Time indicating ink and time indicating label

Abstract

The invention discloses time indication ink and a time indication label. The time indication ink comprises 20-50 parts of film-forming resin, 30-90 parts of a solvent and 4-10 parts of stannous hydroxide powder. According to the time indicating ink, the components of the ink contain stannous hydroxide, the stannous hydroxide is easily subjected to intramolecular dehydration in a dry environment to generate stannic oxide, the color of the stannous hydroxide is changed from white to black in the process, and the color change degree of the stannous hydroxide can be used for indicating the time progress. The time indicating label contains the time indicating ink.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and in particular to a time indicating ink and a time indicating label. Background Art

[0002] Most existing time-indicating inks are volatile, which can be broadly categorized into two types. One type contains a volatile acid or base. The evaporation of the acid or base changes the pH of the ink, thereby changing the color of the pH indicator, and thus indicating the time. The other type directly contains a volatile dye. The evaporation of the dye directly changes the color of the ink, and thus indicates the time. However, both types of time-indicating inks suffer from poor chemical stability. Both the pH indicator and the volatile dye are easily degraded under light, causing fading. Summary of the Invention

[0003] Based on this, it is necessary to provide a time indicating ink and a time indicating label to solve the above problems.

[0004] A time indicating ink, wherein the raw materials for preparing the time indicating ink include, in parts by mass:

[0005] 20 to 50 parts of film-forming resin;

[0006] 30 to 90 parts of solvent; and

[0007] 4 to 10 parts of stannous hydroxide powder.

[0008] In one embodiment, 0.5 to 2 parts of a ligand material are further included.

[0009] In one embodiment, the ligand material is a carboxylic acid or a metal ion.

[0010] In one embodiment, the carboxylic acid is selected from at least one of a simple carboxylic acid, a polycarboxylic acid, an aromatic carboxylic acid, or an aminocarboxylic acid.

[0011] In one embodiment, the simple carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, and butyric acid.

[0012] In one embodiment, the polycarboxylic acid is selected from at least one of oxalic acid, malic acid, lactic acid, citric acid, or tartaric acid.

[0013] In one embodiment, the aromatic carboxylic acid is selected from at least one of benzoic acid and terephthalic acid.

[0014] In one embodiment, the aminocarboxylic acid is selected from at least one of glycine, serine, or aspartic acid.

[0015] In one embodiment, the metal ions are copper ions or nickel ions.

[0016] The above-mentioned time indicating ink contains stannous hydroxide in its composition. Stannous hydroxide is easily dehydrated in a dry environment to form tin monoxide. During this process, its color changes from white to black. The degree of color change can be used to indicate the time process.

[0017] A time indicating label, comprising:

[0018] A substrate layer is made of a transparent and dense material, and a starting portion is provided on the substrate layer;

[0019] The base layer is made of a dense material, the edge of the base layer is sealed to the edge of the substrate layer, a first cavity and a second cavity are provided between the base layer and the substrate layer, a pressure-peelable seal is provided between the first cavity and the second cavity, a desiccant is provided in the first cavity, and an indicator is provided in the second cavity, wherein the indicator is obtained by printing and drying the time indicating ink according to any one of claims 1 to 9.

[0020] When using the above-mentioned time indicator label, the user presses the activation portion, which depresses downward under pressure, compressing the air in the first cavity and increasing the pressure. The seal peels away under the pressure of the gas, connecting the first and second cavities and activating the time indicator label. Once activated, the desiccant dries the second cavity, allowing the stannous oxide in the indicator portion to undergo slow intramolecular dehydration, resulting in a gradual color change. The degree of color change indicates the passage of time. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the structure of a time indication tag before activation in one embodiment;

[0022] Figure 2 For example Figure 1 Schematic diagram of the sealing part of the time indication label shown;

[0023] Figure 3 For example Figure 1 The time indication tag is shown as a schematic diagram of the structure after activation. DETAILED DESCRIPTION

[0024] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0025] It should be noted that when an element is referred to as being "fixed to" another element, it may be directly on the other element or there may be an intermediate element. When an element is considered to be "connected" or "communicating" with another element, it may be directly connected to the other element or there may be an intermediate element. The terms "upper," "lower," "vertical," "horizontal," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only implementation methods.

[0026] The time indicating ink and the time indicating label will be further described in detail below mainly with reference to the accompanying drawings and specific embodiments.

[0027] The time indicating ink according to one embodiment includes 20 to 50 parts of a film-forming resin, 30 to 90 parts of a solvent, and 4 to 10 parts of stannous hydroxide powder.

[0028] The film-forming resin has a mass fraction of 20 to 50 parts. The film-forming resin is used to make the time indicating ink have the characteristics of drying and forming a film, so that the time indicating ink can be attached to the surface of the substrate.

[0029] In this embodiment, the film-forming resin is a water-based film-forming resin, which can be dissolved in solvent water, has good environmental performance, and can significantly reduce the emission of pollutants such as VOCs.

[0030] Optionally, the molecular weight of the aqueous film-forming resin is 40,000 to 150,000. By limiting the molecular weight of the aqueous film-forming resin, the time indicating ink can have good adhesion, friction resistance and flexibility after being cured into a film.

[0031] Preferably, the molecular weight of the aqueous film-forming resin is 60,000 to 120,000. After the aqueous film-forming resin with a molecular weight within this range is formed into a film, the adhesion, friction resistance and flexibility are in a relatively balanced range.

[0032] Optionally, the aqueous film-forming resin is selected from at least one of aqueous acrylic resin, aqueous polyurethane resin and polyvinyl pyrrolidone.

[0033] It should be understood that other materials that are soluble in solvents and have film-forming properties after drying can also be used as the film-forming resin of the present invention.

[0034] The solvent has a mass fraction of 30 to 90 parts, and is used to dissolve the film-forming resin, so that the time indicating ink is in a colloidal state, thereby making the time indicating ink printable.

[0035] In this embodiment, the solvent is deionized water.

[0036] It should be understood that other materials that can dissolve the film-forming resin can also be used as solvents in the present invention.

[0037] Stannous hydroxide, with a mass fraction of 4 to 10 parts, acts as a pigment in the ink system. Stannous hydroxide is a solid powder that is insoluble in water and is white in color. Stannous hydroxide is relatively stable in natural humidity and temperature environments, but it can rapidly undergo intramolecular dehydration at temperatures above 100°C to produce black tin oxide and water. In addition, it can also undergo slow intramolecular dehydration in a dry environment to produce black tin oxide and water. In this process, its color changes from white to black, and the reaction equation is:

[0038] Sn(OH)2→SnO+H2O

[0039] Preferably, the particle size of stannous hydroxide is 10 nanometers to 10 micrometers, so that the time indicating ink meets the printability requirements.

[0040] In another embodiment, the time-indicating ink further comprises 0.5 to 2 parts of a ligand material, which reacts with the stannous ions in stannous hydroxide to form a complex. This complexation reaction does not affect the chemical properties of stannous oxide, but it can improve the stability of stannous hydroxide to a certain extent, thereby passivating the rate of intramolecular dehydration of stannous hydroxide and thereby extending the color change period of the time-indicating ink. Therefore, the color change period of the time-indicating ink can be controlled by controlling the mass fraction of the ligand.

[0041] Specifically, the ligand substances that can undergo coordination reaction with stannous hydroxide include carboxylic acid and metal ions.

[0042] On the one hand, carboxylic acid acts as a ligand substance of stannous hydroxide and undergoes a coordination reaction with stannous hydroxide. On the other hand, the hydrogen ions generated after the ionization of carboxylic acid are beneficial to promoting the dissolution of stannous hydroxide, thereby improving the stability of the time indicating ink system and the accuracy of the color change process caused by intramolecular dehydration.

[0043] Carboxylic acids include simple carboxylic acids, polycarboxylic acids, aromatic carboxylic acids and aminocarboxylic acids.

[0044] Alternatively, simple carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, and butyric acid.

[0045] Optionally, the polycarboxylic acid includes, but is not limited to, oxalic acid, malic acid, lactic acid, citric acid, and tartaric acid.

[0046] Optionally, the aromatic carboxylic acid includes but is not limited to benzoic acid and terephthalic acid.

[0047] Optionally, the aminocarboxylic acid includes, but is not limited to, glycine, serine, and aspartic acid.

[0048] Preferably, the ligand material is a polycarboxylic acid. During the coordination reaction, the multiple carboxyl groups of the polycarboxylic acid can form a coordination complex with the stannous ions. Surprisingly, the coordination complex formed by the stannous ions of stannous hydroxide and the multiple carboxyl groups of the polycarboxylic acid significantly improves its resistance to temperature changes during intramolecular dehydration. Experiments have found that under dry conditions, at temperatures of 10°C and 40°C, the color changes of the coordination complex due to intramolecular dehydration are essentially synchronized. This significantly enhances the timing accuracy of time-indicating inks and greatly expands their application range.

[0049] Optionally, the metal ions used as ligands include but are not limited to copper ions and nickel ions.

[0050] The above-mentioned time indicating ink contains stannous hydroxide in its composition. Stannous hydroxide is easily dehydrated in a dry environment to form tin monoxide. During this process, its color changes from white to black. The degree of color change can be used to indicate the time process.

[0051] For an embodiment of the time indication label, please refer to Figures 1 to 3 The time indicating label includes a substrate layer 10 and a base layer 20 which are stacked.

[0052] The substrate layer 10 is made of a transparent and dense material, so that the user can see the indicator portion 60 provided in the second cavity 50 through the transparent substrate layer 10. The substrate layer 10 can prevent water vapor from passing through the substrate layer 10 and entering the second cavity 50. A part of the substrate layer 10 is raised upward to form a starting portion.

[0053] Optionally, the materials used to prepare the substrate layer 10 include but are not limited to: PET, PVC and PP.

[0054] In the illustrated embodiment, a first coating layer 11 is further provided below the base material layer 10 .

[0055] The base layer 20 is made of a dense material. The base layer 20 can prevent water vapor from passing through the base layer 20 and entering the first cavity 30. The edge of the base layer 20 is sealed with the edge of the substrate layer 10. A first cavity 30 and a second cavity 50 are provided between the base layer 20 and the substrate layer 10, and a seal 12 is provided between the first cavity 30 and the second cavity 50. A desiccant 40 is provided in the first cavity 30, and an indicator 60 is provided in the second cavity 50. The indicator 60 is obtained by printing and drying any of the time indicating inks mentioned above.

[0056] Optionally, the materials used to prepare the base layer 20 include but are not limited to: PET, PVC, PP and aluminum foil.

[0057] Optionally, the desiccant 40 includes, but is not limited to, silica gel, calcium chloride, calcium hydroxide, activated carbon, anhydrous sodium sulfate, and phosphoric anhydride.

[0058] In the illustrated embodiment, a second coating layer 21 is further provided below the base layer 20. The second coating layer 21 can be hot-melt bonded to the first coating layer 11 at high temperatures, thereby improving the connection strength between the base layer 20 and the substrate layer 10.

[0059] In the illustrated embodiment, the seal 12 is formed by weak bonding between the substrate layer 10 and the base layer 20 . The seal 12 can be peeled off under pressure, so that the first cavity 30 and the second cavity 50 are connected.

[0060] During use, the user presses the activation portion, which depresses it downward under pressure. This compresses the air within the first cavity 30, increasing the pressure. The seal 12 peels away under the pressure, allowing the first cavity 30 to communicate with the second cavity 50, thereby activating the time indicator label. Once activated, the desiccant 40 dries the second cavity 50, allowing the stannous oxide in the indicator portion 60 to undergo slow intramolecular dehydration, resulting in a gradual color change. This color change then indicates the passage of time.

[0061] The following are specific examples.

[0062] Example 1

[0063] This embodiment provides a time indicating ink comprising, by weight, 20 parts of a film-forming resin, 30 parts of a solvent, and 4 parts of stannous hydroxide powder. In this embodiment, the film-forming resin is a water-based acrylic resin, model 207A, provided by Dongguan Delun New Materials Co., Ltd., the solvent is deionized water, and the stannous hydroxide is provided by Shaoyang Ross Chemical Co., Ltd.

[0064] The aforementioned time-indicating ink contains stannous hydroxide, which undergoes intramolecular dehydration in a dry environment, forming tin monoxide. During this process, its color changes from white to black, and the degree of this color change can be used to indicate the passage of time. In this embodiment, experimental testing showed that the time-indicating ink changes color over a period of 40 days at 10°C and 30 days at 40°C.

[0065] Also, see Figure 1-Figure 3 This embodiment also provides a time indicator label, which includes a stacked substrate layer 10 and a substrate layer 20. The substrate layer 10 is made of a transparent and dense material PVC, and a start portion is provided on the substrate layer 10; the substrate layer 20 is made of a dense material aluminum foil, and the edge of the substrate layer 20 is sealed to the edge of the substrate layer 10. A first cavity 30 and a second cavity 50 are provided between the substrate layer 20 and the substrate layer 10. A pressure-peelable seal 12 is provided between the first cavity 30 and the second cavity 50. A desiccant 40 is provided in the first cavity 30, and an indicator portion 60 is provided in the second cavity 50. The indicator portion 60 is obtained by printing and drying the time indicator ink provided in this embodiment.

[0066] In this embodiment, a first coating layer 11 is further provided below the base material layer 10 , and a second coating layer 21 is further provided above the second base material layer 10 . Both the first coating layer 11 and the second coating layer 21 are made of PE.

[0067] When using the above-mentioned time indicator label, the user presses the activation portion, which depresses downward under pressure. This compresses the air within the first cavity 30, increasing the pressure. The seal 12 peels away under the pressure, allowing the first cavity 30 to communicate with the second cavity 50, thereby activating the time indicator label. Once activated, the desiccant 40 maintains a dry environment within the second cavity 50, allowing the stannous oxide in the indicator portion 60 to undergo slow intramolecular dehydration, resulting in a gradual color change. This color change then indicates the passage of time.

[0068] Example 2

[0069] This embodiment is a comparative embodiment of embodiment 1. The difference between the time indicating ink and embodiment 1 is that the ink contains 0.5 parts of the ligand material lactic acid.

[0070] In the aforementioned time-indicating ink, the ligand undergoes a coordination reaction with the stannous ions in the stannous hydroxide. This coordination reaction improves the stability of the stannous hydroxide, thereby passivating the rate of intramolecular dehydration of the stannous hydroxide and thereby extending the color change period of the time-indicating ink. Therefore, the color change period of the time-indicating ink can be controlled by controlling the mass fraction of the ligand.

[0071] In this embodiment, the time indicating ink changes color for 60 days at a temperature of 10° C., and for 60 days at a temperature of 40° C.

[0072] Example 3

[0073] This embodiment provides a time indicating ink comprising, by weight, 35 parts of a film-forming resin, 60 parts of a solvent, and 7 parts of stannous hydroxide powder. In this embodiment, the film-forming resin is a water-based acrylic resin, model 207A, provided by Dongguan Delun New Materials Co., Ltd., the solvent is deionized water, and the stannous hydroxide is provided by Shaoyang Ross Chemical Co., Ltd.

[0074] In this embodiment, the time indicating ink has a color change period of 70 days in an environment of 10° C., and a color change period of 50 days in an environment of 40° C.

[0075] Example 4

[0076] This embodiment is a comparative embodiment of embodiment 3. The difference between the time indicating ink and embodiment 3 is that the ink contains 1.2 parts of the ligand material lactic acid.

[0077] In this embodiment, the time indicating ink changes color for 100 days at a temperature of 10° C., and changes color for 100 days at a temperature of 40° C.

[0078] Example 5

[0079] This embodiment provides a time indicating ink comprising, by weight, 50 parts of a film-forming resin, 90 parts of a solvent, and 10 parts of stannous hydroxide powder. In this embodiment, the film-forming resin is a water-based acrylic resin, model 207A, provided by Dongguan Delun New Materials Co., Ltd., the solvent is deionized water, and the stannous hydroxide is provided by Shaoyang Ross Chemical Co., Ltd.

[0080] In this embodiment, the time indicating ink has a color change period of 150 days in an environment of 10° C., and a color change period of 120 days in an environment of 40° C.

[0081] Example 6

[0082] This embodiment is a comparative embodiment of embodiment 5. The difference between the time indicating ink and embodiment 5 is that the ink contains 2.0 parts of the ligand material lactic acid.

[0083] In this embodiment, the time indicating ink changes color for 200 days at a temperature of 10° C. and for 200 days at a temperature of 40° C.

[0084] The formulas and color change cycles of the time indicating inks of Examples 1 to 6 are shown in the following table.

[0085] Table 1: Time indicating ink formula and color change period table of each embodiment

[0086]

[0087] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0088] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A time indicating ink, characterized in that: The raw materials for preparing the time indicating ink include, by parts by mass: 20 to 50 parts of film-forming resin; 30 to 90 parts of solvent; and 4 to 10 parts of stannous hydroxide powder.

2. The time indicating ink according to claim 1, characterized in that: Also included is 0.5 to 2 parts of a ligand material.

3. The time indicating ink according to claim 2, characterized in that: The ligand material is carboxylic acid or metal ion.

4. The time indicating ink according to claim 3, characterized in that: The carboxylic acid is selected from at least one of simple carboxylic acids, polycarboxylic acids, aromatic carboxylic acids, and aminocarboxylic acids.

5. The time indicating ink according to claim 4, characterized in that: The simple carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, and butyric acid.

6. The time indicating ink according to claim 4, characterized in that: The polycarboxylic acid is selected from at least one of oxalic acid, malic acid, lactic acid, citric acid or tartaric acid.

7. The time indicating ink according to claim 4, characterized in that: The aromatic carboxylic acid is selected from at least one of benzoic acid and terephthalic acid.

8. The time indicating ink according to claim 4, characterized in that: The aminocarboxylic acid is selected from at least one of glycine, serine or aspartic acid.

9. The time indicating ink according to claim 3, characterized in that: The metal ions are copper ions or nickel ions.

10. A time indicating label, characterized in that: include: A substrate layer is made of a transparent and dense material, and a starting portion is provided on the substrate layer; The base layer is made of a dense material, the edge of the base layer is sealed to the edge of the substrate layer, a first cavity and a second cavity are provided between the base layer and the substrate layer, a pressure-peelable seal is provided between the first cavity and the second cavity, a desiccant is provided in the first cavity, and an indicator is provided in the second cavity, wherein the indicator is obtained by printing and drying the time indicating ink according to any one of claims 1 to 9.

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