A polyacrylate-based light-heat warm-keeping antibacterial type leather finishing agent with wide spectral response, a preparation method and application thereof

Abstract

The application discloses a polyacrylate-based light-heat warm-keeping antibacterial type leather finishing agent with wide spectrum response and a preparation method and application thereof, and belongs to the technical field of leather warm-keeping. The method disclosed by the application introduces a light-heat material into a polyacrylate emulsion through a blending method, utilizes the light-heat conversion performance of the light-heat material, and converts sunlight into heat energy under an outdoor light environment, so that the temperature of the surface of the prepared composite leather finishing agent is increased, the temperature difference between the human body and the environment is reduced, the heat dissipation of the human body is reduced, zero-carbon warm-keeping of leather products based on sunlight is realized, the modified light-heat material is adopted, the carbon-based light-heat material is compounded with a semiconductor light-heat material, the transmission efficiency of light-heat electrons can be improved while wide spectrum absorption response is realized, the light-heat conversion efficiency is improved, and the light-heat conversion performance is more excellent.

Description

Technical Field

[0001] This invention belongs to the field of leather thermal insulation technology, specifically relating to a broadband-response polyacrylate-based photothermal thermal insulation and antibacterial leather finishing agent, its preparation method, and its application. Background Technology

[0002] Leather, a natural polymer material composed of collagen fibers, possesses a porous and hydrophilic molecular structure, giving it warmth and breathability, making it an excellent material for clothing. Leather garments offer advantages such as warmth, moisture permeability, sweat absorption, and comfortable and aesthetically pleasing wear. However, in cold winters, leather products alone are insufficient to meet people's needs for warmth. Existing research typically improves warmth by adding linings or increasing thickness, but this results in bulky clothing, affecting both aesthetics and comfort. Therefore, the key research area is how to improve the warmth of leather products while retaining their original moisture permeability, sweat absorption, and comfortable and aesthetically pleasing characteristics. Furthermore, as a biomass-based natural polymer material, leather contains substances necessary for bacterial growth, making it prone to bacterial proliferation during use and storage, thus affecting its quality and lifespan. Based on these issues and considering the inherent characteristics of leather, introducing functional materials into the leather during the finishing stage is an effective method to improve the warmth and antibacterial properties of leather products.

[0003] Chinese patent CN111534178B discloses a method for preparing a photothermal heat-insulating leather coating agent, but the photothermal materials used, such as Ti3C2, gold, and silver, are costly. Chinese patent CN115505059B discloses a method using Ti3C2T... x The method for preparing photothermal polyacrylate emulsions using powder as an emulsifier is complex and cannot effectively utilize Ti3C2T in the field of photothermal conversion. x Excellent performance. Therefore, there is a need to develop a simple, wide light response range, fast response rate, and low-cost process for preparing a photothermal insulating and antibacterial leather finishing agent. Summary of the Invention

[0004] The purpose of this invention is to provide a broad-spectrum-response polyacrylate-based photothermal insulating and antibacterial leather coating agent, its preparation method, and its application, in order to solve the technical problem that existing photothermal leather coating agents cannot fully utilize the photothermal properties of materials.

[0005] To achieve the above objectives, the present invention employs the following technical solution:

[0006] This invention discloses a method for preparing a broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent, comprising the following steps:

[0007] Modified photothermal materials are prepared using photothermal materials and modifiers as raw materials;

[0008] After mixing the modified photothermal material and polyacrylate emulsion, a polyacrylate-based photothermal heat-insulating and antibacterial leather coating agent with a broad spectrum response is obtained.

[0009] The photothermal material is one or both of carbon-based photothermal materials and semiconductor photothermal materials.

[0010] Furthermore, modified photothermal materials are prepared using photothermal materials and modifiers as raw materials, specifically including the following steps:

[0011] The modifier was added to water and stirred until dissolved. Then the photothermal material was added and stirred again. Subsequently, the mixture was centrifuged and freeze-dried to obtain the modified photothermal material.

[0012] The amount of the modifier added is 3%-15% of the mass of the photothermal material;

[0013] The amount of water used is 200% to 350% of the mass of the photothermal material;

[0014] The stirring speed is 200-600 rpm.

[0015] Furthermore, before mixing the modified photothermal material and the polyacrylate emulsion, the pH of the polyacrylate emulsion is adjusted to 5-9.

[0016] Furthermore, the amount of the modified photothermal material used is 0.5%-5% of the solid mass in the polyacrylate emulsion.

[0017] Furthermore, the mixing method is mechanical stirring; the mechanical stirring speed is 200-600 rpm, and the time is 3-25 min.

[0018] Furthermore, the modifier is one or more selected from potassium perfluorobutyl sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, and γ-aminopropyltriethoxysilane.

[0019] Furthermore, the carbon-based photothermal material is one or more of graphene, nano-carbon powder, and carbon black;

[0020] The semiconductor photothermal material is one or more of black titanium dioxide, Prussian blue, and iron oxide;

[0021] When the photothermal material is a mixture of carbon-based photothermal material and semiconductor photothermal material, the mass ratio of carbon-based photothermal material to semiconductor photothermal material is (1-4):(0.5-1).

[0022] The present invention also discloses a broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared by the above preparation method.

[0023] This invention also discloses the application of the above-mentioned broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent in the preparation of leather garments.

[0024] Furthermore, the broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent has a spraying amount of 20-30 g / m² on leather. 2 .

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] This invention discloses a method for preparing a broadband-response polyacrylate-based photothermal insulating and antibacterial leather coating. The method involves combining modified photothermal materials with polyacrylate emulsions. The photothermal materials are introduced into the polyacrylate emulsions via a blending method. Utilizing the photothermal conversion properties of these materials, the prepared composite leather coating can convert sunlight into heat energy under outdoor sunlight, increasing the surface temperature of the leather. This reduces the temperature difference between the human body and the environment, minimizing heat loss and achieving zero-carbon insulation of leather products based on sunlight. Using carbon-based photothermal materials, semiconductor photothermal materials, or a mixture of both as modified photothermal materials can improve the transmission efficiency of photothermal electrons while achieving a broadband absorption response, thus enhancing photothermal conversion efficiency and exhibiting superior photothermal conversion performance.

[0027] Furthermore, the heat generated by the photothermal material causes protein denaturation, which works synergistically with the physical cutting effect of the nanomaterial to destroy the bacterial cell wall and basic life activities, inhibiting bacterial growth and achieving an antibacterial effect.

[0028] Furthermore, the process of the present invention is simple, with a wide light response range, fast response rate, low cost, environmental friendliness, and good repeatability. Adding a small amount of photothermal material can enable coated leather to achieve warmth and antibacterial properties using clean solar energy. Attached Figure Description

[0029] Figure 1 The temperature rise curve of the leather sample surface coated with the polyacrylate-based photothermal heat-insulating and antibacterial leather finishing agent with a wide spectrum response prepared in this invention is shown.

[0030] Figure 2 The image shows an antibacterial image of a leather sample coated with a broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared using the present invention. Detailed Implementation

[0031] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0032] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0033] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0034] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0035] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0036] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0037] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0038] Example 1

[0039] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0040] 0.1g of polyvinylpyrrolidone was added to 100mL of water and dissolved by magnetic stirring at 600rpm. Then, 1g of graphene and 1g of Prussian blue were added and the mixture was magnetically stirred at 600rpm at room temperature for 2h. After centrifugation and freeze-drying, the modified photothermal material was obtained.

[0041] The pH of the polyacrylate emulsion was adjusted to 7.5 with 0.5% ammonia. 0.32g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 600rpm at room temperature for 10min to obtain a broad-spectrum responsive polyacrylate-based photothermal warming and antibacterial leather finishing agent.

[0042] Example 2

[0043] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0044] 0.06g of polyvinylpyrrolidone was added to 100mL of water and dissolved by magnetic stirring at 400rpm. Then, 1g of carbon black and 0.8g of black titanium dioxide were added and the mixture was magnetically stirred at 400rpm at room temperature for 3h. After centrifugation and freeze-drying, the modified photothermal material was obtained.

[0045] The pH of the polyacrylate emulsion was adjusted to 7 with 0.5% ammonia. 0.35g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 400rpm at room temperature for 15min to obtain a broad-spectrum responsive polyacrylate-based photothermal warming and antibacterial leather finishing agent.

[0046] Example 3

[0047] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0048] 0.12 g of potassium perfluorobutyl sulfonate was added to 100 mL of water and dissolved by magnetic stirring at 500 rpm. Then, 1 g of nano carbon powder was added and the mixture was magnetically stirred at 500 rpm at room temperature for 4 h. After centrifugation and freeze drying, the modified photothermal material was obtained.

[0049] The pH of the polyacrylate emulsion was adjusted to 7.5 with 0.5% ammonia. 0.15g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 500rpm at room temperature for 20min to obtain a broad-spectrum responsive polyacrylate-based photothermal warming and antibacterial leather coating agent.

[0050] Example 4

[0051] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0052] 0.2g sodium dodecyl sulfate was added to 100mL of water and dissolved by magnetic stirring at 600rpm. Then, 1g carbon black, 0.25g iron oxide and 0.1g black titanium dioxide were added respectively. The mixture was magnetically stirred at 600rpm at room temperature for 4h, then centrifuged and freeze-dried to obtain the modified photothermal material.

[0053] The pH of the polyacrylate emulsion was adjusted to 8 with 0.5% ammonia. 0.5g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 600rpm at room temperature for 25min to obtain a broad-spectrum responsive polyacrylate-based photothermal warming and antibacterial leather finishing agent.

[0054] Example 5

[0055] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0056] 0.09 g of γ-aminopropyltriethoxysilane was added to 100 mL of water and dissolved by magnetic stirring at 200 rpm. Then, 1 g of nano carbon powder and 0.75 g of iron oxide were added. The mixture was stirred magnetically at 200 rpm at room temperature for 4 h. After centrifugation and freeze-drying, the modified photothermal material was obtained.

[0057] The pH of the polyacrylate emulsion was adjusted to 9 with 0.5% ammonia. 0.8g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 200rpm at room temperature for 12min to obtain a polyacrylate-based photothermal warming and antibacterial leather coating agent with a broad spectrum response.

[0058] Example 6

[0059] A method for preparing a broadband-responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent includes the following steps:

[0060] 0.12 g sodium dodecyl sulfate was added to 100 mL of water and dissolved by magnetic stirring at 500 rpm. Then, 1 g of graphene and 0.5 g of Prussian blue were added and the mixture was magnetically stirred at 500 rpm at room temperature for 4 h. After centrifugation and freeze drying, the modified photothermal material was obtained.

[0061] The pH of the polyacrylate emulsion was adjusted to 5 with 0.5% ammonia. 0.1g of modified photothermal material and 30g of water were added to 50g of polyacrylate emulsion and mechanically stirred at 500rpm at room temperature for 3min to obtain a broad-spectrum responsive polyacrylate-based photothermal warming and antibacterial leather coating agent.

[0062] Application Example 1

[0063] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 1 was sprayed onto goatskin, with a coating amount of 25 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in the sunlight outdoors for 5 minutes at an outdoor temperature of 20℃.

[0064] like Figure 1 As shown, after 5 minutes of exposure to sunlight in winter, the surface temperature of the leather sample coated with the photothermal heat-insulating and antibacterial leather finishing agent rose to 32.4℃, which was 7.2℃ higher than that of the leather sample coated with polyacrylate emulsion.

[0065] like Figure 2 As shown, the antibacterial and heat-insulating leather coating agent achieved inhibition rates of 96% and 99% against Escherichia coli and Staphylococcus aureus, respectively, under simulated sunlight irradiation.

[0066] Application Example 2

[0067] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 2 was sprayed onto goatskin, with a coating amount of 27 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in outdoor sunlight for 5 minutes at an outdoor temperature of 20℃.

[0068] After 5 minutes of exposure to sunlight in winter, the surface temperature of leather samples coated with the photothermal heat-insulating and antibacterial leather finishing agent increased to 30.1℃, which was 5℃ higher than that of leather samples coated with polyacrylate emulsion. The inhibition rates against Staphylococcus aureus and Escherichia coli were 95% and 96%, respectively.

[0069] Application Example 3

[0070] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 3 was sprayed onto goatskin, with a coating amount of 25 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in outdoor sunlight for 5 minutes at an outdoor temperature of 20℃.

[0071] After 5 minutes of exposure to sunlight in winter, the surface temperature of leather samples coated with the photothermal heat-insulating and antibacterial leather finishing agent increased to 35.9℃, which was 10℃ higher than that of leather samples coated with polyacrylate emulsion. The inhibition rates against Staphylococcus aureus and Escherichia coli were 94% and 96%, respectively.

[0072] Application Example 4

[0073] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 4 was sprayed onto goatskin, with a coating amount of 26 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in outdoor sunlight for 5 minutes at an outdoor temperature of 20℃.

[0074] After 5 minutes of exposure to sunlight in winter, the surface temperature of leather samples coated with the photothermal heat-insulating and antibacterial leather finishing agent increased to 32.8℃, which was 7.4℃ higher than that of leather samples coated with polyacrylate emulsion. The inhibition rates against Staphylococcus aureus and Escherichia coli were 95% and 97%, respectively.

[0075] Application Example 5

[0076] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 5 was sprayed onto goatskin, with a coating amount of 20 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in outdoor sunlight for 5 minutes at an outdoor temperature of 20℃.

[0077] After 5 minutes of exposure to sunlight in winter, the surface temperature of leather samples coated with the photothermal heat-insulating and antibacterial leather finishing agent increased to 32.8℃, which was 12℃ higher than that of leather samples coated with polyacrylate emulsion. The inhibition rates against Staphylococcus aureus and Escherichia coli were 95% and 97%, respectively.

[0078] Application Example 6

[0079] The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent prepared in Example 6 was sprayed onto goatskin, with a coating amount of 30 g / m². 2 After drying in an oven at 60℃ for 30 minutes, remove the coated leather sample and place it in outdoor sunlight for 5 minutes at an outdoor temperature of 20℃.

[0080] After 5 minutes of exposure to sunlight in winter, the surface temperature of leather samples coated with the photothermal heat-insulating and antibacterial leather finishing agent rose to 32.8℃, which was 15℃ higher than that of leather samples coated with polyacrylate emulsion. The inhibition rates against Staphylococcus aureus and Escherichia coli were 95% and 97%, respectively.

[0081] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for preparing a broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent, characterized in that, Includes the following steps: Modified photothermal materials are prepared using photothermal materials and modifiers as raw materials; After mixing the modified photothermal material and polyacrylate emulsion, a polyacrylate-based photothermal heat-insulating and antibacterial leather coating agent with a broad spectrum response is obtained. The photothermal material is one or both of carbon-based photothermal materials and semiconductor photothermal materials; The modified photothermal material is prepared using photothermal materials and modifiers as raw materials, specifically including the following steps: The modifier was added to water and stirred until dissolved. Then the photothermal material was added and stirred again. Subsequently, the mixture was centrifuged and freeze-dried to obtain the modified photothermal material. The amount of the modifier added is 3%-15% of the mass of the photothermal material; The amount of water used is 200% to 350% of the mass of the photothermal material; The stirring speed is 200-600 rpm; The amount of the modified photothermal material used is 0.5%-5% of the solid mass in the polyacrylate emulsion; The carbon-based photothermal material is one or more of graphene, nano-carbon powder, and carbon black; The semiconductor photothermal material is one or more of black titanium dioxide, Prussian blue, and iron oxide; When the photothermal material is a mixture of carbon-based photothermal material and semiconductor photothermal material, the mass ratio of carbon-based photothermal material to semiconductor photothermal material is (1~4):(0.5~1); Before mixing the modified photothermal material and the polyacrylate emulsion, the pH of the polyacrylate emulsion is adjusted to 5-9; The mixing method is mechanical stirring; the mechanical stirring speed is 200-600 rpm, and the time is 3-25 min. The modifier is one or more of potassium perfluorobutyl sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, and γ-aminopropyltriethoxysilane.

2. A broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent, characterized in that, It was prepared using the preparation method described in claim 1.

3. The application of the broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent as described in claim 2 in the preparation of leather garments.

4. The application of the broadband-response polyacrylate-based photothermal insulating and antibacterial leather finishing agent according to claim 3 in the preparation of leather garments, characterized in that, The broad-spectrum responsive polyacrylate-based photothermal insulating and antibacterial leather finishing agent has a spraying amount of 20-30 g / m² on leather. 2 .

Images