A weaken-free polyurethane composite material, its preparation method and application

Abstract

This invention relates to a non-weakening polyurethane composite material, its preparation method, and its application. The non-weakening polyurethane composite material comprises, from top to bottom, a polyurethane surface layer, a high-strength polyurethane adhesive layer, and a base fabric layer. The high-strength polyurethane adhesive layer is prepared from a high-strength polyurethane adhesive slurry, which is composed of the following components in parts by weight: 100 parts reactive polyurethane prepolymer, 5-10 parts crosslinking agent, 20-50 parts filler, and 5-10 parts colorant. The high-strength polyurethane adhesive layer of this invention forms a three-dimensional network crosslinked structure through the reaction of the reactive polyurethane prepolymer with the crosslinking agent and filler in a certain proportion. This gives the film a certain strength and brittleness, enabling the non-weakening polyurethane composite material to undergo overall brittle fracture under point-explosion impact, ensuring the safe deployment of the airbag.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a weaken-free polyurethane composite material, its preparation method, and its application. Background Technology

[0002] With the rapid development of the automotive industry, the quality and performance requirements for automotive interior materials are becoming increasingly stringent. Traditional automotive interior polyurethane leather requires a weakening treatment in the dashboard airbag area, which not only increases subsequent processing costs but also affects the product's aesthetics, leaving weakening marks. Furthermore, to reduce these marks, traditional automotive interior leather requires a thicker adhesive layer, leading to increased weight and consequently impacting the vehicle's fuel economy and power performance.

[0003] Despite some attempts at existing technologies to avoid weakening polyurethane skins for automotive interiors, several problems remain. For example, while improving solvent-free adhesion can address the weakening issue to some extent, the toughness of the solvent-free film makes it difficult for airbags to deploy safely during a burst. Furthermore, while bonding a solvent-free skin to a L-type polylactic acid (PLA) base fabric achieves weakening-free protection, PLA's poor resistance to high temperatures and UV radiation limits its application in dashboard areas. Summary of the Invention

[0004] Based on this, the present invention provides a non-weakening polyurethane composite material, its preparation method and application. This non-weakening polyurethane composite material can undergo overall brittle fracture under point-explosion impact, ensuring the safe deployment of the airbag.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] The present invention first provides a polyurethane composite material that is free from weakening, which includes a polyurethane surface layer, a polyurethane high-strength adhesive layer, and a base fabric layer arranged sequentially from top to bottom;

[0007] The polyurethane high-solids adhesive layer is prepared from a polyurethane high-solids adhesive layer slurry, which is prepared from the following components in parts by weight: 100 parts reactive polyurethane prepolymer, 5-10 parts crosslinking agent, 20-50 parts filler, and 5-10 parts colorant.

[0008] The polyurethane high-strength adhesive layer of the present invention forms a three-dimensional network cross-linked structure by reacting a reactive polyurethane prepolymer with a cross-linking agent and filler in a certain proportion, which gives the film a certain strength and brittleness, thereby enabling the weakened polyurethane composite material to undergo overall brittle fracture under point-explosion impact, ensuring the safe deployment of the airbag.

[0009] As a further improvement to the above-described scheme of the present invention, the reactive polyurethane prepolymer is an aliphatic isocyanate prepolymer with a solid content of 100% and a free NCO content of 4.5% ± 1%. The reactive polyurethane prepolymer of the present invention is an aliphatic isocyanate prepolymer. After reacting with the crosslinking agent and filler, the unreacted isocyanate groups in the reactive polyurethane prepolymer can react with the active hydrogen groups on the base fabric, thereby obtaining higher adhesive strength.

[0010] As a further improvement to the above-described scheme of the present invention, the crosslinking agent is one of aliphatic amine crosslinking agents, acid anhydrides, and polyamides.

[0011] As a further improvement to the above-mentioned solution of the present invention, the filler is at least one of diatomaceous earth, powdered calcium carbonate, aluminum hydroxide, halogenated flame retardant, and phosphorus-based flame retardant.

[0012] As a further improvement to the above-described solution of the present invention, the polyurethane surface layer is prepared from a polyurethane surface layer slurry, which is prepared from the following components in parts by weight: 150 parts aliphatic polyurethane resin, 10-50 parts N,N-dimethylformamide, and 5-10 parts colorant. It should be noted that in the present invention, there are no special requirements for the aliphatic polyurethane resin and colorant in the polyurethane surface layer; they can be adjusted according to product requirements. The colorant can also be selected according to product performance requirements, therefore, it is not specifically limited here.

[0013] As a further improvement to the above-mentioned solution of the present invention, the base fabric layer is a low-density polyester knitted mesh fabric, and the tear strength of the base fabric layer is 10-25N / 3cm.

[0014] The present invention further provides a method for preparing the aforementioned non-weakening polyurethane composite material, comprising the following steps:

[0015] S1. Coat the release paper with a polyurethane surface layer slurry with a blade gap of 10-20 mils, place it at 100-140℃ for 1-2 minutes, and dry to form a polyurethane surface layer;

[0016] S2. Apply a high-solids polyurethane resin slurry to the polyurethane surface layer with a blade gap of 30-40 mils, and bake it at 110-140℃ until semi-dry to form a high-solids polyurethane adhesive layer.

[0017] S3. The base fabric and the polyurethane high-strength adhesive layer are bonded together with a lamination gap of 60-80 mils, and then dried to obtain a polyurethane composite material that is free from weakening.

[0018] As a further improvement to the above-described solution of the present invention, the preparation method of the weaken-free polyurethane composite material further includes the following steps:

[0019] S4. Using a roller coating process, after coating the surface of the non-weakening polyurethane composite material with water-based polyurethane slurry, treat it at 130-160℃ for 2-5 minutes, and after drying, form a surface treatment layer on the surface of the non-weakening polyurethane composite material.

[0020] As a further improvement to the above-described solution of the present invention, the waterborne polyurethane slurry is prepared from the following components in parts by weight: 100 parts aliphatic waterborne polyurethane, 1-1.5 parts leveling agent, and 5-8 parts curing agent. It should be noted that the preparation of the waterborne polyurethane slurry is not particularly limited in the present invention, and those skilled in the art can select it according to actual conditions. The curing agent of the waterborne polyurethane slurry can be selected from at least one of polycarbodiimide crosslinking agents and isocyanate crosslinking agents, and the leveling agent can be selected from polyether-modified siloxanes.

[0021] The present invention also provides the application of the non-weakening polyurethane composite material as described above, or the non-weakening polyurethane composite material prepared by the preparation method described above, in automotive interiors.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The polyurethane high-strength adhesive layer of the present invention forms a three-dimensional network cross-linked structure by reacting a reactive polyurethane prepolymer with a cross-linking agent and filler in a certain proportion, which gives the film a certain strength and brittleness, thereby enabling the weakened polyurethane composite material to undergo overall brittle fracture under point-explosion impact, ensuring the safe deployment of the airbag.

[0024] 2. In the polyurethane high-strength adhesive layer of the present invention, the reactive polyurethane prepolymer is an aliphatic isocyanate prepolymer. The excess -NCO groups in the reactive polyurethane prepolymer can react with the active hydrogen groups on the surface of the base fabric to form strong urethane bonds (-NH-COO-) and urea bonds (-NH-CONH-), thereby achieving good adhesion between the polyurethane high-strength adhesive layer and the base fabric. Good adhesion to the base fabric can be achieved through a relatively thin polyurethane high-strength adhesive layer, thereby reducing the weight of the product.

[0025] 3. The surface layer and adhesive layer of this invention are both aliphatic structures without benzene ring structures, which improves the light degradation resistance of automotive interior materials. In addition, the base fabric is still made of polyester base fabric with good heat resistance and strength, which ensures the overall durability of the non-weakening material in automotive interior applications.

[0026] 4. Compared with traditional weakening methods, the non-weakening polyurethane composite material of the present invention does not require a thicker adhesive layer to reduce the aesthetic loss caused by weakening. Therefore, the non-weakening adhesive layer is thinner and lighter. In addition, the non-weakening base fabric layer uses a mesh fabric with a lighter basis weight. The overall weight of the product is reduced by about 20%, which improves the energy economy and power performance of automobiles.

[0027] 5. This invention reduces the weakening process, lowers the cost of subsequent processing, and improves the aesthetics of the product. Detailed Implementation

[0028] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0030] The specific information on the raw materials used in the above embodiments and comparative examples is as follows:

[0031] (1) The polyurethane resin LY-58PC (aliphatic polycarbonate polyurethane, 100% modulus 4.5±1.0MPa) and the reactive isocyanate prepolymer PU-28 (aliphatic, NCO content 5%) were both sourced from Hefei Anli Polyurethane New Materials Co., Ltd.

[0032] (2) The solvent-free polyether polyurethanes Haptex CC 6945 / 100C-A and Haptex CC 6945 / 100C-B, and the solvent-free catalyst Additive CX 93600 are all from BASF Polyurethane Specialty Products (China) Co., Ltd.

[0033] (3) NX-128 was purchased from Nantong Aidewang Co., Ltd.;

[0034] (4) The crosslinking agent HMDA was purchased from Hubei Jusheng Technology Co., Ltd.

[0035] (5) The crosslinking agent MTHPA was purchased from Kunshan Jiulimei Electronic Materials Co., Ltd.

[0036] (6) The color paste was purchased from Foshan Shunde Baoster Pigment Co., Ltd.;

[0037] (7) Filler: Antimony trioxide, purchased from Hunan Xikuangshan Shanxing Antimony Industry Import and Export Co., Ltd.;

[0038] (8) Filler: calcium carbonate, purchased from Jiangxi Darui Chemical Co., Ltd.;

[0039] (9) Polycarbonate-type waterborne polyurethane WF-3649 was purchased from Starr Fine Coatings (Suzhou) Co., Ltd.

[0040] (10) Curing agent XR-5580 and leveling agent LA-91-120 were purchased from Starr Fine Coatings (Suzhou) Co., Ltd.

[0041] (11) Mesh fabric B30D0087 and weft knitted fabric PK280 were both purchased from Jiangsu Beltefu New Materials Co., Ltd.

[0042] (12) Polylactic acid-based fabric PLA-1 was purchased from Zhangjiagang Jimei Biotechnology Co., Ltd.

[0043] All of the above-mentioned raw materials are commercially available. The above-mentioned raw materials are only used to illustrate the source and composition of the reagents used in the experiments of this invention, so as to fully disclose them, and do not mean that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0044] Unless otherwise specified, the reagents, methods and equipment used in this invention are conventional reagents, methods and equipment in this technical field.

[0045] Example 1

[0046] This embodiment proposes a non-weakening polyurethane composite material for automotive interiors, which includes a polyurethane surface layer, a polyurethane high-strength adhesive layer, and a base fabric layer arranged sequentially from top to bottom. The preparation method includes the following four steps S1-S4.

[0047] S1. Apply polyurethane surface layer slurry to the release paper with a blade gap of 10 mils, place it at 140℃ for 2 minutes, and dry to form a polyurethane surface layer. The surface layer polyurethane slurry is prepared from the following raw materials in parts by weight: 150 parts aliphatic polyurethane resin LY-58PC, 50 parts N,N-dimethylformamide, and 5 parts color paste.

[0048] S2. Apply a high-strength polyurethane adhesive layer slurry to the polyurethane surface layer with a blade gap of 30 mils, and bake at 140℃ for 2 minutes to form a semi-dry polyurethane high-strength adhesive layer. The high-strength polyurethane adhesive layer slurry is prepared from the following raw materials in parts by weight: 100 parts PU-28, 5 parts crosslinking agent HMDA, 20 parts antimony trioxide, and 5 parts color paste.

[0049] S3. The mesh fabric B30D0087 is bonded to the polyurethane high-strength adhesive layer with a lamination gap of 60 mils, and then dried to obtain the non-weakening polyurethane composite material.

[0050] S4. Using a roller coating process, a water-based polyurethane slurry is coated onto the surface of the non-weakening polyurethane composite material. After drying at 160℃ for 6 minutes, a surface treatment layer is formed, resulting in the finished non-weakening polyurethane composite material for automotive interiors. The water-based polyurethane slurry is prepared from the following raw materials in parts by weight: 100 parts aliphatic water-based polyurethane WF-3649, 0.5 parts leveling agent LA-91-120, and 3 parts curing agent XR 5580.

[0051] Example 2

[0052] This embodiment proposes a non-weakening polyurethane composite material for automotive interiors, which includes a polyurethane surface layer, a polyurethane high-strength adhesive layer, and a base fabric layer arranged sequentially from top to bottom. The preparation method includes the following four steps S1-S4.

[0053] S1. Apply polyurethane surface layer slurry to the release paper with a blade gap of 15 mils, place it at 120℃ for 1.5 min, and dry to form a polyurethane surface layer. The surface layer polyurethane slurry is prepared from the following raw materials in parts by weight: 150 parts aliphatic polyurethane resin LY-58PC, 30 parts N,N-dimethylformamide, and 7.5 parts color paste.

[0054] S2. Apply a high-strength polyurethane adhesive layer slurry to the polyurethane surface layer with a blade gap of 35 mils, and bake at 125℃ for 1.5 minutes until semi-dry to form a high-strength polyurethane adhesive layer. The high-strength polyurethane adhesive layer slurry is prepared from the following raw materials in parts by weight: 100 parts PU-28, 7.5 parts crosslinking agent HMDA, 35 parts antimony trioxide, and 7.5 parts color paste.

[0055] S3. The mesh fabric B30D0087 is bonded to the polyurethane high-strength adhesive layer with a lamination gap of 70 mils, and then dried to obtain the non-weakening polyurethane composite material.

[0056] S4. Using a roller coating process, a water-based polyurethane slurry is coated onto the surface of the non-weakening polyurethane composite material. After drying at 140℃ for 4.5 minutes, a surface treatment layer is formed, resulting in the finished non-weakening polyurethane composite material for automotive interiors. The water-based polyurethane slurry is prepared from the following raw materials in parts by weight: 100 parts aliphatic water-based polyurethane WF-3649, 0.75 parts leveling agent LA-91-120, and 4 parts curing agent XR 5580.

[0057] Example 3

[0058] This embodiment proposes a non-weakening polyurethane composite material for automotive interiors, which includes a polyurethane surface layer, a polyurethane high-strength adhesive layer, and a base fabric layer arranged sequentially from top to bottom. The preparation method includes the following four steps S1-S4.

[0059] S1. Apply polyurethane surface layer slurry to the release paper with a blade gap of 20 mils, place it at 100℃ for 1 minute, and dry to form a polyurethane surface layer. The surface layer polyurethane slurry is prepared from the following raw materials in parts by weight: 150 parts aliphatic polyurethane resin LY-58PC, 10 parts N,N-dimethylformamide, and 10 parts color paste.

[0060] S2. Apply a high-strength polyurethane adhesive layer slurry to the polyurethane surface layer with a blade gap of 40 mils, and bake at 110℃ for 1 minute to partially dry, forming a high-strength polyurethane adhesive layer. The high-strength polyurethane adhesive layer slurry is prepared from the following raw materials in parts by weight: 100 parts PU-28, 10 parts crosslinking agent HMDA, 50 parts antimony trioxide, and 10 parts color paste.

[0061] S3. The mesh fabric B30D0087 is bonded to the polyurethane high-strength adhesive layer with a lamination gap of 80 mils, and then dried to obtain a weaken-free polyurethane composite material.

[0062] S4. Using a roller coating process, a water-based polyurethane slurry is coated onto the surface of the non-weakening polyurethane composite material. After drying at 120℃ for 3 minutes, a surface treatment layer is formed, resulting in the finished non-weakening polyurethane composite material for automotive interiors. The water-based polyurethane slurry is prepared from the following raw materials in parts by weight: 100 parts aliphatic water-based polyurethane WF-3649, 1.5 parts leveling agent LA-91-120, and 5 parts curing agent XR 5580.

[0063] Example 4

[0064] This embodiment adopts the same implementation method as Embodiment 1, except that: in this embodiment, the polyurethane high-solids adhesive layer slurry is prepared from the following raw materials in parts by weight: 100 parts PU-28, 5 parts crosslinking agent MTHPA, 20 parts antimony trioxide, and 5 parts color paste.

[0065] Example 5

[0066] This embodiment adopts the same implementation method as Embodiment 1, except that: in this embodiment, the polyurethane high-solids adhesive layer slurry is prepared from the following raw materials in parts by weight: 100 parts PU-28, 5 parts crosslinking agent MTHPA, 20 parts calcium carbonate, and 5 parts color paste.

[0067] Comparative Example 1

[0068] This comparative example presents a conventional weakened polyurethane composite material for automotive interiors, comprising a polyurethane surface layer, a solvent-free adhesive layer, and a base fabric layer arranged sequentially from top to bottom. The preparation method includes the following four steps, S1-S4.

[0069] S1. Apply polyurethane surface layer slurry to the release paper with a blade gap of 20 mils, place it at 100℃ for 1 minute, and dry to form a polyurethane surface layer. The surface layer polyurethane slurry is prepared from the following raw materials in parts by weight: 150 parts aliphatic polyurethane resin LY-58PC, 10 parts N,N-dimethylformamide, and 10 parts color paste.

[0070] S2. Apply a solvent-free adhesive layer slurry to the polyurethane surface layer with a blade gap of 45 mils, and bake at 120℃ for 1 minute to partially dry, forming a solvent-free adhesive layer. The solvent-free adhesive layer slurry is prepared by mixing polyether-type polyol composition A and aromatic Haptex CC 6945 / 100C-B at a mass ratio of 100:70. Polyether-type polyol composition A is prepared from the following parts by mass: 100 parts Haptex CC 6945 / 100C-A, 20 parts antimony trioxide, 0.4 parts NX-128, and 0.15 parts Additive CX 93600.

[0071] S3. High-density weft-knitted fabric PK280 is bonded to a solvent-free adhesive layer with a lamination gap of 80 filaments, and then dried to obtain conventional weakened automotive interior polyurethane composite material.

[0072] S4. Using a roller coating process, a water-based polyurethane slurry is coated onto the surface of the automotive interior polyurethane composite material. After drying at 120℃ for 3 minutes, a surface treatment layer is formed, resulting in the finished automotive interior polyurethane composite material that is free from weakening. The water-based polyurethane slurry is prepared from the following raw materials in parts by weight: 100 parts aliphatic water-based polyurethane WF-3649, 1.5 parts leveling agent LA-91-120, and 5 parts curing agent XR 5580.

[0073] Comparative Example 2

[0074] This comparative example uses the same implementation method as Comparative Example 1, except that in this comparative example, the base fabric layer is a left-handed polylactic acid (PLA-1) backing fabric.

[0075] Comparative Example 3

[0076] This comparative example uses the same implementation method as Example 3, except that in this comparative example, the HMDA content in the polyurethane high-solids adhesive layer slurry is 15 parts.

[0077] Test case

[0078] The performance of the above-described embodiments and comparative examples of non-weakening polyurethane composite materials for automotive interiors was tested, and the test results are shown in Table 1.

[0079] Table 1. Performance of the finished non-weakening polyurethane composite materials for automotive interiors in the examples and comparative examples.

[0080]

[0081] As can be seen from the results in Table 1:

[0082] Compared with the polyurethane composite material prepared in Comparative Example 1, the polyurethane composite materials prepared in Examples 1-5 of the present invention have certain advantages in terms of appearance and weight reduction. This shows that the structural design of the polyurethane high-solids adhesive layer of the present application can not only improve the aesthetics of the appearance, but also improve the energy economy and power performance of automobiles.

[0083] Compared with the polyurethane composite material prepared in Comparative Example 2, the polyurethane composite materials prepared in Examples 1-5 of the present invention have excellent heat resistance and light resistance. This shows that the use of low-density polyester knitted mesh fabric in this application can improve the heat resistance and light resistance of polyurethane composite materials.

[0084] Compared with the polyurethane composite material prepared in Comparative Example 3, the polyurethane composite materials prepared in Examples 1-5 of the present invention have excellent peel strength and bursting effect. This shows that the polyurethane high-solids adhesive layer and the base fabric of the present application can undergo overall brittle fracture under point burst force impact, and the airbag can be safely deployed, ensuring the reliability of the safety function.

[0085] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0086] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A polyurethane composite material that is free from weakening, characterized in that, It includes, from top to bottom, a polyurethane surface layer, a polyurethane high-strength adhesive layer, and a base fabric layer; The polyurethane high-solids adhesive layer is prepared from a polyurethane high-solids adhesive layer slurry, which is prepared from the following components in parts by weight: 100 parts of reactive polyurethane prepolymer, 5-10 parts of crosslinking agent, 20-50 parts of filler, and 5-10 parts of colorant. The reactive polyurethane prepolymer is an aliphatic isocyanate prepolymer with a solid content of 100% and a free NCO content of 4.5% ± 1%; the crosslinking agent is one of aliphatic amine crosslinking agents, acid anhydrides, or polyamides. The polyurethane surface layer is prepared from a polyurethane surface layer slurry, which is prepared from the following components in parts by weight: 150 parts aliphatic polyurethane resin, 10-50 parts N,N-dimethylformamide, and 5-10 parts color paste; the base fabric layer is a low-density polyester knitted mesh fabric with a tear strength of 10-25 N / 3 cm.

2. The non-weakening polyurethane composite material according to claim 1, characterized in that, The filler is at least one of diatomaceous earth, powdered calcium carbonate, aluminum hydroxide, halogenated flame retardant, and phosphorus-based flame retardant.

3. A method for preparing a non-weakening polyurethane composite material as described in any one of claims 1-2, characterized in that, It includes the following steps: S1. Coat the release paper with a polyurethane surface layer slurry with a blade gap of 10-20 mils, place it at 100-140℃ for 1-2 minutes, and dry to form a polyurethane surface layer; S2. Apply a high-solids polyurethane resin slurry to the polyurethane surface layer with a blade gap of 30-40 mils, and bake it at 110-140℃ until semi-dry to form a high-solids polyurethane adhesive layer. S3. The base fabric and the polyurethane high-strength adhesive layer are bonded together with a lamination gap of 60-80 mils, and then dried to obtain a polyurethane composite material that is free from weakening.

4. The method for preparing the non-weakening polyurethane composite material according to claim 3, characterized in that, The preparation method of the weaken-free polyurethane composite material further includes the following steps: S4. Using a roller coating process, after coating the surface of the non-weakening polyurethane composite material with water-based polyurethane slurry, treat it at 130-160℃ for 2-5 minutes, and after drying, form a surface treatment layer on the surface of the non-weakening polyurethane composite material.

5. The method for preparing the non-weakening polyurethane composite material according to claim 4, characterized in that, The waterborne polyurethane slurry is prepared from the following components in parts by weight: 100 parts aliphatic waterborne polyurethane, 1-1.5 parts leveling agent, and 5-8 parts curing agent.

6. The application of a non-weakening polyurethane composite material as described in any one of claims 1-2 or a non-weakening polyurethane composite material prepared by the preparation method described in any one of claims 3-5 in automotive interiors.

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