Temperature detection ink, method for initializing temperature detection ink, temperature indicator, and article management system
阅读说明：本技术 温度检测油墨、温度检测油墨的初始化方法、温度指示器和物品管理系统 (Temperature detection ink, method for initializing temperature detection ink, temperature indicator, and article management system ) 是由 会田航平 森俊介 荒谷康太郎 坪内繁贵 川崎昌宏 于 2018-11-16 设计创作，主要内容包括：本发明提供一种温度检测油墨,其能够利用简便的方法实现颜色的初始化,在反应温度以上时,颜色根据时间和温度的累计而发生变化。为了解决上述课题,本发明的温度检测油墨的特征在于,含有温度检测材料和溶剂,温度检测材料具有含有隐色染料、显色剂和消色剂的示温材料内包于微胶囊中的结构或者包含示温材料的相与基质材料相分离的结构,示温材料通过以规定的速度以上从熔解状态冷却至玻璃化转变温度以下在保持消色的状态下凝固,示温材料的玻璃化转变温度为－20℃以上60℃以下,示温材料的熔点为60℃以上250℃以下并且低于上述溶剂的沸点。(The invention provides a temperature detection ink, which can realize color initialization by a simple method, and when the reaction temperature is higher than the reaction temperature, the color changes according to the accumulation of time and temperature. In order to solve the above problems, a temperature detecting ink of the present invention includes a temperature detecting material and a solvent, wherein the temperature detecting material has a structure in which a temperature indicating material containing a leuco dye, a color developer and a decolorizer is encapsulated in a microcapsule or a structure in which a phase containing the temperature indicating material and a matrix material are separated from each other, the temperature indicating material is solidified while maintaining a decolorized state by being cooled from a molten state to a glass transition temperature or lower at a predetermined rate or more, the glass transition temperature of the temperature indicating material is-20 ℃ to 60 ℃ inclusive, and the melting point of the temperature indicating material is 60 ℃ to 250 ℃ inclusive and lower than the boiling point of the solvent.)
1. A temperature detecting ink, characterized in that:
comprises a temperature detection material and a solvent,
the temperature detection material has a structure in which a temperature indicating material containing a leuco dye, a color developer, and a decolorizer is encapsulated in a microcapsule or a structure in which a phase containing the temperature indicating material is separated from a matrix material,
the temperature indicating material is solidified while maintaining the decolored state by being cooled from the molten state to a glass transition temperature or lower at a predetermined rate or higher,
the glass transition temperature of the temperature indicating material is more than-20 ℃ and less than 60 ℃,
the melting point of the temperature indicating material is 60 ℃ to 250 ℃ inclusive and is lower than the boiling point of the solvent.
2. The temperature sensing ink of claim 1, wherein:
the glass transition temperature of the temperature indicating material is more than-20 ℃ and less than 25 ℃.
3. The temperature detecting ink according to claim 1 or 2, wherein:
the melting point of the temperature indicating material is 60-150 ℃.
4. The temperature detecting ink according to any one of claims 1 to 3, wherein:
the boiling point of the solvent is higher than the melting point of the temperature indicating material by more than 20 ℃.
5. A method for initializing a temperature detecting ink according to any one of claims 1 to 4, comprising:
a heating step of heating the temperature detection ink to a temperature equal to or higher than the melting point of the temperature indicating material and equal to or lower than the boiling point of the solvent; and
and a step of cooling the substrate to a temperature not higher than the glass transition temperature of the temperature indicating material at a predetermined cooling rate after the heating step.
6. The method for initializing temperature detecting ink according to claim 5, wherein:
the cooling speed or the cooling temperature is adjusted according to a detection time required for the temperature detection ink.
7. A temperature indicator, characterized by:
having a substrate and a temperature detecting ink disposed on the substrate,
the temperature detecting ink according to any one of claims 1 to 4.
8. An item management system, comprising:
a management device for collecting color tone information of the temperature detection ink according to any one of claims 1 to 4 attached to an article and managing an environment in which the article is located based on the color tone information; and
a management terminal that acquires article identification information identifying the article carried by the article and acquires color tone information of the temperature detection material,
when the management terminal acquires the color tone information, the management terminal associates the time when the article identification information and the color tone information are acquired with information on whether or not there is a color change in the temperature detection ink, and transmits the information to the management device.
9. The item management system of claim 8, wherein:
the management terminal is provided with a display part, and when the color changes, the display part displays the information that the circulation of the articles is not proper; when the color change does not exist, the display unit displays information that the article is appropriately distributed.
10. The item management system of claim 8, wherein:
in the management device, color density time information indicating a relationship between a color density of the temperature detection ink carried by the article and a time in the environment is stored in a storage unit,
the management terminal acquires the color density time information based on the acquired article identification information from the management device, calculates the time in the environment based on the color density of the acquired color tone information and the color density time information, displays the calculated time on a display unit, and transmits the article identification information to the management device in association with the calculated time.
11. The item management system of claim 8, wherein:
in the management device, color density time information indicating a relationship between a color density of the temperature detection ink carried by the article and a time in the environment is stored in a storage unit,
the management device calculates the time of the environment based on the color density of the acquired color tone information and the color density time information, associates the calculated time with the article identification information, and transmits the article identification information to the management terminal,
the management terminal displays the time calculated by the management device on a display unit.
Technical Field
The present invention relates to a temperature detection ink for checking a temperature of a temperature detection target, an initialization method for the temperature detection ink, a temperature indicator, and an article management system.
Background
Low-temperature preservation medicines such as fresh foods, frozen foods, vaccines, and biological medicines require a cold chain system that maintains a low temperature continuously during distribution in production, transportation, and consumption. In practice, in order to constantly measure and record the temperature during circulation, a data recorder capable of continuously recording the time and temperature is generally mounted in a transport container, and if a product is damaged, the responsibility thereof can be found.
In the case of managing the quality of individual articles, there is a method of using a temperature indicator without using a data recorder. The temperature indicator does not have recording accuracy as in a data recorder, but can be attached to a single product, and since the surface is colored when the temperature is higher or lower than a predetermined temperature, the change in the temperature environment can be detected.
However, the temperature indicator has a problem that it is necessary to perform temperature control during storage and transportation of the temperature indicator before product management, and the temperature indicator cannot be reused. When a temperature indicator is attached to a single product, there is a need for forgery prevention in the management of expensive products such as pharmaceuticals, and complete irreversibility is required for indicators that are out of temperature. However, in the management of inexpensive products such as fresh foods, it is sufficient from the viewpoint of cost that the products are irreversible at ambient temperature or lower, and the reuse of the temperature indicator, the transportation at normal temperature, and the storage at normal temperature are required rather than the complete irreversibility. Therefore, a temperature indicator capable of achieving color initialization by a somewhat simple method is demanded.
In the case of managing products whose quality deteriorates with temperature and Time, such as fresh foods and biological medicines, a Time-temperature indicator (TTI) in which a color changes according to the accumulation of Time and temperature is used. Examples of such a temperature indicator include an indicator in which ink, the viscosity of which changes due to temperature, permeates into a permeable material and changes its color. However, in the case of such a temperature indicator, since the function as a temperature indicator cannot be realized by using ink alone, there is a problem that the structure of the temperature indicator is complicated and it is difficult to realize a low price. And cannot be reused, i.e. color initialization cannot be achieved.
As a temperature detection ink capable of realizing color initialization, patent document 1 discloses a reversible thermal discoloration microcapsule pigment containing a reversible thermal discoloration composition exhibiting the following discoloration behavior: the color developing state is maintained by cooling after the color developing state is changed from the decolored state to the color developing state by heating at a relatively low temperature, and the color developing state can be restored again through the decolored state by heating.
Patent document 2 discloses a temperature indicating material that is irreversible at ambient temperature and changes color by a crystal-amorphous transition or a phase separation state-non-phase separation state change.
Disclosure of Invention
Problems to be solved by the invention
The reversible heat color developable microcapsule pigment disclosed in patent document 1 does not take into consideration the color change caused by the accumulation of time and temperature. In addition, the reversible thermal discoloration microcapsule pigment disclosed in patent document 1 exhibits the following discoloration behavior: the color developing state is maintained by cooling after the color developing state is changed from the decolored state to the color developing state by heating, and the color developing state can be restored again through the decolored state by heating. This reversible thermochromatic microcapsule pigment utilizes the following principle: when the electron-donating color-developing organic compound, the electron-accepting compound and the reaction medium are compatible, the electron-donating color-developing organic compound and the electron-accepting compound are combined to develop color; when the electron accepting compound is incompatible with the reaction medium, the electron donating color developing organic compound is not bonded to the electron accepting compound, and the color is reduced.
Patent document 1 discloses that the decolored state is changed to the developed state by heating at a relatively low temperature, but a temperature detection material capable of detecting a temperature at a further low temperature and initializing a color by a simple method is desired for a cold chain system of foods, pharmaceuticals, and the like.
The temperature indicating material disclosed in patent document 2 utilizes a crystal-amorphous transition or a change in a phase separation state-non-phase separation state, and therefore, the state changes from a solid to a liquid and from a liquid to a solid with temperature. Therefore, it is difficult to produce an ink using other materials such as a solvent and a resin.
Accordingly, an object of the present invention is to provide a temperature detecting ink which can initialize a color by a simple method and in which the color changes with time and temperature accumulation at a reaction temperature or higher.
Means for solving the problems
In order to solve the above problems, a temperature detecting ink according to the present invention includes a temperature detecting material and a solvent, the temperature detecting material having a structure in which a temperature indicating material containing a leuco dye, a color developer and a decolorizer is encapsulated in a microcapsule or a structure in which a phase containing the temperature indicating material and a matrix material are separated from each other, the temperature indicating material being solidified while maintaining a decolorized state by being cooled from a molten state to a glass transition temperature or less at a predetermined rate or more, the glass transition temperature of the temperature indicating material being-20 ℃ to 60 ℃ inclusive, and the melting point of the temperature indicating material being 60 ℃ to 250 ℃ inclusive and lower than the boiling point of the solvent. Other embodiments of the present invention will be described in the following embodiments.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there is provided a temperature detection ink which can initialize a color by a simple method and in which the color changes in accordance with the accumulation of time and temperature at or above a reaction temperature.
Drawings
Fig. 1 is a schematic view of a temperature detection ink according to an embodiment of the present invention.
FIG. 2 is a differential scanning calorimetry curve of a temperature indicating material.
Fig. 3 is a graph showing a change in color density of the temperature indicating material of fig. 2.
Fig. 4 is a schematic view showing a phase separation structure of the temperature detection material.
Fig. 5 is an optical microscope photograph of the temperature detection material.
Fig. 6 is a schematic diagram showing a first example of the structure of the temperature indicator.
Fig. 7 is a schematic diagram showing a second example of the structure of the temperature indicator.
Fig. 8 is a schematic diagram showing a third example of the structure of the temperature indicator.
Fig. 9 is a configuration diagram of an article management system.
Fig. 10 is a diagram showing a configuration of the management server.
Fig. 11 is a schematic diagram showing a configuration of a temperature indicator according to an embodiment.
Detailed Description
In view of the above problems, the present inventors have focused on a material in which when a leuco dye as an electron donating compound, a color developer as an electron accepting compound, and a decolorizer for controlling the reaction between the electron donating compound and the electron accepting compound are compatible with each other, the leuco dye and the color developer are separated from each other and decolorized, and when the color developer and the decolorizer are in a non-compatible state due to crystallization, the leuco dye and the color developer are compatible with each other and develop color. Since this material (hereinafter referred to as a temperature indicating material) develops color by crystallization, the color can be changed by controlling the temperature and time at which crystallization occurs, and by integrating the time and temperature. Further, since the temperature indicating material is decolored by melting, it has irreversibility at a temperature not higher than the melting temperature, and color initialization can be performed depending on the temperature at which melting occurs.
Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the accompanying drawings as appropriate. In the drawings, the same reference numerals are given to the common portions, and redundant description is omitted. .
< ink for temperature detection >
The temperature detection ink contains a temperature detection material and a solvent. Fig. 1 is a schematic view of a temperature detection ink according to an embodiment of the present invention. The temperature detection ink 1 is in a form in which the temperature detection material 2 is dispersed in the solvent 3. By forming the temperature detecting ink, the temperature detecting material can be used as ink for pens, stamps, crayons, inkjet, and the like, or paint for printing.
As will be described in detail later, by using a temperature detecting material having a structure in which a temperature indicating material containing a leuco dye, a developer and a decolorizer is encapsulated in microcapsules or a structure in which a phase composed of a temperature indicating material containing a leuco dye, a developer and a decolorizer is separated from a matrix material, even if the state of the temperature indicating material changes from a solid to a liquid or from a liquid to a solid due to temperature detection, the temperature indicating material can be separated from other materials constituting the ink.
In the temperature detection ink, an additive may be further added to a solution such as an organic solvent or water to such an extent that the temperature detection function is not affected. By varying the amounts of the temperature sensing material and the additives, the viscosity can also be adjusted. Thus, the ink composition is suitable for use as an ink for various printing apparatuses such as offset printing, gravure printing, flexographic printing, label printers, and thermal printers.
[ temperature-detecting Material ]
The temperature detection material has a structure in which the temperature indicating material is encapsulated in a microcapsule or a structure in which a phase made of the temperature indicating material is separated from a matrix material. In the present specification, a state in which the temperature indicating material is protected so that the temperature indicating material is not dissolved in the solvent of the ink is referred to as a temperature detecting material.
(temperature indicating Material)
As the temperature indicating material, a material is used in which the color density reversibly changes due to a temperature change (temperature increase/decrease) and the material solidifies in a state of being kept decolored by cooling from a molten state to a glass transition temperature or lower at a predetermined rate or higher. The temperature indicating material contains a leuco dye as an electron donating compound, a color developer as an electron accepting compound, and a decolorizer for controlling a color developing temperature.
Fig. 2 shows a Differential Scanning Calorimetry (DSC) curve of a temperature indicating material according to an embodiment of the present invention. In the temperature decreasing process (left arrow (←) in the figure), crystallization did not occur, and therefore, no exothermic peak due to crystallization was observed. On the other hand, in the temperature rising process (rightward arrow of the figure (→)), an exothermic peak (crystallization peak) due to crystallization was observed. T isaIs the crystallization initiation temperature in the course of temperature rise, TgIs the glass transition temperature, TdIs the melting point.
Fig. 3 is a graph showing a change in color density of the temperature indicating material of fig. 2. In fig. 3, the vertical axis represents color density, and the horizontal axis represents temperature. As can be seen from fig. 3, the color density change of the temperature indicating material has a hysteresis characteristic. The temperature indicating material reaches the crystallization starting temperature TaWhen the color is changed from the decolored state to the developed state. When the temperature is raised while maintaining the color development, the melting point T is setdThe color erasing is started. The melted material is cooled at a predetermined rate or more to a glass transition temperature or less, and solidified while maintaining the decolored state. As can be seen from fig. 2, the temperature indicating material is solidified while remaining amorphous.
Crystallization initiation temperature TaDepending on the rate of temperature rise and the elapsed time. When the temperature is raised at a low speed, the initial temperature is low, and when the temperature is raised at a high speed, the initial temperature is high, or the initial temperature is not high but is at the melting point TdAnd (4) melting. Since color is developed when crystallization occurs, the crystallization start temperature T is set according to the requirements of the detection temperature and the detection timeaAnd (4) finishing. For example, if the material is a temperature indicating material which starts to crystallize after 1 hour at a certain temperature, the temperature may be used as a starting temperature and the material which detects 1 hour at the starting temperature may be used.
In addition, below the glass transition temperature, crystallization does not start. In the case of a material which is easily crystallized, crystallization is easily caused when the material reaches a temperature equal to or higher than the glass transition temperature, and therefore, the onset temperature and the glass transition temperature are often the same temperature. When a material which is difficult to crystallize is used as a decolorizer for a temperature indicating material, the temperature is set at a temperature T from the decolorization temperaturedThe above molten state P is rapidly cooled to the color development temperature TaIn the following case, the decolorizer is mixed with the developer, and is in an amorphous state, and the decolorized state is maintained. From this state, the temperature rises to the color development temperature TaIn the above case, the decolorizer is crystallized and develops color.
In the case of using a temperature indicating material that reversibly changes color due to a temperature change, even if the temperature temporarily rises and the color of the temperature indicating material changes, the color is restored by lowering or raising the temperature again, and it is impossible to know whether or not there is a change in temperature. However, in the case of a material having a hysteresis characteristic in color density change, it is sufficient if it is not heated to the decoloring temperature TdIn the above molten state, the color does not return, and thus the change in the temperature environment can be recognizedAnd (4) transforming.
The glass transition temperature of the temperature indicating material is-20 ℃ to 60 ℃, preferably-20 ℃ to 25 ℃, and more preferably-20 ℃ to 15 ℃. By setting the glass transition temperature to-20 ℃ or higher and 25 ℃ or lower, the temperature control state of low-temperature control products such as fresh foods, frozen foods, vaccines, and biological medicines can be detected.
The melting point of the temperature indicating material is 60 ℃ to 250 ℃ and lower than the boiling point of the solvent. In order to confirm the temperature history and prevent initialization in the vicinity of a desired temperature (upper limit of the control temperature), it is necessary that the color initialization temperature is a temperature deviated from the desired temperature. On the other hand, from the viewpoint of easy initialization, a temperature range in which heating can be performed by a general-purpose device is preferable. Therefore, the melting point of the temperature indicating material is 60 ℃ to 250 ℃, preferably 60 ℃ to 150 ℃.
As described above, by using the temperature indicating material according to the present embodiment, it is possible to provide a temperature detecting material in which the color changes according to the accumulation of time and temperature and the color can be initialized by heating at a high temperature.
The leuco dye, developer, and decolorizer of the temperature indicating material will be described below.
Leuco dyes are electron-donating compounds, and compounds known as dyes for pressure-sensitive copying papers or dyes for thermal recording papers can be used. Examples thereof include triphenylmethane phthalide type, fluorane type, phenothiazine type, indolylphthalein type, Leucoauramine (Leucoauramine) type, spiropyrane type, rhodamine lactam type, triphenylmethane type, triazene type, spirodihydroisobenzofuran xanthene type, naphtholactam type, azomethine type, and the like. Specific examples of leuco dyes include 9- (N-ethyl-N-isopentylamino) spiro [ benzo [ a ] xanthene-12, 3 '-phthalide ], 2-methyl-6- (N-p-tolyl-N-ethylamino) -fluoran 6- (diethylamino) -2- [ (3-trifluoromethyl) anilino ] xanthene-9-spiro-3' -phthalide, 3-bis (p-diethylaminophenyl) -6-dimethylaminobenzoide, 2 '-anilino-6' - (dibutylamino) -3 '-methylspiro [ phthalide-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-dihydrospiro [ 11H-chromeno [2, 3-g ] quinoline-11, 3' -phthalide ].
The temperature indicating material may use more than 2 kinds of leuco dyes in combination.
The color-developing agent is a substance that develops color by contacting an electron-donating leuco dye to change the structure of the leuco dye. As the developer, those known as developers used for thermal recording paper, pressure-sensitive copying paper, and the like can be used. Specific examples of such a developer include phenols such as benzyl 4-hydroxybenzoate, 2' -biphenol, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bisphenol a, bisphenol F, bis (4-hydroxyphenyl) sulfide, p-hydroxybenzoate, and gallate. The color-developer is not limited to these, and any compound may be used as long as it is an electron acceptor and can change the color of the leuco dye. Further, metal salts of carboxylic acid derivatives, salicylic acid and metal salts of salicylic acid, sulfonic acids, sulfonic acid salts, phosphoric acids, metal phosphate salts, acidic phosphoric acid esters, metal acidic phosphoric acid esters, phosphorous acids, metal phosphorous acid salts, and the like can be used. Particularly, an organic color developer such as benzyl 4-hydroxybenzoate, 2' -biphenol, bisphenol a, or gallic acid ester is preferable as a compound having high compatibility with the leuco dye and a decolorizer described later.
The temperature indicating material may contain 2 or more of these color developers. The color density of the leuco dye can be adjusted by combining a plurality of color developing agents. The amount of the color developer to be used is selected according to the desired color density. For example, it is usually selected from the range of about 0.1 to 100 parts by mass relative to 1 part by mass of the leuco dye.
The decolorizer is a compound capable of dissociating the binding between the leuco dye and the color developer, and is a compound capable of controlling the color development temperature of the leuco dye and the color developer. Generally, the decolorizer is cured in a phase-separated state in a temperature range in which the leuco dye is in a colored state. In addition, the decolorizer melts in a temperature range in which the leuco dye is in a decolorized state, and the leuco dye and the developer can be bound and dissociated. Therefore, the state change temperature of the decolorizer is important for temperature control of the temperature indicating material.
As the material of the decolorizer, a material capable of dissociating the binding between the leuco dye and the developer can be used. Various materials may be used as the decolorizer as long as the polarity is low, the color former does not exhibit color developability with respect to the leuco dye, and the polarity is high enough to dissolve the leuco dye and the developer.
Typically, various organic compounds such as a hydroxyl compound, an ester compound, a peroxide, a carbonyl compound, an aromatic compound, an aliphatic compound, a halogen-containing compound, an amino compound, an imino compound, an N-oxide compound, a hydroxylamine compound, a nitro compound, an azo compound, a diazo compound, an azide compound, an ether compound, an oil or fat compound, a sugar compound, a peptide compound, a nucleic acid compound, a alkaloid compound, and a steroid compound can be used. Specifically, there may be mentioned: glycerol tricarbamate, isopropyl myristate, m-toluate, diethyl sebacate, dimethyl adipate, 1, 4-diacetoxybutane, decyl decanoate, diethyl phenylmalonate, diisobutyl phthalate, triethyl citrate, benzylbutyl phthalate, butyl phthalyl butyl glycolate, methyl N-methylanthranilate, ethyl anthranilate, 2-hydroxyethyl salicylate, methyl nicotinate, butyl 4-aminobenzoate, methyl p-methylbenzoate, ethyl 4-nitrobenzoate, 2-phenylethylphenylacetate, benzyl cinnamate, methyl acetoacetate, geranyl acetate, dimethyl succinate, dimethyl sebacate, diethyl oxaloacetate, glycerol monooleate, butyl palmitate, ethyl stearate, methyl palmitate, methyl stearate, linalyl acetate, Di-n-octyl phthalate, benzyl benzoate, diethylene glycol dibenzoate, methyl p-anisate, m-toluate, cinnamyl cinnamate, 2-phenylethyl propionate, butyl stearate, ethyl myristate, methyl anthranilate, neryl acetate, isopropyl palmitate, ethyl 4-fluorobenzoate, cyclandelate (isomer mixture), delphine, ethyl 2-bromopropionate, glyceryl tricaprylate, ethyl levulinate, cetyl palmitate, t-butyl acetate, 1-ethylene glycol diacetate, dimethyl oxalate, glyceryl tristearate, glyceryl trimyristate, methyl acetylsalicylate, benzylidene diacetate, methyl 2-benzoylbenzoate, ethyl 2, 3-dibromobutyrate, ethyl 2-furancarboxylate, ethyl acetylacetonate, methyl n-butyl acetate, ethyl p-toluate, m-toluyl acetate, cinnamyl acetate, n-butyl acetate, ethyl vanillate, dimethyl itaconate, methyl 3-bromobenzoate, monoethyl adipate, dimethyl adipate, 1, 4-diacetoxybutane, diethylene glycol diacetate, ethyl palmitate, diethyl terephthalate, phenyl propionate, phenyl stearate, 1-naphthyl acetate, methyl behenate, methyl arachinate, methyl 4-chlorobenzoate, methyl sorbate, ethyl isonicotinate, dimethyl dodecanoate, methyl heptadecanoate, ethyl alpha-cyanocinnamate, ethyl N-phenylglycinate, diethyl itaconate, methyl picolinate, methyl isonicotinate, methyl DL-mandelate, methyl 3-aminobenzoate, methyl 4-methylsalicylate, diethyl phenylmethylmalonate, isoamyl DL-mandelate, triethyl methanetricarboxylate, diethyl formylaminomalonate, 1, 2-bis (chloroacetoxy) ethane, ethyl 1, 4-diacetoxybutane, diethyl palmitate, diethylene glycol diacetate, ethyl palmitate, diethyl N-phenylglycinate, diethyl methanesulphonate, diethyl methylaminomalonate, ethyl N-phenylglycinate, ethyl N-methyl N-phenylglycinate, Pentadecanoic acid methyl ester, arachidic acid ethyl ester, 6-bromohexanoic acid ethyl ester, pimelic acid monoethyl ester, cetyl lactate, diphenylglycolic acid ethyl ester, Mefenpyr-diethyl ester, procaine, dicyclohexyl phthalate, salicylic acid-4-tert-butyl phenyl ester, 4-isobutyl aminobenzoate, butyl 4-hydroxybenzoate, glycerol tripalmitate, 1, 2-diacetoxybenzene, dimethyl isophthalate, fumaric acid monoethyl ester, vanillic acid methyl ester, 3-amino-2-thiophenecarboxylic acid methyl ester, etomidate (etomidate), cloquintocet-mexyl, diphenylglycolic acid methyl ester, diphenyl phthalate, phenyl benzoate, 4-propyl 4-benzoate, ethylene glycol dibenzoate, glycerol triacetate, ethyl pentafluoropropionate, 3-methyl nitrobenzoate, 4-nitro-phenyl acetate, Methyl 3-hydroxy-2-naphthoate, trimethyl citrate, ethyl 3-hydroxybenzoate, methyl 3-hydroxybenzoate, trimebutine (trimebutine), 4-methoxybenzyl acetate, pentaerythritol tetraacetate, methyl 4-bromobenzoate, ethyl 1-naphthylacetate, 5-nitro-2-furfural diacetate, ethyl 4-aminobenzoate, propyl p-hydroxybenzoate, 1,2, 4-triacetoxybenzene, methyl 4-nitrobenzoate, diethyl acetamidomalonate, pentazamide (valthamobromide), 2-naphthyl benzoate, dimethyl fumarate, alfenine hydrochloride (anilide hydrochloride), benzyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, vinyl butyrate, vitamin K4, methyl 4-iodobenzoate, methyl 3, 3-dimethacrylate, propyl gallate, 1, 4-diacetoxybenzoate, methyl 3, 3-dimethoxybenzoate, 1, 4-diacetoxybenzoate, trimethoprim (trimetkinine), trimethoprim (trimethobenzamide), and the like, Diethyl mesooxalate, dimethyl 1, 4-cyclohexanedicarboxylate (cis, trans mixture), triethyl 1,1, 2-ethaneditricarboxylate, 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 fumarate, diethyl maleate, diethyl malonate, diethyl phthalate, dimethyl 1, 3-acetonate, dimethyl phthalate, ethyl 3-aminobenzoate, ethyl benzoate, ethyl 4- (dimethylamino) benzoate, ethyl nicotinate, ethyl phenylpropionate, ethyl pyridine-2-carboxylate, ethyl 2-pyridylacetate, ethyl 3-pyridylacetate, Methyl benzoate, ethyl phenylacetate, pentyl 4-hydroxybenzoate, ethyl 2, 5-diacetoxytoluene, ethyl 4-oxazolecarboxylate, trimethyl 1,3, 5-cyclohexanetricarboxylate (cis, trans mixture), methyl 3- (chlorosulfonyl) -2-thiophenecarboxylate, pentaerythritol distearate, benzyl laurate, diethyl acetylenedicarboxylate, phenyl methacrylate, benzyl acetate, dimethyl glutarate, ethyl 2-oxocyclohexanecarboxylate, ethyl phenylcyanoacetate, ethyl 1-piperazinecarboxylate, methyl benzoylformate, methyl phenylacetate, phenyl acetate, diethyl succinate, glycerol tributyrate, diethyl methylmalonate, dimethyl oxalate, diethyl 1, 1-cyclopropanedicarboxylate, dibenzylmalonate, methyl 4-tert-butylbenzoate, ethyl 2-oxocyclopentanecarboxylate, methyl cyclohexanecarboxylate, Ethyl 4-methoxyphenylacetate, methyl 4-fluorobenzoylacetate, dimethyl maleate, methyl p-formylbenzoate, ethyl 4-bromobenzoate, methyl 2-iodobenzoate, ethyl 3-furancarboxylate, diallyl phthalate, benzyl bromoacetate, dimethyl bromomalonate, methyl m-methylbenzoate, diethyl 1, 3-acetonate, methyl phenylpropionate, 1-naphthyl butyrate, ethyl o-methylbenzoate, methyl 2-oxocyclopentanoate, isobutyl benzoate, ethyl 3-phenylpropionate, di-tert-butyl malonate, dibutyl sebacate, diethyl adipate, diethyl terephthalate, dipropyl phthalate, 1-ethylene glycol diacetate, diisopropyl adipate, diisopropyl fumarate, ethyl cinnamate, ethyl acrylate, diisopropyl adipate, diethyl fumarate, diethyl phthalate, dimethyl benzoate, diethyl phthalate, diisopropyl 1, 1-ethylene glycol diacetate, diisopropyl adipate, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate, neopentyl glycol diacrylate, glycerol trioleate, ethyl benzoylacetate, ethyl p-anisate, diethyl suberate, sorbitan tristearate, sorbitan monostearate, stearamide, glycerol monostearate, glycerol distearate, 3- (tert-butoxycarbonyl) phenylboronic acid, racecadotril (racecadotril), 4- [ (6-acryloyloxy) hexyloxy ] -4 '-cyanobiphenyl, 2- (dimethylamino) vinyl-3-pyridinone, stearyl acrylate, ethyl 4-bromophenylacetate, dibenzyl phthalate, methyl 3, 5-dimethoxybenzoate, eugenol acetate, 3' -didodecyl thiodipropionate, vanillin acetate, diphenyl carbonate, ethyl anilinecarbonate (ethyl oxanilate), Methyl p-formylbenzoate, dimethyl 4-nitrophthalate, ethyl (4-nitrobenzoyl) acetate, dimethyl nitroterephthalate, methyl 2-methoxy-5- (methylsulfonyl) benzoate, methyl 3-methyl-4-nitrobenzoate, dimethyl 2, 3-naphthalenedicarboxylate, bis (2-ethylhexyl) adipate, 4 '-acetoxyacetophenone, ethyl trans-3-benzoylacrylate, ethyl coumarin-3-carboxylate, BAPTA tetraethyl, methyl 2, 6-dimethoxybenzoate, di-tert-butyl iminodicarboxylate, benzyl p-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-dipropoyloxybenzene, 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 '-diacetoxybiphenyl, dimethyl 5-aminoisophthalate, diethyl 1, 4-dihydro-2, 6-dimethyl-3, 5-pyridinedicarboxylate, dimethyl 4, 4' -biphenyldicarboxylate, caprylic-4-benzyloxyphenylethyl ester, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, 4-benzyloxyphenylethyl dodecanoate, Ester compounds such as tridecanoic acid-4-benzyloxyphenylethyl ester, tetradecanoic acid-4-benzyloxyphenylethyl ester, pentadecanoic acid-4-benzyloxyphenylethyl ester, hexadecanoic acid-4-benzyloxyphenylethyl ester, heptadecanoic acid-4-benzyloxyphenylethyl ester, octadecanoic acid-4-benzyloxyphenylethyl ester, octanoic acid-1, 1-diphenylmethyl ester, nonanoic acid-1, 1-diphenylmethyl ester, decanoic acid-1, 1-diphenylmethyl ester, undecanoic acid-1, 1-diphenylmethyl ester, dodecanoic acid-1, 1-diphenylmethyl ester, tridecanoic acid-1, 1-diphenylmethyl ester, tetradecanoic acid-1, 1-diphenylmethyl ester, pentadecanoic acid-1, 1-diphenylmethyl ester, hexadecanoic acid-1, 1-diphenylmethyl ester, heptadecanoic acid-1, 1-diphenylmethyl ester, octadecanoic acid-1, 1-diphenylmethyl ester; or cholesterol, cholesterol bromide, beta-estradiol, methylandrostenediol, pregnenolone, cholesteryl benzoate, cholesteryl acetate, cholesteryl linoleate, cholesteryl palmitate, cholesteryl stearate, cholesteryl n-caprylate, cholesteryl oleate, 3-chlorocholestene, cholesteryl trans-cinnamate, cholesteryl decanoate, cholesteryl hydrocinnamate, cholesteryl laurate, cholesteryl butyrate, cholesteryl formate, cholesteryl heptanoate, cholesteryl hexanoate, cholesteryl succinate, cholesteryl myristate, cholesteryl propionate, cholesteryl valerate, cholesteryl phthalate, cholesteryl phenylacetate, cholesteryl chloroformate, cholesteryl 2, 4-dichlorobenzoate, cholesteryl nonanoate, cholesteryl nonyl carbonate, cholesteryl heptyl carbonate, cholesteryl 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) -dehydro-nolone (dehydronandrolone), estrone, ethinyl estradiol, estriol, estradiol benzoate, beta-estradiol-17-cypionate, 17-valeric acid-beta-estradiol ester, alpha-estradiol, 17-heptanoic acid-beta-estradiol ester, pregnenolone, mestranol (mestranol), 2-methoxy-beta-estradiol, nanolone, (-) -methyl norethindrone, estradiol ether (quinestrol), trenbolone (trenbolone), tibolone (tibolone), androsterone (sinolone), androsterone, abiraterone (androsterone), androsterone (androsterone), epiandrosterone acetate, epihydrindolone acetate, dehydro (dehydro-lactone), androsterone (testosterone), estrerone (mestranesterone), Ethisterone, epiandrosterone, 17 beta-hydroxy-17-methylandrost-1, 4-dien-3-one, methylandrostenediol, methyltestosterone, delta 9(11) -methyltestosterone, 1 alpha-methylandrostan-17 beta-ol-3-one, 17 alpha-methylandrostan-17 beta-ol-3-one, stanozolol (stanozolol), testosterone propionate, altrenogest, 16-dehydropregnenolone acetate, 16, 17-epoxypregnenolone acetate, 11 alpha-hydroxyprogesterone, 17 alpha-hydroxyprogesterone hexanoate, 17 alpha-hydroxyprogesterone, pregnenolone acetate, 17 alpha-hydroxyprogesterone acetate, megestrol acetate, medroxyprogesterone acetate, pregnenolone acetate, 5 beta-pregnane-3 alpha, 20 alpha-diol, budesonide, cortisone acetate, cortisone, deoxycortisol, corticosterone acetate, and deflazacort (desogestrel) And steroids such as hydrocortisone acetate, hydrocortisone 17-butyrate, 6 α -methylprednisolone, prednisolone, prednisone, prednisolone acetate, sodium deoxycholate, sodium cholate, methyl hyodeoxycholate, β -cholestanol, cholesterol-5 α,6 α -epoxide, diosgenin, ergosterol, β -sitosterol, stigmasterol, and β -sitosterol acetate. These compounds are preferably contained from the viewpoint of compatibility with the leuco dye and the color developer. Of course, the leuco dye and the color developer may be bonded to each other by any material, without being limited to these compounds.
The temperature indicating material may contain 2 or more of these decolorizers. The combination of 2 or more decolorizers can adjust the solidification point, crystallization rate, and melting point.
As a decolorizer used for a temperature indicating material for temperature detection, it is necessary that the decolorizer is not crystallized in the process of rapid cooling from the temperature at which the decolorizer melts, but is amorphized in the vicinity of the glass transition temperature. Therefore, a material which is not easily crystallized is preferable. If the quenching rate is made extremely high, most of the material will be in an amorphous state, but in view of practical use, it is preferable that the material is not easily crystallized to such an extent that the material is in an amorphous state during quenching by a general-purpose cooling device. Further, it is preferable that the material is not easily crystallized to such an extent that the material is formed into an amorphous state in the course of natural cooling from a molten state of not less than the melting point. As the conditions, it is preferable that the decolorizer forms an amorphous state when cooled from the melting point to the glass transition temperature at a rate of 1 ℃/min or more, and it is more preferable that the decolorizer forms an amorphous state when cooled from the melting point to the glass transition temperature at a rate of 20 ℃/min or more.
In order to initialize the color, the temperature needs to be raised to a temperature higher than the melting point of the decolorizer of the temperature indicating material. The color initialization temperature needs to be high enough to be difficult to occur near the control temperature, and in consideration of practicality, it is desirable to be a temperature range in which heating can be performed by a general-purpose heating device. In addition, since microcapsules or a matrix material are used as a temperature detection material for protecting the temperature indicating material, it is necessary to consider heat resistance of the materials. Specifically, the color initialization temperature is preferably about 60 to 250 ℃, and more preferably about 60 to 150 ℃.
(microcapsules)
The structure in which the temperature indicating material is encapsulated in the microcapsule will be described.
Examples of the resin coating film used for the microcapsules include: a urea resin coating film formed of a polyamine and a carbonyl compound; a melamine resin coating film formed from a melamine/formalin prepolymer, a methylolmelamine prepolymer, and a methylated melamine prepolymer; a polyurethane resin coating film formed from a polyisocyanate and a polyol compound; an amide resin coating film formed of a polybasic acid chloride and a polybasic amine; a vinyl resin coating film formed from various monomers such as vinyl acetate, styrene, (meth) acrylate, acrylonitrile, and vinyl chloride, but is not limited thereto. In addition, the following additional processing can be performed: the formed resin coating is subjected to surface treatment to adjust the surface energy in the case of forming an ink or a paint, thereby improving the dispersion stability of the microcapsules.
The diameter of the microcapsule is preferably in the range of about 0.1 to 100 μm, more preferably 0.1 to 10 μm, from the viewpoint of device suitability, storage stability, and the like.
Microencapsulation can be carried out by various known methods. Examples thereof include, but are not limited to, emulsion polymerization, suspension polymerization, coacervation, interfacial polymerization, and spray drying. In addition, 2 or more different methods may be combined.
Microencapsulation improves the environmental resistance of the temperature indicating material to light, humidity, and the like, and can stabilize the storage stability and discoloration characteristics. Moreover, microencapsulation can prevent the leuco dye, the developer, and the decolorizer from being affected by compounds derived from other resin agents, additives, and the like when the ink is prepared.
(phase separation Structure)
A structure in which a phase composed of a temperature indicating material is phase-separated from a matrix material (hereinafter referred to as a phase-separated structure) will be described. The phase-separated structure can be stabilized in storage stability and discoloration characteristics in the same manner as microcapsules by a simpler method than microencapsulation. Further, in the preparation of the ink, the leuco dye, the developer, and the decolorizer can be prevented from being affected by compounds derived from other resin agents, additives, and the like.
Fig. 4 is a schematic view showing a phase separation structure of the temperature detection material. (a) The color is developed, and (b) is decolored. Fig. 5 shows an optical micrograph of the temperature detection material according to the present embodiment. (a) The color is developed, and (b) is decolored. The
The matrix material needs to be a material that does not impair the color developability or color erasing properties of the temperature indicating material when mixed with the temperature indicating material. Therefore, a material in which the matrix material itself does not exhibit color developability is preferable. Examples of such a material include nonpolar materials that are not electron acceptors.
In order to form a phase separation structure in which a temperature indicating material is dispersed in a matrix material, the matrix material is required to have: the temperature detection material is in a solid state at the use temperature; the melting point is higher than that of the temperature indicating material; the compatibility with the leuco dye, decolorizer, and developer is low.
Since the matrix material is solid at the use temperature of the temperature detection material and the melting point of the matrix material is higher than the melting point of the temperature indicating material, the temperature detection material can maintain a solid state even when the temperature indicating material changes from a solid state to a liquid state or from a liquid state to a solid state. Further, since the temperature detecting material has low compatibility with the leuco dye, the decolorizer, and the color developer, the temperature detecting function of the temperature indicating material can be maintained.
As satisfy the aboveConditioned matrix material, preferably using energy generated by intermolecular dipolar interactions predicted by Hansen (Hansen) solubility parameterspAnd energy generated by intermolecular hydrogen bondinghEach of which is 3 or less. Specifically, the material is a material having no polar group, and is composed of only hydrocarbon. More specifically, waxes such as paraffin waxes, microcrystalline waxes, olefin waxes, polypropylene waxes, and polyethylene waxes, low molecular weight materials and high molecular weight materials having a large amount of a skeleton such as propylene, ethylene, styrene, cycloolefin, siloxane, and terpene, and copolymers thereof are exemplified.
Among these, a material which is a low-viscosity melt at a melting point or higher and which is easily solidified at a melting point or lower is preferable because of its good workability. In addition, the material which is dissolved in the organic solvent and solidified in the process of volatilizing the organic solvent is also good in handling property. As the matrix material, paraffin, microcrystalline wax, polyolefin, terpene resin, and the like are particularly preferable. Examples of the polyolefin include low molecular weight polyethylene and low molecular weight polypropylene. The molecular weight of the polyolefin and the viscosity in a liquid state are not particularly limited, but when the viscosity in a liquid state is low, the inclusion of bubbles is small, and the moldability is good. Specifically, the molecular weight is preferably 5 ten thousand or less and the viscosity near the melting point is 10Pa · S or less, and more preferably 1 ten thousand or less and the viscosity near the melting point is 1Pa · S or less.
These matrix materials may be used in combination.
In addition, even a matrix material that is liquid at the use temperature can be used as the temperature detection material as long as it has a phase separation structure from the temperature indicating material and the solvent of the temperature detection ink. When the base material is a high-viscosity liquid, the handling property is excellent as in the case of a solid base material. However, when the matrix material is a high-viscosity liquid, sedimentation of the temperature indicating material in the matrix material is inevitable in long-term use, and the temperature indicating material is eventually separated into two phases. Therefore, the long-term stability as a temperature detection material is low.
The concentration of the matrix material in the matrix material is not particularly limited, and is preferably 0.1 parts by mass or more and 100 parts by mass or less based on 1 part by mass of the matrix material. When the concentration of the matrix material is 100 parts by mass or less with respect to 1 part by mass of the temperature indicating material, a decrease in visibility as a temperature detecting material can be suppressed. Further, by setting the concentration of the matrix material to be equal to or higher than the concentration of the temperature indicating material, it is possible to suppress formation of a structure in which the matrix material and the temperature indicating material are connected to each other (hereinafter referred to as a co-continuous structure). Even in the co-continuous structure, the function as the temperature detection material is not impaired by the separation of the matrix material from the temperature indicating material, but the temperature indicating material may leak from the matrix material and may impair the long-term stability. Therefore, the matrix material is preferably about 1 to 10 parts by mass relative to 1 part by mass of the temperature indicator material.
The major axis of the phase of the temperature indicating material dispersed in the matrix material is preferably 100nm to 1mm, more preferably 1 μm to 100 μm. Although the size of the phase made of the temperature indicating material is not particularly limited, the influence on the detection temperature due to the interface between the temperature indicating material and the matrix material can be suppressed by setting the phase to 100nm or more. Further, by setting the thickness to 1mm or less, it becomes difficult to distinguish the temperature-indicating material from the matrix material, and color unevenness of the temperature-detecting material can be suppressed. The size of the phase made of the temperature indicating material can be reduced by adding a surfactant or by cooling with stirring in the cooling step. The major axis of the phase made of the temperature indicating material is a major axis of an approximate ellipse when the phase made of the temperature indicating material is approximated to an ellipse.
The phase separation structure can be pulverized into powder by a mortar or the like. This enables the same operation as in the case of microcapsules.
The phase separation structure and the microcapsule may be subjected to surface treatment such as silane coupling treatment, surface grafting, corona treatment, or the like for dispersion stabilization for ink formation, improvement of resistance to a solvent, improvement of environmental resistance to light, humidity, or the like. In addition, the phase separation structure and the microcapsule may be coated with a matrix material or a microcapsule.
The phase separation structure can be produced, for example, by the following method. The leuco dye, the color developer, the decolorizer, and the matrix material are heated to a temperature higher than the melting point of the matrix material and mixed, and the resulting mixture is cooled to a temperature lower than the freezing point of the matrix material. During cooling, the matrix material rapidly phase separates from the temperature indicating material to form a phase separation structure in which a phase composed of the leuco dye, the developer, and the decolorizer is dispersed in the matrix material.
When the temperature is increased to the melting point or higher of the matrix material and the matrix material is in a liquid state, the temperature indicating material and the matrix material may be compatible or incompatible depending on the compatibility between the temperature indicating material and the matrix material. In this case, the compatibility is preferable from the viewpoint of easy handling. The temperature indicating material and the matrix material need to be phase-separated at the use temperature at which the matrix material is in a solid state, but need not be phase-separated at the elevated temperature at which the matrix material is in a liquid state. The polarity of the decolorizer to be used may be adjusted so that the phase of the temperature indicating material is separated from the matrix material at the use temperature and the temperature indicating material is compatible with the matrix material in a heated state. When the polarity of the decolorizer is too small, the matrix material is compatible with the temperature indicating material at the use temperature of the temperature detection material, and when the polarity of the decolorizer is too large, the decolorizer is separated from the matrix material in a temperature-raised state. Specifically, it is preferable to use energy generated by dipolar interaction between molecules predicted from hansen solubility parameterspAnd energy generated by intermolecular hydrogen bondinghEach of which is 1 to 10 inclusive. In addition, when the polarity of the decolorizer is large and the temperature indicating material and the matrix material are incompatible even in a temperature-raised state, a phase separation structure can be formed by cooling the decolorizer while stirring. In addition, a surfactant may be added to make the temperature indicating material compatible with the matrix material.
When the temperature indicating material is cooled to a temperature lower than the solidification point of the matrix material to form a phase separation structure, the size of the dispersion structure of the temperature indicating material differs depending on the compatibility between the temperature indicating material and the matrix material. Particularly, when the compatibility between the decolorizer and the matrix material is good, the decolorizer is finely dispersed; when the compatibility is poor, the dispersion is sparse. The size of the dispersed structure is not particularly limited, but is preferably 100nm to 1mm, and particularly most preferably 1 μm to 100 μm. By setting the thickness to 100nm or more, the influence on the detection temperature due to the influence of the interface between the temperature indicating material and the matrix material can be suppressed. Further, by setting the thickness to 1mm or less, it becomes difficult to distinguish between the temperature-indicating material and the matrix material, and the color unevenness of the temperature-detecting material can be reduced.
[ solvent ]
In the temperature detection ink, in order to initialize the color, the temperature detection ink needs to be heated to a temperature equal to or higher than the melting point of the temperature indicating material. Therefore, the boiling point of the solvent must be higher than the melting point of the temperature indicating material. In view of workability, the boiling point of the solvent of the temperature detection ink is preferably higher than the melting point of the temperature indicating material by 20 ℃ or more. For example, when water having a boiling point of 100 ℃ is used as the solvent, the melting point of the temperature indicator material is required to be lower than 100 ℃, and most preferably about 60 ℃ to 80 ℃.
In addition, the solvent preferably has low compatibility with the matrix material or the microcapsule encapsulating the temperature indicating material.
When the phase separation structure using the matrix material is used as the temperature detection material, it is preferable to use a solvent having high polarity as the solvent. The highly polar solvent is most preferably water, alcohols such as glycerol, methanol, ethanol, and propanol, and 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.
When the microencapsulated temperature detection material is used, it is preferable to use a solvent that is resistant to the material of the microcapsule.
When a material having high polarity is used for the microcapsule, an organic solvent having low polarity is preferably used as the solvent. The organic solvent having a low polarity is most preferably a nonpolar solvent such as hexane, benzene or toluene, an oil such as petroleum, mineral oil or silicone oil, and preferably ketones such as acetone, methyl ethyl ketone or cyclohexanone, esters such as ethyl acetate, methyl acetate, ethyl propionate or methyl propionate, ethers such as dimethyl ether or tetrahydrofuran, and the like are used.
When a material having low polarity is used for the microcapsule, an organic solvent having high polarity is preferably used as the solvent. As the organic solvent having high polarity, alcohols such as glycerol, methanol, ethanol, and propanol are most preferable, and ketones such as acetone, methyl ethyl ketone, and cyclohexanone, esters such as ethyl acetate, methyl acetate, ethyl propionate, and methyl propionate, ethers such as dimethyl ether and tetrahydrofuran, and the like can be used. In addition, water may be used as the solvent.
The temperature detecting ink also has a temperature detecting function in a liquid state. When the temperature detecting ink is printed, written, or pressed on a printing object or the like, the printed matter is constituted only by the temperature detecting material when the solvent is volatilized. The temperature indicator may use the printout.
< ink for ink jet >
The temperature detecting ink can be applied to an ink for an electrostatic control type ink jet printer. An ink for an electrostatic control type ink jet printer contains a temperature detecting material, a volatile organic solvent, a resin and a conductive agent.
When the resistance of the ink solution is high, ink particles tend to turn and not fly straight in an ink ejection portion of an electrostatic control type ink jet printer. Therefore, the resistance of the ink solution needs to be about 2000 Ω cm or less.
The resins, pigments, and organic solvents (particularly, 2-butanone and ethanol, which are commonly used as organic solvents for ink for inkjet printers) contained in the ink have low conductivity, and therefore, the resistance of the ink solution is as high as about 5000 to several tens of thousands Ω cm. When the resistance is high, it is difficult to perform desired printing by an electrostatic control type ink jet printer. Therefore, in order to reduce the resistance of the ink solution, it is necessary to add a conductive agent to the ink.
As the conductive agent, a complex compound is preferably used. The conductive agent needs to be dissolved in a solvent, and is also important not to affect the color tone. In addition, a salt structure is generally used as the conductive agent. Since a charge bias exists in the molecule, it is presumed that high conductivity can be exhibited.
From the above-described viewpoint studies, it was found that the conductive agent preferably has a salt structure and the cation preferably has a tetraalkylammonium ion structure. The alkyl chain may be linear or branched, and the larger the number of carbon atoms, the higher the solubility in a solvent. However, the smaller the number of carbon atoms, the lower the addition rate, the lower the resistance. The actual number of carbon atoms when used in an ink is about 2 to 8.
The anion is preferably a hexafluorophosphate ion, tetrafluoroborate ion or the like, in view of high solubility in the solvent.
Further, perchlorate ions are also highly soluble but explosive, and therefore are not practical for use in inks. In addition, chlorine, bromine, and iodide ions are also included, but when they come into contact with metals such as iron and stainless steel, these metals tend to be corroded, which is not preferable.
As described above, preferred examples of the conductive agent include tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetrapentylammonium hexafluorophosphate, tetrahexylammonium hexafluorophosphate, tetraoctylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrapentylammonium tetrafluoroborate, tetrahexylammonium tetrafluoroborate, and tetraoctylammonium tetrafluoroborate.
< initialization Process of color >
The color of the temperature detection ink can be initialized by heating the temperature detection ink to a temperature range of not less than the melting point of the temperature indicator material and not more than the boiling point of the solvent, and then cooling the temperature detection ink at a predetermined rate or more. In this case, the heating method is not particularly limited. When the ink in the ink container is heated, for example, a method of heating the ink container by a heater, a hot plate, a heated solvent, or the like can be cited. When the ink in the temperature indicator is heated, a laminator or the like may be used.
The cooling method after heating is also not particularly limited. For example, a method of cooling the ink container by natural cooling, a cooler (cooler), a refrigerator (freezer), or the like is mentioned. Depending on the crystallization rate of the temperature indicating material, a cooling rate of not less than a certain value is required, and a material having a high crystallization rate needs to be rapidly cooled by a cooling device.
The time for detecting the temperature detection ink can also be adjusted by adjusting the cooling rate of the cooling device. The temperature detection ink undergoes a color change according to the accumulation of the crystallization rate with time and temperature. Therefore, by intentionally slowing down the cooling rate, crystallization can be performed in advance before use for temperature management, and a slight color development can be achieved. Thus, the detection time can be made shorter for the same temperature detection ink than in the case of performing the quenching treatment.
As described above, the method for initializing the color of the temperature detection ink includes: a heating step of heating the temperature detection ink to a temperature equal to or higher than the melting point of the temperature indicating material and equal to or lower than the boiling point of the solvent; and a step of cooling the substrate to a temperature not higher than the glass transition temperature of the temperature indicating material at a predetermined cooling rate after the heating step. The cooling speed or cooling temperature is adjusted according to the detection time required for detecting the ink temperature.
< temperature indicator >
Hereinafter, a temperature indicator using the temperature detection ink will be described. Fig. 6 is a schematic diagram showing a first example of the structure of the temperature indicator. The temperature indicator includes: a
The material of the substrate and the transparent substrate is not particularly limited as long as the color of the temperature detection ink or the temperature detection material can be recognized. The base material may be one that can sandwich the temperature detection ink, and is preferably larger than the temperature detection material. The material of the substrate can be freely selected according to the desired function. Organic materials such as paper and plastic, inorganic materials such as ceramics and metals, and composite materials thereof can be freely selected. The layer structure may also be formed from a variety of materials. The properties required for the temperature indicator are selected according to the properties such as high strength, heat resistance, weather resistance, chemical resistance, heat insulation, and electrical conductivity. By using the sealing material, the object to be detected can be brought into close contact with the sealing material.
In addition, as the substrate, a continuous porous material may also be used. The processability can be changed by immersing the temperature detecting ink in the continuous porous material. The processability depends on the material of the continuous porous material. As the continuous porous material, a material which is not modified even when it is in contact with the temperature detection material for a long period of time is required. Specifically, materials such as polyethylene, polypropylene, and cellulose that are difficult to dissolve in common organic solvents, and inorganic compounds such as silica can be used. Examples of the structure of the continuous porous material include sponge, nonwoven fabric, woven fabric, and the like. In the case of cellulose, the cellulose may be paper used for making books and documents. The continuous porous body may be formed by holding powder of silica, polyethylene, or polypropylene with a binder having the same chemical structure. The larger the density of the voids of the continuous porous body is, the higher the density the temperature detection material penetrates into, and therefore, the decrease in the color density can be suppressed.
The size of the transparent base material is not limited as long as the temperature detection material can be recognized. From the viewpoint of visibility, the shorter side direction is preferably 30 μm or more in the case where the transparent base material is rectangular, and the shorter side is preferably 30 μm or more in the case where the transparent base material is elliptical.
The material of the transparent substrate can be freely selected according to the desired function. Organic materials such as paper and plastic, inorganic materials such as ceramics and metals, and composite materials thereof can be freely selected. Since it is necessary to recognize discoloration of at least a part of the temperature detecting ink, transparency is required. Examples thereof include highly transparent paper, highly transparent organic materials such as acrylic resins, highly transparent plastics such as polycarbonates and cycloolefins, and highly transparent inorganic compounds such as glass and transparent electrode films. In addition to these materials having high transparency, the transparent material may be a material having improved transparency by making the film thinner. The layer structure may also be formed from a variety of materials. These materials can be selected from among those required for the temperature indicator, such as high strength, heat resistance, weather resistance, chemical resistance, heat insulation, electrical conductivity, and resistance to thermal shock due to rapid cooling.
Fig. 7 shows a second example of the structure of the temperature indicator. Fig. 7 shows a modification of the temperature indicator of fig. 6. The temperature indicator shown in fig. 7 includes: a
The transparent substrate and the substrate may be subjected to processing such as drilling. Through the opening, the printing paper between the transparent base material and the spacer is exposed. With such a configuration, information can be written on the exposed printing paper during transportation.
Fig. 8 is a schematic diagram showing a third example of the structure of the temperature indicator. Fig. 8 is a schematic diagram showing a configuration of a temperature indicator according to another modification of fig. 6. The temperature indicator includes: a
The
By disposing the
As described above, by providing the
When the
A plurality of temperature detection inks may be used. By using a plurality of temperature detection inks, a temperature indicator that detects 3 temperatures with different colors can be provided.
< article management System >
Next, a quality control system using a temperature indicator will be described. The quality management system includes: a management device for managing the environment in which the article is located, and a management terminal for acquiring color tone information of the temperature detection material. When the management terminal acquires the color tone information, the management terminal associates the time when the article identification information and the color tone information are acquired with information on whether or not a color change has occurred, and transmits the information to the management device.
Fig. 9 is a diagram showing a configuration of the quality control system. Here, the description will be given taking, as an example, quality control in a distribution route in which the
The quality management system QCS (article management system) includes a quality management terminal 30 (management terminal) for acquiring codes (article identification information) (for example, a barcode 21) carried by an
The distribution route includes a
The collection of quality management data is performed when the
In each place, the operator can visually confirm the temperature management status of each process and the temperature load state of the
During each process of shipment, transportation, storage, and the like, the operator transmits the optical state of the
The
In the
The
In the present embodiment, the
Fig. 10 is a diagram showing a configuration of the management server. The
In the management server, it is preferable that color density time information indicating a relationship between a color density of the temperature detection ink attached to the article and time in the environment is stored in the storage unit in advance. By storing the color density time information in the management server in advance, the management terminal can acquire the color density time information based on the acquired article identification information from the management device, and calculate the time in the environment based on the color density and the color density time information of the acquired color information. Further, the calculated time may be displayed on the display unit, and the article identification information may be transmitted to the management device in association with the calculated time. In addition, the calculation of the time in the environment may be performed on the management server side.
As examples of the item information stored in the management server, the item information 421 as information on the management target item may be a code (item identification information), a name (product name), a production date, a distribution date, a size, a price, a surface color, whether or not temperature management by the
As described above, the quality management system QCS (article management system) according to the present embodiment includes: a management device (for example, a management server 40) that collects color tone information of temperature detection ink carried by an article and manages the environment in which the article is located based on the color tone information; and a management terminal (for example, quality management terminal 30) that acquires article identification information identifying the article carried by the article and acquires color tone information of the temperature detection ink, wherein when the management terminal acquires the acquired color tone information, the management terminal displays information on whether or not there is a color change on the display unit, and associates information on whether or not there is a color change (for example, temperature display data) with the time when the article identification information and the color tone information are acquired, and transmits the information to the management device. This enables centralized management of the acquired temperature indicating data at each location in the distribution stage.
The management terminal displays information that the circulation of the articles is improper on the display part when the color changes; when there is no color change, information indicating that the article is properly distributed is displayed on the display unit. Thus, the operator at each location in the distribution stage can immediately confirm whether or not the currently carried article is appropriately carried.
In the management device, color density time information indicating a relationship between a color density of a temperature detection material carried by an article and a time in the environment is stored in a storage unit, and a management terminal acquires color density time information based on acquired article identification information from the management device, calculates the time in the environment based on the color density and color density time information of the acquired color tone information, displays the calculated time on a display unit, and transmits the article identification information to the management device in association with the calculated time. Thus, article management can be performed based on color tone information based on the temperature detection material having the heating integral characteristic or the cooling and heating integral characteristic.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：智能线缆传感器