Highly folding-resistant flame-retardant artificial leather for vehicles and preparation method thereof

Abstract

The invention discloses high-folding-resistance flame-retardant artificial leather for a vehicle and a preparation method of the artificial leather, and relates to the technical field of artificial leather. The artificial leather comprises a base cloth layer, a PVC bottom layer and a PVC surface layer which are arranged in sequence; a composite additive is added to each of the PVC bottom layer and the PVC surface layer, and the composite additive is prepared from hydroxyl-terminated polybutadiene, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and methyl vinyl phenyl silicone rubber. The artificial leather disclosed by the invention has good folding resistance and flame retardance.

Description

Technical Field

[0001] The present invention relates to the technical field of artificial leather, and particularly to a high flex-resistant and flame-retardant artificial leather for vehicles and a preparation method thereof. Background Art

[0002] Nowadays, driven by issues such as the continuous increase in the environment, economy, and consumer demand, the artificial leather and synthetic leather industry is developing towards the direction of functional diversity. Vehicle-use PVC leather is prone to hardening, becoming brittle, and having poor flexibility under extreme environments, resulting in a decrease in physical properties. It will arch and break when encountering external factors, affecting aesthetics and normal use. Currently, the prices of various flame retardants are high, resulting in a significant increase in the preparation cost of artificial leather. Summary of the Invention

[0003] Based on the technical problems existing in the background art, the present invention provides a high flex-resistant and flame-retardant artificial leather for vehicles and a preparation method thereof, which have good flex resistance and flame retardancy.

[0004] A high flex-resistant and flame-retardant artificial leather for vehicles proposed by the present invention includes a base fabric layer, a PVC bottom layer, and a PVC top layer arranged in sequence; Both the PVC bottom layer and the PVC top layer are added with a composite additive, and the composite additive is composed of hydroxyl-terminated polybutadiene, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and methyl vinyl phenyl silicone rubber.

[0005] Preferably, the mass ratio of hydroxyl-terminated polybutadiene, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and methyl vinyl phenyl silicone rubber is 1:0.5 - 1:0.5 - 2.

[0006] Preferably, the PVC bottom layer contains the following raw materials in parts by weight: 100 parts of PVC resin, 60 - 90 parts of plasticizer, 1 - 5 parts of foaming agent, 1 - 5 parts of stabilizer, 10 - 30 parts of composite additive, 10 - 30 parts of flame retardant, 20 - 40 parts of filler, and 10 - 20 parts of colorant.

[0007] Preferably, the PVC top layer contains the following raw materials in parts by weight: 100 parts of PVC resin, 60 - 90 parts of plasticizer, 1 - 5 parts of stabilizer, 10 - 30 parts of composite additive, 10 - 30 parts of filler, and 5 - 10 parts of colorant.

[0008] Preferably, the plasticizer is a phthalate plasticizer; the foaming agent is an azo foaming agent; the flame retardant is an antimony flame retardant; the stabilizer is a calcium-zinc stabilizer; the filler is a carbonate mineral powder filler.

[0009] A preparation method of a high flex-resistant and flame-retardant artificial leather for vehicles proposed by the present invention, the artificial leather is as described above, and the method steps are as follows: S1: Mix PVC resin, plasticizer, foaming agent, stabilizer, composite additive, flame retardant, filler and colorant in a blender at 100 - 140°C for 5 - 10 min, and then mix in a high-temperature internal mixer at 140 - 170°C for 5 - 10 min to form the PVC bottom layer mixture; S2: Thermally press and bond the PVC bottom layer mixture and the base fabric layer at 150 - 190°C to obtain the semi-finished bottom material; S3: Mix PVC resin, plasticizer, stabilizer, composite additive, filler and colorant in a blender at 100 - 140°C for 5 - 10 min, and then mix in a high-temperature internal mixer at 140 - 170°C for 5 - 10 min to form the PVC surface layer mixture; S4: Thermally press and bond the PVC surface layer mixture and the semi-finished bottom material at 150 - 190°C to obtain the semi-finished raw material; S5: Foam the semi-finished raw material at 180 - 230°C for 50 - 100 seconds; S6: Treat the surface of the foamed raw material with a water-based treatment agent, and then perform embossing decoration to obtain the finished artificial leather.

[0010] Mechanism of action: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) can react with the carbon-carbon double bond in hydroxyl-terminated polybutadiene (HTPB) at room temperature or high temperature to form a stable chemical bond; and HTPB can form a three-dimensional network structure through chain extension and cross-linking curing reactions. In addition, the P-H bond of DOPO can also form a P-C bond with the vinyl group in polymethylvinylphenylsilicone rubber (PVMQ) at high temperature through free radical addition or electrophilic addition, thereby grafting DOPO onto the PVMQ molecular chain and significantly improving the flame retardancy of the silicone rubber. Through the synergistic effect of HTPB, DOPO and PVMQ, the artificial leather prepared by the present invention has good folding resistance and flame retardancy.

[0011] Advantageous technical effects of the present invention: The present invention prepares artificial leather by adding high polymers to the polyvinyl chloride bottom layer and surface layer, so that it has good folding resistance at different temperature environments. In addition, due to the high stability and flame resistance characteristics of these three high polymers HTPB, DOPO and PVMQ themselves, they can replace some expensive flame retardants, thereby reducing the preparation cost while meeting the vehicle-use flame retardancy standard. Description of the drawings

[0012] Figure 1 It is a schematic structural diagram of the highly fold-resistant and flame-retardant vehicle-use artificial leather proposed by the present invention.

[0013] In the figure: 1 - base fabric layer, 2 - PVC bottom layer, 3 - PVC top layer. Specific embodiments

[0014] The present invention will be further explained below in conjunction with specific embodiments.

[0015] In the embodiments of the present invention, the PVC resin is polyvinyl chloride resin with a polymerization degree of 1300, purchased from Ningbo Weiye Plastic Co., Ltd.; the plasticizer is a phthalate plasticizer, and in the embodiment, n-decyl phthalate is selected, purchased from Shandong Xuchen Chemical Technology Co., Ltd.; the foaming agent is an azo foaming agent, and in the embodiment, azodicarbonamide is selected, purchased from Wuxi Aodecheng Chemical Co., Ltd.; the flame retardant is an antimony-based flame retardant, and in the embodiment, antimony trioxide is selected, purchased from Shanghai Zhaoqian Chemical Co., Ltd.; the stabilizer is a calcium-zinc stabilizer, and in the embodiment, a calcium-zinc composite stabilizer is selected, purchased from Byk-Chemie New Materials Technology Co., Ltd.; the filler is a carbonate mineral powder filler, and in the embodiment, calcium carbonate is selected, purchased from Zhangjiagang Qinchang Calcium Carbonate Co., Ltd.; the colorant is purchased from Guangzhou Huihe Color Pigment Co., Ltd.; HTPB is purchased from Zhongshan Yuanda New Materials Co., Ltd.; DOPO is purchased from Jiangsu Chiyu Chemical Co., Ltd.; PVMQ is purchased from Hubei Longsheng Sihai New Materials Co., Ltd.

[0016] Example 1 The preparation method of the high flexural fatigue resistant and flame retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2 and a PVC top layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 80 parts of plasticizer, 4 parts of foaming agent, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of flame retardant, 35 parts of filler, and 15 parts of colorant.

[0017] The PVC top layer 3 contains the following preparation raw materials by weight: 100 parts of PVC resin, 60 parts of plasticizer, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of filler, and 5 parts of colorant.

[0018] In the present invention, the colorants for the PVC bottom layer and the top layer are carbon black, titanium dioxide (white titanium dioxide), hydrated iron oxide yellow, iron trioxide (red), phthalocyanine blue, phthalocyanine green, etc. The colorants are generally several mixtures according to color requirements.

[0019] The composite additive in the present invention is a compound of HTPB, DOPO and PVMQ in a mass ratio of 1:1:2.

[0020] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0021] The preparation method steps of the above-mentioned high flexural fatigue resistant and flame retardant automotive artificial leather proposed by the present invention are as follows: S1: Mix PVC resin, plasticizer, foaming agent, stabilizer, composite additive, flame retardant, filler, and colorant in a mixer at 120°C for 5 minutes, and then mix in a high-temperature internal mixer at 155°C for 10 minutes to form the bottom layer mixture. S2: Thermally press and bond the bottom layer mixture and the base fabric layer at 160°C to obtain the semi-finished bottom material. S3: Mix PVC resin, plasticizer, stabilizer, composite additive, filler, and colorant in a mixer at 120°C for 5 minutes, and then mix in a high-temperature internal mixer at 155°C for 10 minutes to form the surface layer mixture. S4: Thermally press and bond the surface layer mixture and the semi-finished bottom material at 160°C. S5: Foam the semi-finished raw material obtained in S4 at 220°C for 60 seconds. S6: Treat the surface of the foamed raw material with an aqueous treatment agent, and then emboss and decorate it.

[0022] Example 2 The preparation method of the highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 60 parts of plasticizer, 1 part of foaming agent, 1 part of stabilizer, 10 parts of composite additive, 10 parts of flame retardant, 20 parts of filler, and 10 parts of colorant.

[0023] The PVC surface layer 3 contains the following preparation raw materials by weight: 100 parts of PVC resin, 60 parts of plasticizer, 1 part of stabilizer, 10 parts of composite additive, 10 parts of filler, and 5 parts of colorant.

[0024] The composite additive in the present invention is a compound of HTPB, DOPO, and PVMQ in a mass ratio of 1:1:2.

[0025] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0026] The steps of the preparation method of the above-mentioned highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0027] Example 3 The highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 90 parts of plasticizer, 5 parts of foaming agent, 5 parts of stabilizer, 30 parts of composite additive, 10 parts of flame retardant, 40 parts of filler, and 20 parts of colorant.

[0028] The PVC surface layer 3 contains the following raw materials for preparation by weight: 100 parts of PVC resin, 90 parts of plasticizer, 5 parts of stabilizer, 30 parts of composite additive, 30 parts of filler, and 10 parts of colorant.

[0029] The composite additive in the present invention is a compound of HTPB, DOPO, and PVMQ in a mass ratio of 1:1:2.

[0030] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0031] The preparation method steps of the above high-fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0032] Comparative Example 1 The high-fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 80 parts of plasticizer, 4 parts of foaming agent, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of flame retardant, 35 parts of filler, and 15 parts of colorant.

[0033] The PVC surface layer 3 contains the following raw materials for preparation by weight: 100 parts of PVC resin, 60 parts of plasticizer, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of filler, and 5 parts of colorant.

[0034] The composite additive in the present invention is a compound of HTPB and DOPO in a mass ratio of 1:1.

[0035] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0036] The preparation method steps of the above high-fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0037] Comparative Example 2 The high-fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 80 parts of plasticizer, 4 parts of foaming agent, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of flame retardant, 35 parts of filler, and 15 parts of colorant.

[0038] The PVC surface layer 3 contains the following raw materials for preparation by weight: 100 parts of PVC resin, 60 parts of plasticizer, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of filler, and 5 parts of colorant.

[0039] The composite additive in the present invention is a compound of HTPB and PVMQ in a mass ratio of 1:2.

[0040] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0041] The preparation method steps of the above-mentioned highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0042] Comparative Example 3 The preparation method of the highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 80 parts of plasticizer, 4 parts of foaming agent, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of flame retardant, 35 parts of filler, and 15 parts of colorant.

[0043] The PVC surface layer 3 contains the following preparation raw materials by weight: 100 parts of PVC resin, 60 parts of plasticizer, 2 parts of stabilizer, 20 parts of composite additive, 10 parts of filler, and 5 parts of colorant.

[0044] The composite additive in the present invention is a compound of DOPO and PVMQ in a mass ratio of 1:2.

[0045] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0046] The preparation method steps of the above-mentioned highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0047] Comparative Example 4 The preparation method of the highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention includes a base fabric layer 1, a PVC bottom layer 2, and a PVC surface layer 3 arranged in sequence, wherein: The PVC bottom layer 2 contains the following raw materials by weight: 100 parts of PVC resin, 80 parts of plasticizer, 4 parts of foaming agent, 2 parts of stabilizer, 20 parts of flame retardant, 35 parts of filler, and 15 parts of colorant.

[0048] The PVC surface layer 3 contains the following preparation raw materials by weight: 100 parts of PVC resin, 60 parts of plasticizer, 2 parts of stabilizer, 10 parts of filler, and 5 parts of colorant.

[0049] The base fabric layer 1 in the present invention is made of polyester synthetic fiber.

[0050] The preparation method steps of the above-mentioned highly fold-resistant and flame-retardant automotive artificial leather proposed by the present invention are the same as those in Example 1.

[0051] Perform performance measurements on the automotive artificial leather prepared in Examples 1-3 and Comparative Examples 1-4. The fold resistance fastness test at normal temperature and -30°C is carried out according to the international standard QB / T 2714-2018; the flame retardancy test is carried out according to the national standard GB 8410-2006. The test results are shown in Table 1.

[0052] Table 1 Flexural Fatigue and Flame Retardancy Performance Tests

[0053] From the test results of Example 1 and Comparative Examples 1-3 in Table 1, it can be seen that these three high polymers have a good synergistic promotion effect, can better exert their own properties, and significantly improve the low-temperature flexural fatigue performance of artificial leather. From the test results of Examples 1-3 and Comparative Example 4, it can be seen that the optimal ratio of these three high polymers can replace some expensive flame retardants, reduce the preparation cost, and further improve the stability of the material and the safety of application.

[0054] Although the embodiments of the present application have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principle and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents, and all should be included within the protection scope of the present application.

Claims

1. A highly folding-resistant and flame-retardant artificial leather for automobiles, characterized in that: It comprises a base fabric layer (1), a PVC bottom layer (2) and a PVC surface layer (3) which are arranged in sequence; The PVC bottom layer (2) and the PVC surface layer (3) are both added with a composite additive, wherein the composite additive is composed of terminal hydroxyl polybutadiene, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and methyl vinyl phenyl silicone rubber.

2. The highly folding-resistant flame-retardant artificial leather for automobile according to claim 1, characterized in that: The mass ratio of terminal hydroxyl polybutadiene, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and methyl vinyl phenyl silicone rubber is 1:0.5-1:0.5-2.

3. The highly folding-resistant flame-retardant artificial leather for automobile according to claim 1, characterized in that: The PVC bottom layer comprises the following raw materials in parts by weight: 100 parts of PVC resin, 60-90 parts of plasticizer, 1-5 parts of foaming agent, 1-5 parts of stabilizer, 10-30 parts of composite additives, 10-30 parts of flame retardant, 20-40 parts of filler and 10-20 parts of colorant.

4. The highly folding-resistant flame-retardant artificial leather for automobile according to claim 1, characterized in that: The PVC surface layer comprises the following raw materials in parts by weight: 100 parts of PVC resin, 60-90 parts of plasticizer, 1-5 parts of stabilizer, 10-30 parts of composite additives, 10-30 parts of filler and 5-10 parts of colorant.

5. The highly folding-resistant flame-retardant artificial leather for vehicles according to claim 3 or 4, characterized in that: The plasticizer is a phthalate plasticizer; the foaming agent is an azo foaming agent; the flame retardant is an antimony flame retardant; the stabilizer is a calcium zinc stabilizer; and the filler is a carbonate mineral powder filler.

6. A method for preparing highly folding-resistant and flame-retardant artificial leather for automobiles, the artificial leather being as described in any one of claims 1 to 5, characterized in that: The steps are as follows: S1: Mix PVC resin, plasticizer, foaming agent, stabilizer, composite additive, flame retardant, filler and colorant in a mixer at 100-140°C for 5-10 minutes, and mix in a high-temperature internal mixer at 140-170°C for 5-10 minutes to form a PVC base layer mixture; S2: The PVC base layer mixture and the base fabric layer are laminated by hot pressing at 150-190°C to obtain a semi-finished base material; S3: Mix PVC resin, plasticizer, stabilizer, compound additive, filler and colorant in a mixer at 100-140°C for 5-10 minutes, and mix in a high-temperature internal mixer at 140-170°C for 5-10 minutes to form a PVC surface layer mixture; S4: subjecting the PVC surface layer mixture and the semi-finished base material to a hot pressing bonding process at 150-190° C. to obtain a semi-finished raw material; S5: Foaming the semi-finished raw material at a temperature of 180-230° C. for 50-100 seconds; S6: The surface of the foamed raw material is treated with a water-based treatment agent, and then embossed to obtain a finished artificial leather.

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