Coating for anti-radiation fabric as well as preparation method and application of coating

Abstract

The invention discloses a coating for an anti-radiation fabric as well as a preparation method and application thereof, and the coating comprises an anti-radiation metal oxide, soluble polycarboxylic acid and deionized water, wherein the anti-radiation metal oxide accounts for 4-8 parts by mass, the soluble polycarboxylic acid accounts for 5-10 parts by mass, and the deionized water accounts for 1-2 parts by mass. The metal oxide is converted into the water-soluble carboxylate, the problem of particle dispersion is thoroughly solved, the prepared coating is high in coating binding force and resistant to washing, the protection efficiency reaches 80% or above (120kV X-ray), the formula is adjustable, and the coating is suitable for different base materials, simple in process and suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a coating for radiation-proof fabrics and a preparation method and application thereof. Background Art

[0002] Electromagnetic radiation has been recognized as the fourth largest environmental hazard. More and more experiments have shown that long-term exposure to radiation doses exceeding the safe range will cause a decline in visual, auditory and olfactory functions, and symptoms such as headaches and dizziness, decreased learning and memory abilities, irritability, loss of appetite, etc. It can also lead to male and female infertility, congenital malformations of the fetus, and increase the incidence of childhood tumors.

[0003] Traditional lead-containing radiation protection materials are gradually being eliminated due to toxicity, poor mechanical properties and other problems. Radiation protection fabric coatings can be obtained by treating metal or metal oxide particles with radiation protection properties with a dispersant or directly dispersing them in a polymer emulsion. This method can overcome the shortcomings of lead-containing materials, but there are defects such as poor compatibility between inorganic particles and organic matrices, reliance on coupling agents, which are easily affected by moisture and fail, and uneven dispersion when added in high amounts, easy detachment of the coating, and short service life. For example, the CN20231120131 patent improves the polarity of particles through sulfonation modification, but the process is complicated; the CN202410325170 patent uses nickel powder mixed with polyurethane emulsion, and there is still a problem of insufficient dispersion stability. Summary of the invention

[0004] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0005] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0006] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a coating for radiation-proof fabrics.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: a coating for radiation-proof fabrics, characterized in that the coating for radiation-proof fabrics is composed of radiation-proof metal oxides, soluble polycarboxylic acids and deionized water;

[0008] Calculated by weight, the radiation-proof metal oxide is 4 to 8 parts, the soluble polycarboxylic acid is 5 to 10 parts, and the deionized water is 1 to 2 parts.

[0009] As a preferred embodiment of the coating for radiation - resistant fabric of the present invention, wherein: the coating for radiation - resistant fabric further comprises triethanolamine and aqueous polymer emulsion.

[0010] Another object of the present invention is to overcome the deficiencies in the prior art and provide a preparation method of a coating for radiation - resistant fabric, which is characterized in that it includes:

[0011] Mix the radiation - resistant metal oxide, soluble polycarboxylic acid and deionized water and stir, then drop - add triethanolamine and stir to adjust the pH value to neutral to obtain a metal carboxylate solution;

[0012] Mix the metal carboxylate solution and the aqueous polymer emulsion and stir to obtain the coating for radiation - resistant fabric.

[0013] As a preferred embodiment of the preparation method of the present invention, wherein: the radiation - resistant metal oxide includes one or more of bismuth oxide, tungsten oxide, lanthanum oxide and yttrium oxide.

[0014] As a preferred embodiment of the preparation method of the present invention, wherein: the soluble polycarboxylic acid is an organic acid containing 2 - 3 carboxyl groups in the molecule.

[0015] As a preferred embodiment of the preparation method of the present invention, wherein: the soluble polycarboxylic acid includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid and citric acid.

[0016] As a preferred embodiment of the preparation method of the present invention, wherein: the mass ratio of the metal carboxylate solution to the aqueous polymer emulsion is 1 - 4:1.

[0017] As a preferred embodiment of the preparation method of the present invention, wherein: the aqueous polymer emulsion includes one or several of epoxy resin emulsion, polyvinyl acetate emulsion, acrylate emulsion, polyurethane emulsion and polyester emulsion, its solid content is 40% - 60%, and the pH value is 6 - 8.

[0018] Another object of the present invention is to overcome the deficiencies in the prior art and provide an application of the coating for radiation - resistant fabric prepared by the preparation method in radiation - resistant fabric.

[0019] As a preferred embodiment of the application of the present invention, wherein: the coating is coated on the fabric, heated and dried to obtain the radiation - resistant fabric.

[0020] Advantages of the present invention:

[0021] In the present invention, the metal oxide is converted into a water-soluble carboxylate, completely solving the problem of particle dispersion. The prepared coating has a strong binding force, is wash-resistant, and has a protection efficiency of over 80% (120 kV X-rays). Moreover, the formulation is adjustable, suitable for different substrates, the process is simple, and it is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings. Among them:

[0023] Figure 1 It is a pattern prepared by coating the coating prepared in Example 1 of the present invention on a non-woven fabric.

[0024] Figure 2 It is a pattern prepared by coating the coating prepared in Comparative Example 3 of the present invention on a non-woven fabric. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] In order to make the above objects, features, and advantages of the present invention more obvious and understandable, the following will give a detailed description of the specific embodiments of the present invention in conjunction with the embodiments of the specification.

[0026] In the following description, many specific details are set forth to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar extensions without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0027] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that can be included in at least one implementation manner of the present invention. The "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment that excludes other embodiments.

[0028] Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commercially available. Among them, the metal oxide and acids are all purchased from the Shanghai Testing Branch of the China National Pharmaceutical Group Corporation, and the polymer emulsion is of the brand CN-840 (Beijing Dongfang Chennuo Chemical Technology Co., Ltd.).

[0029] Example 1

[0030] This example provides a method for preparing a coating for radiation-proof fabrics:

[0031] (1) By mass fraction, prepare 4.66 parts of bismuth oxide, 5.40 parts of oxalic acid, and 1 part of deionized water; the molar ratio of bismuth oxide to oxalic acid is 0.01:0.06, and the oxalic acid is in excess.

[0032] (2) Add the reactants to the reactor, stir and heat to 80 °C, and continue stirring for 3 hours until the product is a clear liquid; dropwise add triethanolamine and continue stirring until the reactants are neutral in pH to end the reaction. At this time, the excess oxalic acid in step (1) of the reaction is completely neutralized by triethanolamine to obtain a metal carboxylate solution.

[0033] (3) By mass fraction, take 2 parts of the metal carboxylate solution generated in step (2), and mix it with 1 part of polyurethane emulsion to obtain a coating for radiation-proof fabric.

[0034] Figure 1 The pattern prepared by coating the coating prepared in Example 1 of the present invention on non-woven fabric.

[0035] Example 2

[0036] The difference from Example 1 is that in step (3), take 3 parts of the metal carboxylate solution generated in step (2), and mix it with 1 part of polyurethane emulsion (mass ratio is 3:1), and the process of the remaining steps refers to Example 1 to obtain the coating for radiation-proof fabric prepared in this example.

[0037] Example 3

[0038] The difference from Example 1 is that in step (3), take 4 parts of the metal carboxylate solution generated in step (2), and mix it with 1 part of polyurethane emulsion to obtain the coating for radiation-proof fabric prepared in this example.

[0039] Example 4

[0040] (1) By mass fraction, prepare 3.26 parts of lanthanum oxide, 5.40 parts of oxalic acid, and 1 part of deionized water; the molar ratio of lanthanum oxide to oxalic acid is 0.01:0.06.

[0041] (2) Add the reactants to the reactor, heat to 80 °C, stir until the product is a clear liquid; continue stirring, dropwise add triethanolamine and continue stirring until the reactants are neutral to end the reaction to obtain a metal carboxylate solution.

[0042] (3) By mass fraction, take 2 parts of the metal carboxylate solution generated in step (2), and mix it with 1 part of polyurethane emulsion to obtain a coating for radiation-proof fabric.

[0043] Example 5

[0044] The difference from Example 4 is that in step 3, three portions of the metal carboxylate solution generated in step (2) are taken and mixed with one portion of the polyurethane emulsion, and the processes of the remaining steps are all referred to Example 1 to obtain the coating for radiation-proof fabric prepared in this example.

[0045] Example 6

[0046] The difference from Example 4 is that in step 3, four portions of the metal carboxylate solution generated in step (2) are taken and mixed with one portion of the polyurethane emulsion, and the processes of the remaining steps are all referred to Example 1 to obtain the coating for radiation-proof fabric prepared in this example.

[0047] The coatings prepared in Examples 1 to 6 are coated on polyester non-woven fabric with a gram weight of 100, heated and dried, and the gram weight after coating is controlled to be 200 to obtain the radiation-proof fabric.

[0048] Referring to GB / T18318-2001 "Standard for the Determination of Bending Length of Textiles", a bending length tester is used to test the softness performance of the coating. Referring to GBZ / T147-2002 "Determination of Attenuation Performance of X-ray Protective Materials", an X-ray air kerma (protection level) standard device is used to conduct radiation protection tests on the coating, and the measurement range is 1.0×10 -5 ~1.0 Gy / h. The test results are shown in Table 1 below.

[0049] Table 1 Softness, Radiation Protection and Wash Resistance Performance of Examples

[0050]

[0051]

[0052] Comparative Example 1

[0053] (1) Calculated by mass parts, prepare 4.66 parts of bismuth oxide, 4.05 parts of oxalic acid, and 1 part of deionized water; the molar ratio of bismuth oxide to oxalic acid is 0.01:0.045.

[0054] (2) Add the reactants to the reactor, stir and heat to 80 °C, continue to stir for 3 hours until the product is a clear liquid; dropwise add triethanolamine and continue to stir until the reactants are neutral to end the reaction; at this time, the excessive oxalic acid in reaction step 1 is completely neutralized by triethanolamine to obtain the reaction product.

[0055] (3) Calculated by mass parts, take 4 parts of the metal carboxylate solution generated in step (2) and mix it with 1 part of the polyurethane emulsion to obtain the coating for radiation-proof fabric.

[0056] Comparative Example 2

[0057] (1) By mass fraction, prepare 4.66 parts of bismuth oxide, 2.7 parts of oxalic acid, and 1 part of deionized water; the molar ratio of bismuth oxide to oxalic acid is 0.01:0.03.

[0058] (2) Add the reactants to the reactor, stir and heat to 80 °C, and continue stirring for 3 hours until the product is a clear liquid. Since the molar ratio of bismuth oxide to oxalic acid is 0.01:0.03 and they can react completely, there is no need to add ethanolamine to adjust the pH value.

[0059] (3) By mass fraction, take 4 parts of the metal carboxylate solution produced in step (2) and mix it with 1 part of the polyurethane emulsion to obtain the coating for radiation-proof fabric.

[0060] Comparative Example 3

[0061] Add 4.66 parts by mass of bismuth oxide to 15 parts by mass of the polyurethane emulsion and stir to mix, to prepare the coating for radiation-proof fabric.

[0062] Figure 2 The pattern prepared by coating the coating obtained in Comparative Example 3 of the present invention on the non-woven fabric.

[0063] Comparative Example 4

[0064] (1) By mass fraction, prepare 3.26 parts of lanthanum oxide, 4.05 parts of oxalic acid, and 1 part of deionized water; the molar ratio of bismuth oxide to oxalic acid is 0.01:0.045.

[0065] (2) Add the reactants to the reactor, stir and heat to 80 °C, and continue stirring for 3 hours until the product is a clear liquid; dropwise add triethanolamine and continue stirring until the reactants are neutral to end the reaction; at this time, the excessive oxalic acid in reaction step 1 is completely neutralized by triethanolamine to obtain the reaction product.

[0066] (3) By mass fraction, take 4 parts of the metal carboxylate solution produced in step (2) and mix it with 1 part of the polyurethane emulsion to obtain the coating for radiation-proof fabric

[0067] Comparative Example 5

[0068] (1) By mass fraction, prepare 3.26 parts of lanthanum oxide, 2.7 parts of oxalic acid, and 1 part of deionized water; the molar ratio of lanthanum oxide to oxalic acid is 0.01:0.03.

[0069] (2) Add the reactants to the reactor, stir and heat to 80 °C, and continue stirring for 3 hours until the product is a clear liquid. Since the molar ratio of bismuth oxide to oxalic acid is 0.01:0.03 and they can react completely, there is no need to add ethanolamine to adjust the pH value.

[0070] (3) Taking 4 parts by mass of the metal carboxylate solution generated in step (2) and mixing it with 1 part of the polyurethane emulsion to obtain a coating for radiation protection fabric.

[0071] Comparative Example 6

[0072] Adding 3.26 parts by mass of bismuth oxide to 15 parts by mass of the polyurethane emulsion and stirring and mixing to prepare a coating for radiation protection fabric.

[0073] Table 2 Flexibility, Radiation Protection and Washability of Comparative Examples

[0074]

[0075] As can be seen from Table 2, the carboxyl content in Comparative Examples 1 and 4 is less than that in the examples, and the water-soluble ammonium salts generated by the reaction and neutralization with triethanolamine are also correspondingly reduced, resulting in a decrease in water solubility. The carboxyl groups in Comparative Examples 2 and 5 are completely reacted, no water-soluble ammonium salts are generated, and the water solubility is even worse. Poor water solubility leads to poor dispersibility in the polyurethane emulsion. While the radiation protection efficiency decreases, the protection efficiency after 10 washes decreases significantly. In Comparative Examples 3 and 6, the particles are directly mixed with the polyurethane emulsion, and their dispersibility is the worst, and both the initial protection efficiency and the protection efficiency after 10 washes are poor.

[0076] It should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the present invention.

Claims

1. A coating for radiation-proof fabrics, characterized in that: The coating for radiation-proof fabrics includes radiation-proof metal oxides, soluble polycarboxylic acids and deionized water; Calculated by weight, the radiation-proof metal oxide is 4 to 8 parts, the soluble polycarboxylic acid is 5 to 10 parts, and the deionized water is 1 to 2 parts.

2. The coating for radiation-proof fabric according to claim 1, characterized in that: Coatings for radiation-proof fabrics also include triethanolamine and water-based polymer emulsions.

3. The method for preparing the coating for radiation-proof fabrics according to claim 1 or 2, characterized in that: include, The radiation-proof metal oxide, the soluble polycarboxylic acid and deionized water are mixed and stirred, and then triethanolamine is added dropwise and stirred to adjust the pH value to neutral to obtain a metal carboxylate solution; The coating for radiation-proof fabrics is obtained by mixing and stirring the metal carboxylate solution and the aqueous polymer emulsion.

4. The preparation method according to claim 3, characterized in that: The radiation-proof metal oxide includes one or more of bismuth oxide, tungsten oxide, lanthanum oxide and yttrium oxide.

5. The preparation method according to claim 3, characterized in that: Soluble polycarboxylic acids are organic acids containing 2 to 3 carboxyl groups in the molecule.

6. The preparation method according to claim 5, characterized in that: The soluble polycarboxylic acid includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid and citric acid.

7. The preparation method according to claim 3, characterized in that: The mass ratio of the metal carboxylate solution to the aqueous polymer emulsion is 1 to 4:

1.

8. The preparation method according to claim 7, characterized in that: The water-based polymer emulsion includes one or more of epoxy resin emulsion, polyvinyl acetate emulsion, acrylic emulsion, polyurethane emulsion and polyester emulsion, and has a solid content of 40% to 60% and a pH value of 6 to 8.

9. Use of the coating for radiation-proof fabrics prepared by the preparation method according to claims 3 to 8 in radiation-proof fabrics.

10. The use according to claim 9, characterized in that: The coating is applied to the fabric, and then heated and dried to obtain the radiation-proof fabric.

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