WO1990010868A1 - Indicateur, procede de fabrication et utilisation - Google Patents

Indicateur, procede de fabrication et utilisation Download PDF

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Publication number
WO1990010868A1
WO1990010868A1 PCT/EP1990/000377 EP9000377W WO9010868A1 WO 1990010868 A1 WO1990010868 A1 WO 1990010868A1 EP 9000377 W EP9000377 W EP 9000377W WO 9010868 A1 WO9010868 A1 WO 9010868A1
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WO
WIPO (PCT)
Prior art keywords
electron
compound
layer
excess
indicator
Prior art date
Application number
PCT/EP1990/000377
Other languages
German (de)
English (en)
Inventor
Hubert Müller
Dietrich Frahne
Bruno Langenfeld
Original Assignee
Badische Tabakmanufactur Roth-Händle Gmbh
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 Badische Tabakmanufactur Roth-Händle Gmbh filed Critical Badische Tabakmanufactur Roth-Händle Gmbh
Priority to BR909007203A priority Critical patent/BR9007203A/pt
Publication of WO1990010868A1 publication Critical patent/WO1990010868A1/fr

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Classifications

    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07C—TIME OR ATTENDANCE REGISTERS; REGISTERING OR INDICATING THE WORKING OF MACHINES; GENERATING RANDOM NUMBERS; VOTING OR LOTTERY APPARATUS; ARRANGEMENTS, SYSTEMS OR APPARATUS FOR CHECKING NOT PROVIDED FOR ELSEWHERE
    • G07C1/00—Registering, indicating or recording the time of events or elapsed time, e.g. time-recorders for work people
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/52—Use of compounds or compositions for colorimetric, spectrophotometric or fluorometric investigation, e.g. use of reagent paper and including single- and multilayer analytical elements
    • G01N33/525—Multi-layer analytical elements

Definitions

  • the invention relates to an indicator for recording the course of an event according to the preamble of claim 1, a method for its production and its use.
  • Indicators are mainly used for the temperature control of, in particular, chilled and frozen products as well as active substances or drugs, such as vaccines or blood preserves, which have to be stored at a certain temperature.
  • a change in the optimum storage temperature for these products is usually indicated by an irreversible change in the color of the indicator, which represents a measure for exceeding the permissible maximum temperature and thus for the unusability of these products.
  • DE-PS 32 10 907 describes an indicator for detecting the time / temperature load of an object, in which the d control is to be carried out over relatively long periods of time and / or at higher temperatures.
  • the start delay of the indicator requires a special adjustment of the melting range of the active chemical substance as well as storage below the start temperature.
  • Measuring system consisting of a label containing a vaporizable organic or inorganic solid is used up on the consumer goods or its packaging. Because of their structure, the proposed indicators cannot be used for an exact recording of the maximum storage time and do not allow any setting of the start time.
  • REPLACEMENT LEAF 5 DE-PS 37 17 025 discloses a display device for time-dependent processes, in particular for the display of the usability of perishable or time-limited products with a depot containing an indicator mass, and an indicator strip that changes
  • the depot channel is spatially separated from the indicator strip and connected to it via a channel, and the depot is deformable by external pressure in such a way that the indicator mass can be removed by the
  • the display device can be defined as an indicator for the temporal recording of the course of an event (for example validity time or shelf life of products) by reaction of a first chemical compound with a second chemical compound that occurs with a visible color change, whereby reaction-delaying means are provided in accordance with the time sequence to be recorded and the start of the time sequence constitution can be controlled, if necessary, by initially preventing the reaction.
  • reaction-delaying means are provided in accordance with the time sequence to be recorded and the start of the time sequence constitution can be controlled, if necessary, by initially preventing the reaction.
  • the reaction which takes place with visible color change could also be a loose color reaction of the colored indicator mass with the indicator strip without a chemical reaction
  • the reaction-delaying agents in the case of DE-PS 37 17 o25 are formed by the wick-like structure of the indicator strip, which allows the color reaction to proceed only slowly
  • the control of the start of the time lapse detection by initially preventing the color reaction in DE-PS 37 17 025 is given when the intended Compression of the depot chamber containing the indicator mass is carried out earlier or later with a plunger. If this happens immediately when the indicator is being manufactured or attached, the time lapse recording begins immediately, and if the depot chamber is pressed together later, the time lapse recording also begins later. The time recording can start immediately or later if you wish.
  • the delayed effect of the color reaction due to the wick structure and the resulting time lapse are independent of whether the color reaction is initially completely prevented and only started when the depot chamber is compressed, or is started immediately.
  • REPLACEMENT LEAF DE-AS 23 46 598 describes an indicator for the temperature control from a carrier film and a cover film, in which, by choosing the degree of saponification, the saponification agent or the molecular weight of the starting ester, the degree of solubility of the film up to the time of the color change can be adjusted. To avoid condensation, however, both foils must be applied at room temperature and at a uniform temperature, otherwise the reaction will be triggered too early.
  • the object of the invention is therefore to provide an indicator with a simplified structure, which can be produced in a simple manner and in which the start time can be controlled by the user independently of the type of previous storage.
  • the invention characterized in claim 1 is characterized in particular by the fact that the indicator can be easily produced and, regardless of the type of previous storage, allows simple control of the starting time of the time lapse recording as desired by the user.
  • the indicator can be designed in a simple manner for an initial inhibition of the chemical reaction between excess electron compound and electron deficiency compound or, if desired, no means need to be provided for the initial inhibition of the chemical reaction, so that the timing sequence can then be recorded immediately
  • the indicator is produced or applied to a product. Even then, the reaction-in the dependent claims in each specified center permit an exact delay of the indicator display corresponding to the running time intervals to be detected '.
  • SHEET arises, but an adduct with different light absorption properties than the starting materials.
  • the color characteristics of the output • ** ⁇ materials and incurred in responding Farbände ⁇ draw tion by particular color stability.
  • Significant colorations on the excess or deficient electron compounds and the adduct formed by reaction can only be brought about by chromatographic treatment, and in particular the products provided with such indicators are under no circumstances exposed to the usual storage conditions.
  • the invention also has the advantage that regardless of ⁇ he like warehousing and environmental influences the user. the situation
  • the electron deficiency and excess electron compounds are preferably substituted aromatic compounds and / or unsubstituted and / or substituted heterocyclic compounds. Because of the properties of these compounds to form colored donor-acceptor complexes, the user has, in an essentially minor dependence on the temperature, many compounds which are distinguished by a different color reaction and which enable an analog display ⁇ lichen.
  • microencapsulation technology for the connections used which can also be used advantageously in the context of the present invention, it should be noted that the technology of microencapsulation as such belongs to the prior art.
  • FIG. 1 illustrates an indicaotr with electron donor and electron acceptor in separate polymer embeddings with a spacing intermediate layer.
  • Fig. 2 illustrates such an indicator without a spacing intermediate layer.
  • FIG 3 illustrates such an indicator with a polymer (aromatic polyurethane) as an electron donor and an electron acceptor in a polymer bed.
  • FIG. 4 illustrates an indicator with an electron donor component which gradually changes into an electron acceptor component due to the action of oxygen from the air and thus forms the DA complex.
  • Fig. 5 illustrates an indicator with an electron - * 1 acceptor component, which is converted into an electron donor component by a reducing agent and thus gradually forms the DA complex.
  • FIGS. 8 and 9 illustrate decay indicators which respond more slowly, the response speed being controllable by choice of the thickness and the per eability of the intermediate layer
  • FIG. 1o illustrates an indicator with a reaction partner dissolved in polymer and with a micro-encapsulated reaction partner embedded therein
  • FIG 11 illustrates an indicator with two separate polymer layers, microencapsulated reactants.
  • the area of the indicators can be designed largely differently depending on the application.
  • strips of approximately 4 cm in area can be used.
  • the indicators can also have a different shape or be larger or smaller, with good visibility being ensured.
  • the electron excess compounds used according to the invention are unsubstituted and / or substituted in the 2-, 3-, 5- or 6-position quinones, phenolic polymeric compounds and / or corresponding polymeric aromatic amines and / or phenylogous compounds.
  • Suitable compounds here are hydroquinone, hydroquinone derivatives, for example alkylated and / or oxalkylated and / or carboxylated and their esterified compounds, pyrocatechol and its derivatives, phloroglucinol, aniline and its derivatives, ,minophenols, o-, m-, p-phenylenediamine, tannin and its alkylated, halogenated, ethers and esters Deri ⁇ derivatives and other tannins' Aminotriphenylmethanfarbstoffe
  • REPLACEMENT LEAF and their leuco compounds, as well as aromatic polyurethanes.
  • Compounds with phenolic groups are preferably used.
  • the advantages of the above-mentioned compounds are their easy availability and their physiological safety.
  • Low molecular weight aromatics or those substituted with electronegative (-M) groups have proven to be suitable electron deficiency compounds for the indicator according to the invention.
  • Preferred are o- and p-benzoquinones and their 2-, 3-, 5- or 6-positions with e.g. Halogen-substituted derivatives, nitrated aromatics, such as phenol nitrated in 2-, 4-, 6- or 2,, 6-position or analogous phenols carrying several hydroxyl groups or o-, m-, p-nitroaniline or 2,4,6-trinitroaniline or phenylogue of these compounds, e.g. Picric acid, aniline picrate and chloranil, since they are easy to manufacture and physiologically unproblematic.
  • Excess compound are used, which gradually changes into an electron compound by oxidation or action of a second, slow-acting reaction partner.
  • the action of, for example, atmospheric oxygen, a comparatively stable peroxide or reducing agents which have reducing aldehyde groups, for example ascorbic acid, hydrocellulose, hydrolyzed starch or generally reducing mono-, oligo- or polyglucosides leads to a gradual reduction Conversion of the excess electron compound into the electron beam compound, whereby under the conditions, ie the simultaneous presence of a remaining part of the original excess electron and electron deficiency compounds, it is sufficient to form the colored donor-acceptor complex.
  • 'nat ⁇ Lich also an electron-deficient compound be used which passes over the aforementioned second under the action, lang ⁇ sam acting reactant partially into the Elektronen ⁇ over connection.
  • the electron deficiency compound used as one of the components of the indicator of the present invention is preferably in a substrate in from 0.01 to 10 wt. -%, based on the substrate. Before the electron deficiency is in 1 to 3 wt. -% contained in the substrate. This makes it possible, on the one hand, to eliminate any health concerns that may otherwise be associated with aromatic compounds, and, on the other hand, to control the formation of the colored complex, while at the same time keeping the concentration of the excess electron compound constant, as required.
  • the excess electron compound is contained in a substrate in from 0.01 to 10% by weight, based on the substrate, preferably in from 3 to 8% by weight. This gives the user the option of using both different concentrations of the excess electron compound and different concentrations of the electrons.
  • REPLACEMENT LEAF to control the rate of formation of the color complex and the intensity of the color complex.
  • the substrate consists of a polymer and / or oligomer building block.
  • the building blocks used should essentially not be crystalline, serve on the one hand as a carrier for the electron deficiency and excess electron connection or themselves as one of these reaction components and on the other hand to control the chronological sequence. In addition, they serve to simplify stabilization against harmful environmental influences such as light, temperature or moisture.
  • the substrate is a polymer of acrylic acid, an acrylic acid ester, vinyl acetate, vinyl chloride, vinyl alcohol and / or a mixture thereof.
  • the polymer is preferably a polyacrylic acid or polyvinyl acetate derivative.
  • the indicator of the present invention may contain an oligomer of acrylic acid, an acrylic acid ester, vinyl acetate, vinyl chloride, vinyl alcohol and / or a mixture thereof as a substrate.
  • the oligomer is a Acrylklareester.Dh is the user of the indicator of the invention a further possibility ness by varying the diffusion conditions into the hand, the time _blauf, ie the formation of far ⁇ -lived complex to set more accurate.
  • the polymer and / or old building blocks of the substrate in from 2 to 70% by weight dissolved in an inorganic and / or organic solvent.
  • the preferred range is from 20 to 40% by weight.
  • the suitable solvents are water, lower alcohols, ketones, esters of organic acids and / or mixtures thereof.
  • the preferred solvents are water, methanol, ethanol, propanol, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate or mixtures thereof.
  • the advantage of these solvents is that they are physiologically unobjectionable and harmless and easy to handle with regard to the separate application of different substrate layers.
  • a substrate can additionally be formed as a cover and / or intermediate layer without one of the electron deficiency connections and / or excess electron connections. This gives the user the option of triggering the formation of the colored donor-acceptor complex by simply pulling off, for example, the cover layer and the associated access of atmospheric oxygen.
  • An additional, formed between the Elektronen ⁇ Hz- and Elektronenschreibschußtagen- substrate layer intermediate layer serves as a time ⁇ Licher spacer and enables control of the union zeit ⁇ sequence. This intermediate layer is not to be regarded as a reaction-triggering part, but nevertheless as a reaction-determining part.
  • the substrate of the indicator according to the present invention can additionally contain migration-influencing additives in from 0 to 20% by weight, based on the substrate. These additives are preferably contained in from 2 to 15% by weight. By admixing these additives, which are essentially only diluting and inert components, the reaction time and the color depth to be achieved can be achieved in a simple manner influence. These additives can be contained both in the top layer and in the intermediate layer.
  • these additives are alkyl glycol ethers, polyglycol ethers, esters of aliphatic and aromatic carboxylic acids and / or a mixture thereof.
  • the additive is preferably a phthalic acid ester or a glycol ether.
  • the indicator according to the invention can be manufactured in a simple manner.
  • a 0.01 to 10% by weight solution of an excess of electron compound is prepared in a suitable inorganic and / or organic solvent. If necessary, the excess electron compound can be introduced in from 1 to 5% by weight in a solution of a suitable substrate, which can serve as a carrier substance. Migration-promoting, inert additives in an amount of 0 to 20% by weight can be added to the solution of the excess electron compound and to the substrate made of polymer and / or oligomer building blocks serving as carrier substance.
  • the solution thus formed is then in at least one preparation oincr layer applied by known methods, such as brushing or spraying, and then dried at a temperature of 20 to 100 ° C., preferably 25 to 50 ° C.
  • Solution of the excess electron compound are prepared, which are subsequently by z. B. mechanical pressure is applied to the preparation.
  • a 0.5 to 5 is selected.
  • the same additives as before can be added to this solution.
  • This solution optionally in the form of a viscous paste, is then applied to the layer or. applied to the film or foil of the electron excess compound in o at least one layer. In a preferred one
  • the solution of the electron deficiency connection is applied in the form of a film or a film with an applied adhesive layer on one side facing the side to be acted on by means of known application methods or by applying mechanical pressure to the first 5 layer of the excess electron connection.
  • Similarity or the more or less different similarity of the polymers and the solvents is either a relatively spontaneous or, depending on the additives, a delayed formation of the colored complex.
  • the polymers are not spontaneously miscible, e.g. of polymers of different solubility and the use of solvents which are miscible with one another only to a limited extent, electron deficiency and excess electron compounds slowly diffuse to one another and form the colored donor-acceptor complex with a time delay.
  • the electron deficiency connection can be applied first and then the excess electron connection.
  • the solutions formed from an electron deficiency and excess electron compound are applied in layers of different thicknesses, the concentration or the electron deficiency and excess electron connection in the solution or in the substrate, which may contain additives, if appropriate the formation of the visible colored complex can be controlled in a simple manner. It has proven to be advantageous to apply these solutions in layer thicknesses of 1 to 250 ⁇ m, preferably 5 to 100 ⁇ m.
  • an intermediate layer made of a substrate which contains both polymeric and / or oligomeric building blocks and optionally the aforementioned inert additives, can transfer between the two layers of electron deficiency compound and electrons ⁇ shot connection introduced. In this way it is possible for the user to control the visible color change, which is the measure for the course of an event.
  • This intermediate layer is of different thickness depending on the requirements. It is preferably from 1 to 250 ⁇ m, in particular from 5 to 50 ⁇ m. In addition, immediate mixing or diffusion of the two compounds together can be avoided.
  • a cover layer which is inert to damaging environmental influences, such as atmospheric oxygen, temperature or moisture, can be arranged over the layers containing excess electrons and electron deficiency compounds become.
  • This cover layer can fulfill two functions: firstly, by removing the cover layer, the user can trigger the course of the desired event, and secondly, because of the considerable adhesive and abrasion resistance of this cover layer, damage and thus a disturbance of the intended reaction can be avoided.
  • the solution of the electron deficiency compound and / or electron excess compound and / or another reaction partner can be introduced separately into the substrate in the form of microcapsules. become.
  • the spatial separation of the microcapsule-containing substrate applied to the preparation prevents the reaction of the two chemical compounds. This has the advantage that the start time for the change of state can be controlled by the user alone, regardless of the type of previous storage.
  • the intended event is preferably triggered by the action of mechanical pressure when the indicator produced according to the invention is applied to a product, the pressure destroying the capsules containing electron deficiency and excess electron compounds, and the compounds, depending on the substrate used and any NEN additives diffuse to each other, wherein the visual indicating ⁇ bare color change of the formed donor-acceptor complex, the flow of, for example, the maximum allowable storage time of Produk ⁇ tes.
  • the indicator of the present invention can also be made by applying a film or layer of a solution of an electron deficiency or electron excess compound to a product, and then the starting time by the user by applying a corresponding other film or layer of the electron deficiency - or the excess electron connection, which is necessary for the formation of the grain
  • top layers and / or intermediate layers which slow down the formation of the visible color changes or accelerating additives can be applied within intermediate layers.
  • the indicator can also be started by applying a cover layer with an electron deficiency or excess electron compound as a reaction partner or a further reaction partner or by pulling off a cover layer which protects against damaging environmental influences.
  • the indicator produced according to the invention it is thus possible, depending on the type of electron deficiency and excess electron compound used, the substrate used and the additives used, the course of an event and various visible color changes in a simple and trouble-free manner, i.e. regardless of e.g. Environmental influences, adjust and control.
  • the indicator of the present invention is used both in products that are limited in time and that have a shelf life that is limited in time. For example, use here only as a day pass, monthly stamp, for bulk items, foodstuffs with a limited shelf life, e.g. Dairy products, or medicines and active substances that can be stored for a limited period of time.
  • DA complex donor-acceptor complex
  • a layer of aniline picrate is applied in polyacrylate.
  • An optionally overlying layer of polyvinyl acetate or polyacrylic acid ester acts as a spacing layer which controls the temporal formation of the DA complex of the layer of 1,4-quinone in polyacrylate applied over it.
  • An optionally covering layer made of polyvinyl acetate or a polyvinyl chloride-acetate copolymer protects against damaging environmental influences.
  • a dark brown colored DA complex is formed.
  • the discoloration begins immediately without an intermediate layer and is completed within 2 hours. Depending on the type and thickness of the intermediate layer, the discoloration occurs in a few weeks, e.g. with a 100 ⁇ m thick intermediate layer made of polyacrylic acid ester in about 6 weeks.
  • a layer of chloranil in polyurethane, optionally a layer of polyacrylic acid ester and a layer of polyurethane with electron donor component are applied in succession to any preparation.
  • a layer of polyurethane is applied to any preparation
  • Electron deficiency compound initiates the formation of the DA complex. If necessary, a cover layer made of a polyacrylic acid ester can be applied.
  • a cocoa brown colored DA complex forms within 6-8 weeks, with an intermediate layer (depending on type and thickness) in more than 3 months.
  • a layer of a polyvinyl chloride-acetate copolymer, a layer of ascorbic acid in polyacrylate for reducing quinone diffusing into hydroquinone, a layer of 1,4-quinone in polyacrylic acid ester and, if appropriate, a covering layer of polyacrylic acid ester are applied in succession to any preparation.
  • a reddish brown DA complex forms in 1 week.
  • a layer of aniline picrate in polyacrylate and a layer of benzoquinone in polyacrylic acid ester are applied to any preparation.
  • a chocolate brown colored DA complex forms immediately, the discoloration being complete after about 2 hours.
  • a layer of 1,4-quinone in polyvinyl acetate is applied to any preparation, and a layer of an aromatic polyurethane with an electron excess compound is applied over it.
  • a coffee brown colored DA complex forms in 1 to days.
  • Acetate copolymers and a layer of benzoquinone in polyacrylic acid ester applied in succession Acetate copolymers and a layer of benzoquinone in polyacrylic acid ester applied in succession.
  • a dark brown colored DA complex forms in 3 weeks.
  • a layer of 1,4-quinone in polyacrylic acid ester, a layer of polyvinyl acetate and a layer of polyurethane with aromatic excess electron compound are successively applied to any preparation.
  • a dark brown colored DA complex forms within 8 weeks.
  • a layer of phloroglucin in polyacrylate, a layer of microencapsulated 1,4-benzoquinone in polyurethane and optionally one are placed on any preparation
  • a layer of microencapsulated aniline picrate in polyurethane, a layer of microencapsulated 1,4-benzoquinone in polyurethane and optionally a layer of polyacrylic acid ester are applied in succession to any preparation.
  • microcapsules are broken open by applying mechanical pressure and a dark brown DA complex is formed within 30 minutes.
  • Formation of a DA complex by combining a low-molecular electron deficiency compound and a polymeric excess electron compound in each case in a separate layer and with a controlling intermediate layer.
  • 1,4-benzoquinone 1 g is dissolved in 10 ml of ethyl acetate at 35 ° C. and then this solution is added to 89 g of polyacrylic acid propyl ester solution (20% in ethyl acetate). The solution obtained is applied in a 100 ⁇ m thick layer to a preparation (packaging box) and dried at 40 ° C.
  • aqueous polyurethane layer (50% strength, with an aromatic amine as a fixed component of the polyurethane as a donor component) is then applied to the dried layer and air-dried.
  • the almost colorless layer sequence forms a black-brown layer at 20 ° C
  • Example 2 was repeated, but no controlling intermediate layer was introduced between the layer with the electron deficiency compound and the layer with the electron excess compound.
  • the black-brown DA complex begins to form immediately and is completed within 1 day.
  • the polyvinyl acetate layer according to Example 1 is applied as the top layer.

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Abstract

Indicateur pour suivre le déroulement d'un processus grâce à la réaction d'un premier composé chimique avec un second composé chimique, cette réaction entraînant un changement de couleur visible. L'invention est caractérisée par le fait que le premier composé chimique est un composé à foisonnement d'électrons et que le second composé chimique est un composé à manque d'électrons, le début du processus étant déclenché par la mise en contact simultanée ou successive des deux composés. L'invention porte également sur des développements de ce concept de base, ainsi que sur des procédés de fabrication de cet indicateur, où l'on dissout un composé à foisonnement d'électrons dans un solvant approprié, le cas échéant dans une solution d'un substrat servant de support, on applique au moins une couche de la solution ainsi obtenue sur une préparation et on la laisse ensuite sécher; on dissout un composé à manque d'électrons dans un solvant approprié, le cas échéant dans une solution d'un substrat servant de support, et l'on applique au moins une couche de cette solution sur la couche séchée du composé à foisonnement d'électrons appliquée sur la préparation, ce qui déclenche le processus. L'invention porte enfin sur des développements de ce procédé et sur les utilisations d'un tel indicateur dans des produits à durée de vie ou de conservation déterminée.
PCT/EP1990/000377 1989-03-09 1990-03-08 Indicateur, procede de fabrication et utilisation WO1990010868A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BR909007203A BR9007203A (pt) 1989-03-09 1990-03-08 Indicador,processo para sua fabricacao bem como seu emprego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3907683A DE3907683A1 (de) 1989-03-09 1989-03-09 Indikator, verfahren zu seiner herstellung sowie seine verwendung
DEP3907683.0 1989-03-09

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WO1990010868A1 true WO1990010868A1 (fr) 1990-09-20

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EP (1) EP0462134A1 (fr)
JP (1) JPH04505213A (fr)
AU (1) AU5189490A (fr)
BG (1) BG60124B2 (fr)
BR (1) BR9007203A (fr)
CA (1) CA2050280A1 (fr)
DD (1) DD299084A5 (fr)
DE (1) DE3907683A1 (fr)
WO (1) WO1990010868A1 (fr)
ZA (1) ZA901841B (fr)

Cited By (3)

* 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
EP0608820A1 (fr) * 1993-01-27 1994-08-03 Kyoto Daiichi Kagaku Co., Ltd. Composition analytique
EP0735368A1 (fr) * 1995-03-31 1996-10-02 Toyo Ink Manufacturing Co., Ltd. Procédé d'indication de la valeur accumulée du temps ou température-temps par un changement de couleur, et matériaux

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3936542C1 (fr) * 1989-11-02 1991-04-11 Badische Tabakmanufaktur Roth-Haendle Gmbh, 7630 Lahr, De
DE4316688A1 (de) * 1993-05-06 1994-11-10 Schwerdtle & Schantz Gmbh Anzeigevorrichtung

Citations (3)

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Publication number Priority date Publication date Assignee Title
GB2180964A (en) * 1985-08-29 1987-04-08 Johnson Matthey Plc Indicator element
EP0247845A1 (fr) * 1986-05-30 1987-12-02 EASTMAN KODAK COMPANY (a New Jersey corporation) Utilisation de colorants méthiniques pour déterminer le péroxyde d'hydrogène ou des analytes produisant le même
US4826762A (en) * 1987-10-23 1989-05-02 Massachusetts Industry Of Technology Enzymatic temperature change indicator

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EP0462134A1 (fr) 1991-12-27
DE3907683C2 (fr) 1991-04-11
DE3907683A1 (de) 1990-09-20
BG60124B2 (bg) 1993-10-29
CA2050280A1 (fr) 1990-09-10
JPH04505213A (ja) 1992-09-10
DD299084A5 (de) 1992-03-26
AU5189490A (en) 1990-10-09
ZA901841B (en) 1991-03-27
BR9007203A (pt) 1991-12-10

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