Super-soft PVC artificial leather for vehicle with excellent low-temperature toughness and non-iron wire net supporting flame resistance and preparation method thereof

Abstract

This invention discloses an ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support, and its preparation method, belonging to the field of PVC artificial leather technology. The invention consists of the following raw materials in parts by weight: 100 parts PVC resin powder, 40-50 parts phthalic plasticizer, 40-50 parts high-molecular polyester plasticizer, 15-25 parts antimony trioxide, 15-25 parts solid halogen-free flame retardant, 3-8 parts synergistic flame retardant, 3-8 parts heat stabilizer, and 1-2 parts lubricant. The leather prepared by this invention not only exhibits outstanding flame retardancy and low-temperature toughness, but also possesses good surface feel, abrasion resistance, and aging resistance, fully meeting the application requirements of high-end automotive interiors. The synergistic effect of antimony trioxide, solid halogen-free flame retardant, and synergistic flame retardant achieves a flame retardant effect greater than the sum of its parts (1+1+1>3), meeting the stringent requirement of a wire mesh-free support with a relatively low total addition amount.

Description

Technical Field

[0001] This invention belongs to the field of PVC artificial leather technology, specifically relating to an ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support, and its preparation method. Background Technology

[0002] With the development of the automotive industry, consumers are increasingly demanding higher levels of comfort, safety, and a premium feel from car interiors. Ultra-soft leather (typically referring to leather with a Shore A hardness of 50-70) has become the preferred material for high-end car seats, door panels, armrests, and other parts due to its delicate feel and luxurious appearance.

[0003] However, an ultra-soft feel usually relies on the addition of large amounts of plasticizers, but this brings two serious problems:

[0004] 1. Deterioration of Flame Retardancy: Most plasticizers (such as phthalates and parabens) are flammable organic compounds. Their excessive addition significantly reduces the flame retardant properties of materials, making them unable to pass stringent automotive interior flame retardant standards, such as Volkswagen PV 3012 and General Motors GM9090P, especially the more demanding wire mesh-free test (Honda HES D 6003). In this test, the sample is placed directly on a flame without a wire mesh to disperse heat, placing extremely high demands on the material's inherent flame retardancy and anti-dripping properties.

[0005] 2. "Excessive oil" and decreased physical properties: Plasticizers are prone to migration and precipitation (i.e., the "excessive oil" phenomenon), which not only causes the surface to become sticky and contaminated, but also leads to material aging, making it hard and brittle in low-temperature environments. Low-temperature toughness and flexural strength decrease sharply, making it unable to meet the usage requirements of vehicles in cold regions. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide an ultra-soft PVC automotive artificial leather that has both excellent low-temperature toughness and flame retardancy without wire mesh support. This PVC automotive artificial leather not only has outstanding flame retardancy and low-temperature toughness, but also has good surface feel, wear resistance and aging resistance, which fully meets the application requirements of high-end automotive interiors. Another technical problem to be solved by the present invention is to provide a method for preparing ultra-soft PVC automotive artificial leather that has both excellent low-temperature toughness and flame retardancy without wire mesh support.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0008] An ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support is composed of the following raw materials in parts by weight: 100 parts PVC resin powder, 40-50 parts phthalic plasticizer, 40-50 parts high molecular weight polyester plasticizer, 15-25 parts antimony trioxide, 15-25 parts solid halogen-free flame retardant, 3-8 parts synergistic flame retardant, 3-8 parts heat stabilizer, and 1-2 parts lubricant.

[0009] Furthermore, the PVC resin powder is PVC resin or thermoplastic polyurethane with a degree of polymerization of 1300~1700.

[0010] Furthermore, the phthalic plasticizer is phthalate diester.

[0011] Furthermore, the polymeric polyester plasticizer is adipic acid polyester.

[0012] Furthermore, the solid halogen-free flame retardant is aluminum hydroxide or magnesium hydroxide surface modified with a silane coupling agent, and its average particle size D50 is 1~5μm.

[0013] Furthermore, the synergistic flame retardant is zinc borate or zinc stannate.

[0014] Furthermore, the heat stabilizer is a calcium-zinc composite heat stabilizer.

[0015] Furthermore, the lubricant is selected from calcium stearate and zinc stearate.

[0016] Furthermore, the method for preparing the ultra-soft PVC automotive artificial leather that combines excellent low-temperature toughness and flame retardancy without wire mesh support is characterized by comprising the following steps:

[0017] 1) Add PVC resin powder, heat stabilizer, lubricant, phthalic plasticizer, and high molecular weight polyester plasticizer into the mixing equipment and mix at high speed for 150-200 seconds at a temperature of 85-95℃ and a speed of 450-500r / min.

[0018] 2) Add antimony trioxide, solid halogen-free flame retardant, and synergistic flame retardant to the mixture in step 1), maintain the temperature at 85~95℃ and the rotation speed at 450~500r / min, and continue high-speed mixing for 180~220s to obtain a dry mixture;

[0019] 3) The dry mixture is sequentially melt-plasticized, calendered, coated and printed, and foamed and embossed to obtain the finished product.

[0020] Further, in step 3), the process parameters for melt plasticizing are: temperature 140~160℃, time 340~380s, and rotation speed 45~55r / min; the process parameters for calendering are: temperature 150~170℃ and speed 25~40m / min; the process parameters for surface coating printing are: temperature 100~120℃ and speed 15~25m / min; and the process parameters for foaming embossing are: temperature 190~210℃ and speed 10~20m / min.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] (1) The leather prepared by this invention not only has outstanding flame retardancy and low temperature toughness, but also has good surface feel, wear resistance and aging resistance, which fully meets the application requirements of high-end automotive interiors.

[0023] (2) In this invention, antimony trioxide, solid halogen-free flame retardant, and zinc borate / zinc stannate synergistically promote the formation of a dense char layer. The three work together to achieve a flame retardant effect of 1+1+1>3, and meet the stringent requirements of no wire mesh support with a relatively low total addition amount.

[0024] (3) This invention resolves the contradiction between "excessive oil content" and low-temperature brittleness by using a combination of plasticizers and molecular polyester plasticizers, fundamentally reducing the risk of plasticizer migration and precipitation. At the same time, the precisely controlled solid flame retardant and synergist have little impact on polymer chain segment movement, thus perfectly preserving the material's toughness at low temperatures. Attached Figure Description

[0025] Figure 1 A physical image of the PVC artificial leather for automotive use prepared in this application. Detailed Implementation

[0026] The present invention will be further illustrated below with reference to specific embodiments. These embodiments are implemented based on the technical solutions of the present invention, and it should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0027] The solid halogen-free flame retardants used in the following examples are commercially available aluminum hydroxide or magnesium hydroxide with surface modification by silane coupling agents.

[0028] The degree of polymerization of the PVC resin powder used in the following examples is 1300-1700.

[0029] Example 1

[0030] A method for preparing ultra-soft PVC automotive artificial leather that combines excellent low-temperature toughness and flame retardancy without wire mesh support includes the following steps:

[0031] 1) 100 parts of PVC resin powder, 4 parts of calcium-zinc composite heat stabilizer, 1 part of calcium stearate, 45 parts of phthalate (911P) and 45 parts of adipic acid polyester are sequentially added to a high-speed mixer and mixed at high speed for 180s at a temperature of 90℃ and a speed of 450r / min to obtain a preliminary mixture.

[0032] 2) Add 20 parts of antimony trioxide, 20 parts of modified aluminum hydroxide, and 5 parts of zinc borate to the mixture in step 1). Maintain the temperature at 90℃ and the rotation speed at 450r / min, and continue high-speed mixing for 200s to obtain a dry mixture.

[0033] 3) The dry mixture is fed into an internal mixer, set at 150℃ and 50 r / min, and melted and plasticized for 360 seconds to obtain a uniform molten material. The molten material is then fed into a four-roll calender, set at 165℃ and 33 m / min, and calendered into a leather substrate with a thickness of 1.0 mm. The calendered substrate is then fed into a coating machine, where a polyurethane surface treatment agent is used for coating printing. The temperature is set at 115℃ and the conveying speed at 20 m / min, resulting in a coating thickness of 12 μm. The printed substrate is then fed into a foaming and embossing machine, set at 205℃ and the conveying speed at 16 m / min. After mold embossing and foaming treatment, the final product is an ultra-soft PVC automotive artificial leather. Figure 1 As shown.

[0034] Example 2

[0035] A method for preparing ultra-soft PVC automotive artificial leather that combines excellent low-temperature toughness and flame retardancy without wire mesh support includes the following steps:

[0036] 1) 100 parts of PVC resin powder, 3 parts of calcium-zinc composite heat stabilizer, 1 part of calcium stearate, 40 parts of phthalate (911P) and 40 parts of adipic acid polyester are sequentially added to a high-speed mixer and mixed at 90℃ and 450r / min for 180s to obtain a preliminary mixture.

[0037] 2) Add 15 parts of antimony trioxide, 15 parts of modified aluminum hydroxide, and 3 parts of zinc borate to the mixture in step 1). Maintain the temperature at 90℃ and the rotation speed at 450r / min, and continue high-speed mixing for 200s to obtain a dry mixture.

[0038] 3) The dry mixture is fed into an internal mixer, the temperature is set at 150℃ and the speed at 50r / min, and the mixture is melted and plasticized for 360s to obtain a uniform molten material. The molten material is then fed into a four-roll calender, the roller temperature is set at 165℃ and the calendering speed at 33m / min, and the calendering speed is set to 1.0mm thick leather substrate. The calendered substrate is then fed into a coating machine, where a polyurethane surface treatment agent is used for coating printing. The temperature is set at 115℃ and the conveying speed at 20m / min, and the coating thickness is 12um. The printed substrate is then fed into a foaming embossing machine, the temperature is set at 205℃ and the conveying speed at 16m / min, and after mold embossing and foaming treatment, the ultra-soft PVC automotive artificial leather product is finally obtained.

[0039] Example 3

[0040] A method for preparing ultra-soft PVC automotive artificial leather that combines excellent low-temperature toughness and flame retardancy without wire mesh support includes the following steps:

[0041] 1) 100 parts of PVC resin powder, 8 parts of calcium-zinc composite heat stabilizer, 2 parts of calcium stearate, 50 parts of phthalate (911P) and 50 parts of adipic acid polyester are sequentially added to a high-speed mixer and mixed at 90℃ and 450r / min for 180s to obtain a preliminary mixture.

[0042] 2) Add 25 parts of antimony trioxide, 25 parts of modified aluminum hydroxide, and 8 parts of zinc borate to the mixture in step 1). Maintain the temperature at 90℃ and the rotation speed at 450r / min, and continue high-speed mixing for 200s to obtain a dry mixture.

[0043] 3) The dry mixture is fed into an internal mixer, with a set temperature of 150℃ and a rotation speed of 50 r / min, and melted and plasticized for 360 seconds to obtain a uniform molten material. The molten material is then fed into a four-roll calender, with a set roll temperature of 165℃ and a calendering speed of 33 m / min, to calender a leather substrate with a thickness of 1.0 mm. The calendered substrate is then fed into a coating machine, where a polyurethane surface treatment agent is used for coating printing, with a set temperature of 115℃, a conveying speed of 20 m / min, and a coating thickness of 12 μm. The printed substrate is then fed into a foaming embossing machine, with a set temperature of 205℃ and a conveying speed of 16 m / min. After mold embossing and foaming treatment, the final product is an ultra-soft PVC automotive artificial leather.

[0044] Example 4

[0045] A method for preparing ultra-soft PVC automotive artificial leather that combines excellent low-temperature toughness and flame retardancy without wire mesh support includes the following steps:

[0046] 1) 100 parts of PVC resin powder, 4 parts of calcium-zinc composite heat stabilizer, 1 part of calcium stearate, 45 parts of phthalate (911P) and 45 parts of adipic acid polyester are sequentially added to a high-speed mixer and mixed at high speed for 150 seconds at a temperature of 85℃ and a speed of 450r / min to obtain a preliminary mixture.

[0047] 2) Add 20 parts of antimony trioxide, 20 parts of modified aluminum hydroxide, and 5 parts of zinc borate to the mixture in step 1). Maintain the temperature at 85℃ and the rotation speed at 450r / min, and continue high-speed mixing for 180s to obtain a dry mixture.

[0048] 3) The dry mixture is fed into an internal mixer, the temperature is set at 140℃ and the speed at 50r / min, and the mixture is melted and plasticized for 340s to obtain a uniform molten material. The molten material is then fed into a four-roll calender, the roller temperature is set at 165℃ and the calendering speed at 33m / min, and the calendering speed is set to 1.0mm thick leather substrate. The calendered substrate is then fed into a coating machine, where a polyurethane surface treatment agent is used for coating printing. The temperature is set at 115℃ and the conveying speed at 20m / min, and the coating thickness is 12um. The printed substrate is then fed into a foaming embossing machine, the temperature is set at 205℃ and the conveying speed at 16m / min, and after mold embossing and foaming treatment, the ultra-soft PVC automotive artificial leather product is finally obtained.

[0049] Comparative Example 1

[0050] The difference from Example 1 is that in step 1), phthalate (911P) and adipic acid polyester are replaced with 90 parts of phthalate (911P) to obtain the ultra-soft PVC automotive artificial leather product.

[0051] Comparative Example 2

[0052] The difference from Example 1 is that in step 2), the modified aluminum hydroxide is replaced with 25 parts of unmodified aluminum hydroxide to obtain the finished product of ultra-soft PVC automotive artificial leather.

[0053] Comparative Example 3

[0054] The difference from Example 1 is that antimony trioxide was not added in step 2), resulting in an ultra-soft PVC automotive artificial leather product.

[0055] Comparative Example 4

[0056] The difference from Example 1 is that in step 2), modified aluminum hydroxide was not added, resulting in the ultra-soft PVC automotive artificial leather product.

[0057] Comparative Example 5

[0058] The difference from Example 1 is that zinc borate was not added in step 2), resulting in an ultra-soft PVC automotive artificial leather product.

[0059] Comparative Example 6

[0060] The difference from Example 1 is that in step 2), antimony trioxide and modified aluminum hydroxide were not added, resulting in the ultra-soft PVC automotive artificial leather product.

[0061] Comparative Example 7

[0062] The difference from Example 1 is that in step 2), antimony trioxide and zinc borate were not added, resulting in the ultra-soft PVC automotive artificial leather product.

[0063] Comparative Example 8

[0064] The difference from Example 1 is that in step 2), modified aluminum hydroxide and zinc borate were not added, resulting in the ultra-soft PVC automotive artificial leather product.

[0065] The ultra-soft PVC automotive artificial leathers prepared in Examples 1-4 and Comparative Examples 1-8 were subjected to performance tests. Shore A hardness was tested according to GB / T 2411-2008, flexural endurance according to GB / T 3903.1-2017, flame retardancy without wire mesh support according to GB 8624-2012, and mass loss after heat aging according to GB / T 18244-2022. The results are shown in Table 1.

[0066] Table 1. Performance tests of the ultra-soft PVC automotive artificial leather prepared in Examples 1-4 and Comparative Examples 1-8

[0067]

[0068] As shown in Table 1, the raw material ratio and process parameters of Example 1 are well-matched, and the ultra-soft touch, low oiliness, high and low temperature toughness and flame retardancy all meet the standards, with balanced overall performance. In Example 2, the amount of plasticizer and flame retardant is insufficient, the low oiliness is not good, and the flame retardancy performance does not meet the standards. In Example 3, the amount of plasticizer is too high, the touch is ultra-soft, but the flame retardancy is not up to standard, and the quality loss due to heat aging is large. In Example 4, the mixing and melt plasticizing process parameters are inappropriate, the flame retardant is not evenly dispersed, and the flame retardancy performance does not meet the standards. Comparative Example 1, using a traditional single plasticizer, showed acceptable flame retardancy, but low-temperature toughness decreased, and significant quality loss occurred during thermal aging. Comparative Example 2, using a traditional unmodified aluminum hydroxide flame retardant, showed a decreased flame retardant effect. Comparative Example 3, without antimony trioxide, showed a decreased flame retardant effect. Comparative Example 4, without modified aluminum hydroxide, showed a decreased flame retardant effect. Comparative Example 5, without zinc borate, showed a decreased flame retardant effect. Comparative Example 6, without both antimony trioxide and modified aluminum hydroxide, showed a decreased flame retardant effect. Comparative Example 7, without both antimony trioxide and zinc borate, showed a decreased flame retardant effect. Comparative Example 8, without both modified aluminum hydroxide and zinc borate, showed a decreased flame retardant effect. This demonstrates the necessity of the synergistic effect of the three agents.

[0069] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A super-soft PVC automotive artificial leather that combines excellent low-temperature toughness with flame retardancy without wire mesh support, characterized in that: It is composed of the following raw materials in parts by weight: 100 parts PVC resin powder, 40-50 parts phthalic plasticizer, 40-50 parts high molecular weight polyester plasticizer, 15-25 parts antimony trioxide, 15-25 parts solid halogen-free flame retardant, 3-8 parts synergistic flame retardant, 3-8 parts heat stabilizer, and 1-2 parts lubricant.

2. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The PVC resin powder is PVC resin or thermoplastic polyurethane with a degree of polymerization of 1300~1700.

3. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The phthalic plasticizer is phthalate diester.

4. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The polymeric polyester plasticizer is adipic acid polyester.

5. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The solid halogen-free flame retardant is aluminum hydroxide or magnesium hydroxide with a surface modified by a silane coupling agent, and its average particle size D50 is 1~5μm.

6. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The synergistic flame retardant is zinc borate or zinc stannate.

7. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The heat stabilizer is a calcium-zinc composite heat stabilizer.

8. The ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 1, characterized in that: The lubricant is selected from calcium stearate and zinc stearate.

9. The method for preparing ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in any one of claims 1 to 8, characterized in that: Includes the following steps: 1) Add PVC resin powder, heat stabilizer, lubricant, phthalic plasticizer, and high molecular weight polyester plasticizer into the mixing equipment and mix at high speed for 150-200 seconds at a temperature of 85-95℃ and a speed of 450-500r / min. 2) Add antimony trioxide, solid halogen-free flame retardant, and synergistic flame retardant to the mixture in step 1), maintain the temperature at 85~95℃ and the rotation speed at 450~500r / min, and continue high-speed mixing for 180~220s to obtain a dry mixture; 3) The dry mixture is sequentially melt-plasticized, calendered, coated and printed, and foamed and embossed to obtain the finished product.

10. The method for preparing ultra-soft PVC automotive artificial leather with excellent low-temperature toughness and flame retardancy without wire mesh support as described in claim 9, characterized in that: In step 3), the process parameters for melt plasticizing are: temperature 140~160℃, time 340~380s, and rotation speed 45~55r / min; the process parameters for calendering are: temperature 150~170℃ and speed 25~40m / min; the process parameters for surface coating printing are: temperature 100~120℃ and speed 15~25m / min; and the process parameters for foaming embossing are: temperature 190~210℃ and speed 10~20m / min.

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