PVC (polyvinyl chloride) artificial leather as well as preparation method and application thereof

Abstract

The invention discloses PVC artificial leather and a preparation method and application thereof.The PVC artificial leather comprises a surface layer material and a bottom layer material of a substrate, and the surface layer material comprises, by weight, 98-102 parts of PVC powder A, 20-50 parts of macromolecular polyester plasticizer, 90-110 parts of organic bio-based plasticizer, 2-6 parts of stabilizer, 5-6 parts of additive and 5-20 parts of calcium carbonate; the bottom layer material comprises the following components in parts by weight: 20-50 parts of PVC powder A, 50-80 parts of PVC powder B, 120-140 parts of an organic bio-based plasticizer, 2-3 parts of a stabilizer, 5-6 parts of an additive, 10-30 parts of calcium carbonate, 4-6 parts of a foaming agent and 1-3 parts of a pigment color cake, the PVC powder A is PVC resin with a porous structure and an ultrahigh polymerization degree, and the PVC powder B is PVC powder with a common polymerization degree. The PVC artificial leather disclosed by the invention has excellent low-temperature bending resistance and low oil separation property, and also has low heat loss, so that the application range of the PVC artificial leather in a low-temperature environment is widened.

Description

Technical Field

[0001] The invention relates to the technical field of PVC calendering, and in particular to PVC artificial leather and a preparation method and application thereof. Background Art

[0002] PVC artificial leather is a composite material. It is a mixture of polyvinyl chloride resin, plasticizer, stabilizer and other additives, which is coated or laminated on a substrate and then processed through processes such as surface functional treatment and embossing.

[0003] At present, the PVC leather used in car seats is required to have a low-temperature flexural resistance of (-10)℃*30,000 times. However, in some northern regions, the winter temperature is much lower than (-10)℃, and the low-temperature flexural resistance of the product is required to be higher. However, PVC leather is subject to the poor low-temperature performance of polyvinyl chloride and cannot meet the flexural use environment of (-30)℃. After long-term use under extreme weather conditions, it is easy to crack to varying degrees, which limits the application scope of PVC artificial leather.

[0004] At present, most of the cold-resistant PVC leather for car seats on the market are achieved by increasing the amount of cold-resistant plasticizers or cold-resistant additives. However, such plasticizers have poor compatibility with PVC resin powder, making them too soft to be molded and pulled during manufacturing, and easily causing surface precipitation in the finished product. At the same time, the large amount of cold-resistant plasticizers added will also increase the heat loss of PVC leather. Therefore, it is urgent to develop a PVC artificial leather that can achieve low-temperature bending resistance while maintaining low surface precipitation and low heat loss, so as to meet the application requirements of PVC artificial leather below (-30)℃. Summary of the invention

[0005] In view of the defects in the prior art, the present invention provides a PVC artificial leather and a preparation method and application thereof.

[0006] The present invention provides a PVC artificial leather, wherein the surface layer material and the bottom layer material of the base material respectively comprise the following components by weight:

[0007] Surface material: PVC powder A 98-102 parts, such as 98, 99, 100 parts; high molecular polyester plasticizer 20-50 parts, such as 20, 25, 30, 35, 40, 45, 50 parts; organic bio-based plasticizer 90-110 parts, such as 90, 95, 100, 105, 110 parts; stabilizer 2-6 parts, such as 2, 3, 4, 5, 6 parts; additive 5-6 parts, such as 5, 5.2, 5 .4, 5.6, 5.8, 6 parts; calcium carbonate 5-20 parts, such as 5, 10, 15, 20 parts; antioxidant 0.5-1 part, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1 part; anti-ultraviolet agent 0.5-1 part, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1 part; pigment dilution film 1-6 parts, such as 1, 2, 3, 4, 5, 6 parts;

[0008] Bottom material: PVC powder A 20-50 parts, such as 20, 25, 30, 35, 40, 45, 50 parts; PVC powder B 50-80 parts, such as 50, 55, 60, 65, 70, 75, 80 parts; organic bio-based plasticizer 120-140 parts, such as 120, 125, 130, 135, 140 parts; stabilizer 2-3 parts, such as 2, 2.2, 2.4, 2.6, 2.8, 3 parts; additive 5-6 parts, such as 5, 5.2, 5.4, 5.6, 5.8, 6 parts; calcium carbonate 10-30 parts, such as 10, 15, 20, 25, 30 parts; foaming agent 4-6 parts, such as 4, 5, 6 parts; pigment color cake 1-3 parts, such as 1, 2, 3 parts;

[0009] The PVC powder A is a porous structure ultra-high polymerization degree PVC resin with a polymerization degree of 3000-4000; the PVC powder B is a common polymerization degree PVC powder (SG-3 type) with a polymerization degree of 1000-1400.

[0010] The present invention uses porous structure ultra-high polymerization degree PVC resin and its high particle surface area to significantly improve the oil absorption capacity of the system, effectively solve the problem of precipitation and volatilization, and can maintain continuous mixing and pulling of materials during the production process, significantly improve the low-temperature bending resistance of PVC leather, and meet the long-term use in low-temperature scenes; and the modified porous structure ultra-high polymerization degree PVC resin is matched with a polymer polyester plasticizer and an organic bio-based plasticizer to improve various performances: adding a certain proportion of polymer polyester plasticizer can effectively reduce the precipitation problem caused by folding the product during use, and the organic bio-based plasticizer can improve the compatibility with the ultra-high polymerization degree PVC resin, and the components are matched with each other for absorption, which can increase the upper limit of the oil adsorption of the system, and meet the low-temperature bending resistance requirements while significantly reducing the performance indicators such as heat loss of the product;

[0011] In the formula design of the present invention, various properties are further improved by adding specific plasticizers. Among them, the molecular weight of the high molecular weight polyester plasticizer is above 4000, which is significantly higher than the molecular weight of 1000 of the general plasticizer. It can increase the intermolecular force of the plasticizer, strengthen the entanglement between molecules, enhance the affinity between plasticizers, and inhibit the surface migration of plasticizers. At the same time, it helps to improve the atomization performance and crease precipitation of the material.

[0012] Regarding the formula of the bottom material, the present invention creatively combines ultra-high polymerization degree PVC powder with ordinary polymerization degree PVC powder to avoid excessive ultra-high polymerization degree PVC powder and the base cloth from penetrating each other, resulting in too low peeling strength. At the same time, it can also improve the resilience of the foaming layer, giving the leather back-end processing a high crease recovery effect.

[0013] The pigment color cake in the surface material is made into a diluted film in advance, which can avoid the surface color line problem caused by the large difference in oil content between the pigment and the trial surface formula. The oil content of the pigment color cake is 30-40PHR, while the oil content of the trial surface formula is above 98-102PHR. At this time, the pigment color cake cannot be fully integrated into the PVC powder due to the large difference in oil content, resulting in surface color line problems. After the color cake is made into a diluted film, the oil content can be diluted by more than twice to 90PHR, and by cooperating with high-polymerization PVC powder and plasticizer, the dispersibility of the pigment in the system is improved, effectively solving the above problems.

[0014] Furthermore, the polymer polyester plasticizer is one or more of UN615 or E100.

[0015] Furthermore, the organic bio-based plasticizer is one or more of SH0102 and W-221.

[0016] Furthermore, the PVC powder A in the base material is 30-40 parts by weight.

[0017] Furthermore, the stabilizer includes but is not limited to any one or more of a calcium zinc stabilizer and a barium zinc stabilizer.

[0018] Furthermore, the additive may be an amine-resistant agent, such as hypochlorite, acrylate ACR, etc.

[0019] Furthermore, the preparation method of the pigment dilution film comprises the following steps: drawing the pigment color cake into a film (mixing the pigment color cake with a transparent base material having 98-102 oil content, and then rolling it into a film), and pre-diluting and pre-dispersing it to obtain a diluted film.

[0020] Furthermore, the preparation method of the bottom layer material comprises the following steps:

[0021] Weigh PVC powder A, PVC powder B, stabilizer and additives by weight and mix them. Stir them evenly at a high speed of 800-1400r / min in the state of dry powder, then add organic bio-based plasticizer and continue stirring until the plasticizer is completely absorbed, finally add calcium carbonate and stir well for 250-400s, then pour into an internal mixer, finally add pigment cake and foaming agent and mix them together, and the base material is obtained after the materials are kneaded.

[0022] Furthermore, the preparation method of the surface layer material comprises the following steps:

[0023] Weigh PVC powder A, antioxidant, anti-ultraviolet agent, stabilizer and additives by weight and mix them. Stir evenly in the state of dry powder, then add high molecular polyester plasticizer and organic bio-based plasticizer and continue stirring until the plasticizer is completely absorbed, continue to add calcium carbonate and stir well for 20-30 seconds, then pour into the internal mixer, add pigment dilution film, and knead the materials to obtain the surface material.

[0024] Furthermore, the preparation method of the substrate comprises the following steps:

[0025] S1. The bottom material is sheared by a four-roll calender, and is pulled into a film by a traction roller in a molten state and attached to the base fabric coated with glue to obtain a bottom layer;

[0026] S2. The surface layer material is pulled into a film by a pulling roller in a molten state and attached to the bottom layer to obtain a base material.

[0027] The present invention also provides a method for preparing the PVC artificial leather, comprising the following steps:

[0028] Surface treatment process:

[0029] A. Stir and disperse the pre-prepared mixed slurry (special water-based slurry) in the slurry tank through a diamond anilox roller to ensure that it is evenly dispersed without agglomeration or precipitation;

[0030] B. The mixed slurry is attached to the substrate by traction of the equipment, passed through a 80-120 mesh sizing roller, and then dried and cooled in an oven (135±5°C) and coiled (13±3m / min, drying time is 50-60s) to fix the mixed slurry on the substrate to obtain PVC fabric. The mixed slurry attached to the substrate can play a protective role;

[0031] Embossing process:

[0032] The PVC fabric is passed through a foaming furnace for surface preheating, and then passed through a patterned steel rod to obtain PVC artificial leather with a texture effect; the temperature of the four zones of the foaming furnace is 170 / 215 / 215 / 130°C;

[0033] Among them, the mixed slurry (special water-based coating slurry) adopts the existing formula, specifically:

[0034] Formula of top coating material: 100% polycarbonate polyurethane + water-based polycarbonate aliphatic polyurethane, 20%-40% polycarbonate self-matting polyurethane. After the above three materials are evenly mixed, slowly add 3%-15% of α-tridecyl-ω-hydroxy-poly(oxy-1,2-ethylene)(branched chain). After continuing to stir evenly, slowly add 2%-6% of modified polycarbodiimide crosslinker while stirring. Formula of primer material: 100% water-based aliphatic polyurethane emulsion. Slowly add 2%-6% of isocyanate crosslinker while stirring. First apply the primer material on the substrate, dry it, and then apply the top coating material on it.

[0035] The present invention also provides the use of the PVC artificial leather as automobile seat leather, especially automobile seat leather used in an environment of (-30)°C or below for a long time.

[0036] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0037] (1) The PVC artificial leather provided by the present invention has excellent low-temperature bending resistance;

[0038] (2) The PVC artificial leather provided by the present invention has low surface precipitation;

[0039] (3) The PVC artificial leather provided by the present invention has low heat loss;

[0040] (4) The peeling strength between the PVC artificial leather bottom layer and the base fabric provided by the present invention is high. DETAILED DESCRIPTION

[0041] In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only embodiments of a part of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0042] Example

[0043] The present invention is further described below in conjunction with specific examples and comparative examples. The following specific examples are all preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following examples, and are particularly not limited to the types of the various component raw materials used in the following specific examples.

[0044] 1. The sources of raw materials for the embodiments and comparative examples are as follows:

[0045] PVC powder A#1: S-100, degree of polymerization 3000-4000, Huadeng Trading;

[0046] PVC powder A#2: LS-400, degree of polymerization 3000-4000, LG, South Korea;

[0047] PVC powder B: brand SG-3, degree of polymerization 1300, Tianjin Dagu;

[0048] Polyester plasticizer: brand name UN615, Zhongshan Liancheng;

[0049] Organic bio-based plasticizer: brand SH0102, Senhe;

[0050] 911P plasticizer: brand 911P, Nan Ya;

[0051] Stabilizer: Calcium zinc powder stabilizer, the same substance was used in all parallel experiments;

[0052] Additives: ACR, all parallel experiments used the same substance;

[0053] Calcium carbonate: CAS: 471-34-1, all parallel experiments used the same substance;

[0054] Antioxidant: Antioxidant 1076, the same substance was used in all parallel experiments;

[0055] UV-resistant agent: UV-31, the same substance was used in all parallel experiments;

[0056] Pigment dilution film: homemade, the preparation method is: rutile titanium dioxide and 98-102 oil transparent base material according to the mass ratio of 1: (0.9-1.1), and then rolled into a film to obtain the pigment dilution film;

[0057] Pigment color cake: Rutile titanium dioxide, Guangzhou Juli.

[0058] The preparation method of the PVC artificial leather of the embodiment of the present invention and the comparative example comprises the following steps:

[0059] Preparation of bottom material: PVC powder A, PVC powder B, stabilizer and additives are weighed and mixed according to weight, and stirred evenly in the state of dry powder, and then organic bio-based plasticizer is added and stirred continuously until the plasticizer is completely absorbed, and finally calcium carbonate is added and stirred for 250-400 seconds, and then poured into a mixer, and finally pigment color cake and foaming agent are added and mixed together, and the bottom material is obtained after the materials are kneaded;

[0060] Preparation of surface layer material: PVC powder A, antioxidant, anti-ultraviolet agent, stabilizer and additives are weighed and mixed by weight, and stirred evenly in the state of dry powder, and then high molecular polyester plasticizer and organic bio-based plasticizer are added and stirred continuously until the plasticizer is completely absorbed, and calcium carbonate is added and stirred fully for 20-30 seconds, and then poured into an internal mixer, and then pigment dilution film is added, and the surface layer material is obtained after the material is kneaded;

[0061] Preparation of the base material: S1. Mixing and shearing the base material through a calender, pulling it in a molten state to form a film and attaching it to a base fabric coated with glue to obtain a base material; S2. Pulling the surface material in a molten state to form a film and attaching it to the base material to obtain a base material;

[0062] Surface treatment: A. Stir and disperse the pre-prepared mixed slurry in the slurry tank to ensure uniform dispersion. B. Use equipment to pull the mixed slurry onto the substrate, pass it through an 80-120 mesh sizing roller, and then dry and cool it in an oven (135±5℃) to roll it up, so that the mixed slurry is fixed on the substrate to obtain PVC fabric.

[0063] Embossed molding: The above PVC fabric is passed through a foaming furnace for surface preheating, and then passed through a patterned steel rod to obtain PVC artificial leather with a textured effect.

[0064] 2. Various performance test methods

[0065] (1) Low-temperature flexural resistance test: According to QB-T 2714-2005 Leather Physical and Mechanical Test Folding Fastness Test, the sample is subjected to a -30°C / 20,000-time flexural resistance test to observe the surface cracking of the sample. The product is qualified if there is no cracking on the warp and weft surfaces.

[0066] (2) Surface oil leakage test: Fold the sample in half along the long side with the base fabric facing outwards, press the sample with a hard pressing plate, and place a load of 2 kg in the middle of the pressing plate. The test time is 4 hours. Wipe the oil leakage area with cigarette paper and rate the oil traces of the cigarette paper. The oil traces in the warp and weft directions of the product are required to be ≥ Level 4. The judgment is based on the following standards. If the situation is between the two levels, a rating of 0.5 is allowed:

[0067] Level 1: There is a large area of ​​oil soaked area on the paper;

[0068] Level 2: There is a continuous area of ​​oil soaked on the paper;

[0069] Level 3: There are dot-shaped oil-soaked areas on the paper;

[0070] Level 4: There are slight oil stains on the paper and they are not continuous;

[0071] Level 5: No oil stains on the paper;

[0072] (3) Surface effect test: The test is carried out by visual observation on site.

[0073] (4) Heat loss test: The test shall be conducted in accordance with the standard specified in 4.12 of GWTA L50-01:2023-07, requiring the product heat loss to be ≤5%.

[0074] (5) Peel strength test: The test is carried out in accordance with the standard of GB / T 8088-1988, and the product peel strength is required to be ≥30N / 5cm.

[0075] Table 1. Technical solutions and effects of the embodiments (in parts by weight)

[0076]

[0077]

[0078] Table 2. Comparative Examples Technical Scheme and Effects (Units are parts by weight)

[0079]

[0080] In the design of the surface layer material of Examples 1-5, high molecular weight polyester plasticizers and organic bio-based plasticizers are introduced at the same time, and the PVC powders used are all porous structure high polymerization degree PVC powders, and the added pigments are in the form of diluted tablets. In the design of the bottom layer material, a mixture of two PVC powders is used. Through formula design and reasonable matching of components, the prepared PVC artificial leather has excellent low-temperature flexural resistance and low oil separation while taking into account low heat loss, which broadens the application of PVC artificial leather in low-temperature environments.

[0081] Comparative Examples 1-4 are all compared with Example 1. The PVC powder of the bottom layer in Comparative Example 1 is all high-polymerization PVC powder. The bottom PVC glue has too high elasticity and cannot be effectively compatible with the base cloth, resulting in poor peeling strength; 911P plasticizer is used in the surface layer of Comparative Example 2 to replace the high-molecular polyester plasticizer, and its low-temperature flexural performance is unstable. At the same time, due to the increase in the amount of plasticizer but the low molecular weight, the volatility is affected, the heat loss is increased, and the degree of oil separation is increased; 911P plasticizer is used in the surface layer of Comparative Example 3 to replace the organic bio-based plasticizer, which also leads to higher heat loss and increased oil separation. The pigment used in the surface layer of Comparative Example 4 is in the form of a color cake. Because the oil content of the color cake is low, it is not easy to be compatible with the PVC base material, resulting in color lines and flowery surface problems on the surface layer, affecting the surface use effect.

[0082] Based on the test data of low temperature bending resistance, oil separation, heat loss and peel strength between the bottom layer and the base fabric in Table 1 and Table 2, the PVC artificial leather prepared by Examples 1-5 has obvious advantages over the comparative example and can effectively meet the high standard requirements of customers and the market. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. 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 PVC artificial leather, characterized in that: The surface layer material and the bottom layer material of the substrate respectively include the following components by weight: Surface material: Bottom Material: Wherein, the PVC powder A is a porous structure ultra-high polymerization degree PVC resin with a polymerization degree of 3000-4000; the PVC powder B is a common polymerization degree PVC powder with a polymerization degree of 1000-1400.

2. The PVC artificial leather according to claim 1, characterized in that: The polymer polyester plasticizer is one or more of UN615 and E100.

3. The PVC artificial leather according to claim 1, characterized in that: The organic bio-based plasticizer is one or more of SH0102 and W-221.

4. The PVC artificial leather according to claim 1, characterized in that: The PVC powder A in the bottom layer material is 30-40 parts by weight.

5. The PVC artificial leather according to claim 1, characterized in that: The method for preparing the pigment dilution sheet film comprises the following steps: pulling the pigment color cake into a sheet film, and pre-diluting and pre-dispersing the pigment color cake to obtain a dilution sheet.

6. The PVC artificial leather according to claim 1, characterized in that: The preparation method of the bottom layer material comprises the following steps: Weigh PVC powder A, PVC powder B, stabilizer and additives by weight and mix them. Stir evenly in the state of dry powder, then add organic bio-based plasticizer and continue stirring until the plasticizer is completely absorbed. Finally, add calcium carbonate and stir well for 250-400 seconds, then pour into an internal mixer. Finally, add pigment cake and foaming agent and mix together. Knead the materials until cooked to obtain the base material.

7. The PVC artificial leather according to claim 1, characterized in that: The preparation method of the surface layer material comprises the following steps: Weigh PVC powder A, antioxidant, anti-ultraviolet agent, stabilizer and additives by weight and mix them. Stir evenly in the state of dry powder, then add high molecular polyester plasticizer and organic bio-based plasticizer and continue stirring until the plasticizer is completely absorbed, continue to add calcium carbonate and stir well for 20-30 seconds, then pour into the internal mixer, add pigment dilution film, and knead the materials to obtain the surface material.

8. The PVC artificial leather according to claim 1, characterized in that: The preparation method of the substrate comprises the following steps: S1. The bottom material is mixed and sheared by a calender, and is pulled into a film in a molten state and attached to a base fabric coated with glue to obtain a bottom layer; S2. The surface layer material is pulled into a film in a molten state and attached to the bottom layer to obtain the base material.

9. The method for preparing the PVC artificial leather according to any one of claims 1 to 8, characterized in that: The steps include: Surface treatment process: A. Stir and disperse the pre-prepared mixed slurry in the slurry tank to ensure that it is evenly dispersed; B. The mixed slurry is attached to the substrate by traction of the equipment, passed through an 80-120 mesh sizing roller, and then dried, cooled and coiled in an oven (135±5℃) to fix the mixed slurry on the substrate to obtain PVC fabric; Embossing process: The PVC fabric is passed through a foaming furnace for surface preheating and then passed through a patterned steel rod to obtain PVC artificial leather with a texture effect.

10. Use of the PVC artificial leather according to any one of claims 1 to 8 as automobile seat leather.

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