EP2904361A1 - Dispositif d'affichage - Google Patents

Dispositif d'affichage

Info

Publication number
EP2904361A1
EP2904361A1 EP13767007.1A EP13767007A EP2904361A1 EP 2904361 A1 EP2904361 A1 EP 2904361A1 EP 13767007 A EP13767007 A EP 13767007A EP 2904361 A1 EP2904361 A1 EP 2904361A1
Authority
EP
European Patent Office
Prior art keywords
layer
indicator
activator
layers
preferred
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.)
Pending
Application number
EP13767007.1A
Other languages
German (de)
English (en)
Inventor
Philipp Wötzer
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.)
Schubro Labels Ag
Original Assignee
Innorese AG
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 Innorese AG filed Critical Innorese AG
Priority to EP13767007.1A priority Critical patent/EP2904361A1/fr
Publication of EP2904361A1 publication Critical patent/EP2904361A1/fr
Pending 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
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K1/00—Details of thermometers not specially adapted for particular types of thermometer
    • G01K1/02—Means for indicating or recording specially adapted for thermometers
    • 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
    • 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

Definitions

  • the present invention relates to display devices, and more particularly to devices for detecting and displaying the thermal history of refrigerated goods, and in particular frozen products. It also relates to processes for their preparation and the application of the devices according to the invention in monitoring the thermal history of refrigerated products and Tiefkiihl exign particular.
  • Temperature-time indicators indicate whether the product's cold chain has been interrupted, ie, whether the product has exceeded a critical temperature for a relevant period of time for frozen products of interest, in this case, the device indicates whether the product could warm to a temperature above the critical temperature of 0 ° C.
  • time-temperature indicators are not able to reliably indicate interruptions of the cold chain.
  • there is the risk that a short-term warming of the packaging eg due to the hype of the consumer in the supermarket
  • Another problem that occurs, for example, in the commercial indicator of the company Timestrip is the uniformity of the displayed color change (ie, the constant time between reaching a critical temperature of the indicator and color change - regardless of the nature of the goods to be cooled). Such uniformity is undesirable because some frozen products thaw significantly faster than others. A reliable ad should consider such differences.
  • time-temperature indicator which reliably indicates cold chain interruptions without false-positive indications in which interruptions of the cold chain are reliably displayed, even if there is air between the refrigerated goods and the display device. Furthermore, the display of the indicator according to the invention should take into account the actual thawing speed of the refrigerated goods.
  • the present invention further relates to methods for producing the display devices according to the invention. These methods are characterized in the following claims 11-13.
  • the present invention also relates to packages for frozen products as described in the following patent claim 14, as well as the deep-frozen products comprising this package according to the following claim 15.
  • Figure 1 illustrates the layer sequence of the device according to the invention in its simplest embodiment.
  • FIG. 2 shows the layer sequence of the device according to the invention in a further embodiment with adhesive layers.
  • FIGS. 3 to 13 illustrate the layer sequences of further devices according to the invention.
  • the reference numerals used in the figures have the following meanings;
  • indicator in the context of the present invention refers to a substance which, upon interaction with the activator (chemical or physical reaction), changes its visual appearance, in particular comprising a color change, the colors (including colorless) before and after the color change are not fixed.
  • activator in the context of the present invention refers to a substance which is suitable, by interaction with the indicator, to bring about a change in the optical appearance of the indicator.
  • the suitability of a substance as an indicator or activator in the context of the present invention depends on the identity of the respective reaction partner. Thus, the fulfillment of the criterion "indicator” is always to be considered in connection with the fulfillment of the criterion “activator” (and vice versa).
  • the suitability of the indicator also includes the presence of the indicator in a form suitable for reaction with the activator, eg, the presence of a pH indicator in the protonated form when the activator is a base, or the presence of a pH indicator in the deprotonated form if the activator is an acid.
  • the indication of the "time between the start of thawing and color change" refers to the period of time which can be measured to the color change detectable to the naked eye when a product of frozen peas (300 g, frozen temperature - 18 ° C, standard package, no film inside, only artonum packaging 320 g / m 2 ) in a room temperature environment (wooden table below, side and top air, each tempered to + 20 ° C) is brought.
  • the turnaround time is essentially determined by the “total delay effect” of the “relevant layers”.
  • the “total retardation effect” refers to the amount of time it takes for a color change sufficient amount of moisture to migrate from the chilled goods through all the relevant layers to the top working layer.
  • relevant layers refers to all layers of the device according to the invention from the lowest layer up to and including the uppermost coloring layer, and the product packaging below the device according to the invention is also a relevant layer determining the entire delay effect it is not known that the determination of the overall retarding effect is to be based on the use of a 320 g / m 2 carton.
  • the device according to the invention It is an essential characteristic of the device according to the invention that it is dry before the ingress of moisture from the chilled goods.
  • “Dry” in this context means a content of moisture which is so low that the color reaction which leads to the desired color change, This applies in particular to the storage conditions to be expected, eg when the device according to the invention is stored at 25 ° C. and ⁇ 5% relative atmospheric humidity over a period of 2 months, preferably 6 months no visible to the naked eye color reaction when storing the inventive device at -18 ° C and 100% relative humidity over 12 months, preferably 24 months instead.
  • Basis weights of paper and cardboard refer to basis weights according to DIN 6730.
  • the sensitivity of the device according to the invention can be increased by using materials with particularly pronounced hygroscopicity (for example as matrix material of the indicator and / or activator layer explained in more detail below).
  • hygroscopicity for example as matrix material of the indicator and / or activator layer explained in more detail below.
  • this measure is limited by the required storage stability. Especially hygroscopic materials will "draw" a large amount of moisture even with short shelf life under moderate humidity conditions, causing an unwanted premature color reaction.
  • the operation of the device according to the invention is based on the released during thawing of the refrigerated moisture. Consequently, it is neither necessary nor provided for in the device according to the invention that moisture reservoirs are present in one or more of the layers of the device according to the invention.
  • the required duration of exceeding the minimum thawing temperature of the goods to be cooled to the color change can be adjusted by a suitable choice of the layer materials used or their thicknesses.
  • the device according to the invention is characterized in that no adaptation of the underlying product packaging is necessary (if it consists of cardboard or other moisture permeable material). In particular, no opening in the product packaging and no "wick" through the product packaging is required.
  • Another essential aspect of the present invention is the possibility of producing the device according to the invention in layers by means of a common printing process, such as, for example, offset or flexographic printing processes.
  • the present invention is based on a spatial separation of indicator and activator by providing these components in separate layers.
  • the device according to the invention is characterized by the following layers.
  • the sequence of layers given below (starting from the side remote from the item to be cooled) represents a preferred embodiment of the apparatus according to the invention:
  • At least the indicator layer must be further away from the refrigerated goods than the delay layer that may be present.
  • the position of the activator layer may be between the cover and indicator layers, between the indicator and retarder layers, or below the retardation layer.
  • the result the following other layer orders in addition to the above layer order (l) ⁇ (2) - (3) - (4): (l) - (3) - (2) - (4) and (1) ⁇ 2) 4 (3).
  • Adhesive layers (5, 6 » 7) can be added to ensure the cohesion of the layer sequence. In particular, it lends itself to the layer sequence shown above
  • a separating layer (8) can be provided between indicator layer (2) and activator layer (3) so as to avoid a direct contact of activator and indicator at the interface between the layers and a further possibility for regulating the activation duration up to Moreover, said separating layer (8) can simplify the production of the device according to the invention.
  • the upper adhesive layer (5) omit or even omit both the lower and the upper adhesive layer (5, 7).
  • FIG. 1 illustrates the layer sequence according to one of the simplest embodiments of the present invention. Since no adhesive layers are provided in this embodiment, this embodiment is particularly suitable in cases in which the device according to the invention is to be integrated into the product package, i. In which the cover layer forms a layer of the product packaging, Alternatively, the layer sequence according to FIG. 1 could be held together by a glued-on product label. In this case, the product label must be transparent in the region of the device according to the invention.
  • the retardation layer is formed by or disposed on a further inner layer of the product package.
  • the cohesion of the layers and integrity of the device are achieved by suitable adhesive layers. This is shown in FIG. 2.
  • the middle adhesive layer is a release layer
  • the release layer (8) is optional, ie a further embodiment relates to the same layer sequence, but in the absence of the release layer.
  • FIG. 4a shows the sequence of layers of a further embodiment of the present invention.
  • a single adhesive layer namely the upper adhesive layer (5)
  • cover layer (1) and indicator layer (2) The cohesion of the layers and thus the integrity of the device are ensured by a larger dimensioning of the cover layer and the upper adhesive layer (5),
  • the above indicator layer (2), activator layer (3) and retardation layer (4) also reaching upper adhesive layer comes into direct contact with the product packaging and forms a stable adhesive bond with this.
  • This embodiment is shown again with the optional separation layer (8).
  • FIG. 4b shows a variant of the embodiment according to FIG. 4a.
  • the delay layer (4) has been omitted
  • FIG. 4c shows a variant of the embodiment according to FIG. 4a.
  • the separating layer (8) has been omitted.
  • FIG. 5a shows a variant of the embodiment according to FIG. 4a.
  • the retardation layer (4) is integrated in the product packaging, i. the retardation layer (4) is formed exclusively by a layer of the product package. In this case, the bonding between upper adhesive layer (5) and retardation layer (4, layer of the product package) takes place.
  • FIG. 5b illustrates a further variant of this embodiment.
  • the sequence of layers corresponds to that of FIG. 5a, but the indicator layer (2) and activator layer (3) are interchanged with one another.
  • FIG. 6 shows a further variant of the embodiments of FIGS. 4a and 5a.
  • a separate delay layer (4) is present in addition to the product packaging.
  • This layer is slightly wider than the layers above it. The cohesion of the layers is ensured by the contact between upper adhesive layer (5) and the protruding portion of the retardation layer (4).
  • the region of the adhesive layer (5) projecting beyond the retardation layer (4) allows the device to be fixed on the product package (which serves as an additional retardation layer (not shown in FIG.
  • FIG. 7 shows a variant of the embodiment according to FIG. 3.
  • the optional separating layer 8 has been omitted.
  • the lower adhesive layer (7) is arranged only in the areas outside the overlying indicator layer (2) and activator layer (3). This variant also allows the use of pressure-sensitive adhesives, which have no or a very low permeability to moisture or water vapor.
  • FIG. 8 relates to a mold in which the activator layer (3) is arranged below the retardation layer (4). In this case, the activator migrates together with the moisture through the retardation layer (4) to the indicator layer (5).
  • FIGS. 9a 9b and 9c illustrate further embodiments in which the activator layer is arranged elsewhere: These embodiments correspond to those of FIGS. 4a, 4b and 4c, wherein only the indicator layer 2 and the activator pushes 3 are interchanged were.
  • FIG. 10 shows an embodiment according to FIG. 7, which additionally has a second activator layer (3) below the retardation layer (4) and within the regions covered by the lower adhesion layer (7).
  • the provision of a second activator layer has the advantage that the color change takes place gradually or stepwise. It is therefore preferred in those cases where the display is intended to allow a distinction between short and longer breaks in the cold chain.
  • a second Aktivator für also on. another position, the device, e.g. between indicator layer (2) and upper adhesive layer (5),
  • Figure 11 illustrates another variation of the embodiments.
  • the activator layer (3) below the retardation layer (4) is arranged. In this layer order, the
  • Delay layer (4) act as a release layer, and so replace the separation layer shown in. 4a and 9a.
  • FIG. 12 relates to a further embodiment in which the product packaging serves as a delay layer (4) and in which a separating layer (8) is provided between the indicator layer
  • the separating layer projects beyond indicator layer (2) and activator layer (3).
  • This allows for direct contact between upper adhesive layer (5) and release layer (8), which contributes to the integrity of the device.
  • Another lower adhesive layer (7) is between separating layer (8) and Product Vibration / Delay Angle (4)., So that it encloses the activator layer (3) partially or completely.
  • FIG. 13 shows a further embodiment of the device according to the invention.
  • two delay layers (4) are provided.
  • a first retardation layer (4) between indicator layer (2) and activator layer (3) is formed by the product layer.
  • This retardation layer (4) also serves as a separation layer.
  • a second retardation layer (4) is located below the Aktivatorschi cht (3).
  • This can e.g. a water vapor-permeable thin protective film, such as is commonly used in the interior of food packaging.
  • the device of this embodiment can be produced particularly easily at once with the remaining product packaging.
  • the delay layers shown in FIG. 13 are also used in all other devices according to the present invention, provided that the invention is applied to suitably designed product packaging. In each case, the entire delay effect caused by all the delay layers, including the product packaging, must be taken into account.
  • Cover layer has the following functions:
  • the top layer prevents » moisture from penetrating to the indicator layer and / or activator layer from the outside.
  • the cover layer has sufficient transparency to make a color change in the indicator layer visible from the outside.
  • the cover layer allows further identification of the display device according to the invention, e.g. by applying a logo,
  • cover layer all film materials can be used, which are suitable to meet the above requirements.
  • first two film materials can be used, which are suitable to meet the above requirements.
  • all transparent films can be used, which have no or a low permeability to moisture, that this has no effect on the functionality of the device according to the invention.
  • cover layers in which the passage of moisture is so low that, when the device according to the invention is stored for 1 year at 25 ° C. and 75% relative humidity, the amount of moisture penetrating during this period does not have an influence on the function which is discernible to the naked eye the device has.
  • PP polypropylene
  • HDPE high density polyethylene
  • materials with lower water vapor permeability it is of course possible to reduce the thickness of the film accordingly.
  • materials with a higher water vapor permeability can also be used, provided the film thickness is adjusted accordingly.
  • Another suitable film material is Polyvinyiidenchlorid, since its water vapor permeability is lower by about one order of magnitude than that of polypropylene.
  • Biodegradable films based on starch or cellulose which also fulfill the requirements for transparency and impermeability to moisture, can also be used.
  • cover layers can be used, which in turn are composed of several layers of different plastics (as far as the above requirements are met by the multi-layer cover layers).
  • the cover layer can be formed by applying a moisture-impermeable protective lacquer.
  • a moisture-impermeable protective lacquer In this case, the above-mentioned requirements with regard to transparency and water vapor permeability must be set in the same way to the covering layer formed from protective lacquer. The thickness of the protective lacquer is to be adjusted accordingly. Suitable materials for the protective lacquer are silicones formed by polysiloxanes and lacquers formed by polymeric synthetic resins.
  • Preferred cover layer is a film of polypropylene having a thickness in the range of 40-80 ⁇ m, more preferably about 60 ⁇ m. 5.5.
  • Upper adhesive layer is a film of polypropylene having a thickness in the range of 40-80 ⁇ m, more preferably about 60 ⁇ m. 5.5.
  • the optional upper adhesive layer may be formed by any adhesive.
  • pressure-sensitive adhesives are described, for example, in the standard work "Handbook of Pressure-Sensitive Adhesive Technology" by Donatas Satas (van Nostrand, New York 1 89), in particular adhesive acrylate, natural rubber, synthetic rubber, silicone or EVA based adhesives
  • pressure-sensitive adhesives on a natural basis, such as adhesives based on casein, gelatine and starch, and hot-melt adhesives and flexographic adhesives such as Novarad® RCL-6015 from Novamelt® and other UV-curable monomer / oligomer compositions on acrylate urethane are also conceivable Base or acrylate-epoxy base.
  • the adhesive layer is used in a thickness of typically 5-1000 ⁇ m, preferably 10-250 ⁇ m.
  • the abovementioned flexographic printing adhesives are typically applied in amounts of 1-50 g / m 2 , preferably 5-40 gm 2 , more preferably 10-30 g / m 2 .
  • the indicator layer is characterized by the presence of at least one indicator.
  • the term "indicator” refers to any substance or mixture of substances that exhibits a color change by chemical reaction or other interaction with a suitable activator, a typical representative of these substances are the so-called pH indicators Indicators show a color change as soon as the pH changes to such an extent that a characteristic value characteristic of the respective pH indicator is exceeded, eg if the pH indicator is blue in a basic medium (pH> 7) and acidic (pH ⁇ 7) red, a color change can take place if the medium in the indicator layer is basic and an acid is used as the activator It is equally possible to use said pH indicator in an acidic medium and to use a base as an activator.
  • pH indicator it is necessary to match the pH indicator, the surrounding environment, and the activator to ensure that the desired color change occurs upon migration of the activator into the indicator layer.
  • this may be done by appropriate choice of the pH indicator (in terms of color change pH), adjustment of the pH of the indicator layer and appropriate choice of activator.
  • pH indicators are dyes of natural origin as well as artificial ones
  • Dyes Preference is given to natural dyes which can be obtained, for example, from plants such as vegetables or fruit. These include, among others, the flavonoids such as the Anthocyanins. Preferably, in this case are the anthocyanidins. Particularly preferred is the use of cyanidin. Likewise, delphinidin, malvidin, peonidine and petunidin can be mentioned. Mixtures of dyes can also be used. However, it should be ensured that the color change behavior of the individual dyes is coordinated so that under the given conditions (presence of activator and moisture possibly in the presence of a matrix and other constituents) a clearly recognizable color change takes place.
  • redox indicators should be mentioned here. This is uro. Dyes that show a color change on reduction and / or oxidation. Typical examples are ferroin or methylene blue. A comprehensive list of redox indicators can be found in the English version of Wikipedia under the entry "Redox indicator” (September 2012) .Accordingly, suitable reducing agents and / or oxidants can be used as activator substances.
  • Preferred indicator material are pH indicators and in particular the above-mentioned anthocyanidins and very particularly preferably cyanidin.
  • the indicator layer may include other optional ingredients in addition to the indicator substance. Suitable further optional constituents may in particular be selected from the following components;
  • matrix materials such as agar-agar, cellulose, starch, gum arabic, guar gum, gelatin and arrowroot starch; cellulose is preferred. Also suitable is polyethylene glycol. If the device according to the invention is produced by the preferred printing method, care must be taken that the viscosity of the matrix materials used is adapted to the printing method. This can be done by suitable choice of the chain length of the polymeric matrix materials. It is also possible a homogeneous or heterogeneous mixture of the matrix material It is also conceivable to use a textile fabric or fleece with a suitable solvent of suitable viscosity. When the indicator is applied to a fabric or nonwoven, said fabric or nonwoven acts as a support rather than an indicator encircling matrix. In these cases, the material to be used for fabric or nonwoven is not subject to any further restriction (except that it is said to be inert to the indicator and activator).
  • a suitable material is, for example, cellulose, for example a layer of a paper tissue.
  • the medium with bases such as N ⁇ CC ⁇ NaHCC, CaO or CaC.03 can be adjusted to an alkaline pH; an acidic pH adjustment can be made with acids such as e.g. Milk, oxalic, tartaric and citric acid take place;
  • Hygroscopic materials including hygroscopic polymers such as e.g.
  • Acrylic acid acylate polymers and hygroscopic salts such as e.g. Magnesium chloride, potassium chloride and calcium chloride, which can affect the color change (e.g., accelerate);
  • salts to lower the melting point of water are useful when the inventive.
  • Device on saline refrigerated goods e.g., pretzels.
  • the device according to the invention can be activated already at temperatures below 0 ° C, in which the refrigerated goods begins to thaw. Since melting point depression is a colligative phenomenon, any salts can be used.
  • non-toxic salts e.g. NaCl.
  • Stabiiistoren such. Potassium sorbate for mold suppression; other preservatives include calcium chloride and. ethanol; the use of such stabilizers is particularly preferred when using natural dyes.
  • the amount of indicator dye to be applied is typically in the range of 0.1 to 100 g / m 2, preferably 1 to 40 gm 2 3, more preferably 4 to 12 g / m 2 .
  • the amount of indicator applied affects the speed and intensity of the color change.
  • a strong paint application ie order quantities in the upper half of the above
  • a strong application of paint can complicate the drying in the Hersgnacsvons. It has proved to be advantageous to apply a plurality of thin layers instead of a strong indicator layer and to dry before the respective subsequent indicator layer is applied. For example, 2-40 layers can be applied. Preferred are 4-10 layers, more preferably 6-8 layers.
  • the ease of drying is also dependent on the composition of the pH indicator layer (eg hygroscopic properties of the constituents and water content).
  • the water content choice of the matrix material and the amount applied per shift, a desired rate of drying could be set.
  • the applied amount of indicator can be adjusted to the draw volume of the printing press.
  • the information in section 5.5 on the upper adhesive layer applies analogously.
  • the middle adhesive layer ensures "that sufficient moisture transport is guaranteed by the material to be cooled to the indicator layer.
  • the desired suitability for moisture transport can be achieved on the one hand by choosing suitable adhesives / adhesives.
  • Adhesives capable of allowing moisture to pass through are particularly starch or gelatin based adhesives. By reducing the amount applied, the moisture permeability of other adhesives, which per se have lower moisture permeability (based on equal application rates), can be brought to an acceptable level. Thus, with a suitable adjustment of the order amount, a variety of other adhesives are used.
  • the middle adhesive layer pores or openings in which no adhesive is present and through which the moisture can migrate unhindered into the indicator layer.
  • the shape and size of the openings are not specified as far as it is ensured that the total area of the openings is sufficient to ensure the moisture transport required for the desired color change.
  • a separating layer between indicator layer and activator layer is particularly recommended if the device according to the invention is to be produced by applying layer by layer.
  • a direct coating of the activator layer by the (still moist) material of the indicator layer could lead to a color reaction at the interface before the indicator layer has dried sufficiently.
  • indicator layer and activator layer can be separated from one another by said separating layer, thus avoiding the premature color reaction.
  • the release layer must be able to absorb and store small amounts of moisture without passing them on to the adjacent layer before the subsequent drying cycle.
  • the release layer Before applying the next layer, the release layer must be dry. This means that the separating layer may need to be dried.
  • the release layer can also be applied in the form of several separate layers.
  • the above-mentioned middle adhesive layer can act as a release layer.
  • plastic films with suitable moisture permeability could be used.
  • the use of a layer formed from starch is conceivable. Particularly preferred are separating layers which are formed from gelatin or paper (cellulose).
  • cellulose gelatin or paper
  • the use of a fabric or fleece is also possible.
  • the fabric to be used for fabric or nonwoven is not subject to any further restriction (except that it is said to be inert to the indicator and activator), cellulose is preferred.
  • Other suitable materials for the release layer are waxes and especially low ( ⁇ 25 ° C) melting waxes.
  • Fats and particularly low ( ⁇ 25 ° C) fats polyethylene glycol, dextrin, casein, starch, polyvinyl alcohol, gelatin, polysaccharides such as agar-agar or pectin, and mixtures thereof.
  • the activator is chosen so that a chemical reaction or other interaction with the indicator results in a color change.
  • the activator is either an acid or a base. If an acid is selected, the milieu of the indicator layer must be basic (or at least more basal than the pH of the indicator). Similarly, when using a base as an activator, the milieu of the indicator layer must be acidic (or at least more acidic than the pH trans-point of the indicator).
  • Preferred acids are oxalic acid, lactic acid and tartaric acid, citric acid is particularly preferred.
  • bases are used as the activator, in turn, N, CC, NaHCO 3,
  • CaO or CaCO 3 find use.
  • redox indicators are used, the same applies to pH indicators.
  • oxidizing agents can be used as .Activators, provided that the redox indicator is in the reduced state. In this.
  • a reducing environment in the indicator layer can stabilize the redox indicator.
  • a reducing agent as the activator if the redox indicator is present in the oxidized form. In this case, an oxidizing environment in the indicator layer can stabilize the redox indicator.
  • Suitable oxidizing agents include organic percarboxylic acids and metal salts such as MnO 2; Suitable reducing agents include ascorbic acid, sulfite salts and stannous salts.
  • suitable oxidants and reducing agents it is important to ensure sufficient stability under the given conditions, i. There must be no reaction with the other constituents of the activator layer over the intended storage period. If the device is used for foodstuffs, care must also be taken to ensure that the antioxidants and / or reducing agents used do not pose a health risk.
  • the matrix materials mentioned for the indicator layer can be used.
  • fabrics or nonwovens can be used.
  • the fabric to be used for fabric or nonwoven is not subject to any further limitation (except that it is said to be inert to the indicator and activator). Cellulose is preferred.
  • a dye can be absorbed in the activator.
  • Suitable dyes include titanium dioxide or food grade dyes.
  • hygroscopic materials such as hygroscopic polymers (eg acrylic acid-acrylate polymers) or hygroscopic salts (eg magnesium chloride, potassium chloride and calcium chloride).
  • the amount of activator in the activator layer is typically 0.1 to 100 g / m 2 , preferably from 1 to 40 g / m 2 , particularly preferably from 4 to 12 g / m 2 .
  • the retardation layer forms a kind of "moisture buffer” which absorbs some moisture before it is passed on to the activator layer, which has the advantage that no color change occurs due to the release of very small amounts of moisture of the indicator by the consumer.
  • the retardation layer is an optional component of the device according to the invention.
  • the delay effect required for the successful implementation of the invention can also be achieved by further layers of the device according to the invention, e.g. Separating or adhesive layers can be achieved. Also to be considered is the delay effect caused by the product packaging.
  • the period of time from the first formation of moisture to the color change can be adjusted by suitably selecting the delay-causing layers (in terms of presence or absence, materials used and their thickness), taking into account the retardation effect of the product package.
  • Decisive for this period of time is the overall retarding effect of all layers between product and the outermost layer relevant to the interaction (i.e., activator or indicator layer).
  • the materials which can be used for the retardation layer correspond to the materials mentioned under point 5.8 for the separating layer, such as e.g. Waxes. Fats, polyethylene glycol, dextrin, etc .. D.h. films having sufficient moisture permeability, a layer formed of starch or, more preferably, a layer formed of gelatin may be used.
  • paper or paperboard ie, a layer of cellulose
  • newsprint paper or paper of comparable thickness of about 40-60 g / m 2 , in particular 50 g / m 2
  • silk papicr or paper of comparable thickness of about 20-30 g / m 2 , in particular 25 g / m 2 may prove to be advantageous.
  • the use of paper or cardboard is particularly preferred in cases where indicator layer and activator layer are to be laminated on each other. In these cases, in addition to achieving the desired retarding effect, the retardation layer can also serve as a carrier material for the (indicator or activator) layer which is closer to the item to be cooled.
  • the moisture permeability of the further layers of the device up to and including the outermost coloring layer (ie indicator or activator layer) and the underlying product packaging If one of the other layers and / or the If the product packaging has a low moisture permeability, the moisture permeability of the retardation layer should be as high as possible (or the retardation layer is omitted completely if maximum permeability is required, see below). On the other hand, if the moisture permeability of the other layers and the product package is high, a retardation layer should be used which is closer to the lower range of the above interval to set the desired time to color change.
  • a further embodiment of the present invention is to use only the packaging of the item to be cooled (or a layer thereof) as a delay layer, so omit the retardation layer as part of the device according to the invention.
  • This embodiment is particularly suitable for use with product packaging, which already have a sufficiently high delay effect and / or in devices in which the other layers present (such as adhesive and / or release layers) in combination with the Artsverpaekung have a sufficiently high delay ,
  • the same product packaging requirements apply here, ie. the packaging material (or its constituent) must be able to absorb moisture and release it with appropriate delay.
  • Cardboard packaging is well suited for this purpose.
  • the package is coated with a moisture-impermeable material, it must be ensured that this moisture-impermeable material in the area in which the device of the invention is applied, is not present or at least provided with pores.
  • said moisture-impermeable material can be applied only after application of the device according to the invention, so that the moisture transport through the packaging for the device according to the invention takes place underneath the moisture-impermeable layer and is not hindered by it.
  • the desired period of time between the beginning of the thawing process and color change of the device according to the invention is in the range from a few minutes to several hours, in particular from 10 minutes to 5 hours, preferably from 30 minutes to 4 hours, even more preferably from 1 h to 3 h and especially about 2 h.
  • a fast color change device should discolor after about 60 minutes (e.g., in the range of 60 to 100 minutes).
  • a device with a medium color change rate should discolour after about 90 minutes (e.g., in the range of 90 to 140 minutes).
  • a slow color change device should discolor after about 140 minutes (e.g., in the range of 140 to 200 minutes).
  • the base device is applied to the product packaging of the refrigerated goods of interest.
  • the turnaround time at the beginning of thawing is determined.
  • step 4 is performed; if the determined turnaround time is shorter than the predetermined target value, the following step 5 is performed; otherwise, there is no further need for adjustment, the process is terminated with step 8. 4.
  • the current device in the first, pass: base device
  • the current device is reworked in a modified form so that the overall delay effect of all relevant layers of the device is reduced when transporting moisture. This is done by using one or more materials with better suitability for transporting moisture in at least one relevant layer, and / or the layer thickness of at least one relevant layer is reduced.
  • the device thus obtained is tested according to the following step 6.
  • the current device in the first pass: basic device
  • the current device is reworked in modified form so that the overall delay effect of all relevant layers of the device is increased in the transport of moisture. This is done by using one or more materials with poorer suitability for transporting moisture in at least one relevant layer, and / or increasing the layer thickness of at least one relevant layer.
  • the device thus obtained is tested according to the following step 6.
  • the modified device is applied to the product packaging of the refrigerated goods of interest.
  • the turnaround time at the beginning of thawing is determined.
  • step 7 If the determined turnaround time is longer than the predetermined target value, the above step 4 is performed; if the determined turnaround time is shorter than the predetermined target value, the above step 5 is performed; otherwise, the process is ended with step 8.
  • the retarding effect of one or more layers is adjusted by using polyethyleneglycol as a matrix material (eg in the indicator layer, release layer and / or activator layer).
  • polyethyleneglycol as a matrix material
  • the retardation effect can be set as desired.
  • Suitable molar masses are in the range from 600 to 4000 g / mol, preferably in the range from 800 to 1500 g / mol.
  • liquid polyethylene glycols having a molecular weight of less than 600 g / mol can also be used.
  • the retarding effect can be adjusted.
  • the device according to the invention can be produced by all methods in which the respective layers are formed or provided and can be brought into contact with the respectively adjacent layers. In this case, neither the sequence of the individual process steps (provision or formation of the respective layer, as well as contacting with the neighbor or the adjacent), nor the techniques used for the formation of layers. However, the following procedures have proved to be advantageous.
  • Optional additional layers such as release or adhesive layers are introduced at a suitable location by performing the following additional steps:
  • the relevant steps (XI) and (X-2) may be carried out before step (BI) or at any later date.
  • the order of application of the individual layers is determined by the desired order of the layers in the device to be manufactured. However, it is possible to reverse the order of application of the individual layers, i. it may be provided as a first step, the cover layer (a) or the retardation layer (d). Thus, the following procedures for an exemplary encryption order result:
  • any additional layers present can be introduced at a suitable point by carrying out the additional steps (XI) and (X-2) described above.
  • ethanol examples include ethanol, acetone, diethyl ether, methanol, isopropanol, ethyl acetate and methyl acetate, and mixtures of such solvents. Preferred is ethanol.
  • Printing is done layer by layer as above. It is very advantageous that the layer printed as the second printed color formation layer is dried as quickly as possible immediately after application. In the above methods, this means that steps D6 and D7 are performed almost simultaneously and directly after step D-3 (or that steps D'-6 and D'-7 are performed almost simultaneously and directly after step D'-3 become). Immediate drying can be achieved by creating a gas stream, preferably an air stream, over the printed surface. The volatile solvent is removed by the gas stream before it comes to an unwanted Wanderang the activator in the indicator layer.
  • the application of the layers can be done by any technology suitable for forming thin layers.
  • Particularly suitable printing presses have been found that are able to apply several layers of material in succession and each to dry directly after the order.
  • printing presses that work according to the offset, flexographic or screen printing methods are suitable.
  • Other methods of applying thin layers include spraying, doctoring, dipping, etc.
  • compositions to be applied for each layer of material are selected in view of their viscosity to the requirements of the. (Pressure) method adapted.
  • suitable thickening agents can be used. Suitable are all thickeners that are inert to the indicator and activator, and do not hinder the desired transport of activator to indicator.
  • polysaccharides such as pectin, xanthan, guar gum, agar-agar, cellulose and cellulose To name derivatives as well as calcium acetate and glycerin.
  • the desired viscosity can also be achieved by suitably adjusting the concentration of the materials in the chosen solvent. If a further increase in the concentration is desired, the preparation of the solution can also be carried out at elevated temperature.
  • the drying of the individual layers applied are important to prevent premature color change.
  • the degree of drying must be selected to meet this requirement.
  • the drying can be accelerated by a gas flow, preferably air flow.
  • the preparation proceeds analogously, where expediently variant (II) is selected and the layer structure is based on the Verzögemngs Mrs.
  • the layer structure according to variant (II) could start from the cover layer and end before the delay layer, eg with formation of the activator layer.
  • the intermediate thus produced can then be applied to the packaging.
  • Another possibility is to proceed according to variant (I) and to produce arrangement (A) as described above.
  • the activator layer and optionally further layers are applied directly to the package. Subsequently, arrangements (A) and (B) are laminated.
  • the inventive device is suitable for monitoring the thermal history of any products that need to be permanently cooled.
  • any products that need to be permanently cooled are primarily frozen food into consideration.
  • the device according to the invention is also suitable for use in connection with other products which must be permanently cooled or deep-frozen.
  • the product to be cooled should contain moisture to ensure proper functioning of the device according to the invention.
  • the practical application is expediently carried out by applying the device according to the invention to the outer packaging of the product to be cooled.
  • an easy recognizability of the color change can be ensured. It is of course important to ensure that moisture from the inside of the package can get to the device according to the invention, as soon as the cold chain is interrupted.
  • a significant advantage of the present invention is that a reliable display takes place, regardless of whether there is a direct contact between refrigerated goods and display device. Therefore, the device according to the invention can be mounted anywhere on the package.
  • the size of the area covered by the device according to the invention is not specified. In view of the easy recognizability of the color change, however, this area should advantageously not be less than 0.2 cm 2 , preferably 0.5 cm 2 , more preferably 0.8 cm 2 .
  • logo, lettering, etc. can be done on the device according to the invention. However, it is important to ensure that the logo, lettering, etc. are attached so that the color change can be reliably detected. A complete top cover of the device according to the invention with e.g. a logo is to be avoided. Of course, it is within the scope of the present invention also possible to apply logo, lettering, etc. next to the device according to the invention on the packaging.
  • devices according to the invention More preferred are those devices according to the invention in which the above-mentioned preferred combinations are further combined, ie devices with the feature combinations (i) - (ii), (i) - (iii), (i-iv), (i) - ( v), (i) - (vi), (i) - (vii), (i) - (viii), (i) - (ix), (i) -
  • a preferred variant has the following layer sequence
  • the separating layer is avoided by suitable production methods.
  • suitable preparation may be accomplished using an industrial printing process (e.g., flexographic printing).
  • the cover layer is first printed with the indicator layer, followed by further printing with the activator layer.
  • suitable measures must be taken in this case so that the activator layer dries so quickly immediately after application that no significant migration takes place in the activator layer. As described above, this can be done by using a volatile solvent.
  • the device thus obtained can, e.g. on silicone paper, to be stored.
  • an anthocyanidin dye is preferably used as indicator and citric acid, lactic or tartaric acid as activator.
  • a cyanidin dye is used as indicator in conjunction with citric acid as activator.
  • Another preferred variant has the following layer sequence:
  • These layers are optionally applied over the adhesive layer on the product packaging serving as a delay layer (with the adhesive layer preferably laterally of the indicator and activator layer).
  • Such a layer sequence is shown in FIG. 5a.
  • the resulting intermediate product can be punched out in the appropriate format and adhered to a cover layer provided with an adhesive layer.
  • the device obtained in this way can be stored, for example on silicon paper. It is adhered to the product packaging in a (possibly spatially and / or temporally) separate process step.
  • an anthocyanidin dye is preferably used as indicator and citric acid, lactic or tartaric acid as activator.
  • an anthocyanidin dye is preferably used as indicator and citric acid, lactic or tartaric acid as activator.
  • a cyanidin dye is preferably used as an indicator in conjunction with citric acid as activator.
  • a device according to the invention is produced according to production variant I using a flexographic method.
  • the layer structure corresponds to the layer sequence shown in FIG. 9c.
  • the cover layer is off.
  • This PP film is already provided with an adhesive layer ex works and the UPM Rafiatac® acrylate-based adhesion layer "SP38" is therefore also available.
  • the activator layer is formed on the citric acid adhesive in a cellulosic matrix.
  • the application rate is 6 g / m.
  • the layer is in the printing process in the form of an aqueous dispersion with a. Content of cellulose of about 5 wt.% And a content of citric acid of about 1 wt.% Applied and then dried directly.
  • Cyanidin is used as an indicator in a cellulose matrix.
  • the indicator layer is applied to tissue paper of a thickness of 25 g / m 2 as a retardation layer.
  • the application rate is 6 g / m 2 .
  • the layer is in the form of an aqueous Dispersion in which the content of cellulose at 5 wt.% And the content of cyanidin is 1 wt.%. The layer is dried immediately after application.
  • activator layer and indicator layer are laminated on each other.
  • a color change can be seen between the first thawing of the chilled product (30 ° frozen peas temperature increase from -1 8 ° C to 20 ° C) after 150 minutes.
  • a device according to the invention is produced analogously to Example 1, with the difference that newsprint of a thickness of 50 g / m 2 is used.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Packages (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne des dispositifs permettant d'afficher l'historique de produits, par exemple en ce qui concerne la variation de la température. Le dispositif selon l'invention comprend une couche extérieure, une couche d'indicateur, une couche d'activateur ainsi que, optionnellement, une couche retardatrice. Sous l'effet d'une augmentation de température, il se dégage de l'humidité laquelle migre, dans certains modes de réalisation, d'abord dans la couche retardatrice et ensuite dans la couche d'activateur. Celli-ci contient un activateur qui est mobilisé pour ainsi migrer, ensemble avec l'humidité, dans la couche d'indicateur. L'interaction de l'indicateur avec l'activateur en présence d'humidité provoque un changement de couleur indiquant un dépassement de la température critique. En outre, la présente invention concerne des procédés permettant de fabriquer le dispositif selon l'invention ainsi que sa mise en œuvre, par exemple dans le domaine de la surveillance de la température de produits sensibles.
EP13767007.1A 2012-10-01 2013-09-30 Dispositif d'affichage Pending EP2904361A1 (fr)

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EP12186803 2012-10-01
PCT/EP2013/070328 WO2014053435A1 (fr) 2012-10-01 2013-09-30 Dispositif d'affichage
EP13767007.1A EP2904361A1 (fr) 2012-10-01 2013-09-30 Dispositif d'affichage

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EP (1) EP2904361A1 (fr)
JP (1) JP6318159B2 (fr)
AR (1) AR092754A1 (fr)
AU (1) AU2013326675B2 (fr)
BR (1) BR112015007263B1 (fr)
CA (1) CA2886912A1 (fr)
CU (1) CU20150030A7 (fr)
MX (1) MX2015004090A (fr)
MY (1) MY174733A (fr)
PE (1) PE20150952A1 (fr)
RU (1) RU2640093C2 (fr)
SA (1) SA515360219B1 (fr)
TN (1) TN2015000122A1 (fr)
WO (1) WO2014053435A1 (fr)
ZA (1) ZA201502995B (fr)

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AU2015239668B2 (en) * 2014-03-31 2019-12-19 Innorese Ag Indicating device
CN104019920A (zh) * 2014-05-30 2014-09-03 赵新华 一种用于冷链追踪的温度敏感型智能物品编码
CN105160994A (zh) * 2015-06-11 2015-12-16 合肥鑫晟光电科技有限公司 显示色卡及制备方法、解冻时间监控标签、***和方法
WO2019098517A1 (fr) * 2017-11-15 2019-05-23 주식회사 디바이스넷 Indicateur destiné à être fixé sur un matériau d'emballage de sorte que la décongélation d'un aliment congelé ou d'un produit alimentaire stocké congelé puisse être identifiée visuellement
KR102218602B1 (ko) * 2018-09-13 2021-02-23 주식회사 디바이스넷 냉동식품 또는 냉동보관 중인 식품원료의 해동을 가시적으로 판별할 수 있는 포장재 부착용 시트형 인디케이터
KR102263878B1 (ko) * 2018-11-19 2021-06-11 한국식품연구원 신선식품 포장재

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AU2013326675A1 (en) 2015-05-21
US20150260584A1 (en) 2015-09-17
JP2015537192A (ja) 2015-12-24
BR112015007263B1 (pt) 2021-06-29
AR092754A1 (es) 2015-04-29
RU2015116813A (ru) 2016-11-27
US10571341B2 (en) 2020-02-25
JP6318159B2 (ja) 2018-04-25
CA2886912A1 (fr) 2014-04-10
ZA201502995B (en) 2022-05-25
MY174733A (en) 2020-05-12
BR112015007263A2 (pt) 2017-08-08
PE20150952A1 (es) 2015-06-20
RU2640093C2 (ru) 2017-12-26
AU2013326675B2 (en) 2018-03-01
MX2015004090A (es) 2015-11-23
SA515360219B1 (ar) 2018-11-18
CU20150030A7 (es) 2015-09-29
WO2014053435A1 (fr) 2014-04-10
TN2015000122A1 (en) 2016-06-29

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