CN111732798A - Low-gloss PVC material for automobile external water cut surface and preparation method thereof - Google Patents
Low-gloss PVC material for automobile external water cut surface and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K2201/00—Specific properties of additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08K2201/00—Specific properties of additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a low-gloss PVC material for an automobile external water cut surface and a preparation method thereof, belonging to the field of high polymer material processing. The invention selects the resin powder with high polymerization degree to be compounded with the extinction resin powder with low polymerization degreeCaCO of very different particle sizes3Screening of the compound mixture and other low-gloss raw material components, and fully blending and plasticizing in an internal mixer, so that the prepared PVC finished product has excellent performance, good tensile state elongation at break state, low gloss and high material practicability, and various appearance problems caused by high gloss of the traditional modified PVC material are solved on the premise of not reducing the mechanical property of the original modified PVC material.
Description
Technical Field
The invention relates to a low-gloss PVC material for an automobile external water cut surface and a preparation method thereof, belonging to the field of high polymer material processing.
Background
At present, the outer water cutting products in the automobile market are generally formed by co-extruding two or three materials of modified PP (polypropylene), PVC (polyvinyl chloride) and TPV (thermoplastic vulcanizate) through an extruder, the modified PP materials are generally used for producing outer water cutting frameworks, the strength and the toughness of the products are improved, and the PVC and TPV are used for producing the surfaces and the edges of the outer water cutting. The modified PVC material has the advantages of good heat resistance and weather resistance and high elasticity, simple production process and low material cost, and is generally used for automobile external water cut surface materials at present.
In order to meet the processing performance of products, a plasticizer, a lubricant and other processing aids are used for improving the plasticizing capacity of the materials, meanwhile, the glossiness of the materials can be improved, appearance defects are prone to occurring when the materials are used for products with low requirements on glossiness, especially on the surface of an automobile outer water cut, the appearance matching performance of the outer water cut and other part products can be directly influenced due to overhigh glossiness, the weather resistance of the products can be reduced due to higher glossiness, the surface glossiness of the products is greatly changed after long-term use, and finally the service life of the automobile can be reduced.
Disclosure of Invention
Aiming at the existing problems of the PVC material, the invention provides a low-gloss PVC material for the surface of an automobile outside water cut product, which is used for reducing the gloss of the surface of the outside water cut product and solving the technical problem that the traditional modified PVC material has high gloss and causes the product to shine.
The purpose of the invention is realized by the following technical scheme:
a low-gloss PVC material for an automobile external water cutting surface comprises the following raw materials in parts by weight: PVC resin powder: 60-85 parts; PVC matting resin powder: 15-40 parts; 40-50 parts of a plasticizer; calcium zinc stabilizer: 2-5 parts; CaCO3Compounding a mixture: 15-25 parts; carbon black color paste: 2-4 parts; PE wax: 0.3-0.6 part; antioxidant: 0.1-0.5 part; anti-ultraviolet agent: 0.3-0.6 part; nitrile rubber: 1-10 parts.
According to the invention, the resin powder with high polymerization degree and the PVC extinction resin powder with low polymerization degree are selected for compounding, so that the raw materials are high in processing viscosity and good in mechanical property, and the glossiness of the base material can be greatly reduced. By different granulesCaCO of diameter3The screening of the compound mixture and other low-gloss raw material components not only maintains the better mechanical property of the material, but also reduces the gloss of the material, and the existence of the nitrile rubber component can improve the toughness and elasticity of the material on one hand, and on the other hand, can play a certain positive role in reducing the gloss of the PVC resin powder due to the low gloss of the nitrile rubber component.
In the low-gloss PVC material for the automobile external water-cut surface, the PVC resin powder is S-80, and the polymerization degree is 1700-1900. The high molecular weight of the material ensures that the base material has high processing viscosity, good mechanical property and lower glossiness.
In the above low gloss PVC material for automobile exterior water cut surfaces, the plasticizer is isoheptyl isosorbide. The addition of the diheptyl isosorbide can effectively improve the flexibility and the elongation at break of PVC, and because the diheptyl isosorbide and PVC have strong intermolecular force, a crystallization area in PVC resin can be effectively dissolved, so that the movement capacity of PVC molecules is improved, the free volume is increased, a better plasticizing effect is shown, and the toughness of PVC is improved.
In the low-gloss PVC material for the external water-cut surface of the automobile, CaCO3The compound mixture is nano CaCO with the grain diameter of 10-100nm3With ordinary CaCO having a particle diameter of 1000nm or more3Mixing to obtain the final product.
In the low-gloss PVC material for the external water-cut surface of the automobile, the nano CaCO3With ordinary CaCO3The mass ratio of (A) to (B) is 6-8: 1. CaCO of large particle size3CaCO with small grain diameter and capable of greatly reducing glossiness of material3The dispersion in PVC resin powder can be improved, the good mechanical property and the fine degree of appearance of the material are provided, the good mechanical property of the material is maintained, and the glossiness of the material is reduced.
In the low-gloss PVC material for the automobile external water cutting surface, the anti-ultraviolet agent is nano TiO2And ZnO. The PVC movement is limited due to the acting force between PVC molecules, and the nano TiO2And ZnO canSo as to play a certain spacing role, can reduce the mutual pinning state among PVC molecules, and the nano TiO2And a crosslinked three-dimensional network is easily formed in the matrix with ZnO, and when the PVC material is stressed, the nanoparticles enable the matrix not to be easily subjected to destructive cracking through the crosslinked network.
In the low-gloss PVC material for the automobile external water cutting surface, the nano TiO2The mass ratio of the ZnO to the ZnO is 1: 3.5-4.0. Nano TiO 22The proportion of ZnO to the nano particles mainly influences the crosslinking network of the nano particles in the PVC material, and the large crosslinking network can be formed only by adding the nano particles into the PVC material in a proper proportion. When excessive nano TiO2Or rod-like ZnO and spherical TiO are hardly formed in the presence of ZnO2Effect of intercrossing and spacing, surplus nano TiO2Or ZnO is easy to agglomerate in the material, so that the mechanical property of the final material is reduced.
A preparation method of a low-gloss PVC material for an automobile external water-cut surface comprises the following steps:
(1) weighing the raw materials;
(2) adding weighed PVC resin powder, PVC extinction resin powder, plasticizer, calcium-zinc stabilizer, carbon black color paste, PE wax, antioxidant, anti-ultraviolet agent and nitrile butadiene rubber into an internal mixer, and adding CaCO when the internal mixing temperature reaches 70-80 DEG C3Mixing and banburying the compound mixture;
(3) and (3) bracing and shearing the internally mixed materials, and preparing a finished product of the PVC particles by a granulator.
The resin powder with high polymerization degree, the extinction resin powder and the plasticizer can be fully fused and dispersed during high-temperature banburying, the extinction resin powder is fully plasticized and enters a system to achieve an extinction effect, and other auxiliary agents can be uniformly dispersed.
Compared with the prior art, the invention has the following advantages:
the invention selects resin powder with high polymerization degree to be compounded with extinction resin powder with low polymerization degree, and CaCO with different grain diameters is used3Screening the compound mixture and other low-gloss raw material components, and fully blending and plasticizing in an internal mixer to prepare the productThe obtained PVC finished product has excellent performance, good elongation at break state in a stretching state, low glossiness and high material practicability, and various appearance problems caused by high glossiness of the traditional modified PVC material are solved on the premise of not reducing the mechanical property of the original modified PVC material.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
(1) weighing raw materials: PVC resin powder: 75 parts of a mixture; PVC matting resin powder: 25 parts of (1); 45 parts of a plasticizer; 4 parts of calcium zinc stabilizer; nano CaCO3: 18 parts of a mixture; common CaCO3:2 parts of (1); 3 parts of carbon black color paste; PE wax: 0.6 part; antioxidant: 0.4 part; anti-ultraviolet agent: 0.3 part; 2.5 parts of nitrile rubber. Wherein the PVC resin powder is S-80 with higher molecular weight, and the polymerization degree is 1800; the PVC extinction resin powder is PX-1300; the plasticizer is isosorbide diheptyl ester; the antioxidant is a nontoxic hindered phenol antioxidant Irganox 1076; the uvioresistant agent is nano TiO2Mixtures with ZnO, nano TiO2The mass ratio of the ZnO to the ZnO is 1: 3.8.
(2) adding weighed PVC resin powder, PVC extinction resin powder, plasticizer, calcium-zinc stabilizer, carbon black color paste, PE wax, antioxidant, anti-ultraviolet agent and nitrile rubber into an internal mixer, and adding nano CaCO when the internal mixing temperature reaches 80 DEG C3And ordinary CaCO3And (4) mixing and banburying.
(3) And (3) bracing and shearing the internally mixed materials, and preparing a finished product of the PVC particles by a granulator.
Example 2:
(1) weighing the raw materials: PVC resin powder: 60 parts; PVC matting resin powder: 14 parts of (1); 40 parts of a plasticizer; 2 parts of calcium zinc stabilizer; nano CaCO3: 18 parts of a mixture; common CaCO3:3 parts of a mixture; 2 parts of carbon black color paste; PE wax: 0.3 part; antioxidant: 0.3 part; anti-ultraviolet agent: 0.5 part; 1 part of nitrile rubber. Wherein the PVC resin powder is S-80 with higher molecular weight, and the polymerization degree is 1800; the PVC extinction resin powder is PX-1300; the plasticizer is isosorbide diheptyl ester; resist againstThe oxygen agent is a nontoxic hindered phenol antioxidant Irganox 1076; the uvioresistant agent is nano TiO2Mixtures with ZnO, nano TiO2The mass ratio of the ZnO to the ZnO is 1: 3.8.
(2) adding weighed PVC resin powder, PVC extinction resin powder, plasticizer, calcium-zinc stabilizer, carbon black color paste, PE wax, antioxidant, anti-ultraviolet agent and nitrile rubber into an internal mixer, and adding nano CaCO when the internal mixing temperature reaches 75 DEG C3And ordinary CaCO3Mixing and banburying;
(3) and (3) bracing and shearing the internally mixed materials, and preparing a finished product of the PVC particles by a granulator.
Example 3:
(1) weighing the raw materials: PVC resin powder: 85 parts of a mixture; PVC matting resin powder: 40 parts of a mixture; 50 parts of a plasticizer; 5 parts of calcium zinc stabilizer; nano CaCO3: 18 parts of a mixture; common CaCO3:2 parts of (1); 4 parts of carbon black color paste; PE wax: 0.6 part; antioxidant: 0.5 part; anti-ultraviolet agent: 0.67 part; 10 parts of nitrile rubber. Wherein the PVC resin powder is S-80 with higher molecular weight, and the polymerization degree is 1800; the PVC extinction resin powder is PX-1300; the plasticizer is isosorbide diheptyl ester; the antioxidant is a nontoxic hindered phenol antioxidant Irganox 1076; the uvioresistant agent is nano TiO2Mixtures with ZnO, nano TiO2The mass ratio of the ZnO to the ZnO is 1: 3.8.
(2) adding weighed PVC resin powder, PVC extinction resin powder, plasticizer, calcium-zinc stabilizer, carbon black color paste, PE wax, antioxidant, anti-ultraviolet agent and nitrile rubber into an internal mixer, and adding nano CaCO when the internal mixing temperature reaches 70 DEG C3And ordinary CaCO3Mixing and banburying;
(3) and (3) bracing and shearing the internally mixed materials, and preparing a finished product of the PVC particles by a granulator.
Example (b): 4
The only difference from example 1 is that the plasticizer of comparative example 3 is DINP.
Example (b): 5
The difference from example 1 is only that in comparative example 4, nano TiO2The mass ratio of the ZnO to the ZnO is 1: 3.0.
example 6:
the difference from example 1 is only CaCO in comparative example 23The compounded mixture is only nano CaCO3。
Example 7:
the difference from example 1 is only CaCO in comparative example 23The compound mixture is only ordinary CaCO3。
Comparative example 1:
the difference with example 1 is only that no PVC matting resin powder is added to the raw material in comparative example 1.
Table 1: performance test results of finished PVC particles obtained in examples 1 to 7 and comparative example 1
From the above results, it can be seen that the present invention achieves the objects of the invention by reducing gloss in terms of materials and processes, and particularly by making a special design from a plurality of raw materials in terms of formulation. The high-temperature banburying and the common milling are carried out to realize a fully plasticized state, compared with common-grade modified PVC, the glossiness of the scheme of the invention is obviously reduced and improved, and the extrusion molding has advantages in producing products requiring lower glossiness, especially low-gloss external water cutting.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (8)
1. A low-gloss PVC material for an automobile external water cutting surface comprises the following raw materials in parts by weight: PVC resin powder: 60-85 parts;PVC matting resin powder: 15-40 parts; 40-50 parts of a plasticizer; calcium zinc stabilizer: 2-5 parts; CaCO3Compounding a mixture: 15-25 parts; carbon black color paste: 2-4 parts; PE wax: 0.3-0.6 part; antioxidant: 0.1-0.5 part; anti-ultraviolet agent: 0.3-0.6 part; nitrile rubber: 1-10 parts.
2. The low gloss PVC material for automobile external water cutting surface as claimed in claim 1, wherein the PVC resin powder is S-80, and the degree of polymerization is 1700-1900.
3. A low gloss PVC material for automobile exterior water cut surfaces according to claim 1, wherein the plasticizer is diheptyl isosorbide.
4. The low gloss PVC material for automobile external water cutting surface according to claim 1, wherein the CaCO3The compound mixture is nano CaCO with the grain diameter of 10-100nm3With ordinary CaCO having a particle diameter of 1000nm or more3Mixing to obtain the final product.
5. The low gloss PVC material for automobile external water cutting surface according to claim 4, wherein the nano CaCO3With ordinary CaCO3The mass ratio of (A) to (B) is 6-8: 1.
6. The low-gloss PVC material for the external water-cutting surface of the automobile according to claim 1, wherein the anti-ultraviolet agent is nano TiO2And ZnO.
7. The low gloss PVC material for automobile external water cutting surface according to claim 6, wherein said nano TiO is2The mass ratio of the ZnO to the ZnO is 1: 3.5-4.0.
8. A preparation method of a low-gloss PVC material for an automobile external water-cut surface is characterized by comprising the following steps:
(1) weighing the feedstock of claim 1;
(2) adding weighed PVC resin powder, PVC extinction resin powder, plasticizer, calcium-zinc stabilizer, carbon black color paste, PE wax, antioxidant, anti-ultraviolet agent and nitrile butadiene rubber into an internal mixer, and adding CaCO when the internal mixing temperature reaches 70-80 DEG C3Mixing and banburying the compound mixture;
(3) and (3) bracing and shearing the internally mixed materials, and preparing a finished product of the PVC particles by a granulator.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051736A (en) * | 1983-08-31 | 1985-03-23 | Toyo Soda Mfg Co Ltd | Thermoplastic elastomer compositon |
| US5422399A (en) * | 1988-02-23 | 1995-06-06 | The Geon Company | Rigid article having a stucco appearance made from a blend of PVC and crosslinked PVC |
| CN102898755A (en) * | 2012-11-15 | 2013-01-30 | 天津市天塑科技集团有限公司第四塑料制品厂 | Matting resin modified polyvinyl chloride (PVC) matt film |
| CN103059468A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | Low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material and preparing method thereof |
-
2020
- 2020-06-22 CN CN202010577019.8A patent/CN111732798A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051736A (en) * | 1983-08-31 | 1985-03-23 | Toyo Soda Mfg Co Ltd | Thermoplastic elastomer compositon |
| US5422399A (en) * | 1988-02-23 | 1995-06-06 | The Geon Company | Rigid article having a stucco appearance made from a blend of PVC and crosslinked PVC |
| CN102898755A (en) * | 2012-11-15 | 2013-01-30 | 天津市天塑科技集团有限公司第四塑料制品厂 | Matting resin modified polyvinyl chloride (PVC) matt film |
| CN103059468A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | Low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material and preparing method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘伯元: "《中国非金属矿开发与应用》", 31 January 2003, 冶金工业出版社 * |
| 李永朋等: "生物基增塑剂异山梨醇二庚酯在PVC中的应用", 《工程塑料应用》 * |
| 王冲等: "纳米TiO_2与ZnO纳米棒协同改性PVC性能", 《工程塑料应用》 * |
| 由井浩: "《复合塑料的材料设计》", 30 September 1986, 上海科学技术文献出版社 * |
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