High-stability anti-aging PVC color masterbatch and application thereof in automobile interior decoration

Abstract

The application relates to a high-stability anti-aging PVC color master batch and application thereof in automobile interior decoration, and the components of the high-stability anti-aging PVC color master batch include PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment and additive; wherein the modified fumed silica is obtained by the following steps: firstly, reacting pentaerythritol and fumaric acid to obtain a modifier; secondly, reacting hydroxylated fumed silica and KH570 to obtain an intermediate product; and finally, reacting the modifier and the intermediate product; the modified rare earth salt is obtained by reacting pentaerythritol, fumaric acid and lanthanum acetate. The modified fumed silica limits the migration of VOC, improves the compatibility of components, in addition, the fumed silica has a porous structure, can adsorb VOC, and reduces the migration and volatilization of VOC. The modified rare earth salt can also limit the migration of VOC, improve the compatibility of components, inhibit the continuous and rapid degradation of PVC, and improve the stability.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a highly stable and anti-aging PVC color masterbatch and its application in automotive interiors. Background Technology

[0002] PVC masterbatch, also known as polyvinyl chloride masterbatch, is a pre-dispersed pigment concentrate specifically designed for coloring polyvinyl chloride (PVC) resin. When producing colored PVC products (such as pipes, films, artificial leather, and automotive interiors), it is not necessary to add pigment powder directly to the PVC powder; instead, this masterbatch is added directly. Using pigment powder directly would introduce many problems, such as uneven dispersion, dust pollution, measurement difficulties, and color deviation.

[0003] A typical PVC masterbatch usually consists of the following parts: Pigment: This is the core of the masterbatch, providing the desired color. It can be an organic pigment, inorganic pigment, or dye; Carrier resin: Usually a resin with good compatibility with PVC. Its role is to carry the pigment and blend well with the PVC matrix resin during processing; Dispersant: Helps pigment particles to be evenly dispersed in the carrier resin and prevents them from agglomerating; Additives: Added as needed, such as antioxidants, light stabilizers, plasticizers, etc., to improve the performance of the masterbatch or the final product.

[0004] Compared to pigments, PVC masterbatches offer the following advantages: Excellent dispersibility: Pigments undergo high-temperature, high-shear dispersion during masterbatch production, making secondary dispersion during PVC processing easier and more uniform, resulting in no dust pollution, stable color, and minimal batch-to-batch color variation; Convenient and environmentally friendly: Granular form facilitates automatic metering and conveying, eliminating dust and improving the workshop environment while reducing waste and time spent on cleaning and color changes; Enhanced product quality: Uniform dispersion reduces stress concentration points caused by pigment agglomeration, helping to maintain or even improve the mechanical properties of products; Flexible and efficient color matching: Standard masterbatches can be purchased directly for color matching, or customized color matching services can be provided by the masterbatch manufacturer, simplifying the color matching process for production enterprises; Potentially lower overall cost: Although the unit price of masterbatch is higher than that of powdered pigments, considering reduced waste, increased production efficiency, more stable yield, and environmental costs, the overall cost is often more advantageous.

[0005] Currently, PVC masterbatch has a wide range of applications, including building materials, wires and cables, daily consumer goods, industrial products, and specialty products. However, some problems still exist, such as: excessive VOC release, which can directly irritate the eyes, nose, and throat, causing symptoms such as tearing and coughing; for vehicles, it can deteriorate the air quality inside the vehicle, seriously affecting passenger comfort and brand image, and accelerating material aging; and insufficient stability, especially at high temperatures, where products may develop color spots, streaks, black spots, or the overall color may darken or become dull, deviating significantly from the expected color standard and resulting in substandard product appearance.

[0006] In conclusion, it is necessary to develop a new technical solution to address the shortcomings of existing technologies. Summary of the Invention

[0007] This invention provides a highly stable and anti-aging PVC masterbatch and its application in automotive interiors. The composition of the highly stable and anti-aging PVC masterbatch includes PVC resin, ABS resin, modified fumed silica, modified rare earth salts, pigments, and additives. The modified fumed silica and modified rare earth salts are incorporating active groups, which improves the compatibility and interaction of the components, enhances the various properties of the product, and has good application prospects.

[0008] The purpose of this invention is to provide a highly stable and anti-aging PVC color masterbatch, wherein the highly stable and anti-aging PVC color masterbatch comprises the following components in parts by weight: 40-60 parts of PVC resin 10-15 parts of ABS resin 4-8 parts of modified fumed silica 4-8 parts of modified rare earth salt 30-50 parts of pigment 4-10 parts of auxiliary agent; The modified fumed silica is obtained by first reacting pentaerythritol and fumaric acid to obtain a modifier, then reacting hydroxylated fumed silica and KH570 to obtain an intermediate product, and finally reacting the modifier and the intermediate product. The modified rare earth salt is obtained by reacting pentaerythritol, fumaric acid, and lanthanum acetate.

[0009] Furthermore, the additive is selected from one or more of stabilizers, dispersants, toughening agents, and weathering agents.

[0010] Furthermore, the particle size of the fumed silica is 5-50 nm.

[0011] Another object of the present invention is to provide a method for preparing the highly stable and anti-aging PVC masterbatch, the method comprising the following steps: S1. Under an inert atmosphere, pentaerythritol, fumaric acid, and catalyst are mixed and heated and stirred to react, thereby obtaining the modifier. S2. Hydroxylated fumed silica is obtained. S3. The hydroxylated fumed silica and KH570 are mixed and heated and stirred to react, yielding an intermediate product; S4. Under an inert atmosphere, the modifier, intermediate product and initiator are mixed and heated and stirred to react, thereby obtaining modified fumed silica. S5. The modifier and lanthanum acetate are mixed and heated and stirred to react, thereby obtaining modified rare earth salts. S6. The PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment, and additives are mixed, heated and stirred, and extruded and granulated to obtain the highly stable anti-aging PVC masterbatch.

[0012] Further, in step S1, the mass ratio of pentaerythritol to fumaric acid is (25-30):(8-14).

[0013] Further, in step S3, the mass ratio of the hydroxylated fumed silica to KH570 is (1-3):(1-5).

[0014] Furthermore, in step S3, the heating temperature is 40-60°C.

[0015] Further, in step S4, the mass ratio of the modifier to the intermediate product is (1-4):(1-4).

[0016] Further, in step S5, the mass ratio of the modifier to lanthanum acetate is (1-3):(1-2).

[0017] Another object of the present invention is to provide the application of the highly stable and anti-aging PVC color masterbatch in automotive interiors.

[0018] The present invention has the following beneficial effects: This invention provides a highly stable, anti-aging PVC masterbatch and its application in automotive interiors. The highly stable, anti-aging PVC masterbatch comprises PVC resin, ABS resin, modified fumed silica, modified rare earth salts, pigments, and additives. The modified fumed silica is obtained by first blending pentaerythritol and fumaric acid and undergoing an esterification reaction to obtain a modifier, then reacting hydroxylated fumed silica with KH570 to obtain an intermediate product, and finally polymerizing the modifier and the intermediate product. The modified rare earth salt is obtained by first blending pentaerythritol and fumaric acid and undergoing an esterification reaction to obtain a modifier, then blending the modifier with lanthanum acetate.

[0019] The modified fumed silica of this invention incorporates hydroxyl and ester groups. The hydroxyl groups can interact with the other components, particularly with VOCs, thus limiting VOC migration. The ester groups can improve the compatibility of the components, promote uniform distribution of the components, and prevent component aggregation that could lead to a decrease in product performance. Furthermore, the fumed silica has a porous structure, which can adsorb VOCs and reduce VOC migration and volatilization.

[0020] The modified rare earth salt of this invention introduces hydroxyl, ester, and metal alkoxy groups; the introduced hydroxyl and ester groups effectively limit the migration of VOCs, while improving compatibility, promoting uniform distribution, and enhancing the binding effect between different components; the oxygen atom of the metal alkoxy group can attack the carbon atom of allyl chloride generated by the thermal degradation of PVC, thereby inhibiting the continuous and rapid degradation of PVC and improving stability. Detailed Implementation

[0021] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0022] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0023] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0024] The embodiments of the present invention use the following raw materials: PVC resin, grade S1300, was purchased from Ningbo Yushun Plastics Co., Ltd.

[0025] ABS resin, purchased from Jiangsu Leien Environmental Protection Technology Co., Ltd.

[0026] Catalyst, p-toluenesulfonic acid.

[0027] Water-removing agent, cyclohexane.

[0028] Fumed silica with a particle size of 5-50 nm.

[0029] The pigment is made by mixing titanium dioxide and iron oxide red in a mass ratio of 1:3; wherein the titanium dioxide has a particle size of 100-200nm.

[0030] The stabilizer is a mixture of zinc stearate, calcium stearate, and phosphite (brand name F618, purchased from Greenlink (Jining) Chemical Technology Co., Ltd.) in a mass ratio of 4:4:5.

[0031] Dispersant, vinyl bis-stearamide.

[0032] Toughening agent, brand name B-564, purchased from Guangzhou Yinuo Chemical Technology Co., Ltd.

[0033] The weathering agent is a mixture of antioxidant, light stabilizer and ultraviolet absorber in a mass ratio of 2:1:1. Among them, the antioxidant brand AT-76 was purchased from Wuhan Jinqu New Materials Co., Ltd., the light stabilizer brand UV-2908 was purchased from Jiangsu Xinluda Polymer Materials Co., Ltd., and the ultraviolet absorber brand UV531 was purchased from Nanjing Milan Chemical Co., Ltd.

[0034] The initiator is ammonium persulfate.

[0035] The emulsifier is Span 40.

[0036] Example 1 A highly stable and anti-aging PVC color masterbatch, wherein the highly stable and anti-aging PVC color masterbatch comprises the following components in parts by weight: 60 parts of PVC resin 15 parts ABS resin 8 parts of modified fumed silica 8 parts of modified rare earth salt 50 parts pigment stabilizer 2 parts 2 parts dispersant 2 parts toughening agent 2 parts weather resistant agent; The preparation method of the highly stable and anti-aging PVC masterbatch includes the following steps: S1. Under a nitrogen atmosphere, pentaerythritol, fumaric acid, catalyst, and dehydrating agent are mixed in a mass ratio of 27:11:0.3:30, heated to 160°C and stirred under reflux for 2 hours, washed and dried to obtain the modifier. S2. Immerse fumed silica in a 33wt% hydrogen peroxide solution, heat to 105℃ and stir for 5 hours, filter, wash and dry to obtain hydroxylated fumed silica. S3. Using ethanol and water in a volume ratio of 1:1 as solvents, the hydroxylated fumed silica and KH570 are mixed in a mass ratio of 1:1.5, heated to 50°C and stirred for 24 hours, filtered, washed and dried to obtain the intermediate product. S4. Using water as a solvent, under a nitrogen atmosphere, the modifier, intermediate product, initiator, and emulsifier are mixed in a mass ratio of 1.5:3:0.05:0.2, heated to 80°C and stirred for 4 hours, filtered, washed, and dried to obtain modified fumed silica. S5. Using anhydrous ethanol as a solvent, the modifier and lanthanum acetate are mixed at a mass ratio of 2:1, heated to 135°C and stirred for 4 hours, the solvent is removed and the mixture is dried to obtain the modified rare earth salt. S6. The PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment and other components are mixed together, heated to 190°C and stirred, stirred and cooled to 70°C, and allowed to cool naturally. The mixture is then extruded and granulated using a conical twin-screw extruder (the working temperature of the conical twin-screw extruder is 150°C) to obtain the highly stable anti-aging PVC masterbatch.

[0037] Example 2 A highly stable and anti-aging PVC color masterbatch, wherein the highly stable and anti-aging PVC color masterbatch comprises the following components in parts by weight: 50 parts of PVC resin 13 parts of ABS resin 6 parts of modified fumed silica 6 parts of modified rare earth salt 40 parts pigment stabilizer 2 parts 2 parts dispersant 2 parts toughening agent 2 parts weather resistant agent; The preparation method of the highly stable and anti-aging PVC masterbatch includes the following steps: S1. Under a nitrogen atmosphere, pentaerythritol, fumaric acid, catalyst, and dehydrating agent are mixed in a mass ratio of 27:11:0.3:30, heated to 160°C and stirred under reflux for 2 hours, washed and dried to obtain the modifier. S2. Immerse fumed silica in a 33wt% hydrogen peroxide solution, heat to 110℃ and stir for 5 hours, filter, wash and dry to obtain hydroxylated fumed silica. S3. Using ethanol and water in a volume ratio of 1:1 as solvents, the hydroxylated fumed silica and KH570 are mixed in a mass ratio of 1:1.5, heated to 50°C and stirred for 24 hours, filtered, washed and dried to obtain the intermediate product. S4. Using water as a solvent, under a nitrogen atmosphere, the modifier, intermediate product, initiator, and emulsifier are mixed in a mass ratio of 1.5:3:0.05:0.2, heated to 80°C and stirred for 4 hours, filtered, washed, and dried to obtain modified fumed silica. S5. Using anhydrous ethanol as a solvent, the modifier and lanthanum acetate are mixed at a mass ratio of 2:1, heated to 135°C and stirred for 4 hours, the solvent is removed and the mixture is dried to obtain the modified rare earth salt. S6. The PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment and other components are mixed together, heated to 190°C and stirred, stirred and cooled to 70°C, and allowed to cool naturally. The mixture is then extruded and granulated using a conical twin-screw extruder (the working temperature of the conical twin-screw extruder is 150°C) to obtain the highly stable anti-aging PVC masterbatch.

[0038] Example 3 A highly stable and anti-aging PVC color masterbatch, wherein the highly stable and anti-aging PVC color masterbatch comprises the following components in parts by weight: 40 parts of PVC resin 10 parts ABS resin 5 parts of modified fumed silica 5 parts of modified rare earth salt 30 parts pigment stabilizer 2 parts 2 parts dispersant 2 parts toughening agent 2 parts weather resistant agent; The preparation method of the highly stable and anti-aging PVC masterbatch includes the following steps: S1. Under a nitrogen atmosphere, pentaerythritol, fumaric acid, catalyst, and dehydrating agent are mixed in a mass ratio of 27:11:0.3:30, heated to 160°C and stirred under reflux for 2 hours, washed and dried to obtain the modifier. S2. Immerse fumed silica in a 33wt% hydrogen peroxide solution, heat to 105℃ and stir for 5 hours, filter, wash and dry to obtain hydroxylated fumed silica. S3. Using ethanol and water in a volume ratio of 1:1 as solvents, the hydroxylated fumed silica and KH570 were mixed in a mass ratio of 1:1.5, heated to 60°C and stirred for 24 hours, filtered, washed and dried to obtain the intermediate product. S4. Using water as a solvent, under a nitrogen atmosphere, the modifier, intermediate product, initiator, and emulsifier are mixed in a mass ratio of 1.5:3:0.05:0.2, heated to 80°C and stirred for 4 hours, filtered, washed, and dried to obtain modified fumed silica. S5. Using anhydrous ethanol as a solvent, the modifier and lanthanum acetate are mixed at a mass ratio of 2:1, heated to 135°C and stirred for 4 hours, the solvent is removed and the mixture is dried to obtain the modified rare earth salt. S6. The PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment and other components are mixed together, heated to 190°C and stirred, stirred and cooled to 70°C, and allowed to cool naturally. The mixture is then extruded and granulated using a conical twin-screw extruder (the working temperature of the conical twin-screw extruder is 150°C) to obtain the highly stable anti-aging PVC masterbatch.

[0039] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that step S4 is deleted and the modified fumed silica is replaced with an intermediate product, while the remaining components and preparation methods are the same as in Example 1.

[0040] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that step S5 is deleted and the modified rare earth salt is replaced with lanthanum acetate. The remaining components and preparation methods are the same as in Example 1.

[0041] Test case The products prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests.

[0042] Test method: Anti-aging: The anti-aging performance is tested in accordance with 6.12 of GB / T 8815-2008. The thermo-oxidative aging temperature is 115℃ and the aging time is 240h.

[0043] Stability: PVC masterbatch samples were placed in a hot air drying oven and treated at 180°C for 100 minutes. The stability of the samples was evaluated by comparing the colors of all samples.

[0044] Color dispersion: This is determined by comparing the uniformity of the surface color distribution of PVC color masterbatch samples.

[0045] Odor rating: Tested according to PV 3900-2000. The higher the rating, the more pronounced the odor.

[0046] The test results are shown in Table 1.

[0047] Table 1 Test Results As can be seen from Table 1, the results of Examples 1-3 are better than those of Comparative Examples 1-2. This is because the intermediate product of Comparative Example 1 was not modified with a modifier, which reduced the compatibility of the components and weakened their interaction, resulting in a decrease in product performance. Similarly, Comparative Example 2 was not modified with lanthanum acetate, which also reduced the compatibility of the components and weakened their interaction, resulting in a decrease in product performance.

[0048] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0049] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A highly stable and anti-aging PVC color masterbatch, characterized in that, The highly stable, anti-aging PVC color masterbatch comprises the following components in parts by weight: 40-60 parts of PVC resin 10-15 parts of ABS resin 4-8 parts of modified fumed silica 4-8 parts of modified rare earth salt 30-50 parts of pigment 4-10 parts of auxiliary agent; The modified fumed silica is obtained by first reacting pentaerythritol and fumaric acid to obtain a modifier, then reacting hydroxylated fumed silica and KH570 to obtain an intermediate product, and finally reacting the modifier and the intermediate product. The modified rare earth salt is obtained by reacting pentaerythritol, fumaric acid, and lanthanum acetate.

2. The high-stability, anti-aging PVC color masterbatch according to claim 1, characterized in that, The additives are selected from one or more of stabilizers, dispersants, toughening agents, and weather-resistant agents.

3. The high-stability, anti-aging PVC color masterbatch according to claim 1, characterized in that, The particle size of the fumed silica is 5-50 nm.

4. The method for preparing the highly stable anti-aging PVC color masterbatch according to any one of claims 1-3, characterized in that, The preparation method of the highly stable and anti-aging PVC masterbatch includes the following steps: S1. Under an inert atmosphere, pentaerythritol, fumaric acid, and catalyst are mixed and heated and stirred to react, thereby obtaining the modifier. S2. Hydroxylated fumed silica is obtained. S3. The hydroxylated fumed silica and KH570 are mixed and heated and stirred to react, yielding an intermediate product; S4. Under an inert atmosphere, the modifier, intermediate product and initiator are mixed and heated and stirred to react, thereby obtaining modified fumed silica. S5. The modifier and lanthanum acetate are mixed and heated and stirred to react, thereby obtaining modified rare earth salts. S6. The PVC resin, ABS resin, modified fumed silica, modified rare earth salt, pigment, and additives are mixed, heated and stirred, and extruded and granulated to obtain the highly stable anti-aging PVC masterbatch.

5. The method for preparing the highly stable anti-aging PVC color masterbatch according to claim 4, characterized in that, In step S1, the mass ratio of pentaerythritol to fumaric acid is (25-30):(8-14).

6. The method for preparing the highly stable anti-aging PVC color masterbatch according to claim 4, characterized in that, In step S3, the mass ratio of the hydroxylated fumed silica to KH570 is (1-3):(1-5).

7. The method for preparing the highly stable anti-aging PVC masterbatch according to claim 4, characterized in that, In step S3, the heating temperature is 40-60℃.

8. The method for preparing the highly stable anti-aging PVC color masterbatch according to claim 4, characterized in that, In step S4, the mass ratio of the modifier to the intermediate product is (1-4):(1-4).

9. The method for preparing the highly stable anti-aging PVC masterbatch according to claim 4, characterized in that, In step S5, the mass ratio of the modifier to lanthanum acetate is (1-3):(1-2).

10. The application of the high-stability, anti-aging PVC color masterbatch according to any one of claims 1-3 in automotive interiors.

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