PVC / PMMA material, its preparation method and application

Abstract

The application discloses a PVC / PMMA material, which comprises the following components in parts by weight: first PVC 78-92 parts; second PVC 5-15 parts; PMMA 25-40 parts; infrared reflection material 10-20 parts; stabilizer 0.5-3 parts; compatible agent 2-5 parts; and polytetrafluoroethylene 0.5-2.5 parts. The polymerization degree of the first PVC ranges from 900 to 1500, and the polymerization degree of the second PVC ranges from 400 to 700. The PVC / PMMA material is suitable for preparing automobile interior decoration.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a PVC / PMMA material, its preparation method, and its applications. Background Technology

[0002] Polyvinyl chloride (PVC) is one of the most widely used plastic materials. It has advantages such as low price, adjustable hardness, good flame retardancy, good chemical corrosion resistance, and excellent electrical properties. Therefore, it is widely used in all aspects of people's lives.

[0003] Although PVC material has many advantages, its adhesion to most existing paint technologies is relatively poor. Therefore, manufacturers generally need to treat the surface of PVC parts before painting, which adds an extra step. Furthermore, in automotive interior applications, exposure to direct sunlight in summer can cause PVC interior parts to become very hot, thus affecting the passenger experience.

[0004] Polymethyl methacrylate (PMMA), commonly known as acrylic, is an engineering plastic with high transparency, ultra-high weather resistance, and high hardness. Therefore, PMMA is often used in alloys with other resins. However, due to the poor compatibility between PMMA and PVC, the choice of compatibilizer significantly affects the alloy's performance. Chinese patent CN105504626A discloses a PMMA / PVC alloy material containing 4-60 parts PMMA and 2-40 parts PVC. This patented PMMA / PVC alloy material exhibits advantages such as weather resistance, scratch resistance, and high gloss. However, the adhesion of this PMMA / PVC alloy material to paint or coatings needs further improvement.

[0005] Some patents disclose methods to reduce infrared absorption in PVC materials by adding infrared-reflecting functional materials, thereby lowering the temperature after exposure to sunlight. However, there are no reports of PVC composite materials that simultaneously satisfy the requirements of surface paintability and reduced infrared absorption to meet the needs of automotive interiors. Summary of the Invention

[0006] The purpose of this invention is to overcome the above-mentioned technical defects and provide a PVC / PMMA material with good adhesion to paint or coating and low temperature rise after exposure to light, as well as its preparation method and application.

[0007] This invention is achieved through the following technical solution: A PVC / PMMA material, by weight, comprises the following components: First PVC, 78-92 parts; Second PVC, 5-15 parts; PMMA 25-40 servings; 10-20 parts of infrared reflective material; 2-5 parts compatibilizer; Stabilizer 0.5-3 parts; 0.5-2.5 parts of polytetrafluoroethylene; The degree of polymerization of the first PVC is in the range of 900-1500; The degree of polymerization of the second PVC is in the range of 400-700.

[0008] In the PVC / PMMA material of this invention, the weight ratio of PMMA to infrared reflective material ranges from (1.25-3):1. The weight ratio can be 3:1, 2.75:1, 2.5:1, 2.25:1, 2:1, 1.75:1, 1.5:1, 1.25:1, etc.

[0009] In the PVC / PMMA material of the present invention, the first PVC accounts for not less than 43 wt% of the total weight of the PVC / PMMA material.

[0010] The degree of polymerization of the second PVC can be any value among 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, and 700, or a range between the two.

[0011] The degree of polymerization of the first PVC can be any value among 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, and 1500, or a range between the two.

[0012] The test method for the degree of polymerization of PVC is the GPC method (refer to GB / T 36214.1-2018). After dissolving PVC in tetrahydrofuran, molecules with different degrees of polymerization are separated by passing them through a gel column, and the degree of polymerization is calculated based on the molecular weight distribution.

[0013] The compatibilizer is selected from at least one of ABS-g-MAH (maleic anhydride grafted ABS), PE-g-MAH (maleic anhydride grafted polyethylene), PP-g-MAH (maleic anhydride grafted polypropylene), and POE-g-MAH (maleic anhydride grafted POE).

[0014] The infrared reflective material is selected from at least one of metal oxide pigments, such as chromium iron oxide, chrome green black, titanium dioxide, zirconium oxide, cobalt blue, and nickel titanium yellow.

[0015] The present invention does not limit the average particle size of the infrared reflective material, which can range from 50 to 100 nm. Specifically, it can be any value among 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, and 100 nm, or a range between the two. The average particle size is measured by a laser particle size analyzer.

[0016] Preferably, the degree of polymerization of the second PVC is in the range of 500-650.

[0017] The stabilizer is selected from stearate metal salt stabilizers, and the stearate metal salt stabilizer is selected from at least one of zinc stearate stabilizer and calcium stearate stabilizer.

[0018] The present invention does not limit the average particle size of PTFE, which can be 1-50 micrometers. Specifically, it can be any value or a range between 1 micrometer, 5 micrometer, 10 micrometer, 15 micrometer, 20 micrometer, 25 micrometer, 30 micrometer, 35 micrometer, 40 micrometer, 45 micrometer, and 50 micrometer.

[0019] Those skilled in the art can choose whether to add 0-2 parts of lubricant according to actual needs. The processing lubricant is one or more of the following: stearic acid lubricant, polyethylene lubricant, ester lubricant, paraffin lubricant, and amide lubricant.

[0020] Those skilled in the art can choose whether to add 0-30 parts of filler according to actual needs. The filler may be talc, calcium silicate, etc.

[0021] The preparation method of PVC / PMMA material includes the following steps: mixing first PVC, second PVC and stabilizer evenly, heating to 80-110℃ and mixing evenly with other components, and then granulating through an extruder with an extruder temperature range of 110-180℃ to obtain PVC / PMMA material.

[0022] The present invention also includes an automotive interior component containing the above-mentioned PVC / PMMA material.

[0023] The present invention has the following beneficial effects: This invention utilizes the differences in compatibility between PMMA, PTFE, and the resin matrix to create a composite material surface with a certain amount of PMMA and PTFE. This increases surface roughness, effectively improving the compatibility of the surface with paints or coatings. Simultaneously, the presence of PMMA (presumably due to the better compatibility between near-infrared reflective materials and PMMA) causes the infrared reflective material to disperse more readily on the surface, improving the near-infrared radiation reflection efficiency. The PVC / PMMA material of this invention is suitable for manufacturing automotive interior trim. Detailed Implementation

[0024] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0025] The raw materials used in this invention are sourced from the following sources: First PVC-1: Degree of polymerization is 1320, PVC TG-1300, Tosoh Chemical Co., Ltd.; First PVC-2: Degree of polymerization is 1010, PVC TL-1000, Bohai LG Chemical Co., Ltd.; Second PVC-1: Degree of polymerization is 410, Zhongyuan Chemical PVC S400; Second PVC-2: Degree of polymerization is 500, Formosa Chemicals PVC S-50; Second PVC-3: Degree of polymerization is 620, Formosa Plastics Chemical PVC S-57; Second PVC-4: Degree of polymerization is 690, Bohai LG PVC TL-700; Second PVC-5: Degree of polymerization is 930, Zheng Yuan Chemical PVC SG-6; PMMA-1: Melt index approximately 25 g / 10 min (230℃, 3.8 kg), CP-41, Lucaite; PMMA-2: Melt index approximately 1.8 g / 10 min (230℃, 3.8 kg), CM-205, Chi Mei; Polytetrafluoroethylene was purchased from Xijia Chemical, and raw materials with specific particle sizes were obtained through screening. Polytetrafluoroethylene A: Average particle size is approximately 1.2 micrometers; Polytetrafluoroethylene B: The average particle size is approximately 48.3 micrometers.

[0026] ABS-g-MAH: KT-2H, Shenyang Ketong Plastics Co., Ltd.; POE-g-MAH: Energy Light, N406; Iron chromium oxide: Huasheng Paint & Pigment Co., Ltd., KFBK95, average particle size 32 microns; Chrome Green Black: Hunan Jufa Technology Co., Ltd., KFB17, average particle size is 30 micrometers; Zinc stearate stabilizer: brand name RUP-110C, purchased from Adico Investment Co., Ltd.; Lubricant: 316A.

[0027] The preparation method of the PVC / PMMA material in the examples and comparative examples includes the following steps: mixing the first PVC, the second PVC, and the stabilizer evenly, heating to 80-110°C, and then mixing evenly with other components (PMMA, infrared reflective material, maleic anhydride graft compatibilizer, polytetrafluoroethylene, etc.), and then granulating through an extruder. The extruder temperature range is 110-180°C to obtain the PVC / PMMA material.

[0028] Test methods: (1) Paint adhesion test method: The PVC / PMMA material was injection molded into a 100mm*100mm*2mm sample and sprayed with dry PVC paint 767 (purchased from Wan Hui Coatings Co., Ltd.). Five straight scratches of 50mm length were made on the sample at 10mm intervals horizontally and vertically, with the scratches reaching the surface of the sample. Then, observe whether there is any cracking or peeling of paint (or coating) at the scratches, especially at the intersection of horizontal and vertical scratches. If there is no cracking or peeling, it indicates good adhesion. If there is cracking, it indicates poor adhesion. If the paint (or coating) is peeled off, it indicates very poor adhesion. Specifically, the adhesion test results are divided into five levels: good, cracked, obviously cracked, severely cracked, and flaky peeling. Among them, good means no cracking, cracked means there are cracks less than 0.5mm in length on both sides of the scratch, obviously cracked means the cracks on both sides of the scratch are longer than 1mm but do not cause paint peeling, severely cracked means the cracks on both sides of the scratch are longer than 1.5mm but do not cause paint peeling, and severely cracked means there are small pieces of paint peeling off.

[0029] (2) Temperature rise under light: PVC / PMMA material was injection molded into a 100mm*100mm*2mm sample. According to the standard test method of ASTM D4803:2018 for predicting the heat accumulation effect in polyvinyl chloride building products, the sample was continuously irradiated under the light source required by the standard for 15 minutes and the temperature was measured: the surface temperature was required to be <100℃.

[0030] Table 1: Weight parts and test results of each component in the PVC / PMMA material of the example First PVC-1 80 85 85 85 85 85 First PVC-2 90 Second PVC-1 15 10 5 10 Second PVC-2 10 Second PVC-3 10 Second PVC-4 10 PMMA-1 25 30 30 30 30 30 PMMA-2 40 Iron oxide chromium 10 15 20 15 15 15 Chrome Green Black 15 ABS-g-MAH 3 5 3 3 3 3 POE-g-MAH 2 Zinc stearate stabilizer 0.5 1.5 3 1.5 1.5 1.5 1.5 Polytetrafluoroethylene A 0.5 1 1 1 1 1 Polytetrafluoroethylene B 2.5 lubricant / 0.5 0.5 0.5 0.5 0.5 0.5 Paint adhesion test good good good good good good good Surface temperature, °C 93 87 85 80 77 82 88 As can be seen from the examples, the PVC / PMMA material of the present invention has the advantages of good surface paint spraying performance and low temperature rise after exposure to light; further, as can be seen from Examples 2 / 4 / 5 / 6, the examples of the second PVC with preferred polymerization degree have even less temperature rise after exposure to light.

[0031] Table 2: Weight parts of each component and test results of comparative PVC / PMMA materials First PVC-1 85 95 75 85 85 85 85 Second PVC-1 0 20 10 10 10 10 Second PVC-5 10 PMMA-1 30 30 30 15 50 30 30 Iron oxide chromium 15 15 15 15 15 15 15 ABS-g-MAH 3 3 3 3 3 0 8 Zinc stearate stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Polytetrafluoroethylene A 1 1 1 1 1 1 1 lubricant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Paint adhesion test Obvious cracks sheet-like peeling There are cracks There are cracks Severe cracking sheet-like peeling Severe cracking Surface temperature, °C 108 117 102 107 114 122 112 As can be seen from Comparative Example 1, when the polymerization rate of the second PVC is too high, the surface paint spraying performance is insufficient, and the surface temperature rises too much after irradiation due to poor dispersion of infrared reflective material.

[0032] As can be seen from Comparative Example 2 / 3, when there is no second PVC or the content is too high, the surface paint spraying performance is poor, and the surface temperature rises too much after irradiation due to poor dispersion of infrared reflective material.

[0033] As can be seen from Comparative Example 4 / 5, when the weight ratio of PMMA to near-infrared reflective material is not within the range of this invention, the near-infrared reflective material has poor dispersion in PMMA, resulting in excessive temperature rise after surface illumination.

[0034] As can be seen from Comparative Example 6 / 7, when ABS-g-MAH is not present or its content is too high, the surface paint spraying performance is poor, and the surface temperature rises too much after irradiation due to poor dispersion of infrared reflective materials.

Claims

1. A PVC / PMMA material, characterized in that, By weight, it includes the following components: First PVC, 78-92 parts; Second PVC, 5-15 parts; PMMA 25-40 servings; 10-20 parts of infrared reflective material; 2-5 parts compatibilizer; Stabilizer 0.5-3 parts; 0.5-2.5 parts of polytetrafluoroethylene; The degree of polymerization of the first PVC is in the range of 900-1500; The degree of polymerization of the second PVC is in the range of 400-700.

2. The PVC / PMMA material according to claim 1, characterized in that, The weight ratio of PMMA to infrared reflective material ranges from (1.25-3):

1.

3. The PVC / PMMA material according to claim 1, characterized in that, The compatibilizer is selected from at least one of ABS-g-MAH, PE-g-MAH, PP-g-MAH, and POE-g-MAH.

4. The PVC / PMMA material according to claim 1, characterized in that, The infrared reflective material is selected from metal oxide pigments, and the metal oxide pigments are selected from at least one of iron chromium oxide, chrome green black, titanium dioxide, zirconium oxide, cobalt blue, and nickel titanium yellow.

5. The PVC / PMMA material according to claim 1, characterized in that, The infrared reflective material has an average particle size of 50-100 nm.

6. The PVC / PMMA material according to claim 1, characterized in that, The degree of polymerization of the second PVC is in the range of 500-650.

7. The PVC / PMMA material according to claim 1, characterized in that, The average particle size range of polytetrafluoroethylene is 1-50 micrometers by weight.

8. The PVC / PMMA material according to claim 1, characterized in that, The product also includes 0-2 parts by weight of a lubricant, wherein the lubricant is one or a mixture of stearic acid lubricants, polyethylene lubricants, ester lubricants, paraffin lubricants, and amide lubricants.

9. A method for preparing the PVC / PMMA material according to any one of claims 1-8, characterized in that, The process includes the following steps: mixing the first PVC, the second PVC, and the stabilizer evenly, then mixing them evenly with other components, and finally granulating them through an extruder to obtain PVC / PMMA material.

10. An automotive interior component, characterized in that, Contains the PVC / PMMA material as described in any one of claims 1-8.