CN112485243A - Novel time-temperature indicator and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of indicators, and particularly discloses a novel time-temperature indicator, which at least comprises a skeleton structure layer, a color development layer and a consumption layer, wherein the indicator comprises the following components in percentage by mass: 75-90% of film forming material, 0.2-10% of catalytic material, 5-20% of color developing agent and 0.1-1% of auxiliary agent. The indicator provided by the invention has the advantage of high accuracy, the consumption layer is decomposed under the synergistic action of illumination, heat or photo-heat, after the certain part of the consumption layer is completely decomposed, the exposed color development layer can show color change in the air, and the information of time, temperature and the like of the product can be judged according to the color change of the color development layer, so that the information of the product such as transportation time, storage time, product quality change and the like can be judged, and the product information tracing is facilitated.

Description

Novel time-temperature indicator and preparation method thereof

Technical Field

The invention relates to the technical field of indicators, in particular to a novel time-temperature indicator and a preparation method thereof.

Background

In the circulation process of the product, the product relates to many links such as production, storage, transportation, sale, quality tracing and the like, factors such as time, illumination, temperature and the like all influence the product quality, however, because each factor influencing the product in the circulation process of the product has unpredictability, the time period and the product quality change of the product in each link lack indication information, and the product information acquired by a consumer is asymmetric in the circulation process of the product.

With the technical progress, a Time-Temperature Indicator (TTI for short) capable of monitoring the quality change process of a product is widely used. The time-temperature indicator refers to a technology for indicating the change of product information by causing the color of the indicator to change through time and temperature changes, and the time-temperature change process of the product can be recorded according to the color change.

Most of the time-temperature indicators currently on the market are mainly classified into diffusion type, polymerization reaction type and enzyme reaction type according to the indication principle; according to the chemical principle of indicator in working, it can be divided into solution diffusion type and pH color-changing reaction type; the temperature indicators may be classified into critical temperature indicators, critical temperature/time integrators, and time temperature indicators according to the kind of the transmitted information. However, the preparation technology adopted by the time-temperature indicator is complex, high in cost and not suitable for wide-range application, and the reaction on parameters such as time, light, temperature and the like is inaccurate, so that the change information of the product can not be accurately indicated.

Therefore, how to simplify the preparation process and the preparation cost of the indicator and improve the detection accuracy of the indicator simultaneously becomes a technical problem which needs to be solved urgently.

Disclosure of Invention

The first purpose of the invention is to provide a novel time-temperature indicator to solve the problem of poor accuracy of indicator detection.

In order to achieve the purpose, the invention adopts the following technical scheme:

a novel time-temperature indicator, the indicator at least comprises a skeleton structure layer, a color development layer and a consumption layer, and the indicator comprises the following components in percentage by mass: 75-90% of film forming material, 0.2-10% of catalytic material, 5-20% of color developing agent and 0.1-1% of auxiliary agent.

Further, the film forming material comprises one or more of aliphatic polyester, polyester copolymer, polyvinyl alcohol, polyethylene glycol, plant cellulose, polylactic acid, starch, polyacrylic resin, chitosan, alkyd resin, chlorinated polypropylene resin, silicate, chitosan, animal glue, natural organic matters and marine algae, wherein the silicate comprises aluminum silicate, ferric silicate, calcium silicate, magnesium silicate, potassium silicate and sodium silicate.

Further, the catalytic material comprises a photocatalytic material, a thermocatalytic material and a photothermal co-catalytic material.

Further, the color developer comprises one or more of carotenoid pigment, astaxanthin, anthocyanin and other plant pigment, plant phenols and phenol substances.

Further, the auxiliary agent comprises a photosensitizer, an antioxidant and a lubricant.

Further, the solvent comprises one or more of water, ethanol, acetone and glycol.

Further, the skeleton structure layer is one or more of porous alumina, cordierite, silica gel, molecular sieve, sepiolite, foam metal, attapulgite, shell powder, diatom ooze and bentonite.

Further, the photocatalytic material includes C₃N₄Doped C₃N₄Composite C₃N₄One or more of nanometer bismuth series oxide; the thermal catalytic material comprises a noble metal material, and the photo-thermal catalytic material comprises cerium oxide and copper oxide.

Further, the photosensitizer comprises one or more of aromatic diazonium salts, diaryl iodine compounds, triaryl sulfur compounds, alkyl metals, metal carbonyls, benzoin and derivatives thereof, acetophenone derivatives, aromatic ketone compounds, pigments, arones, fused ring aromatic hydrocarbons, polysilanes, acyl phosphonates, azos and metal organic complexes.

Further, the antioxidant comprises one or more of phenolic antioxidant, flavonoid antioxidant, vitamin E, melatonin, vitamin C and ascorbic acid.

Further, the lubricant comprises one or more of calcium stearate, zinc stearate, stearic acid amide, paraffin wax, and polyethylene wax.

A second object of the present invention is to provide a method for preparing the novel time-temperature indicator, which comprises the following steps:

weighing the raw material components for preparing the indicator according to the proportion, and mixing and stirring the color developing agent, the film forming material and the solvent to obtain a first mixed solution;

mixing and stirring the film forming material and the catalytic material to obtain a second mixed solution;

soaking the skeleton structure layer in the first mixed solution, and drying at a first temperature to form a color development layer on the skeleton structure layer;

soaking the skeleton structure layer with the color development layer in the second mixed solution, drying at a second temperature, and forming a consumption layer on the surface of the color development layer to obtain the indicator;

wherein the first temperature is greater than the second temperature.

Further, the rotation speed of the mechanical stirring is 200-900r/min, and the stirring time is 0.5-2 h.

Further, the stirring and mixing manner includes mechanical stirring and ball-milling stirring.

Further, the first temperature drying is heating temperature of 60-100 ℃, and drying time is 6-12 h; the second temperature drying is heating temperature of 20-40 ℃, and drying time is 24-48 h.

Further, the first temperature drying is vacuum high temperature drying.

The invention has the beneficial effects that:

the novel time-temperature indicator provided by the invention comprises the following components in percentage by mass: the indicator at least comprises a skeleton structure layer, a color development layer and a consumption layer, and the indicator comprises the following components in percentage by mass: 75-90% of film forming material, 0.2-10% of catalytic material, 5-20% of color developing agent and 0.1-1% of auxiliary agent. The indicator provided by the invention has the advantage of high accuracy, the consumption layer is decomposed under the synergistic action of illumination, heat or photo-heat, after the certain part of the consumption layer is completely decomposed, the exposed color development layer can show color change in the air, and the information of time, temperature and the like of the product can be judged according to the color change of the color development layer, so that the information of the product such as transportation time, storage time, product quality change and the like can be judged, and the product information tracing is facilitated.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.

FIG. 1 is a schematic diagram of the overall structure of a novel time-temperature indicator in an embodiment of the present invention;

FIG. 2 is a flow chart of a method of making a novel time temperature indicator in an embodiment of the present invention.

Reference numerals: 1. a framework structure layer; 2. a color development layer; 3. the sacrificial layer.

Detailed Description

The numerical values set forth in the examples of the present invention are approximations, not necessarily values. All values within the error range may be included without limiting to the specific values disclosed in the embodiments of the present invention, where the error or experimental conditions allow.

The numerical ranges disclosed in the examples of the present invention are intended to indicate the relative amounts of the components in the mixture and the ranges of temperatures or other parameters recited in the other method examples.

The invention provides a novel time-temperature indicator, which at least comprises a skeleton structure layer 1, a color development layer 2 and aconsumption layer 3, wherein the indicator comprises the following components in percentage by mass: 75-90% of film forming material, 0.2-10% of catalytic material, 5-20% of color developing agent and 0.1-1% of auxiliary agent.

From the preparation technology and the actual use effect of the traditional time-temperature indicators, such as the indicators of diffusion type, polymerization reaction type, enzyme reaction type and the like, it can be known that most time-temperature indicators have the defects of complex preparation technology, high cost, unsuitability for wide-range application, inaccurate reaction on parameters such as time, light, temperature and the like, and incapability of accurately indicating the information change information of products.

In order to solve the above problem, in the present embodiment, the time-temperature indicator is designed to include at least the skeleton structure layer 1, the color-developing layer 2, and theexpendable layer 3. The skeleton structure layer 1, the color-developing layer 2, and theexpendable layer 3 constituting the time-temperature indicator may be designed to be circular or square, etc., and are not limited thereto. By utilizing the characteristic that the material selected by theconsumption layer 3 is decomposed under the influence of factors such as temperature and illumination, the temperature critical point or the illumination intensity critical point of theconsumption layer 3 is predetermined, and it can be judged that when theconsumption layer 3 is completely decomposed, the temperature critical point or the illumination intensity critical point corresponding to theconsumption layer 3 is the temperature or illumination intensity environment extreme value where the indicator is located. Thus, by using the indicator provided with theexpendable layer 3 as a single item on a product to be tested, for example a product susceptible to deterioration by the influence of temperature or light intensity. When theconsumption layer 3 of the indicator is completely decomposed, and the color development layer 2 is exposed, the product can be judged to be changed to a certain degree, and a user is reminded that the product cannot be used continuously.

Further, the time period of the indicator in the above-mentioned ambient value of temperature or illumination intensity can be reflected by the corresponding decomposition time when theconsumable layer 3 is completely decomposed, and the time period of the product in the condition causing the deterioration can be detected. Specifically, since the time for which theconsumption layer 3 is completely decomposed, that is, the decomposition time corresponding to the time for which the color development layer 2 can be exposed, can be predetermined, the time for which the product is present in the condition causing the quality change (for example, a certain product needs to be stored in an environment at-2 ℃, the condition for the quality change is 10 ℃) can be determined by the decomposition time corresponding to theconsumption layer 3.

Further, since thesacrificial layer 3 is finite, once decomposed, it is not possible to continue through thesacrificial layer 3 for the length of time that the reaction product is present in the conditions that cause the deterioration. Therefore, in order to be able to continue to estimate the time that the product has elapsed after the complete decomposition of theconsumable layer 3, the invention can also estimate the time that the product has elapsed after the complete decomposition of theconsumable layer 3, by using the characteristic that the color-developing layer 2 reacts with air when exposed to air and shows a different degree of shade depending on the reaction time. Specifically, the color can be determined by changing from an initial color to another color using the color-developing layer or by the length of time that elapses while the color depth is changed.

Specifically, the skeleton structure layer 1 in the invention is used as a carrier of an indicator, and can be one or more of porous alumina, cordierite, silica gel, molecular sieve, sepiolite, foam metal, attapulgite and bentonite. Wherein, the aperture of the material for preparing the skeleton structure layer 1 is 10nm-200nm, and the color of the material is pure color. Further, in order to make the color of the material purer, the material may be pretreated, for example, the material may be subjected to ultrasonic cleaning, and high temperature impurity removal and decontamination.

The color development layer 2 is supported on the skeleton structure layer 1, and the main components of the color development layer comprise a film forming material, a color development agent and a solvent. Wherein the film forming material can be one or more of aliphatic polyester, polyester copolymer, polyvinyl alcohol, polyethylene glycol, plant cellulose, polylactic acid, starch, polyacrylic resin, chitosan, alkyd resin, chlorinated polypropylene resin, silicate, chitosan, animal glue, natural organic matters and marine algae. The developer is one or more of carotenoid pigment, astaxanthin, anthocyanin, plant phenols, and phenol.

Theconsumption layer 3 covers the color development layer 2, and the main components of the consumption layer comprise a film forming material, a catalytic material, an auxiliary agent and a solvent. Wherein the film forming material can be one or more of aliphatic polyester, polyester copolymer, polyvinyl alcohol, polyethylene glycol, plant cellulose, polylactic acid, starch, polyacrylic resin, chitosan, alkyd resin, chlorinated polypropylene resin, silicate, chitosan, animal glue, natural organic matters and marine algae. The catalytic material comprises a photocatalytic material, a thermocatalytic material and a photothermal concerted catalytic material.

Specifically, the photocatalytic material includes C₃N₄Doped C₃N₄Composite C₃N₄And one or more of nanometer bismuth series oxides. Doped C₃N₄The doping element is selected from one or more of K, Na, C, O, N and Cu. Compound C₃N₄Selected from TiO₂/C₃N₄polyaniline/C₃N₄graphene/C₃N₄、GO/C₃N₄、SiO₂/C₃N₄、BiOCl/C₃N₄、Fe₃O₄/C₃N₄、ZnO/C₃N₄One or more of (a). The nanometer bismuth-based oxide is selected from BiOCl and (BiO)₂CO₃BiOBr and BiOI.

The thermal catalytic material comprises noble metals such as Au, Ag, Pt, Ru and the like and oxides.

The photo-thermal catalytic material comprises noble metal catalysts such as oxide, carbon-based compound, Au-based catalyst, Pt-based catalyst, Ru-based catalyst, Pd-based catalyst, etc., and other compounds, wherein the oxide comprises cerium oxide, Fe₃O₄，MnFe₂O₄，ZnFe₂O₄，CoFe₂O₄，MoO₃-xNiO, copper oxide, Mn₃O₄/MnCO₃Tricobalt tetraoxide, Co/TiO₂，CoFeAl，LaFeO₃Co, etc.; the carbon-based compounds comprise carbon sponge/rGO, carbon nano tube/carbon wood, GO/carbon wood, polyamine/carbon wood and the like; au-based catalysts include Au/ZnS, Au/Ag₂S，Au/Cu₂O，Au/C₃N₄，Au/TiO₂GO-Au, etc.; the Pt-based catalyst comprises Pt/porphyrin MOFs, Pt/TiO₂，Pt/Ag，Pt/ZIF，Pt/C₃N₄Etc.; the Ru-based catalyst comprises Ru/TiO₂，Ru/C₃N₄、Ru/SiO₂Etc. the Pd-based catalyst includes Pd/ZIF-8, Pd/Nb₂O₅And the like. Other compounds include Ti₃C₂Polypyrrole, TiN, and the like.

The auxiliary agent comprises a photosensitizer, an antioxidant and a lubricant.

The photosensitizer comprises benzoin, ether, riboflavin, and/or zinc oxide. The light energy can be effectively absorbed, and the obtained energy can be efficiently transferred to the sensitized substance, namely the catalytic material layer.

The antioxidant comprises one or more of phenolic antioxidant, flavonoid antioxidant, vitamin E, melatonin, vitamin C, and ascorbic acid. Oxidation of the oxidizing substance can be prevented or prevented.

The lubricant comprises one or more of calcium stearate, zinc stearate, stearic acid amide, paraffin wax and polyethylene wax. Can improve the compatibility between substances and improve the fluidity.

The solvent comprises one or more of water, ethanol, acetone, and ethylene glycol. Convenient material obtaining and low cost.

Compared with the traditional indicator, the time-temperature indicator provided by the invention has the advantages of higher accuracy and lower cost, is beneficial to large-scale popularization, and has great application potential in the aspects of product production, storage, transportation, sale and quality tracing. The indicator can accurately calculate the product information such as the production date, the storage time, the transportation time, the product quality change and the like of the product by utilizing the color development of the indicator, and the raw materials related to the indicator are environment-friendly materials, can be quickly decomposed in a natural environment, are harmless to the environment, and avoid the pollution and the damage to the environment. Therefore, the indicator can be widely applied to the fields of various products such as food, medicine, fruits and vegetables, fresh food, vehicles, home furnishing, ornaments, coatings and the like.

In another aspect, the present invention further provides a method for preparing a novel time-temperature indicator, as shown in fig. 1, the method comprises the following steps:

s1: weighing the raw material components for preparing the indicator according to the proportion, and mixing and stirring the color developing agent, the film forming material and the solvent to obtain a first mixed solution;

s2: mixing and stirring the film forming material and the catalytic material to obtain a second mixed solution;

s3: soaking the skeleton structure layer 1 in the first mixed solution, and drying at a first temperature to form a color development layer 2 on the skeleton structure layer;

s4: soaking the skeleton structure layer 1 with the color development layer 2 in the second mixed solution, drying at a second temperature, and forming aconsumption layer 3 on the surface of the color development layer 2 to obtain the indicator;

wherein the first temperature is greater than the second temperature.

In the embodiment, the rotation speed of the mechanical stirring is 200-900r/min, and the stirring time is 0.5-2 h. The stirring and mixing modes comprise mechanical stirring and ball milling stirring. The first temperature drying is heating temperature of 60-100 ℃, and drying time is 6-12 h; the second temperature drying is heating temperature of 20-40 ℃, and drying time is 24-48 h. More preferably, the first temperature drying adopts vacuum high temperature drying, and the influence of air moisture on the indicating effect of the indicator can be reduced.

Compared with the traditional indicator, the time-temperature indicator provided by the invention has the advantages of higher accuracy and lower cost, is beneficial to large-scale popularization, and has great application potential in the aspects of product production, storage, transportation, sale and quality tracing. The indicator can accurately calculate the information of the product such as the production date, the storage time, the transportation time, the product quality change and the like by utilizing the color development of the indicator, and the raw materials related to the indicator are environment-friendly materials, can be quickly decomposed in the natural environment, are harmless to the environment and avoid the pollution and the damage to the environment. Therefore, the indicator can be widely applied to the fields of various products such as food, medicine, fruits and vegetables, fresh food, vehicles, home furnishing, ornaments, coatings and the like.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1:

weighing the following raw materials in percentage by mass:

polyacrylic acid resin: 90 percent of

Photocatalytic Material C₃N₄：2％

Astaxanthin: 5 percent of

Deionized water: 2.5 percent

Auxiliary agent: 0.5 percent

Wherein, photosensitizer benzoin 0.2%, antioxidant vitamin C0.2%, lubricant calcium stearate 0.1%.

The preparation method of the time-temperature indicator comprises the following steps:

s1: mixing astaxanthin, a proper amount of polyacrylic resin and deionized water, ball-milling and stirring to obtain a first mixed solution;

s2: adding proper amount of polyacrylic resin, assistant and photocatalytic material C₃N₄Mixing, ball-milling and stirring to obtain a second mixed solution;

s3: putting the pretreated porous adsorption molecular sieve into a first mixed solution, soaking, filtering, and drying at high temperature to form a color development layer 2 on the porous adsorption molecular sieve (skeleton structure layer) 1;

s4: and (3) soaking the porous adsorption molecular sieve with the color development layer 2 into the second mixed solution, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 700r/min, the time is 1 hour, the high-temperature drying temperature is 80 ℃, the drying time is 6 hours, and the normal-temperature drying time is 48 hours.

The time-temperature indicator in the embodiment is an environmental indicator, the skeleton structure layer 1 can be recycled, and the time-temperature indicator has great application potential in the aspects of product production, storage, transportation, sale and quality tracing, particularly products greatly influenced by illumination in the circulation link, and can be widely applied to the fields of various products such as food, medicine, fruits and vegetables, fresh food, vehicles, home furnishing, ornaments, coatings and the like.

Example 2:

weighing the following raw materials in percentage by mass:

alkyd resin: 80 percent of

Photocatalytic material TiO₂/C₃N₄：3％

Plant phenolics apple juice: 10 percent of

Deionized water: 2.5 percent

Auxiliary agent: 1 percent of

Wherein, the photosensitizer riboflavin is 0.3 percent, the ascorbic acid is 0.2 percent, and the lubricant calcium stearate is 0.5 percent.

The preparation method of the time-temperature indicator comprises the following steps:

s1: mixing plant phenolic apple juice, a proper amount of alkyd resin and deionized water, and carrying out ball milling and stirring to obtain a first mixed solution;

s2: adding appropriate amount of alkyd resin, auxiliary agent and photocatalytic material TiO₂/C₃N₄Mixing, ball-milling and stirring to obtain a second mixed solution;

s3: firstly putting the pretreated porous adsorption alumina material into the mixed solution A, soaking, filtering, and drying at high temperature to form a color development layer 2 on the porous adsorption alumina material (skeleton structure layer) 1;

s4: and immersing the porous adsorption alumina material with the color development layer 2 into the second mixed solution, soaking, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 300r/min, the time is 1 hour, the high-temperature drying temperature is 60 ℃, the drying time is 6 hours, and the normal-temperature drying time is 24 hours.

The time-temperature indicator in the embodiment is an environmental indicator, the skeleton structure layer 1 can be recycled, and the indicator has huge application potential in the aspects of product production, storage, transportation, sale and quality tracing, and particularly in products which are greatly influenced by time and illumination in the circulation link, and the color developing agent in the indicator is a sensitive color developing agent, so that the indicator can be widely applied to the fields of instant products such as food, fruits and vegetables, fresh foods and the like and products such as medicines.

Example 3:

weighing the following raw materials in percentage by mass:

and (3) chitosan: 75 percent of

Thermal catalytic material Pt: 0.2 percent of

Purple jasmine juice: 20 percent of

Deionized water: 4 percent of

Auxiliary agent: 0.8 percent

Wherein, the photosensitizer zinc oxide is 0.5 percent, the antioxidant vitamin E is 0.15 percent, and the lubricant calcium stearate is 0.15 percent.

The preparation method of the time-temperature indicator comprises the following steps:

s1: mixing Mirabilis jalapa juice, a proper amount of chitosan and deionized water, ball-milling and stirring to obtain a first mixed solution;

s2: adding a proper amount of chitosan, an auxiliary agent and a thermal catalysis material Pt, mixing, ball-milling and stirring to obtain a second mixed solution;

s3: firstly putting the pretreated porous adsorption kyanite balls into the mixed solution A, soaking, filtering, and drying at high temperature to form a color development layer 2 on the porous adsorption kyanite balls (skeleton structure layer) 1;

s4: and (3) soaking the porous adsorption sepiolite ball with the color development layer 2 into the second mixed solution, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 800r/min, the time is 1 hour, the high-temperature drying temperature is 80 ℃, the drying time is 8 hours, and the normal-temperature drying time is 36 hours.

The time-temperature indicator in the embodiment is an environmental indicator, the framework structure layer 1 can be recycled, and the time-temperature indicator has great application potential in the aspects of production, storage, transportation, sale and quality tracing, particularly products greatly influenced by time and temperature in a circulation link, can be suitable for products needing long product quality guarantee time, and can be widely applied to the fields of various products such as vehicles, home furnishings, ornaments, coatings and the like.

Example 4:

weighing the following raw materials in percentage by mass:

sodium silicate: 85 percent of

Thermal catalytic material Pt/TiO₂：1％

Diacetylene: 10 percent of

Deionized water: 3.5 percent

Auxiliary agent: 0.5 percent

Wherein, photosensitizer benzoin 0.2%, antioxidant melatonin 0.2%, lubricant zinc stearate 0.1%.

S1: mixing diacetylene, a proper amount of sodium silicate and deionized water, ball-milling and stirring to obtain a first mixed solution;

s2: adding proper amount of sodium silicate, assistant and thermal catalytic material Pt/TiO₂Mixing, ball-milling and stirring to obtain a second mixed solution;

s3: putting pretreated porous adsorption cordierite into the mixed solution A, soaking, filtering, and drying at high temperature to form a color development layer 2 on the porous adsorption cordierite (skeleton structure layer) 1;

s4: and soaking the porous adsorption cordierite with the color development layer 2 into the second mixed solution, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 500r/min, the time is 2 hours, the high-temperature drying temperature is 60 ℃, the drying time is 12 hours, and the normal-temperature drying time is 48 hours.

The time-temperature indicator in the embodiment is an environment-friendly indicator, the skeleton structure layer 1 can be recycled, and the time-temperature indicator has great application potential in the aspects of production, storage, transportation, sale and quality tracing, particularly in products with large influence of time and temperature in a circulation link, has more color change and accurate change, and can be widely applied to the field of products with short quality guarantee periods such as food, medicines, fruits and vegetables, fresh foods and the like.

Example 5:

weighing the following raw materials in percentage by mass:

polylactic acid: 90 percent of

Photo-thermal catalytic material Pt/TiO₂：2％

Carotenoid pigments: 7 percent of

Ethanol: 2.5 percent

Auxiliary agent: 0.5 percent

Wherein, photosensitizer benzoin 0.3%, antioxidant vitamin C0.1%, lubricant calcium stearate 0.1%.

The preparation method of the time-temperature indicator comprises the following steps:

s1: mixing carotenoid pigment, a proper amount of polylactic acid and ethanol, and carrying out ball milling and stirring to obtain a first mixed solution;

s2: adding proper amount of polylactic acid, auxiliary agent and photo-thermal catalytic material Pt/TiO₂Mixing, ball-milling and stirring to obtain a second mixed solution;

s3: firstly putting the pretreated porous adsorption concave-convex baseball into the mixed solution A, soaking, filtering, and drying at high temperature to form a color development layer on the porous adsorption concave-convex baseball (skeleton structure layer) 1;

s4: and immersing the porous adsorption concave-convex baseball with the color development layer into the second mixed solution, soaking, filtering, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 900r/min, the time is 1 hour, the high-temperature drying temperature is 80 ℃, the drying time is 12 hours, and the normal-temperature drying time is 48 hours.

The time-temperature indicator in the embodiment is an environment-friendly indicator, the skeleton structure layer 1 can be recycled, and the time-temperature indicator has great application potential in the aspects of production, storage, transportation, sale and quality tracing of products, particularly products which are greatly influenced by time, light and temperature in a circulation link, has more influencing factors and sensitive change of the indicator, is suitable for products with medium and short quality guarantee periods, is applied to the fields of products with short quality guarantee periods such as food, medicines, fruits and vegetables and fresh and the like, and the fields of products with long quality guarantee periods such as home furnishing, ornaments and coatings.

Example 6

Weighing the following raw materials in percentage by mass:

chlorinated polypropylene resin: 85 percent of

Photothermal catalytic material Ru/SiO₂：2％

Anthocyanins: 10 percent of

Ethanol: 2.5 percent

Auxiliary agent: 0.5 percent

Wherein, the photosensitizer riboflavin is 0.1 percent, the antioxidant vitamin E is 0.2 percent, and the lubricant calcium stearate is 0.2 percent.

S1: mixing anthocyanin, a proper amount of chlorinated polypropylene resin and deionized water, and carrying out ball milling and stirring to obtain a first mixed solution;

s2: adding proper amount of chlorinated polypropylene resin, auxiliary agent and photothermal catalytic material Ru/SiO₂Mixing, ball-milling and stirring to obtain a second mixed solution;

s3: firstly putting the pretreated porous adsorption alumina material into a first mixed solution, soaking, filtering, and drying at high temperature to form a color development layer 2 on the porous adsorption alumina material (skeleton structure layer) 1;

s4: and immersing the porous adsorption alumina material with the color development layer 2 into the second mixed solution, soaking, and drying at normal temperature to obtain the time-temperature indicator.

Wherein the ball milling speed is 700r/min, the time is 1 hour, the high-temperature drying temperature is 100 ℃, the drying time is 10 hours, and the normal-temperature drying time is 48 hours.

The time-temperature indicator in the embodiment is an environment-friendly indicator, the skeleton structure layer 1 can be recycled, and the time-temperature indicator has great application potential in the aspects of production, storage, transportation, sale and quality tracing, particularly for products which are greatly influenced by time, light and temperature in a circulation link, has more influencing factors and sensitive change of the indicator, is suitable for products with shorter quality guarantee period, and is applied to the field of products with shorter quality guarantee period, such as food, medicines, fruits and vegetables, fresh and fresh products and the like.

In conclusion, compared with the traditional indicator, the time-temperature indicator provided by the invention has the advantages of higher accuracy and lower cost, is beneficial to large-scale popularization, and has great application potential in the aspects of product production, storage, transportation, sale and quality tracing. The indicator can accurately calculate the information of the product such as the production date, the storage time, the transportation time, the product quality change and the like by utilizing the color development of the indicator, and the raw materials related to the indicator are environment-friendly materials, can be quickly decomposed in the natural environment, are harmless to the environment and avoid the pollution and the damage to the environment. Therefore, the indicator can be widely applied to the fields of various products such as food, medicine, fruits and vegetables, fresh food, vehicles, home furnishing, ornaments, coatings and the like.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (16)

1. A novel time-temperature indicator is characterized by at least comprising a skeleton structure layer, a color development layer and a consumption layer, wherein the indicator comprises the following components in percentage by mass: 75-90% of film forming material, 0.2-10% of catalytic material, 5-20% of color developing agent and 0.1-1% of auxiliary agent.

2. A novel time-temperature indicator according to claim 1, wherein the film-forming material comprises one or more of aliphatic polyesters, polyester copolymers, polyvinyl alcohol, polyethylene glycol, vegetable cellulose, polylactic acid, starch, polyacrylic resins, chitosan, alkyd resins, chlorinated polypropylene resins, silicates, polyglucose, animal glues, natural organics, and marine algae.

3. The novel time-temperature indicator according to claim 1, wherein the catalytic material comprises a photocatalytic material, a thermocatalytic material and a photothermal co-catalytic material.

4. A novel time-temperature indicator according to claim 1, characterized in that the colour developer comprises one or more of carotenoid pigments, astaxanthin, anthocyanins and like plant pigments, plant phenols, phenols.

5. A novel time-temperature indicator according to claim 1, characterized in that the auxiliaries comprise photosensitizers, antioxidants, lubricants.

6. A novel time-temperature indicator according to claim 1, characterized in that the solvent comprises one or more of water, ethanol, acetone, ethylene glycol.

7. The novel time-temperature indicator according to claim 1, wherein the framework structure layer is one or more of porous alumina, cordierite, silica gel, molecular sieves, sepiolite, foamed metal, attapulgite, shell powder, diatom ooze and bentonite.

8. The novel time-temperature indicator according to claim 1, characterized in that the photocatalytic material comprises C₃N₄Doped C₃N₄Composite C₃N₄One or more of nanometer bismuth series oxide; the thermal catalytic material comprises a noble metal material, and the photo-thermal catalytic material comprises cerium oxide and copper oxide.

9. A novel time temperature indicator according to claim 5, wherein the photosensitizer comprises one or more of aromatic diazonium salts, diaryl iodonium compounds, triaryl sulphur compounds, metal alkyls, metal carbonyls, benzoin and its derivatives, acetophenone derivatives, aromatic ketone compounds, pigments, arones, fused ring aromatics, polysilanes, acyl phosphonates, azos and organometallic complexes.

10. The catalyzed time temperature indicator article of claim 5, wherein the antioxidant comprises one or more of a phenolic antioxidant, a flavonoid antioxidant, vitamin E, melatonin, vitamin C, ascorbic acid.

11. The catalyzed time temperature indicator article of claim 5, wherein the lubricant comprises one or more of calcium stearate, zinc stearate, stearic acid amide, paraffin wax, and polyethylene wax.

12. A process for the preparation of a novel time temperature indicator according to any one of claims 1 to 11, characterized in that it comprises the following steps:

weighing the raw material components for preparing the indicator according to the proportion, and mixing and stirring the color developing agent, the film forming material and the solvent to obtain a first mixed solution;

mixing and stirring the film forming material and the catalytic material to obtain a second mixed solution;

soaking the skeleton structure layer in the first mixed solution, and drying at a first temperature to form a color development layer on the skeleton structure layer;

soaking the skeleton structure layer with the color development layer in the second mixed solution, drying at a second temperature, and forming a consumption layer on the surface of the color development layer to obtain the indicator;

wherein the first temperature is greater than the second temperature.

13. The preparation method according to claim 12, characterized in that the rotation speed of the mechanical stirring is 200-900r/min, and the stirring time is 0.5-2 h.

14. The novel time-temperature indicator according to claim 13, wherein the stirring and mixing means comprises mechanical stirring and ball milling stirring.

15. The preparation method according to claim 12, characterized in that the first temperature drying is heating temperature 60-100 ℃, drying time 6-12 h; the second temperature drying is heating temperature of 20-40 ℃, and drying time is 24-48 h.

16. The production method according to claim 15, characterized in that the first temperature drying is vacuum high temperature drying.

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