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WO1987003367A1 - Integrateur temps-temperature a base leuco photoactivable - Google Patents

Integrateur temps-temperature a base leuco photoactivable Download PDF

Info

Publication number
WO1987003367A1
WO1987003367A1 PCT/US1986/002301 US8602301W WO8703367A1 WO 1987003367 A1 WO1987003367 A1 WO 1987003367A1 US 8602301 W US8602301 W US 8602301W WO 8703367 A1 WO8703367 A1 WO 8703367A1
Authority
WO
WIPO (PCT)
Prior art keywords
indicator
temperature
leuco
time
reflectivity
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/US1986/002301
Other languages
English (en)
Inventor
Himangshu Ranjan Bhattacharjee
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.)
Honeywell International Inc
Original Assignee
Allied Corp
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 Allied Corp filed Critical Allied Corp
Publication of WO1987003367A1 publication Critical patent/WO1987003367A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00—Thermometers giving results other than momentary value of temperature
    • G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/229—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating time/temperature history

Definitions

  • This invention relates to a time-temperature indicator and, more particularly, to an indicator that is inactive until it is activated by actinic radiation.
  • U.S. Patent 3,768,976, issued October 30, 1973, to Hu et al. has disclosed a temperature-time integrating indicator that is based on temperature-dependent oxygen diffusion into a package that includes an aqueous solution of a redox dye. The dye is dark in the reduced state and becomes colorless when it is oxidized.
  • a photo- activatable time-temperature indicator comprises a mix ⁇ ture of:
  • the mixture is dispersed in a medium and coated, onto a substrate.
  • the present invention provides a method of measuring an incremental time-temperature exposure, which comprises the steps:
  • time-temperature indicator refers to a composition that responds in a measurable and predic ⁇ table way to the integrated effect of time and tempera ⁇ ture.
  • the activation of the time-temperature indicators of this invention is by photogeneration of an "acid,”
  • Figure 1 depicts the time dependence of reflectivity at 632 nm of an activated indicator label
  • Fig. 2 depicts the time dependence of the rate of change of reflectivity on indicator coating thickness and photoactivation.
  • a time-temperature indicator is a useful tool for those who are concerned with the freshness of perishable products.
  • the indicator must comprise a composition
  • Some disadvantages or concerns include ,- (i) possibility of activation by ambient light exposure,
  • a suitable time-temperature indicator can be based on color development of a leuco base.
  • Leuco bases are the colorless (i.e., white) forms, and can be considered to be the precursors, of dyes such as diphenylmethane _ and triarylmethane dyes. (Detailed information concerning these dyes - preparation, properties, etc. - appears in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. II, Academic Press, N.Y., 1952, pp 705 ff.)
  • triarylmethane leuco 0 bases (I) are generally preferred:
  • Each R is independently H, (C 1 -C 2 )alkyl, hydroxyalkyl, sulfonated alkyl, or a substituted phenyl group.
  • Each R' is independently H,C 1 -alkyl, or a sulfite group.
  • Each R" is independently H or C ⁇ -alkyl.
  • 1-R5 are independently H,(C 1 -C 4 )alkyl, halogen, amine, NfC ⁇ -C ⁇ al yl, carboxylic acid, sulfite, hydroxyl, or a substituted phenyl group.
  • Ar may also be replaced by naphthalene or substituted naphthalenes, in which case the leuco base is a diphenylnaphthylmethane leuco.
  • a He-Ne laser which emits at 632 run, is a convenient light source for monitoring the reflectivity of the indicators of the present invention.
  • the preferred leuco bases are those that provide final colors green, blue, or violet. Speci ⁇ fically, malachite green leuco (II), brilliant green leuco (III), and crystal violet leuco (IV) are particularly preferred.
  • HY is an acid.
  • the rate at which color develops depends on the temperature; i.e., the color development is an indication of time-temperature exposure.
  • the photoactivation process generates a carbinol or carbinol equivalent that then reacts with the photoacid to start the development of color.
  • the dye being formed by the (time-temperature dependent) action of photoacid on the leuco base.
  • a number of chemical compounds are known to gene ⁇ rate acids upon excitation with actinic radiation.
  • photoacids are o-nitrobenzaldehydes and substituted o-nitrobenzaldehydes; trihaloalcohols (X 3 ROH, where X is a halogen and R is an alkyl having at least 2 carbon atoms) ; and compounds of the form ⁇ n (I,S) (P,Sb,As)F m , where n is 2 or 3 and m is 4 for P and 6 for Sb or As.
  • X 3 ROH trihaloalcohols
  • the photoacid generator either not respond to ambient light exposure or that the indicator be protected from such exposure (e.g., by incorporating an opaque cover sheet or by keeping the indicator in the dark).
  • the photoactivation step must be reproducible. That can be accomplished conveniently and easily by, for example, using a reproducible light source or monitoring the photoactivation exposure.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biophysics (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Investigating Or Analyzing Materials Using Thermal Means (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)

Abstract

Un indicateur intégrateur de temps-température photoactivé se fonde sur un système à base leuco. Une base leuco blanche (''inactive'') insensible à la chaleur (ou un mélange de base leuco de ce type) est mélangée, de préférence dans une matrice polymère, à une substance produisant un acide lorsqu'elle est exposée à la lumière. La photoexcitation, de préférence par lumière ultraviolette ou une longueur d'ondes proche de l'ultraviolet, provoque la formation d'un produit chromogène (''actif'') sensible à la chaleur. A la suite de cette étape d'activation, un développement progressif de couleur se produit à une cadence augmentant avec la température. L'indicateur est utile pour contrôler la fraîcheur de denrées périssables, notamment celles stockées à une température inférieure à la température ambiante.
PCT/US1986/002301 1985-12-02 1986-10-28 Integrateur temps-temperature a base leuco photoactivable Ceased WO1987003367A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80375085A 1985-12-02 1985-12-02
US803,750 1985-12-02

Publications (1)

Publication Number Publication Date
WO1987003367A1 true WO1987003367A1 (fr) 1987-06-04

Family

ID=25187342

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/002301 Ceased WO1987003367A1 (fr) 1985-12-02 1986-10-28 Integrateur temps-temperature a base leuco photoactivable

Country Status (2)

Country Link
JP (1) JP2557362B2 (fr)
WO (1) WO1987003367A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2260813A (en) * 1991-10-26 1993-04-28 Raymond * Williams Terry Cryogenic labels to detect an exposure to sub zero temperatures for a predetermined period of time
WO1994012858A1 (fr) * 1990-03-16 1994-06-09 Jp Laboratories, Inc. Semiconducteur utilise dans le controle de valeurs integrales de temps et de temperature de stockage de produits perissables
WO2006021953A2 (fr) 2004-08-24 2006-03-02 Skyrad Ltd. Dispositif indiquant des produits sensibles a la temperature
US7294379B2 (en) 2002-03-07 2007-11-13 Avery Dennison Corporation Color changing device for time indicating label and methods of making and using the same
US11398167B2 (en) 2016-07-11 2022-07-26 Intray Ltd. Time temperature indicator label

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR66066E (fr) * 1956-05-03
GB880859A (en) * 1959-06-25 1961-10-25 Ncr Co Method for indicating temperature variations in a refrigerating apparatus
EP0117390A2 (fr) * 1983-02-25 1984-09-05 Lifelines Technology, Inc. Procédé de surveillance de l'exposé incrémental à l'environnement des produits, subissant des changements de qualité progressifs suite aux stimulations extérieures

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445232A (en) * 1965-10-21 1969-05-20 Horizons Research Inc Photography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR66066E (fr) * 1956-05-03
GB880859A (en) * 1959-06-25 1961-10-25 Ncr Co Method for indicating temperature variations in a refrigerating apparatus
EP0117390A2 (fr) * 1983-02-25 1984-09-05 Lifelines Technology, Inc. Procédé de surveillance de l'exposé incrémental à l'environnement des produits, subissant des changements de qualité progressifs suite aux stimulations extérieures

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012858A1 (fr) * 1990-03-16 1994-06-09 Jp Laboratories, Inc. Semiconducteur utilise dans le controle de valeurs integrales de temps et de temperature de stockage de produits perissables
GB2260813A (en) * 1991-10-26 1993-04-28 Raymond * Williams Terry Cryogenic labels to detect an exposure to sub zero temperatures for a predetermined period of time
US7294379B2 (en) 2002-03-07 2007-11-13 Avery Dennison Corporation Color changing device for time indicating label and methods of making and using the same
WO2006021953A2 (fr) 2004-08-24 2006-03-02 Skyrad Ltd. Dispositif indiquant des produits sensibles a la temperature
US8183045B2 (en) 2004-08-24 2012-05-22 Skyrad, Ltd. Indicating device for temperature sensitive products
US11398167B2 (en) 2016-07-11 2022-07-26 Intray Ltd. Time temperature indicator label

Also Published As

Publication number Publication date
JP2557362B2 (ja) 1996-11-27
JPS63502772A (ja) 1988-10-13

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