Suede PVC artificial leather and preparation method thereof

Abstract

The invention provides suede PVC artificial leather and a preparation method thereof, and relates to the technical field of artificial leather. The suede PVC artificial leather comprises the following raw materials in parts by mass: 100 parts of PVC powder, 100 parts of a plasticizer, 0.5-3 parts of an antioxidant, 0.5-3 parts of an anti-ultraviolet agent, 3-10 parts of a stabilizer, 1-3 parts of a processing aid, 1-10 parts of a pigment and 5-20 parts of MBS. According to the suede PVC artificial leather provided by the invention, through formula combination and process adjustment, the prepared suede PVC artificial leather is unlikely to become white after being subjected to subsequent processing, sewing and splicing, the surface is free of obvious oil separation condition, the suede PVC artificial leather is bent at low temperature and is free of breakage condition, and the texture depth of suede reaches 115 microns; the suede PVC artificial leather provided by the invention has excellent aging resistance.

Description

Technical Field

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

[0002] Suede PVC artificial leather is a composite material, which is a mixture of polyvinyl chloride resin, plasticizer, stabilizer and other additives, and then laminated into a base material through a calender. A layer of oily surface treatment agent is applied on the base material, and then hot-pressed by a special suede roller. Finally, a layer of smooth feel surface treatment agent is applied to the formed suede base material, and then dried to form.

[0003] Suede-like PVC artificial leather can be used for automotive interior covering. In the design and production process of suede-like PVC artificial leather, it is easy to have whitening problem after sewing and splicing in the later stage. In addition, although oily treatment has its unique effect in the design of suede-like PVC artificial leather, especially in giving the material matte and delicate texture. However, the coating of the oily surface treatment agent cracks after high-temperature foaming, which reduces the oil sealing ability of the base plasticizer and affects the adhesion of the coating. Summary of the invention

[0004] Based on the technical problems existing in the background technology, the present invention proposes a suede-like PVC artificial leather and a preparation method thereof.

[0005] The invention provides a suede-like PVC artificial leather, which comprises PVC powder and a plasticizer.

[0006] Preferably, the plasticizer includes DPHP, adipic acid polyester plasticizer, and DOS.

[0007] More preferably, the mass ratio of DPHP, adipic acid polyester plasticizer and DOS is (45-55):30:(15-25).

[0008] More preferably, the molecular weight of the adipic acid polyester plasticizer is 3000-4000.

[0009] The molecular weight of adipic acid polyester plasticizer within a certain range helps to bind more firmly to the PVC molecular chain and is conducive to reducing precipitation.

[0010] Preferably, the suede-like PVC artificial leather further comprises an antioxidant, an anti-ultraviolet agent, a stabilizer, a processing aid, and a pigment.

[0011] Preferably, the suede-like PVC artificial leather further comprises MBS.

[0012] MBS is a terpolymer of methyl methacrylate, butadiene and styrene. The addition of MBS rubber elastic material improves the surface's temperature and pressure resistance. Due to the compatibility of MBS's core-shell structure with PVC, it helps to improve PVC's low-temperature impact resistance. MBS has a typical "core-shell" structure, with the core being styrene-butadiene rubber and the shell being polystyrene and grafted methyl methacrylate. This structure enables MBS to absorb and disperse energy when subjected to external impact, thereby improving PVC's impact resistance.

[0013] More preferably, the antioxidant is selected from one or more of n-octadecyl propionate, pentaerythritol ester and phosphite.

[0014] More preferably, the anti-ultraviolet agent is selected from one or more of 2-(2'-hydroxy-3',5'-di-tert-phenyl)-5-chlorobenzotriazole, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and benzotriazole.

[0015] More preferably, the stabilizer is selected from one or more of a calcium-zinc composite metal soap stabilizer and a solid composite calcium-zinc soap stabilizer.

[0016] More preferably, the solid composite calcium zinc soap stabilizer includes stearic acid soap, lauric acid soap, and oleic acid soap.

[0017] More preferably, the processing aid is ACR.

[0018] More preferably, the pigment is selected from one or more of titanium dioxide, red iron oxide and carbon black.

[0019] Preferably, the suede-like PVC artificial leather comprises the following raw materials in parts by weight: 100 parts of PVC powder, 100 parts of plasticizer, 0.5-3 parts of antioxidant, 0.5-3 parts of anti-ultraviolet agent, 3-10 parts of stabilizer, 1-3 parts of processing aid, 1-10 parts of pigment, and 5-20 parts of MBS.

[0020] The present invention also provides a method for preparing suede-like PVC artificial leather, comprising the following steps: S1. After PVC powder and DOS are evenly mixed, antioxidant, anti-ultraviolet agent, stabilizer, processing aid and MBS are added and stirred at high speed to obtain mixed material A; S2, adding DPHP and adipic acid polyester plasticizer to the mixed material A, mixing evenly, to obtain a mixed material B; S3, mixing the mixed material B and the pigment to obtain a clinker; S4, rolling and laminating the clinker to obtain a substrate, applying a water-based primer on the surface of the substrate, and drying to obtain a primer-coated substrate; S5, subjecting the primed substrate to a suede-like embossing process, and performing heating and roller pressing to obtain an embossed substrate; S6, treating the embossed substrate with a smooth water-based treatment agent and then drying to obtain suede-like PVC artificial leather.

[0021] The dry-mixing modification method of hot mixing of DOS is to pre-add DOS to a certain amount of PVC synthetic resin powder, stir it under certain temperature conditions, and obtain a dry-mixed powder that looks the same as the original synthetic resin. The purpose of pre-mixing modification is to consider that DOS has a small molecular weight and is easy to separate from PVC molecules. DOS is heated and dry-mixed in advance to enter the PVC particle cavity structure in advance to reduce precipitation.

[0022] Preferably, in S1, the mixing temperature is 30-70° C., and the mixing time is 10-25 min.

[0023] Mixing temperature and time within a certain range are conducive to sufficient intermolecular movement, and intense thermal movement can improve the degree of mixing.

[0024] Preferably, in S1, the rotation speed of high-speed stirring is 1000-2000 r / min.

[0025] Preferably, in S2, the stirring speed is 1000-1500 r / min.

[0026] Preferably, in S3, the temperature of banburying is 140-150° C., and the speed of banburying is 700-900 r / min.

[0027] Preferably, in S4, the water-based primer is coated on the surface of the substrate by an anilox roller.

[0028] Preferably, in S4, the water-based primer is polyurethane urea polyurethane resin.

[0029] The water-based primer is polyurethane urea polyurethane resin, which helps to block the plasticizer precipitation of the PVC substrate and can be combined with the surface treatment agent to achieve the purpose of bonding layer. Polyurethane urea is a polyurethane resin formed by the reaction of urea and polyisocyanate, and has excellent wear resistance, tensile strength and aging resistance.

[0030] Preferably, in S4, the mesh number of the sizing roller of the water-based primer is 150-250 mesh, and the sizing amount is 5-12 g / m 2 .

[0031] The mesh number of the sizing roller and the amount of sizing within a certain range can help ensure the leveling of the coating surface, reduce the impact of the coating hardness, and reduce the cost. Too little sizing will affect the coating thickness and cause the surface to be poorly leveled and shiny; too much sizing will result in high costs and is not conducive to actual production applications.

[0032] Preferably, in said S4, the drying temperature is 100-150°C.

[0033] Preferably, in said S5, the heating temperature is 180-190°C.

[0034] The present invention controls the heating temperature of the suede-like embossing process within a certain range and adds MBS rubber elastic material for synergistic effect, thereby increasing the depth of the suede-like texture and preventing surface cracking.

[0035] Preferably, in the S6, the slippery water treatment agent is selected from one or more of Stahl WF 3649 or Foshan Yike WK-01.

[0036] Preferably, in said S6, the drying temperature is 100-150°C.

[0037] The beneficial effects of the present invention are: The invention provides a suede-like PVC artificial leather. The suede-like PVC artificial leather prepared by formula combination and process adjustment is not prone to whitening after sewing and splicing in the later stage, has no obvious oil separation on the surface, and has no cracking when bent at low temperature. The depth of the suede-like PVC artificial leather reaches 115 μm. In addition, the suede-like PVC artificial leather provided by the invention has excellent aging resistance.

[0038] The present invention considers the problem of plasticizer precipitation of PVC substrate, corrodes oily primer, and affects the adhesion of surface coating. Optimize the plasticizer combination formula and preparation process to reduce the risk of plasticizer precipitation; at the same time, take into account the increase in cost. In the prior art, the primer material of the oily acrylic surface treatment agent is not resistant to high temperature, and the coating is prone to cracking in the high temperature of foaming embossing, and there is a gap that blocks the plasticizer; the oily treatment agent easily leads to reduced adhesion of the coating, causing seam delamination. The present invention replaces the primer with a water-based polyurethane urea polyurethane surface treatment agent to increase adhesion, and then foams it again. It has good performance and high hardness. Although it may be unfavorable for the fine problems of suede molding, the present invention adjusts the sizing roller to reduce the sizing amount and reduce the hardness of the primer through process coordination adjustment, solving the molding problem of suede. In addition, the present invention improves the suede texture depth of the finished product and the temperature and pressure resistance of the surface by regulating the molding temperature of the heating cover in the suede embossing process and adding MBS rubber elastic material. The plasticizer of the present invention includes three plasticizers: DPHP, adipic acid polyester plasticizer, and DOS. DPHP is cheap, but has a low molecular weight (about 1000), and its bonding strength with PVC resin is relatively weak; adipic acid polyester plasticizer is a polar polymer with good weather resistance, low heat loss, large molecular weight, and good compatibility with PVC resin. The use of polymer plasticizer can attract and fix other plasticizers, enhance the bonding strength with PVC resin molecules, and reduce the amount of plasticizer precipitation on the surface under bending and extrusion, but the adipic acid polyester plasticizer has high viscosity, slow oil absorption speed, and high price; DOS dioctyl sebacate utilizes its low-temperature softness to improve the overall bending performance of the product at low temperatures; but because DOS has a low molecular weight and is easy to precipitate, it is necessary to control the amount of DOS added. The present invention obtains the optimal ratio of the three plasticizers by regulating the addition amounts of DOS, DPHP, and adipic acid polyester plasticizer. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a diagram showing the sewing effect of the suede-like PVC artificial leather after high-temperature treatment in Example 1 of the present invention.

[0040] Figure 2 This is a diagram of the sewing effect of the suede-like PVC artificial leather after high-temperature treatment in Comparative Example 18 of the present invention. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is described in detail through specific embodiments.

[0042] In the following examples and comparative examples, the specific information of the raw materials used is as follows: Adipic acid polyester plasticizer: Manufacturer: Zhongshan Liancheng, Model: UN-615H.

[0043] Water-based primer: Manufacturer: Stahl, Brand: polyurethane urea polyurethane resin WF-417.

[0044] Smooth water-based treatment agent: Manufacturer: Starr, Brand: Water-based polyurethane WF-3649.

[0045] Calcium zinc complex metal soap stabilizer: Manufacturer: Kaimisen, brand: PXD9283CZ.

[0046] Unless otherwise specified, the materials, reagents, etc. used in the following examples and comparative examples can be obtained from commercial sources. Example 1

[0047] A suede-like PVC artificial leather comprises the following raw materials by weight: 100 parts of PVC powder, 100 parts of plasticizer, 1 part of antioxidant, 1 part of anti-ultraviolet agent, 5 parts of stabilizer, 1 part of processing aid, 3 parts of pigment, and 10 parts of MBS. Among them, the antioxidant is pentaerythritol ester, the anti-ultraviolet agent is 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, the stabilizer is calcium zinc composite metal soap stabilizer, the processing aid is ACR, and the pigment is titanium dioxide and carbon black. The plasticizer includes DPHP, DOS, and adipic acid polyester plasticizer.

[0048] A method for preparing suede-like PVC artificial leather comprises the following steps: S1. Mix PVC powder and DOS at 50°C for 15 minutes, add antioxidant, anti-ultraviolet agent, stabilizer, processing aid and MBS, and stir at high speed in the state of dry powder to obtain mixed material A; the speed of high-speed stirring is 1500r / min; S2. Add DPHP and adipic acid polyester plasticizer to the mixed material A and mix evenly until the plasticizer is completely absorbed to obtain a mixed material B; the stirring speed is 1500r / min; S3, pouring the mixed material B into a mixer, and then adding pigment, until the material is kneaded to obtain a clinker; the kneading temperature is 140°C, and the kneading speed is 800r / min; S4, the clinker is calendered and laminated to obtain a substrate, and a water-based primer is applied to the substrate surface by an anilox roller, and the sizing roller is 200 mesh, and the sizing amount is 8.5g / m 2 , and then dried at 125℃ to achieve a matte effect, and obtain a primer-coated substrate; calendering and laminating includes: laminating the PVC surface layer, the PVC foaming layer, and the base fabric layer together; S5, subjecting the primed substrate to a suede-like embossing process, setting the heating cover molding temperature to 185° C., and performing high-temperature heating and roller pressing to obtain an embossed substrate; S6. The embossed substrate is treated with a smooth water-based treatment agent and dried at 125°C to obtain suede-like PVC artificial leather.

[0049] Embodiment 2-4 The only difference from Example 1 is that the contents of plasticizer and MBS are different, see Table 1 for details, and the rest are the same as Example 1.

[0050] Comparative Example 1 The only difference from Example 1 is that the contents of plasticizer and MBS are different, see Table 1 for details, and the rest are the same as Example 1.

[0051] Comparative Examples 2-3 Compared with Example 1, the only difference is that the molding temperature of the heating hood in S5 is set to 170° C., and the contents of plasticizer and MBS are different, see Table 1 for details, and the rest is the same as Example 1.

[0052] Comparative Example 4 The only difference from Comparative Example 1 is that the molding temperature of the heating hood in S5 is set to 170° C., and the rest is the same as Comparative Example 1.

[0053] Comparative Examples 5-7 The only difference from Example 1 is that the contents of plasticizer and MBS are different, see Table 1 for details, and the rest are the same as Example 1.

[0054] Comparative Examples 8-14 The only difference from Comparative Example 4 is that the content of the plasticizer is different, see Table 1 for details, and the rest is the same as Comparative Example 4.

[0055] Comparative Examples 15-17 The only difference from Example 1 is that the contents of plasticizer and MBS are different, see Table 1 for details, and the rest are the same as Example 1.

[0056] Comparative Example 18 A suede-like PVC artificial leather comprises the following raw materials in parts by weight: 100 parts of PVC powder, 100 parts of DPHP, 1 part of antioxidant, 1 part of UV inhibitor, 5 parts of stabilizer, 1 part of processing aid, 3 parts of pigment, 10 parts of MBS.

[0057] A method for preparing suede-like PVC artificial leather comprises the following steps: S1. Stir PVC powder, antioxidant, anti-ultraviolet agent, stabilizer, processing aid and MBS at high speed in a dry powder state to obtain a mixed material A; the speed of high-speed stirring is 1500r / min; S2. Add DPHP to the mixed material A and stir until the plasticizer is completely absorbed to obtain a mixed material B; the stirring speed is 1500 r / min; S3, pouring the mixed material B into a mixer, and then adding pigment, until the material is kneaded to obtain a clinker; the kneading temperature is 140°C, and the kneading speed is 800r / min; S4, the clinker is calendered and laminated to obtain a substrate, and an oily matte treatment agent is applied to the surface of the substrate through an anilox roller, the sizing roller is 100 mesh, and the sizing amount is 13g / m 2 , and then dried at 115℃ to achieve the matte effect, and obtain the base material after primer coating; calendering and laminating include: laminating the PVC surface layer, PVC foam layer and base fabric layer together; S5, subjecting the primed substrate to a suede-like embossing process, setting the heating cover molding temperature to 175° C., and performing high-temperature heating roller molding to obtain an embossed substrate; S6. The embossed substrate is treated with a layer of oily matte treatment agent and dried at 115°C to obtain suede-like PVC artificial leather. Manufacturer of oily matte treatment agent: Nantong Shengguang, brand: RD033 / 34.

[0058] Table 1

[0059] The above-mentioned suede-like PVC artificial leather was tested for surface oiling and low-temperature bending resistance. Surface oiling test: Fold the sample in half along the long side with the base fabric facing outward, press the sample with a hard pressing plate, place a load of 2kg in the middle of the pressing plate, test for 4 hours, wipe the oiling area with cigarette paper, and rate the oily marks on the cigarette paper; Level 1: There is a large area of ​​oily marks on the paper, Level 2: There is a continuous oily mark on the paper, Level 3: There is a dotted oily mark on the paper, Level 4: There is a slight and discontinuous oily mark on the paper, and Level 5: There is no oily mark on the paper. Low temperature flexural resistance test: According to QB / T 2714-2018 Determination of folding fastness of leather physical and mechanical tests, the samples are subjected to -30℃ / 20,000 times flexural resistance test to observe the surface cracking of the samples; Level 1: All test samples have serious surface cracks, Level 2: Half of the samples have surface cracks, Level 3: There are continuous shallow marks, and less than half of the samples have surface cracks, Level 4: There are intermittent shallow marks, no surface cracks, and Level 5: There are slight creases, no surface cracks. The test results are shown in Table 2.

[0060] Table 2

[0061] The pattern depth test of Examples 1-4 and Comparative Examples 1-4 was carried out, and the surface texture depth was tested by SJ-20 depth meter, and the Rz value was read. Example 1: 110μm; Example 2: 110μm; Example 3: 115μm; Example 4: 100μm; Comparative Example 1: 90μm; Comparative Example 2: 83μm; Comparative Example 3: 85μm; Comparative Example 4: 83μm. From the pattern depth test results of Examples 1-4 and Comparative Example 1, it can be seen that as the addition amount of MBS increases, the pattern depth also increases.

[0062] It can be seen from the data in Table 2 that the surface oil separation of the suede-like PVC artificial leather of Examples 1-4 of the present invention is level 4 without obvious precipitation, and there are intermittent or slight shallow marks after the low-temperature bending resistance test, without surface cracks, and the pattern depth is deep, indicating that the suede-like PVC artificial leather prepared by the present invention has excellent performance. It can be seen from the data of Comparative Example 1 and Example 1 that without adding MBS, the PVC surface is overheated and cracked under high temperature conditions, and the pattern depth is shallow. It can be seen from the data of Comparative Examples 2-4 that after lowering the molding temperature of the heating hood, the surface oil separation is level 4 without obvious precipitation, the low-temperature bending resistance is level 3 or 4, and the pattern depth is reduced.

[0063] It can be seen from the data of Comparative Examples 5-7 and Example 1 that adding only one plasticizer will cause surface oil separation or low-temperature cracking. It can be seen from the data of Comparative Examples 8-14 that the present invention adjusts the raw material ratio of three plasticizers, DPHP, adipic acid polyester plasticizer, and DOS, to obtain a suede-like PVC artificial leather with no obvious oil separation on the surface and no cracking at low temperature. It can be seen from the data of Comparative Examples 15-17 and Example 1 that adding only two of the three plasticizers, DPHP, adipic acid polyester plasticizer, and DOS, cannot achieve the effect of the present invention.

[0064] Figure 1 This is a sewing effect diagram of the suede-like PVC artificial leather after high temperature treatment in Example 1 of the present invention (110°C, 30min). Figure 2 This is the sewing effect diagram of the suede PVC artificial leather after high temperature treatment of comparative example 18 of the present invention (110°C, 5min). It can be seen that Figure 1 The middle seam is intact, without whitening. Figure 2 It can be seen that the suede-like PVC artificial leather prepared by adjusting the raw material ratio and process of the present invention is not prone to the phenomenon of whitening in the seams.

[0065] The anti-adhesion property of the suede-like PVC artificial leather obtained in Example 1 was tested according to QJ / XP 16JT.027-2021, and the test conditions were: temperature 23±2°C, humidity: 50±10%RH, sample size: 60mm*60mm / 6 pieces, experimental conditions: two pieces as a group of samples, sandwiched in glass, applied load: 10N, test temperature: 80°C, test time 3h, and taken out and placed at room temperature for 30min. The test results are shown in Table 3.

[0066] Table 3

[0067] It can be seen from the data in Table 3 that the anti-adhesion property of the suede-like PVC artificial leather prepared by the present invention is level 5, indicating that no plasticizer is precipitated on the surface to cause adhesion.

[0068] The aging resistance of the suede-like PVC artificial leather obtained in Example 1 was tested according to QJ / XP 16JT.027-2021. Before testing, the sample was placed in a standard laboratory under the conditions of 23±2°C and 50±5%RH for at least 24 hours. The test standard was SAE J2412-2015, and the test energy was 602KJ / m 2 The specific test conditions are shown in Table 4. The test results are shown in Table 5.

[0069] Table 4

[0070] Table 5

[0071] It can be seen from the data in Table 5 that the suede-like PVC artificial leather prepared by the present invention has no obvious change in appearance after the aging resistance test, indicating that the suede-like PVC artificial leather prepared by the present invention has excellent aging resistance.

[0072] In summary, the suede-like PVC artificial leather provided by the present invention is not prone to whitening after sewing and splicing in the later stage, has no obvious oil separation on the surface, and has no cracking when bent at low temperature. In addition, the suede-like PVC artificial leather provided by the present invention has excellent aging resistance.

[0073] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A suede-like PVC artificial leather, characterized in that: It comprises PVC powder and plasticizer, wherein the plasticizer comprises DPHP, adipic acid polyester plasticizer and DOS, wherein the molecular weight of the adipic acid polyester plasticizer is 3000-4000; and the mass ratio of the DPHP, adipic acid polyester plasticizer and DOS is (45-55):30:(15-25).

2. The suede-like PVC artificial leather according to claim 1, characterized in that: The suede-like PVC artificial leather also includes an antioxidant, an anti-ultraviolet agent, a stabilizer, a processing aid and a pigment.

3. The suede-like PVC artificial leather according to claim 2, characterized in that: The suede-like PVC artificial leather also includes MBS.

4. The suede-like PVC artificial leather according to claim 3, characterized in that: The suede-like PVC artificial leather comprises the following raw materials in parts by weight: 100 parts of PVC powder, 100 parts of plasticizer, 0.5-3 parts of antioxidant, 0.5-3 parts of anti-ultraviolet agent, 3-10 parts of stabilizer, 1-3 parts of processing aid, 1-10 parts of pigment and 5-20 parts of MBS.

5. The suede-like PVC artificial leather according to claim 4, characterized in that: The antioxidant is selected from one or more of n-octadecyl propionate, pentaerythritol ester, and phosphite; the UV inhibitor is selected from one or more of 2-(2'-hydroxy-3', 5'-di-tert-phenyl)-5-chlorobenzotriazole, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and benzotriazole; the stabilizer is selected from one or more of calcium-zinc composite metal soap stabilizers and solid composite calcium-zinc soap stabilizers.

6. A method for preparing the suede-like PVC artificial leather according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. After PVC powder and DOS are evenly mixed, antioxidant, anti-ultraviolet agent, stabilizer, processing aid and MBS are added and stirred at high speed to obtain mixed material A; S2, adding DPHP and adipic acid polyester plasticizer to the mixed material A, mixing evenly, to obtain a mixed material B; S3, mixing the mixed material B and the pigment to obtain a clinker; S4, rolling and laminating the clinker to obtain a substrate, applying a water-based primer on the surface of the substrate, and drying to obtain a primer-coated substrate; S5, subjecting the primed substrate to a suede-like embossing process, and performing heating and roller pressing to obtain an embossed substrate; S6, treating the embossed substrate with a smooth water-based treatment agent and then drying to obtain suede-like PVC artificial leather.

7. The preparation method according to claim 6, characterized in that: In the S4, the water-based primer is polyurethane urea polyurethane resin; the mesh number of the sizing roller of the water-based primer is 150-250 mesh, and the sizing amount is 5-12g / m 2 .

8. The preparation method according to claim 6, characterized in that: In the step S5, the heating temperature is 180-190°C.

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