EP2810034A1 - Temperature range compliance indicator - Google Patents
Temperature range compliance indicatorInfo
- Publication number
- EP2810034A1 EP2810034A1 EP13704200.8A EP13704200A EP2810034A1 EP 2810034 A1 EP2810034 A1 EP 2810034A1 EP 13704200 A EP13704200 A EP 13704200A EP 2810034 A1 EP2810034 A1 EP 2810034A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermochromic
- temperature
- color
- compositions
- product
- 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
Links
Classifications
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- 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
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- 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
- C09D11/16—Writing inks
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- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/26—Thermosensitive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
Definitions
- the present invention relates to an indicator or control, which may take the form of a label, allowing, by simple visual control, to instantly check the status of good conversation of a product and in particular to detect if the product has momentarily leave a certain temperature range, and memorize this event.
- an indicator or control which may take the form of a label, allowing, by simple visual control, to instantly check the status of good conversation of a product and in particular to detect if the product has momentarily leave a certain temperature range, and memorize this event.
- strict monitoring of a temperature range is essential to guarantee their quality.
- the invention applies to any product or device requiring temperature monitoring between two thresholds.
- the document FR 2 899 684 describes a product conservation status indicator, making it possible to detect whether the temperature of a product has crossed a predetermined threshold, the so-called set temperature.
- This indicator comprises two transparent films hermetically assembled so as to trap two doses of liquid or viscous products, these doses being separated by an adhesive seal sealingly connecting the opposite faces of the two films.
- the glue is such that it loses its adhesive properties when a predetermined temperature is exceeded, so that if, after the activation of the indicator, the set temperature is reached, then the viscous products are free to mix, this mixture resulting in an irreversible state change such as a color change.
- EP 1 410 368 discloses a fuel tank having a security tag located on the outer face of a tank, said tag containing at least one reversible thermochromic material.
- This label changes color beyond a temperature threshold to warn the user of a possible burn on the skin if it does not have protection.
- the label only detects a temperature crossing up (overheating). This label is therefore unusable as a temperature control down (gel) for products which, for example, should not be frozen under any circumstances.
- the problem that the present invention seeks to solve is to provide a simple and reliable system for accurately determining whether an object or product has left a certain temperature range, and to memorize this event.
- This system must be capable of being manufactured to react at different temperature thresholds, it must be inexpensive, resistant to the environment in which it is used, and it must not contaminate the product to which it is affixed.
- thermochromic product (E) such as an ink, a paint, or a thermochromic plastics material (E), composed of at least two thermochromic compositions (Ei) and (E 2 ), each having a first and a second state of color as a function of temperature, the passage of said first said second state of color being reversible, characterized in that said compositions thermochromic (Ei, E 2 ) have a thermal hysteresis, so that during the heating of said thermochromic compositions (Ei, E 2 ), the transition from said first color state to said second color state occurs at a different threshold temperature than the passage of said second color state to said first color state upon cooling of said system.
- said thermochromic product (E) has several color states, which depend not only on the temperature at which it is located, but also the thermal history that it has undergone.
- said system has an adjustable thermal hysteresis.
- adjustable it is meant that the thermal hysteresis is such that the response curve (color density-temperature curve) of one of the two thermochromic compositions, for example (Ei), frames that of the second thermochromic composition ( E 2 ).
- thermochromic compositions (Ei, E 2 ) contained in said system are in microencapsulated form. This preserves the chemical integrity of the mixture and protects it from the external environment. More particularly, each of the thermochromic compositions (E 1 , E 2 ) can be microencapsulated separately from each other; thus, the thermochromic product (E) comprises at least two different types of microcapsules, namely a first type for the thermochromic composition (Ei) and a second type for the thermochromic composition (E 2 ). As will be explained below, each thermochromic composition (E 1 , E 2 ) comprises at least two components intended to interact optically or visually.
- control system is in the form of a support, in particular a flexible, semi-rigid or rigid support, such as a plastic film, preferably transparent, on which an ink has been applied.
- thermochromic (E) thermochromic product (E) composed of at least two thermochromic compositions ( ⁇ !, ⁇ 2 ). More particularly, said support, after application of said thermochromic product (E), may be affixed to a package or product or batch of products (P).
- control system is in the form of a support, in particular a flexible, semi-rigid or rigid support, such as a plastic film, preferably transparent, in which at least one embodiment has been incorporated.
- a support in particular a flexible, semi-rigid or rigid support, such as a plastic film, preferably transparent, in which at least one embodiment has been incorporated.
- said support after application of said thermochromic compositions (Ei, E 2 ), may be affixed to a package or a product.
- control system is in the form of a thermochromic label with a white background, colored or transparent, comprising a transparent substrate, white or colored, on which was applied a thermochromic ink (E) in as a thermochromic product (E), composed of at least two thermochromic compositions (E 1 , E 2 ).
- control system is characterized in that at least one of the color states of at least one of the thermochromic compositions (E 1 , E 2 ) can be detected outside the visible spectrum, and in a variant of this embodiment only outside the visible spectrum. More particularly, at least one of the color states of at least one of the thermochromic compositions (E 1 , E 2 ) can be detected in the ultraviolet and / or infrared range, and in particular near ultraviolet and / or near infrared.
- the control system comprises a thermochromic product (E) composed of more than two thermochromic compositions
- E thermochromic product
- the control system according to the invention can be used as an indicator of compliance with a temperature range, particularly as an indicator of good conservation of temperature-sensitive products.
- the control system according to the invention can serve in particular as an indicator of good conservation of pharmaceutical products (in particular: blood bags, injectables, vaccines, pharmaceutical preparations, pharmaceutical emulsions, creams, gels), of food products (in particular: dairy products , alcoholic beverages, non-alcoholic drinks, especially wines and spirits), industrial emulsions (in particular: varnishes, paints, concrete additives, cleaning products) and other products such as flowers and plants.
- the subject of the invention is also a method of using the control system according to the invention, comprising at least two thermochromic compositions (Ei, E 2 ), in which process:
- thermochromic compositions (E 1 , E 2 ) (b) transferring said system to a desired color initial state by heating or cooling it to a temperature leading to the color change of at least one of the thermochromic compositions (E 1 , E 2 ),
- step (c) affixing said system to a product or batch of products (P) to be monitored so that between step (b) and (c) said system is maintained in a temperature range
- thermochromic compositions (Ei, E 2 ) which does not lead to a change in the color state of one of the thermochromic compositions (E 1 , E 2 ).
- the control system is in particular a thermochromic label.
- a transparent or translucent control system according to the invention above a bar code of a product or a batch of products (P) to be monitored, and wherein said thermochromic compositions (Ei, E 2 ) are chosen so that:
- the following steps are carried out when the system, after affixing to said product or batch of products (P) to be monitored, indicates a change in the color state:
- thermochromic ink (E) composed of at least two thermochromic compositions (Ei) and (E 2 ), each of said thermochromic compositions (Ei, E 2 ) being microencapsulated separately from one another. and each having a first and a second state of color as a function of temperature, the passage of said first said first color state being reversible, characterized in that said thermochromic compositions (E 1 , E 2 ) exhibit a adjustable thermal hysteresis so that the response curve (color density-temperature curve) of one of the two thermochromic compositions (Ei) surrounds that of the second thermochromic composition (E 2 ), and so that during warming of said thermochromic ink (E), the transition from said first color state to said second color state occurs at a different threshold temperature than the transition from said second color state to said first color state upon cooling of said thermochromic ink (E ).
- a final object of the invention is an instrument to be written or drawn, in particular a pen, a felt pen, a wax pencil or a chalk, comprising the thermochromic ink (E) according to the invention.
- thermochromic product such as an ink, a paint or a thermochromic plastics material (E), composed of at least two thermochromic compositions, for example (Ei) and (E). 2 ), each having binary color variations (eg color state / bleached state) as a function of temperature.
- thermochromic compositions it is possible to use known thermochromic compositions, for example those described in FR 2,591,534 or EP 1,477,320. These compositions typically comprise:
- (B) an electron acceptor compound which may be chosen in particular from the group formed by phenolic compounds, metal salts of phenolic compounds, aromatic carboxylic acids, aliphatic carboxylic acids, metal salts of carboxylic acids, esters phosphoric acids, metal salts of acidic phosphoric esters and triazole derivatives, and,
- (C) a solvent, as a reaction medium which controls the color reactions between the compounds (A) and (B): it is generally a polar solvent.
- Solvents may be alcohols, esters, amides or acids, especially long-chain aliphatic.
- thermochromic compositions the components (A), (B) and (C) respectively act on the type of shade, the color density and the color temperature and discoloration.
- various reversible thermochromic compositions can be obtained depending on the relative proportions of the components of the composition, these relative proportions making it possible to determine the type of shade, the color density, the fading temperature and the temperature range of the composition. preservation of the recording.
- thermochromic compositions used in a thermochromic product (E) are in microencapsulated form.
- the advantage of microencapsulation is to maintain the chemical integrity of the composition of each thermochromic composition (eg (A) + (B) + (C)) and to protect it from the external environment.
- the products necessary to carry out microencapsulation must not react with the thermochromic composition.
- the size of the microcapsules depends on several factors such as the concentration and the type of product used for microencapsulation. For example, an epoxy or melamine resin can be used for interfacial polymerization.
- component (A), (B) and (C) are exemplified in an illustrative manner in the following.
- component (A) of the invention namely an organic electron-donating compound, it is possible to use known compounds such as crystal violet lactone.
- the electron acceptor compound of component (B) a group of compounds which have an active proton, a group of pseudo-acid compounds (a group of compounds which are not acidic but which cause a color development of the component (A) acting as an acid in the composition) and a group of compounds that have electronic gaps can be used.
- the compound of the solvent (C) may be a fatty acid ester, for example ethyl palmitate.
- the solubilized mixture comprising the abovementioned compounds may form a thermochromic product (E), such as an ink, a paint or a thermochromic plastic, with micro-encapsulated color memory by inserting the mixture into microcapsules.
- the microcapsules have a mean diameter of between 0.5 and 50 ⁇ , preferably between 1 and 15 ⁇ .
- the microcapsules When the microcapsules are too large, their dispersion in the liquid phase leads to a system that lacks stability. When the microcapsules are too small, it is difficult to obtain a high density coloration, clearly visible to the naked eye.
- Examples of the method of a microencapsulation system include interfacial polymerization of an isocyanate system of known type, in situ polymerization of, for example, a melamine system, submerged coating quenching, phase separation. from an aqueous solution, phase separation from an organic solvent, melt dispersion cooling, air suspension coating and spray drying.
- control system may be in the form of a thermochromic label, with a transparent or translucent white background, comprising a substrate (for example a polymer film or a sheet of paper) that is transparent or of a white color on which thermochromic ink (E) has been applied as a thermochromic product (E) having at least two thermochromic compositions
- control system may be in the form of a color-bottomed thermochromic label, comprising a colored-bottom substrate onto which a thermochromic ink (E) has been applied as a thermochromic product having at least two thermochromic compositions (E 1 , E 2 ).
- thermochromic product (E) composed of at least two thermochromic compositions, for example (E 1 and (E 2 ), preferably with thermal hysteresis, each of which is characterized by four critical temperatures - a temperature called "lower temperature of beginning of color transition in the increasing direction" T 1 2 , T 2 2 ;
- T 1 3 , T 2 3 a temperature called “lower temperature of end of color transition in the increasing direction” T 1 3 , T 2 3 ; a temperature called “upper temperature of the beginning of color transition in the decreasing direction” T 1i4 , T 2, 4;
- T-IJ represents a critical temperature for the thermochromic composition (E ⁇
- T 2j represents a critical temperature for the thermochromic composition (E 2 ).
- thermochromic label with a white or transparent background comprising a substrate (for example a polymer film) which is transparent or white color on which has been applied a thermochromic ink (E) as a thermochromic product (E) composed of two thermochromic compositions (Ei, E 2 ).
- thermochromic compositions (Ei, E 2 ) contained in the thermochromic ink (E) is described in the following on the basis of the graph shown in FIG.
- the color density is plotted on the ordinate and the temperature as abscissa.
- the variation of the color density due to a change in temperature progresses along the arrows.
- Curve 1 represents the variation of the black color density of the thermochromic composition (E-i) as a function of temperature.
- Curve 2 represents the variation of the red color density of the thermochromic composition (E 2 ) as a function of temperature.
- thermochromic composition (E-i) You are the upper end temperature of the color transition in the decreasing direction of the thermochromic composition (E-i);
- Ti , 2 is the lower color transition start temperature in the increasing direction of the thermochromic composition ( ⁇ - ⁇ ) (T 1 2 > ⁇ - ⁇ , - ⁇ );
- thermochromic composition E 1 (T 1 3 > T 1 2 );
- TI 4 is the upper temperature of color transition start in the decreasing direction of the thermochromic composition (Ei) (T 1 4 ⁇ T 1 3 );
- T 2 , i is the upper temperature of the end of the color transition in the decreasing direction of the thermochromic composition (E 2 ) (T 2 , i> ⁇ 1);
- T 2 2 is the lower color transition start temperature in the increasing direction of the thermochromic composition (E 2 ) (T 2 2 > T 2 1 and T 1 2 ⁇ T 2 2 );
- T 24 is the upper color transition start temperature in the decreasing direction of the thermochromic composition (E 2 ) (T 1 4 ⁇ T 24 ⁇ T 2 3 ).
- Zone 3 corresponds to the "ideal" temperature range of good preservation of the product or batch of products (P), here called “temperature range to be monitored” or "set temperature range”.
- Zone 1 corresponds to a temperature range below the temperature range to be monitored for the product or batch of products (P).
- Zone 2 is the activation zone of the control. To activate this one, the user will have to place the control in very precise conditions of temperature: those of the window of Zone 2.
- Zone 4 corresponds to a temperature range higher than the temperature range to be monitored for the product or batch of products (P).
- thermochromic label (control) has been affixed undergoes overheating.
- the phenomenon of overheating of the product or batch of products (P) can be described in several steps.
- Step 1 in a first step, the user activates the control by placing it at a temperature T such that T 1 4 ⁇ T ⁇ T 24 (Zone 2) for which only the thermochromic composition (E 2 ) is in its state colored (the temperature is still insufficient for the thermochromic composition (Ei) to turn color). The witness is red.
- Step 2 the temperature is increased such that T 24 ⁇ T ⁇ T 1 2 (Zone 3), the thermochromic composition (E 2 ) is still in its colored state, the thermochromic composition (E 1 ) is always in its discolored state. The indicator is therefore red, the product or batch of products (P) is still in the temperature range to be monitored.
- Step 3 the temperature such as T 1 2 ⁇ T ⁇ T 1 3 (Zone 3) is increased again, then the temperature such as T> T 1 3 (Zone 4) is increased. the thermochromic composition (E 2 ) fades to a complete discoloration for T> T 1 3 .
- the indicator becomes white or transparent (as the case may be). This means that the product or batch of products (P) has been overheated (ie the temperature has temporarily exceeded the preset limit of the setpoint) and the cookie keeps the memory, even if the temperature returns later in the temperature range to monitor.
- Step 4 This temperature is lowered so that T 2.4 ⁇ T ⁇ T 13 (Zone 3); because of their hysteresis, neither of the two thermochromic compositions (Ei, E 2 ) is recolored: the control is therefore white or transparent (as the case may be), the ink being invisible. This means that the product or batch of products (P) has been overheated, and the witness has kept the memory, even if the temperature has since returned to the temperature range to be monitored.
- Step 1 in a first step, the user activates the control by placing it at a temperature T such that T 1 4 ⁇ T ⁇ T 24 (Zone 2) for which only the thermochromic composition (E 2 ) is in its state colored (the temperature is still insufficient for the thermochromic composition (Ei) to turn color).
- the witness is red.
- Step 2 the temperature is lowered to a temperature T such that ⁇ , - ⁇ ⁇ T ⁇ T 1 4 (Zone 1). the thermochromic composition (Ei) is colored in turn.
- the witness gets blackened by keeping a red shade. The appearance of the black color means that the product or batch of products (P) has been cooled below the temperature range to be monitored.
- the control is always black with a red shade (the color-donating organic compound can be chosen so that this red shade is visible or not to the naked eye and / or in the infrared and / or in the near infrared).
- the appearance of the black color therefore means that the product or the batch of products (P) has been cooled below the critical temperature, and the witness keeps the memory even if, since then, the temperature has returned to the range temperature to monitor.
- the two thermochromic compositions (Ei, E 2 ) become discolored and the control becomes white or transparent (as the case may be). This means that the product or batch of products (P) has been overheated and the cookie retains its memory, but it is not clear whether the product or batch of products (P) was overcooled or had already previously overheated.
- the control is colored (eg yellow).
- Curve 1 represents the variation in density of the blue color of the thermochromic composition (E-i) as a function of temperature.
- Curve 2 represents the variation of the density of the green color of the thermochromic composition (E 2 ) as a function of temperature.
- Figure 1
- thermochromic composition (E-i) You are the upper end temperature of the color transition in the decreasing direction of the thermochromic composition (E-i);
- thermochromic composition TI 2 is the lower color transition start temperature in the increasing direction of the thermochromic composition ( ⁇ - ⁇ ) (T 1 2 > ⁇ , - ⁇ );
- TI 3 is the lower temperature of end of color transition in the increasing direction of the thermochromic composition (Ei) (T 1 3 > T 1 2 );
- TI 4 is the upper temperature of color transition start in the decreasing direction of the thermochromic composition (Ei) (T 1 4 ⁇ T 1 3 );
- T 2 , i is the upper temperature of the end of the color transition in the decreasing direction of the thermochromic composition (E 2 ) (T 2 , i> ⁇ - ⁇ , - ⁇ );
- T 2 , 2 is the lower color transition start temperature in the increasing direction of the thermochromic composition (E 2 ) (T 22 > T 2 1 and T 1 2 ⁇ T 22 );
- T 24 is the upper color transition start temperature in the decreasing direction of the thermochromic composition (E 2 ) (T 1 4 ⁇ T 24 ⁇ T 23 ).
- Zone 3 corresponds to the temperature range to be monitored.
- Zone 1 corresponds to a temperature range below the temperature range to be monitored.
- Zone 2 is the activation zone of the control. To activate this one, the user will have to place the control in very precise conditions of temperature: those of the window of Zone 2.
- Zone 4 corresponds to a temperature range higher than the temperature range to be monitored.
- Step 1 in a first step, the user activates the control by placing it at a temperature T such that T 1 4 ⁇ T ⁇ T 24 (Zone 2) for which only the thermochromic composition (E 2 ) is in its state colored (the temperature is still insufficient for the thermochromic composition (Ei) to turn color). The witness is therefore green on a yellow background.
- Step 2 the temperature is increased such that T 2.4 ⁇ T ⁇ T 1 2 (Zone 3), the thermochromic composition (E 2 ) is still in its colored state, the thermochromic composition (Ei) is always in its faded state.
- the indicator is green on a yellow background, the product or batch of products (P) is still in the set temperature range.
- Step 3 the temperature such as T 1 2 ⁇ T ⁇ T 1 3 (Zone 3) is increased again, then the temperature such as T> T 1 3 (Zone 4) is increased.
- the thermochromic composition (E 2 ) fades to a complete discoloration for T> T 1 3 (Zone 4).
- the indicator turns yellow. This means that the product or batch of products (P) has been overheated and the cookie retains its memory, even though the temperature has since returned to the temperature range to be monitored.
- Step 4 This temperature is lowered such that T 24 ⁇ T ⁇ T 1 3 (Zone 3), because of their hysteresis, neither of the two thermochromic compositions (Ei, E 2 ) is recoloured: the control so is yellow.
- the witness is yellow background.
- Step 1 initially, the control is activated by placing itself at a temperature T such that T 1 4 ⁇ T ⁇ T 24 (Zone 2) for which only the thermochromic composition (E 2 ) is in its colored state (the temperature is still insufficient for the thermochromic composition (Ei) to turn color). The witness is therefore green on a yellow background.
- Step 2 the temperature is lowered to a temperature T such that ⁇ , - ⁇ ⁇ T ⁇ T 1 4 (Zone 1).
- the thermochromic composition (Ei) is colored in turn.
- the appearance of the blue color means that the product or batch of products (P) has been cooled below the temperature range to be monitored.
- the appearance of the blue color means that the product or batch of products (P) has been cooled below the the temperature remains in the set range.
- the two thermochromic compositions (Ei, E 2 ) become discolored and the control becomes yellow (background color). Yellow means that the product or batch of products (P) has been overheated and the cookie retains its memory, but it is not clear whether the product or batch of products (P) was overcooled or had already previously overheated.
- thermochromic label (control) can be reset (ie the label can be reset to its original state) by a suitable heat treatment.
- the term "initial state” means the state of the control system (label) when it is placed under the temperature conditions of zone 2 (see FIG. activation of said system.
- the label can be reset to its original state by cooling to a temperature between T 1 4 and T 2,4 .
- this may be of interest when a batch of products (for example a batch of food products) has momentarily exceeded the target set temperature (for example T 1 3 ), but it is concluded after the analysis of the product (for example a microbiological and / or taste analysis) that said product has not suffered by this brief passage at a temperature too high.
- the control system according to the invention can be made in the form of a thermochromic label, preferably self-adhesive, which can be easily affixed to a product (P) or the packaging of said product (P).
- the label advantageously comprises a substrate on which a thermochromic ink (E) is applied as a thermochromic product; this application can be done by any inking technique known, for example, by inkjet.
- thermochromic ink (E) can be protected by a transparent film.
- Said substrate may be a common type of polymer film (for example PP, PE, PVC, PET) or a sheet of paper, in the two cases transparent, translucent, opaque, colored or not.
- Said substrate may also be a metal sheet, or a metallized polymer sheet, or any other suitable substrate.
- the invention may also be in the form of a flexible, semi-rigid or rigid support, preferably transparent or translucent, for example a thermochromic plastic film (E) as a thermochromic product (E), in which at least two thermochromic compositions (E 1 , E 2 ) have been incorporated in said plastic film.
- a thermochromic plastic film E
- E thermochromic product
- thermochromic compositions E 1 , E 2
- This incorporation can be done during the manufacture of said support, for example by a method in which a plastic raw material (for example granules or a powder) and at least two thermochromic compositions (Ei, E 2 ) according to the invention are supplied.
- thermochromic compositions (Ei, E 2 ) are incorporated in said raw material, preferably in the form of a powder, and said support is formed, for example in the form of a flexible, semi-rigid or rigid sheet or plate, which we can then cut to the desired dimensions.
- Said support can be flexible, semi-rigid or rigid. This gives a particularly resistant control system, possibly reusable, for example in the form of a label or a wafer; this system, label or wafer can be coated with an adhesive glue on one side to be affixed to a product or packaging.
- thermochromic product (E) may be in the form of a thermochromic ink (E) that can be used in a writing or drawing instrument, for example a pen, a ballpoint pen, a fountain pen, a felt pen, a wax pencil, or a chalk.
- Felt pens, ballpoint pens or fountain pens may use the thermochromic ink (E) according to the invention directly in liquid form.
- a mineral powder of appropriate color typically white
- a block of chalk of appropriate shape is optionally formed by compression.
- thermochromic ink (E) is incorporated in a suitable wax, preferably a colorless wax, and a pencil of the desired shape is formed.
- suitable wax preferably a colorless wax
- pencil of the desired shape is formed.
- thermochromic product (E) composed of at least two thermochromic compositions (Ei, E 2 ) for the control system according to the invention is presented below, but the invention is not limited to this one. All percentages characterizing a composition are indicated in percentages by weight. a) Preparation of the thermochromic product (Ei)
- Step 1 In a solution A of 100 grams of water are dispersed 2 g of sodium alginate and 0.7 g of Uramine P-1500.
- Step 2 a solution B containing 5% of Pergascript Green® (CI BA) (CAS No. 34372-72-0), 10% of Bisphenol-A, 10% of ethyl palmitate and 73% of trilaurate of glycerol are solubilized by heating to 100 ° C.
- Step 3 solution B is poured without solution A with stirring (550 rpm) for two minutes, then 25 grams of a 25% solution of melamine formaldehyde in 75% of water are poured slowly. The resulting emulsion is transferred with slow stirring at 700 rpm and kept in a water bath for 8 hours.
- CI BA Pergascript Green®
- thermochromic product E?)
- Step 1 in a solution A of 100 grams of water are dispersed 2% of sodium alginate and 0.7% of Uramine P-1500.
- Step 2 a solution B containing 2.3% of Pergasy Blue® (BASF) (CAS No. 1552-42-7), 10.25% of Bisphenol A, 8.25% of ethyl palmitate and 79% of glycerol trilaurate.
- Step 3 solution B is poured into solution A with stirring (550 rpm) for two minutes, then 25 grams of a 25% solution of melamine formaldehyde and 75% of water are poured slowly. The resulting emulsion is transferred with slow stirring at 700 rpm and kept in a water bath for 8 hours. After cooling the resulting microcapsule suspension, a fading temperature of 32 ° C and a blue coloring temperature of 6 ° C are measured.
- BASF Pergasy Blue®
- the control system may be in the form of a thermochromic label on which a thermochromic ink (E) has been affixed as a thermochromic product (E), which label may be prepared as follows:
- thermochromic ink (E) was printed on a flexible, transparent or colored substrate to form a label.
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1250833A FR2986324A1 (en) | 2012-01-30 | 2012-01-30 | RESPECT INDICATOR OF A TEMPERATURE RANGE |
PCT/FR2013/050151 WO2013114025A1 (en) | 2012-01-30 | 2013-01-25 | Temperature range compliance indicator |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2810034A1 true EP2810034A1 (en) | 2014-12-10 |
Family
ID=47714438
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13704200.8A Ceased EP2810034A1 (en) | 2012-01-30 | 2013-01-25 | Temperature range compliance indicator |
Country Status (4)
Country | Link |
---|---|
US (1) | US9464944B2 (en) |
EP (1) | EP2810034A1 (en) |
FR (1) | FR2986324A1 (en) |
WO (1) | WO2013114025A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7562811B2 (en) | 2007-01-18 | 2009-07-21 | Varcode Ltd. | System and method for improved quality management in a product logistic chain |
WO2007129316A2 (en) | 2006-05-07 | 2007-11-15 | Varcode Ltd. | A system and method for improved quality management in a product logistic chain |
US8528808B2 (en) | 2007-05-06 | 2013-09-10 | Varcode Ltd. | System and method for quality management utilizing barcode indicators |
WO2009063464A2 (en) | 2007-11-14 | 2009-05-22 | Varcode Ltd. | A system and method for quality management utilizing barcode indicators |
US11704526B2 (en) | 2008-06-10 | 2023-07-18 | Varcode Ltd. | Barcoded indicators for quality management |
US8807422B2 (en) | 2012-10-22 | 2014-08-19 | Varcode Ltd. | Tamper-proof quality management barcode indicators |
US10113920B2 (en) * | 2014-12-01 | 2018-10-30 | Chromatic Technologies, Inc. | Thermochromic efficiency indicator |
CN107615027B (en) | 2015-05-18 | 2020-03-27 | 发可有限公司 | Thermochromic ink labels for activatable quality labels |
WO2017006326A1 (en) | 2015-07-07 | 2017-01-12 | Varcode Ltd. | Electronic quality indicator |
JP6533833B2 (en) | 2015-10-21 | 2019-06-19 | 株式会社日立製作所 | Temperature detector |
JP2017170664A (en) * | 2016-03-22 | 2017-09-28 | パイロットインキ株式会社 | Counterfeit-preventing medium |
CN109153266B (en) * | 2016-05-18 | 2020-07-03 | 株式会社日立制作所 | Printing apparatus, control method of printing apparatus, and writing apparatus |
JP7022516B2 (en) * | 2017-04-17 | 2022-02-18 | 株式会社日立産機システム | Temperature detection materials, temperature detection inks using them, temperature indicators, and article management systems |
JP6817151B2 (en) * | 2017-06-07 | 2021-01-20 | 三菱鉛筆株式会社 | Water-based ink composition for writing instruments |
WO2020229744A1 (en) | 2019-05-16 | 2020-11-19 | Gem Innov | Method for preparing biodegradable microcapsules and microcapsules obtained in this manner |
FR3095965B1 (en) | 2019-05-16 | 2023-07-14 | Gem Innov | METHOD FOR PREPARING BIODEGRADABLE MICROCAPSULES AND MICROCAPSULES THUS OBTAINED |
FR3099406B1 (en) | 2019-07-30 | 2022-08-12 | Commissariat Energie Atomique | Process for multi-forming the same article at least partly based on a multi-state supramolecular polymer, in order to configure the article several times in different geometric shapes |
FR3099481B1 (en) | 2019-07-30 | 2022-01-28 | Commissariat Energie Atomique | Multi-state supramolecular polymer |
JP6800299B2 (en) * | 2019-10-29 | 2020-12-16 | パイロットインキ株式会社 | Temperature indicator |
JP2021015124A (en) * | 2020-10-15 | 2021-02-12 | パイロットインキ株式会社 | Temperature indicator |
FR3116211A1 (en) | 2020-11-17 | 2022-05-20 | Gem'innov | METHOD FOR THE PREPARATION OF BIODEGRADABLE MICROCAPSULES AND USE OF THE MICROCAPSULES THUS OBTAINED |
FR3116212B1 (en) | 2020-11-18 | 2022-12-30 | Gem Innov | METHOD FOR PREPARING BIODEGRADABLE MICROCAPSULES AND MICROCAPSULES THUS OBTAINED |
US12005408B1 (en) | 2023-04-14 | 2024-06-11 | Sharkninja Operating Llc | Mixing funnel |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4452995A (en) * | 1978-08-30 | 1984-06-05 | Allied Corporation | Dialkoxycarbonylmethyleneurethane diynes |
JPS60264285A (en) * | 1984-06-13 | 1985-12-27 | Pilot Ink Co Ltd | Reversible thermal recording composition |
JPS619488A (en) * | 1984-06-26 | 1986-01-17 | Pilot Ink Co Ltd | Preversible heat-sensitive, temperature-indicating composition |
CA2318700A1 (en) * | 1999-09-17 | 2001-03-17 | Katsuyuki Fujita | Thermochromic microencapsulated pigments |
GB0102671D0 (en) * | 2001-02-02 | 2001-03-21 | B & H Liquid Crystal Devices | Temperature indicator |
US6694912B2 (en) | 2001-06-27 | 2004-02-24 | Blyth, Inc. | Thermochromic ink safety label for chafing fuel cans and methods of making the same |
JP2004137614A (en) * | 2002-10-16 | 2004-05-13 | Pilot Ink Co Ltd | Multicolor thermochromic fiber |
JP4376506B2 (en) * | 2002-10-31 | 2009-12-02 | パイロットインキ株式会社 | Multicolor discoloring water-based ink composition for writing instruments and ballpoint pen using the same |
JP4219776B2 (en) * | 2003-05-16 | 2009-02-04 | パイロットインキ株式会社 | Temperature-sensitive color-change color memory composition and temperature-sensitive color-change color memory microcapsule pigment containing the same |
US7335624B2 (en) * | 2005-01-27 | 2008-02-26 | The Pilot Ink Co., Ltd. | Reversible thermochromic display article |
FR2899684B1 (en) * | 2006-04-11 | 2008-07-04 | Cryolog Sa Sa | TEMPERATURE CROSSING INDICATOR FOR A PRODUCT TO BE PRESERVED AT A DATA TEMPERATURE AND METHOD OF MANUFACTURING THE SAME |
FR2919721B1 (en) * | 2007-07-30 | 2017-05-19 | Sa Cryolog | CROSSING INDICATOR WITH TEMPERATURE THRESHOLD |
WO2010009441A2 (en) * | 2008-07-18 | 2010-01-21 | Segan Industries, Inc. | Co-topo-polymeric compositions, devices and systems for controlling threshold and delay activation sensitivities |
-
2012
- 2012-01-30 FR FR1250833A patent/FR2986324A1/en not_active Withdrawn
-
2013
- 2013-01-25 WO PCT/FR2013/050151 patent/WO2013114025A1/en active Application Filing
- 2013-01-25 US US14/375,541 patent/US9464944B2/en active Active
- 2013-01-25 EP EP13704200.8A patent/EP2810034A1/en not_active Ceased
Non-Patent Citations (2)
Title |
---|
None * |
See also references of WO2013114025A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2986324A1 (en) | 2013-08-02 |
US20150047552A1 (en) | 2015-02-19 |
WO2013114025A1 (en) | 2013-08-08 |
US9464944B2 (en) | 2016-10-11 |
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