Scratch-resistant water-based easy-to-clean polyurethane synthetic leather as well as preparation method and application thereof

Abstract

The invention discloses scratch-resistant water-based easy-to-clean polyurethane synthetic leather as well as a preparation method and application thereof. The polyurethane synthetic leather is structurally composed of a water-based antifouling layer, a water-based surface layer, a water-based polyurethane bonding layer and a base material layer in sequence from top to bottom, the water-based antifouling layer is prepared from water-based antifouling layer slurry consisting of the following components in parts by weight: 50-100 parts of water-based polyurethane resin, 20-30 parts of hydrophilic hydroxyl silicone oil, 10-15 parts of a water-based isocyanate curing agent and 2-5 parts of color paste; the waterborne polyurethane resin is hydroxyl acrylic acid modified polyurethane resin, and the hydrophilic silicone oil is hydroxyl silicone oil. According to the invention, water-based antifouling treatment is adopted, so that the scratch-resistant water-based easy-to-clean polyurethane synthetic leather is prepared. The prepared product has good environment-friendly and durable characteristics, and can meet the application in the field of polyurethane synthetic leather for home furnishing and engineering decoration.

Description

Technical Field

[0001] The invention relates to a preparation process of functional polyurethane, in particular to a scratch-resistant and easily decontamination-resistant polyurethane synthetic leather and a preparation method and application thereof, belonging to the technical field of polyurethane synthetic leather. Background Art

[0002] Polyurethane synthetic leather materials are widely used in sofa home furnishings and engineering decoration due to their durability, comfort and easy processing. Their softness, skin-friendliness and easy modification properties are favored by modern home decoration.

[0003] As people's living standards improve, sofas, home furnishings and engineering decoration products are inevitably contaminated by various solvents, cosmetics, coffee, oil stains and ballpoint pens. However, it is difficult to remove the contamination of the surface of general polyurethane synthetic leather, resulting in a decrease in product performance. Therefore, polyurethane synthetic leather with anti-fouling function is very popular.

[0004] The traditional antifouling technology is to use an oily antifouling coating to treat the surface of polyurethane synthetic leather. The oily antifouling coating has the advantages of good bonding with the polyurethane dry surface layer, outstanding antifouling performance, and good durability. However, the traditional oily antifouling coating will produce organic solvent emissions, a strong odor, and excessive VOC, which not only causes serious pollution to the production environment and the surrounding living environment, but also affects the health of production and users. Therefore, water-based antifouling technology has become a new trend. In the past, water-based antifouling technology was usually limited to water-based antifouling layers, while the surface layer and adhesive layer were both oily coatings. However, with the increasing environmental protection requirements and consumers' extreme pursuit of product odor, a fully water-based antifouling product from top to bottom has become a new demand. However, in order to ensure the wear resistance of waterborne polyurethane coating, wear-resistant additives need to be added. However, the compatibility of wear-resistant additives with waterborne polyurethane is usually worse than that with oily antifouling coatings, which leads to poor bonding of the components in the waterborne antifouling coating and insufficient scratch resistance. In addition, the bonding between the waterborne antifouling layer, the waterborne polyurethane surface layer, and the waterborne polyurethane adhesive layer is usually worse than that between the oily polyurethane layers, which further leads to insufficient scratch resistance and durability of waterborne antifouling polyurethane products. Therefore, improving scratch resistance and durability has become a difficult problem for the further promotion of waterborne antifouling products. Summary of the invention

[0005] In view of this, the present invention provides a method for preparing a scratch-resistant, water-resistant and easy-to-remove polyurethane synthetic leather to address the problems of the prior art. The present invention uses a water-based process for the antifouling layer, the surface layer and the adhesive layer, which is highly environmentally friendly. At the same time, it adopts a blending technology with water-based organic silicon, and cooperates with a specific curing and processing technology to form a scratch-resistant water-based antifouling coating, thereby improving the antifouling performance of the product.

[0006] The objective of the present invention is achieved through the following technical solutions:

[0007] The first aspect of the present invention is to provide a scratch-resistant and water-resistant easy-to-decontaminate polyurethane synthetic leather, which comprises, from top to bottom, a water-based antifouling layer, a water-based polyurethane surface layer, a water-based polyurethane adhesive layer and a substrate layer, wherein the water-based antifouling layer is prepared from a water-based antifouling layer slurry composed of the following components in parts by weight: 50-100 parts of water-based polyurethane, 20-30 parts of hydrophilic silicone oil, 10-15 parts of water-based isocyanate curing agent, and 2-5 parts of color paste. Among them:

[0008] The waterborne polyurethane antifouling layer is prepared from a waterborne polyurethane antifouling layer slurry composed of the following components by weight: 50-100 parts of waterborne polyurethane, 20-30 parts of hydrophilic silicone oil, 10-15 parts of waterborne isocyanate curing agent, and 2-5 parts of color paste. Furthermore, the waterborne polyurethane is a polyurethane resin modified by hydroxyl acrylic resin; the hydrophilic silicone oil is hydroxyl silicone oil;

[0009] The waterborne polyurethane surface layer is prepared from a waterborne polyurethane surface layer slurry composed of the following components by weight: 100 parts of polyether polyurethane resin, 2-4 parts of wear-resistant additive, 2-3 parts of curing agent A, 2-3 parts of curing agent B and 1-5 parts of color paste. Further, the curing agent A is waterborne isocyanate and the curing agent B is polycarbodiimide.

[0010] The waterborne polyurethane adhesive layer is prepared from an adhesive layer slurry composed of the following components by weight: 100 parts of waterborne polyurethane adhesive layer polyurethane resin, 2-4 parts of curing agent C, and 0.2-0.4 parts of catalyst. Further, the waterborne polyurethane resin is a polyether / polycarbon blended resin, the curing agent is a waterborne isocyanate curing agent, and the catalyst is an amine catalyst.

[0011] The second aspect of the present invention is to provide a method for preparing the scratch-resistant and easily decontamination-resistant polyurethane synthetic leather as described in the first aspect, comprising the following steps:

[0012] Step 1: coating a waterborne polyurethane surface layer slurry on the release paper, and drying and molding at a temperature of 100-110° C. to obtain a waterborne polyurethane surface layer;

[0013] Step 2: coating the water-based polyurethane adhesive layer slurry on the water-based polyurethane surface layer, and pre-reacting at a temperature of 70-80° C. for 1-2 minutes to form a semi-dried water-based polyurethane adhesive layer;

[0014] Step 3: Laminating a substrate on the semi-dry aqueous polyurethane adhesive layer, heating and aging at 140-150° C., keeping the temperature for 8-10 minutes, and peeling off the release paper to obtain a polyurethane synthetic leather dry process semi-finished product;

[0015] Step 4: Roll-coating the surface of the water-based polyurethane surface layer of the dry process semi-finished product with a water-based antifouling layer slurry at a temperature of 140-150° C. for 6-8 minutes to obtain a scratch-resistant and easily decontamination polyurethane synthetic leather.

[0016] The third aspect of the present invention is to provide the use of the scratch-resistant and easily stain-removable polyurethane synthetic leather as described in the first aspect, wherein the polyurethane synthetic leather can be used for home furnishing materials.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] The present invention adopts water-based technology from top to bottom, is highly environmentally friendly, and overcomes the defects of traditional water-based antifouling products in terms of scratch resistance and insufficient durability through silicon-based materials, curing agents and matching optimization.

[0019] At the same time, this product not only focuses on the scratch resistance of the waterborne polyurethane surface, but also optimizes the bonding between the layers of the waterborne polyurethane. Through the regulation of the groups between the layers, the durability of the product is achieved. The principle is as follows: the waterborne antifouling layer uses waterborne hydroxyl acrylic modified polyurethane mainly to improve the defects of the individual polyurethane components, such as low rigidity, poor temperature resistance and poor scratch resistance, through the acrylic structure. The hydroxyl groups on the surface of hydroxyl acrylic and hydroxyl silicone oil interact with the isocyanate curing agent in the waterborne antifouling layer and the surface layer within and between layers to form a cross-layer cross-linked network structure to ensure the scratch resistance of the product; the surface material uses polyether polyurethane mainly considering that the material needs to be used in various sofa furniture. This type of material requires extremely high folding resistance requirements and can provide the product with folding resistance performance; the bonding layer uses polyether / polycarbon blended resin, which comprehensively considers that the bonding layer resin needs higher adhesion and durability, and combines the higher adhesion of polycarbon resin and the better folding resistance of polyether resin.

[0020] The product obtained by the present invention can effectively improve the scratch resistance and durability of water-based antifouling products while ensuring the antifouling and decontamination effects, greatly improve the service life of the product, and improve the customer's experience. The product can meet the requirements of 5-year hydrolysis resistance (70℃*95%RH*5W leather surface without cracking or powdering); antifouling ≥4 level (ordinary oily ballpoint pen and napped cloth dry wipe); Wisbo wear resistance 50,000 times without breaking; alcohol rubbing color fastness 20 times ≥4 level; peel strength ≥20N / 3cm, room temperature flexing, 50,000 times without cracking; five fingers scratching (10N) without damage. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with the embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0022] In addition, unless otherwise specified, the preparation processes in the following embodiments are all conventional means in the prior art in the art, and therefore, they are not described in detail; the parts in the following embodiments are all parts by weight.

[0023] The raw material information used in the following examples is as follows:

[0024] Hydroxyl acrylic acid modified polyurethane resin brand 2318, produced by Wuhan Shiquanxing New Materials Technology Co., Ltd.;

[0025] The unmodified waterborne polyurethane resin in Comparative Example 1 is waterborne polycarbonate polyurethane resin 3920 produced by Wanhua Chemical Co., Ltd.

[0026] The brand of hydrophilic silicone oil is CN-169CN-169, and the manufacturer is Guangdong Zhongke Hongtai New Materials Co., Ltd.;

[0027] The brand of water-based isocyanate curing agent is Aquolin 268 water-dispersible isocyanate curing agent, and the manufacturer is Yantai Wanhua Chemical;

[0028] Color paste: SM series water-based color paste from Suzhou Shiming Technology;

[0029] The grade of waterborne surface polyurethane is DL 1343, manufactured by Shanghai Covestro;

[0030] The grade of wear-resistant additive is SY-3520, and the manufacturer is Jiangxi Mitsukoshi;

[0031] The water-based carbonized diamine curing agent is brand XR-5580, and the manufacturer is Starr Fine Coatings (Suzhou) Co., Ltd.;

[0032] The polyurethane resin grade of the water-based polyurethane adhesive layer is Ecoexc TM T133, the manufacturer is Dongguan Longsui Industrial Investment Co., Ltd.

[0033] The catalyst brand is AUCAT-101W and the manufacturer is Guangzhou Yourun Synthetic Materials Co., Ltd.

[0034] The above reagents are only used to illustrate the sources and components of the reagents used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0035] Example 1

[0036] A scratch-resistant and easy-to-decontaminate polyurethane synthetic leather and a preparation method thereof, comprising the following steps:

[0037] Step 1: Coat the release paper with a water-based polyurethane surface slurry with a coating thickness of 0.1 mm and dry at 100°C for 1 min to form a water-based polyurethane surface layer; wherein: the composition of the water-based polyurethane surface slurry is 100 parts of Covestro DL 1343, 2 parts of Mitsukoshi's SY-3520 wear-resistant additive, 2.5 parts of Wanhua Chemical's Aquolin 268 curing agent, 2.5 parts of Starr's XR-5580 curing agent and 3 parts of Shiming SM water-based black slurry were mixed according to weight parts.

[0038] Step 2: coating the water-based polyurethane adhesive layer slurry on the water-based polyurethane surface layer, wherein the coating thickness of the water-based polyurethane adhesive layer slurry is 0.1 mm; pre-reacting at 70° C. for 2 minutes to form a semi-dry water-based polyurethane adhesive layer, wherein the water-based polyurethane adhesive layer has a certain adhesiveness; wherein: the water-based polyurethane adhesive layer slurry is composed of 100 parts of Ecoexc TM T133 from Longsui, 2 parts of Aquolin 268 curing agent from Wanhua Chemical, and 0.2 parts of AUCAT-101W catalyst synthesized from Guangzhou Yourun;

[0039] Step 3: Laminating a 0.7 mm nylon non-woven fabric on the semi-dry aqueous polyurethane adhesive layer, heating and aging at 140° C., keeping the temperature for 10 minutes, and peeling off the release paper to obtain a polyurethane synthetic leather dry process semi-finished product;

[0040] Step 4: Based on the dry semi-finished product, a water-based antifouling polyurethane slurry is used for coating on the surface of the water-based polyurethane surface layer, and fully crosslinked and cured for 8 minutes at a temperature of 140°C to obtain a scratch-resistant and easy-to-remove polyurethane synthetic leather. The composition of the water-based antifouling polyurethane slurry is 50 parts of Wuhan Shiquanxing's 2318 water-based polyurethane, 20 parts of Anhui Feidian's FCN-169, 100,000 Huahua Chemical's Aquolin 268 curing agent, and 2 parts of Shiming SM water-based black slurry.

[0041] Example 2

[0042] A scratch-resistant and easy-to-decontaminate polyurethane synthetic leather and a preparation method thereof, comprising the following steps:

[0043] Step 1: Coat the release paper with a water-based polyurethane surface slurry with a coating thickness of 0.12 mm and dry at 100°C for 1.5 min to form a water-based polyurethane surface layer; wherein: the composition of the water-based polyurethane surface slurry is 100 parts of Covestro DL 1343, 3 parts of Mitsukoshi's SY-3520 wear-resistant additive, 2 parts of Wanhua Chemical's Aquolin 268 curing agent, 2 parts of Stahl's XR-5580 curing agent and 1 part of Shiming SM water-based black slurry were mixed according to weight parts.

[0044] Step 2: coating the water-based polyurethane adhesive layer slurry on the water-based polyurethane surface layer, wherein the coating thickness of the water-based polyurethane adhesive layer slurry is 0.12 mm; pre-reacting at 75° C. for 1.5 min to form a semi-dry water-based polyurethane adhesive layer, wherein the water-based polyurethane adhesive layer has a certain adhesiveness; wherein the water-based polyurethane adhesive layer slurry is composed of 100 parts of Ecoexc TM T133 from Longsui, 3 parts of Aquolin 268 curing agent from Wanhua Chemical, and 0.3 parts of AUCAT-101W catalyst synthesized from Guangzhou Yourun;

[0045] Step 3: Laminating a 0.7 mm nylon non-woven fabric on the semi-dry aqueous polyurethane adhesive layer, heating and aging at 145° C., keeping the temperature for 9 minutes, and peeling off the release paper to obtain a polyurethane synthetic leather dry process semi-finished product;

[0046] Step 4: Based on the dry semi-finished product, a water-based antifouling polyurethane slurry is used for coating on the surface of the water-based polyurethane surface layer, and fully crosslinked and cured for 7 minutes at a temperature of 145°C to obtain a scratch-resistant and easy-to-remove polyurethane synthetic leather. The composition of the water-based antifouling polyurethane slurry is 70 parts of Wuhan Shiquanxing's 2318 water-based polyurethane, 25 parts of Anhui Feidian's FCN-169, 12 parts of Wanhua Chemical's Aquolin 268 curing agent, and 3 parts of Shiming SM water-based black slurry.

[0047] Example 3

[0048] A scratch-resistant and easy-to-decontaminate polyurethane synthetic leather and a preparation method thereof, comprising the following steps:

[0049] Step 1: Coat the release paper with a water-based polyurethane surface slurry with a coating thickness of 0.15 mm and dry at 100°C for 2 minutes to form a water-based polyurethane surface layer; wherein: the composition of the water-based polyurethane surface slurry is 100 parts of Covestro DL 1343, 3 parts of Mitsukoshi's SY-3520 wear-resistant additive, 3 parts of Wanhua Chemical's Aquolin268 curing agent, 3 parts of Starr's XR-5580 curing agent and 5 parts of Shiming SM water-based black slurry were mixed according to weight parts.

[0050] Step 2: coating the water-based polyurethane adhesive layer slurry on the water-based polyurethane surface layer, wherein the coating thickness of the water-based polyurethane adhesive layer slurry is 0.15 mm; pre-reacting at 80° C. for 2 minutes to form a semi-dry water-based polyurethane adhesive layer, wherein the water-based polyurethane adhesive layer has a certain adhesiveness; wherein the water-based polyurethane adhesive layer slurry is composed of 100 parts of Ecoexc TM T133 produced by Longsui, 4 parts of Aquolin 268 curing agent produced by Wanhua Chemical, and 0.4 parts of AUCAT-101W catalyst produced by Guangzhou Yourun Synthesis;

[0051] Step 3: Laminating a 0.7 mm nylon non-woven fabric on the semi-dry aqueous polyurethane adhesive layer, heating and aging at 150° C., keeping the temperature for 10 minutes, and peeling off the release paper to obtain a polyurethane synthetic leather dry process semi-finished product;

[0052] Step 4: Based on the dry semi-finished product, a water-based antifouling polyurethane slurry is used for coating on the surface of the water-based polyurethane surface layer, and fully crosslinked and cured at a temperature of 150°C for 8 minutes to obtain a scratch-resistant and easy-to-remove polyurethane synthetic leather. The composition of the water-based antifouling polyurethane slurry is 100 parts of Wuhan Shiquanxing's 2318 water-based polyurethane, 30 parts of Anhui Feidian's FCN-169, 15 parts of Wanhua Chemical's Aquolin 268 curing agent, and 5 parts of Shiming SM water-based black slurry.

[0053] Comparative Example 1

[0054] Compared with Example 1, the only difference of Comparative Example 1 is that the waterborne polyurethane in step 4 is not modified with hydroxyl acrylic acid, that is, the unmodified waterborne polyurethane resin is used to replace the hydroxyl acrylic acid-modified polyurethane resin in Example 1, and the other processes are consistent with Example 1.

[0055] Compared with Example 2, in Comparative Example 2, only curing agent A is used in step 2, and curing agent B is not used; the amount of curing agent A used in Comparative Example 2 is the sum of the amounts of curing agent A and curing agent B used in Example 2; the other processes of Comparative Example 2 are consistent with Example 2.

[0056] Compared with Example 3, in Comparative Example 3, curing agent A is not used in step 2, and only curing agent B is used. The amount of curing agent B used in Comparative Example 3 is the sum of the amounts of curing agent A and curing agent B used in Example 3; other processes of Comparative Example 3 are consistent with Example 3.

[0057] Comparative Example 4 Compared with Example 1, the surface layer resin in step 2 adopts Wanhua Chemical's water-based polycarbonate polyurethane resin.

[0058] The performance of the products obtained in the above embodiments and comparative examples was tested, and the test results are shown in Table 1 below:

[0059] Table 1

[0060]

[0061] Performance test results: From the comparison between Example 1 and Comparative Example 1 in Table 1, it can be seen that the scratch resistance of the waterborne polyurethane resin modified with hydroxyl acrylic acid is significantly improved compared with the unmodified waterborne polyurethane formula; from the comparison between Example 2 and Comparative Example 2, and between Example 3 and Comparative Example 3, it can be seen that in the waterborne surface material, different types of waterborne curing agents have a certain synergistic effect, and the two together improve the cross-linking network of the material and improve the peeling characteristics of the product; from the comparison between Example 1 and Comparative Example 4, it can be seen that when the surface material uses polyether resin than when using polycarbonate resin, the material has better folding resistance.

[0062] In summary, the embodiment obtains a durable, water-resistant, and easily decontamination-resistant polyurethane synthetic leather by adjusting the formula of each layer.

[0063] Obviously, the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A scratch-resistant and easily decontamination-resistant polyurethane synthetic leather, characterized in that: The invention comprises, from top to bottom, an aqueous antifouling layer, an aqueous polyurethane surface layer, an aqueous polyurethane bonding layer and a substrate layer. The aqueous antifouling layer is prepared from an aqueous antifouling layer slurry composed of the following components in parts by weight: 50-100 parts of aqueous polyurethane resin, 20-30 parts of hydrophilic silicone oil, 10-15 parts of aqueous isocyanate curing agent, and 2-5 parts of color paste; the aqueous polyurethane resin is a hydroxyl acrylic modified polyurethane resin.

2. The scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 1, characterized in that: The hydrophilic silicone oil is hydroxy silicone oil.

3. The scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 1, characterized in that: The waterborne polyurethane surface layer is prepared from a waterborne polyurethane surface layer slurry composed of the following components in parts by weight: 100 parts of polyether polyurethane resin, 2-4 parts of wear-resistant additive, 2-3 parts of curing agent A, 2-3 parts of curing agent B and 1-5 parts of color paste.

4. The scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 3, characterized in that: Curing agent A is water-based isocyanate and curing agent B is polycarbodiimide.

5. The scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 1, characterized in that: The waterborne polyurethane adhesive layer is prepared from an adhesive layer slurry composed of the following components in parts by weight: 100 parts of waterborne polyurethane resin, 2-4 parts of curing agent C, and 0.2-0.4 parts of catalyst.

6. The scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 5, characterized in that: The waterborne polyurethane resin is a polyether / polycarbonate blended resin, the curing agent is a waterborne isocyanate curing agent, and the catalyst is an amine catalyst.

7. The method for preparing the scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1: coating a waterborne polyurethane surface layer slurry on the release paper, and drying and molding at a temperature of 100-110° C. to obtain a waterborne polyurethane surface layer; Step 2: coating the water-based polyurethane adhesive layer slurry on the water-based polyurethane surface layer, and pre-reacting at a temperature of 70-80° C. for 1-2 minutes to form a semi-dried water-based polyurethane adhesive layer; Step 3: Laminating a substrate on the semi-dry aqueous polyurethane adhesive layer, heating and aging at 140-150° C., keeping the temperature for 8-10 minutes, and peeling off the release paper to obtain a polyurethane synthetic leather dry process semi-finished product; Step 4: Roll-coating the surface of the water-based polyurethane surface layer of the semi-finished dry product with a water-based antifouling layer slurry at a temperature of 140-150° C. for 6-8 minutes to obtain a scratch-resistant and easily decontamination-resistant polyurethane synthetic leather.

8. The method for preparing the scratch-resistant and easily decontamination-resistant polyurethane synthetic leather according to claim 7, characterized in that: The coating thickness of the waterborne polyurethane surface layer slurry is 0.1-0.15 mm; the coating thickness of the waterborne polyurethane bonding layer slurry is 0.1-0.15 mm.

9. The method for preparing the scratch-resistant and antifouling polyurethane synthetic leather according to claim 7, characterized in that: The viscosity of the aqueous antifouling slurry is 1000-1500rpm / 25°C.

10. The scratch-resistant and antifouling polyurethane synthetic leather according to any one of claims 1 to 6 is used for sofa home furnishing materials.

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