Irradiation effect sensing inkpad and preparation method and application thereof
By using a covalent organic framework compound and encapsulated small molecules to sense the irradiation effect of the ink pad, the problem of high detection limit, complex preparation and unstable color development of existing radiation color-changing label dosimeters has been solved. This invention achieves low-dose irradiation detection and stable color development performance, simplifies the preparation process and reduces waste.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- TIANXING INTELLIGENT CONTROL (CHENGDU) TECH CO LTD
- Filing Date
- 2023-06-02
- Publication Date
- 2026-08-04
AI Technical Summary
Existing radiation color-changing label dosimeters have high detection limits, complex preparation processes, unstable color development performance, and are prone to waste.
The irradiation effect sensing ink, composed of covalent organic framework compounds and encapsulated small molecules, forms dimers through covalent bond reactions, resulting in irreversible color changes. This simplifies the preparation process and reduces energy consumption.
It enables low-dose irradiation detection, has stable colorimetric performance, is easy to operate, is environmentally friendly and waste-free, and is suitable for low-dose irradiation indication and quantitative observation.
Smart Images
Figure CN116660966B_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of radiation dosimeter technology, specifically relating to an irradiation effect sensing ink pad, its preparation method, and its application. Background Technology
[0002] Radiation color-changing dosimeters typically change color noticeably under certain ionizing radiation. The degree of color change indicates the amount of radiation dose. They can be used for visual observation and dose level estimation, and are suitable for qualitative and semi-quantitative applications.
[0003] Patent CN103048673A, entitled "A Method for Preparing a Radiation-Changing Thin Film," discloses a method for preparing a radiation-changing thin film for radiation processing dose monitoring. This film can undergo a visible color change under a certain dose of ionizing radiation. However, this radiation-changing thin film has the following problems:
[0004] 1. It has no indication capability for low doses and uses a high detection limit, only indicating radiation above 3 kGy;
[0005] 2. The formula includes three components: a polymer film-forming substrate, a dye, and an auxiliary color-changing substance. The preparation process is complex, including steps such as dissolving the polymer to form a solution, heating and drying to form a film, and bonding. It requires a large amount of reagents and heating and drying to form a film, resulting in high energy consumption and low preparation efficiency.
[0006] 3. The principle of color change is that radiation causes the auxiliary color-changing substance to decompose and form protons, which changes the acidity or alkalinity of the material system. This leads to a change in the electron configuration of the dye molecule's chemical structure, resulting in a color change. The color change reaction is reversible. The color-changing structure of the color-changing substance is easily affected by the environment, especially the acidity or alkalinity. The main components have low chemical stability and unstable color-changing performance.
[0007] 4. During use, manual peeling and pasting are required, which can easily lead to waste in actual operation. Summary of the Invention
[0008] The purpose of this application is to provide an irradiation effect sensing ink pad, its preparation method, and its application, so as to solve the technical problems of existing radiation color-changing label dosimeters, such as high detection limit, cumbersome preparation process, complex composition, unstable color development performance, and easy waste caused by use.
[0009] To achieve the above objectives, one technical solution adopted in this application is:
[0010] An irradiation-effect sensing ink pad is provided, comprising the following components:
[0011] Substrate oil components;
[0012] Substrate components;
[0013] Color-changing components include covalent organic framework compounds and encapsulated small molecules.
[0014] In one or more embodiments, the following components by weight are included:
[0015] Substrate oil component, 20-35 parts;
[0016] Substrate composition, 60–79.5 parts;
[0017] Color-changing component, 0.5 to 5 parts.
[0018] In one or more embodiments, the minimum pore size of the covalent organic framework compound is 3.3–10 nm.
[0019] In one or more embodiments, the encapsulated small molecule is one or more combinations of naphthalene, phenanthrene, anthracene, indene, and pyrene, and the encapsulation concentration of the encapsulated small molecule is 3 to 30 of the encapsulated small molecules encapsulated in each COF cage of the covalent organic framework compound.
[0020] In one or more embodiments, the substrate oil component includes one or more combinations of edible oil, castor oil, and chlorinated paraffin oil.
[0021] In one or more embodiments, the substrate component includes one or more combinations of cellulose, cellulose acetate, sodium alginate, and starch.
[0022] To achieve the above objectives, another technical solution adopted in this application is:
[0023] A method for preparing the irradiation effect sensing inkpad according to any of the above embodiments is provided, comprising:
[0024] Prepare a saturated solution of the encapsulated small molecule, add the covalent organic framework compound to the saturated solution of the encapsulated small molecule, shake, then filter and dry to obtain the color-changing component;
[0025] The color-changing component, the substrate oil component, and the substrate pigment component are stirred and mixed evenly to obtain the irradiation effect sensing ink pad.
[0026] In one or more embodiments, the solvent of the saturated solution is one or a combination of ethanol and carbon tetrachloride.
[0027] To achieve the above objectives, another technical solution adopted in this application is:
[0028] An application of the irradiation effect sensing ink pad described in any of the above embodiments in irradiation dose detection is provided, comprising applying the irradiation effect sensing ink pad to a sample to be irradiated, wherein the encapsulated small molecules are irradiated and form dimers within the COF cage of the covalent organic framework compound, resulting in color change to indicate the irradiation dose.
[0029] In one or more embodiments, the lower limit for detecting the irradiation dose of the irradiation effect sensing ink pad is 1 kGy.
[0030] The advantages of this application, which differ from existing technologies, are:
[0031] The irradiation-sensing ink pad material of this application has stable performance and color development effect, and has good thermal stability, light stability, high humidity stability and ultraviolet stability.
[0032] The irradiation effect sensing ink pad preparation process of this application is simple, and the preparation process does not require solvent dissolution, heating, drying and other steps, and has low energy consumption and stable materials.
[0033] The irradiation effect sensing inkpad marking of this application has a rapid response and can monitor the irradiation status online. When the irradiation dose reaches 1 kGy or above, high-energy ionizing radiation can quickly cause small molecules to produce dimers. The dimers develop color, causing the marking to change color. It has high sensitivity and high recognition, which can broaden the application range of existing irradiation indicator tags, especially for indicating under low-dose irradiation. It can quantitatively observe the irradiation dose and is an irradiation indicator marking that can be automatically marked, has high recognition, and is quick to identify.
[0034] The method for using the irradiation effect sensing ink pad described in this application allows for direct application to various types of packaging requiring radiation marking. It is convenient, environmentally friendly, and waste-free. Attached Figure Description
[0035] Figure 1 This is a flowchart illustrating one embodiment of the method for preparing the irradiation effect sensing ink pad of this application.
[0036] Figure 2 These are images of the irradiated sample with irradiation effect sensing ink applied in Example 1 of this application after being irradiated with different doses;
[0037] Figure 3 These are images of the irradiated samples before and after thermal testing, bearing the irradiation effect sensing ink of Examples 1 to 5, as shown in Example 2 of this application.
[0038] Figure 4 These are images of the irradiated sample bearing the irradiation effect sensing ink paste of Examples 1 to 5 before and after light exposure test in Example 3 of this application.
[0039] Figure 5These are images of the irradiated samples of the ink pads used in Examples 1 to 5 of this application before and after a moisture resistance test, which are stamped with the irradiation effect sensing ink pads of this application in Example 4.
[0040] Figure 6 These are images of the irradiated samples of the ink pads used in Examples 1 to 5 of this application, before and after UV resistance testing. Detailed Implementation
[0041] The present application will now be described in detail with reference to the embodiments shown in the accompanying drawings. However, these embodiments do not limit the present application, and any structural, methodological, or functional modifications made by those skilled in the art based on these embodiments are included within the protection scope of the present application.
[0042] As mentioned in the background technology, the color-changing principle of current radiation color-changing tag dosimeters is that radiation causes the auxiliary color-changing substance to decompose and form protons, which changes the acidity or alkalinity of the material system, thereby causing the electron configuration in the chemical structure of the dye molecules to change and thus change color. The color-changing reaction is reversible.
[0043] This color-changing principle is affected by the fact that the color-changing structure of the color-changing substance is easily affected by the environment, especially by the acidity and alkalinity. The chemical properties of the color-changing material are unstable, which leads to unstable color-changing performance and affects the detection results.
[0044] In addition, current radiation color-changing tag dosimeters have a high detection limit and no indication capability for low doses; the preparation process is complex, requires a large amount of reagents, and requires heating and drying, resulting in high energy consumption and low preparation efficiency.
[0045] To address the aforementioned issues, the applicant has developed an irradiation-effect sensing ink pad. This sensing ink pad material exhibits stable performance, stable color development, a low detection limit for irradiation dose, is simple to prepare, low in cost, and easy to use.
[0046] Specifically, the irradiation effect sensing ink of this application includes a substrate oil component, a substrate pigment component, and a color-changing component.
[0047] The color-changing components include covalent organic framework compounds and encapsulated small molecules.
[0048] Small molecules can be encapsulated in COF cages of covalent organic framework compounds. Due to the limited space inside the COF cage, when irradiated, the encapsulated small molecules inside the COF cage will react in the form of covalent bonds to produce dimer compounds under the initiation of irradiation, which leads to a color change and serves as an indicator of irradiation. The reaction is irreversible and the color development performance is stable.
[0049] The substrate pigment component is used to combine with the color-changing component to form the ink paste, and to support and disperse the color-changing component. The substrate oil component is used to improve the oiliness of the ink paste, thereby allowing the ink paste to be picked up and sealed.
[0050] In one embodiment, to ensure the irradiation indication effect, the weight parts of the substrate oil component, substrate pigment component, and color-changing component are (20-35): (60-79.5): (0.5-5).
[0051] To ensure the polymerization effect of encapsulated small molecules, in one embodiment, the minimum pore size of the covalent organic framework compound can be 3.3–10 nm, thereby ensuring the confined space within the COF cage; in another embodiment, the encapsulated small molecule can be one or more combinations of naphthalene, phenanthrene, anthracene, indene, and pyrene, and the encapsulation concentration of the encapsulated small molecule can be 3–30 encapsulated small molecules within each COF cage of the covalent organic framework compound.
[0052] In one embodiment, the substrate oil component may include one or more combinations of edible oil, castor oil, and chlorinated paraffin oil.
[0053] In one embodiment, the substrate component may include one or more combinations of cellulose, cellulose acetate, sodium alginate, and starch.
[0054] In other embodiments, the substrate oil component can also be other types of oil, and the substrate pigment component can also be other types of substrate materials, as long as it can be mixed with the color-changing component and the substrate pigment component to form Indonesia.
[0055] This application also provides a method for preparing the irradiation effect sensing ink paste according to the above embodiments. Please refer to [link to relevant documentation]. Figure 1 , Figure 1 This is a flowchart illustrating one embodiment of the method for preparing the irradiation effect sensing ink pad of this application.
[0056] The preparation method includes:
[0057] S100. Prepare a saturated solution for encapsulating small molecules. Add the covalent organic framework compound to the saturated solution for encapsulating small molecules, shake, then filter and dry to obtain the color-changing component.
[0058] In one embodiment, the solvent for the saturated solution may be one or a combination of ethanol and carbon tetrachloride.
[0059] In one embodiment, the shaking can be performed at room temperature for 1 hour, thereby ensuring that the adsorption capacity of the covalent organic framework compound for the encapsulated small molecules reaches more than 5%.
[0060] S200. Stir and mix the color-changing component, substrate oil component and substrate pigment component evenly to obtain irradiation effect sensing ink.
[0061] In one embodiment, a homogenizer can be used to stir and mix the components evenly, so that the mixture supports a certain degree of adhesion.
[0062] In other embodiments, other stirring and mixing methods can be used to ensure that the components are mixed evenly.
[0063] The beneficial effects of the technical solution of this application will be described in detail below with reference to specific embodiments.
[0064] Example 1:
[0065] An irradiation-sensitive ink pad is prepared using the following steps:
[0066] (1) Add 0.05g of COF powder to a prepared saturated ethanol solution of naphthalene, shake at room temperature for 1h to make the adsorption capacity of naphthalene reach more than 5%, filter to obtain COF encapsulated small molecules, and dry at room temperature.
[0067] (2) The COF-encapsulated small molecules were mixed evenly with 2g of edible oil and 7.95g of cellulose powder using a homogenizer to obtain irradiation effect sensing ink pad.
[0068] The COF has a pore diameter of 3.5 nm and its structural formula is as follows:
[0069]
[0070] Example 2:
[0071] (1) Add 0.1g of COF powder to the prepared saturated ethanol solution of phenanthrene, shake at room temperature for 1h to make the adsorption capacity of phenanthrene reach more than 5%, filter to obtain COF encapsulated small molecules, and dry at room temperature.
[0072] (2) The COF-encapsulated small molecules were mixed evenly with 2.5g castor oil and 7.4g cellulose acetate powder using a homogenizer to obtain irradiation effect sensing ink.
[0073] The COF has a pore diameter of 3.3 nm and its structural formula is as follows:
[0074]
[0075] Example 3:
[0076] (1) Add 0.5g of COF powder to a prepared saturated carbon tetrachloride solution of anthracene, shake at room temperature for 1h to make the adsorption capacity of anthracene reach more than 5%, filter to obtain COF-encapsulated small molecules, and dry at room temperature.
[0077] (2) The COF-encapsulated small molecules were mixed evenly with 3g of chlorinated paraffin oil and 6.5g of sodium alginate powder using a homogenizer to obtain irradiation effect sensing ink.
[0078] The COF has a pore diameter of 4.9 nm and its structural formula is as follows:
[0079]
[0080] Example 4:
[0081] An irradiation-sensitive ink pad is prepared using the following steps:
[0082] (1) Add 0.15g of COF powder to the prepared indene carbon tetrachloride saturated solution, shake at room temperature for 1h to make the adsorption capacity of indene reach more than 5%, filter to obtain COF encapsulated small molecules, and dry at room temperature.
[0083] (2) The COF-encapsulated small molecules were mixed evenly with 3.5g of chlorinated paraffin oil and 6.35g of starch powder using a homogenizer to obtain irradiation effect sensing ink.
[0084] The COF has a pore diameter of 3.5 nm and its structural formula is as follows:
[0085]
[0086] Example 5:
[0087] An irradiation-sensitive ink pad is prepared using the following steps:
[0088] (1) Add 0.5g of COF powder to the prepared carbon tetrachloride saturated solution of pyrene, shake at room temperature for 1h to make the adsorption capacity of pyrene reach more than 5%, filter to obtain COF encapsulated small molecules, and dry at room temperature.
[0089] (2) The COF-encapsulated small molecules were mixed evenly with 3.5g castor oil and 6.00g cellulose powder using a homogenizer to obtain irradiation effect sensing ink.
[0090] The COF has a pore diameter of 3.5 nm and its structural formula is as follows:
[0091]
[0092] Example of effect 1:
[0093] A certain amount of the irradiation effect sensing ink prepared in Examples 1 to 5 was applied to the sample to be irradiated, and the sample was irradiated with different doses. Photos of the irradiation effect sensing material before and after irradiation were taken to obtain... Figure 2 .
[0094] The irradiation doses of the samples to be irradiated with the irradiation effect sensing ink pad of Example 1 were 1, 10, and 20 kGy, respectively; the irradiation doses of the samples to be irradiated with the irradiation effect sensing ink pad of Example 2 were 3, 15, and 35 kGy, respectively; the irradiation doses of the samples to be irradiated with the irradiation effect sensing ink pad of Example 3 were 10, 30, and 50 kGy, respectively; the irradiation doses of the samples to be irradiated with the irradiation effect sensing ink pad of Example 4 were 10, 30, and 50 kGy, respectively; and the irradiation doses of the samples to be irradiated with the irradiation effect sensing ink pad of Example 5 were 10, 30, and 50 kGy, respectively.
[0095] Please see Figure 2 , Figure 2 These are images of the irradiated sample with irradiation effect sensing ink applied in Example 1 of this application, after being irradiated with different doses.
[0096] like Figure 2 As shown, the irradiation effect sensing ink pad of Example 1 was orange before irradiation, turned red after irradiation with a dose of 1 kGy, and then gradually darkened in color as the irradiation dose increased.
[0097] The irradiation effect sensing ink pad in Example 2 was orange before irradiation, turned red after irradiation with a dose of 3 kGy, and then gradually darkened in color as the irradiation dose increased.
[0098] The irradiation effect sensing inkpad in Example 3 was orange before irradiation, turned red after irradiation with a dose of 10 kGy, and then gradually darkened in color as the irradiation dose increased.
[0099] The irradiation effect sensing inkpad in Example 4 was orange before irradiation, turned red after irradiation with a dose of 10 kGy, and then gradually darkened in color as the irradiation dose increased.
[0100] The irradiation effect sensing inkpad in Example 5 was orange before irradiation, turned red after irradiation with a dose of 10 kGy, and then gradually darkened in color as the irradiation dose increased.
[0101] As can be seen from the above experiments, the irradiation effect sensing ink pad of this application embodiment can effectively indicate irradiation, with a detection limit as low as 1 kGy. At the same time, by observing the color depth of the irradiation effect sensing ink pad after irradiation, the irradiation dose can be quantitatively detected to a certain extent.
[0102] Example of effect 2:
[0103] After the irradiated samples, stamped with the irradiation effect sensing ink paste of Examples 1 to 5, underwent color change due to irradiation, they were placed in a 60-degree drying oven for a 10-day heat test. Images were taken before and after the test. Figure 3 .
[0104] Please see Figure 3 , Figure 3 These are images of the irradiated samples before and after thermal testing, bearing the irradiation effect sensing ink from Examples 1 to 5, as shown in Example 2 of this application.
[0105] like Figure 3 After 10 days of heat testing, the irradiation effect sensing ink pads in Examples 1 to 5 remained stable in color and showed no change, indicating good thermal stability of the material.
[0106] Example of effect 3:
[0107] The irradiated samples, stamped with the irradiation effect sensing ink pastes of Examples 1 to 5, underwent color change after irradiation and were placed outdoors for 60 days for light testing. Images were taken before and after placement to obtain... Figure 4 .
[0108] Please see Figure 4 , Figure 4 These are images of the irradiated samples of the ink pads used in Examples 1 to 5 of this application, before and after light exposure testing, which are stamped with the irradiation effect sensing ink pads of Examples 1 to 5.
[0109] like Figure 4 After 60 days of outdoor light exposure, the irradiation effect sensing ink pads in Examples 1 to 5 showed stable red color without change, indicating good light stability of the material.
[0110] Example of effect 4:
[0111] The irradiated samples, coated with the irradiation effect sensing ink from Examples 1 to 5, underwent color change after irradiation and were placed in air with 95% humidity for 10 days to conduct a moisture resistance test. Images were taken before and after placement to obtain... Figure 5 .
[0112] Please see Figure 5 , Figure 5 These are images of the irradiated samples of the inkpads used in Examples 1 to 5, before and after a moisture resistance test, in Example 4 of this application.
[0113] like Figure 5 After 10 days of moisture resistance testing, the irradiation effect sensing materials in Examples 1 to 5 showed stable red color with no significant changes, indicating good stability in high humidity environments.
[0114] Example 5:
[0115] After the irradiated samples, stamped with the irradiation effect sensing ink paste of Examples 1 to 5, underwent color change due to irradiation, they were placed under 254nm ultraviolet light for 8 hours to conduct an ultraviolet resistance test. Images were taken before and after the irradiation. Figure 6 .
[0116] Please see Figure 6 , Figure 6 These are images of the irradiated samples of the ink pads used in Examples 1 to 5 of this application, before and after UV resistance testing.
[0117] like Figure 6 After 8 hours of UV resistance testing, the irradiation effect sensing ink pads in Examples 1 to 5 remained stable in color and showed no change, indicating good UV stability of the material.
[0118] The foregoing description of this disclosure is provided to enable any person skilled in the art to implement or use this disclosure. Various modifications to this disclosure will be apparent to those skilled in the art, and the general principles applicable herein can be applied to other variations without departing from the scope of this disclosure. Therefore, this disclosure is not limited to the examples and designs described herein, but is consistent with the widest scope of the principles and novel features disclosed herein.
Claims
1. An irradiation effect-aware inkpad, characterized in that, Includes the following components: The substrate oil component includes one or more combinations of edible oil, castor oil, and chlorinated paraffin oil. The substrate component includes one or more of cellulose, cellulose acetate, sodium alginate, and starch. The color-changing component includes a covalent organic framework compound and encapsulated small molecules. The encapsulated small molecules are one or more combinations of naphthalene, phenanthrene, anthracene, indene, and pyrene. The encapsulation concentration of the encapsulated small molecules is 3 to 30 encapsulated small molecules within each COF cage of the covalent organic framework compound. When irradiated, the encapsulated small molecules inside the COF cage react in the form of covalent bonds under irradiation to produce a dimer compound. The reaction is irreversible and the color development performance is stable.
2. The radiation effect aware inkpad of claim 1, wherein, Includes the following components by weight: Substrate oil component, 20-35 parts; Substrate composition, 60–79.5 parts; Color-changing component, 0.5 to 5 parts.
3. The irradiation effect sensing inkpad according to claim 1 or 2, characterized in that, The minimum pore size of the covalent organic framework compound is 3.3–10 nm.
4. A method for preparing the irradiation effect sensing inkpad according to any one of claims 1 to 3, characterized in that, include: Prepare a saturated solution of the encapsulated small molecule, add the covalent organic framework compound to the saturated solution of the encapsulated small molecule, shake, then filter and dry to obtain the color-changing component; The color-changing component, the substrate oil component, and the substrate pigment component are stirred and mixed evenly to obtain the irradiation effect sensing ink pad.
5. The preparation method according to claim 4, characterized in that, The solvent of the saturated solution is one or a combination of ethanol and carbon tetrachloride.
6. An application of the irradiation effect sensing inkpad as described in any one of claims 1 to 3 in irradiation dose detection, characterized in that, The method involves applying the irradiation effect sensing ink pad to the sample to be irradiated, wherein the encapsulated small molecules are irradiated and form dimers within the COF cage of the covalent organic framework compound, resulting in color change to indicate the irradiation dose.
7. The application according to claim 6, characterized in that, The lower limit for detecting the irradiation dose of the irradiation effect sensing ink pad is 1 kGy.