WO2020009245A1 - 温度検知材料およびそれを用いた温度検知インク - Google Patents

温度検知材料およびそれを用いた温度検知インク Download PDF

Info

Publication number
WO2020009245A1
WO2020009245A1 PCT/JP2019/026957 JP2019026957W WO2020009245A1 WO 2020009245 A1 WO2020009245 A1 WO 2020009245A1 JP 2019026957 W JP2019026957 W JP 2019026957W WO 2020009245 A1 WO2020009245 A1 WO 2020009245A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
resin
methyl
ink
ethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/026957
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
暢一郎 岡崎
航平 會田
森　俊介
昌宏 川崎
憲一 相馬
雅彦 荻野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Industrial Equipment Systems Co Ltd
Original Assignee
Hitachi Industrial Equipment Systems Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Industrial Equipment Systems Co Ltd filed Critical Hitachi Industrial Equipment Systems Co Ltd
Publication of WO2020009245A1 publication Critical patent/WO2020009245A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B9/00—Esters or ester-salts of leuco compounds of vat dyestuffs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G01K11/16—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance of organic materials

Definitions

  • the present invention relates to a temperature detection material for confirming the temperature of a temperature detection target and the like and an ink using the same.
  • Cold storage medicines such as fresh foods, frozen foods, vaccines, and biopharmaceuticals need a cold chain that keeps them at a constant low temperature during the production, transportation, and consumption distribution processes.
  • shipping containers are usually equipped with a data logger that can continuously record time and temperature, and if there is damage to the product, the responsibility is assumed. It is possible to clarify the location.
  • the temperature indicator is not as accurate as a data logger, it can be attached to individual products and the surface is dyed when the temperature rises above or falls below a preset temperature. It is possible. A temperature detecting material is used for the temperature indicator.
  • the temperature sensing material itself has a low resistance to an organic solvent, so that when it comes into contact with the organic solvent, the color changes, or the color change due to the original temperature change is hindered. Also. A similar effect may occur in a mixture with a binder resin from which protons can be eliminated. Therefore, encapsulation of the temperature detecting material in microcapsules has been studied.
  • Patent Literatures 1 and 2 disclose a reversible composition comprising an electron-donating color-forming organic compound, an electron-accepting compound, and a compound that is a reaction medium that causes an electron transfer reaction between the electron-donating color-forming organic compound and the electron-accepting compound.
  • a microcapsule pigment containing a discoloring composition is disclosed. It is disclosed that a urethane-based or melamine-based material is used as a wall film material of the microcapsule.
  • an object of the present invention is to provide a temperature detecting material that changes color stably with respect to temperature change even in an organic solvent.
  • the temperature detection material according to the present invention includes a temperature indicator containing a leuco dye, a developer and a decolorant, and a resin film containing the temperature indicator, wherein the resin film is formed of silicone. It is a resin or an epoxy resin.
  • the present invention it is possible to provide a temperature detecting material that changes color stably with respect to temperature change even in an organic solvent.
  • FIG. 3 is a diagram showing a temperature change of a color density of a temperature indicating material A.
  • FIG. 5 is a diagram showing a temperature change of a color density of a temperature indicating material B. It is a figure showing the manufacturing method of the temperature sensing material concerning an embodiment. It is a figure showing the manufacturing method of the temperature sensing material concerning an embodiment.
  • FIG. 4 is a diagram showing a color change according to the temperature of a printed matter using the temperature detecting material of Example 1.
  • FIG. 9 is a diagram showing a color change depending on the temperature of a printed matter using the temperature detecting material of Example 2.
  • the temperature detection material 10 a includes a temperature indicating material 6 and a resin coating 4 that contains the temperature indicating material 6.
  • the temperature indicating material 6 includes a leuco dye 1, a developer 2, and a decolorant 3.
  • the temperature detecting material 10b according to one embodiment may have a structure in which the resin 13 is present inside the resin film 4 and the temperature indicating material 6 is dispersed in the resin.
  • each configuration of the temperature detecting materials 10a and 10b will be described in detail.
  • the temperature-indicating material 6 is a material whose color density is reversibly changed by a temperature change (heating / cooling), and includes a leuco dye 1 which is an electron-donating compound, a developer 2 which is an electron-accepting compound, and a color changing agent. Includes decolorizer 3 for controlling the temperature range.
  • FIG. 3 is a diagram illustrating a temperature change of the color density of the temperature indicating material A according to the embodiment.
  • the vertical axis represents color density
  • the horizontal axis is the temperature
  • T a is developer starting temperature
  • T d is the decolorization initiation temperature.
  • the temperature indicating material A has a hysteresis characteristic with respect to the temperature change of the color density.
  • the temperature indicating material A is a material that has been melted and rapidly cooled to be solidified in an amorphous state without being crystallized.
  • FIG. 4 is a diagram illustrating a temperature change of the color density of the temperature indicating material B according to the embodiment.
  • the horizontal axis in FIG. 4 is a temperature
  • T a is developer starting temperature
  • T d is decoloring starting temperature.
  • the temperature indicating material B has a hysteresis characteristic in a change in color density.
  • the temperature indicating material B is a material that becomes a supercooled liquid when cooled after being melted.
  • the leuco dye 1 is an electron-donating compound, and conventionally known dyes for pressure-sensitive copying paper and thermosensitive recording paper can be used.
  • conventionally known dyes for pressure-sensitive copying paper and thermosensitive recording paper can be used.
  • An azomethine type is exemplified.
  • 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] xanthen-9-spiro-3′-phthalide, 3,3-bis (p-diethylaminophenyl) -6-dimethylamino Phthalide, 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-[N
  • 2Two or more leuco dyes individually listed may be used in combination.
  • the developer 2 changes the structure of the leuco dye 1 by contact with the electron-donating leuco dye 1 to give a color.
  • a known color developer used for thermosensitive recording paper, pressure-sensitive copying paper, or the like can be used.
  • Specific examples of such a developer include benzyl 4-hydroxybenzoate, 2,2'-biphenol, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3 Examples thereof include phenols such as -cyclohexyl-4-hydroxyphenyl) propane, bisphenol A, bisphenol F, bis (4-hydroxyphenyl) sulfide, paraoxybenzoate, and gallic ester.
  • the developer 2 is not limited to these, but may be any compound as long as it is an electron acceptor and can change the color of the leuco dye 1.
  • metal salts of carboxylic acid derivatives, salicylic acid and salicylic acid metal salts, sulfonic acids, sulfonates, phosphoric acids, metal phosphates, acid phosphates, acid phosphate metal salts, phosphorous acid, phosphorous acid Metal salts or the like may be used.
  • those having high compatibility with Leuco Dye 1 and a decoloring agent described later are preferable, and organic developers such as benzyl 4-hydroxybenzoate, 2,2'-bisphenol, bisphenol A, and gallic esters are preferable. .
  • the temperature indicating material 6 may use one type of these color developers 2 or a combination of two or more types. By combining the color developer 2, the color density of the leuco dye 1 at the time of coloring can be adjusted. The amount of the developer 2 is selected according to the desired color density. For example, usually, the above leuco dye 1 may be selected within a range of about 0.1 to 100 parts by mass with respect to 1 part by mass.
  • the decoloring agent 3 is a compound capable of dissociating the bond between the leuco dye 1 and the developer 2, and a compound capable of controlling the coloration temperature of the leuco dye 1 and the developer 2.
  • the decolorizing agent 3 is solidified in a state of phase separation.
  • the decoloring agent 3 is melted, and the function of dissociating the bond between the leuco dye 1 and the developer 2 is exhibited. Therefore, the state change temperature of the decoloring agent 3 is important for controlling the temperature of the temperature indicating material 6.
  • the material of the decoloring agent 3 a material capable of dissociating the bond between the leuco dye 1 and the color developing agent 2 can be widely used. As long as the polarity is low and does not show color development with respect to the leuco dye 1 and the polarity is high enough to dissolve the leuco dye 1 and the color developing agent 2, various materials can be used as the decoloring agent.
  • organic compounds such as compounds, azimuth compounds, ether compounds, fat compounds, sugar compounds, peptide compounds, nucleic acid compounds, alkaloid compounds, and steroid compounds can be used.
  • tricaprin isopropyl myristate, m-tolyl acetate, diethyl sebacate, dimethyl adipate, 1,4-diacetoxybutane, decyl decanoate, diethyl phenylmalonate, diisobutyl phthalate, triethyl citrate, phthalate Benzyl butylate, butylphthalylbutyl 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 oxalate, monoolein, butyl
  • the compounds are not limited to these compounds, and any material can be used as long as the bond between the leuco dye 1 and the developer 2 can be dissociated.
  • decolorizing agents 3 may be used alone or in combination of two or more.
  • the discoloring temperature can be adjusted by changing the discoloring time by combining the decoloring agent.
  • the temperature indicating material 6 can be produced by mixing the leuco dye 1, the developer 2, and the decolorant 3. It is also possible to use a material obtained by heating the temperature indicating material 6 to a liquid state by heating it to a temperature equal to or higher than the melting point thereof, and then cooling the temperature indicating material 6 to a temperature below the freezing point and solidifying the material.
  • the resin film 4 used for the microcapsules it is possible to use a photo-curing or thermosetting resin that is cured by ultraviolet rays, and use a silicone resin or an epoxy resin as a material having high water resistance and high light transmittance. be able to. From the viewpoint of heat resistance, a silicone resin is particularly preferable.
  • the silicone resin and the epoxy resin specifically, methyl silicone resin, methylphenyl silicone resin, bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, and aliphatic epoxy resin can be used. .
  • the film thickness is large.
  • the thickness of the resin film is preferably 5 to 30% of the microcapsule diameter.
  • the printing ink must have a viscosity suitable for the printing apparatus, and the concentration of the temperature detecting materials 10a and 10b included in the printing ink is preferably 5 to 20% by mass. Further, the concentration of the binder resin is preferably 1 to 30% by mass.
  • a method using a device such as gravure printing, screen printing, a dispenser, or an ink jet printer. It is preferable to adjust the diameter of the microcapsules in consideration of device compatibility, storage stability, and the like by a marking method.
  • the distribution (particle size distribution) of the particle diameter of the microcapsules can be measured by, for example, a Coulter counter, and as the index of the particle diameter, an average diameter, a median diameter, and a mode diameter are used. .
  • the particle size of the temperature sensing material is defined as a median size.
  • the particle diameter (median diameter) of the microcapsules is preferably from 0.1 ⁇ m to 100 ⁇ m, more preferably from 0.1 ⁇ m to 10 ⁇ m.
  • the thickness is preferably 0.1 ⁇ m or more and 2 ⁇ m or less.
  • microencapsulation examples include, but are not limited to, emulsion polymerization, suspension polymerization, coacervation, interfacial polymerization, and spray drying. Further, two or more different methods may be combined. When an aqueous reaction solvent is used, the pH is preferably adjusted to around 7.0.
  • FIG. 5A An example of a method for manufacturing a temperature detecting material will be described with reference to FIG.
  • a reaction medium 5 adjusted to pH 7.0 is prepared (FIG. 5A).
  • the temperature indicating material 6 is dropped to form temperature indicating material particles (particle-shaped temperature indicating material) 7 in the reaction medium 5 (FIG. 5B).
  • a mixture 8 of the resin composition and the surfactant constituting the resin film is further dropped to coat the temperature indicating material with the resin (FIG. 5C).
  • a temperature detecting material 10 having the structure shown in FIG. 1 can be obtained (FIG. 5D).
  • FIG. 6 shows another method of manufacturing the temperature detecting material.
  • a reaction medium 5 whose pH has been adjusted is prepared (FIG. 6A).
  • a temperature indicating material, and a surfactant constituting a resin film onto the reaction medium 5, the temperature indicating material is coated with the resin (FIG. 6B).
  • the temperature detecting material 10 having the structure shown in FIG. 2 can be obtained.
  • a temperature detection ink or paint By mixing the above-mentioned temperature detection material, a solvent, and a binder resin, a temperature detection ink or paint can be produced. By dispersing the temperature detecting material in a solvent, it becomes possible to apply the ink to inks such as pens, stamps, crayons, and ink jets, and to paints for printing.
  • a solvent a volatile organic solvent other than water can be used.
  • the organic solvent it is preferable to use a highly polar organic solvent from the viewpoint of improving the dispersibility of the temperature detecting material.
  • a highly polar organic solvent for example, in addition to water, glycerin, methanol, ethanol, alcohols such as propanol are most preferable, in addition, acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, methyl acetate, Esters such as ethyl propionate and methyl propionate; and ethers such as dimethyl ether and tetrahydrofuran.
  • methyl ethyl ketone and ethanol which are generally used as printing inks, have high resistance to water, it is particularly preferable to use them.
  • the binder resin is preferably a polyvinyl alcohol resin for an aqueous solvent, an acrylic resin or a polyamide resin for an ethanol solvent, or an acrylic resin or a polyester resin for methyl ethyl ketone.
  • the concentration of the temperature detecting agent contained in the printing ink is preferably about 5 to 20% by mass. Further, the concentration of the binder resin is preferably 1 to 30% by mass. It can be appropriately adjusted according to the viscosity at the time of printing.
  • These temperature detecting inks have a temperature detecting function even in a liquid state, and the solvent is volatilized by printing, writing, stamping, etc. on an object to be printed, so that only the temperature detecting material constitutes a printed matter.
  • An additive may be further added to the temperature detection ink to a solution such as an organic solvent or water as long as it does not affect the temperature detection function.
  • the temperature detection ink according to the embodiment can be applied to ink for an inkjet printer.
  • the ink for an ink jet printer includes a temperature detection material, a solvent (a volatile organic solvent), and a resin (a binder resin).
  • the ink jet printer ink of the charge control system includes a temperature detecting material, a volatile organic solvent, a resin, and a conductive agent.
  • a temperature detecting material When the resistance of the ink solution is high, the ink particles in the ink discharge section of the charge control type ink jet printer do not fly straight but tend to bend. Therefore, the resistance of the ink solution needs to be approximately 2000 ⁇ cm or less.
  • Resins, pigments, and organic solvents (especially 2-butanone and ethanol, which are often used as organic solvents for ink-jet printer inks) contained in the ink have low conductivity, so that the resistance of the ink solution is as large as about 5,000 to tens of thousands ⁇ cm. . If the resistance is high, it is difficult to perform desired printing with a charge control type ink jet printer. Therefore, it is necessary to add a conductive agent to the ink in order to reduce the resistance of the ink solution.
  • the conductive agent must be dissolved in the solvent used, and it is important that the conductive agent does not affect the color tone.
  • the conductive agent generally has a salt structure. It is presumed that this has a bias of electric charge in the molecule, so that high conductivity can be exhibited.
  • 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 carbon number, the higher the solubility in a solvent. However, the smaller the number of carbon atoms, the lower the resistance with a small addition rate. The practical number of carbon atoms when used for ink is about 2 to 8.
  • Anions are preferred because hexafluorophosphate ion, tetrafluoroborate ion and the like have high solubility in a solvent.
  • perchlorate ions also have high solubility, they are explosive, so it is not practical to use them for ink.
  • chlorine, bromine, and iodine ions are also included, but these are not preferable because they tend to corrode metals such as iron and stainless steel when they come into contact with them.
  • preferred conductive agents include tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetrapentylammonium hexafluorophosphate, tetrahexylammonium hexafluorophosphate, and tetraoctyl Ammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetrapentylammonium tetrafluoroborate, tetrahexylammonium tetrafluoroborate, tetraoctylammonium tetrafluoroborate, etc. It
  • a leuco dye a color developer: a color eraser is mixed at a ratio of 3: 3: 100 (mass ratio), and the mixture is stirred at 40 ° C. to prepare a temperature indicating material (mixed liquid of a leuco dye, a color developer, and a color eraser) 6. did.
  • the prepared temperature indicating material is in a decolored state at room temperature (25 ° C.), but develops black when cooled to 4 ° C. or lower.
  • a surfactant polymeric carboxylic acid-based aqueous dispersant
  • a photo-curable silicone resin Shin-Etsu Chemical: KER4000-UV
  • the material 6 was dropped one by one (FIG. 5B). Since the materials constituting the temperature indicating material are all hydrophobic, they tend to be spherical in the reaction solvent solution (aqueous solution). As a result, the temperature indicating material becomes spherical in the phosphate buffer and becomes temperature indicating material particles 7. In this state, the silicone resin mixture 8 was further dropped one by one (FIG. 5C).
  • the temperature indicating material particles are coated with the silicone resin, resulting in temperature indicating material particles 9 coated with the silicone resin.
  • the temperature indicating material, surfactant (polymeric carboxylic acid-based aqueous dispersant), and photocurable silicone resin were used in a mass ratio of 10: 100: 5.
  • the temperature detecting material 10 was produced by irradiating the temperature indicating material particles 9 coated with the silicone resin with ultraviolet rays from an ultraviolet lamp (high-pressure mercury lamp) to cure the photocurable silicone resin (FIG. 5D). .
  • the particle size (median size) of the produced temperature detecting material was 2.0 ⁇ m according to the Coulter counter measurement. Further, the thickness of the silicone resin was about 20% of the particle diameter of the temperature detection material.
  • the prepared temperature detecting material was mixed with a binder resin and a solvent to prepare an ink for an inkjet printer.
  • An acrylic binder resin manufactured by Joncryl, J682
  • an ethanol-based solvent AP7, manufactured by Japan Ethanol Sales Co., Ltd.
  • the temperature detection material and the binder resin concentration of the ink for an ink jet printer were all 5% by mass.
  • FIG. 7 shows a color change depending on the temperature of a printed matter printed with the ink of the first embodiment.
  • room temperature 25 ° C.
  • the color was erased and printing could not be confirmed, but it was found that the color was developed by cooling to 4 ° C., and printing could be confirmed. From this result, it was found that a temperature detecting material that stably changes color with respect to temperature change can be obtained even in an ethanol-based solvent.
  • Example 2 An ink was prepared in the same manner as in Example 1 except that lithium nitrate as a conductive agent was added in an amount of 5% by mass. As in Example 1, printing was performed on a printing substrate using a CIJ (Continuous Injection) type, which is a charge control type ink jet printer, as a printing device.
  • CIJ Continuous Injection
  • FIG. 8 shows the color change of the printed matter of the ink of Example 2 depending on the temperature.
  • room temperature 25 ° C.
  • the color of the temperature detecting material was erased and printing could not be confirmed.
  • the temperature detecting material developed color and printing could be confirmed. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent.
  • Example 3 a temperature detecting material was manufactured by a method of simultaneously mixing a temperature indicating material, a silicone resin, and a surfactant.
  • a leuco dye As a leuco dye, 2'-anilino-6 '-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] (manufactured by Yamada Chemical Industry Co., Ltd .; 205), octyl gallate as a color developer, and a mixture of methyl p-toluate and 2-phenylethyl phenylacetate at a mass ratio of 9: 1 were used as a decolorizer.
  • a leuco dye: a developer: a decoloring agent was mixed at a mass ratio of 3: 3: 100, and the mixture was stirred at 40 ° C. to prepare a temperature indicating material.
  • a temperature indicating material, a surfactant (polymeric carboxylic acid-based aqueous dispersant), and a photocurable silicone resin are mixed at a mass ratio of 10: 100: 5, and the mixture is stirred at 40 ° C. to obtain a temperature indicating material, A mixture 11 of a surfactant and a silicone resin was prepared.
  • the temperature detection material 10 was produced by irradiating ultraviolet rays to the state (FIG. 6C).
  • the produced temperature detecting material had the structure shown in FIG. 2, and had a structure in which the temperature detecting material was included in the silicone resin particles.
  • the particle diameter (median diameter) of the temperature detection material particles was 1.9 ⁇ m according to the Coulter counter measurement.
  • Example 1 Using this temperature detecting material, an ink was prepared in the same manner as in Example 1, and printing was performed with an ink jet printer. As a result, characters having a temperature detecting function could be printed in the same manner as in Example 1. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent. Further, the coloring property was slightly improved as compared with Example 1.
  • 0.5 g of the present core material and 2.5 g of an anionic surfactant are mixed with 20 cc of a phosphate buffer solution (pH 7.0), and heated at 140 ° C. for 1 hour in an autoclave container to obtain phosphoric acid.
  • a dispersion was prepared in which the core material was uniformly dispersed in the buffer.
  • the dispersion liquid and the photocurable silicone resin are mixed such that the core material, the surfactant (polymeric carboxylic acid-based aqueous dispersant), and the photocurable silicone resin have a mass ratio of 10: 100: 5. Stirred at ° C.
  • the particle size (median size) of the produced temperature detecting material was 1.8 ⁇ m according to the Coulter counter measurement. Further, the thickness of the silicone resin was about 20% of the particle diameter of the temperature detecting material.
  • Example 2 An ink was prepared using this temperature detecting material in the same manner as in Example 1, and was printed by an inkjet printer.
  • the printed characters were colorless at room temperature, but were confirmed to develop a blue color when heated to 50 ° C. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent.
  • Example 5 A temperature indicating material, a temperature detecting material, and an ink were produced in the same manner as in Example 4, except that a mixture of vitamin K4 and propyl gallate at a mass ratio of 1: 1 was used as a decolorizing agent.
  • the temperature indicating material of Example 5 is a material that is in a decolored state at room temperature but becomes colored (blue) when heated to 50 ° C.
  • Example 2 The prepared ink was printed by an ink jet printer in the same manner as in Example 1.
  • the printed characters were colorless at room temperature, but it was confirmed that heating to 25 ° C developed a blue color. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent.
  • thermosetting silicone resin in place of the photocurable silicone resin, heating at 90 ° C. for 5 hours to cure and encapsulate the silicone resin to produce a temperature detecting material and ink in the same manner as in Example 1. Then, printing was performed using an inkjet printer.
  • the print was erased at room temperature (25 ° C.) and could not be confirmed, but it was confirmed that the color developed when cooled to 4 ° C. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent.
  • thermosetting epoxy resin instead of a photocurable silicone resin, heating the epoxy resin at 90 ° C. for 5 hours to cure the epoxy resin and produce a temperature detecting material and ink in the same manner as in Example 1 except that the epoxy resin was encapsulated. Then, printing was performed using an inkjet printer.
  • the print was erased at room temperature (25 ° C.) and could not be confirmed, but it was confirmed that the color developed when cooled to 4 ° C. It has been found that a temperature detecting material that changes color stably with respect to temperature change can be obtained even in an ethanol-based solvent.
  • thermoelectric material was prepared in the same manner as in Example 1, and the thermoelectric material was coated with cross-linked melamine using a general known method (Source: Application development of micro / nano-based capsules and fine particles, CMC Publishing, p. 59). The prepared temperature detecting material was manufactured.
  • thermoelectric material dispersion solution An aqueous solution in which poly (ethylene-alt-maleic anhydride) was dissolved as a surfactant was heated to 40 ° C. and stirred at 600 rpm.
  • the temperature indicating material prepared in Example 1 was dropped and dispersed in this aqueous solution to prepare a temperature indicating material dispersion solution. At this time, the temperature indicating material was heated to 40 ° C.
  • an aqueous solution of melamine and formalin was prepared, the pH was appropriately adjusted with sodium hydroxide, and the resulting solution was added dropwise to the dispersion of the thermoelectric material to produce microcapsules in which the surface of the thermoelectric material particles was coated with crosslinked melamine.
  • Example 2 An ink was prepared in the same manner as in Example 1 except that the temperature detecting material of Comparative Example 1 was used, and the ink was printed on a PET film by an inkjet printer.
  • Comparative Example 2 A temperature detecting material and ink were prepared in the same manner as in Comparative Example 1 except that a urethane-based resin was used instead of the melamine-based resin, and printing was performed on a PET film by an inkjet printer.
  • the print was erased and could not be confirmed. In addition, it was confirmed that printing did not appear even when the temperature was changed from room temperature to 4 ° C. or lower. It is considered that the temperature detection material was affected by the ethanol used as the solvent, and the temperature detection function was lost. As described above, according to the present invention, it has been shown that a temperature detecting material that can stably change color with respect to a temperature change even in an organic solvent can be provided. Note that the present invention is not limited to the above-described embodiment, and includes various modifications. For example, the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described above.
  • a part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of one embodiment can be added to the configuration of another embodiment. Further, for a part of the configuration of each embodiment, it is possible to add / delete / replace another configuration.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
PCT/JP2019/026957 2018-07-06 2019-07-08 温度検知材料およびそれを用いた温度検知インク Ceased WO2020009245A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-128720 2018-07-06
JP2018128720A JP7220528B2 (ja) 2018-07-06 2018-07-06 温度検知インク

Publications (1)

Publication Number Publication Date
WO2020009245A1 true WO2020009245A1 (ja) 2020-01-09

Family

ID=69060890

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/026957 Ceased WO2020009245A1 (ja) 2018-07-06 2019-07-08 温度検知材料およびそれを用いた温度検知インク

Country Status (2)

Country Link
JP (1) JP7220528B2 (OSRAM)
WO (1) WO2020009245A1 (OSRAM)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102423464B1 (ko) * 2020-07-28 2022-07-20 이장희 시온 안료를 이용한 체온 체크 키트
JP7733485B2 (ja) * 2021-06-30 2025-09-03 株式会社パイロットコーポレーション 可逆熱変色性インクジェットプリンター用水性インキ組成物、ならびにそれを用いたインクジェットプリンターおよびインクカートリッジ
JP7719646B2 (ja) * 2021-07-09 2025-08-06 株式会社パイロットコーポレーション 筆記具用可逆熱変色性インキ組成物およびそれを収容してなる筆記具

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS555787A (en) * 1978-06-27 1980-01-16 Dow Corning Method of preparing corpuscular matter containing solid organopolysiloxane
JP2006095795A (ja) * 2004-09-29 2006-04-13 Sato Corp 転写箔
JP2008239810A (ja) * 2007-03-27 2008-10-09 Nichiyu Giken Kogyo Co Ltd 耐光性温度管理インジケーター

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031884A (ja) * 1999-07-22 2001-02-06 Pilot Ink Co Ltd 可逆熱変色性顔料
JP2012213738A (ja) * 2011-04-01 2012-11-08 Seiko Epson Corp マイクロカプセルの製造方法、マイクロカプセル塗布膜の形成方法及びマイクロカプセルの製造装置
JP6294173B2 (ja) * 2014-06-30 2018-03-14 株式会社パイロットコーポレーション 固形筆記体及びそれを用いた固形筆記体セット

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS555787A (en) * 1978-06-27 1980-01-16 Dow Corning Method of preparing corpuscular matter containing solid organopolysiloxane
JP2006095795A (ja) * 2004-09-29 2006-04-13 Sato Corp 転写箔
JP2008239810A (ja) * 2007-03-27 2008-10-09 Nichiyu Giken Kogyo Co Ltd 耐光性温度管理インジケーター

Also Published As

Publication number Publication date
JP7220528B2 (ja) 2023-02-10
JP2020008384A (ja) 2020-01-16

Similar Documents

Publication Publication Date Title
EP3730911B1 (en) Temperature sensing material, and temperature deviation time estimating system employing same
US11572486B2 (en) Temperature detection material, temperature detection ink using same, temperature indicator, method for manufacturing temperature detection material, and product management system
CN111433577B (zh) 温度检测标签和使用该温度检测标签的物品管理装置
EP3745106B1 (en) Temperature detection ink, temperature detection ink initialization method, temperature indicator, and article management system
WO2018193781A1 (ja) 温度検知材料、それを用いた温度検知インク、温度インジケータ、および物品管理システム
WO2020009245A1 (ja) 温度検知材料およびそれを用いた温度検知インク
CN108139279B (zh) 温度检测体
JP2020008384A5 (OSRAM)
WO2018193680A1 (ja) レーザーマーキング用塗料及びそれを用いたレーザーマーキング方法
JP7734864B2 (ja) 温度インジケータおよび温度インジケータ製造方法
JP7297624B2 (ja) インク、該インクの製造方法、および該インクを用いた温度インジケータ
WO2020080313A1 (ja) 温度検知材料、それを用いた温度検知インク、温度インジケータ、及び物品管理システム
JP7017996B2 (ja) 感熱塗料及びそれを用いたレーザーマーキング方法
JP2022052104A (ja) インク、該インクの製造方法、および該インクを用いた温度インジケータ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19830658

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19830658

Country of ref document: EP

Kind code of ref document: A1