Wear-resistant and stain-resistant PETG composite material and application thereof in preparation of furniture building materials

Abstract

The invention discloses a wear-resistant and stain-resistant PETG composite material and application thereof in preparation of furniture building materials, and particularly belongs to the technical field of high polymer materials. The PETG composite material is prepared from the following components in parts by mass: 40 to 50 parts of PETG, 30 to 36 parts of PCTG, 20 to 28 parts of PC, 10 to 15 parts of poly (4-vinyl tert-butyl benzoate), 1 to 3 parts of a coupling agent, 6 to 12 parts of an antioxidant, 2 to 3 parts of an ultraviolet absorbent and 40 to 60 parts of silicon dioxide. A PETG composite film prepared from the PETG composite material provided by the invention has excellent longitudinal and transverse tensile strength and excellent wear resistance and stain resistance, and can be used for preparing a flat film, a highlight film, a protective film, a matte film and / or a skin-touch film for furniture and building materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and specifically relates to a wear-resistant and stain-resistant PETG composite material and its application in the preparation of flat films, high-gloss films, protective films, matte films, and / or skin-friendly films for furniture and building materials. Background Art

[0002] PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester) is a transparent, amorphous copolyester with excellent physical and chemical properties. It is formed by polycondensing three monomers, terephthalic acid (PTA), ethylene glycol (EG), and 1,4-cyclohexanedimethanol (CHDM), through the transesterification method. Due to its good transparency, gloss, toughness, impact strength, and chemical resistance, PETG has been widely used in many fields.

[0003] In the furniture and building materials industry, traditional decorative materials often suffer from insufficient wear resistance and stain resistance. These materials are prone to wear and scratching during long-term use, and are difficult to clean and maintain, which affects the overall aesthetics and service life. Therefore, the development of a new composite material that is both wear-resistant and stain-resistant is of great significance for improving the performance and quality of furniture and building materials.

[0004] Due to its unique properties, PETG has become a potential choice to solve this problem. PETG not only has excellent transparency and gloss, capable of presenting a realistic picture effect and a luxurious texture, but also has good heat resistance and cold resistance, capable of meeting the usage requirements under different climate conditions. In addition, PETG materials also have the characteristics of fingerprint resistance and oil resistance, are not easily stained with fingerprints and stains, and are easy to clean and maintain. These characteristics make PETG have broad application prospects in the field of furniture and building materials.

[0005] However, pure PETG materials may still have certain limitations in some specific application scenarios, such as insufficient hardness and easy scratching.

[0006] In summary, the development of a wear-resistant and stain-resistant PETG composite material and its application in the preparation of decorative materials for furniture and building materials can not only improve the aesthetics and service life of products, but also meet the market demand for high-quality furniture and building materials. The research and application of this composite material will be of great significance for promoting the technological progress and industrial upgrading of the furniture and building materials industry. Summary of the Invention

[0007] Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide a wear-resistant and stain-resistant PETG composite material. By blending other polymers with PETG for compound modification, its comprehensive performance can be further improved to meet the high requirements of the furniture and building materials industry for wear-resistant and stain-resistant performance.

[0008] To achieve the above object, the present invention discloses the following technical solutions: In a first aspect, the present invention provides a wear-resistant and stain-resistant PETG composite material. By mass, the PETG composite material contains the following components: 40 - 50 parts of PETG; 30 - 36 parts of PCTG; 20 - 28 parts of PC; 10 - 15 parts of poly(tert-butyl 4-vinylbenzoate); 1 - 3 parts of coupling agent; 6 - 12 parts of antioxidant; 2 - 3 parts of ultraviolet absorber; 40 - 60 parts of silica.

[0009] Preferably, the coupling agent is selected from at least one of neopentoxy tris(dioctylpyrophosphatooxy)titanate, tetraisopropoxy bis(dioctylphosphite)titanate, and isopropyl tris(dioctylpyrophosphatooxy)titanate.

[0010] Preferably, the antioxidant is selected from at least one of antioxidant DSTDP, antioxidant 1010, and antioxidant DLTDP.

[0011] Preferably, the ultraviolet absorber is selected from ultraviolet absorber UV-531 and / or ultraviolet absorber UV-329.

[0012] Preferably, the silica is ultrafine silica powder with a particle size ≤ 2.6 μm.

[0013] In a second aspect, the present invention provides a preparation method of the PETG composite material described in the first aspect. The preparation method includes the following steps: (1) Preparation of materials: Weigh PETG, PCTG, PC, poly(tert-butyl 4-vinylbenzoate), coupling agent, antioxidant, silica, and ultraviolet absorber according to the formula amount; (2) Mixing: First, place PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) in a dryer and dry them at 70 °C for 12 h to obtain the dried base material. Then, add the dried base material, coupling agent, antioxidant, and ultraviolet absorber to a mixer in sequence, stir and mix for 30 min, and then add silica and continue mixing for 30 min to obtain a mixed material; (3) Granulation: Extrude the mixed material obtained in step (2) uniformly on a twin-screw extruder, extrude and draw into strips under the conditions of an extrusion temperature of 250 °C and a screw speed of 200 r / min, then cool with water and cut into pellets to obtain the PETG composite material.

[0014] In a third aspect, the present invention provides a wear-resistant and stain-resistant PETG composite film, and the PETG composite film comprises the wear-resistant and stain-resistant PETG composite material described in the first aspect.

[0015] In a fourth aspect, the present invention provides the application of the wear-resistant and stain-resistant PETG composite film described in the third aspect in preparing flat films, high-gloss films, protective films, matte films and / or skin-friendly films for furniture building materials and having wear-resistant and / or stain-resistant properties.

[0016] In the present invention: As copolyester materials, PETG and PCTG have good toughness and wear resistance. The addition of polycarbonate (PC) further improves the wear resistance of the material because PC itself has extremely high wear resistance and toughness. As a high-performance polymer, poly(tert-butyl 4-vinylbenzoate) plays multiple roles in the PETG system. First of all, it can significantly improve the chemical stability and hydrophobicity of PETG, enhance the resistance of the composite material to acids, alkalis and organic solvents, and thus improve the stain resistance of the PETG system, making it not easily eroded by stains. Secondly, the addition of poly(tert-butyl 4-vinylbenzoate) can improve the physical properties of PETG plastics, such as tensile strength, making it not easily break or damage when subjected to external forces. In addition, poly(tert-butyl 4-vinylbenzoate) can also enhance the thermal properties of the PETG system, increase its glass transition temperature (Tg), making it suitable for various processing technologies, and improve the thermal stability, enabling it to withstand a relatively high temperature environment. The present invention studies and finds that the polymer system composed of PETG, PCTG, PC and poly(tert-butyl 4-vinylbenzoate) shows excellent performance in terms of tensile strength and stain resistance evaluation, and the wear amount is also relatively low, indicating that this compound composition provides good mechanical properties and stain resistance.

[0017] Advantages of the present invention: The PETG composite film prepared from the PETG composite material provided by the present invention has excellent longitudinal and transverse tensile strengths and excellent wear resistance and stain resistance, and can be used to prepare flat films, high-gloss films, protective films, matte films and / or skin-friendly films for furniture building materials and having wear-resistant and / or stain-resistant properties. Specific embodiments

[0018] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a 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 those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0019] The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0020] In the present invention: PETG: purchased from Shanghai Huachang Trading Co., Ltd.; PCTG: model TX1001, purchased from Yihongdi New Material Technology (Shanghai) Co., Ltd.; PC: model PC-122, purchased from Qingdao Zhongxin Huamei Plastic Co., Ltd.; Poly(tert-butyl 4-vinylbenzoate): purchased from Hangzhou Yuhao Chemical Technology Co., Ltd.; PMMA: polymethyl methacrylate, purchased from Shanghai Huachang Trading Co., Ltd.; Coupling agent: neoalkoxy tris(dioctylpyrophosphatooxy)titanate, tetraisopropoxybis(dioctylphosphiteoxy)titanate, and isopropyl tris(dioctylpyrophosphatooxy)titanate are all purchased from Nanjing Nengde New Material Technology Co., Ltd.; Antioxidant: antioxidant DSTDP, antioxidant 1010, and antioxidant DLTDP are all purchased from Tianjin Lisheng Chemical Industry Co., Ltd.; Ultraviolet absorber: models UV-531 and UV-329, purchased from Tianjin Lisheng Chemical Industry Co., Ltd.; Silica: model J-181, ultrafine silica powder, particle size ≤ 2.6 μm, purchased from Jinchun Silicon Materials Co., Ltd.; Other raw materials are commercially available.

[0021] Preparation of PETG composite film: (1) Prepare materials: Accurately weigh PETG, PCTG, PC, poly(tert-butyl 4-vinylbenzoate), coupling agent, antioxidant, silica, and ultraviolet absorber respectively according to the mass ratio in Table 1; (2) Mix materials: First, place PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) in a dryer and dry at 70 °C for 12 h to obtain the dried base material. Then, add the dried base material, coupling agent, antioxidant, and ultraviolet absorber to a mixer in sequence, stir and mix for 30 min, and then add silica and continue to mix for 30 min to obtain a mixed material; (3) Granulate: Melt and extrude the mixed material obtained in step (2) on a twin-screw extruder, extrude and draw into strips under the conditions of an extrusion temperature of 250 °C and a screw speed of 200 r / min, then cool with water and cut into pellets to obtain the PETG composite masterbatch; (4) Molding: The PETG composite masterbatch was dried in an oven at 60 °C for 6 h, and then injection molded using an injection molding machine at an injection temperature of 270 °C to obtain a PETG composite film based on the PETG composite material described in step (3).

[0022] Table 1 Raw materials of the PETG composite material and their mass parts

[0023] Note: "-" in the table indicates no addition.

[0024] To verify the performance of the PETG composite material provided by the present invention and at the same time verify the necessity of each raw material in the PETG composite material, based on Composite Material 2 in Table 1, the default and replacement of raw materials were carried out on it, and the PETG composite film prepared therefrom was subjected to performance testing, as follows: Composite Material 4: On the basis of Composite Material 2, PCTG was missing, and the reduced mass parts were correspondingly distributed to PETG, PC, and poly(tert-butyl 4-vinylbenzoate) according to the mass ratio of PETG, PC, and poly(tert-butyl 4-vinylbenzoate) in Composite Material 2. See Table 1 for details, and the rest was the same as Composite Material 2; Composite Material 5: On the basis of Composite Material 2, PC was missing, and the reduced mass parts were correspondingly distributed to PETG, PCTG, and poly(tert-butyl 4-vinylbenzoate) according to the mass ratio of PETG, PCTG, and poly(tert-butyl 4-vinylbenzoate) in Composite Material 2. See Table 1 for details, and the rest was the same as Composite Material 2; Composite Material 6: On the basis of Composite Material 2, poly(tert-butyl 4-vinylbenzoate) was missing, and the reduced mass parts were correspondingly distributed to PETG, PCTG, and PC according to the mass ratio of PETG, PCTG, and PC in Composite Material 2. See Table 1 for details, and the rest was the same as Composite Material 2; Composite Material 7: On the basis of Composite Material 2, while keeping the total amount of PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) unchanged, the mass ratio among PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) was adjusted to 1:1:1:1. See Table 1 for details, and the rest was the same as Composite Material 2; Composite Material 8: On the basis of Composite Material 2, while keeping the total amount of PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) unchanged, the compounded mass ratio among PETG, PCTG, PC, and poly(tert-butyl 4-vinylbenzoate) was adjusted to 20:1:1:1. See Table 1 for details, and the rest was the same as Composite Material 2; Composite material 9: Based on composite material 2, poly (tert-butyl 4-vinylbenzoate) is replaced with PMMA (polymethyl methacrylate), and the rest is the same as composite material 2.

[0025] Performance Testing The PETG composite films prepared from the PETG composite materials 1-9 (corresponding to Examples 1-9 in Table 2, respectively) were subjected to the following tests, respectively. The test results are shown in Table 2.

[0026] Tensile strength test: Tested according to the method in GB / T 25255-2010; Anti-fouling performance test: Write on the PETG composite film with a Deli 6824 marker pen, wait for 1 minute, and then wipe it with a dust-free cloth and / or a dust-free cloth dipped in alcohol. If the handwriting can be wiped clean directly with a dust-free cloth, it is excellent; if it cannot be wiped clean with a dust-free cloth but can be wiped clean with a dust-free cloth dipped in alcohol, it is good; if it cannot be wiped clean with a dust-free cloth dipped in alcohol, it is poor; Wear resistance test: The wear resistance test was carried out according to the method in GB / T 1768-2006.

[0027] Table 2 Performance test results

[0028] Result analysis: It can be seen from the test data in Table 2 that the PETG composite films prepared by using the PETG composite materials provided by the present invention in Examples 1-3 have excellent longitudinal and transverse tensile strengths and excellent wear resistance and stain resistance; It can be seen from the results of Examples 4-9 that when any one of PCTG, PC and poly (tert-butyl 4-vinyl benzoate) is missing, or when the mass ratio of PETG, PCTG, PC and poly (tert-butyl 4-vinyl benzoate) is not within the mass ratio range provided in the present application, or when PMMA is replaced with poly (tert-butyl 4-vinyl benzoate), the overall performance of the composite material is greatly affected, indicating that the four raw materials of PETG, PCTG, PC and poly (tert-butyl 4-vinyl benzoate) play a key role in the formula in the present invention.

[0029] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A wear-resistant and stain-resistant PETG composite material, characterized in that: The PETG composite material comprises the following components by mass: PETG 40-50 parts; PCTG 30-36 parts; PC 20-28 copies; Poly(tert-butyl 4-vinylbenzoate) 10-15 parts; 1-3 parts of coupling agent; 6-12 parts of antioxidants; 2-3 parts of UV absorber; 40-60 parts of silicon dioxide.

2. The wear-resistant and stain-resistant PETG composite material according to claim 1, characterized in that: The coupling agent is selected from at least one of neoalkoxy tris(dioctyl pyrophosphate acyloxy) titanate, tetraisopropoxy bis(dioctyl phosphite acyloxy) titanate and isopropyl tris(dioctyl pyrophosphate acyloxy) titanate.

3. The wear-resistant and stain-resistant PETG composite material according to claim 1, characterized in that: The antioxidant is selected from at least one of antioxidant DSTDP, antioxidant 1010 and antioxidant DLTDP.

4. The wear-resistant and stain-resistant PETG composite material according to claim 1, characterized in that: The ultraviolet absorber is selected from ultraviolet absorber UV-531 and / or ultraviolet absorber UV-329.

5. The wear-resistant and stain-resistant PETG composite material according to claim 1, characterized in that: The silicon dioxide is ultrafine silicon dioxide powder with a particle size of ≤2.6 μm.

6. A method for preparing the PETG composite material according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: (1) Preparation of materials: weigh PETG, PCTG, PC, poly(tert-butyl 4-vinyl benzoate), coupling agent, antioxidant, silica and UV absorber according to the formula; (2) Mixing: First, PETG, PCTG, PC and poly (tert-butyl 4-vinyl benzoate) are placed in a dryer and dried at 70°C for 12 hours to obtain a dried base material. Then, the dried base material, coupling agent, antioxidant and ultraviolet absorber are added to the mixer in sequence and stirred for 30 minutes. Then, silica is added and the mixing is continued for 30 minutes to obtain a mixture. (3) Granulation: The mixed material uniformly mixed in step (2) is melt-extruded on a twin-screw extruder, and extruded into strands at an extrusion temperature of 250° C. and a screw speed of 200 r / min, and then water-cooled and pelletized to obtain the PETG composite material.

7. A wear-resistant and stain-resistant PETG composite film, characterized in that: The PETG composite film comprises the wear-resistant and stain-resistant PETG composite material according to any one of claims 1 to 5.

8. Use of the wear-resistant and stain-resistant PETG composite film according to claim 7 in preparing flat films, high-gloss films, protective films, matte films and / or skin-feel films for furniture and building materials with wear resistance and / or stain resistance.

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