Plant polyurethane wet-process automobile leather

Abstract

The invention discloses plant-based polyurethane wet-process automobile leather, relates to the technical field of environment-friendly materials, and aims to solve the problem of insufficient adhesive force between a plant-based compact layer and a Bass foaming layer. The foaming layer comprises the following components: bio-based wet-process polyurethane resin, dimethylformamide, a halogen-free flame retardant, a dispersing agent, a foaming agent and a cell regulator. The bonding layer comprises the following components: bio-based high-solid-content polyurethane resin I, dimethyl amide, ethyl acetate and a cross-linking agent I; the surface layer II comprises the following components: bio-based high-solid-content polyurethane resin II, dimethylformamide, ethyl acetate, a dispersing agent and a cross-linking agent II; the surface layer I comprises the following components: bio-based non-yellowing polyurethane resin, dimethyl amide, ethyl acetate and a dispersing agent; the surface layer comprises the following components: bio-based waterborne polyurethane I, bio-based waterborne polyurethane II, isopropanol, water, an antibacterial agent, a slipping agent, a dispersing agent, a tackifier and a defoaming agent; the adhesive force between the foaming layer and the second surface layer is good, and the peeling strength performance is excellent.

Description

Technical Field

[0001] The invention relates to the technical field of environmentally friendly materials, in particular to a plant-based polyurethane wet-process automobile leather. Background Art

[0002] The vast majority of automotive interior leathers on the market rely primarily on petroleum-based polyurethane resins, whose production process generates high carbon emissions and uses non-renewable resources. Therefore, bio-based polyurethanes have become a research hotspot due to their environmentally friendly properties. By extracting plant-based components from non-economic crops and directly incorporating them into the synthesis of polyurethane polymers, they can replace traditional petroleum-based polyurethanes, achieving low carbon emissions and sustainable development. However, in existing plant-based polyurethane technologies, the design of the adhesive layer fails to effectively address the adhesion issues between the plant-based dense layer and the base foam layer, which can easily lead to insufficient product durability. Therefore, a plant-based polyurethane wet-process automotive leather is urgently needed to address this problem. Summary of the Invention

[0003] The purpose of the present invention is to provide a plant-based polyurethane wet-process automobile leather to solve the problem of insufficient adhesion between the plant-based dense layer and the base foaming layer.

[0004] To achieve the above object, the present invention provides the following technical solution: a plant-based polyurethane wet-process automotive leather, comprising a surface layer, a first surface layer, a second surface layer, an adhesive layer, and a foaming layer arranged in sequence, wherein the foaming layer is bonded to the second surface layer via the adhesive layer;

[0005] The components of the foaming layer are calculated by weight, including 100 to 150 parts of bio-based wet-process polyurethane resin, 10 to 80 parts of dimethylamide, 1 to 10 parts of halogen-free flame retardant, 0.1 to 5 parts of dispersant, 0.1 to 5 parts of foaming agent, and 0.1 to 5 parts of cell regulator;

[0006] The components of the bonding layer are calculated by weight, including 100 to 150 parts of a bio-based high-solid polyurethane resin, 10 to 80 parts of dimethylamide, 10 to 80 parts of ethyl acetate, and 0.1 to 5 parts of a cross-linking agent;

[0007] The components of the surface layer II are calculated in parts by weight, including 100-150 parts of a bio-based high-solid polyurethane resin II, 10-80 parts of dimethylamide, 10-80 parts of ethyl acetate, 0.1-5 parts of a dispersant, and 0.1-5 parts of a cross-linking agent II;

[0008] The components of the surface layer 1 are calculated in parts by weight, including 100 to 150 parts of bio-based non-yellowing polyurethane resin, 10 to 80 parts of dimethylamide, 10 to 80 parts of ethyl acetate, and 0.1 to 5 parts of a dispersant;

[0009] The components of the surface layer are calculated by weight and include 100-150 parts of bio-based waterborne polyurethane 1, 100-150 parts of bio-based waterborne polyurethane 2, 0.1-5 parts of isopropyl alcohol, 10-50 parts of water, 2-40 parts of functional additives, 0.1-5 parts of dispersant, 0.1-5 parts of tackifier, and 0.1-5 parts of defoaming agent.

[0010] Preferably, in the above-mentioned adhesive layer, the crosslinking agent 1 is HB-5580 produced by Dongguan Hongbai Chemical Co., Ltd.

[0011] Preferably, the components of the surface layer 1 are mixed and coated on a release paper and dried, and then the mixed components of the surface layer 2 are coated thereon and dried to obtain a dry surface layer.

[0012] Preferably, the components of the foaming layer are mixed and then coated on the base fabric using a wet process to prepare the base layer, and the components of the adhesive layer are mixed and then coated on the surface of the foaming layer, and then laminated with the second surface layer and reacted at 90-120°C for 5-10 minutes.

[0013] Preferably, after coating, the first and second surface layers are dried in an oven at 90-120° C. for 5-10 minutes respectively.

[0014] Preferably, the components of the surface layer, the first surface layer, the second surface layer, the bonding layer and the foaming layer are respectively mixed uniformly by stirring at 1000 to 1500 rpm for 30 to 60 minutes using a high-speed stirrer to prepare slurries for each layer.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The plant-based polyurethane wet-process automotive leather has good adhesion between the plant-based dense layer and the base foam layer, and has excellent interlayer peel strength. The bio-based polyurethane resin and cross-linking agent used have better bonding properties, which is beneficial to the durability of the product and facilitates the further application of renewable and environmentally friendly materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Schematic diagram of the positional relationship of each layer of the automotive leather of the present invention.

[0018] In the figure: 1, surface layer; 2, surface layer 1; 3, surface layer 2; 4, adhesive layer; 5, foaming layer; 6, base fabric. DETAILED DESCRIPTION

[0019] See Figure 1 A plant-based polyurethane wet-process automotive leather comprises a surface layer, a first surface layer, a second surface layer, an adhesive layer and a foaming layer arranged in sequence, wherein the foaming layer is bonded to the second surface layer via the adhesive layer;

[0020] The components of the foaming layer are calculated by weight, including 100 to 150 parts of bio-based wet-process polyurethane resin, 10 to 80 parts of dimethylamide, 1 to 10 parts of halogen-free flame retardant, 0.1 to 5 parts of dispersant, 0.1 to 5 parts of foaming agent, and 0.1 to 5 parts of cell regulator;

[0021] The components of the bonding layer are calculated by weight, including 100-150 parts of bio-based high-solid polyurethane resin, 10-80 parts of dimethylamide, 10-80 parts of ethyl acetate, and 0.1-5 parts of a crosslinking agent; the crosslinking agent is HB-5580 produced by Dongguan Hongbai Chemical Co., Ltd.

[0022] The components of the surface layer II are calculated in parts by weight, including 100-150 parts of a bio-based high-solid polyurethane resin II, 10-80 parts of dimethylamide, 10-80 parts of ethyl acetate, 0.1-5 parts of a dispersant, and 0.1-5 parts of a cross-linking agent II;

[0023] The components of the surface layer 1 are calculated in parts by weight, including 100 to 150 parts of bio-based non-yellowing polyurethane resin, 10 to 80 parts of dimethylamide, 10 to 80 parts of ethyl acetate, and 0.1 to 5 parts of a dispersant;

[0024] The components of the surface layer are calculated by weight and include 100-150 parts of bio-based waterborne polyurethane 1, 100-150 parts of bio-based waterborne polyurethane 2, 0.1-5 parts of isopropyl alcohol, 10-50 parts of water, 2-40 parts of functional additives, 0.1-5 parts of dispersant, 0.1-5 parts of tackifier, and 0.1-5 parts of defoamer. The functional additives can be selected according to process requirements, such as feel additives, wear-resistant additives, etc. The surface layer does not affect the adhesion between the surface layer 2 and the foaming layer of the present invention.

[0025] The present invention does not improve the processes for preparing the base layer by a wet method or the dense layer by a dry method, and the existing process technology can be used for preparation. The main improvement is in the above components, especially the components of the foaming layer, the second surface layer and the bonding layer. The components of other layers are mainly bio-based materials and the formulations adapted to bio-based materials are improved. The following is provided for illustrative purposes and some existing preparation methods are provided for reference:

[0026] For reference, the components of the surface layer, the first surface layer, the second surface layer, the bonding layer and the foaming layer are respectively mixed uniformly by using a high-speed stirrer at 1000 to 1500 rpm for 30 to 60 minutes to prepare the slurry for each layer.

[0027] For reference, the components of the surface layer 1 are mixed and coated on the release paper and dried, and then the mixed components of the surface layer 2 are coated thereon and dried to obtain a dry surface layer (i.e., a dense layer). The two drying steps can be dried in an oven at 90-120°C for 5-10 minutes respectively.

[0028] For reference, the components of the foaming layer are mixed evenly and then coated on the base fabric using a wet process to prepare the base layer (generally, the base fabric is pre-impregnated, pre-solidified, ironed at 80-100°C, and then coated with the foaming layer slurry, and then solidified with a 20-35% DMF aqueous solution, washed with water, dried at 150-170°C, and cooled to complete the preparation). The components of the bonding layer are mixed evenly and then coated on the surface of the foaming layer on the prepared base layer, and then laminated with the surface layer. After lamination, it is heated in an oven at 90-120°C for 5-10 minutes for a cross-linking reaction.

[0029] For reference, the surface layer components are mixed evenly and then applied to the surface of the surface layer and dried in an oven at 100-120°C for 2-3 minutes.

[0030] The technical solutions and effects of the present invention are further illustrated below through several embodiments. It should be noted that the following are not all embodiments of the present invention, but are only randomly selected samples from many embodiments. They are representative but should not be understood as absolute limitations on the present invention.

[0031] In the following examples and comparative examples, some of the common raw materials are as follows:

[0032] Foaming layer: Bio-based wet-process polyurethane resin uses Wanhua Chemical's WANNATE WB-730, halogen-free flame retardant uses Qingdao Lianmei Chemical's LMP-220, dispersant uses Luoxing Chemical's KW-71, foaming agent uses Tokuda Chemical's DT-F7, and cell regulator uses Tokuda Chemical's DT-80P.

[0033] Adhesive layer: Bio-based high-solid polyurethane resin - Asahikawa Chemical XC-8150M, cross-linker - Dongguan Hongbai Chemical Co., Ltd. HB-5580;

[0034] Surface layer 2: Bio-based high-solid polyurethane resin 2 uses Wanhua Chemical's WANNATE HB-501B, dispersant uses Efcona HT-Dis 3250, and crosslinker 2 uses Jiangsu Jianghuan Chemical's JH-5580;

[0035] Surface layer 1: Bio-based non-yellowing polyurethane resin uses Asahikawa Chemical XC-204N, and dispersant uses Efcona 3254;

[0036] Surface treatment layer: Bio-based water-based polyurethane uses Wanhua Chemical Witobond W-9600, dispersant uses Hubei New Blue Sky New Materials Hostavin 3070, tackifier uses Huitian New Materials HT-4450, and defoamer uses Haichuan Chemical H-2459.

[0037] Example 1:

[0038] The components of the foaming layer are calculated by weight and include 100 parts of bio-based wet-process polyurethane resin, 20 parts of dimethylamide, 2 parts of halogen-free flame retardant, 1 part of dispersant, 3 parts of foaming agent, and 1 part of cell regulator;

[0039] The components of the bonding layer are calculated by weight and include 100 parts of bio-based high-solid polyurethane resin, 10 parts of dimethylamide, 10 parts of ethyl acetate, and 3 parts of a cross-linking agent;

[0040] The components of the surface layer 2 are calculated in parts by weight, including 100 parts of bio-based high-solid polyurethane resin 2, 10 parts of dimethylamide, 10 parts of ethyl acetate, 1 part of dispersant, and 2 parts of cross-linking agent 2;

[0041] The components of the surface layer 1 are calculated in parts by weight, including 100 parts of bio-based non-yellowing polyurethane resin, 10 parts of dimethylamide, 10 parts of ethyl acetate, and 1 part of dispersant;

[0042] The components of the surface layer are calculated by weight and include 100 parts of bio-based water-based polyurethane 1, 100 parts of bio-based water-based polyurethane 2, 2 parts of isopropyl alcohol, 20 parts of water, 5 parts of Zhenguang antibacterial powder, 5 parts of Zhenguang 960 lubricant, 1 part of dispersant, 2 parts of tackifier, and 2 parts of defoaming agent.

[0043] The components of each layer were stirred at 1500 rpm in a high-speed stirrer for 30 minutes to obtain uniform mixture to prepare the slurry of each layer; the surface layer 1 slurry was coated on the release paper, dried in an oven at 110°C for 5 minutes, and then the surface layer 2 slurry was coated thereon, and dried in an oven at 120°C for 8 minutes to obtain a dry dense layer; the foaming layer slurry was coated on the base cloth by a wet process to obtain the base layer; the bonding layer slurry was then coated on the surface of the foaming layer, laminated with the surface layer 2 of the dense layer, and reacted at 120°C for 6 minutes; finally, the surface layer slurry was coated on the surface of the surface layer 1 and dried in an oven at 110°C for 2 minutes to obtain the sample.

[0044] Example 2:

[0045] The components of the foaming layer are calculated by weight, including 120 parts of bio-based wet-process polyurethane resin, 40 parts of dimethylamide, 8 parts of halogen-free flame retardant, 3 parts of dispersant, 4 parts of foaming agent, and 3 parts of cell regulator;

[0046] The components of the bonding layer, calculated by weight, include 150 parts of a bio-based high-solid polyurethane resin, 50 parts of dimethylamide, 30 parts of ethyl acetate, and 2 parts of a cross-linking agent;

[0047] The components of the surface layer 2 are calculated in parts by weight, including 100 parts of bio-based high-solid polyurethane resin 2, 20 parts of dimethylamide, 20 parts of ethyl acetate, 1 part of dispersant, and 2 parts of cross-linking agent 2;

[0048] The components of the surface layer 1 are calculated in parts by weight, including 110 parts of bio-based non-yellowing polyurethane resin, 20 parts of dimethylamide, 20 parts of ethyl acetate, and 2 parts of dispersant;

[0049] The components of the surface layer are calculated by weight and include 120 parts of bio-based water-based polyurethane 1, 120 parts of bio-based water-based polyurethane 2, 0.5 parts of isopropyl alcohol, 30 parts of water, 10 parts of Zhenguang antibacterial powder, 10 parts of Zhenguang 960 lubricant, 3 parts of dispersant, 2 parts of tackifier, and 3 parts of defoaming agent.

[0050] The components of each layer were stirred at 1500 rpm in a high-speed stirrer for 30 minutes to obtain uniform mixture to prepare the slurry of each layer; the surface layer 1 slurry was coated on the release paper, dried in an oven at 110°C for 5 minutes, and then the surface layer 2 slurry was coated thereon, and dried in an oven at 120°C for 8 minutes to obtain a dry dense layer; the foaming layer slurry was coated on the base cloth by a wet process to obtain the base layer; the bonding layer slurry was then coated on the surface of the foaming layer, laminated with the surface layer 2 of the dense layer, and reacted at 120°C for 6 minutes; finally, the surface layer slurry was coated on the surface of the surface layer 1 and dried in an oven at 110°C for 2 minutes to obtain the sample.

[0051] Example 3:

[0052] The components of the foaming layer are calculated by weight, including 150 parts of bio-based wet-process polyurethane resin, 60 parts of dimethylamide, 10 parts of halogen-free flame retardant, 4 parts of dispersant, 3 parts of foaming agent, and 3 parts of cell regulator;

[0053] The components of the bonding layer, calculated by weight, include 135 parts of a bio-based high-solid polyurethane resin, 45 parts of dimethylamide, 20 parts of ethyl acetate, and 5 parts of a cross-linking agent;

[0054] The components of the surface layer 2 are calculated in parts by weight, including 150 parts of bio-based high-solid polyurethane resin 2, 40 parts of dimethylamide, 40 parts of ethyl acetate, 5 parts of dispersant, and 5 parts of cross-linking agent 2;

[0055] The components of the surface layer 1 are calculated in parts by weight, including 120 parts of bio-based non-yellowing polyurethane resin, 20 parts of dimethylamide, 15 parts of ethyl acetate, and 4 parts of dispersant;

[0056] The components of the surface layer are calculated by weight and include 100 parts of bio-based water-based polyurethane 1, 100 parts of bio-based water-based polyurethane 2, 2 parts of isopropyl alcohol, 20 parts of water, 5 parts of Zhenguang antibacterial powder, 5 parts of Zhenguang 960 lubricant, 1 part of dispersant, 2 parts of tackifier, and 2 parts of defoaming agent.

[0057] The components of each layer were stirred at 1500 rpm in a high-speed stirrer for 30 minutes to obtain uniform mixture to prepare the slurry of each layer; the surface layer 1 slurry was coated on the release paper, dried in an oven at 110°C for 5 minutes, and then the surface layer 2 slurry was coated thereon, and dried in an oven at 120°C for 8 minutes to obtain a dry dense layer; the foaming layer slurry was coated on the base cloth by a wet process to obtain the base layer; the bonding layer slurry was then coated on the surface of the foaming layer, laminated with the surface layer 2 of the dense layer, and reacted at 120°C for 6 minutes; finally, the surface layer slurry was coated on the surface of the surface layer 1 and dried in an oven at 110°C for 2 minutes to obtain the sample.

[0058] Example 4:

[0059] The components of the foaming layer are calculated by weight, including 120 parts of bio-based wet-process polyurethane resin, 16 parts of dimethylamide, 4 parts of halogen-free flame retardant, 1.5 parts of dispersant, 2 parts of foaming agent, and 0.5 parts of cell regulator;

[0060] The components of the bonding layer, calculated by weight, include 120 parts of a bio-based high-solid polyurethane resin, 16 parts of dimethylamide, 16 parts of ethyl acetate, and 0.8 parts of a cross-linking agent;

[0061] The components of the surface layer II are calculated in parts by weight, including 120 parts of bio-based high-solid polyurethane resin II, 16 parts of dimethylamide, 16 parts of ethyl acetate, 0.5 parts of dispersant, and 0.5 parts of cross-linking agent II;

[0062] The components of the surface layer 1 are calculated in parts by weight, including 120 parts of bio-based non-yellowing polyurethane resin, 16 parts of dimethylamide, 16 parts of ethyl acetate, and 0.5 parts of dispersant;

[0063] The components of the surface layer are calculated by weight and include 100 parts of bio-based water-based polyurethane 1, 100 parts of bio-based water-based polyurethane 2, 2 parts of isopropyl alcohol, 20 parts of water, 5 parts of Zhenguang antibacterial powder, 5 parts of Zhenguang 960 lubricant, 1 part of dispersant, 2 parts of tackifier, and 2 parts of defoaming agent.

[0064] The components of each layer were stirred at 1500 rpm in a high-speed stirrer for 30 minutes to obtain uniform mixture to prepare the slurry of each layer; the surface layer 1 slurry was coated on the release paper, dried in an oven at 110°C for 5 minutes, and then the surface layer 2 slurry was coated thereon, and dried in an oven at 120°C for 8 minutes to obtain a dry dense layer; the foaming layer slurry was coated on the base cloth by a wet process to obtain the base layer; the bonding layer slurry was then coated on the surface of the foaming layer, laminated with the surface layer 2 of the dense layer, and reacted at 120°C for 6 minutes; finally, the surface layer slurry was coated on the surface of the surface layer 1 and dried in an oven at 110°C for 2 minutes to obtain the sample.

[0065] Comparative Example 1:

[0066] On the basis of Example 3, only the cross-linking agent 1 of the bonding layer was changed, and it was replaced from HB-5580 of Dongguan Hongbai Chemical Co., Ltd. to DB-75N of Yantai Debang Technology.

[0067] Comparative Example 2:

[0068] On the basis of Example 4, only the cross-linking agent 1 of the bonding layer was changed, and it was replaced from HB-5580 of Dongguan Hongbai Chemical Co., Ltd. to DB-75N of Yantai Debang Technology.

[0069] The peel strength test of each embodiment and comparative example sample was carried out according to GB / T 2791-1995 "Determination of peel strength of adhesives". The equipment used was an INSTRON 5565 tensile testing machine, a tensile speed of 100 mm / min, a sample width of 25 mm, and a test environment of 25°C / 50% RH. The peel strength test results of Example 1 were 8.5 N / mm, and the failure mode was cohesive failure (no delamination); Example 2 was 8.2 N / mm, and the failure mode was cohesive failure (no delamination); Example 3 was 8.7 N / mm, and the failure mode was cohesive failure (no delamination); Example 4 was 8.0 N / mm, and the failure mode was cohesive failure (no delamination); Comparative Example 1 was 5.2 N / mm, and the failure mode was interface delamination; Comparative Example 2 was 4.5 N / mm, and the failure mode was interface delamination.

[0070] From the results of the examples and comparative examples, it can be seen that the formulation of the present invention has the advantage of high peel strength. Compared with Comparative Example 1, and compared with Comparative Example 2, Example 3 and Example 4 are adjusted only in the cross-linking agent used in the adhesive layer. This also shows that the cross-linking agent used in the present invention is more suitable for cross-linking between the bio-based polyurethane resins used in the present invention.

[0071] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection defined by the claims.

[0072] Any matters not described in detail in the present invention are well-known technologies to those skilled in the art.

Claims

1. A plant-based polyurethane wet-process automotive leather, characterized by: It comprises a surface layer, a first surface layer, a second surface layer, an adhesive layer and a foaming layer which are arranged in sequence, wherein the foaming layer is bonded to the second surface layer via the adhesive layer; The components of the foaming layer are calculated by weight, including 100 to 150 parts of bio-based wet-process polyurethane resin, 10 to 80 parts of dimethylamide, 1 to 10 parts of halogen-free flame retardant, 0.1 to 5 parts of dispersant, 0.1 to 5 parts of foaming agent, and 0.1 to 5 parts of cell regulator; The components of the bonding layer are calculated by weight, including 100 to 150 parts of a bio-based high-solid polyurethane resin, 10 to 80 parts of dimethylamide, 10 to 80 parts of ethyl acetate, and 0.1 to 5 parts of a cross-linking agent; The components of the surface layer II are calculated in parts by weight, including 100-150 parts of a bio-based high-solid polyurethane resin II, 10-80 parts of dimethylamide, 10-80 parts of ethyl acetate, 0.1-5 parts of a dispersant, and 0.1-5 parts of a cross-linking agent II; The components of the surface layer 1 are calculated in parts by weight, including 100 to 150 parts of bio-based non-yellowing polyurethane resin, 10 to 80 parts of dimethylamide, 10 to 80 parts of ethyl acetate, and 0.1 to 5 parts of a dispersant; The components of the surface layer are calculated by weight and include 100-150 parts of bio-based waterborne polyurethane 1, 100-150 parts of bio-based waterborne polyurethane 2, 0.1-5 parts of isopropyl alcohol, 10-50 parts of water, 2-40 parts of functional additives, 0.1-5 parts of dispersant, 0.1-5 parts of tackifier, and 0.1-5 parts of defoaming agent.

2. The plant-based polyurethane wet-process automotive leather according to claim 1, characterized in that: In the bonding layer, the crosslinking agent 1 is HB-5580 produced by Dongguan Hongbai Chemical Co., Ltd.

3. The plant-based polyurethane wet-process automotive leather according to claim 1, characterized in that: The components of the surface layer 1 are mixed and coated on the release paper and dried, and then the mixed components of the surface layer 2 are coated on the release paper and dried to obtain a dry surface layer.

4. The plant-based polyurethane wet-process automotive leather according to claim 3, characterized in that: The components of the foaming layer are mixed and coated on the base fabric using a wet process to prepare the base layer. The components of the adhesive layer are mixed and coated on the surface of the foaming layer, and then laminated with the second surface layer and reacted at 90-120° C. for 5-10 minutes.

5. The plant-based polyurethane wet-process automotive leather according to claim 3, characterized in that: After coating, the first and second surface layers are dried in an oven at 90-120° C. for 5-10 minutes.

6. The plant-based polyurethane wet-process automotive leather according to claim 1, characterized in that: The components of the surface layer, the first surface layer, the second surface layer, the bonding layer and the foaming layer are respectively mixed uniformly by using a high-speed stirrer at 1000 to 1500 revolutions per minute for 30 to 60 minutes to prepare slurries for each layer.

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