Wear-resistant silicone leather and preparation method thereof

Abstract

The present application relates to a kind of organic silicon leather, especially a kind of wear-resistant organic silicon leather and preparation method, wear-resistant organic silicon leather includes silicone rubber layer, and silicone rubber layer is cured by liquid glue, and the hardness range of liquid glue after curing is 60-70A, preparation method includes the preparation of wear-resistant layer raw material, the preparation of adhesive layer, the formation of wear-resistant layer, the formation of silicone rubber layer and the preparation of wear-resistant organic silicon leather, the hardness of the liquid glue of 60-80A is used in the silicone rubber layer of the present application, improve the tear strength of silicone rubber layer, improve the wear resistance of organic silicon leather.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of silicone leather, in particular a kind of wear-resistant silicone leather and preparation method. BACKGROUND

[0002] At present, a variety of synthetic leather has been developed to replace natural leather on the market, among which polyurethane (PU) or polyvinyl chloride (PVC) materials are widely used in furniture, decoration, clothing, footwear, automobiles, etc., but in order to meet the increasingly stringent safety, environmental protection and other aspects, they cannot meet the use requirements in some physical properties such as heat resistance, stain resistance, solvent resistance, hydrolysis resistance, weather resistance, etc. Compared with PU / PVC, silicone leather has good heat resistance, stain resistance, solvent resistance, hydrolysis resistance and weather resistance, but silicone rubber also has its own shortcomings. Because the crosslinking density is low and the network structure is simple during the curing process of silicone rubber, the wear resistance of silicone leather is worse than that of PU / PVC.

[0003] Therefore, there is an urgent need for a silicone leather that can solve the problem of not being wear-resistant. SUMMARY

[0004] To solve the above technical problems, the purpose of the present application is to provide a kind of wear-resistant silicone leather and preparation method.

[0005] The technical scheme adopted by the present application to solve the problem is: a kind of wear-resistant silicone leather, comprising a silicone rubber layer, the silicone rubber layer is cured by liquid glue, and the hardness of the cured liquid glue ranges from 60 to 70A.

[0006] As a further improvement of the above technical scheme, the hardness of the cured liquid glue is 60A.

[0007] As a further improvement of the above technical scheme, an abrasion-resistant layer is provided on the upper surface of the silicone rubber layer, and the raw material of the abrasion-resistant layer includes a filler, and the filler is polymethyl methacrylate.

[0008] As a further improvement of the above technical scheme, an abrasion-resistant layer is provided on the upper surface of the silicone rubber layer, and the raw material of the abrasion-resistant layer includes a filler, and the filler is a copolymer of polyvinyl chloride and polymethyl methacrylate.

[0009] As a further improvement of the above technical scheme, the lower surface of the silicone rubber layer is fixedly connected to the base cloth through an adhesive layer, and the raw material of the adhesive layer includes the liquid glue.

[0010] A method for preparing a wear-resistant silicone leather, comprising a wear-resistant silicone leather as claimed in claim 5, wherein the silicone rubber layer is cured from a first liquid glue; the wear-resistant layer is made from the following raw materials in parts by weight: 5-15 parts of a vinyl silicone rubber base glue, 40-60 parts of a vinyl MQ resin, 10-20 parts of a first vinyl silicone oil, 2-8 parts of a filler, 5-15 parts of a high hydrogen-containing silicone oil, 1-3 parts of a first silane coupling agent, 0.5-1 part of a first platinum catalyst, and 0.02-0.1 part of a first inhibitor; the adhesive layer is made from the following raw materials in parts by weight: 50-70 parts of a second liquid glue, 15-35 parts of a second vinyl silicone oil, 4-10 parts of a hydrogen-containing MQ resin, 1-3 parts of a second silane coupling agent, 0.5-1 part of a second platinum catalyst, and 0.02-0.1 part of a second inhibitor; and the preparation steps are as follows:

[0011] S1: Put the above-mentioned raw materials in parts by weight of the vinyl silicone rubber base glue, the vinyl MQ resin, the first vinyl silicone oil, the filler, the high hydrogen-containing silicone oil, the first silane coupling agent, the first platinum catalyst, and the first inhibitor into a planetary dispersion mixer, pass cooling water, open the vacuum device, and disperse and stir for 10-20 minutes to obtain the wear-resistant layer raw material.

[0012] S2: Put the above-mentioned raw materials in parts by weight of the second liquid glue, the second vinyl silicone oil, the hydrogen-containing MQ resin, the second silane coupling agent, the second platinum catalyst, and the second inhibitor into a planetary dispersion mixer, pass cooling water, open the vacuum device, and disperse and stir for 10-20 minutes to obtain the adhesive layer raw material.

[0013] S3: Coat the wear-resistant layer raw material on release paper or leather paper, convey it to a tunnel oven through a conveyor belt, bake it at a temperature of 110-130°C for 5-8 minutes, and form the wear-resistant layer.

[0014] S4: Coat the first liquid glue on the surface of the wear-resistant layer through a hydraulic silicone glue feeder, then convey it to a tunnel oven through a conveyor belt, bake it at a temperature of 110-130°C for 5-8 minutes, and form the silicone rubber layer.

[0015] S5: Coat the adhesive layer raw material on the surface of the silicone rubber functional layer, adhere it to the base cloth after coating, then convey it to a tunnel oven, bake it at a temperature of 110-130°C for 5-8 minutes, and finally peel off the release paper or leather paper to obtain the wear-resistant silicone leather.

[0016] As a further improvement of the above technical solution, the first silane coupling agent and the second silane coupling agent are one or a mixture of two or more of 2-(3,4-epoxycyclohexane) ethyl trimethoxysilane, KH-560, and KH-570; and the first inhibitor and the second inhibitor are one or a mixture of two of ethynylcyclohexanol and maleic acid diallyl ester.

[0017] As a further improvement of the above technical solution, the thickness of the wear-resistant layer is 0.05-0.1 mm; the thickness of the silicone rubber layer is 0.1-0.2 mm; and the thickness of the adhesive layer is 0.05-0.1 mm.

[0018] The beneficial effects of the present invention are as follows: the silicone rubber layer of the present invention improves the tear strength of the silicone rubber layer and improves the wear resistance of the silicone leather by adopting liquid glue with a hardness of 60-80A. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The present invention will be further explained below with reference to the accompanying drawings and specific embodiments.

[0020] Figure 1 This is the effect diagram after the wear resistance test of Example 1;

[0021] Figure 2 This is the effect diagram after the wear resistance test of Example 2;

[0022] Figure 3 This is the effect diagram after the wear resistance test of comparative example 1;

[0023] Figure 4 This is the effect diagram after the wear resistance test of comparative example 2;

[0024] Figure 5 The figure is a comparison chart of the effects after the wear resistance test of Example 1, Example 2, Comparative Example 1 and Comparative Example 2. DETAILED DESCRIPTION

[0025] In all embodiments of the present invention, unless otherwise specified regarding temperature and pressure, normal temperature and pressure shall prevail. Unless otherwise specified regarding the use of equipment, conventional settings may be used.

[0026] To make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with specific embodiments. It should be noted that the embodiments of the present invention and the features therein can be combined with each other without conflict.

[0027] It is to be understood that these descriptions are illustrative only and are not intended to limit the scope of the invention.

[0028] Reference Figures 1 to 5Embodiment one: a wear-resistant organic silicon leather, which comprises a wear-resistant layer, a silicone rubber layer, an adhesive layer and a base cloth designed in sequence, the base cloth can be but not limited to non-woven fabric, the thickness of the wear-resistant layer is 0.1 mm, the thickness of the silicone rubber layer is 0.1 mm, and the thickness of the adhesive layer is 0.07 mm. It is understood that, in actual use, from top to bottom, they are wear-resistant layer, silicone rubber layer, adhesive layer and base cloth; while in the preparation process, they are in the opposite order, from top to bottom, they are base cloth, adhesive layer, silicone rubber layer and wear-resistant layer.

[0029] The wear-resistant layer is made of raw materials in the following proportions by weight: 5 parts of vinyl silicone rubber base glue, 40 parts of vinyl MQ resin (which can be but not limited to Longsheng Sihai SH-5202), 20 parts of first vinyl silicone oil, 6 parts of filler, 8 parts of high hydrogen-containing silicone oil, 1.5 parts of first silane coupling agent, 0.5 parts of first platinum catalyst and 0.02 parts of first inhibitor; the vinyl content in the vinyl silicone rubber base glue is 0.2%; the viscosity of the vinyl MQ resin is 20000 cs, and the vinyl content is 2.0%; the viscosity of the first vinyl silicone oil is 500 cs, and the vinyl content is 5.0%; the filler is polymethyl methacrylate with a particle size of 100 um; the viscosity of the high hydrogen-containing silicone oil is 50 cs, and the hydrogen content is 1.6%; the first silane coupling agent is 2-(3,4-epoxycyclohexane) ethyl trimethoxysilane; the first platinum catalyst is an ethanol solution of 5000 ppm; and the first inhibitor is maleic acid diallyl ester.

[0030] The silicone rubber layer is formed by curing the first liquid glue, which is purchased from Shandong Dongyue Organic Silicon Material Co., Ltd. and is a liquid glue of type LSR-60A-M I (LSR-60A / B-M I). The hardness of the liquid glue after curing is 60A.

[0031] The adhesive layer is made of raw materials in the following proportions by weight: 60 parts of second liquid glue, 15 parts of second vinyl silicone oil, 8 parts of hydrogen-containing MQ resin, 1 part of second silane coupling agent, 0.5 parts of second platinum catalyst and 0.02 parts of second inhibitor; the manufacturer and type of the second liquid glue are the same as those of the first liquid glue; the viscosity of the second vinyl silicone oil is 500 cs, and the vinyl content is 5.0%; the viscosity of the hydrogen-containing MQ resin is 100 cs, and the hydrogen content is 0.7%; the second silane coupling agent is 2-(3,4-epoxycyclohexane) ethyl trimethoxysilane; the second platinum catalyst is an ethanol solution of 5000 ppm; and the second inhibitor is maleic acid diallyl ester.

[0032] Preparation method of embodiment one:

[0033] S1: Preparation of the wear-resistant layer raw material: Put the above-mentioned weight parts of the vinyl silicone rubber-based glue, vinyl MQ resin, first vinyl silicone oil, filler, high hydrogen-containing silicone oil, first silane coupling agent, first platinum catalyst and first inhibitor into a planetary dispersion stirrer, pass cooling water, open the vacuum device, and disperse and stir for 15 minutes to obtain the wear-resistant layer raw material.

[0034] S2: Preparation of the adhesive layer: Put the above-mentioned weight parts of the second liquid glue, second vinyl silicone oil, hydrogen-containing MQ resin, second silane coupling agent, second platinum catalyst and second inhibitor into a planetary dispersion stirrer, pass cooling water, open the vacuum device, and disperse and stir for 15 minutes to obtain the adhesive layer raw material.

[0035] S3: Formation of the wear-resistant layer: The wear-resistant layer raw material is coated on release paper or leather paper, conveyed to a tunnel oven by a conveyor belt, baked at a temperature of 110°C for 8 minutes to form the wear-resistant layer.

[0036] S4: Formation of the silicone rubber layer: The first liquid glue is coated on the surface of the wear-resistant layer by a hydraulic silicone glue feeder, then conveyed to a tunnel oven by a conveyor belt, baked at a temperature of 130°C for 5 minutes to form the silicone rubber layer.

[0037] S5: Preparation of the wear-resistant silicone leather: The adhesive layer raw material is coated on the surface of the silicone rubber functional layer, and after coating, it is attached to the base cloth, then conveyed to a tunnel oven, baked at a temperature of 130°C for 8 minutes, and finally the release paper or leather paper is peeled off to obtain Example One.

[0038] Example Two: A wear-resistant silicone leather, which comprises a wear-resistant layer, a silicone rubber layer, an adhesive layer and a base cloth designed in sequence, the base cloth can be but is not limited to non-woven fabric, the thickness of the wear-resistant layer is 0.7mm, the thickness of the silicone rubber layer is 0.15mm, and the thickness of the adhesive layer is 0.1mm.

[0039] The wear-resistant layer is made of raw materials in the following weight proportions: 10 parts of vinyl silicone rubber base glue, 50 parts of vinyl MQ resin, 10 parts of first vinyl silicone oil, 8 parts of filler, 15 parts of high hydrogen-containing silicone oil, 1 part of first silane coupling agent, 0.5 part of first platinum gold catalyst and 0.02 part of first inhibitor; the vinyl content in the vinyl silicone rubber base glue is 0.5%; the viscosity of the vinyl MQ resin is 10000 cs and the vinyl content is 2.5%; the viscosity of the first vinyl silicone oil is 2000 cs and the vinyl content is 3.0%; the filler is a copolymer of polyvinyl chloride and polymethyl methacrylate with a particle size of 50 um; the viscosity of the high hydrogen-containing silicone oil is 100 cs and the hydrogen content is 1.2%; the first silane coupling agent is a mixture of KH-560 and KH-570; the first platinum gold catalyst is an ethanol solution with a concentration of 5000 ppm; and the first inhibitor is ethynyl cyclohexanol.

[0040] The silicone rubber layer is formed by curing the first liquid glue, which is purchased from Shandong Dongyue Organic Silicon Material Co., Ltd. and has a model of LSR-70A-M I (LSR-70A / B-M I). The hardness of the liquid glue after curing is 70A.

[0041] The adhesive layer is made of raw materials in the following weight proportions: 50 parts of second liquid glue, 20 parts of second vinyl silicone oil, 8 parts of hydrogen-containing MQ resin, 1 part of second silane coupling agent, 0.5 part of second platinum gold catalyst and 0.02 part of second inhibitor; the manufacturer and model of the second liquid glue are the same as those of the first liquid glue; the viscosity of the second vinyl silicone oil is 2000 cs and the vinyl content is 3.0%; the viscosity of the hydrogen-containing MQ resin is 50 cs and the hydrogen content is 1%; the second silane coupling agent is a mixture of KH-560 and KH-570; the second platinum gold catalyst is an ethanol solution with a concentration of 5000 ppm; and the second inhibitor is ethynyl cyclohexanol.

[0042] Preparation method of example two:

[0043] S1: Preparation of wear-resistant layer raw materials: put the above-mentioned raw materials in the following weight proportions: vinyl silicone rubber base glue, vinyl MQ resin, first vinyl silicone oil, filler, high hydrogen-containing silicone oil, first silane coupling agent, first platinum gold catalyst and first inhibitor into a planetary dispersion mixer, pass cooling water, open the vacuum device, and disperse and stir for 15 minutes to obtain wear-resistant layer raw materials.

[0044] S2: Preparation of adhesive layer: put the above-mentioned raw materials in the following weight proportions: second liquid glue, second vinyl silicone oil, hydrogen-containing MQ resin, second silane coupling agent, second platinum gold catalyst and second inhibitor into a planetary dispersion mixer, pass cooling water, open the vacuum device, and disperse and stir for 15 minutes to obtain adhesive layer raw materials.

[0045] S3: Abrasion-resistant layer formation: Abrasion-resistant layer raw materials are coated on release paper or leather paper, conveyed by a conveyor belt to a tunnel oven, baked at a temperature of 110°C for 8 minutes to form an abrasion-resistant layer.

[0046] S4: Silicon rubber layer formation: The first liquid glue is coated on the surface of the abrasion-resistant layer by a hydraulic silicone glue feeder, then conveyed by a conveyor belt to a tunnel oven, baked at a temperature of 130°C for 5 minutes to form a silicon rubber layer.

[0047] S5: Preparation of abrasion-resistant silicone leather: The adhesive layer raw materials are coated on the surface of the silicon rubber functional layer, and after coating, the base cloth is attached, then conveyed to a tunnel oven, baked at a temperature of 130°C for 8 minutes, and finally the release paper or leather paper is peeled off to obtain Example Two.

[0048] Example Three: The difference from Example One is that the first liquid glue is purchased from Shandong Dongyue Silicone Material Co., Ltd., and the model is LSR-70A-M I liquid glue, and the hardness of the cured and formed liquid glue is 70A.

[0049] Example Four: The difference from Example Two is that the first liquid glue is purchased from Shandong Dongyue Silicone Material Co., Ltd., and the model is LSR-60A-M I liquid glue, and the hardness of the cured and formed liquid glue is 60A.

[0050] Comparative Example One: The difference from Example One is that the raw material composition of the abrasion-resistant layer lacks the filler (polymethyl methacrylate).

[0051] Comparative Example Two: The difference from Example Two is that the first liquid glue is purchased from Shandong Dongyue Silicone Material Co., Ltd., and the model is LSR-30A-M I (LSR-30A / B-M I) liquid glue, and the hardness of the cured and formed liquid glue is 30A.

[0052] Comparative Example Three: The difference from Example One is that the filler is a copolymer of polyvinyl chloride and polymethyl methacrylate.

[0053] The silicone leather of the above Examples One to Four and Comparative Examples One to Three is subjected to steel wool abrasion resistance test.

[0054] Among them, the steel wool abrasion resistance test: refer to the standard ASTM F2496 for testing, sample size: 5*5cm; Steel wool model: Japan #0000 steel wool; Load: 500g weight; Times: 2500 times; Speed: 60rpm.

[0055] Combined Figures 1 to 4 , Figure 1 is the effect picture after abrasion resistance test of Example One;Figure 2 The effect picture after abrasion resistance test of Example 2; the effect picture after abrasion resistance test of Example 3 is similar to that of Example 2; the effect picture after abrasion resistance test of Example 4 is similar to that of Example 1. Figure 3 The effect picture after abrasion resistance test of Comparative Example 1; Figure 4 The effect picture after abrasion resistance test of Comparative Example 2; the effect picture after abrasion resistance test of Comparative Example 3 is similar to that of Example 2.

[0056] It can be known from Example 1, Example 3 and Comparative Example 3 (or Example 2, Example 4 and Comparative Example 2) that when the silicone rubber layer adopts liquid glue with higher curing hardness, the tear strength of the silicone leather prepared is better, and the silicone leather is resistant to scratch and abrasion, and the hardness is preferably 60A-70A, and it can be known from Comparative Example 1 and Example 3 that the abrasion resistance of 60A is relatively better.

[0057] In addition, combined with Example 1, Example 2 and Comparative Example 3, the applicant finds through preliminary research that on the basis that the hardness of the liquid glue is in the range of 60A-70A, the type of the filler of the wear-resistant layer also affects the abrasion resistance of the silicone leather, and according to the existing data, it is shown that when the curing hardness of the first liquid glue is 60A and the filler of the wear-resistant layer is polymethyl methacrylate, the abrasion resistance of the silicone leather is better, and the silicone leather is resistant to steel wool abrasion.

[0058] The above embodiments cannot limit the protection scope of the present application, and the present application can also have various changes and improvements without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the present application.

Claims

1. A method for preparing a wear-resistant organic silicon leather, comprising a silicon rubber layer, the silicon rubber layer being cured by a first liquid glue, an upper surface of the silicon rubber layer being provided with a wear-resistant layer, raw materials of the wear-resistant layer comprising fillers, a lower surface of the silicon rubber layer being fixedly connected with a base cloth through an adhesive layer, raw materials of the adhesive layer comprising a second liquid glue; the wear-resistant layer being made of raw materials in the following proportions by weight: 5-15 parts of a vinyl silicone rubber base glue, 40-60 parts of a vinyl MQ resin, 10-20 parts of a first vinyl silicone oil, 2-8 parts of fillers, 5-15 parts of a high hydrogen-containing silicone oil, 1-3 parts of a first silane coupling agent, 0.5-1 part of a first platinum catalyst, and 0.02-0.1 part of a first inhibitor; the adhesive layer being made of raw materials in the following proportions by weight: 50-70 parts of the second liquid glue, 15-35 parts of a second vinyl silicone oil, 4-10 parts of a hydrogen-containing MQ resin, 1-3 parts of a second silane coupling agent, 0.5-1 part of a second platinum catalyst, and 0.02-0.1 part of a second inhibitor; the preparation steps being as follows: S1: the above-mentioned raw materials in the following proportions by weight: the vinyl silicone rubber base glue, the vinyl MQ resin, the first vinyl silicone oil, the fillers, the high hydrogen-containing silicone oil, the first silane coupling agent, the first platinum catalyst, and the first inhibitor are put into a planetary dispersion stirrer, cooling water is passed, a vacuum device is opened, and dispersion stirring is performed for 10-20 minutes to obtain the wear-resistant layer raw materials; S2: the above-mentioned raw materials in the following proportions by weight: the second liquid glue, the second vinyl silicone oil, the hydrogen-containing MQ resin, the second silane coupling agent, the second platinum catalyst, and the second inhibitor are put into a planetary dispersion stirrer, cooling water is passed, a vacuum device is opened, and dispersion stirring is performed for 10-20 minutes to obtain the adhesive layer raw materials; S3: the wear-resistant layer raw materials are coated on release paper or leather paper, conveyed to a tunnel oven through a conveyor belt, baked at a temperature of 110-130℃ for 5-8 minutes to form the wear-resistant layer; S4: the first liquid glue is coated on the surface of the wear-resistant layer through a hydraulic silicone glue feeder, then conveyed to a tunnel oven through a conveyor belt, baked at a temperature of 110-130℃ for 5-8 minutes to form the silicon rubber layer; S5: the adhesive layer raw materials are coated on the surface of the silicon rubber functional layer, then the coated layer is attached with the base cloth, then conveyed to a tunnel oven, baked at a temperature of 110-130℃ for 5-8 minutes, and finally the release paper or leather paper is peeled off to obtain the wear-resistant organic silicon leather; characterized in that: the hardness of the first liquid glue after curing is 60A, and the fillers are polymethyl methacrylate.

2. A method of preparing a wear-resistant silicone leather according to claim 1, characterized in that: the first silane coupling agent and the second silane coupling agent are one or a mixture of two or more of 2-(3,4-epoxycyclohexane)ethyl trimethoxysilane, KH-560, and KH-570; and the first inhibitor and the second inhibitor are one or a mixture of two of ethynylcyclohexanol and maleic acid diallyl ester.

3. A method of making a wear resistant silicone leather according to claim 1, characterized in that: the thickness of the wear-resistant layer is 0.05-0.1mm, the thickness of the silicon rubber layer is 0.1-0.2mm, and the thickness of the adhesive layer is 0.05-0.1mm.

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