JP7174590B2 - Temperature sensing material, temperature sensing ink using the same, temperature indicator, and article management system - Google Patents

Description

The present invention relates to a temperature sensing material for checking the temperature of an object to be temperature sensed, a temperature sensing ink using the same, a temperature indicator, and an article management system.

Cold-preserved medicines such as perishables, frozen foods, vaccines, and biopharmaceuticals require an uninterrupted cold chain that keeps them at low temperatures during the distribution processes of production, transportation, and consumption. In fact, in order to constantly measure and record the temperature during distribution, shipping containers are usually equipped with data loggers that can continuously record time and temperature, and if there is damage to the product, we will not be held responsible. It is possible to reveal the whereabouts. Furthermore, there is a method of using a temperature indicator to guarantee the quality of each individual product. Although the temperature indicator does not have the recording accuracy of a data logger, it can be attached to individual products, and if the temperature exceeds or falls below a preset temperature, the surface will be dyed, making it possible to detect changes in the temperature environment. It is possible. However, an inexpensive temperature indicator is required for use in quality control of inexpensive foods and medicines.

A temperature indicator using, for example, a leuco dye is used as the temperature indicator.

Patent Document 1 discloses a polyolefin composition containing a colorant comprising an electron-donating color-developing organic compound, a compound having a phenolic hydroxyl group, and an alcoholic hydroxyl group-containing carboxylic acid ester compound. It is disclosed that the discoloration temperature can be determined by the type or blending amount of the alcoholic hydroxyl group-containing carboxylic acid ester compound.

Patent Document 2 discloses a micro-particle containing a temperature-sensitive color-changing color-memory composition comprising an electron-donating color-forming organic compound, an electron-accepting compound, and a reaction medium that reversibly causes an electron transfer reaction within a specific temperature range. A solid writing material using a capsule pigment and a styrene-modified polyolefin wax as an excipient is disclosed.

Patent Document 3 discloses a thermochromic polyolefin composition comprising an electron-donating color-developing organic compound, a compound having a phenolic hydroxyl group, an alcoholic hydroxyl group-containing carboxylic acid ester compound, and a polyolefin.

Japanese Patent Publication No. 52-6748 JP 2014-118422 A JP-A-60-173028

A temperature indicating material consisting of a leuco dye, a developer, and a decolorant changes its color depending on the combination of materials depending on the accumulation of time and temperature. Therefore, by using a temperature indicating material whose color changes with the accumulation of time and temperature, it is possible to estimate the time that has elapsed since the color changed.

However, in the materials disclosed in Patent Documents 1 to 3, reproducibility of color change due to integration of time and temperature has not been sufficiently studied. The degree of color change due to the accumulation of time and temperature is influenced not only by the combination of materials constituting the temperature indicating material, but also by the material mixed with the temperature indicating material (hereinafter referred to as matrix material). As a result, the response temperature and response time may change significantly.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a temperature sensing material that enables response temperature and response time to a wide range of thermal discoloration and maintains the response temperature and response time.

In order to solve the above problems, a temperature sensing material according to the present invention includes a matrix material and a temperature indicating material dispersed in the matrix material, and the temperature indicating material contains a leuco dye, a color developer, and a decolorant. The matrix material is a non-polar material, and the half width of the endothermic peak derived from the melting point measured when the temperature is raised at a rate of 5 ° C./min using a differential scanning calorimeter is 30 ° C. or more , The melting point of the matrix material is lower than that of the temperature indicating material.

According to the present invention, it is possible to provide a temperature sensing material that maintains the response temperature and response time.

FIG. 4 is a diagram showing a differential scanning calorimetry curve of a temperature indicating material according to one embodiment; It is a figure which shows the color density change of the temperature indicating material which concerns on one Embodiment. 1 is a diagram schematically showing a temperature sensing material according to one embodiment; FIG. 1 is an optical micrograph of a temperature sensing material according to one embodiment. FIG. 3 is a schematic diagram showing the configuration of a temperature indicator; FIG. 3 is a schematic diagram showing the configuration of a temperature indicator; FIG. 4 is a diagram showing an example of color density-time information of a temperature sensing material; 1 is a configuration diagram of a time estimation system; FIG. 1 is a configuration diagram of an article management system; FIG. 1 is a differential scanning calorimetry curve of the matrix material used in Example 1. FIG. 4 is a differential scanning calorimetry curve of the matrix material used in Comparative Example 1. FIG. 4 is a photograph showing the elapsed time from temperature deviation and color density in the temperature sensing materials of Example 1 and Comparative Example 1. FIG. 4 is a graph showing time dependence of color density of the temperature sensing materials of Example 1 and Comparative Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "embodiment") for implementing this invention is demonstrated in detail, referring drawings suitably. In addition, in each figure, the same code|symbol is attached|subjected to the common part and the overlapping description is abbreviate|omitted.

<Temperature sensing material>
A temperature sensing material according to an embodiment of the present invention has a structure in which a temperature indicating material that changes color upon crystallization is dispersed in a dispersion medium.

[Temperature indicating material]
As the temperature indicating material, a material whose color density reversibly changes according to temperature change (temperature increase/temperature decrease) is used. The temperature indicating material includes a leuco dye that is an electron-donating compound, a color developer that is an electron-accepting compound, and a decolorant for controlling the temperature range of color change.

FIG. 1 is a diagram showing a differential scanning calorimetry (DSC) curve of a temperature indicating material according to one embodiment. The temperature indicating material A is a material that solidifies in an amorphous state without being crystallized when rapidly cooled after melting, and the temperature indicating material B is a material that becomes a supercooled liquid state when cooled after melting.

FIG. 1(a) is a DSC curve of the temperature indicating material A. FIG. Since crystallization does not occur in the temperature lowering process (leftward arrow (←) in the figure), no exothermic peak due to crystallization is observed. On the other hand, an exothermic peak due to crystallization is observed in the temperature rising process (rightward arrow (→) in the figure). Ta is the starting temperature in the heating process (crystallization starting temperature in the heating process). Td is the melting point.

The starting temperature depends on the heating rate and elapsed time. When the temperature is raised slowly, the starting temperature appears at a low temperature, and when the temperature is raised at a high speed, the starting temperature appears at a high temperature, or the starting temperature does not appear and melts at the melting point Td. Color develops when crystallization occurs. The starting temperature can be set according to the required detection temperature and detection time. For example, a temperature indicating material that starts to crystallize after 1 hour at a certain temperature can be used as a material for detecting that 1 hour has passed at the starting temperature, using that temperature as the starting temperature. Also, Tg is the glass transition point. Crystallization does not start below the glass transition point. In the case of a material that crystallizes easily, it crystallizes easily at a temperature above the glass transition point, so the starting temperature and the glass transition point are often the same temperature.

FIG. 1(b) is a DSC curve of the temperature indicating material B. FIG. Ta is the starting temperature of the exothermic peak due to crystallization in the temperature-lowering process (crystallization-starting temperature in the temperature-lowering process). Td is the melting point. The starting temperature depends on the cooling rate and elapsed time. When the temperature is lowered slowly, the onset temperature appears at high temperature, and when the temperature is lowered at high speed, the onset temperature appears at low temperature. Since color develops when crystallization occurs, the starting temperature is set according to the detection temperature and detection time required for the temperature detection material. For example, a temperature indicating material that starts to crystallize after 1 hour at a certain temperature can be used as a material for detecting that 1 hour has passed at the starting temperature, using that temperature as the starting temperature. Also, in the case of a material that is unlikely to be supercooled, it will crystallize easily at a temperature below the melting point, so the starting temperature and the melting point will be the same temperature. Such materials cannot be used as temperature indicating materials. That is, it is preferable to use a material that is likely to be supercooled and that has a large difference between the crystallization start temperature and the melting point.

FIG. 2 is a diagram showing changes in color density of a temperature indicating material. The vertical axis in FIG. 2 is color density, and the horizontal axis is temperature. FIG. 2(a) is a diagram showing the relationship between the color density of the temperature indicating material A and the temperature. The temperature indicating material A has a hysteresis characteristic in color density change. The temperature indicating material A uses a material that is difficult to crystallize as a color erasing agent. The coloring agent forms an amorphous state while taking in the developer, and maintains the decolored state. From this state, when the temperature is raised to the color development start temperature Ta or higher in the temperature rising process, the decolorant is crystallized and the color is developed. Therefore, by using the temperature detecting material containing the temperature indicating material A, it is possible to detect whether or not the temperature exceeds the control range when the temperature is controlled below the color development start temperature Ta.

FIG. 2(b) is a diagram showing the relationship between the color density of the temperature indicating material B and the temperature. The temperature indicating material B has a hysteresis characteristic in color density change. When the temperature of the temperature indicating material B is lowered from the state of P, which is the molten state above the color-discoloring temperature Td, the color-discoloring state is maintained up to the color-developing temperature Ta. When the color developing temperature falls below Ta, the decolorizing agent becomes crystalline below the freezing point, the leuco dye and the developer are separated, and the leuco dye and the developer combine to develop the color. Therefore, if the temperature detecting material containing the temperature indicating material B is used, it is possible to detect whether or not the temperature exceeds the control range and the temperature reaches Ta or less when the temperature is controlled to a temperature higher than the color development start temperature Ta. can.

When the temperature sensing material is used for temperature control of goods such as commodities during distribution, it is required that the material does not undergo color reversion. This is because even if the temperature rises once during distribution and the color changes, if the temperature drops or rises again during the distribution process and the color returns to the original color, it is not possible to grasp the presence or absence of the temperature change. However, since the temperature indicating material according to the present embodiment does not change its color unless it is heated to the decoloring temperature Td or higher, it is possible to know the change in the temperature environment.

Next, the leuco dye, color developer, and decolorant of each temperature indicating material will be described.

(leuco dye)
The leuco dye is an electron-donating compound, and conventionally known dyes for pressure-sensitive copying paper and heat-sensitive recording paper can be used. For example, triphenylmethanephthalide, fluoran, phenothiazine, indolylphthalide, leuco auramine, spiropyran, rhodaminelactam, triphenylmethane, triazene, spirophthalanexanthene, naphtholactam, azomethine series and the like. Specific examples of leuco dyes include 9-(N-ethyl-N-isopentylamino)spiro[benzo[a]xanthene-12,3′-phthalide], 2-methyl-6-(Np-tolyl-N- Ethylamino)-fluoran 6-(diethylamino)-2-[(3-trifluoromethyl)anilino]xanthene-9-spiro-3′-phthalide, 3,3-bis(p-diethylaminophenyl)-6-dimethylamino phthalide, 2'-anilino-6'-(dibutylamino)-3'-methylspiro[phthalido-3,9'-xanthene], 3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl -2-methylindol-3-yl)-4-azaphthalide, 1-ethyl-8-[N-ethyl-N-(4-methylphenyl)amino]-2,2,4-trimethyl-1,2-dihydro spiro[11H-chromeno[2,3-g]quinoline-11,3′-phthalide].

The temperature indicating material may be used in combination of two or more leuco dyes.

(developer)
The color developer changes the structure of the electron-donating leuco dye by contacting it with the electron-donating leuco dye to develop a color. As the color developer, those known as color developers used for heat-sensitive recording paper, pressure-sensitive copying paper, and the like can be used. Specific examples of such developers include benzyl 4-hydroxybenzoate, 2,2′-biphenol, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 2,2-bis(3 -Cyclohexyl-4-hydroxyphenyl)propane, bisphenol A, bisphenol F, bis(4-hydroxyphenyl)sulfide, p-hydroxybenzoic acid ester, phenols such as gallic acid ester, and the like. The developer is not limited to these, and may be any compound that is an electron acceptor and can change the color of the leuco dye. In addition, metal salts of carboxylic acid derivatives, salicylic acid and salicylic acid metal salts, sulfonic acids, sulfonates, phosphoric acids, phosphoric acid metal salts, acidic phosphoric acid esters, acidic phosphoric acid ester metal salts, phosphorous acids, phosphorous acid Metal salts and the like may also be used. In particular, those having high compatibility with leuco dyes and decolorizing agents described later are preferable, and organic color developers such as benzyl 4-hydroxybenzoate, 2,2'-bisphenol, bisphenol A and gallic acid esters are preferable.

The temperature indicating material may be one type of these color developers or a combination of two or more types. It is possible to adjust the color density when the leuco dye develops color by combining the developer. The amount of developer used is selected according to the desired color strength. For example, it may be selected within the range of about 0.1 to 100 parts by weight per 1 part by weight of the leuco dye.

(Decoloring agent)
The decolorizing agent is a compound capable of dissociating the bond between the leuco dye and the developer, and is a compound capable of controlling the coloration temperature of the leuco dye and the developer. In general, in the temperature range in which the leuco dye is colored, the decolorant solidifies in a phase-separated state. Moreover, in the temperature range where the leuco dye is in a decolorized state, the decolorant is melted, and the function of dissociating the bond between the leuco dye and the developer is exerted. Therefore, the state change temperature of the color erasing agent is important for temperature control of the temperature indicating material.

A wide range of materials that can dissociate the bond between the leuco dye and the color developer can be used as the decolorizing agent. A wide variety of materials can be decolorizers, provided they are low in polarity and do not exhibit developer properties for the leuco dye, and are highly polar enough to dissolve the leuco dye and the developer. Typically, hydroxy compounds, ester compounds, peroxy compounds, carbonyl compounds, aromatic compounds, aliphatic compounds, halogen compounds, amino compounds, imino compounds, N-oxide compounds, hydroxylamine compounds, nitro compounds, azo compounds, diazo A wide variety of organic compounds can be used, such as chemical compounds, azide compounds, ether compounds, fat compounds, sugar compounds, peptide compounds, nucleic acid compounds, alkaloid compounds, and steroid compounds. Specifically, tricaprin, isopropyl myristate, m-tolyl acetate, diethyl sebacate, dimethyl adipate, 1,4-diacetoxybutane, decyl decanoate, diethyl phenylmalonate, diisobutyl phthalate, triethyl citrate, phthalate Benzyl butyl acid, butyl phthalyl butyl glycolate, methyl N-methylanthranilate, ethyl anthranilate, 2-hydroxyethyl salicylate, methyl nicotinate, butyl 4-aminobenzoate, methyl p-toluate, 4-nitrobenzoic acid Ethyl, 2-phenylethyl phenylacetate, benzyl cinnamate, methyl acetoacetate, geranyl acetate, dimethyl succinate, dimethyl sebacate, diethyl oxalacetate, monoolein, butyl palmitate, ethyl stearate, methyl palmitate, stearic acid Methyl, linalyl acetate, di-n-octyl phthalate, benzyl benzoate, diethylene glycol dibenzoate, methyl p-anisate, m-tolyl acetate, cinnamyl cinnamate, 2-phenylethyl propionate, butyl stearate, myristic acid Ethyl, methyl myristate, methyl anthranilate, neryl acetate, isopropyl palmitate, ethyl 4-fluorobenzoate, cyclanderate (mixture of isomers), butopyronoxyl, ethyl 2-bromopropionate, tricaprylin, ethyl levulinate, hexadecyl palmitate , tert-butyl acetate, 1,1-ethanediol diacetate, dimethyl oxalate, tristearin, methyl acetylsalicylate, benzal diacetate, methyl 2-benzoylbenzoate, ethyl 2,3-dibromobutyrate, 2-furan Ethyl carboxylate, ethyl acetopyruvate, ethyl vanillate, dimethyl itaconate, methyl 3-bromobenzoate, monoethyl adipate, dimethyl adipate, 1,4-diacetoxybutane, diethylene glycol diacetate, ethyl palmitate, terephthalate diethyl acid, phenyl propionate, phenyl stearate, 1-naphthyl acetate, methyl behenate, methyl arachidate, methyl 4-chlorobenzoate, methyl sorbate, ethyl isonicotinate, dimethyl dodecanedioate, methyl heptadecanoate, α - ethyl cyanocinnamate, N-phenylglycine ethyl, diethyl itaconate, methyl picolinate, methyl isonicotinate, DL-methyl mandelate, methyl 3-aminobenzoate methyl 4-methylsalicylate, diethyl benzylidenemalonate, isoamyl DL-mandelic acid, triethyl methanetricarboxylate, diethyl formaminomalonate, 1,2-bis(chloroacetoxy)ethane, methyl pentadecanoate, ethyl arachidate, 6 -ethyl bromohexanoate, monoethyl pimelate, hexadecyl lactate, ethyl benzilate, mefenpyr-diethyl, procaine, dicyclohexyl phthalate, 4-tert-butylphenyl salicylate, isobutyl 4-aminobenzoate, butyl 4-hydroxybenzoate, tri Palmitin, 1,2-diacetoxybenzene, dimethyl isophthalate, monoethyl fumarate, methyl vanillate, methyl 3-amino-2-thiophenecarboxylate, etomidate, cloquintocet-mexyl, methyl benzilate, diphenyl phthalate, benzoin phenyl acid, propyl 4-aminobenzoate, ethylene glycol dibenzoate, triacetin, ethyl pentafluoropropionate, methyl 3-nitrobenzoate, 4-nitrophenyl acetate, methyl 3-hydroxy-2-naphthoate, trimethyl citrate, ethyl 3-hydroxybenzoate, methyl 3-hydroxybenzoate, trimebutine, 4-methoxybenzyl acetate, pentaerythritol tetraacetate, methyl 4-bromobenzoate, ethyl 1-naphthaleneacetate, 5-nitro-2-furaldehyde dia Cetate, ethyl 4-aminobenzoate, propylparaben, 1,2,4-triacetoxybenzene, methyl 4-nitrobenzoate, diethyl acetamidomalonate, valetamate bromide, 2-naphthyl benzoate, dimethyl fumarate, adiphenin Hydrochloride, benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, vinyl butyrate, vitamin K4, methyl 4-iodobenzoate, methyl 3,3-dimethylacrylate, propyl gallate, 1,4-diacetoxybenzene , diethyl mesooxalate, dimethyl 1,4-cyclohexanedicarboxylate (cis-, trans-mixture), triethyl 1,1,2-ethanetricarboxylate, dimethyl hexafluoroglutarate, amyl benzoate, ethyl 3-bromobenzoate , ethyl 5-bromo-2-chlorobenzoate, bis(2-ethylhexyl) phthalate, diethyl allylmalonate, diethyl bromomalonate, diethyl ethoxymethylenemalonate, diethyl ethylmalonate, diethyl malate, diethyl maleate, diethyl malonate, diethyl phthalate, dimethyl 1,3-acetonedicarboxylate, dimethyl phthalate, ethyl 3-aminobenzoate, ethyl benzoate, ethyl 4-(dimethylamino)benzoate, ethyl nicotinate, ethyl phenylpropiolate, ethyl pyridine-2-carboxylate, ethyl 2-pyridylacetate, ethyl 3-pyridylacetate, methyl benzoate, ethyl phenylacetate, amyl 4-hydroxybenzoate, 2,5-diacetoxy Toluene, ethyl 4-oxazolecarboxylate, trimethyl 1,3,5-cyclohexanetricarboxylate (cis-, trans-mixture), methyl 3-(chlorosulfonyl)-2-thiophenecarboxylate, pentaerythritol distearate, lauric acid benzyl, diethyl acetylenedicarboxylate, phenyl methacrylate, benzyl acetate, dimethyl glutarate, ethyl 2-oxocyclohexanecarboxylate, ethyl phenylcyanoacetate, ethyl 1-piperazinecarboxylate, methyl benzoylformate, methyl phenylacetate, phenyl acetate, Diethyl succinate, tributyrin, diethyl methylmalonate, dimethyl oxalate, diethyl 1,1-cyclopropanedicarboxylate, dibenzyl malonate, methyl 4-tert-butylbenzoate, ethyl 2-oxocyclopentanecarboxylate, cyclohexanecarboxylic acid methyl, ethyl 4-methoxyphenylacetate, methyl 4-fluorobenzoylacetate, dimethyl maleate, methyl terephthalaldehyde, ethyl 4-bromobenzoate, methyl 2-bromobenzoate, methyl 2-iodobenzoate, 3-iodobenzoate ethyl acetate, ethyl 3-furancarboxylate, diallyl phthalate, benzyl bromoacetate, dimethyl bromomalonate, methyl m-toluate, diethyl 1,3-acetonedicarboxylate, methyl phenylpropiolate, 1-naphthyl butyrate, o-toluyl ethyl acetate, methyl 2-oxocyclopentanecarboxylate, isobutyl benzoate, ethyl 3-phenylpropionate, di-tert-butyl malonate, dibutyl sebacate, diethyl adipate, diethyl terephthalate, dipropyl phthalate, 1, 1 - ethanediol diacetate, diisopropyl adipate, diisopropyl fumarate, ethyl cinnamate, 2-cyano-3, 2-ethylhexyl 3-diphenylacrylate, neopentyl glycol diacrylate triolein, ethyl benzoylacetate, ethyl p-anisate, diethyl suberate, sorbitan tristearate, sorbitan monostearate, stearamide, glycerol monostearate, glycerol distearate, 3-(tert-butoxycarbonyl) Phenylboronic acid, racecadotril, 4-[(6-acryloyloxy)hexyloxy]-4'-cyanobiphenyl, 2-(dimethylamino)vinyl 3-pyridyl ketone, stearyl acrylate, ethyl 4-bromophenylacetate, phthalic acid Dibenzyl, methyl 3,5-dimethoxybenzoate, eugenol acetate, didodecyl 3,3′-thiodipropionate, vanillin acetate, diphenyl carbonate, ethyl oxalylate, methyl terephthalaldehyde, dimethyl 4-nitrophthalate, (4-nitro benzoyl)ethyl acetate, dimethyl nitroterephthalate, methyl 2-methoxy-5-(methylsulfonyl)benzoate, methyl 3-methyl-4-nitrobenzoate, dimethyl 2,3-naphthalenedicarboxylate, bis(2- ethylhexyl), 4′-acetoxyacetophenone, ethyl trans-3-benzoylacrylate, ethyl coumarin-3-carboxylate, BAPTA tetraethyl ester, methyl 2,6-dimethoxybenzoate, di-tert-butyl iminodicarboxylate, p- benzyl benzyloxybenzoate, methyl 3,4,5-trimethoxybenzoate, methyl 3-amino-4-methoxybenzoate, diethylene glycol distearate, ditetradecyl 3,3'-thiodipropionate, ethyl 4-nitrophenylacetate, methyl 4-chloro-3-nitrobenzoate, 1,4-dipropionyloxybenzene, dimethyl terephthalate, ethyl 4-nitrocinnamate, dimethyl 5-nitroisophthalate, triethyl 1,3,5-benzenetricarboxylate, Diethyl N-(4-aminobenzoyl)-L-glutamate, 2-methyl-1-naphthyl acetate, 7-acetoxy-4-methylcoumarin, methyl 4-amino-2-methoxybenzoate, 4,4'-diacetoxy biphenyl, dimethyl 5-aminoisophthalate, diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate, dimethyl 4,4′-biphenyldicarboxylate, 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, decanoic acid -4-benzyloxyphenylethyl, -4-benzyloxyphenylethyl undecanoate, -4-benzyloxyphenylethyl dodecanoate, -4-benzyloxyphenylethyl tridecanoate, -4-benzyloxyphenylethyl tetradecanoate, pentadecanoic acid -4-benzyloxyphenylethyl, 4-benzyloxyphenylethyl hexadecanoate, 4-benzyloxyphenylethyl heptadecanoate, 4-benzyloxyphenylethyl octadecanoate, 1,1-diphenylmethyl octanoate, 1 nonanoic acid , 1-diphenylmethyl, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, 1,1-diphenylmethyl dodecanoate, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate , 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, 1,1-diphenylmethyl octadecanoate, cholesterol, cholesteryl bromide, β-estradiol , methylandrostenediol, pregnenolone, cholesterol benzoate, cholesterol acetate, cholesterol linoleate, cholesterol palmitate, cholesterol stearate, cholesterol n-octanoate, cholesterol oleate, 3-chlorocholestene, trans-cholesterol cinnamate, Cholesterol decanoate, cholesterol hydrocinnamate, cholesterol laurate, cholesterol butyrate, cholesterol formate, cholesterol heptanoate, cholesterol hexanoate, cholesterol hydrogen succinate, cholesterol myristate, cholesterol propionate, cholesterol valerate, cholesterol hydrogen phthalate , cholesterol phenylacetate, cholesterol chloroformate, cholesterol 2,4-dichlorobenzoate, cholesterol pelargonate, cholesterol nonyl carbonate, cholesterol heptyl carbonate, cholesterol oleyl carbonate, cholesterol methyl carbonate, cholesterol ethyl carbonate, cholesterol isopropyl Carbonate, cholesterol butyl carbonate, cholesterol isobutyl carbonate, cholesterol amyl carbonate, cholesterol n-octyl carbonate , cholesterol hexyl carbonate, allylestrenol, altrenogest, 9(10)-dehydronandrolone, estrone, ethinyl estradiol, estriol, estradiol benzoate, β-estradiol 17-cypionate, β-estradiol 17-valerate, α -estradiol, beta-estradiol 17-heptanoate, gestrinone, mestranol, 2-methoxy-beta-estradiol, nandrolone, (-)-norgestrel, quinestrol, trenbolone, tibolone, stanolone, androsterone, abiraterone, abiraterone acetate, dehydro Epiandrosterone, dehydroepiandrosterone acetate, ethisterone, epiandrosterone, 17β-hydroxy-17-methylandrosta-1, 4-dien-3-one, methylandrostenediol, methyltestosterone, Δ9(11)- methyltestosterone, 1α-methylandrostane-17β-ol-3-one, 17α-methylandrostane-17β-ol-3-one, stanozolol, testosterone, testosterone propionate, altrenogest, 16-dehydropregnenolone acetate, 16,17-epoxypregnenolone acetate, 11α-hydroxyprogesterone, 17α-hydroxyprogesterone caproate, 17α-hydroxyprogesterone, pregnenolone acetate, 17α-hydroxyprogesterone acetate, megestrol acetate, medroxyprogesterone acetate, pregnenolone acetate, 5β - pregnane-3α,20α-diol, budesonide, corticosterone, cortisone acetate, cortisone, cortexolone, deoxycorticosterone acetate, deflazacort, hydrocortisone acetate, hydrocortisone, hydrocortisone 17-butyrate, 6α-methylprednisolone, prednisolone, prednisone, prednisolone acetate, sodium deoxycholate, sodium cholate, methyl cholate, methyl hyodeoxycholate, β-cholestanol, cholesterol-5α, 6α-epoxide, diosgenin, ergosterol, β-sitosterol, stigmasterol, β- Examples include steroid compounds such as sitosterol acetate. From the viewpoint of compatibility with leuco dyes and color developers, it is preferable to contain these compounds. Of course, the material is not limited to these compounds, and any material can be used as long as it can dissociate the bond between the leuco dye and the color developer.

Also, these decolorizing agents may be used singly or in combination of two or more. By combining a decolorizing agent, it is possible to adjust the freezing point, crystallization rate, and melting point.

The decolorizing agent used for the temperature indicating material A needs to be amorphous in the vicinity of the glass transition point without being crystallized in the process of rapid cooling from the melting temperature of the decolorizing agent. Therefore, a material that is difficult to crystallize is preferable. If the quenching rate is very high, most materials will form an amorphous state, but from the practical point of view, it is preferable that the quenching by a general-purpose cooling device is difficult to crystallize to the extent that an amorphous state is formed. More preferably, the material is less likely to crystallize to the extent that it forms an amorphous state during the process of spontaneous cooling from a molten state above its melting point. Specifically, a decolorant that forms an amorphous state when cooled from the melting point to the glass transition point at a rate of 1° C./min or more is preferable, and is cooled from the melting point to the glass transition point at a rate of 20° C./min or more. More preferred is a decolorant that forms an amorphous state when decolorized.

The decolorizing agent used for the temperature indicating material B preferably has a wide supercooled temperature range, that is, a large temperature difference between the freezing point and the melting point of the decolorizing agent. Also, the temperature of the melting point or freezing point depends on the target temperature control range.

In order to initialize the color, it is necessary to raise the temperature above the melting point of the decolorant of the temperature indicating material. The color initialization temperature should be high enough not to initialize near the control temperature, but from the practical point of view, it is desirable to be in a temperature range that can be heated by a general-purpose heating device. As the temperature sensing material, microcapsules and matrix materials are used to disperse the temperature indicating material, so it is necessary to consider their heat resistance. Specifically, it is preferably about 40°C to 250°C, most preferably about 60°C to 150°C.

The temperature indicating material contains at least the above leuco dye, developer, and decolorant. However, when a material containing a color developing action and a color erasing action in one molecule is contained, the color developer and the color erasing agent may be omitted. Materials other than leuco dyes, color developers, and decolorants may also be included as long as the ability to change color upon crystallization is maintained. For example, by including a pigment, it is possible to change the color during decolorization and development.

[Matrix material]
FIG. 3 is a schematic diagram showing the form of a temperature sensing material according to one embodiment. The temperature sensing material 1 has a phase form in which a large number of temperature indicating materials 2 are dispersed in a matrix material 3 as a dispersion medium.

The temperature indicating material A is a material whose color change rate changes depending on the temperature when it reaches the starting temperature Ta or higher, and the temperature indicating material B is a material whose color change rate changes depending on the temperature when it reaches the starting temperature Ta or lower. be. These color changes are caused by crystallization. Therefore, the color change is a phenomenon that occurs randomly depending on the crystallization rate, and has low temporal reproducibility.

Crystallization is a phenomenon caused by the generation of crystal nuclei, and is a phenomenon that occurs randomly according to the temperature-dependent crystal nucleus generation frequency (crystallization speed) for each material. Therefore, the time for the formation of crystal nuclei, that is, the time for crystallization, is not constant, and the temporal reproducibility is low. However, when there are many temperature indicating materials with the same crystallization rate and the time for each temperature indicating material to crystallize is measured, the average time will approach a constant value as the number of temperature indicating materials to be measured increases. be done. Therefore, if a large number of temperature indicating materials are present, the average time for crystallization of the temperature indicating materials is always uniform. Therefore, if a temperature detecting material having a form in which a large number of temperature indicating materials are present is used, the color at the time of observation will be the average color of the large number of temperature indicating materials, so that the reproducibility of color change can be improved.

Crystallization is also highly susceptible to the presence of impurities and interfaces such as the walls of containers. Therefore, in order to have a large number of temperature indicating materials with the same crystallization rate, it is necessary to uniformize the influence of the interface on the crystallization of all the temperature indicating materials. Furthermore, when the temperature indicating materials are close to each other, crystallization occurs when a crystal nucleus is generated in one place, and the crystallization speed increases due to the influence of the nucleus and propagation to the surroundings. the crystallization rates of the Therefore, in a large number of temperature indicating materials, it is necessary to isolate the temperature indicating materials to such an extent that the influence of crystallization between the respective temperature indicating materials can be ignored.

Once the crystallization of the temperature indicating material starts at one point, the color change is completed abruptly, so it is difficult to estimate the elapsed time from the degree of color change. Therefore, there is a demand for a temperature sensing material whose color density changes continuously (slowly) with time. In the case of a material whose color density changes continuously over time, it is possible to estimate the elapsed time from the color density of the material. By allowing a large number of temperature indicating materials to exist and observing the average color of the large number of temperature indicating materials, it is possible to provide a temperature sensing material whose color density changes continuously (gradually) with time.

In order to satisfy the above conditions, the temperature sensing material has a form (hereinafter referred to as a phase-separated structure) in which a large number of temperature indicating materials are dispersed in a matrix material, as shown in FIG.

FIG. 4 shows an optical micrograph showing the phase separation structure of the temperature sensing material. FIG. 4(a) shows a developed state, and FIG. 4(b) shows a decolored state. From the optical microscope photograph, it can be confirmed that the temperature sensing material 1 forms a phase separation structure in which the temperature indicating material 2 is dispersed in the matrix material 3 .

In order to estimate the elapsed time from the color density, the size of the temperature indicating material dispersed in the matrix material of the temperature sensing material is important. Specifically, the diameter of the particles of the temperature indicating material is preferably equal to or less than the resolving power during observation. When the diameter of the temperature indicating material particles is larger than the resolution at the time of observation, it is difficult to observe the average color of a large number of temperature indicating materials. The particle diameter of the temperature indicating material is smaller than the resolution at the time of observation, and by observing the average color of a large number of temperature indicating materials, the temporal reproducibility of color change is high, and the color density is continuous with time ( A slowly changing temperature sensitive material can be obtained. In particular, considering practicality, the average diameter of the particles of the temperature indicating material is preferably less than the resolution of visual observation and camera. Therefore, the average particle size of the temperature indicating material is preferably 20 μm or less, more preferably 5 μm or less.

As the number of temperature-indicating materials increases, the average time for color change of the temperature-indicating materials to be observed approaches a constant value, resulting in higher temporal reproducibility and improved performance as a temperature-sensing material. do. Therefore, it is preferable that the number of temperature indicating materials in the temperature sensing material is large. Therefore, it is considered preferable that the average particle diameter of the temperature indicating material is small and the volume fraction of the temperature indicating material to the matrix material is high. However, if the volume fraction of the temperature indicating material to the matrix material is too high, it becomes difficult to disperse the temperature indicating material. Therefore, the volume fraction of the temperature indicating material in the temperature sensing material is preferably 5% or more and less than 90%, more preferably 10% or more and 50% or less.

In addition, by protecting the temperature indicating material with a matrix material that does not have a color or decoloring effect, when the temperature detecting material is dispersed in a solvent and ink is prepared, the leuco dye, the developer, and the decolorant are not mixed with other resin agents. , it is possible to suppress the influence received from compounds such as additives.

As the matrix material, a material that can disperse the temperature indicating material and that does not impair the color developability and color erasability of the temperature indicating material when mixed with the temperature indicating material can be used. Such materials include non-polar materials that are not electron acceptors.

Also, the matrix material is a material that is poorly compatible with leuco dyes, decolorants, and color developers. This is because the function of detecting temperature and time is impaired when any one of the leuco dye, the developer, and the decolorant is compatible with the matrix material.

As a matrix material satisfying the above conditions, a material having an energy δp due to intermolecular dipole interaction and an energy δh due to intermolecular hydrogen bonding predicted by the Hansen solubility parameter of 3 or less can be preferably used. Specifically, a material having no polar group and a material composed only of hydrocarbons can be preferably used.

Further, as a result of experimental verification by the inventor, it was found that a material having a wide temperature range (melting point range) of melting and solidifying temperatures is preferable as the matrix material. The phase-separated structure is formed in a cooling process from a state in which the temperature indicating material and the matrix material are heated, melted, and mixed. At this time, although it depends on the cooling rate, the phase separation structure is gradually formed when the melting point width is large to some extent, that is, when the solidification temperature width is large. This makes it easier to form a structure in which the temperature indicating material is uniformly dispersed in the matrix material with a certain size. Conversely, if a matrix material with a narrow melting point width is used, the matrix material solidifies abruptly in the process of forming a phase-separated structure by cooling from a state in which both the temperature indicating material and the matrix material are heated, melted, and mixed. In the case of the phase-separated structure formed in this way, the color change due to the crystallization of the temperature indicating material does not occur normally, and the reproducibility of the color change time may not be observed, or the color change itself may not occur. A good melting point width depends on the cooling rate. The temperature at which the phase-separated structure is heated and melted must be 60° C. to 150° C. or higher, which is preferable as the melting point of the decolorant of the temperature indicating material, and specifically, the temperature range that can be heated by a general-purpose heating device. 120° C. to 180° C. is preferable. When a phase-separated structure is formed by naturally cooling from this temperature to the management temperature for cold chain distribution such as frozen products and refrigerated products, the cooling rate is 20, depending on the heat capacity of the phase-separated structure. It is envisaged to have a rate of 0 C/min or higher. At this time, the matrix material preferably has a melting point width of 30° C. or higher. In this specification, the melting point width is defined as the half width of the endothermic peak derived from the melting point measured when the temperature is raised at a rate of 5° C./min using a differential scanning calorimeter (DSC). .

Further, as a result of experiments conducted by the inventors, it was found that the melting point of the matrix material is preferably lower than that of the temperature indicating material. When the temperature indicating material and the matrix material are heated and melted and mixed together to form a phase-separated structure in the cooling process, when the temperature indicating material solidifies to form fine particles, the matrix material solidifies. Form a phase-separated structure. If the melting point of the matrix material is only higher than the melting point of the temperature indicating material (if the minimum temperature of the melting point range of the matrix material is higher than the melting point of the temperature indicating material), before the temperature indicating material solidifies and forms fine particles, the matrix material coagulation is completed. In this case, the color change due to the crystallization of the temperature indicating material does not occur normally, and the color change may occur at an unexpected temperature, or the color change itself may not occur.

When the temperature sensing material is used for temperature control during cold chain distribution of frozen or refrigerated goods, the melting point range is preferably 15° C. or higher and 120° C. or lower, and 30° C. or higher and 60° C. or lower. is more preferred. In order to be compatible with the temperature indicating material, it is more preferable to use a material having a melting point width of 30° C. or more at a temperature lower than the melting point of the temperature indicating material.

In addition, a material that becomes a low-viscosity melt above the melting point and easily solidifies below the melting point is easy to handle. Also, a material that dissolves in an organic solvent and solidifies during the volatilization process of the organic solvent is easy to handle.

From the above, as the matrix material, specifically, polyolefin-based, paraffin-based, microcrystalline-based waxes, propylene, ethylene, styrene, cycloolefin, siloxane, terpene, etc. materials, copolymers thereof, and the like. Among these, polyolefin waxes, paraffin waxes, microcrystalline waxes and terpene resins are preferably used as matrix materials, and polyolefin waxes and paraffin waxes are more preferably used since they have a wide melting point range.

Examples of polyolefin waxes include waxes such as low-molecular-weight polyethylene and low-molecular-weight polypropylene. The molecular weight of the polyolefin and the viscosity in the liquid state are not particularly limited, but when the viscosity is low in the liquid state, the entrapment of air bubbles is small and the moldability is good. Specifically, it preferably has a molecular weight of 50,000 or less and a viscosity of 10 Pa·S or less near the melting point, and a molecular weight of 10,000 or less and a viscosity of 1 Pa·S or less near the melting point. is more preferred.

The melting point of the matrix material is preferably 120° C. or lower, more preferably 100° C. or lower.

These matrix materials can also be used in combination of multiple types.

The phase-separated structure can be pulverized with a mortar or the like. This enables handling similar to microcapsules.

The powdered phase-separated structure is used for dispersion stabilization for making ink, improved resistance to solvents, and improved environmental resistance to light and humidity. Surface treatment may be performed by corona treatment or the like. It is also possible to further coat the phase-separated structure with a matrix material or microcapsules.

The phase-separated structure is formed by, for example, heating a leuco dye, a developer, a decolorant, and a matrix material to a temperature equal to or higher than the melting point of the matrix material, mixing the resulting mixture with the matrix material. can be obtained by cooling to a temperature below the freezing point of In the cooling process, the matrix material and the temperature indicating material rapidly phase-separate to form a phase-separated structure in which the phases composed of the leuco dye, the developer, and the decolorant are dispersed in the matrix material.

When the matrix material is heated to the melting point or higher to be in a liquid state, the temperature indicating material and the non-color-developing material may or may not be compatible depending on the compatibility between the temperature indicating material and the matrix material. At this time, it is preferable that they are compatible with each other from the viewpoint of ease of handling. In order for the temperature indicating material and the matrix material to phase-separate at the use temperature and to dissolve the temperature indicating material and the matrix material in a heated state, it is preferable to adjust the polarity of the decolorant, which is particularly contained in the temperature indicating material, in a large amount. If the polarity of the decolorizing agent is too small, it will dissolve with the matrix material at the temperature of use, and if the polarity is too large, it will separate from the matrix material when heated. As a specific method for calculating the polarity, it is preferable to use a decolorant in which the energy δp due to intermolecular dipole interaction and the energy δh due to intermolecular hydrogen bonding predicted by the Hansen solubility parameter are 1 or more and 10 or less. can be done. However, it is possible to form a phase-separated structure by cooling with stirring even for a material in which the polarity of the decolorizing agent is large and the temperature indicating material and the matrix material are not compatible even in a heated state. Further, a surfactant may be added to make them compatible.

When the temperature indicating material is cooled below the freezing point of the matrix material to form a phase separation structure, the size of the dispersed structure of the temperature indicating material varies depending on the compatibility between the temperature indicating material and the matrix material. In particular, when the decolorant and the matrix material have a high content, they are finely dispersed when the compatibility is good to some extent, and they are widely dispersed when the compatibility is poor. In the cooling process, it is possible to reduce the size of the dispersed structure by cooling while stirring or adding a surfactant.

The temperature sensing material may contain dyes, pigments, and various additives in addition to the temperature indicating material and matrix material. Additives include heat storage capsules, conductive agents, and the like.

<Temperature detection ink>
A temperature sensing ink can be produced by preparing a phase-separated structure in which a temperature indicating material is dispersed in a matrix material in advance, and mixing the phase-separated structure with a solvent. The phase-separated structure may be pulverized into fine particles and mixed with the solvent. The temperature-sensing ink can be applied to pens, stamps, crayons, inkjet inks, and printing paints. Further, by heating and melting the phase separation structure, it is possible to utilize it as it is as a temperature detection ink. In this case, it applies to a printing apparatus having a heating mechanism.

The temperature sensing ink has a form in which a temperature sensing material is dispersed in a solvent. For that purpose, it is necessary to use a solvent having low compatibility with the matrix material containing the temperature indicating material.

As the solvent, it is preferable to use a highly polar solvent. Water, alcohols such as glycerin, methanol, ethanol and propanol can be preferably used as highly polar solvents. In addition, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, methyl acetate, ethyl propionate and methyl propionate, and ethers such as dimethyl ether and tetrahydrofuran can be used.

These temperature-sensing inks have temperature and time-sensing functions even in a liquid state, and when the solvent is volatilized by printing, writing, or imprinting on an object to be printed, only the temperature-sensing material constitutes the printed material. do. This print can be used as a temperature and time sensitive indicator.

Additives may be added to a solution such as an organic solvent or water to the temperature sensing ink as long as they do not affect the temperature and time sensing functions. For example, by including a pigment, it is possible to change the color during decolorization and development.

Various additives and solvents can be used for the temperature sensing ink. It is also possible to adjust the viscosity by changing the amount of the temperature sensing material and additives. As a result, it can be applied as an ink for various printing devices such as offset printing, gravure printing, flexographic printing, label printers, and thermal printers.

[Inkjet ink]
The temperature-sensing ink can be applied to charge control ink jet printer inks. A charge-controlled inkjet printer ink includes a temperature sensing material, a volatile organic solvent, a resin, and a conductive agent.

If the resistance of the ink solution is high, the ink particles tend to bend rather than fly straight at the ink ejection portion of the charge-controlled inkjet printer. Therefore, the resistance of the ink solution should be approximately 2000 Ωcm or less.

Resins, pigments, and organic solvents (particularly 2-butanone and ethanol, which are often used as organic solvents for ink for inkjet printers) contained in ink have low conductivity, so the resistance of the ink solution is as high as 5,000 to tens of thousands of Ωcm. . If the resistance is high, it becomes difficult for the charge control type ink jet printer to print as desired. Therefore, it is necessary to add a conductive agent to the ink in order to lower the resistance of the ink solution.

A complex is preferably used as the conductive agent. The conductive agent must be dissolved in the solvent used, and it is also important not to affect the color tone. Also, the conductive agent is generally of a salt structure. It is presumed that high conductivity can be exhibited because this has an uneven charge in the molecule.

As a result of examination from the above viewpoints, it is preferable that the conductive agent has a salt structure and the cation has a tetraalkylammonium ion structure. The alkyl chain may be linear or branched, and the larger the number of carbon atoms, the better the solubility in solvents. However, the smaller the number of carbon atoms, the lower the resistance can be achieved with a small addition rate. The practical number of carbon atoms for use in ink is about 2 to 8.

Hexafluorophosphate ions, tetrafluoroborate ions, and the like are preferred as anions because of their high solubility in solvents.

Although perchlorate ions are also highly soluble, they are not practical to use in ink because they are explosive. In addition, chlorine, bromine, and iodine ions may also be mentioned, but these tend to corrode metals such as iron and stainless steel when they come into contact with them, and are therefore not preferred.

From the above, preferred conductive agents are tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetrapentylammonium hexafluorophosphate, tetrahexylammonium hexafluorophosphate, and tetraoctylammonium. hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrapentylammonium tetrafluoroborate, tetrahexylammonium tetrafluoroborate, tetraoctylammonium tetrafluoroborate and the like.

<Temperature indicator>
FIG. 5 is a schematic diagram showing the configuration of the temperature indicator. The temperature indicator comprises a substrate (support) 5, a temperature sensing material 1 placed on the substrate, a transparent substrate (protective layer) 6 placed on the temperature sensing material, a spacer 7, and a temperature It has a structure in which a sensing material 1 is sandwiched between a substrate 5 and a transparent substrate 6 .

Materials for the substrate and the transparent substrate are not particularly limited as long as the temperature sensing material is sandwiched between the transparent substrate and the substrate and the discoloration of the temperature sensing material can be visually recognized. It is also possible not to use a transparent substrate. In this case, spacers may not be used.

The material for the base material can be freely selected according to the required functions. Organic materials such as paper and plastics, inorganic materials such as ceramics and metals, and composite materials thereof can be freely selected. Several materials may form a layered structure. Materials are selected according to the properties required for temperature and time indicators, such as high strength, heat resistance, weather resistance, chemical resistance, heat insulation, and electrical conductivity. By using a sticker, it is also possible to bring the sensor into close contact with the object to be detected. It is preferable that the substrate be larger than the temperature sensing material so that the temperature sensing material can be sandwiched between the substrates.

A continuous porous material may also be used as the substrate. In this case, the structure is such that a continuous porous material is impregnated with a temperature sensing material. By impregnating the temperature sensing material into the continuous porous material, the processability of the temperature indicator can be changed according to the processability of the continuous porous material. The continuous porous material is required to be a material that does not denature even when the temperature sensing material is in contact with it for a long period of time. Therefore, specifically, materials such as polyethylene, polypropylene, and cellulose that are difficult to dissolve in ordinary organic solvents are suitable. Silicon dioxide is also suitable as an inorganic compound.

Structures of continuous porous materials include sponges, nonwoven fabrics, woven fabrics, and the like. In the case of cellulose, paper used for producing books and documents may be used. It is also possible to form a continuous porous body by holding powders of silicon dioxide, polyethylene, and polypropylene with a binder having a similar chemical structure and use it. The higher the density of the voids in the continuous porous body, the higher the density at which the temperature sensing material permeates, so it is possible to suppress the decrease in color density.

The material of the transparent substrate can also be freely selected according to the required functions. Organic materials such as paper and plastics, inorganic materials such as ceramics and metals, and composite materials thereof can be freely selected. Transparency is required because the temperature and time sensing ink must be visible for discoloration in at least some locations. Examples include organic materials such as highly transparent paper, highly transparent plastics such as acrylic, polycarbonate, and cycloolefin, and highly transparent inorganic compounds such as glass and transparent electrode films. In addition to these highly transparent materials, it is also possible to use materials that are thinned to have higher transparency. Several materials may form a layered structure. From these, it can be selected according to the properties required for the temperature and time indicator, such as high strength, heat resistance, weather resistance, chemical resistance, heat insulation, electrical conductivity, and resistance to thermal shock due to rapid cooling.

The size of the transparent substrate is not limited as long as the temperature and time detector can be visually recognized. From the viewpoint of visibility, it is preferable that the short axis is 30 μm or more when the transparent base material is rectangular and the short axis is 30 μm or more when the transparent base material is elliptical.

The temperature indicator may comprise other material between the transparent substrate and the temperature sensing material or on top of the transparent substrate to the extent that the temperature sensing material is visible. For example, printing information printed on the printing paper can be displayed by providing the printing paper between the transparent substrate and the temperature sensing material. The transparent base material and the base material may be subjected to processing such as perforation. By punching the holes, the printing paper between the transparent substrate and the spacer is exposed. By adopting such a structure, information can be written on the printed paper that has been exposed during transportation or the like.

The temperature indicator may also include an insulating layer between the transparent substrate and the temperature sensitive material. Examples of heat insulating layers include air layers, gas layers such as argon and nitrogen, vacuum layers, porous materials such as sponge and airgel, fiber materials such as glass wool, rock wool, and cellulose fibers, and materials such as urethane, polystyrene, and foam rubber. Foamed materials can be used. By arranging the heat insulating layer, it is possible to adjust the time from when the temperature outside the temperature sensing material deviates from the control temperature (after reaching the sensing temperature of the temperature sensing material) until the temperature sensing material changes color. Also, this time can be adjusted depending on the material and thickness of the substrate and the transparent substrate. Alternatively, either the base material or the transparent base material may be made of a heat insulating material instead of installing the heat insulating layer. As described above, by providing a heat insulating layer and adjusting the material and thickness of the substrate and the transparent substrate, the thermal conductivity from the substrate to the temperature sensing material and the thermal conductivity from the transparent substrate to the temperature sensing material It becomes possible to control the thermal conductivity.

When the base material 5 is used as a sticker and attached to an object, it is assumed that the temperature of the outside air and the temperature of the surface of the object are different. When it is desired to detect the temperature of the surface of the object, the thermal conductivity from the substrate to the temperature sensing material should be improved, and the thermal conductivity from the transparent substrate to the temperature sensing material should be decreased. For example, a heat insulating layer may be provided on top of the temperature sensing material, or the material and thickness of the transparent substrate and the substrate may be adjusted to make the thermal conductivity of the substrate higher than that of the transparent substrate. On the other hand, when it is desired to detect the temperature of the outside air, the thermal conductivity from the base material to the temperature detection material should be decreased, and the thermal conductivity from the transparent base material to the temperature detection material should be increased. For example, a heat insulating layer may be provided under the temperature sensing material, or the material and thickness of the transparent base material and the base material may be adjusted so that the thermal conductivity of the transparent base material is higher than that of the base material.

A plurality of types of temperature sensing materials may be used for the temperature indicator. FIG. 6 shows a temperature indicator using three types of temperature sensing materials. The temperature indicator comprises a substrate 5 having a recess (indentation) 4 and a protective layer 6 provided on the surface of the substrate. The protective layer is, for example, a sheet film. The recesses 4 each hold a temperature sensing material.

<Color initialization process>
The temperature sensing material can be initialized (reset) by heating the temperature sensing material to a temperature equal to or higher than the melting point of the temperature indicating material and then cooling at a predetermined rate or higher. In the case of the temperature detection ink, the temperature detection ink is heated to a temperature higher than the melting point of the temperature indicating material and lower than the boiling point of the solvent.

A heating method is not particularly limited. When the ink in the ink container is heated, for example, a heater, a hot plate, or means for heating the ink container in a heated solvent or the like can be used. A laminator or the like may be used to heat the material in the temperature indicator.

The cooling method after heating is also not particularly limited. For example, means for cooling the ink container by natural cooling, a cooler, a freezer, or the like can be used. Depending on the crystallization rate of the temperature indicating material, a certain or higher cooling rate is required. Materials with a high crystallization rate require rapid cooling with a cooling device, and materials with a slow crystallization rate can preferably be cooled by natural cooling. .

It is also possible to adjust the detection time of the temperature detection material by adjusting the cooling rate of the cooling device. The temperature sensing material changes color with the accumulation of time and temperature according to the crystallization speed. Therefore, by intentionally slowing down the cooling rate, crystallization can be advanced in advance and the color can be slightly developed before use for temperature control. As a result, it is possible to shorten the detection time for the same temperature and time detection ink as compared to the case where the rapid cooling process is performed.

<Temperature Deviation Time Estimation Method and Estimation System>
A method for estimating the temperature deviation time using the temperature sensing material will be described.

In the case of the temperature detecting material using the temperature indicating material A for detecting the upper limit temperature, the color develops at a predetermined temperature (color development start temperature Ta) or higher, and the higher the temperature, the faster the color development speed. From this, it can be inferred that if the temperature sensing material has not developed color, it has only been exposed to a temperature higher than the predetermined temperature for a short period of time.

Further, in the case of the temperature detecting material using the temperature indicating material B for detecting the lower limit temperature, the color develops at a predetermined temperature (color development start temperature Ta) or lower, and the lower the temperature, the faster the color development speed. From this, it can be inferred that if the temperature sensing material has not developed color, it has only been exposed to a temperature below the predetermined temperature for a short period of time.

By storing in advance the relationship between time and color density for each temperature of the temperature sensing material, if the temperature sensing material develops color, the relationship between temperature and time at the time of temperature deviation can be calculated backward from the color density. be able to. FIG. 7 shows the relationship between color density and time of the temperature sensing material according to one embodiment. When the temperature sensing material reaches the crystallization start temperature, the color changes continuously with time as shown in FIG. When the temperature sensing material is initialized and exposed to the same temperature again, it repeats the same changes it had before initialization. Therefore, by recording the relationship between time and color density for each temperature in advance, it is possible to estimate the time that has elapsed since the temperature deviated from the color density (hereinafter referred to as temperature deviation time).

A plurality of temperature sensing materials may be combined to estimate the temperature excursion time. For example, when two upper limit temperature detection materials with a color development start temperature of 10 ° C. and an upper limit temperature detection material with a color development start temperature of 20 ° C. are used together, the upper limit temperature detection material with a color development start temperature of 10 ° C. If only the color changes, it can be identified that the object has been exposed to temperatures of 10° C. or more and less than 20° C., so the accuracy of estimating the temperature deviation time is improved.

In addition, estimation accuracy can be improved by using temperature that can be obtained from a thermometer, weather information, or the like for estimating the temperature deviation time. For example, if a temperature indicator with a maximum temperature material having a color development start temperature of 10°C is attached to an article being transported at 0°C in an ambient temperature of 20°C, if the color of the indicator changes, It can be identified that it has been exposed to 10°C to 20°C. Also in this case, the accuracy of estimating the temperature deviation time can be improved.

A system for estimating a temperature deviation time using the temperature sensing material will be described. FIG. 8 shows a block diagram of the temperature deviation time estimation system. The temperature deviation time estimation system 10 includes a reading device 11 for acquiring color information of a temperature sensing material, an input device 12, an output device 13, a communication device 14, a storage device 15, color information acquired by the reading device, temperature a processing unit 16 for estimating the time elapsed since the sensing material exceeded temperature.

The reader 11 acquires color information of the temperature sensing material. A method of reading the color information of the temperature sensing material is not particularly limited. For example, the temperature sensing material can be photographed with a camera, and the well concentration can be calculated from the gradation of the photographed image. Alternatively, light may be projected onto the temperature detection material using a laser or the like, and the color information may be calculated from the amount of reflection or absorption of the projected light. In addition to the CIE color space such as L*a*b* and L*C*h*, RGB color space, HSV color space, Munsell color space, and the like can be used as numerical information of color tone.

The storage device 15 stores the relationship between the color density for each temperature of the temperature sensing material and time. In addition, the identification information of the temperature detection material and the temperature indicator, and the color information of the temperature detection material read by the reading device may be stored.

The processing device 16 determines whether the temperature detection material deviates from the temperature based on the color information of the temperature detection material acquired by the reading device and the relationship between the color density and time for each temperature of the temperature detection material stored in the storage unit. Estimate the time that has passed since The processing device may further estimate the temperature deviation time using temperature information such as the outside air temperature acquired by the communication device or the like. Also, the temperature deviation time may be estimated using color information of a plurality of temperature sensing materials having different sensing temperatures (color development start temperatures). The estimation accuracy can be improved by using temperature information and color information of a plurality of temperature sensing materials with different sensing temperatures.

<Item management system>
Next, a quality control system using temperature indicators will be described. The quality control system includes a management device that manages the environment in which the article is placed, and a management terminal that acquires color tone information of the temperature sensing material. When acquiring the color tone information, the management terminal associates the item identification information, the time when the color tone information was acquired, and whether or not there was a color change, and transmits the information to the management device.

FIG. 9 is a diagram showing the configuration of the quality control system. Here, an example of quality control in a distribution route in which goods manufactured in a factory are transported to a store, managed by the store, and delivered to a customer will be described.

The quality control system (article management system) includes a management terminal and a management server 20 (management device) that acquire a code attached to an article (article identification information) (for example, a barcode) and color tone information of a temperature indicator. be done. The management terminal and management server 20 are communicably connected via a network NW.

A distribution route includes a factory that manufactures goods, a warehouse that stores goods, a shipping area, a transport vehicle, a transshipment site that transships goods to another transport vehicle, a transport vehicle, and a store. At each location, workers use management terminals to collect quality control data.

Quality control data is collected when goods are manufactured at a factory, stored in a warehouse, shipped at a shipping site, transported by a vehicle, and transshipped at a transshipment site. When the product is being transported by a transport vehicle, when it is received at a store, and when it is stored for sale at the store.

By checking the color tone of the temperature sensing material at each location, the worker can visually check the temperature control status of each process and the temperature load status of the article. In addition to visual confirmation by the operator, it is preferable to obtain numerical information as the color tone.

In each process such as shipping, transportation, and storage, the worker uses the management terminal to transmit quality control information such as the optical state of the article and its temperature detection ink, its image, reading place, and time to the management server 20 .

A control terminal may be used to read the optical state of the temperature sensitive material. As a result, each person involved in the distribution of goods can quantitatively manage and share each state in the distribution process of the goods to be managed by acquiring the color tone of the temperature indicating material as numerical information.

At the store, by checking the color tone of the temperature sensing material for the transported goods, it is possible to visually check the temperature control status and the temperature load status of the goods from the time of shipment from the factory to after the process such as transportation. Furthermore, by connecting to the management server 20 via a management terminal or the like, it is possible to confirm information such as quality control information up to the time of product delivery.

The management terminal determines whether the quality is maintained based on the color tone information of the temperature indicator, and displays the determination result. That is, when there is a color change, the display section displays that the goods are not suitable for distribution, and when there is no color change, the display section displays that the goods are suitable for distribution. The determination result is transmitted from the management server to the management terminal. Quality control data including the judgment result is stored in the management server as quality control information.

In this embodiment, the management terminal side processes the quality judgment as to whether or not the quality is maintained. This is to disperse the concentration of judgment processing and the like in a system that targets a large number of articles. If the processing capability of the management server 20 is high, the quality judgment may be executed on the management server side.

The management server 20 has a processing section, a storage section, an input section, an output section, and a communication section. The storage unit of the management server stores article information, temperature indicator information, distribution condition information, distribution management information, production information, quality control information, etc., which are detailed information of each article to be managed. The management server exchanges information with the management terminal.

The management server preferably stores color density-time information indicating the relationship between the color density of the temperature sensing material attached to the article and the time the article is placed in the environment in the storage unit. By storing the color density-time information in the management server, the management terminal acquires the color density time information based on the acquired article identification information from the management device, and stores the color density and the color density time information of the acquired color tone information. can be calculated based on the time spent in the environment. Further, the calculated time can be displayed on the display unit, and the article identification information and the calculated time can be associated and transmitted to the management device. Note that the calculation of the time spent in that environment may be performed on the management server side.

As an example of product information stored in the management server, the product information, which is the information of the product to be managed, includes code (product identification information), name (product name), production date, expiration date, size, price, surface Color tone, necessity of temperature control for temperature indicator, appropriate temperature, location of temperature indicator (marking location), and the like. The temperature indicator information includes a code (item identification information), appropriate temperature, judgment temperature, and the like.

To summarize the above, the quality control system (article management system) collects the color tone information of the temperature sensing material attached to the article, and manages the environment in which the article is placed based on the color tone information (for example, a management server 20), and a management terminal (which acquires article identification information attached to an article and identifies the article, and acquires color tone information of the temperature-sensing ink. The management terminal acquires the acquired color tone information. At the time of acquisition, the time at which the article identification information and the color tone information were acquired and whether or not there was a color change are associated with each other (for example, temperature reading data) and transmitted to the management device. Temperature reading data can be centrally managed.

Next, the temperature sensing material will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.

<Preparation of Temperature Sensing Material>
1 part by weight of 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (CVL manufactured by Yamada Chemical Industry Co., Ltd.) as a leuco dye, 1 part by weight of octyl gallate manufactured by Tokyo Chemical Industry Co., Ltd. as a developer, 100 parts by weight of vitamin K4 manufactured by Tokyo Kasei Kogyo Co., Ltd. was used as a decolorizing agent, and 110 parts by weight of Neowax manufactured by Yasuhara Chemical Co., Ltd. was used as a matrix material. These materials were melted and mixed at 150° C., which is higher than the melting point of the decolorant and matrix material, and solidified by natural cooling to produce a temperature sensing material having a phase-separated structure.

<DSC measurement of temperature indicating material and matrix material>
DSC measurement was performed for each of the temperature indicating material and the matrix material used above.

The temperature was measured from -40°C to 200°C at a temperature increase rate of 5°C/min. As a result, the melting point of the temperature indicating material was 120.degree. C., and the melting point of the matrix material was 60 to 105.degree. FIG. 10 shows the DSC curve of the matrix material. From this result, it was confirmed that the melting point width of the matrix material was 45°C.

<Evaluation of average particle size of temperature indicating material>
The average particle size of the temperature indicating material was evaluated for the produced temperature detecting material. The average particle size of the temperature indicating material of the temperature detecting material having a phase separation structure was evaluated using a scanning electron microscope (manufactured by Hitachi, Ltd., S4800). The cross section of the temperature sensing material was observed with a scanning electron microscope, and the particle size distribution of each particle was measured from the observed image to evaluate the median diameter. The average particle size of the temperature indicating material was 1 μm.

<Evaluation of temperature and time detection function>
The color was initialized by placing the prepared temperature sensing material in a container and allowing it to stand in an environment above the melting point of the decolorant. After the initialization, the sample was allowed to stand in an environment of 10° C., which is below the color development start temperature, and the state of color change was observed.

(Comparative example 1)
A temperature detection material was prepared in the same manner as in Example 1 except that 110 parts by weight of Mitsui Chemicals Hiwax EX4800 with a melting point width of 30 ° C. or less was used as the matrix material, and the average particle size of the temperature indicating material and the temperature time detection function were evaluated. did. Particles of the temperature indicating material could not be observed.

FIG. 11 shows the DSC curve of the matrix material. From this result, it was confirmed that the melting point of the matrix material was 120 to 130°C and the melting point width was 10°C.

(Comparative example 2)
A temperature detection material was prepared in the same manner as in Example 1 except that 110 parts by weight of Mitsui Chemicals Hi-Wax NP500, which has a higher melting point than the temperature indicating material, was used as the matrix material. evaluated. Particles of the temperature indicating material could not be observed. It was confirmed that the matrix material had a melting point of 150 to 165°C and a melting point range of 15°C.

Evaluation results of the temperature and time detection functions of Example 1 and Comparative Examples 1 and 2 will be described with reference to FIGS. FIG. 12 is a photograph showing the temperature deviation time and color density in the temperature sensing materials according to Example 1 and Comparative Example 1. FIG. 13 is a graph showing the time dependence of the color density of the temperature sensing materials according to Example 1 and Comparative Example 1. FIG. The temperature indicating material used in Example 1 and Comparative Example 1 is a material that begins to develop color by crystallization at a predetermined temperature or higher, like the temperature indicating material A described in FIGS. It was confirmed that the color of the temperature detecting material according to Example 1 changed continuously with time when placed in an environment of 10° C., as in the case of only the temperature indicating material.

On the other hand, with the temperature sensing material according to Comparative Example 1, no color change could be observed in the time expected from the temperature indicating material. In addition, it was observed that only a portion of the temperature sensing material changed color, not the entire temperature sensing material. Further, after the color change was completed, the color was initialized again at the melting point of the decolorizing agent or higher, and when observed again, it was confirmed that the color change started at different points and times. For this reason, it is difficult to estimate the elapsed time from the degree of color change in the temperature sensing material according to Comparative Example 1. This is probably because the temperature sensing material according to Comparative Example 1 is composed only of the temperature indicating material and does not form a dispersed structure. Comparative Example 1 is made of the same temperature indicating material as in Example 1, but since the melting point width of the matrix material is narrower than that in Example 1, the temperature indicating agent is uniformly dispersed in the matrix material when the phase separation structure is formed. It is thought that the structure could not be formed. Moreover, the evaluation result of the temperature and time detection function of the temperature sensing material according to Comparative Example 2 was the same as that of the temperature sensing material according to Comparative Example 1.

A temperature sensing material was prepared in the same manner as in Example 1 except that 110 parts by weight of Wako Pure Chemical paraffin (mp. 68 to 70 ° C.) was used as the matrix material, and the average particle size of the temperature indicating material, the temperature indicating material and the matrix material were measured. was measured by DSC, and the temperature-time detection function was evaluated.

The average particle size of the temperature indicating material was 1 μm. As a result of DSC measurement, it was confirmed that the matrix material had a melting point of 30 to 75°C and a melting point range of 45°C. After the initialization, the sample was allowed to stand in an environment of 10° C., which is lower than the color development start temperature, and the state of color change was observed.

A temperature sensing material was prepared in the same manner as in Example 1, except that 110 parts by weight of Sankei Sangyo's microcrystalline wax Hi-Mic-2095 was used as the matrix material. The DSC measurement and the temperature-time detection function were evaluated.

The average particle size of the temperature indicating material was 0.8 μm. As a result of DSC measurement, it was confirmed that the matrix material had a melting point of 70 to 105°C and a melting point range of 35°C. After the initialization, the sample was allowed to stand in an environment of 10° C., which is lower than the color development start temperature, and the state of color change was observed.

As described above, by using the temperature sensing material according to the present embodiment, temperature sensing material whose color density changes continuously with time under deviating temperature, and temperature deviation information and temperature deviation time estimation using the temperature sensing material can be obtained. I have confirmed that it is possible.

DESCRIPTION OF SYMBOLS 1... Temperature detection material, 2... Temperature indicating material (composition of leuco dye, developer, and decolorant), 3... Matrix material, 4... Concave portion (recess), 5... Base material (support), 6... Transparent Base material (protective layer), 7 spacer, 10 temperature deviation time estimation system, 11 reader, 12 input device, 13 output device, 14 communication device, 15 storage device, 16 processing device, 20... Management device

Claims (13)

comprising a matrix material and a temperature indicating material dispersed in the matrix material ;
The temperature indicating material contains a leuco dye, a developer, and a decolorant,
The matrix material is a non-polar material, and the half width of the endothermic peak derived from the melting point measured when the temperature is raised at a rate of 5° C./min using a differential scanning calorimeter is 30° C. or more , A temperature sensing material , wherein the melting point of the matrix material is lower than the melting point of the temperature indicating material. A temperature sensing material according to claim 1 ,
A temperature sensing material, wherein the matrix material consists only of hydrocarbons. A temperature sensing material according to claim 2 ,
A temperature sensing material, wherein the matrix material is any one of paraffin, microcrystalline wax, polyolefin, and terpene resin. A temperature sensing material according to claim 2 ,
the matrix material comprises polyolefin or paraffin;
A temperature sensing material, wherein the matrix material has a melting point of 120° C. or less. A temperature sensing material according to claim 2 ,
A temperature sensing material, wherein the matrix material is polyethylene having a molecular weight of 50,000 or less. A temperature sensing material according to claim 1 ,
A temperature sensing material, wherein the volume fraction of the temperature indicating material in the temperature sensing material is 10% or more and 50% or less. A temperature sensing ink comprising the temperature sensing material according to claim 1 and a solvent. A substrate comprising the temperature sensing material according to any one of claims 1 to 6 and a substrate, wherein the substrate is a continuous porous material, and the continuous porous material is impregnated with the temperature sensing material. A temperature indicator characterized by: A temperature indicator comprising a substrate and a temperature sensing material provided on the substrate,
A temperature indicator, wherein the temperature sensing material is the temperature sensing material according to any one of claims 1 to 6 . A temperature indicator according to claim 9 ,
A temperature indicator, further comprising a transparent substrate, wherein the substrate, the temperature sensing material, and the transparent substrate are laminated in this order. A temperature indicator according to claim 10 , wherein
A temperature indicator, wherein the base material or the transparent base material is made of a heat insulating material. A temperature indicator according to claim 10 , wherein
A temperature indicator, wherein thermal conductivity from the substrate to the temperature sensing material is different from thermal conductivity from the transparent substrate to the temperature sensing material . a management device that collects color tone information of the temperature sensing material according to any one of claims 1 to 6 attached to an article and manages the environment in which the article is placed based on the color tone information;
a management terminal that acquires article identification information attached to the article that identifies the article and that acquires color tone information of the temperature sensing material;
When the color tone information is acquired, the management terminal transmits the article identification information, the time when the color tone information is acquired, and whether or not the color of the temperature detection material has changed, in association with each other, to the management device. An article management system characterized by:

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