1.

Example 6 In FIG. 1, a polymerization of an acrylic resin adhesive (90 parts by weight of butyl acrylate and 10 parts by weight of 2-hydroxyethyl methacrylate) on a base material sheet 1 (thickness: 25 μm) of polyethylene terephthalate resin. Of 100 parts by weight of the unsaturated monomer mixture and 200 parts by weight of ethyl acetate,
Acrylic resin adhesive obtained by charging a four-necked flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a dropping funnel, adding an appropriate amount of azoisobutyronitrile, and reacting at 80 ° C for 4 hours ) A mixture obtained by adding 0.1 part by weight of an organic chelate coloring agent (diphenylcarbazone) and 5 parts by weight of a temperature control agent (t-butyl alcohol, melting point: 25 ° C.) to 100 parts by weight so that the thickness becomes about 20 μm. Then, the pressure-sensitive adhesive layer 2 was formed by casting into a first label sheet to prepare a polyethylene terephthalate resin release film 3 (thickness: 38 μm). Figure 2
In the above, on the base material sheet 6 of polyethylene terephthalate resin (thickness: 25 μm), 1 part by weight of an acrylic resin adhesive (manufactured by Lintec Co., Ltd., product name: PK) with an organometallic compound (zinc stearate) and a temperature control agent (T-butyl alcohol, melting point: 25 ° C.) 5 parts by weight of a mixture was cast to form a pressure-sensitive adhesive layer 5 to a thickness of about 20 μm, and a temperature control agent (t-butyl alcohol, t-butyl alcohol, Melting point: 25 ° C.) 3 g / m ² impregnated with a thickness of 25 μm and an average pore diameter of 0.15 μm made of polypropylene polypropylene porous membrane 4 (manufactured by Daicel Chemical Industries, Ltd., trade name:
(Celguard) was attached. Next, a pressure-sensitive adhesive for refrigeration (manufactured by Lintec Co., Ltd., product name: PC) was cast on the release surface of the polyethylene terephthalate resin release film 8 (thickness: 38 μm) to a thickness of about 30 μm, and the adhesive layer 7 was formed. Was formed, and it was attached to the base material sheet 6 to prepare a second label sheet. In the same manner as in Example 1, the first label sheet and the second label sheet were stuck together to prepare a temperature control label, and the discolored state of the temperature control label was visually observed. The results are shown in Table 1.

Comparative Example 1 A first label sheet and a second label sheet were prepared in the same manner as in Example 1 except that the porous film was removed, and the temperature was −20 ° C., 5 ° C. and 23 ° C. Then, the first label sheet and the second label sheet were attached to each other to prepare a temperature control label. The state of discoloration of these temperature control labels was visually observed, and the results are shown in Table 1.

[0043]

[Table 1]

[0044]

According to the temperature control label of the present invention, it can be easily and surely attached to various articles such as frozen products and the temperature history of whether or not the storage temperature of the article has reached a predetermined temperature or higher. It is possible to detect and surely know the storage management state of the article.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a first label sheet that is an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a second label sheet that is an embodiment of the present invention.

FIG. 3 is a cross-sectional view showing a temperature management label that is an embodiment of the present invention.

[Explanation of symbols]

 1 Base Material Sheet 2 Adhesive Layer 3 Release Film 4 Porous Membrane 5 Adhesive Layer 6 Base Material Sheet 7 Adhesive Layer 8 Release Film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takanori Saito 2-2-2-604 Satsukidaira, Misato City, Saitama Prefecture

Claims (2)

[Claims] 1. A first label sheet having a pressure-sensitive adhesive layer having an organic chelate coloring agent on one surface of a base sheet, and a metal compound capable of reacting with the organic chelate coloring agent to form a color on one surface of the base sheet. And a second label sheet provided with a pressure-sensitive adhesive layer having, affixed via a porous sheet between the pressure-sensitive adhesive layer of the first label sheet and the pressure-sensitive adhesive layer having a metal compound of the second label sheet A temperature control label comprising at least one of a pressure-sensitive adhesive layer of the first label sheet, a pressure-sensitive adhesive layer having a metal compound of the second label sheet, and a porous sheet. 2. A temperature control label having a pressure-sensitive adhesive layer provided on the surface of one of the first label sheet and the second label sheet.