WO1985001105A1 - Temperature supervision and display unit - Google Patents

Temperature supervision and display unit Download PDF

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Publication number
WO1985001105A1
WO1985001105A1 PCT/JP1984/000148 JP8400148W WO8501105A1 WO 1985001105 A1 WO1985001105 A1 WO 1985001105A1 JP 8400148 W JP8400148 W JP 8400148W WO 8501105 A1 WO8501105 A1 WO 8501105A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
display unit
oxidizing
methine
methine dye
Prior art date
Application number
PCT/JP1984/000148
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Makoto Asano
Iwao Chiba
Masumi Iemura
Original Assignee
Mitsui Toatsu Chemicals, Incorporated
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 Mitsui Toatsu Chemicals, Incorporated filed Critical Mitsui Toatsu Chemicals, Incorporated
Priority to GB08510599A priority Critical patent/GB2155633B/en
Priority to DE19843490397 priority patent/DE3490397C2/de
Publication of WO1985001105A1 publication Critical patent/WO1985001105A1/ja

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Classifications

    • 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
    • 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
    • G01K11/06—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using melting, freezing, or softening

Definitions

  • the present invention relates to a temperature management display unit. More specifically, when exposed to a certain temperature or higher, an irreversible color develops and various temperature control is essential. For example, transportation of frozen foods, refrigerated foods, fresh flowers, medical products, etc. It relates to a temperature control indicator that is suitable for storage, etc. and is effective for detecting whether or not a substance has been maintained at a controlled temperature.
  • Such strict temperature control is not limited to frozen or chilled foods, but may include fresh flowers, medical products (eg, certain anti-cancer agents, vaccines, Blood), photographic drugs, chemical products, etc.
  • a temperature control ink used in such an application there is a heater, such as the melting of a colored solid resin acid as already proposed in XI SP 395 411. Utilizing the phenomenon and the capillary phenomenon of blotting paper, the Lee enzyme is activated by temperature as proposed in Japanese Patent Publication Nos. 57-41319 and 57-28559. There is a proposal to use the fact that the degree of coloration is different, and that the degree can be distinguished by color using a pH indication draft.
  • the primary objective of the present invention is to provide a thermal management unit which is completely different from the already proposed system.
  • a second object of the present invention is to provide a temperature control unit which irreversibly develops color at an arbitrary predetermined temperature or higher and is useful for controlling the storage temperature.
  • These objects of the present invention are as follows: (1) Mic cr capsule containing a hydrophobic organic compound having an arbitrary melting point, (2) methine pigment, and ( 3 ) oxidizable material as a support. This can be achieved by the temperature management display cutout that is held in the storage.
  • OMPI A cut in which a hydrophilic material is combined with a micro-organic cell of a hydrophobic organic compound having a predetermined melting point and these are held on a support is extremely useful for temperature control.
  • the microcapsule of the cut is preferably split at a temperature lower than the desired control temperature.
  • the non-volatile organic compound in the ruptured capsule of the mouth melts and diffuses, and the oxidizing compound comes into contact with the neighboring methine dye. Then, the irreversible coloring of the dye is carried over, and this coloring can be used to detect abnormalities in the temperature control situation.
  • 1 to 4 show a typical configuration example of a temperature display labenore which is an embodiment of the present invention.
  • 1 is a colored eyebrow
  • 2 is a support (which may also serve as a spacer layer)
  • 3 is a mic mouth cover
  • 4 is an adhesive
  • 5 is a template
  • 6 is a protective layer
  • 7 is a protective layer. Indicates ⁇ - ⁇ .
  • the oil mic containing the methine dye is the best form for carrying out the capsule invention.
  • the present invention provides
  • X-CH-Z (wherein, X, Y, and Z may be substituted with a phenyl group, a substituted or unsubstituted nabutyl group, or a substituted group.
  • Tyryl group or aromatic heterocyclic ring residue which may have a substituent, which may be the same or different, and two of X, ⁇ , and Z are bonded
  • (C) a unit formed by combining, as an essential component, a microcapsule capsule containing a water-based organic compound having a desired melting point,
  • These (A), (B), and (C) essential components are temperature-controlled indications, such as those obtained by milling, coating, and printing on a support such as paper or film. It is a unit.
  • the color forming system applied to the display of the temperature abnormality uses an irreversible color forming reaction by contact between the methine dye of the general formula (I) and the oxidizing material.
  • the present invention is characterized in that a microphone-opening capsule containing a hydrophobic organic compound having a desired melting point is combined with the above-described coloring system.
  • OMPI Such a hydrophobic organic compound in the microcapsule undergoes a solid-liquid conversion in the microcapsule at the melting point.
  • the compound encapsulated in the microcapsule is solid below the melting point, and the microvessel is broken by pressure or the like under these temperature conditions, and the contents remain solid. It does not diffuse, but when the melting point is exceeded, the contents melt and dissolve the methine pigment present near the outlet of the capsule at the mouth and dissolve the oxidizing forest material.
  • a field of contact is provided to cause irreversible oxidative color development.
  • the methine compound represented by the general formula (I) includes:
  • Triaminotriphenylmethanine dyes for example, 4,4 ', 4, tris-dimethylamino-trifylmethyl Tan, 4,4,4,4 "-tris-'methylamino-triphenyl meth- ane, 4,4, -s-methyl-mino- ⁇ -" METHYLAMINO — TRIFE-NOREMETHANE, 4, 4 — BIS- (N-METHYL-N-PENNOREAMINO) -4 -METHYLAMINO-TRIFE -Lumetane, 4, 4 no-bis-methyl diamino-4-N-methino-N benzene , "Trisamino 3-methyl-trimethylamine, 4,4'-trimethylamino-4-'dimethylamino-3, 3, one
  • (A-2) diamino-triphenylmethanine dyes for example, 4,4'-bis-dimethylamino-triphenylmethane, 4 , 4 / one screw-, methylamine 4-methyl-tri-methane, 4, 4 / one screw-(N "-pen-kle-N-methyl ⁇ ⁇ )-Triphenyl methane. 4-4-VIS-'Dimethylamino-4 / ⁇ -METRIC CIT.
  • (C) -styrylmethane dyes for example, (Methylaminophenyl)--styrene methane, bis (4-dimethylaminophenol): ⁇ - (4 /-dimethylaminophenyl) (Styryl)-methane, bis (4-'dimethylaminophenyl)-?-(4'-methoxystyryl) methane, bis ( 3 — Methyl-4 (4-7-Men-Methyl-Amino) 7-Men-Lu — Styrene Methane, Vis (31-Men—4'-Methyl-Amino) Nohphenyl) ⁇ ⁇ - ⁇ 4'-methoxystyryl) -Methane
  • Indrillyl methane dyes such as bis (1-ethyl-2—methyl-in, 1- (3-ethyl)) (4,4-ethoxy) 1-Methyl, 2- (Methyl-Indole-3-yl) 1- (4,1-Methyl-methyl) )-Methane, 4-dimethylaminophenyl (1, -ethyl-2, -methyl-indole-1,3 -yl)-phenylmeta , Screws (1 — butyl — 2-methyl-indole 3-yl)-4 — meth.
  • methine dyes include, for example, 3,6-bis-methylamino- 917-norexanthen, 3,6-bis-di'methine Chilamino-191-phenylxanthatene, 3,6-bis-dimethyldimethylamino-9- (4, -dimethylamino) fluorene, etc. Can be Of course, it is not limited to these exemplified compounds.
  • the oxidizing material used as a constituent of the present invention is a methine-based compound that is gradually reduced by contact with the methine-based compound.
  • ⁇ ' means an organic or inorganic material that can be oxidized individually or quickly to develop a color, and includes all materials having such a capability. However, among these oxidizing materials; oxidizing organic compounds are particularly considered in consideration of safety, ease of application to the application, and the like.
  • R 8 is a hydrogen atom, a genogen atom, a cyano group, a thiol group, a carboxyl group, a carboxyl group, an aryloxy group, a aryloxy group.
  • Inorganic pigments having oxidizing ability are preferably used.
  • OMPI As specific examples of the benzoquinone derivative of the general formula ( ⁇ ) or dn) used in the present invention, 2,3-'cuccino-5,6—'chloro 1,4-benzoquinone, 3,4-dibromo 1, 5,6-dicyano-1,4 benzoquinone, 2,3,5,6-tet Lab rom: L, 4—Penzoquinone, 2:, 3, 5, 5, 6—Tetododo 1, 4 Benzoquinone, 2, 3, 5, 5 6 — Tetra 'Ethical Car Rental', 1,4-Penzoquinone, 2,3,5,6 — Tetra-i-Puttoxical Card,- Rules 1 and 4 — Benzoquinone, 3, 4, 5, 5 and 6 — Tetra-pro, Luo's Kiskarbo, -Le-1 and 4-Zonzoquino , .2,5,1 '-
  • inorganic forests having oxidizing ability include acid clay, activated clay, kaolins, and modified titanium oxide.
  • O PI Examples include, but are not limited to, equipment. These oxidizing materials are used alone or in various combinations as required for each application.
  • the hydrophobic organic compound used in the present invention has a desired melting point, dissolves a methine dye in a liquid state, dissolves an oxidizable material, or adsorbs to an oxidizable material. These materials may be used alone or in combination of two or more.
  • hydrophobic organic compounds can be produced by various known methods for forming a matrix of ⁇ -capsules, such as the Yumasel-Sion method using gelatin as a wall material, the interfacial polycondensation method, and the I n- Micro-gapsels are made by the Situ direct method or other methods.
  • the resulting micro gas cells require membrane tightness, resistance to the solvent of each plant: heat resistance, etc.
  • In -Amino-plast membrane microcapsules such as urine resin or melamine resin by Situ polymerization method, or polyurea or polyurethan by interfacial polymerization method Microcapsules for system membranes are preferably used.
  • the display kit of the present invention includes the above-mentioned methine dye, oxidizable material, and microcapsule gabcell containing a hydrophobic organic compound, together with other additives and auxiliaries. Applied to supports.
  • paper As the support, paper, paper, or the like, which can hold the above various components by coating, impregnation, penetration, printing, etc. 1-Various materials such as sheets, sticks, granules, and aggregates such as films can be used.
  • methine pigments or oxidized forestry can be used by dissolving or dispersing them in hydrophobic organic matter in micro-organic form. Included in the embodiments of the invention.
  • the methine dye and the oxidizing material used in this display lapel any of those described above can be used.
  • the hydrophobic organic compound is a compound having a melting point of ⁇ 30 ° C. to + 30 ° C.
  • the hydrophobic organic compound used is selected so that a phase change from a solid to a liquid occurs at a temperature K according to the purpose.
  • OMPI Specific examples of the compound include butyl stearate, pentyl stearate, benzoyl benzoate, and ethyl citrate oxalate.
  • the methine dyes of the general formula (I) have a dispersing or protective colloidal ability in a solvent that does not dissolve them, preferably in water. Mix well with the molecular solution or perform wet microparticulation to form a suspension.
  • a dispersant or a polymer having a protective colloid function used in the preparation of these suspensions an a-on type surfactant is used.
  • Nonionic surfactants polyvinyl alcohol, carbo, xymethyl cellulose, methylcellulose, hydroxylcell Loose, styrene maleic acid copolymer or its salt, disobutylene maleic acid maleic acid copolymer or its salt, aluminate, modified starch And synthetic, natural or modified natural polymers such as, zein, gelatin, and alla-gum.
  • methine compounds of general formula (I) include: Includes those that are unstable to and have a tendency to gradually become colored by air oxidation. In order to ensure the stability of such compounds against storage,
  • An appropriate amount of one or more selected from the following is dispersed when the methine dye is dispersed.
  • the water-soluble alkanolamine is an alkanolamine having a tertiary amino group, and the tris-N- (2—hydro AMIMIN, TRIS -N- (2-HIROXY PROVIL)-AMIMIN, TRIS N- (3 -Hydroxy opening pill) Min,] ⁇ , 1 ⁇ -'Kurohi.
  • the total amount of methamine is used. 1 to 100,000 parts by weight, preferably 1 to 1,000 parts by weight, based on 100 parts by weight of the element.
  • Methine dyes are sometimes treated with various aqueous or oily vehicles and used as aqueous or oily inks. .
  • the oxidizing material like the methine dye, is a hydrophobic organic material that is wet-milled or dispersed into an aqueous suspension in the presence of a surfactant or a protective colloid substance.
  • the compound is microencapsulated by itself or in a state in which a methine dye or an oxidizing material is dissolved or dispersed.
  • micro-gap capsules of the conjugate compound are applied as an essential component on the support, but other
  • various inorganic or organic pigments such as oleoresin, talc, titanium carbide, and acid oxide, are used to adjust the adhesiveness, surface properties, and coloring properties of the coating.
  • water-soluble powders, inders such as polyethylene alcohol, methylcellulose, hydroxyethyl cellulose, soluble starch, and starch.
  • Water-soluble indica such as cinnamon and vegetable gums, and stills to prevent destruction of microcapsules by micro pressure, such as flour starch and horses Starch starch and cellulosic. It is common to use various types of synthetic resin particles in combination.
  • the display label can be obtained by applying the aqueous coating liquid thus obtained on a support such as paper. .
  • composition of the coating layer examples include (1) a single-layer coating of a mixture of a methine dye, an oxidizing material, and a microcapsule of a hydrophobic organic compound on a support. How to
  • a spacer consisting of a polymer layer, and furthermore, the stability of the indicator lapel against water or solvents before or during use can be improved.
  • a water-soluble polymer or a water-based resin emulsion may be provided with a coat or a coat layer (protective layer).
  • the components used for the protective layer may be mixed and used in any coating layer.
  • a display label for temperature control can be obtained.
  • a part of the aqueous coating solution in the foreground may be replaced with a water pallet or an oily ink using a resin vehicle, and those printed by various methods are also within the scope of the present invention. included.
  • FIG. 1 shows a label with a methine dye, an oxidizing material, and a non-volatile organic compound applied to one side of a support, and the other side provided with an adhesive and release paper.
  • Fig. 2 shows a methine dye and an oxidizing material coated on one side of the support, with an overcoat and a coat protection calendar on top, and a micropower calendar on the other side.
  • This is a label that is provided with adhesive and release paper.
  • Fig. 3 shows a microcapsule of a hydrophobic organic compound in which a methine dye has been dissolved on one side of a support, and an oxidizable material together with a water- and oil-resistant polymer material.
  • the display label has a configuration in which an adhesive layer and a release paper are provided on the back side of the support on the ground.
  • Fig. 4 shows a configuration in which an adhesive layer and a release paper are provided on the back side of the support on the ground.
  • O PI -1- is a hydrophobic organic compound, a micro-organic compound that has oxidized materials for hiring and methine dyes for internal hiring, with a surface layer on one side of the support. It holds the tablet.
  • This label uses a substance with a certain melting point, such as microphone or capsule, although it should be sensitive to temperature. There is no anti-S due to contact with sexual forestry, and there is no need to pay attention to the temperature when coating the support, and the usual coating method, for example, Airny 7 Unit It can be coated or printed on a support using a pretender, knuckle coater, gravure printer, gravure printing machine, etc., and heat dried. O Can be stored at room temperature semi-permanently before use o
  • a display wrapper containing a microcapsule eyebrow having a melting point at a target temperature is attached to an article requiring temperature control or a case containing the article.
  • part or all of the microphone mouth capsule is destroyed by a tie printer, writing pressure or other pressing pressure on the lapel surface under an environment of a predetermined temperature or less.
  • micro-cavity destruction at room temperature is also possible by controlling the transit time with a spacer.
  • the contents of the capsule melt and become oily, and the oil diffuses through the gaps in the destroyed capsule wall.
  • the diffused oil is present in the vicinity of the same chromogenic layer or through the support in the molecular layer due to the contact between the methine dye and the oxidizing material in the chromogenic layer. Irreversible oxidative coloring of the methine dye occurs, and a robust color image of the corresponding hue of the methine dye is obtained on the label.
  • This temperature display tube can be used for frozen foods and refrigerated foods by selecting a mic mouth capsule that contains a hydrophobic organic compound that corresponds to the temperature to be controlled. It is extremely useful for managing temperature-sensitive materials.
  • the methine dye used can be selected from various hues suitable for the intended use conditions, for example, red, orange, blue, green, yellow, black, etc. .
  • the unit according to the present invention is not limited to the above-described sheet-shaped labels, but may be used in various shapes, for example, applied to granular materials or applied to rod-shaped materials, and used in various articles. Available according to:
  • a total of 50 ⁇ is dispersed by sand grinding mill to obtain an average particle size.
  • the ethylene maleic acid 10% aqueous solution 100 was mixed with water 100 ⁇ , and ⁇ was adjusted to 4.5 with a NaOH aqueous solution. In this solution, myristic acid was added. (Melting point 10 ° C)
  • Toxitriphenylmethane L 5 Methyl capsule of melamine resin membrane of ethyl ethyl myristate 1 T
  • the sheet After storing the sheet at -5 ° C for 30 minutes, the sheet was cut at the same temperature to destroy the microcapsule.
  • the stamped sheet is divided into six equal parts, and the temperature is constant at -5 ° C, 0 V, +2.5 ° C, +5 ° C, + T. 5 ° C, +10 ° C, respectively.
  • the degree of color development was observed below, it took 10 hours under the condition of -5 to 107.5 ° C. After the time, it was white without any tendency to develop color, but it was + 10 °.
  • the capsule rupture gradually turned green over time, and for 3 hours
  • Example-1 Using the dispersion and the microcapsule prepared in Example-1, two kinds of 20% aqueous solutions (a) and (b) were prepared.
  • Aqueous coating solution (a) was applied to one side of 50 ⁇ Z 'base paper and dried so that the dry coating amount was 5 ⁇ no, and then 2% acid-treated latin aqueous solution was dried. An overcoat, a coat, and a protective layer were provided so as to be 1.5 Zm 2 . Further, an aqueous coating solution (b) was applied on the back surface of the base paper so that the dry coating solution became 6 m 2 and dried to obtain a temperature display sheet.
  • the polymer was polymerized by Redo radial polymerization to obtain a 2.0% aqueous solution of the above three-component copolymer. (Viscosity 4, 3 0 0 C P
  • a 20% water / smear coating liquid having the following composition was prepared using the above dispersion and the microphone mouth capsule.
  • the label label material was cut, and the label as a 3 X 3 CT! Label was affixed to a frozen food packaging box and stamped at ⁇ 50 ° C.
  • the portion where the microcapsule was destroyed by embossing did not show any tendency to develop color under storage conditions of -10 ° C or lower, but the melting point of Under storage conditions higher than (-9 ° C), the color gradually became blue.
  • Methine dyes 109-Triethanolamine 19 Diethylene-triamine pentasulfonic acid Na salt 0.29-Bolibininole alcohol 10% aqueous solution 209-Water 18 1
  • Example 11 Also, according to the method of Example 11 except that dicarboxylic acid (with a melting point of 8) was used as the microcapsule inclusion material.
  • An aqueous coating solution having the following composition was prepared using the above-mentioned dispersion liquid and microcapsule.
  • the aqueous coating solution was coated on a 50 ⁇ base paper with a masker and a coater so that the dry coating amount was 6 ⁇ / 2, and then dried.
  • An I wt% aqueous solution was applied and dried to provide a coloring layer and a protective layer.
  • an allyl emulsion-based adhesive layer was applied to the back surface, and the resultant was overlaid with release paper to form a wrapper.
  • the lapel of this example was affixed to a container and stamped while stored at 4 ° C to break the microcapsule. There is no tendency to develop color at 4 ° C even when stored for a long time, but when stored at +8, the embossed surface gradually develops a yellow-red color with time, and it becomes clear in 15 hours Yellow-red saturation concentration
  • methine dye a,, f , tetrax (p-dimethylaminophenyl) -p-xylene is used as the methine dye.
  • An aqueous coating solution having the following composition was obtained using the microcapsule.
  • water-based coating liquid on one side of 50 ⁇ high-quality paper (b) a dry coating amount drying coating amount of water-based coating solution) is coated and dried on earthenware pots by ing and 1 0 ⁇ Bruno m z to further backside coated and dried in earthenware pots by the 7/2, ⁇ click Li
  • the microcapsule surface was adhered to release paper having a resin-based adhesive calendar (thickness: 40). When this sheet was subjected to the same test as in Example-1, +1 0 was obtained. No color development tendency was observed even after long-term storage up to C. For those stored at 4--12 ° C, the capsule rupture surface gradually developed a blue color after 1 hour, and 10 hours 7 «-»
  • Example-The following composition was used using the aqueous coating liquid used in Example 7. Temperature control sheet was obtained.
  • Aqueous coating liquid (a) is applied to the surface of 7-film synthetic paper (Oji Oil-based Synthetic Paper “Uvo” thickness 80 # 80 :) so that the dry coating amount is 6 S- /
  • partially saponified poly-vinyl alcohol Nippon Synthetic Chemical Co., Ltd. “Go-Sennar T-350”
  • the aqueous coating solution (b) was further applied to the upper layer and dried so as to have a dry coating amount of 59- / to obtain a temperature control sheet. It was pasted on a pattern (made by Sony Chemical).
  • Example 2 In the same manner as in Example 2 except that triplicyl citrate was used as the solvent to be wrapped, an ink for temperature history display for low temperature, When this sheet was subjected to the same test as in Example-1, it did not show a tendency to develop color for a long time when stored at -18 ° C or lower, and when stored at -13 ° C. After 2 hours, the color gradually began to develop green, and reached a saturation concentration after about 24 hours.
  • the sheet of this example is useful for managing the storage temperature history of frozen foods.
  • Microcapsule ⁇ -cell c Mono-sfloc 35 Oxidized starch (20% aqueous solution) 5 Triethanol Rin 5 Separately using an oxidizing inorganic material, the following water properties of 30 wt 9 & A coating liquid (b) was prepared.
  • the release paper having an adhesive on the backside of the high-quality paper was bonded to obtain a temperature history management sheet.
  • the sheet was stored at 2 ° C, 4 ° C, 6 ° C, and 8 ° C, respectively.
  • a blue-violet color developed gradually according to the stamped marks on the preserved product at 6 ° C or higher, and reached a concentration of 48 to 48 hours later. Labels on foods stored at +2 ° C and +4 ° C did not develop color even after 48 hours, but then developed blue-purple color when the temperature was raised to room temperature (18 C). did.
  • Aqueous coating liquid (a) Solid content 2.0 wt%
  • Microcapsule powder * 20 Modified vinyl nitrate derivative (“Ko-Ball” Nippon Gohsei ⁇ ) 50 0 'Octyl monophosphate monomonoethanolamine salt 25 Wheat flour starch 20
  • microcapsules were used for the aqueous inks (b to (!), Respectively).
  • the water-based flexographic inks (b) to (d) were placed at adjacent positions where they did not overlap with each other by a form printing machine with a filling amount of 5 ⁇ 2. Partial printing was performed so that
  • microcapsules were destroyed at -2 ° C and 5, respectively. Stored for 6 hours under the conditions of C, + 10 ° C, and 713: ° C
  • the printed portion of the water-based ink (b) did not show a coloring tendency.
  • Aqueous ink (b) The printed part turned blue.
  • Such a temperature control sheet is useful as a monitor for controlling the storage temperature range of articles.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Laminated Bodies (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Measuring Fluid Pressure (AREA)
  • Instruments For Measurement Of Length By Optical Means (AREA)
  • Color Printing (AREA)
PCT/JP1984/000148 1983-09-05 1984-03-29 Temperature supervision and display unit WO1985001105A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
GB08510599A GB2155633B (en) 1983-09-05 1984-03-29 Temperature supervision and display unit
DE19843490397 DE3490397C2 (de) 1983-09-05 1984-03-29 Indikatoreinheit f}r die Temperaturkontrolle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58/161889 1983-09-05
JP58161889A JPS6053984A (ja) 1983-09-05 1983-09-05 温度管理用表示ユニット

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Publication Number Publication Date
WO1985001105A1 true WO1985001105A1 (en) 1985-03-14

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US (1) US4729671A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0156912B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS6053984A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
KR (1) KR890000778B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA1217042A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (2) DE3490397T1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (2) GB2155623B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203776A3 (en) * 1985-05-24 1988-07-20 MITSUI TOATSU CHEMICALS, Inc. Coloring-time controlling layer
US4931420A (en) * 1986-04-30 1990-06-05 Mitsui Toatsu Chemicals, Inc. Temperature history indicator and its manufacturing method
CN107644583A (zh) * 2017-11-02 2018-01-30 广东天元实业集团股份有限公司 标签

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8410548D0 (en) * 1984-04-25 1984-05-31 Ciba Geigy Ag Colourable assembly
GB8427473D0 (en) * 1984-10-31 1984-12-05 Gen Electric Co Plc Temperature change indicating devices
JPH0684057B2 (ja) * 1985-04-30 1994-10-26 三井東圧化学株式会社 保存温度管理用ラベル
GB8614839D0 (en) * 1986-06-18 1986-07-23 Gen Electric Co Plc Indicating changes in temperatures
US5023366A (en) * 1986-11-05 1991-06-11 Mitsui Toatsu Chemicals, Incorporated Salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of the copolymers, and color-developing sheets employing the agents
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US4729671A (en) 1988-03-08
JPH0518878B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1993-03-15
GB2155633B (en) 1987-12-09
GB2155623B (en) 1986-11-26
GB8510599D0 (en) 1985-05-30
DE3490397C2 (de) 1987-11-05
GB8406319D0 (en) 1984-04-11
GB2155623A (en) 1985-09-25
DE3490397T1 (de) 1985-08-22
EP0156912A4 (en) 1989-03-23
EP0156912B1 (en) 1992-05-13
JPS6053984A (ja) 1985-03-28
KR850002307A (ko) 1985-05-10
CA1217042A (en) 1987-01-27
GB2155633A (en) 1985-09-25
EP0156912A1 (en) 1985-10-09
KR890000778B1 (ko) 1989-04-06

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