JPS63277944A - Heat sensitive label for temperature management - Google Patents

Abstract

PURPOSE:To obtain a stable label which can be stored by forming a couple of coloring agents which colors by irreversible reaction above specific temperature into sheets, and sticking them on base paper temporarily. CONSTITUTION:A glue-applied base body which is coated with a pressure sensitive or adhesive glue part is stuck temporarily on the surface of the peeling base paper 1. A sheet which contains an A part coloring agent 3 coloring above the specific temperature when contacting a B part coloring agent 5 although it never colors by itself is made to cover the surface, and a sheet which contains the B part coloring agent 5 coloring above the specific temperature when contacting the A part coloring agent 3 although it never colors by itself is tuck temporarily through the adhesive glue part 4. When this label is used, the base 2 and sheet 4 are peeled off the base paper 1 and the base 2, A part coloring agent adhesive sheet 3, glue part 4, and B part coloring agent sheet 5 are stuck on the surface of a frozen body one over another in order.

Description

[Detailed description of the invention] (Technical details).

The present invention relates to a temperature indicator label suitable for controlling the temperature of frozen foods, especially frozen foods, etc. The present invention is intended to control the freezing of frozen foods by checking the state of the frozen foods by checking the color change when the temperature reaches a predetermined temperature or higher. It is something to do.

In detail, a temperature indicator is processed into a label, and this label is placed in close contact with a frozen item, and when the temperature of the frozen item exceeds the set temperature over time, the color of the temperature indicator on the label changes irreversibly, and this discolored state can be confirmed. This controls the temperature of frozen items.

(Prior art and its problems) Conventionally, this type of label could only be commercialized as a product that could be used at temperatures above room temperature due to storage issues.

In order to be able to use it at temperatures below room temperature, it was necessary to store it in a low-temperature container such as a refrigerator, and then take it out of the container when it was time to use it.

Moreover, when manufacturing these labels, they must be manufactured within a concentration range in which the temperature indicator does not develop color, making it difficult to easily manufacture and use them under normal conditions.

(Objective of the Invention) An object of the present invention is to provide a temperature-controlled, particularly low-temperature-controlled label that allows stable storage.

(Summary of the Invention) The temperature control label of the present invention has one or more pairs of generators adhered to the back surface, each of which does not develop color by itself but which develops a specific color by irreversibly reacting with each other at a predetermined temperature or higher. It is characterized in that it is formed into a sheet containing the agent and temporarily attached to a mount.

When the label of the present invention is used, it does not develop color as it is at room temperature or environmental temperature, but when one or more pairs of coloring agents are attached to a new test item, such as a frozen food, in contact, the temperature history of the product changes. is memorized through irreversible coloring, and the process of product distribution can be controlled.

As will be described later, the color development temperature can be selected by a specific combination of color formers ASB, but when a combination is specified, if a temperature control agent is used to control the temperature, even more The degree of freedom in label design is increased.

(Detailed Description of the Invention) The present invention has been researched and developed to compensate for the drawbacks of conventional temperature-indicating or temperature-controlled labels, and it has been found that temperature-indicating labels can be produced over a considerable temperature range (e.g., in terms of storage stability during use). It became possible to manufacture and use the product as a stable product at temperatures ranging from 100°C to -100°C.

That is, the temperature indicator is divided into two components, A part and B part, and printed or coated on a mount such as paper, and when used, for example, A part is added to frozen food.
Use by placing part B in close contact with each other, and placing part B on top of it. The method of adhering may be either gluing or crimping. In this way, the temperature label attached to the frozen product will not change in any way below the set temperature of the frozen product (e.g. 10℃), but when the temperature exceeds the set temperature, the temperature indicators in parts A and B will react irreversibly. This is an indicator that causes a color change over time, clearly indicating that the temperature of the frozen product has reached 10°C or higher over time. This kind of temperature label is A
Each of Parts and Parts B alone may be subject to temperature changes (for example, 1
00°C to -100°C), and if the two are in close contact and the temperature rises above the set temperature, Mu-B will react and irreversibly change color. It is.

Therefore, when parts A and B are separated, this temperature label can be stored stably, and changes in ambient temperature do not affect the product at all during manufacture.

The type of temperature indicator label can be determined by arbitrarily selecting and combining temperature indicators that cause a reaction at a set temperature as required (Temperature indicators that change color at various temperatures can be manufactured by combining temperature indicators.

In use, by selecting several types of temperature indicators and arranging them at the same location, temperature changes around the set temperature can be sensed in relative detail. For example, if you want to maintain the freezing temperature of frozen food at 10℃ or below, three types of temperature indicators, 8℃, 10℃, and 12℃, are installed on the same label, and temperature changes over time or through the temperature around 10℃ can be observed in more detail. It is possible to confirm the temperature conditions of frozen products.

Specific examples of the above two examples are shown in FIGS. 1-4 and 5-8, respectively.

Example 1 As shown in FIGS. 1 and 2, a label according to an example of the present invention temporarily adheres a glued support 2 coated with a pressure-sensitive or adhesive glue portion to the surface of a releasable mount 1, and A sheet 3 containing a part A color former which does not develop a color by itself but which develops color at a predetermined temperature or higher when in contact with a part B color former mentioned later is adhered to the surface thereof,
It is also made up of a sheet 5 containing a B part color former which does not produce color by itself but which develops color at a predetermined temperature or above when it comes into contact with the A part color former, and is temporarily attached via a thin pressure-sensitive or adhesive glue@4.

In use, the support 2 and the sheet 4 are peeled off from the mount 1 and pasted onto the surface of the frozen product 6 as shown in Nos. S to 4g. The adhesive layer consists of the support 2, part A color former sheet 3, glue part 4, and part B.
Part color forming agent sheet 5 is in this order. For example, these parts A and B
If the partial color forming agent is selected from materials that react and develop color at 10° C. or higher, its temperature history can be monitored.

Example 2 Refer to Figures 5-8. As shown in FIGS. 5 and 6, the temperature control label according to another example of the present invention has a common releasable backing paper 1 and a corresponding Bl, n,
, B1 part AI, A, and S that react irreversibly when they come into contact with color formers at different specific temperatures or higher.
A glued support 2 carrying a sheet or composition coating 31, '52.33 containing the AsB coloring agent, respectively, is temporarily attached, and similarly, the above BI Sn, which does not develop color by itself, is
The sheets or composition coatings 51, 52, and 53 containing the BSB color former are temporarily attached to other parts of the mount 1 using the thin glue section 4. For example, the Al-B1 color former is
The I-J color former is designed to react at 10°C and the As-B1 color former to develop different colors at 15°C.

Note that, for example, the coloring temperature may be controlled by using the same coloring agents as the 11, n, , and n3 coloring agents, and controlling the coloring temperature in combination with the AI and Am% AI coloring agents.
53 may be a single continuous sheet.

In use, as shown in FIGS. 7 and 8, the glued support 2 peeled off from the mount 1 is first pasted on the surface of the frozen object 6, and then the sheet) 51.52.55 is placed on top of the sheet) 31.52.33. Paste the sheets 51, 52, and 53 so that they overlap each other. In this way, a temperature history of 5 to 15° C. or more can be recorded.

The above is just an example, and in short, substances that do not develop color by themselves at ambient temperature, but react irreversibly when they come into contact with each other (color former for A part, color former for part B) are formed into sheets separately, and the backing material is Any material that can be temporarily attached to the frozen object is acceptable as long as it can be attached to the frozen object in a state where the color-forming substance can move or react with the frozen object.

Example 3 A part A and part B color former (using a binder) are applied to a transparent support, dried, an adhesive substance is applied to at least one surface, and a releasable mount is attached. To use, peel off the backing paper and insert it into a frozen food bag so that A1B1 coloring material comes into contact with it.

This label is characterized by separating the A part and 8 parts as color formers and making them into a sheet, but in addition, a third substance that has an effect as a temperature control agent is added to each A part color former and B part color former. They can also be used in combination. A in Example 1.2 above
, Part B color formers should be understood to include such substances. The color forming agent for part A and the color forming agent for part B can be used in any combination to produce color, and the type of combination is determined by the color of the color.

Next, the following third substances are used as the color former for part A, the color former for part B, and the temperature control agent.

tA Part Color Former Material Name Examples Part A Color former material is a metal compound or a dye intermediate.

(1) Metals CuSAg, Ax, Mg5Cr, S rSB 8%
Z nSa dsHg SA i s T I, Ti5
anSPb, 111% EISVs Ca5M6SW
, G, M! l, F e, N i 1Co, etc. (2)
Dye Intermediates The thermosensitive dye in this invention means a dye that develops color in the presence of heat and a color developer. These dyes are usually electron-donating compounds that have a Rafusin ring in the molecule, and are not particularly limited as long as they are such compounds, and include those known in the field and heat-sensitive dyes included in the above explanations. can be used in this invention. Specific heat-sensitive dyes include fluoran compounds,
Subitabitun compounds, tetra-icoolamine compounds, acyliothymine compounds, arylauramine compounds, tetra-damine B-lactam compounds, diaryl-7-thallide compounds, indolyl-7-thallide compounds, polyaryl carbinol compounds or indoline compounds, more specific compounds include 8-diethylamino-6-methyl-7-ritafluoran, 8
-diethylamino-7-methoxyfluorane, 8-dinithylamino-6-benzyloxyfluorane, t2-pen, two-6-diethylaminofluorane, a6-zip
-) Cyidino-45-dimethylfluorene-7dynylhydrazidolactam, 8-amino-5-methylfluorane, 2-me,thi-8-amino-6-methyl-7-methylfluorane, 2.8- Butylene-6-di-butylaminofluorane, 8-diethylamino-7-anilinofluorane, 8-diethylamino-7 (para-toluidino)
-Fluorane, 7-acetamino-8-diethylaminofluorane, 8-diethylamino-8-methyl-7-anilinofluorane, 8-diethylamino-6-methyl-
7-dibenzylaminofluorane, 2,7-diqua-
8-Methyl-5-nbutylamino 7/&/orane, 2-
4-6-cyclohexyaminofluorane, 8-(N
-Methyl-N-cyclohexyl)amino-8-methyl-
Fluoran compounds such as 7-anilinofluorane or 8-(N-ethyl-N-toluidino)amino-8-methyl-7-anilinofluorane, N-a 8-trimethylindolinobenzospirobilane or 8 -Methoxy-
Subiwabiran J compounds such as N-8,8-)limethylindolinobenzos, pyroviran, N-(2,3--
/chloroaphenyl) leuphoramine type compounds such as N-benzoyl auramine or N-
Acyl auramine compounds such as acetyl auramine, aryl auramine compounds such as N-phenyl auramine, and tetra-damine B such as rhodamine B lactams.
lactam compounds, diaryl7thalide compounds such as 8.8-bis(1-ethyl-2-methy/L/-8-yl) phthalide, 8.8-bis(1-n-butyl-2-methyl) Indolyl 7-thallide compounds such as indol-8-yl) 7-thallide or 8-(4-dimethylaminophenyl)-8-(t2-dimethylindol-8-yl) 7-thallide, crystal violet carbinol or malachite green Polyaryl carbinol compounds such as carbinol, indoline compounds such as 2-(phenyliminoethanedylidene) to 8-dimethylindoline, and lactone rings such as calistal violet lactone or malaca, itogreen lactone Examples include compounds. However, it is also possible to use these precursors in some cases.

Among these thermosensitive dyes, fluoran-based compounds and spiropyran-based compounds are preferred, and specifically, 8-diethylamino-6-methyl-7-trifluoran, 8-diethylamino-7-methoxyfluoran, 8-amino-
5-methoxyfluorane, 8-diethylamino-8-methyl-7-anilinofluorane, 8-(N-methy-N
-cyclotetrahexyl)amino-8-methyl-7-anilinofluorane, 8-(N-ethyl-N-)luidino)amino-8-methyl-7-aniliz7/l/olane, N-8
, 8-trimethylindolinobenzospirobilane are preferred, most preferred are 8-diethylamino-7-methoxyfluorane, 8-amino-5-methylfluorane, N-&8-)limethylindolinobenzospirobilane. be.

zB Part Color Former Material Name Examples Part B color former materials include organic chelate color formers or color developers that react with dyes.

Examples of organic chelate color formers and color developers (110,0'
-Hydroxyazo compound 1-(1-hydroxy-2-
naphthylazo)-6-nitro-2-naphthol-4-sulfonic acid sodium salt 1-(2-hydroxy-1-naphthyl-azo)-2-naphthol-4-sulfonic acid sodium salt 1-(2- and do-4-naphthol-4-sulfonate) 1-naphthylazo)-2-human gastric acid 3-naphthoic acid 5-(S-chloro-2-hydroxyphenylazo) -
a, s -, j Hydroxynaphthalene-2,7-disulfonic acid disodium salt 4-(2-hydroxy-4-sulfonaphthylazo)-3
-Sodium salt of methyl-1-phenyl-2-pyrazolin-5-one 5=(2-hydroxyphenylazo)-45-dihydroxynaphthalene-2,7-disulfonic acid disodium salt 3-(2-hydroxy-4 -sulfophenylazo) -
4,5-dihydroxynaphthalene-2,7-disulfone sodium salt 7-amino-2-(2-hydroxy-8-sulfo-1-
naphthylazo)-1-su7to-3-sulfonic acid 2”-(2-and do-4xyphenylazo)-15-naphthalene diol 2-(2-and doroxy-5-sulfophenylazo)-1
5-Naphthalene diol 1-(2-hydroxy-4-nitrophenylazo)-2-naphthol 1-(2-hydroxyphenylazo)-2-naphthol 1-(2-hydroxy-5-sulfophenylazo)- 2
-Naphthol 1-hydroxy-8-(2- and dinaphthyl azo)
-2-(4-sulfonaphthylazo)-&6-naphthalenedisulfonic acid 1-[1-hydroxy-6-(2-hydroxynaphthylazo)-a-sulfo-2-phenylazo)-2-naphthol-6-sulfonic acid Sodium salt of 4-human poxy&5-bis(2-hydroxynaphthylazo)benzenesulfonic acid 5-(1-(1,8-dihydroxy-4-sulfo-2-
Naphthylazo,)-4-naphthylazocosalcylic acid sodium salt 1-(1-hydroxy-1-tricle-2-funynylazo)-3-7cetamido Sodium salt of 2-naphthol-6-sulfonic acid 3-phenylazo-45 -Dihydro-tetraxinaphthalene-2
．． 7-Disulfone V! Disodium salt 2-(2-hydroxy-46-disulfo-1-naphthylazo)-benzoic acid sodium salt 1-(4,7-disulfo-1-naphthylazo)-4-(1-hydroxy-3-sulfo-6 -amino-2-naphthylazo)naphthalene 2-(5-chloro-2-hydroxy-3-etropheraf)-1-naphthol-4-sulfonic acid sodium salt 2-(5-chloro-2-hydroxy-3-sulfonate) phenylazo]-1-su7toll-5-sulfonic acid 5-(16-U sulfo-8-hydroxynaphthylazo)
-45-Dihydro-naphthalene-λ7-disulfonic acid 1-(2-hydroxy-3-ditro-5-sulfophenylazo)-2-naphthol 4-(4-nitrophenylazo)hylocatechol 4-(t4-t and dota xyphenylazo)benzenesulfonic acid 5-chloro-5-(2,4-uoxyphenylazo)-2-hydroxyinzenesulfonic acid sodium salt 5-chloro-2-hydroxy-3-(1-hydroxy −
Sodium salt of 2-naphthylazo)benzenesulfonic acid 5-chloro-2-humanmaxy-3-(2-hydroxynaphthylazo)benzenesulfonic acid 3-(S-acetamiF-2-hydroxynaphthyla'/)-2- and do Sodium salt of tetraxybenzene sulfonic acid 1-azo-metahydroxynaphthyl-2-hydroxy-3-nitrobenzene-5-sulfonic acid (2) (2-Pyridylazo)resorcinol 2-(2-hydroxynaphthalene-46-lisulfo-1-naphthylazo)benzene arsonic acid sodium salt 5-(2-arsonophenylazo)-4,5-dihydroxynaphthalene-λ7-disulfonic acid Sodium salt of 3-(4-sulfophenylazo)-4,5-dihydroxynaphthalene-247-disulfonic acid 7-(1-naphthylazo)-8-quinolino-5-sulfonic acid 4-trophenylazo )-2-glycylmethyl-1-
Naphthol (4- to triphenylazo)-2-(N,N-li(carboxymethyl)aminomethyl)naphthol (3) Phthalein, sulfo-7thalein and triphenylmethane-based compounds 43'-bis(N,N-di( carboxymethyl)-aminomethyl]-O-cresol phthalein p-catefur sulfophthalein pyrugaryl sulfophthalein dibrom pyrogallol sulfophthalein fluorescein bismethyliminodiacetic acid 5.31-bis(N,N-di( carboxymethyl)aminomethyl]-〇-cresolsulfophthalein 43'-bis(N,N-di(carboxymethyl)aminomethylfuthymolsulfophthalein 2I-sulfophthalein 2I-sulfophthalein)
, S'-t) methyl-4-hydroxythuccisin-5,5
'-Dicarboxylic acid Nasylium Salt Glycine Thymol Pruglycine Cresol Red Nocerafuchsin Combrexon Chromoxane Green GG (4) Phenolic compounds & 4-lioxybutylphenol α-ri no- & 4-dioxyacetophenone 4,5-
:) Chrylocatechol Catechol-45-Disulfonic acid disodium salt 3-Methylcatechol 4-Methylcatechol 5-Isopropylcatechol 4-Isopropylcatechol pt-Methylcatechol 4-t-Octylcatechol 5-t-Butyl -5-Methylcatechol 5-t-butyl-3-methylcatechol 6-t-butyl-3-methylcatechol 5-t-octyl-5-methylcatechol 3-
Methyl-5-t-octylcatechol 45-diisozo4pylcatechol 46-diipsypylcatechol 5-di-t-butylcatechol 44-dioxyphenylacetic acid gallic acid octyl ester gallic acid dodecyl ester gallic acid supersyl ester gallic acid Stearyl ester trioxyacetophenone tannic acid t2-dioxynaphthalene z3-dioxynaphthalene λ3-dioxynaphthalene-6-sulfonic acid sodium salt 47-Shioxynaphthalene-2-sulfonic acid sodium salt' t2-dioxynaphthalene-46- Dissiphon 0 sodium salt (5) Other diphenylcarbazone diphenylcarbazide N,N'-diphenylguanidine diphenylthiocarbazone t3-diphenyl urea It is preferable that the melting point range at each temperature is relatively small.

Temperature control agents used include n-paraffins, higher alcohols, and differential tilt polymers (
carboxylic acids) and their derivatives, higher Ba fatty acid esters and their derivatives, aliphatic sulfonic acids or aromatic sulfonic acids and their derivatives, sulfonic acid esters and their VsW forms, ketone compounds, ether compounds, thiols There are compounds, sulfide compounds, disulfide compounds, sulfocarbon compounds, sulfone compounds, acid phosphate ester compounds and phosphorus ester compounds, and synthetic 9x aQ fat.

Next, specific compound names thereof will be listed.

(1) Paraffins Paraffins with carbon ν10 or more are used in practical use, and 61 examples of substance names are listed based on the use of their melting points.

(2) Higher alcohols Alcohols include monohydric alcohols to polyhydric alcohols and their #s derivatives. Examples of these compounds are shown below.

n-octyl alcohol, n-nonyl alcohol, rs
- Tesyl alcohol, n-lauryl alcohol, n-myristyl alcohol, n-cetyl alcohol, turtle-stearyl alcohol, n-ifcyl alcohol, n+
)1) Cosyl alcohol, n-mericyl alcohol, isocetyl alcohol, instearyl alcohol, isotococyl alcohol, oleyl alcohol, cyclohexanol, cyclopentanol, benzyl alcohol,
Cinnamyl alcohol, ethylene glycol, diethylene glycol, diethylene glycol, polyethylene glycol, fluoropylene glycol, fluoroethylene glycol, hexylene glycol, cyclohexane-14-diol, trimethyalyl alcohol, 1.2.6-hexandriol , Mentaerythrit, Solvit, Manet, etc.

(3) High class IIF? Fatty Acids (Carboxylic Acids) and Their Derivatives (Esters) Carboxylic acids include monocarboxylic acids to polycarboxylic acids and their derivatives. Examples of these compounds are listed below.

Acetic acid, tetrapionic acid, butyric acid, capric acid, caprylic acid,
Capric acid, lauric acid, myristic acid, palmici/e
1. Stearic acid, isostearic acid, behenic acid, crotonic acid, oleic acid, elaidic acid, linoleic acid, linolic acid, monoflurulacetic acid, motuprim acetic acid, mono-7tetraacetic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid , ricinoleic acid, 12-hydrocystearic acid, lactic acid, pyruvic acid, schellaic acid, malonic acid, succinic acid, adipine, cepatic acid, apple snail, tartarus, chirasacic acid, maleic acid, fumaric acid, naphthi 7t& , An,
alpha acid, toluic acid, phenylacetic acid, p -t@rt-
Butylbenzoic acid, cinnamic acid, chlorbenzoic acid, propentabenzoic acid, ethoxybenzoic acid, mandelic acid, protocatechuic acid, vanillic acid, resorcinic acid, dioxybenzoic acid,
Examples include dioxycrylbenzoic acid, gallic acid, naphthoic acid, hydroxynaphthoic acid, phthalic acid, phthalic acid monoethyl ester, naphthalene dicarboxylic acid, naphthalene dicarboxylic acid monomethyl ester, trimellitic acid, pi-tetrameritic acid, and the like.

Carbon drinking party kIJ! ! Examples of the carboxylic acids include sodium, potassium, lithium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, -1, iron, vanadium, titanium,
There are gold II4 salts of metals such as lead and solipdenum.

The carboxylic acid metal salt can be produced by reacting the carboxylic acid with the oxide or hydroxide of the desired metal, or by double decomposition using an alkali salt of the carboxylic acid and a geode of the desired metal. .

(4) The following compounds are exemplified as higher fatty acid esters and their derivative carboxylic acid esters.

Amyl acetate, octyl acetate, butyl propionate, octyl propionate, phenyl propionate, ethyl caproate, ζyl caproate, ethyl caprylate, agyl caprylate, ethyl caprate, amyl caprate, caprin Octyl laurate, methyl laurate, ethyl laurate, butyl laurate, hexyl laurate, octyl laurate, dodecyl laurate, ethyl laurate,
Heptyl laurate, stearyl laurate, ethyl myristate, ethyl myristate, butyl myristate,
myristic dragon hexyl, octyl myristate, lauryl listate, listyl myristate, cetyl myristate, stearyl myristate, ethyl palmitate, ethyl palmitate, butyl palmitate, hexyl palmitate, normitin ff octyl, dodecyl palmitate, Myristyl palmitate, cetyl lumitate, stearyl sormitate, methyl stearate, ethyl stearate, butyl stearate, hexyl stearate, octyl stearate, lauryl stearate, myristyl stearate, cetyl stearate, stearin h? Stearyl, methyl behenate, ethyl behenate, bripyr behenate, behenin M"thyl, ethyl benzoate, butyl benzoate, amyl benzoate 6, phenyl benzoate 4i, ethyl acetoacetate, methyl oleate, butyl oleate, Butyl acrylate, diethyl chelate, diptyl oxalate, diethyl malonate, diethyl marine, diptyllate, dimethyl cepatate, cepatin Ia 9-butyl, dimethyl phthalate, diptyl phthalate, octyl phthalate, diptyl phthalate , diethyl maleate, 8-diptylated maleate, triethyl citrate, tristearyl citrate, 12-hydroxystearic acid triglyceride, castor oil, dioxystearic acid methyl ester, 12-hydroxystearic acid methyl ester, and the like.

(5) Aliphatic sulfonic acid or aromatic sulfonic acid and derivatives thereof Sulfonic acids include aliphatic sulfonic acid, aromatic sulfonic acid and derivatives thereof. Examples of these compounds are shown below.

Octyl sulfonic acid, decyl sulfonic acid, dodecyl sulfonic acid, aminoethane sulfonic acid, sulfosuccinic acid, sulfosucci octyl ester, benzenesulfonic acid,
Toluenesulfonic acid, xylenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, benzenedisulfonic acid, nitrobenzenesulfonic acid, aminobenzenesulfonic acid, sulfanilic acid, stomach rubenzenesulfonic acid, sulfobenzoic acid, Phenol sulfonic acid, phenol disulfone if
, diphenyl ether sulfonic acid, indyl sulfone f
111'-7 enylsulfonic acid, phenylphenolsulfonic acid, diphenylmethanesulfonic acid, benzenesulfonic acid pen/triazole, naphthalenesulfonic acid, ethylnaphthalenesulfonic acid 1. Dodecylnaphthalene sulfonic acid, carboxynaphthalene sulfonic acid, naphthol sulfonic acid, dioxynaphthalene sulfonic acid, dioxynaphthalene sulfonic acid, aminonaphthalene sulfonic acid, nitronaphthalene sulfonic acid, aminonaphthalene sulfonic acid, naphthalene disulfone [I2, dinaphthylmethane] Disulfonic acid, naphthol disulfonic acid, aminonaphthalene disulfonic acid, chlornaphthalene disulfonic acid, dioxynaphthalene disulfonic acid, carboxynaphthalene disulfonic acid, naphthalene trisulfonic acid, naphthalene trisulfonic acid, aminonaphthalene trisulfonic acid, methylnaphthalene disulfonic acid, methyl Naphthalene trisulfonic acid, anthraquinone sulfonic acid, oxyanthraΦ
Nonsulfonic acid, aminoanthraquinonesulfonic acid, chloranthraquinonesulfone N1 anthraquinone disulfonic acid, oxyanthraquinone disulfonic acid, aminoanthraquinone disulfonic acid, anthraquinone trisulfonic acid, and the like.

Examples of metal salts of sulfonic acids include metals such as sodium, potassium, lithium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum of the above-mentioned sulfonic acids. There are metal salts.

Here, the method for producing the metal salt of sulfonic acid is by reacting sulfonic acid with the oxide or hydroxide of the desired metal, or by an alpha decomposition method using an alkali salt of sulfonic acid and a chloride of the desired metal, etc. be able to.

(6) Sulfonic acid esters and derivatives thereof Compounds as the sulfonic esters are illustrated below.

Benzenesulfonic acid ethyl ester, benzenesulfonic acid furoyl ester, benzenesulfonic acid phthyl ester 1 toluenesulfonated ethyl ester, toluenesulfonic acid furoyl ester, toluenesulfonic acid phthyl ester, dotecylbenzenesulfonic acid ethyl ester,
Dodecylbenzenesulfonic acid butyl ester, benzenesulfonic acid phenyl ester, toluenesulfonic acid phenyl ester, dodecylbenzenesulfonic acid phenyl ester, naphthalenesulfonic acid ethyl ester, naphthalenesulfonic acid butyl ester, naphthalenesulfonic acid phenyl ester, octylsulfonic acid phthyl ester, Examples include octyl sulfonic acid octyl ester, dodecyl sulfonic acid octyl ester, dodecyl sulfonic acid octyl ester, and the like.

C Ketone compounds The following compounds are exemplified as ketones.

Diethyl ketone, ethyl butyl ketone, methylhexyl ketone, mesityl oxide, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone, benzophenone, 2.4~tanandione, acetonyl acetone, diacetone alcohol, ketone wax,
etc.

r8) Ether compounds Examples of ethers include compounds below.

Butyl ether, hexyl ether, diisopropyl benzyl ether, diphenyl ether, dioxane, ethylene glycol dibutyl ether, diethylene glycol shiftyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol diphenyl ether, ethylene glycol monophenyl ether, and fat.

(91 thiol compounds Examples of thiol compounds are shown below.

n-decyl mercaptan, n-dodecyl mercaptan,
n-myristyl mercaptan, n-cetyl mercaptan, n-stearyl mercaptan, 1so-dodecyl mercaptan, 1so-myristyl mercaptan, 1so-
Cetyl mercaptan, dodecylbenzyl mercaptan, fathom.

(10) Sulfide compounds and disulfide compounds Examples of sulfide compounds are shown below.

Di-n-octyl sulfide, di-n-7nylsulfide, di-n-decyl sulfide, di-n-dodecyl sulfide, di-n-myristyl sulfide, di-n-cetyl sulfide, di-n-stearyl sulfide, t
@rt-dode silsulfide, octyldodecyl sulfide, diphenyl sulfide, dibenzyl sulfide, ditolyl sulfide, diethylphenyl sulfide,
4.4'-Dichlorodiphenyl sulfide, dilauryl thiodizolopionate, listearyl thiodipropionate, tetra(laurylthiopropionic acid) pentaerythritol ester, tetra(stearylthiofa-hyonic acid) /! : Ester, etc.

Examples of disulfide compounds are shown below.

Di-n-decyl disulfide, di-n-dodecyl disulfide, di-n-myristyl disulfide, di-n-cetyl disulfide, di-n-stearyl disulfide,
Diphenyl disulfide, dibenzyl disulfide, ditolyl disulfide, dinaphthyl disulfide, 4.4
'-dichlorodiphenyl disulfide, etc.

(11) Sulfoxide is also a compound Examples of sulfoxide compounds are shown below.

There are dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide F1 diphenyl sulfoxide, dibenzyl sulfoxide, and so on.

(12) Compounds of sulfonic acids Examples of sulfone compounds are shown below.

Diethyl sulfone, dibutyl sulfone, methylphenyl sulfone, diphenyl sulfone, ditolyl sulfone, dibutylphenyl sulfone, shhendylsulfone, 4.4
'-dichlorodiphenylsulfone, etc.

(13) Compounds of acidic phosphoric acid esters and compounds of phosphoric acid esters Examples of compounds as acidic phosphoric esters are shown below.

Butyl acid phosphate, 2-ethylhexyl acid phosphate, dodecyl acid phosphate, stearyl acid phosphate, phenyl acid phosphate, tolyl acid phosphate, dibutyl phosphite, dioctyl phosphite, didodecyl phosphite, diphenyl phosphite, diptylphosphite, etc. be.

Examples of the metal salts of acidic phosphate esters include sodium, potassium, lithium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium,
There are metal salts of metals such as titanium, lead, and molybdenum.

Here, the method of making a metal salt of an acidic phosphoric acid ester is to react the acidic phosphoric acid ester with an oxide or hydroxide of the desired metal, or to react with an alkali salt of the acidic phosphoric acid ester and a chloride of the desired metal. It can be obtained by decomposition method etc.

The following compounds are exemplified as phosphoric acid esters.

Tributyl phosphate, tristearyl phosphate, diphenyl monocresyl phosphate, tripropylene glycol phosphate, tributyl phosphate,
triphenyl phosphate, diphenyldecyl phosphate, diphenyl-2-ethylhexyl phosphate,
Tris (2-lyloloethyl) phosphate, Tris (,
L s-d chlorofluhir) phosphate, tris(λ
Examples include 5-dibromopropyl) phosphate, tris(5-dibromopropyl) phosphate, tridecyl phosphite, tristearyl phosphite, and the like.

(14) Synthetic waxes Synthetic waxes include coal-based synthetic waxes (-E: tantan wax m, p85°C), including acid waxes (C2・-Cs2) and ester waxes (Cts to Cs
There are ester waxes containing emulsifiers, partially saponified ester waxes (Cgs~03N), etc.

Polyethylene wax is a petroleum-based wax, and there are various types such as bamboo density type, medium density type, and low density type.

Oil-based synthetic waxes include castor oil and 12-hydeoxystearin uWi.

Examples of hydrogenated castor oil include:

Hydroxystearic acid derivatives include the following.

Further, as the binder that can be used in the present invention, commonly used adhesive materials can be used, but alkyd resins, acrylic resins, rogen-modified resins, etc. are particularly preferred. Examples of the support include paper and other plastic films, and the coating method can be easily achieved using a conventional four-coater or the like. The results of a comparative test between the sample obtained by the above method and the temperature indicator label of a conventionally existing similar product are specified here. Existing similar temperature-indicating labels use a sample in which a color-printed paper surface is coated with a heat-fusible white substance to partially hide a portion of the printed color at the bottom.

The purpose of conducting a comparative test is that label sheets may change over time and change color before the temperature indication is displayed, which poses a major obstacle to reading the temperature sensor. Regarding this matter,
As a result of the following tests on label sheets that cause a color reaction at temperatures above 10°C, the results of this label sheet were very superior to existing similar temperature-indicating labels, and the results are described below. .

A. Preservability of temperature sensing (candidate) Test method: Change over time at 5℃ and 80% m degree ○ No discoloration Δ or one discoloration X Completely discolored Existing similar temperature-indicating labels are as shown in the table above. After 3 days, the color began to change, and by the 4th day, it was almost impossible to read the temperature sensor.

On the other hand, this temperature label did not show any discoloration after 6 days, and after 10 days it had completely changed color, but after 30 days it remained in the same state and the temperature sensing was difficult to read. There wasn't.

B. Storage stability (weather resistance) after temperature sensing (after discoloration) O No discoloration Δ or one discoloration By the end of the day, the color had faded to the point that it was almost impossible to read the colored parts. On the other hand, this temperature-indicating label did not show any change over a period of 60 days, and the color faded once after 180 days, but the color remained the same even after 1 year, making it difficult to read the colored part. There were no problems.

Next, examples will be given to specifically explain the present invention.

Although there are a wide variety of known methods for producing mixtures by mixing temperature-indicating substances, we will not use a particularly prescribed mixing method here, but will use a method that has conventionally been used as a general concept in the examples. Thermochromic color former mixtures A and D to be used were produced.

A: 15 parts of phenyl sulfide and 1 part of benzyl sulfide
Add 20 parts of di-7-dylcarbazone fine powder to 100 parts of the mixture and heat and mix uniformly at 110°C and 50 atmospheres. When this pressurized liquid was discharged from the tip of the i 1 rr/rn nozzle into an atmosphere at -20° C., 110 parts of a sulfide mixture containing diphenylcarbazone as a contaminant was obtained as fine powder.

B: A mixture was produced in the same manner except that 100 parts of lauryl alcohol was used instead of sulfide and 100 parts of the mixture in the mixing agent, and 110 parts of the fine powder solid was obtained.

C: Approximately 20 parts of paraffin wax (melting point 60@~80°C) 40 parts! Heat and fill a rotary kiln (diameter 50 cIn x length approx. 100 cln) at 150°C (
1-1 The tally kiln is kept at an internal temperature of 150°C and 100 rpm, and is sealed in a reduced pressure state with four blades of 258,100 mm inside.

Separately, prepare a fine powder of 80 parts of ferric sulfate.

(The particle size should be 5μ or less) After spraying this powder into a rotary kiln filled with paraffin wax (noted separately), the temperature of the kiln was lowered to 5℃ without stopping rotation. 100 parts of iron mixture are produced.

D: 40 parts of sodium metavanadate and 4 parts of anhydrous sodium carbonate instead of 80 parts of ferric sulfate in mixture (C)
All were produced in the same manner except that 0 parts were used to produce 100 parts of paraffin wax mixture.

Example 1 (a) Mixture (A) 25 parts machine-modified resin 5 parts hexane
170 parts The mixture at the above ratio was uniformly dispersed using a mixer to make the total amount 200 parts.

(B) Mixture (C) 50 parts rosin modified resin 5 parts hexane
145 parts The mixture in the above ratio was milled in a ball mill for 48 hours to make a total of 200 parts of a dispersion. Labels A and B were obtained by applying the dispersion (a) in the form of a sheet and the dispersion (b) in the same sheet form to a thickness of about 50 mm on the support using a roll coater. These labels A and B were pasted together to form a temperature indicator label for low temperatures.

When this temperature label was heated at 5°C, a clearly colored red product was obtained.

Example 2 (A) Mixture (A) 25 parts Rosin modified resin 5 parts Mineral spirit 150 parts The mixture in the above ratio was uniformly dispersed in a mixer to make the total amount 200 parts.

(b) Mixture) 50 parts Rosin modified resin 5 parts Mineral spirit 145 parts The mixture in the above proportions was kneaded in a ball mill for 48 hours to make a total of 200 parts of a dispersion.

Labels A/A and B were created by applying the dispersion of (a) in the form of a sheet and the dispersion of (b) in the form of a sheet onto a support using a roll coater to a thickness of approximately 50P. .

These labels A and B were pasted together to form a temperature indicator label for low temperatures. When this temperature label was heated at 3°C, a clearly colored red product was obtained.

Example 3 P) Mixture (B) 45 parts acrylic resin 5 parts toluene
150 parts of the mixture at the above ratio was uniformly dispersed using a mixer to make the total amount 200 parts.

(b) Zinc stearate 25 parts Acrylic resin 5 parts Toluene
170 parts of the mixture in the above ratio was milled in a ball mill for 48 hours to form a dispersion with a total fi of 200 parts. Labels A and B were obtained by applying the dispersion (P) in the form of a sheet and the dispersion (B) in the same sheet form to a thickness of about 50 μm on a support using a roll coater. labels A and B
These were glued together to form a low temperature temperature label. When this temperature label was heated at 3°C, a clearly colored red product was obtained.

[Brief explanation of drawings]

FIG. 1 is a plan view of a temperature control label according to a first embodiment of the present invention, FIG. 2 is a cross-sectional view of the center of FIG. 1, FIG. 3 is a plan view of the same in use, and FIG. 5 is a plan view of the temperature management label of the second embodiment of the present invention, FIG. 6 is a sectional view taken along line A-A, and FIG. 7 is a plan view showing the state of use, and a gs diagram. 7 is a sectional view taken along line B-B in FIG. 7. Hiroshi Kazama, /'-'＞, Figure 1 Figure 3 Figure 2 Figure 4 Figure 5 Figure 7 Figure 8 Procedural amendment May 28, 1988 Commissioner of the Patent Office Kuro 1) Mr. Akio Indication of the case: 1988, Patent Application No. 46765 Title of the invention: Person who corrects temperature control temperature label

Claims (1)

[Claims] 1. A pair of color formers A and B that do not produce white color by themselves but produce color by irreversibly reacting with each other at temperatures above a predetermined temperature, each in the form of a sheet having an adhesive on the back side. A temperature control temperature label characterized by being formed and temporarily attached on a mount. 2. Multiple pairs of coloring agents A_1, B_1; A_2, B_2;... are formed into sheets each having an adhesive on the back side, and the sheets containing these coloring agents A_1, A_2... are placed in the first part of the mount, and the sheets containing the coloring agents B_1, B_2... are placed in the second part of the mount. A temperature control thermometer label characterized in that the molecules are supported in this sequence.