Preparation method of wear-resistant heat-insulating glass film and glass film
By using BaSO4/ATO composite powder and silane coupling agent modified silica in glass film, the problem of insufficient thermal insulation performance of existing glass films is solved, and more efficient heat insulation and wear resistance are achieved.
Patent Information
- Application Number
- CN202411950573.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-27
- Publication Date
- 2025-05-06
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing glass film has shortcomings in thermal insulation performance, which is difficult to meet the growing concept of low-carbon life and the thermal insulation needs in the fields of building curtain walls, automobiles, etc.
A substrate layer was prepared by bidirectional stretching of polyethylene terephthalate, and a ceramic slurry was prepared by dispersing the BaSO4/ATO composite powder in ethyl acetate, and added to a polyacrylate adhesive to form a nanocoated layer. Meanwhile, silica modified with silane coupling agent is added to the epoxy resin to form an wear-resistant layer.
It significantly improves the thermal insulation performance and wear resistance of glass film, and enhances its application value in architectural curtain walls and automobile fields.
Smart Images
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of film pasting, and in particular relates to a preparation method of a wear-resistant heat-insulating glass film and a glass film. Background Art
[0002] Glass film refers to a thin film product used to stick a layer of film on the surface of automobile glass, architectural glass or other glass. Glass film is mainly composed of single-layer or multi-layer functionalized polyester composite film (PET) material. By integrating vacuum multi-layer metal plating technology, ion technology, and advanced technologies in the fields of film physics and fine chemicals, it achieves excellent clarity, outstanding strength and durability, as well as impact resistance and decorative properties. These films are firmly adhered to glass and other materials through the backing layer, thereby optimizing the overall performance of the glass.
[0003] With the development of science and technology, the improvement of people's living standards and the introduction of the concept of "low-carbon life", the demand for heat insulation of curtain wall glass films and car films on the market is gradually increasing. Therefore, a glass film with good heat insulation performance is needed. Summary of the invention
[0004] In view of the above situation, in order to overcome at least part of the defects of the above-mentioned prior art, the present invention provides a method for preparing a wear-resistant and heat-insulating glass film and a glass film.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows: The present invention provides a method for preparing a wear-resistant heat-insulating glass film, comprising: S1, preparing a substrate layer: biaxially stretching polyethylene terephthalate to prepare a substrate layer; S2. preparing a nano coating: dispersing BaSO4 / ATO composite powder in ethyl acetate to obtain a ceramic slurry, adding the ceramic slurry into a polyacrylate adhesive, and coating the ceramic slurry on a substrate layer to form a nano coating; S3. Preparation of a wear-resistant layer: adding silicon dioxide modified by a silane coupling agent into epoxy resin, and coating the epoxy resin on the nano coating to form a wear-resistant layer.
[0006] In some embodiments, in step S2, the method for preparing the BaSO4 / ATO composite powder comprises: SnCl4·5H2O is added to anhydrous ethanol containing acetylacetone, SbCl3 is added, ultrasonic dispersion is performed, stirring is performed for 1h-3h, and aging is performed for 18h-20h to obtain ATO sol, BaSO4 is added to the ATO sol, ultrasonic dispersion is performed, the mixture is sealed and placed for 20h-24h, washed and dried, and calcined at 600℃-700℃ for 1h-3h to obtain BaSO4 / ATO composite powder.
[0007] In some embodiments, the mass ratio of the SnCl4·5H2O to the SbCl3 is 30:1-5.
[0008] In some embodiments, the mass ratio of the SnCl4·5H2O to the BaSO4 is 30:0.5-3.
[0009] In some embodiments, step S2 further comprises, before coating, soaking the substrate layer in water to remove dirt, and then placing it in an oven for drying.
[0010] In some embodiments, step S2 further comprises, during coating, coating the polyacrylate adhesive containing the ceramic slurry onto the substrate layer using a wire bar coater.
[0011] In some embodiments, step S2 further comprises, after coating, placing in an oven and drying at 40° C.-50° C. for 1 h-2 h.
[0012] In some embodiments, the silane coupling agent is an amino-type silane coupling agent.
[0013] In some embodiments, in step S3, the mass ratio of the silane coupling agent-modified silica to the epoxy resin is 1-3:10.
[0014] The invention also provides a glass film, which is prepared by the above method.
[0015] The beneficial effects achieved by the present invention are as follows: BaSO4 / ATO composite powder was prepared by surface modification of BaSO4 using ATO, and ceramic slurry was prepared using it as thermal insulation filler and ethyl acetate as solvent. This can prevent the agglomeration of BaSO4 / ATO composite powder due to van der Waals force and improve the dispersibility of BaSO4 / ATO composite powder.
[0016] Adding ceramic slurry to polyacrylate adhesive and coating it on the substrate layer to obtain a nano coating can improve the thermal insulation performance of the glass film. Among them, BaSO4 has a high solar reflectance and hemispherical emissivity, and ATO (antimony-doped tin dioxide) has good anti-reflection, infrared absorption, and thermal stability. The thermal insulation effect of BaSO4 can be improved by coating BaSO4 with ATO to obtain BaSO4 / ATO composite powder. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 Schematic diagram of glass film according to an embodiment of the present invention. The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION
[0018] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0019] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.
[0020] In view of the deficiencies in the prior art mentioned in the background technology, refer to Figure 1 The first aspect of the present invention provides a method for preparing a wear-resistant heat-insulating glass film, comprising: S1, preparing a substrate layer: biaxially stretching polyethylene terephthalate to prepare a substrate layer; S2. preparing a nano coating: dispersing BaSO4 / ATO composite powder in ethyl acetate to obtain a ceramic slurry, adding the ceramic slurry into a polyacrylate adhesive, and coating the ceramic slurry on a substrate layer to form a nano coating; S3. Preparation of a wear-resistant layer: adding silicon dioxide modified by a silane coupling agent into epoxy resin, and coating the epoxy resin on the nano coating to form a wear-resistant layer.
[0021] The study found that after the BaSO4 / ATO composite powder is directly added to the adhesive, the BaSO4 / ATO composite powder will agglomerate due to the van der Waals force, which will lead to the loss of thermal insulation performance. Moreover, the high viscosity of the adhesive is not conducive to the dispersion of nano-ceramic particles. Therefore, it is necessary to prepare the ceramic slurry first to disperse the nano-ceramic particles evenly, and then disperse them in the adhesive by appropriate methods.
[0022] At the same time, BaSO4 has a high solar reflectance and hemispherical emissivity, and ATO (antimony-doped tin dioxide) has good anti-reflection, infrared absorption, and thermal stability. The thermal insulation effect of BaSO4 can be improved by coating BaSO4 with ATO to obtain BaSO4 / ATO composite powder.
[0023] Untreated nano-silica is easy to agglomerate and difficult to be effectively dispersed in the epoxy resin matrix. However, after modification with silane coupling agent, the agglomeration phenomenon of silica is significantly improved, which is conducive to its uniform dispersion in the epoxy resin. Adding silica with good dispersion can improve the wear resistance of epoxy resin, thereby improving the wear resistance of glass film.
[0024] In some embodiments, in step S2, the method for preparing BaSO4 / ATO composite powder includes: SnCl4·5H2O is added to anhydrous ethanol containing acetylacetone, SbCl3 is added, ultrasonic dispersion is performed, stirring is performed for 1h-3h, and aging is performed for 18h-20h to obtain ATO sol, BaSO4 is added to the ATO sol, ultrasonic dispersion is performed, the mixture is sealed and placed for 20h-24h, washed and dried, and calcined at 600℃-700℃ for 1h-3h to obtain BaSO4 / ATO composite powder.
[0025] Among them, SnCl4·5H2O is used as a tin source to provide the tin element in the ATO sol, SbCl3 provides the antimony element in the ATO sol, acetylacetone is used as a stabilizer to help prevent the sol from agglomerating and precipitating during the preparation process, and anhydrous ethanol is used as a solvent to dissolve SnCl4·5H2O and SbCl3 and promote the formation of the sol. By aging the prepared sol for 18h-20h, the particles in the sol can be further grown and stabilized. Then, by adding BaSO4 to the ATO sol and calcining it at 600℃-700℃, a BaSO4 / ATO composite powder can be obtained.
[0026] In some embodiments, the mass ratio of SnCl4·5H2O to SbCl3 is 30:1-5. A higher tin content can make the BaSO4 / ATO composite powder have better conductivity and optical properties. At the same time, the addition of antimony can improve the thermal stability of the BaSO4 / ATO composite powder, but too much antimony will cause the sol performance to decrease, resulting in an inability to form a stable sol. Therefore, the mass ratio of SnCl4·5H2O to SbCl3 is set to 30:1-5.
[0027] In some embodiments, the mass ratio of SnCl4·5H2O to BaSO4 is 30:0.5-3. In particular, adding too much BaSO4 as an insoluble substance will affect the uniformity and dispersibility of the sol, and adding too little will reduce the thermal insulation effect of the BaSO4 / ATO composite powder. Therefore, the mass ratio of SnCl4·5H2O to BaSO4 is set to 30:0.5-3.
[0028] In some embodiments, step S2 further includes, before coating, soaking the substrate layer in water to remove dirt, and then putting it into an oven for drying. The cleanliness and dryness of the substrate layer will affect the coating effect, and any trace oil, dust and impurities on the surface of the substrate layer will affect the coating, so the substrate layer must be thoroughly cleaned.
[0029] In some embodiments, step S2 further includes, during coating, using a wire rod coater to coat the polyacrylate adhesive containing ceramic slurry onto the substrate layer. Using a wire rod coater can effectively coat the polyacrylate adhesive containing ceramic slurry onto the substrate layer and ensure the coating quality and stability of the coating layer.
[0030] In some embodiments, step S2 further includes, after coating, placing in an oven, drying at 40°C-50°C for 1h-2h. After coating the polyacrylate adhesive containing ceramic slurry on the substrate layer, placing it in an oven for drying to remove the solvent, and setting the drying time of the oven to 1 hour to 2 hours. Too long a drying time may cause the coating to be over-cured or burned, and too short a drying time may not completely remove the solvent.
[0031] In some embodiments, in step S3, the silane coupling agent is an amino-type silane coupling agent. The amino functional group can undergo polymerization reaction with the epoxy group in the epoxy resin, thereby enhancing the interfacial interaction between silicon dioxide and the epoxy resin. The model of the amino-type silane coupling agent can be KH550, KH792 or KH602.
[0032] In some embodiments, in step S3, the mass ratio of silica modified by silane coupling agent to epoxy resin is 1-3: 10. In particular, too little addition of silica modified by silane coupling agent will result in limited improvement in the performance of epoxy resin, and a large amount of silica modified by silane coupling agent will increase the difficulty of coating molding and affect the curing effect of epoxy resin. Therefore, the mass ratio of silica modified by silane coupling agent to epoxy resin needs to be set to 1-3: 10.
[0033] A second aspect of the present invention provides a glass film prepared by the above method.
[0034] The present invention will be further described below by way of specific embodiments.
[0035] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.
[0036] Example 1 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 1gSbCl3, ultrasonically disperse, stir for 1h, and age for 18h to obtain ATO sol, add 0.5gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 20h, wash and dry, and calcine at 600℃ for 1h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 40℃ for 1h to form a nano coating; S3. Add 5g of silica modified by silane coupling agent KH550 into 50g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0037] Example 2 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 2gSbCl3, ultrasonically disperse, stir for 2h, and age for 19h to obtain ATO sol, add 1gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 21h, wash and dry, and calcine at 650℃ for 2h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 45℃ for 1h to form a nano coating; S3. Add 10g of silica modified by silane coupling agent KH550 into 50g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0038] Example 3 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 3gSbCl3, ultrasonically disperse, stir for 3h, and age for 20h to obtain ATO sol, add 2gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 22h, wash and dry, and calcine at 650℃ for 3h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 50℃ for 2h to form a nano coating; S3. Add 15 g of silica modified by silane coupling agent KH550 into 50 g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0039] Example 4 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 4gSbCl3, ultrasonically disperse, stir for 3h, and age for 20h to obtain ATO sol, add 3gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 24h, wash and dry, and calcine at 700℃ for 2h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, and place it in an oven for drying at 50℃ for 1h to form a nano coating; S3. Add 12 g of silicon dioxide modified by silane coupling agent KH550 into 50 g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0040] Example 5 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 5gSbCl3, ultrasonically disperse, stir for 3h, and age for 20h to obtain ATO sol, add 3gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 24h, wash and dry, and calcine at 700℃ for 3h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 50℃ for 2h to form a nano coating; S3. Add 8 g of silicon dioxide modified by silane coupling agent KH550 into 50 g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0041] Example 6 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 1gSbCl3, ultrasonically disperse, stir for 1h, and age for 18h to obtain ATO sol, add 0.5gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 20h, wash and dry, and calcine at 600℃ for 1h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 40℃ for 1h to form a nano coating; S3. Add 15 g of silica modified by silane coupling agent KH550 into 50 g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0042] Example 7 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 5gSbCl3, ultrasonically disperse, stir for 3h, and age for 20h to obtain ATO sol, add 3gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 24h, wash and dry, and calcine at 700℃ for 3h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 50℃ for 2h to form a nano coating; S3. Add 5g of silica modified by silane coupling agent KH550 into 50g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0043] Example 8 A method for preparing a wear-resistant heat-insulating glass film, comprising: S1, biaxially stretching polyethylene terephthalate to form a substrate layer; S2, take 30gSnCl4·5H2O and add it to anhydrous ethanol containing acetylacetone, add 1gSbCl3, ultrasonically disperse, stir for 1h, and age for 18h to obtain ATO sol, add 0.5gBaSO4 to the ATO sol, ultrasonically disperse, seal and place for 20h, wash and dry, and calcine at 600℃ for 1h to obtain BaSO4 / ATO composite powder, disperse the BaSO4 / ATO composite powder in ethyl acetate to obtain ceramic slurry, soak the substrate layer in water to remove dirt, and then put it in an oven for drying, add the ceramic slurry to the polyacrylate adhesive, use a wire rod coater to apply the polyacrylate adhesive containing the ceramic slurry to the substrate layer, place it in an oven, and dry it at 40℃ for 1h to form a nano coating; S3. Add 15 g of silica modified by silane coupling agent KH550 into 50 g of epoxy resin and apply it on the nano coating to form a wear-resistant layer.
[0044] Comparative Example 1 The difference between this comparative example and Example 1 is that in step S2, BaSO4 is used instead of BaSO4 / ATO composite powder.
[0045] Comparative Example 2 The difference between this comparative example and Example 1 is that in step S3, no silicon dioxide modified by a silane coupling agent is added to the epoxy resin.
[0046] Thermal insulation performance test: The thermal insulation performance of Examples 1-8 of the present invention and Comparative Example 1 was tested, and a comparative test was performed with a blank PET glass film. The measured thermal insulation temperature difference was used as an evaluation index. The results are shown in Table 1. It can be seen that the thermal insulation effect of Examples 1-8 is significantly improved compared with Comparative Example 1.
[0047] Table 1
[0048] Wear resistance test: The wear resistance of Examples 1-8 of the present invention and Comparative Example 2 was tested. A ball-disc wear test using an aluminum ball was used to evaluate the wear resistance. The measured wear depth and wear width were used as evaluation indicators. The results are shown in Table 2. It can be seen that the addition of silica modified with a silane coupling agent can improve the wear resistance of the epoxy resin.
[0049] Table 2
[0050] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solutions of the present invention, which should be included in the protection scope of the present invention.
Claims
1. A method for preparing a wear-resistant heat-insulating glass film, characterized in that: include: S1, preparing a substrate layer: biaxially stretching polyethylene terephthalate to prepare a substrate layer; S2. preparing a nano coating: dispersing BaSO4 / ATO composite powder in ethyl acetate to obtain a ceramic slurry, adding the ceramic slurry into a polyacrylate adhesive, and coating the ceramic slurry on a substrate layer to form a nano coating; S3. Preparation of a wear-resistant layer: adding silicon dioxide modified by a silane coupling agent into epoxy resin, and coating the epoxy resin on the nano coating to form a wear-resistant layer.
2. The preparation method according to claim 1, characterized in that: In step S2, the method for preparing the BaSO4 / ATO composite powder comprises: SnCl4·5H2O is added to anhydrous ethanol containing acetylacetone, SbCl3 is added, ultrasonic dispersion is performed, stirring is performed for 1h-3h, and aging is performed for 18h-20h to obtain ATO sol, BaSO4 is added to the ATO sol, ultrasonic dispersion is performed, the mixture is sealed and placed for 20h-24h, washed and dried, and calcined at 600℃-700℃ for 1h-3h to obtain BaSO4 / ATO composite powder.
3. The preparation method according to claim 2, characterized in that: The mass ratio of the SnCl4·5H2O to the SbCl3 is 30:1-5.
4. The preparation method according to claim 2, characterized in that: The mass ratio of the SnCl4·5H2O to the BaSO4 is 30:0.5-3.
5. The preparation method according to claim 1, characterized in that: Step S2 also includes, before coating, soaking the substrate layer in water to remove dirt, and then putting it into an oven for drying.
6. The preparation method according to claim 1, characterized in that: Step S2 also includes, during coating, coating the polyacrylate adhesive containing the ceramic slurry onto the substrate layer using a wire rod coater.
7. The preparation method according to claim 1, characterized in that: Step S2 also includes, after coating, placing in an oven, drying at 40° C.-50° C. for 1 h-2 h.
8. The preparation method according to claim 1, characterized in that: In step S3, the silane coupling agent is an amino-type silane coupling agent.
9. The preparation method according to claim 1, characterized in that: In step S3, the mass ratio of the silane coupling agent-modified silica to the epoxy resin is 1-3:
10.
10. A glass film, characterized in that: The method is prepared by any one of claims 1 to 9.