JPH04505213A - Indicators, methods of their manufacture and their use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] An indicator, a method for manufacturing the same, and a use thereof The present invention resides in the first aspect of claim 1. Indicators for grasping the progress of phenomena according to concepts, how to create them, and It concerns its use.

Indicators are used in particular for particularly cooled products and products that must be stored at a certain temperature. such as frozen and frozen products, as well as active substances or immunizations or stored blood. Used for temperature control of pharmaceutical products. The optimum storage temperature for these products varies little. Irreversible indicator - indicated by a color change in the evening, which indicates the maximum allowable temperature. It represents a measure of excess, a measure of the unusability of these products.

German Patent No. 3210907 discloses a method for determining time-/temperature-load of an object. In this case, management is required for a relatively long period of time. and/or must be carried out at relatively high temperatures. However, the indicator The start delay of the reactor requires especially adjustment of the melting range of the chemical agent and also Requires storage and maintenance at or below temperature.

From German Publication No. 3048425, it is no longer usable. Devices are known that detect when volatile organic or non-volatile A time-/temperature-measuring system consisting of indicators containing mechanical solids is applied to practical products or their packaging. give The proposed metric cannot be used to accurately capture the maximum effective time due to its composition. Furthermore, it does not allow any adjustment of the starting point.

German Patent No. 3717025 discloses that sometimes perishable or time-limited A stock containing one indicator substance and an indicator of the usability of the product Discloses a display device for displaying time-dependent processes in strips. The indicator strip will run over its length when it comes into contact with the indicator material. Discolors over time. In this case, the storage chamber is spatially separated from the indicator strip. and is connected to this via a channel, and this storage chamber is also connected to external pressurization. The indicator substance oozes out from outside the storage chamber through the channel and becomes the indicator substance. deforms to make contact with the data strip. To start this kind of display device The main focus of the patent publication is to press a colored indicator substance into the front chamber visible from the outside. It is recognized from the title.

The display device according to German patent no. The reaction of one compound with a second compound may cause a phenomenon (e.g. shelf life or shelf life of the product). (retention time) can be defined as an indicator to understand temporally. In the case of The onset of overgrasping can be controlled if necessary by blocking the initial response. child This provision forms the basis of the generic concept of claim 1 according to the present invention. Regarding this , German Patent No. 3717025, the reaction resulting in a visible color change is a chemical reaction. A weak coloring reaction between the colored indicator substance and the indicator strip without In the case of German Patent No. 3717025, the retardant test The wick-like structure of the indicator strip allows the drug to undergo a coloring reaction only gradually. and that the specified position by the protrusion of the reservoir containing the indicator substance is In the case of German Patent No. 3717025, if the pressure of Recognize that control over the onset of time course comprehension is obtained by blocking the initial coloring reaction. Should. If this is done directly when creating or applying the indicator, it will Over-grasping starts immediately, and if you press the storage chamber for the first time later, you can grasp the time elapsed. will also start only after that. Therefore, you can instantly grasp the passage of time as desired. Or you can start later. At that time, a delayed reaction reaction based on the core structure is used. The use of color and the resulting time-lapse understanding indicates that the color reaction is completely inhibited at the initial stage. whether it is started for the first time by repression of the storage room, or it is started immediately. Depends on the crab.

German Publication No. 2 346 598 describes a temperature control system consisting of a supporting film and a covering film. In this case, the degree of saponification of the starting ester, the saponification agent Alternatively, the solubility of the thin film can be adjusted up to the point of color change by selecting the molecular weight. Wear. However, to avoid condensate formation, both membranes should be kept uniformly at room temperature. It must be done while doing so. This is because otherwise the reaction will start prematurely. be.

Many studies have already been conducted to solve these problems, but or is currently used to control unavailability easily and largely independently of external influences. I hope you have been successful until now. In addition, normal storage retention or There is also no simple possibility for a natural start by the user.

Therefore, the problem of the present invention can be easily created, Regardless of the storage and holding method, the starting point can be used to The purpose of the present invention is to provide an indicator with a simple configuration.

1 According to the present invention, this problem is solved by the features of claim 1. other Preferred configurations are shown in the embodiment section.

The present invention specified in claim 1 particularly provides for easy creation of indicators. It is possible to grasp the elapsed time according to the user's wishes, regardless of the method of storage and retention in advance. It features scales that allow you to easily control the starting point. If desired, the indicator A simple method to prevent early chemical reactions between electron-rich and electron-deficient compounds. can simply be formed, or if desired, anything to initially stop the chemical reaction. Therefore, it is not necessary to provide other means, so it is possible to understand the passage of time by creating an indicator. or immediately upon application of the indicator to the product. Furthermore, implementation The reaction delay means individually specified in the aspect section are indicated by indicators according to the time elapsed. It also provides accurate delay of data display.

Immediate start (when creating or applying an indicator) or following the above implementation. Compounds used in subsequent indicators, i.e. electron-rich compounds/ Electron-deficient compounds (technical literature describes them as ``electron-donor-acceptor-complex'' or ``charged The choice of "transfer complexes" (also referred to as "transfer complexes") is particularly advantageous for readout purposes. [Note** *: For example, Length Hemi Lection, Stuttgart (1973) ]. IinG-9: Create an adduct with a different absorbance than the starting material without producing any products. Especially for products equipped with this type of indicator, the start point of the normal storage procedure can be Electron deficient compounds and electron The colored donor-acceptor-complex to be replaced with excess compound is virtually independent of temperature for the user. Many compounds can be used in a relationship to produce different coloring reactions and display them in the same way. make it possible to

Microencapsulation techniques that can be used advantageously within the scope of the invention for the compounds used Regarding the technique, it is recognized that this microencapsulation technology itself belongs to the prior art. Let's go.

In this connection, the Length Hemi-Lection, Fairlag Franchisier Verlags Handlung, Stuttgart (1974), Stittgart Hiboldt: Microfair Force Psernck and the literature cited therein are referred to. It will be done.

Figure 3 illustrates an indicator having an electron donor and an electron acceptor in the implant.

FIG. 2 illustrates an indicator without a spacing interlayer.

Figure 3 shows polymers (aromatic) as electron donors and electron acceptors in polymer embedded objects. group polyurethane) to form an DA-complex. Figure 3 illustrates an indicator with a donor moiety.

Figure 5 shows the electrons gradually forming a DA complex by converting the electron donor component with a reducing agent. Figure 3 illustrates an indicator with child receptor components.

FIGS. 6 and 7 illustrate fast-responsive spoilage indicators.

Figures 8 and 9 illustrate a gradually responding spoilage indicator, where the response speed is The degree can be adjusted by selecting the thickness and permeability of the interlayer.

Figure 10 shows a microencapsulated reaction partner dissolved in and embedded in a polymer. 3 illustrates an indicator having a

Figure 1-1 shows a microencapsulated reaction partner encapsulated in two separate polymer layers. 3 illustrates an indicator having a

The planar area of the indicator can be configured differently depending on the application. Ta For example, a strip with a planar area of about 4 cm2 can be used.

The indicator can also be configured differently depending on the use case or It can also be made larger or smaller to provide visibility.

The electron rich compounds used according to the invention are unsubstituted and/or 2-13-15 - or 6-position substituted quinones, phenolic polymer compounds and/or or corresponding polymeric aromatic amine and/or phenyl compounds. suitable here Examples of compounds include hydroquinone, hydroquinone derivatives, such as alkyl and/or oxyalkylated and/or carboxylated compounds and its esterified compounds, Brentkachin and its derivatives, Fluoro Loglucin, aniline and its derivatives, aminophenol, o-1m-1p- Phenyl diamine, tannin and its alkylation, halogenation, etherification and U, stellated derivatives, and other tanning agents, aminotriphenylmethane Examples include dyes and their leuco compounds, as well as aromatic polyurethanes. preferred In other cases, a compound having a phenol group is used. The advantage of the above compounds is that their low high volatility and its physiological safety.

Electron deficient compounds suitable for indicators of the invention include low molecular weight or electronegative compounds. Examples include aromatic substances substituted with a (-M) group. Preferably. - and p- benzoquinone and its 2-13-15- or 6-position is e.g. derivatives substituted with, nitrated aromatic compounds, such as 2-14-16- or is 2.4.4. - positionally nitrated phenols or homologous multiple hydroxyl groups; Phenol having a syl group, or o-1m-1p-nitroaniline or 2 ．． 4.6-Dolinitroaniline or phenyl congeners of these compounds, e.g. Picric acid, aniline picrate, and chloranil. Because these This is because it is easily produced and poses no physiological problems.

According to the invention, the indicator contains oxidation or a second slowly acting reaction partner. Use of an electron-rich compound that partially converts into an electron-deficient compound by its action. can be done.

For example, atmospheric oxygen, relatively stable peroxides or reducing compounds with reducing aldehyde groups. base agents, such as astorbic acid, hydrocellulose, hydrolyzed starch or in general Electron-rich compounds by the action of reducing mono-, oligo- or poly-glucosides A slow conversion of the compound to an electron-deficient compound occurs, in which case under the conditions, i.e. the initial colored donor in the simultaneous presence of the remainder of the electron-rich or electron-poor compound of the phase. - receptor ~ complex is formed. Conversely, the action of the second gradually acting reaction partner mentioned above Use electron-deficient compounds to partially convert up to electron-rich compounds under the scales. Of course.

Electron deficient compounds used as one component of the indicators according to the invention are preferred. Alternatively, it is contained in a support in an amount of 50.01 to 10% by weight based on the support.

Preferably, the electron deficient compound is contained in the support at 1 to 3% by weight. to this on the one hand, ultimately eliminating health considerations such as those associated with aromatic compounds. On the other hand, colored complexes can be produced while simultaneously keeping the concentration of electron-rich compounds constant. The formation of can be controlled as necessary.

According to the invention, the electron-rich compound is present in the support with 0.01 to 1 It is contained in an amount of 0% by weight, preferably 3.-8% by weight. Therefore, the user is for different concentrations of electron-rich compounds and different concentrations of electron-deficient compounds. The possibility is given to control the rate of formation of the colored complex and the strength of the colored complex.

According to the invention, the support is composed of polymeric and/or oligomeric components. Ru. The components used should be substantially amorphous, while electron-deficient compounds as a carrier for compounds and electron-rich compounds or by itself as one of the reactants. On the one hand, it acts to control the passage of time.

Furthermore, they are resistant to harmful environmental effects such as light, temperature or humidity. It acts to facilitate stabilization.

In the indicator of the present invention, the support is acrylic acid, acrylic ester, vinegar. Polymers of vinyl acid, vinyl chloride, vinyl alcohol and/or mixtures thereof. be. Preferably, the polymer is a polyacrylic acid- or polyvinyl acetate-derivative. It is. By bonding one compound into this type of polymer, on the other hand, the environmental and hygienic considerations are alleviated, while the significant adhesive and The abrasion resistance minimizes its failure and disruption of the intended process.

The indicator of the present invention uses acrylic acid, acrylic ester, vinyl acetate as a support. oligomers of vinyl, vinyl chloride, vinyl alcohol and/or mixtures thereof. It can contain. Preferably the oligomer is an acrylic ester.

As a result, the user can change the diffusion conditions of the indicator according to the present invention over time. The possibility of precisely adjusting the course, ie the formation of the colored complex, is furthermore provided.

According to the invention, the polymeric and/or oligomeric components of the support are inorganic and and/or used dissolved in an organic solvent in an amount of 2 to 70% by weight. The preferred range is It is 20 to 40% by weight.

This makes it possible, for example, to use polymers with different solubilities or which are only slightly miscible with each other. The natural miscibility of the polymer in immiscible solvents decreases, where electron-rich compounds and Child-deficient compounds are compounds that diffuse into each other over time to form colored donor-acceptor-complexes. You can start the process with a delay.

Suitable solvents are water, lower alcohols, ketones, esters of organic acids and/or It is a mixture of Suitable solvents are water, methanol, ethanol, propatool, acetic acid. ton, methyl ethyl ketone, ethyl acetate, butyl acetate or the like. It is a mixture of The advantages of these solvents are that they can be used with little physiological consideration or It is easy to process without consideration and to apply the various support layers separately.

In the indicator of the invention, the support further comprises an electron deficient compound and/or It may be formed as a covering layer and/or an intermediate layer without containing one type of electron-rich compound. I can do it. This allows the user to easily remove the coating layer and empty the air. Formation of colored donor-acceptor-complexes can be initiated by supplying atmospheric oxygen gender is given. Between the electron-deficient compound-support layer and the electron-rich compound-support layer The intermediate layer formed additionally acts as a temporal separation holder and Enabling control. In this case, this intermediate layer is not used as a reaction initiation part, but as a reaction determining part. It can be seen as a part.

The support of the indicator according to the invention further supports additive substances that influence migration. It can be contained in an amount of 0 to 20% by weight based on the carrier. Preferably, these additions Additional substances are contained in amounts of 2 to 15% by weight. Substantially only dilutable and inert composition By incorporation of these additive substances, the reaction time and the color depth reached can be easily adjusted in minutes. can have an influence. These additive substances are included in both the coating layer and the intermediate layer. be able to.

According to the invention, these additives include alkyl glycol ethers, polyglycol ethers, ethers, esters of aliphatic and aromatic carboxylic acids and/or mixtures thereof It is a thing. Preferably, the additive material is an ester phthalate or a glycol ether. be. These additive substances that do not inhibit migration promotion or diffusivity are important for the reaction of colored complexes. The onset of It can act as a stabilizer.

The indicators of the present invention are easy to create.

First of all, 0.0% of the electron-rich compound in a suitable inorganic and/or organic solvent is used. 01-10% by weight solution is prepared. Can act as a carrier substance if desired 1 to 5% by weight of the electron rich compound in solution of a suitable support can be introduced. Wear.

Transfer-promoting inert additives in an amount of 0 to 20% by weight are added to the electron-rich compound and the heavy a support that acts as a carrier material consisting of a combined and/or oligomeric component; It can be added to carriers. The solution thus formed is then prepared in at least one layer on the substrate in a known manner, for example by coating or spraying. application and then drying at a temperature of 20-100°C, preferably 25-50°C. Or create a film or foil from a solution of an electron-rich compound, which is then It can also be applied, for example, to the preparation by mechanical pressure. In the second step, the first A 0.5-5% by weight solution of the electron-deficient compound is prepared using another solvent with a polarity different from that of the solvent. At that time, if necessary, an electron-deficient compound is added as a carrier substance in the support solution. It is introduced in an amount of 2 to 70% by weight, based on the support. Additives similar to those above It can also be added to this solution. This solution, in the form of a thick paste, can be used as needed. The liquid is then applied onto the preparation and onto the applied and dried layer or electron-rich It is applied as at least one layer on the film or foil of the compound. Preferred specific example In this case, a film with a layer of adhesive material applied on one side facing the surface to be acted upon is used. As a film or foil, a solution of the electron-deficient compound can be applied by known coating methods or mechanically. Apply pressure to the first layer of electron rich compound. Here, the polymer and Relatively natural or additive due to the identity or more or less different similarity of the solvents Depending on the added substances, a time-delayed formation of the colored complex takes place.

The unnatural miscibility of polymers, e.g. However, with the use of miscible solvents, electron-deficient and electron-rich compounds can be separated from each other. Diffusion forms a colored donor-acceptor-complex with a time delay.

Alternatively, the electron-deficient compound can be applied first and then the electron-rich compound. Ru.

According to the present invention, a solution formed from an electron-deficient compound and an electron-rich compound is The solution is applied in layers of different thickness, and if necessary, can contain additives. or visible depending on the concentration of electron-deficient and electron-rich compounds in the support. The formation of colored complexes can be easily controlled. 1 to 250 μm 1 preferably 5 It has proven advantageous to apply this solution with a layer thickness of ~100 μm.

If relative diffusion occurs relatively naturally or gradually while forming colored complexes as necessary, The intermediate layer may contain polymeric and/or oligomeric components and optionally an inert between the electron-deficient and electron-rich compound layers from the support containing the additive. can be introduced. In this way, the user can detect visible color changes that serve as a measure of the course of the phenomenon. able to control themselves. Depending on your needs, this intermediate layer can be formed with different thicknesses. be done. Preferably they are between 1 and 250 μm, especially between 5 and 50 μm. Sara Additionally, immediate mixing or diffusion of both compounds can also be avoided.

Furthermore, it is inert to harmful environmental effects, such as atmospheric oxygen, temperature or humidity. When a certain coating layer is placed through an electron-rich compound-containing layer and an electron-deficient compound-containing layer, You can also

This covering layer serves a dual function: firstly, by removing the covering layer, the user can The desired course of phenomena can be initiated and, secondly, the remarkable adhesion and adhesion of this coating layer and abrasion resistance to avoid damage and disruption of the reaction.

In other embodiments of the invention, electron-deficient and/or electron-rich compounds and/or other reaction partners separately as microcapsules. It can be inserted into the body. Contains microcapsules applied on preparations The spatial separation of the supports prevents the reaction of both compounds.

This means that the start point of the state change is determined by the user regardless of the prior storage and retention method. Therefore, it has the advantage of being controlled. Preferably, the phenomena considered are Start by applying mechanical pressure to the product when applying the indicator created by Akira. At that time, pressure is applied to separate capsules containing electron-deficient compounds and electron-rich compounds. The capsule is ruptured and, depending on the support used and the additives contained if necessary, These compounds diffuse into each other (-2, the visible part of the donor-acceptor-complex formed) For example, the color change is the maximum allowable value of the product)j': Displays the elapsed storage time.

The indicator of the present invention is a dilute solution of an electron-deficient compound or an electron-rich compound. The film or layer is applied to the product IJ, and then the other electron-deficient compound is also removed. A thin film or layer of electron-rich compounds (these compounds are necessary to form the complex) ) can also be created by the user starting the start point. can do. In this case, if necessary, a coating layer that retards visible color change and /' and +=mediumSi'J layer or promoting additives applied inside the intermediate layer, two 2 can also be done.

According to the present invention 1, the indicator can further be used as a reaction partner or other reaction partner. However, there is a shortage of electrons and things are also 1. (Applying a coating layer containing an electron-rich compound or by protecting against harmful environmental effects and stripping the coating layer. It is also possible to make I.

According to the indicator created according to the present invention, the electron deficient compound used and the Depending on the type of compound, the support used and the additives used, the progress and and many visible color changes easily or 1) without interference, i.e., due to environmental effects. It can be adjusted and controlled independently.

The indicators of the present invention can be manufactured in a time-limited or storage-limited manner. It has uses in many products. For example, as a same-day service menu, monthly meal coupon, or Mass-produced products, foods that can be stored for a limited time, such as milk products, or It has applications in medicinal products and active substances that need to be stored for a limited period of time.

In the following, preferred embodiments of the present invention will be generally illustrated, in which donor-acceptor-complexes (hereinafter referred to as Below, always abbreviated as DA-complex) are the electron-rich and electron-deficient compounds used. From several hours to several weeks depending on the material used, the thickness used, and the presence of an intermediate layer that holds the IJ apart. on any Brevara-1 ('Tayoe (Masho 1, Plastirif or Metal)) :i':、Polyano l Iy・-1・Ki:8 Otjru Ani7 Rimbik I/・-t Apply a layer of Polyvinyl acetate 9- provided on top of E if necessary.

The layer made of polyacrylic acid ester acts as a separation maintainer, and poly()′(, ・-I-11-) consisting of 1,4-quinone in Layer 1) Eight - This is a layer that controls the formation of the rudder body over time. If necessary, mark it as R. ``Polyvinyl acetate t, + < is polyvinyl chloride r'''J, phytoacetate Does a layer of copolymers protect against harmful environmental effects? 5, colored dark brown 17 [I] A-Complex is formed 1. Once the intermediate layer is formed, coloring starts immediately and continues for 2 hours. It will be finished within. If an intermediate layer is used, coloring will take several weeks depending on the type and thickness of the intermediate layer. starting with a 100 μm thick intermediate layer made of polyacrylic acid ester, for example. It will start in about 6 weeks.

Optional slides 8. Polyurethane 1.・Tan: b keruri 1] Consisting of Ranil layer, optionally a layer made of polyacrylic acid ester, and an electron donor component. A layer of polyurethane is applied in succession.

It is colored olive, and a DA-complex is formed in the intermediate layer 1.7 in 2 hours, If you have an intermediate layer of 40 μm, it will form on any preparation in about 4 weeks. A layer consisting of polyurethane with droquinone is applied 2, here by air oxygen Gradually oxidizes an electron-rich compound to 1,4-quinone, an electron-deficient compound. . By allowing an electron-rich compound and an electron-deficient compound to exist simultaneously, D - Complex formation is initiated. Coating made of polyacrylic ester if necessary Layers can also be applied.

No interlayer, cocoa colored (7 DA-complexes formed within 6-8 weeks, If an intermediate layer is used (depending on type and thickness) it will take three months or more to form.

4. The reducing agent gradually transforms the compound into an electron-rich compound and starts forming a DA-complex. Examples using electron-deficient compounds: A layer of chloride-acetate copolymer 1, a diffusing quinone 71 chloride 2 Ascorbic acid layer in polyacrylic 1 note to reduce to non-containing A layer consisting of 1,4-quinone in lyacrylic acid ester and, if necessary, polyamide. A coating layer consisting of acrylic acid ester is applied in sequence.

A reddish-brown colored DA-complex is formed on the surface.

5. Examples of fast-responsive spoilage indicators: (a) Any bulb A layer of aniline picrate in polyacrylate is applied on top, and the On top is applied a layer consisting of benzoquinone in polyacrylic ester.

A DA-complex with a chocolate L/-t color is formed directly, with a coloration of approx. Ends after hours.

(b) 1 in polyvinyl acetate on any preparation.

7. Applying a layer consisting of 4-quinone; 7. Aromatic polyurethane having an electron-rich compound thereon; Apply a layer of letane.

A coffee-colored DA-complex is formed in 1-2 days.

6. Corrosion indicators that gradually respond depending on the thickness and permeability of the interlayer that is kept apart. Examples of data: (a) Aniline picrate in polyacrylate on any preparation a layer of polyvinyl chloride-acetate copolymer, and a layer of polyacrylic A layer of benzoquinone in acid ester is applied sequentially.

A dark brown colored DA-complex is formed in 3 weeks.

(b) 1,4-quinone in polyacrylic ester on any preparation a layer consisting of polyvinyl acetate, a layer consisting of polyvinyl acetate, and a polyvinyl acetate layer containing an aromatic electron-rich compound. The layers of urethane are applied one after the other.

A dark brown colored DA-complex is formed within 8 weeks.

On any preparation a layer consisting of phloroglucin in polyacrylate and , from microencapsulated 1,4-benzoquinone in polyurethane. A layer consisting of polyacrylic acid ester and, if necessary, a layer consisting of polyacrylic ester are sequentially applied.

By applying mechanical pressure, the microcapsules are destroyed and colored orange. A DA-complex is formed in one day.

Microencapsulated anilimpic in polyurethane on any preparation Microencapsulation in polyurethane with a layer of 1. 4-benzoquino A layer consisting of polyacrylic acid ester and a layer consisting of polyacrylic acid ester are applied sequentially as necessary. .

By applying mechanical pressure, the microcapsules were destroyed and colored dark brown. A DA-complex is formed within 30 minutes.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Low-molecular-weight electron-deficient compounds and low-molecular-weight electron-deficient compounds in separated polymer solutions, respectively. Formation of DA-complexes by combination with excess compounds. The rate of formation of complexes in polymer intermediates The layers were controlled and covered by a protective coating layer.

Dissolve 1 g of 1,4-benzoquinone in 1 Q ml of isopropanol at 35°C. Then, this solution was added to 89 g of polyacrylic acid propyl ester solution (ethyl acetate). 20% in ester). The obtained solution was plated in a layer with a thickness of 100 μm. It was applied to palates (packaging cartons) and dried at 40°C.

Water-based polyvinegar acts as an intermediate layer that maintains a distance of 50 μm in thickness from this dry layer. Acid vinyl dispersion (50%, thickened with polyvinyl alcohol) (this requires a diffusion rate 10% dioctyl phthalate was added to increase the strength) and air dried. .

Then, 1 g of hydroquinone was dissolved in IO+nl of 80°C water, and this solution was When hot, introduce Hg into a cold polyacrylate aqueous solution (20%) with stirring and cool. Stirred. The cooled solution was applied to the dry polyvinyl acetate layer at a thickness of 1 μm. , dried again.

After drying, a layer made of polyvinyl acetate (50% dispersion in water, polyvinyl acetate) was used as a coating layer. Thickened with alcohol). At 6 weeks, the first almost colorless calendar month turns into an orange-brown color. A DA-complex was formed.

Example 2 Low-molecular electron-deficient compounds and high-molecular electron-rich compounds in separate layers. Formation of a DA-complex with a regulating interlayer in combination with.

Dissolve 1 g of 1,4-benzoquinone in 10 ml of acetic acid ethyl ester at 35°C. Then, this solution was mixed with 89 g of propyl acrylate solution (ethyl acetate). 20% in ester). The resulting solution was plated as a 100 μm thick layer. It was applied to a palat (packaging carton) and dried at 40°C.

This dried layer was coated with a 50 μm thick aqueous polyvinyl acetate dispersion (50% polyvinyl acetate). (thickened with alcohol) and allowed to air dry.

The dried layer is then replaced with an aqueous polyurethane layer (50%, containing polyurethane as the donor component). with aromatic amine as a predetermined component of tan) and further air-dried. .

In 4 weeks at 20° C., a black-brown DA-complex was formed from the colorless calendar.

Example 3 Example 2 was repeated, but with a layer with an electron-deficient compound and a layer with an electron-rich compound. No adjustment intermediate layer was interposed between the two layers.

A dark brown DA-complex began to form immediately and was complete within 1 day.

Example 4 A form of DA-complex consisting of a low molecular weight electron-rich compound and a slowly acting reaction partner. Completed. A portion of the electron-rich compound generates an electron-deficient compound over time, and this causes Conditions for natural DA-complex formation were formed.

Dissolve 3 g of phloroglucin in 30 ml of 80°C water, then add this solution to 67 g of polyacrylate solution (30% aqueous solution) and stirred while cold. This dark The thick solution was applied to a preparation (packaging carton) as a 200 μm thick layer, and Dry at ℃. A polyvinyl acetate layer according to Example 1 was applied as a covering layer.

In 4 weeks, a milky coffee-colored DA-complex was initially formed in a colorless transparent layer at 20°C. accomplished.

Example 5 A form of DA-complex consisting of a low molecular weight electron-deficient compound and a slowly acting reaction partner. Completed. Over time, a portion of the electron-deficient compound gives rise to an electron-rich compound, thus automatically Conditions for natural DA-complex formation are formed.

3 g of 1,4-benzoquinone was dissolved in 30 ml of ethyl acetate at 60°C, then This solution was added to 67 g of polyacrylic ester (30% in ethyl acetate), Stir while cold. Apply this concentrated solution as a 200 μm thick layer on a suitable preparation plate. (packaging carton) and dried at 40°C. As a coating layer, according to Example 1, A layer of polyvinyl acetate was applied.

In 6 weeks, at 20°C, the first colorless transparent layer was coated with reducing glucose from the cellulose of the paper. A raspberry-colored DA-complex was formed by reaction with cosidic groups.

Fig. 1 Coating layer - if''! acetic acid carbonate (can be omitted) Electron donor component F in polyacrylate! g, 2 i,)5=)L=, . ,7. -Aya? -) #*-Fig, 9 Polyurethane with aromatic electron donor component Fig, 10 , (proud of the abbreviation) international search report international search report

Claims (23)

[Claims] 1. The phenomenon ( For example, when understanding the progress of a product's expiration date or retention date over time, A means for delaying the reaction according to the elapsed time to be ascertained is provided. In indicators whose onset can be controlled by early reaction inhibition if necessary, the first one compound is an electron-rich compound and the second compound is an electron-deficient compound; An indicator characterized in that these form an electron donor-acceptor complex. 2. Electron-deficient and electron-rich compounds are substituted and/or unsubstituted aromatics compound and/or one or more sulfur atoms, nitrogen atoms and/or is a heterocyclic compound having an oxygen atom. indicators. 3. Electron-rich compounds include hydroquinone and its derivatives, phenolic polymerization compounds and/or polymeric aromatic amines and/or phenyl compounds. The indicator according to claim 1 or 2, characterized in that: 4. The electron-deficient compound is benzoquinone and its derivatives or nitrated aromatic compounds. 3. The indicator according to claim 1 or 2, wherein the indicator is a product. 5. Electron-poor compounds act as oxidants or other reaction partners on electron-rich compounds. Any one of claims 1 to 4, characterized in that the compound is a compound produced by Indicators listed in 6. An electron-rich compound is produced by the action of a second reaction partner on an electron-poor compound. The compound according to any one of claims 1 to 4, characterized in that it is a sulfur compound. indicator. 7. Electron-deficient compound or quantum-excess compound is 0.01 to 10% by weight based on the support. Any of claims 1 to 6, characterized in that it is contained in the support in an amount of Indicators listed in 8. The support consists of at least one polymeric and/or oligomeric component. The indicator according to claim 7, characterized in that: 9. If the support is acrylic acid, acrylic ester, vinyl acetate, vinyl chloride, or vinyl polymers and/or oligomers of alcohols and/or mixtures thereof. The indicator according to claim 7, characterized in that: 10. The polymer and/or oligomer component is dissolved in an inorganic and/or organic solvent. The method according to claims 7 to 9, characterized in that it is dissolved in an amount of ~70% by weight. Indicators listed in any of the following. 11. If the solvent is water, lower alcohols, ketones, esters, organic acids and/or The indicator according to claim 10, characterized in that it is a mixture of. 12. The support does not contain either an electron-deficient compound and/or an electron-rich compound. Claim No. The indicator according to any one of items 7 to 11. 13. The support contains from 0 to 20% by weight of additives based on the support. The indicator according to any one of claims 7 to 12. 14. Additives include alkyl glycol ether, polyglycol ether, and fat. esters of group and aromatic carboxylic acids and/or mixtures thereof. 14. The indicator according to claim 13, wherein the indicator is a sign. 15. A solution of the electron-rich compound in a suitable solvent as a carrier if necessary. Prepare a solution of the support and apply the resulting solution to the preparation in at least one layer. applied, then dried, A solution of the electron-deficient compound in a suitable solvent optionally supports the carrier as a carrier. Electron enrichment was prepared with a solution of Apply at least one layer to the compound to initiate the course of the phenomenon. The indicator according to any one of claims 1 to 14, characterized in that: How to create. 16. The special feature is to apply the electron-deficient compound first, followed by the electron-rich compound. 16. The method according to claim 15, characterized in that 17. The application is characterized in that the solution is applied to the preparation in layers of different thickness. The method according to claim 15 or 16. Claim 1, characterized in that the solution is applied with a layer thickness of 18.1 to 250 μm. The method described in Section 7. 19. Characteristic in that the solution of the support is further applied as a covering layer and/or an intermediate layer. 16. The method according to claim 15. 20. A coating layer containing an electron-indeterminate compound or an electron-rich compound is used as a reaction partner. can be applied as another reaction partner or by peeling off the coating layer. 20. The method of claim 19, further comprising starting an indicator. 21. Electron-deficient and/or electron-rich compounds and/or reaction partners Claims characterized in that the solution is inserted into the support as microcapsules The method according to paragraph 15. 22. Claims characterized in that the indicator is started by applying pressure. The method according to paragraph 21. 23. Claims in time-limited or time-limitable products Use of the indicator according to any of paragraphs 1 to 14.