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

Abstract

According to the soft PVC artificial leather and the preparation method and application thereof, by using high-polymerization-degree PVC, a low-volatility plasticizer, a high-molecular ultra-soft base cloth material and the like and through component formula and proportion design, the prepared PVC artificial leather has excellent rigidity and softness performance, meanwhile, the atomization performance can also be taken into account, and the soft PVC artificial leather has the good application prospect. When applied to the soft leather seat, the soft leather seat can meet the scene requirements of the market.

Description

Technical Field

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

[0002] PVC artificial leather is a composite material, which is a mixture of polyvinyl chloride resin, plasticizer, stabilizer and other additives, coated or laminated on the substrate, and then processed through the process of surface functional treatment and embossing. At present, the material used in car seats is mainly PVC leather, and its rigidity and softness requirements are generally 90-110mm. Some customers who pursue softness have higher requirements for the rigidity and softness of the product. However, while artificial leather products focus on solving the soft feel, they are often prone to reduced rubbing resistance and poor atomization. Therefore, how to balance the rigidity and softness of artificial leather, atomization performance and improve rubbing resistance is a technical problem that needs to be solved urgently. Summary of the invention

[0003] In view of the defects in the prior art, the present invention provides a soft PVC artificial leather and a preparation method and application thereof.

[0004] The invention provides a soft PVC artificial leather, comprising a base material and a sizing layer. The surface layer material and the bottom layer material of the base material respectively comprise the following components by weight: the surface layer material: 98-102 parts of a porous structure ultra-high polymerization degree PVC resin, such as 98, 99, 100, 101, and 102 parts; 30-70 parts of a high molecular polyester plasticizer, such as 30, 35, 40, 45, 50, 55, 60, 65, and 70 parts; 60-110 parts of a 911P plasticizer, such as 60, 70, 80, 90, 100, and 110 parts; 20-40 parts of trioctyl trimellitate, such as 20, 25, 3 0, 35, 40 parts; didecyl phthalate 5-20 parts, such as 5, 6, 8, 10, 15, 20 parts; dioctyl sebacate 5-20 parts, such as 5, 6, 8, 10, 15, 20 parts; stabilizer 2-6 parts, such as 2, 3, 4, 5, 6 parts; additives 5-6 parts, such as 5, 6 parts; calcium carbonate 5-20 parts, such as 5, 10, 15, 20 parts; antioxidant 0.5-2 parts, such as 0.5, 1, 1.5, 2 parts; anti-ultraviolet agent 0.5-2 parts, such as 0.5, 1, 1.5, 2 parts; pigment dilution film 4-10 parts, such as 4, 5, 6, 7, 8, 9, 10 parts;

[0005] Bottom material: 20-50 parts of porous structure ultra-high polymerization degree PVC resin, such as 20, 25, 30, 35, 40, 45, 50 parts; 50-80 parts of ordinary polymerization degree PVC powder, such as 50, 55, 60, 65, 70, 75, 80 parts; 90-110 parts of 911P plasticizer, such as 90, 95, 100, 105, 110 parts; 15-35 parts of trioctyl trimellitate, such as 15, 20, 25, 30, 35 parts; 5-20 parts of didecyl phthalate , such as 5, 10, 15, 20 parts; dioctyl sebacate 5-20 parts, such as 5, 10, 15, 20 parts; stabilizer 2-4 parts, such as 2, 3, 4 parts; additives 4-6 parts, such as 4, 5, 6 parts; calcium carbonate 10-30 parts, such as 10, 15, 20, 25, 30 parts; foaming agent 3-5 parts, such as 3, 4, 5 parts; flame retardant 10-30 parts, such as 10, 15, 20, 25, 30 parts; pigment color cake 4-10 parts, such as 4, 5, 6, 7, 8, 9, 10 parts;

[0006] The base fabric of the substrate is any one of 100% polyester weft knitted double-sided fabric or 100% polyester warp knitted interwoven fabric. The polymerization degree of the porous structure ultra-high polymerization degree PVC resin is 3000-4000, and the polymerization degree of ordinary polymerization degree PVC powder is 1000-1400.

[0007] The modified porous structure ultra-high polymerization degree PVC resin is used to double the surface area of ​​the resin particles. It is combined with low-volatile plasticizers such as high-molecular polyester plasticizers, 911P plasticizers, and specific didecyl phthalate, dioctyl sebacate, and trioctyl trimellitate. The basic formula structure can not only increase the upper limit of oil adsorption and ensure that the plasticizer does not precipitate during processing, but also meet the rigidity and softness requirements of 40-60mm. In addition, by limiting the amount of plasticizers and combining with high-molecular ultra-soft base fabrics, the performance indicators such as rubbing resistance, flame retardancy, and atomization value are simultaneously improved.

[0008] The formula of the present invention can achieve a balance between the rigidity and softness of artificial leather and the atomization performance while avoiding the reduction of rubbing resistance, and can meet the strict rigidity and softness and touch requirements of some mainstream automobile OEMs (rigidity and softness are 40-60mm, preferably 48-55mm);

[0009] The use of multiple specific plasticizers such as polymer plasticizer, 911P plasticizer, trioctyl trimellitate, didecyl phthalate and dioctyl sebacate can improve the rigidity and softness of the material, making the product softer and more resilient. At the same time, it can have a high degree of bonding with PVC resin to reduce the risk of plasticizer precipitation, and can avoid the reduction of atomization performance while improving the rigidity and softness of the material. 911P plasticizer can improve compatibility with high-polymerization PVC, improve atomization performance, and significantly improve rubbing resistance at room temperature. Trioctyl trimellitate can effectively reduce heating loss and atomization value, and has high heat resistance. Didecyl phthalate can effectively improve rigidity and softness and atomization performance. At the same time, it can improve low-temperature bending resistance and reduce the occurrence of side reactions by cooperating with dioctyl sebacate and PVC polyester. The addition of dioctyl sebacate can also improve the rigidity and softness of the material, but due to the influence on the atomization performance, the addition amount needs to be controlled. Preferably, the addition amount of dioctyl sebacate in the surface layer / bottom layer material is 8-15 parts by weight. The above-mentioned multiple specific plasticizers are mutually matched and absorbed, and have good low atomization performance.

[0010] The soft leather of the invention uses a high-molecular ultra-soft base fabric, the yarn is 100% polyester, the weft-knitted double-sided fabric or the 100% polyester yarn warp-knitted interwoven fabric, and has a soft feel.

[0011] Furthermore, the porous structure ultra-high polymerization degree PVC resin in the bottom material is 25-35 parts by weight, and the hardness and softness of the artificial leather can be further optimized by controlling the amount of the porous structure ultra-high polymerization degree PVC resin in the bottom material.

[0012] Furthermore, the trioctyl trimellitate is contained in the surface layer / bottom layer material in an amount of 20-30 parts by weight.

[0013] Furthermore, the amount of didecyl phthalate in the surface layer / bottom layer material is 8-15 parts by weight, and the refined didecyl phthalate is used, and the PPM value is 80±20, which is higher in purity than the common didecyl phthalate with a PPM of 200±40, can effectively reduce the generation of by-products, and significantly improve the atomization performance and rigidity and softness performance of the material, and can also reduce the VOC content and temperature strength, further improving the comprehensive performance of artificial leather;

[0014] Furthermore, the dioctyl sebacate plasticizer is 8-15 parts by weight in the surface layer / bottom layer material. Dioctyl sebacate with a relatively small molecular weight can be used with PVC resin to effectively improve the low-temperature bending resistance and reduce the migration and precipitation of the plasticizer. It can also significantly improve the rigidity and softness performance by combining with the attraction and fixation of the polymer plasticizer and trioctyl trimellitate and didecyl phthalate, and effectively reduce the risk of plasticizer precipitation to the surface of PVC leather.

[0015] Furthermore, the 911P plasticizer is 75-95 parts by weight in the surface layer material and 95-105 parts by weight in the bottom layer material.

[0016] Furthermore, the polymer polyester plasticizer is one or more of UN615 or E100. The polymer plasticizer is a polar polymer and has good compatibility with PVC resin. When the polymer plasticizer is used at a concentration of more than 30 parts, it can attract and fix other plasticizers. When used in combination with 911P plasticizer, it can prevent the surface plasticizer from diffusing to the surface of PVC leather, thereby improving the atomization performance and optimizing the rigidity and softness.

[0017] Furthermore, the preparation method of the bottom layer material comprises the following steps:

[0018] Weigh porous structure ultra-high polymerization degree PVC resin, ordinary polymerization degree PVC powder, stabilizer, and additives by weight, and stir them evenly at a speed of 1300-1600r / min in the state of dry powder;

[0019] Add 911P plasticizer, trioctyl trimellitate, didecyl phthalate, and dioctyl sebacate according to weight, and continue stirring until the plasticizer is completely absorbed. Finally, add calcium carbonate and flame retardant, stir thoroughly for 150-250 seconds, and pour into an internal mixer. Finally, add pigment cake and foaming agent and knead the material to obtain the base material.

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

[0021] Weigh and mix porous structure ultra-high polymerization degree PVC resin, antioxidant, anti-ultraviolet agent, stabilizer and additives by weight, stir evenly in the state of dry powder, then add high molecular polyester plasticizer, 911P plasticizer, trioctyl trimellitate, didecyl phthalate and dioctyl sebacate and continue to stir until the plasticizer is completely absorbed, continue to add calcium carbonate and stir thoroughly for 20-30s to obtain a mixture;

[0022] Pour the mixture into an internal mixer, add pigment dilution film and mix, beat the material and hammer it 4 times, the first time is 140±20s, the second time is 260±20s, the third time is 380±20s, and the fourth time is 480±20s, to obtain the surface layer material;

[0023] The temperature of the mixed material in the internal mixer is 185-200°C.

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

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

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

[0027] Furthermore, the stabilizer includes but is not limited to any one or more of a calcium zinc stabilizer, a barium zinc stabilizer or epoxidized soybean oil.

[0028] Furthermore, the additive may be an amine resistant agent, and the amine resistant agent may be any one of hypochlorite, acrylate ACR, and the like.

[0029] 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.

[0030] The present invention also provides a method for preparing the PVC artificial leather, comprising the following steps:

[0031] Surface treatment process:

[0032] A. Stir and disperse the pre-prepared mixed slurry (special water-based slurry) in the slurry tank through the printing roller to ensure that it is evenly dispersed without agglomeration or precipitation;

[0033] 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;

[0034] Embossing process:

[0035] The PVC fabric is preheated on the surface by passing it through a foaming furnace, the temperature of the four zones of the foaming furnace is 170 / 215 / 215 / 130°C, and the line speed is 10±3m / min to preheat the surface, and then the pattern is transferred to the PVC fabric through a patterned steel rod to obtain a PVC artificial leather with a texture effect;

[0036] Among them, the mixed slurry (special water-based coating slurry) adopts the existing formula, specifically:

[0037] Top coating material formula: WF-77-648+RU-13-085 / F 100%, WD-78-143 20%-40%. After the above three materials are evenly mixed, slowly add HM-13-678 3%-15%. After continuing to stir evenly, slowly add XR-5580 2%-6% while stirring; Primer material formula: WF-43-417 100%, slowly add XR-28-404 2%-6% while stirring; first apply the primer material on the substrate, dry it, and then apply the top coating material on it.

[0038] The invention also provides application of the PVC artificial leather in soft leather seats.

[0039] In summary, compared with the prior art, the present invention achieves the following technical effects:

[0040] (1) The PVC artificial leather provided by the present invention has excellent rigidity and softness performance, can meet the requirements of skin-friendly and soft products and has resilience;

[0041] (2) The PVC artificial leather provided by the present invention has high atomization performance and can achieve a balance between rigidity and softness and atomization performance;

[0042] (3) The PVC artificial leather provided by the present invention has high rubbing resistance. DETAILED DESCRIPTION

[0043] 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.

[0044] Example

[0045] 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.

[0046] 1. The sources of raw materials for the embodiments and comparative examples are as follows:

[0047] Porous structure ultra-high polymerization degree PVC resin: S-100, polymerization degree 3000-4000, Huadeng Trading;

[0048] Ordinary polymerization degree PVC powder: brand name DG-1300, polymerization degree 1300, Tianjin Dagu;

[0049] Polyester plasticizer: brand name UN615, Zhongshan Liancheng Chemical Industry Co., Ltd.

[0050] 911P plasticizer: brand SH343, Jiangsu Senhe Chemical Technology Co., Ltd.;

[0051] DOTP plasticizer: dioctyl terephthalate, brand name UN-488, Zhuhai Liancheng Chemical Industry Co., Ltd.;

[0052] Trioctyl trimellitate: brand E100, Zhejiang Xingbang Polymer Materials Co., Ltd.;

[0053] Didecyl phthalate: CAS No.: 84-77-5, Jiangsu Senhe Chemical Technology Co., Ltd.;

[0054] Dioctyl sebacate: CAS No.: 122-62-3, Zhongshan Liancheng Chemical Industry Co., Ltd.;

[0055] Stabilizer: Calcium zinc powder stabilizer, the same substance was used in all parallel experiments;

[0056] Additives: ACR, all parallel experiments used the same substance;

[0057] Calcium carbonate: CAS: 471-34-1, all parallel experiments used the same substance;

[0058] Antioxidant: Antioxidant 1076, the same substance was used in all parallel experiments;

[0059] UV-resistant agent: UV-31, the same substance was used in all parallel experiments;

[0060] Pigment dilution film: homemade, the preparation method is: mix rutile titanium dioxide with 98-102 oil content of transparent base material, and then roll it into a film to obtain the pigment dilution film;

[0061] Pigment color cake: rutile titanium dioxide, Guangzhou Juli;

[0062] The preparation method of the PVC artificial leather of the embodiment of the present invention and the comparative example comprises the following steps:

[0063] Preparation of bottom material: Weigh porous structure ultra-high polymerization degree PVC resin, ordinary polymerization degree PVC powder, stabilizer, additives by weight, stir evenly at a high speed of 1300-1600r / min in the state of dry powder; add 911P plasticizer, trioctyl trimellitate, didecyl phthalate, dioctyl sebacate by weight, continue stirring until the plasticizer is completely absorbed, finally add calcium carbonate and flame retardant, stir well for 150-250s, pour into internal mixer, finally add pigment color cake and foaming agent, and knead the materials to obtain bottom material;

[0064] Preparation of surface layer material: Weigh porous structure ultra-high polymerization degree PVC resin, antioxidant, anti-ultraviolet agent, stabilizer, additives by weight and mix, stir evenly in the state of dry powder, then add high molecular polyester plasticizer, 911P plasticizer, trioctyl trimellitate, didecyl phthalate, dioctyl sebacate and continue stirring until the plasticizer is completely absorbed, continue to add calcium carbonate and stir thoroughly for 20-30s to obtain a mixture; pour the mixture into an internal mixer, add pigment dilution film to mix, beat the material and hammer it 4 times, the first time is 140±20s, the second time is 260±20s, the third time is 380±20s, and the fourth time is 480±20s to obtain the surface layer material;

[0065] Substrate preparation:

[0066] S1. The bottom layer material is kneaded and sheared by a four-roll calender, and is pulled into a film in a molten state and attached to the 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 a base material;

[0067] PVC artificial leather preparation:

[0068] Surface treatment process: A. Stir and disperse the pre-prepared mixed slurry (special water-based coating slurry) in the slurry tank through a printing roller to confirm that the dispersion is uniform and there is no agglomeration or precipitation; B. The mixed slurry is attached to the substrate through equipment traction, passed through an 80-120 mesh sizing roller, and then dried, cooled and rolled up in an oven (135±5℃) (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; Embossing molding process: The above-mentioned PVC fabric is preheated on the surface through a foaming furnace. The temperature of the four zones of the foaming furnace body is 170 / 215 / 215 / 130℃, and the surface is preheated at a line speed of 10±3m / min. Then, the pattern is transferred to the PVC fabric through a patterned steel rod to obtain a PVC artificial leather with a texture effect.

[0069] 2. Various performance test methods

[0070] (1) Atomization performance test: Tested in accordance with QB / T 4043-2010 standard.

[0071] (2) Rigidity and softness test: Test in accordance with Q / 320585RG 015-2021.

[0072] (3) Rub resistance test: After oleic acid treatment, the test was performed in accordance with GB / T 38464-2020, and the number of rubbing times was set to 2000 times.

[0073] Table 1. Technical solutions and effects of the embodiments (unit: weight parts)

[0074]

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

[0076]

[0077]

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

[0079]

[0080] In the design of the surface material, Examples 1-9 simultaneously introduced low-volatile plasticizers, polymer polyester plasticizers, 911P plasticizers, didecyl phthalate, dioctyl sebacate and trioctyl trimellitate plasticizers, which not only improved the rubbing resistance of the soft PVC artificial leather, but also significantly improved the rigidity and softness performance and atomization performance of the artificial leather through formula design. The rigidity and softness performance can reach 40-60mm, and the atomization value is below 2mg, thereby realizing the application of the product in soft leather seats.

[0081] Comparative Examples 1-2 are compared with Example 1. In Comparative Examples 1-2, no 911P plasticizer is added to the bottom layer or the surface layer, and DOTP plasticizer is used as the plasticizer, so that the plasticizers in the artificial leather cannot cooperate with each other, and the atomization performance is significantly reduced. The PVC artificial leathers prepared in the above comparative examples cannot achieve a balance between rigidity and softness and high atomization performance.

[0082] Based on the test data of rigidity and softness and atomization performance in Table 1 and Table 2, the PVC artificial leather prepared by Examples 1-9 has obvious advantages over the comparative examples and can effectively meet the high standards of customers and the market.

[0083] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A soft PVC artificial leather, comprising a base material and a coating layer, 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: The base fabric of the substrate is any one of 100% polyester weft knitted double-sided fabric or 100% polyester warp knitted interwoven fabric. The polymerization degree of the porous structure ultra-high polymerization degree PVC resin is 3000-4000, and the polymerization degree of ordinary polymerization degree PVC powder is 1000-1400.

2. The PVC artificial leather according to claim 1, characterized in that: The porous structure ultra-high polymerization degree PVC resin in the bottom layer material is 25-35 parts by weight.

3. The PVC artificial leather according to claim 1, characterized in that: The trioctyl trimellitate is contained in the surface layer / bottom layer material in an amount of 20-30 parts by weight.

4. The PVC artificial leather according to claim 1, characterized in that: The content of didecyl phthalate in the surface layer / bottom layer material is 8-15 parts by weight.

5. The PVC artificial leather according to claim 1, characterized in that: The dioctyl sebacate plasticizer is contained in the surface layer / bottom layer material in an amount of 8-15 parts by weight.

6. The PVC artificial leather according to claim 1, characterized in that: The 911P plasticizer is 75-95 parts by weight in the surface layer material and 95-105 parts by weight in the bottom layer 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 and mix porous structure ultra-high polymerization degree PVC resin, antioxidant, anti-ultraviolet agent, stabilizer and additives by weight, stir evenly in the state of dry powder, then add high molecular polyester plasticizer, 911P plasticizer, trioctyl trimellitate, didecyl phthalate and dioctyl sebacate and continue to stir until the plasticizer is completely absorbed, continue to add calcium carbonate and stir thoroughly for 20-30s to obtain a mixture; Pour the mixture into an internal mixer, add pigment dilution tablets and mix, pound the material 4 times, the first time is 140±20s, the second time is 260±20s, the third time is 380±20s, and the fourth time is 480±20s, to obtain the surface layer 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 rolled in an oven 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 in soft leather seats.

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