Silicon-based material, preparation method and application of silicon-based material in organic silicon leather

Abstract

The invention provides a silicon-based material, a preparation method and application of the silicon-based material in organic silicon leather. The silicon-based material is prepared from the following raw materials in parts by weight: 100 parts of silicon rubber-based rubber, 1-5 parts of a linear coupling agent, 10-30 parts of hand feeling powder, 1-10 parts of hydrogen-containing silicone oil, 0.025-1 part of an inhibitor and 20-100 parts of an organic solvent, and the silicon rubber-based rubber is prepared from the following raw materials in parts by weight: 100 parts of vinyl-terminated vinyl-side vinyl silicone oil, 20-60 parts of white carbon black, 4-12 parts of hexamethyldisilazane and 0.5-1 part of water. The hydrogen-containing silicone oil is selected from at least one of trimethylsilyl-terminated hydrogen-containing silicone oil and hydrogen-containing MQ resin, the hand feeling powder has a coarse structure and a siloxane group, and the linear coupling agent has a structure shown in the specification. The silicon-based material is obtained by compounding the linear coupling agent and the hand feeling powder with specific structures with the raw materials such as the silicone rubber-based rubber, and the hand feeling, the anti-fouling performance, the wear-resisting performance and the mechanical strength can be effectively improved when the silicon-based material is applied to the organic silicon leather. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of silicon-based material preparation, and in particular to a silicon-based material, a preparation method and application thereof in organic silicon leather. Background Art

[0002] Silicone leather is an artificial leather made from silicone materials. It combines the unique properties of silicone materials with the appearance and touch of traditional leather, and is widely used in clothing, footwear, furniture, automotive interiors, electronic products and other fields. Silicone leather has attracted more and more attention for its excellent physical properties, environmental protection characteristics and sustainability. With the continuous advancement of technology and the increasing maturity of the market, silicone leather is expected to become one of the mainstream artificial leather materials in the future.

[0003] Silicone leather surface material is the core material of leather rubber, providing functions such as touch, wear resistance, anti-fouling, and weather resistance. Invention patent CN 115895268 A discloses a tear-resistant silicone leather and its preparation process and application. Although it provides good mechanical properties, it is limited by the inherent properties of silicone material, and its touch and anti-fouling properties are not up to the level of conventional leather.

[0004] In order to achieve a good hand feel, silicone products often need to be sprayed with hand oil, but their wear resistance is not ideal. In the leather field, wear resistance is one of the important indicators. Silicone leather follows the hand oil formula idea and develops a series of surface treatment agents that add hand powder substances, which improves the feel of the leather to a certain extent, but the wear resistance, scratch resistance and anti-fouling effect are not as good as expected. At present, it is difficult to achieve the unity of good hand feel and mechanical properties with existing technologies. A good hand feel requires a lot of hand powder substances and a dense cross-linked structure (high hardness), which makes the film layer brittle; correspondingly, the folding resistance, wear resistance, scratch resistance and other properties will decrease. Therefore, it has become an urgent need in the industry to develop a material that can not only improve the wear resistance of leather, but also maintain a good hand feel and have anti-fouling function. Summary of the invention

[0005] The purpose of the present invention is to provide a silicon-based material, a preparation method and its application in silicone leather. The present invention obtains a silicon-based material by using a linear coupling agent and a hand-feel powder of a specific structure and compounding them with raw materials such as a silicone rubber base. Applying it in silicone leather can effectively improve the hand feel, anti-fouling performance, wear resistance and mechanical strength.

[0006] To achieve the above object, the first aspect of the present invention provides a silicon-based material, wherein the raw materials for preparation include, by weight, 100 parts of silicone rubber base, 1 to 5 parts of linear coupling agent, 10 to 30 parts of hand feeling powder, 1 to 10 parts of hydrogenated silicone oil, 0.025 to 1 part of inhibitor and 20 to 100 parts of organic solvent, wherein the raw materials for preparation of silicone rubber base include 100 parts of vinyl-terminated side vinyl silicone oil, 20 to 60 parts of white carbon black, 4 to 12 parts of hexamethyldisilazane and 0.5 to 1 part of water, the hydrogenated silicone oil is selected from at least one of trimethylsilyl-terminated hydrogenated silicone oil and hydrogenated MQ resin, the hand feeling powder has a rough structure and has a siloxane group, and the linear coupling agent has a structure as shown below:

[0007]

[0008] Among them, m+n+p+2=12~40, and n+p≥1.5m, p≥2, x=2~5.

[0009] Compared with the prior art, the present invention can give the silicon-based material good hardness and ensure its good mechanical properties such as tear and tensile strength by using end-vinyl side-vinyl silicone oil in combination with trimethylsilyl-terminated hydrogen silicone oil and / or hydrogen-containing MQ resin. On this basis, the present invention further introduces a hand-feeling powder with a rough structure and a siloxane group and a linear coupling agent with a specific structure, wherein the rough structure of the hand-feeling powder gives the hand-feeling powder a higher specific surface area, thereby effectively improving the surface roughness of the silicon-based material after vulcanization, so that it can be given a smooth feel and anti-fouling effect on the basis of ensuring good mechanical properties; the linear coupling agent contains both methoxysilyl groups and silicon-hydrogen bonds, which can react with the siloxane groups on the surface of the hand-feeling powder through the methoxysilyl groups, and can also react with the vinyl in the silicone rubber base through the silicon-hydrogen bonds it contains, thereby connecting the hand-feeling powder to the silicon-based material in the form of chemical bonding, improving the compatibility of the hand-feeling powder with the silicon-based material, ensuring the stability of its structure, and thus significantly improving the overall mechanical strength, wear resistance, smooth feel and anti-fouling effect of the silicon-based material.

[0010] As a preferred technical solution, the hand-feeling powder of the present invention is an organic silicone elastic powder, and the particle size Dv50 of the hand-feeling powder is 0.5 μm to 5 μm.

[0011] As a preferred technical solution, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil of the present invention is 20mPa·s to 200mPa·s and the mass content of active hydrogen is greater than or equal to 0.75%, and the mass content of active hydrogen of the hydrogen-containing MQ resin is greater than or equal to 0.45%.

[0012] As a preferred technical solution, the viscosity of the vinyl-terminated side vinyl silicone oil of the present invention is 80000mpa·s to 200000mpa·s, and the mass content of vinyl is 0.2% to 0.6%.

[0013] As a preferred technical solution, the inhibitor of the present invention is selected from at least one of acetylenic alcohol compounds, hydrocarbon siloxane compounds and maleate compounds, and the organic solvent is selected from alkane compounds.

[0014] As a preferred technical solution, the white carbon black of the present invention is fumed white carbon black, and the specific surface area of ​​fumed white carbon black is 200cm 2 / g~400cm 2 / g.

[0015] The second aspect of the present invention provides a method for preparing the aforementioned silicon-based material, comprising the steps of:

[0016] (1) mixing vinyl-terminated and vinyl-side silicone oil, white carbon black, hexamethyldisilazane and water to obtain a silicone rubber base;

[0017] (2) The silicone rubber base glue, linear coupling agent, hand powder, hydrogenated silicone oil, inhibitor and organic solvent are mixed evenly and filtered to obtain the silicone-based material.

[0018] A third aspect of the present invention provides an application of a silicon-based material in silicone leather, wherein the silicon-based material is used as a surface treatment layer or surface layer of the silicone leather, and the silicon-based material is the aforementioned silicon-based material or a silicon-based material prepared according to the aforementioned method for preparing the silicon-based material.

[0019] As a preferred technical solution, the platinum catalyst, solvent and silicon-based material are evenly mixed to form a mixture with a viscosity of 500mPa·s to 5000mPa·s, the mixture is applied to the surface of the silicone leather and cured to form a surface treatment layer with a thickness of 3μm to 10μm.

[0020] As a preferred technical solution, the platinum catalyst, solvent and silicon-based material are evenly mixed to form a mixture with a viscosity of 2000mPa·s to 10000mPa·s, the mixture is coated on the surface of the release paper and cured to form a surface layer with a thickness of 20μm to 100μm. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of scanning electron microscope of the hand feeling powder A in the embodiment of the present invention.

[0022] Figure 2 Schematic diagram of scanning electron microscope of hand feeling powder B in comparative example of the present invention. DETAILED DESCRIPTION

[0023] The present invention provides a silicon-based material, wherein the raw materials for preparation include 100 parts of silicone rubber base, 1 to 5 parts of linear coupling agent, 10 to 30 parts of hand feeling powder, 1 to 10 parts of hydrogen-containing silicone oil, 0.025 to 1 part of inhibitor and 20 to 100 parts of organic solvent in parts by weight. The raw materials for preparation of the silicone rubber base of the present invention include 100 parts of vinyl-terminated side vinyl silicone oil, 20 to 60 parts of white carbon black, 4 to 12 parts of hexamethyldisilazane and 0.5 to 1 part of water.

[0024] Among them, the viscosity of the vinyl-terminated side vinyl silicone oil is 80000 MPa·s to 200000 MPa·s. As an example, the viscosity of the vinyl-terminated side vinyl silicone oil can be but is not limited to 80000 MPa·s, 85000 MPa·s, 90000 MPa·s, 95000 MPa·s, 100000 MPa·s, 110000 MPa·s, 120000 MPa·s, 130000 MPa·s, 140000 MPa·s, 150000 MPa·s, 160000 MPa·s, 170000 MPa·s, 180000 MPa·s, 190000 MPa·s, and 200000 MPa·s. The mass content of vinyl is 0.2% to 0.6%. As an example, the mass content of vinyl can be but is not limited to 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, and 0.6%. The present invention can effectively ensure the mechanical properties of the silicon-based material of the present invention by adopting a vinyl-terminated side vinyl silicone oil with a viscosity of 80000mpa·s to 200000mpa·s and a vinyl mass content of 0.2% to 0.6%. The vinyl-terminated side vinyl silicone oil of the present invention refers to a silicone oil in which the vinyl groups are located at both ends and side chains of the polysiloxane segment. It should be noted that the present invention has no special restrictions on the source of the vinyl-terminated side vinyl silicone oil, which can be purchased on the market or prepared according to conventional methods familiar to those skilled in the art. Taking the vinyl-terminated side vinyl silicone oil with a vinyl mass content of 0.25% and a viscosity of 100000mpa·s as an example, its structural formula can be shown as follows:

[0025]

[0026] The weight proportion of white carbon black can be, but is not limited to, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, and 60 parts. The white carbon black can be fumed white carbon black, and the specific surface area of ​​the fumed white carbon black is 200 cm 2 / g~400cm 2 / g, in some technical solutions, the specific surface area of ​​fumed silica is 200cm 2 / g~350cm 2 / g, in some technical solutions, the specific surface area of ​​fumed silica is 220cm 2 / g~340cm 2 As an example, the specific surface area of ​​fumed silica can be, but is not limited to, 200 cm 2 / g, 220cm 2 / g, 240cm 2 / g, 260cm 2 / g, 280cm 2 / g、300cm 2 / g, 320cm 2 / g, 340cm 2 / g, 360cm 2 / g, 380cm 2 / g、400cm 2 / g. The specific surface area is 200cm 2 / g~400cm 2 / g of fumed silica can effectively improve the wear resistance of silicon-based materials. The weight proportion of hexamethyldisilazane can be, but not limited to, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, and 12 parts. Hexamethyldisilazane can effectively improve the processing performance of silicone rubber base. The weight proportion of water can be, but not limited to, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and 1 part.

[0027] The weight proportion of the linear coupling agent can be, but is not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, and 5 parts. The linear coupling agent of the present invention has the structure shown below:

[0028]

[0029] Wherein, m+n+p+2=12~40, and n+p≥1.5m, p≥2, x=2~5. The present invention effectively avoids the gel phenomenon caused by the instability of the structure due to the excessive length of the molecular chain segment, or the situation that the molecular chain segment is too short and the good functional group loading effect cannot be achieved, thereby affecting the performance effect. The linear coupling agent of the present invention contains methoxysilyl groups and silicon-hydrogen bonds, which can react with the hand-feeling powder and the vinyl-terminated side vinyl silicone oil respectively, and serve as an intermediate bridge to connect the hand-feeling powder with the vinyl-terminated side vinyl silicone oil, thereby improving the overall structural stability of the silicon-based material of the present invention, thereby ensuring the wear resistance, anti-fouling and hand-feel performance of the silicon-based material. It should be noted that the present invention has no special restrictions on the source of the linear coupling agent, which can be purchased on the market or prepared according to conventional methods familiar to those skilled in the art. As an example, the preparation of the linear coupling agent of the present invention may include mixing hydrogen-containing silicone oil, vinyltrimethoxysilane, and platinum catalyst and then heating and reacting to prepare it. Among them, hydrogen-containing silicone oil and vinyltrimethoxysilane are mixed in the required proportion of the molecular structure and the total mass of the two is 100g. The concentration of platinum element in the platinum catalyst in the reaction system can be but is not limited to 10ppm, the temperature of the heating reaction can be but is not limited to 60°C, and the time of the heating reaction can be but is not limited to 6h.

[0030] The weight proportions of the hand feeling powder of the present invention can be, but are not limited to, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, and 30 parts. The hand feeling powder of the present invention is an organic silicone elastic powder having a rough structure and a siloxane group. The particle size Dv50 of the hand feeling powder is 0.5 μm to 5 μm. As an example, the particle size Dv50 of the hand feeling powder can be, but is not limited to, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, and 5 μm. Since the hand feeling powder of the present invention has a rough structure and a siloxane group, it can react chemically with a linear coupling agent to improve the compatibility with the silicon-based material system of the present invention, thereby ensuring the antifouling effect and smooth feel. It should be noted that the present invention has no special restrictions on the source of the hand feeling powder, and it can be purchased on the market or prepared according to conventional methods well known to those skilled in the art. As an example, the hand-feel powder can be purchased from Guangzhou Rongda Chemical Co., Ltd., model number 3900, but is not limited thereto.

[0031] The weight proportion of the hydrogen-containing silicone oil of the present invention can be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts. The hydrogen-containing silicone oil is selected from at least one of trimethylsilyl-terminated hydrogen-containing silicone oil and hydrogen-containing MQ resin. Among them, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 20mPa·s to 200mPa·s. In some technical schemes, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 20mPa·s to 185mPa·s. In some technical schemes, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 50mPa·s to 145mPa·s. In some technical schemes, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 80mPa·s to 105mPa·s. As an example, the viscosity of trimethylsilyl-terminated hydrogen-containing silicone oil can be, but is not limited to, 20mPa·s, 40mPa·s, 60mPa·s, 80mPa·s, 100mPa·s, 20mPa·s, 20mPa·s, 20mPa·s, 20mPa·s, 200mPa·s. The mass content of active hydrogen in trimethylsilyl-terminated hydrogen-containing silicone oil is greater than or equal to 0.75%. The mass content of active hydrogen in hydrogen-containing MQ resin is greater than or equal to 0.45%. It should be noted that the present invention does not particularly limit the source of hydrogen-containing silicone oil, and it can be purchased on the market or prepared according to conventional methods well known to those skilled in the art. Taking trimethylsilyl-terminated hydrogen-containing silicone oil with a viscosity of 80mPa·s as an example, its structural formula can be shown as follows:

[0032]

[0033] The weight proportion of the inhibitor of the present invention can be, but is not limited to, 0.025, 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1. The inhibitor is selected from at least one of acetylenic alcohol compounds, hydrocarbyl siloxane compounds, and maleic acid ester compounds. Specifically, the acetylenic alcohol compound can be, but is not limited to, at least one of 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl-1-cyclohexanol, and 3-phenyl-1-butyn-3-ol. The hydrocarbyl siloxane compound can be, but is not limited to, methylvinylcyclotetrasiloxane. The maleate compound may be, but is not limited to, at least one of dimethyl maleate, diethyl maleate, diphenyl maleate, diallyl maleate, and di(2-methoxyethyl) maleate.

[0034] The weight proportion of the organic solvent of the present invention can be, but is not limited to, 20, 30, 40, 50, 60, 70, 80, 90, or 100 parts. The organic solvent is selected from an alkane solvent. Specifically, the alkane solvent of the present invention can be white gasoline and isomeric alkanes. As an example, the alkane solvent of the present invention can be isomeric dodecane.

[0035] The present invention provides a method for preparing a silicon-based material, comprising the steps of: (1) mixing vinyl-terminated side vinyl silicone oil, white carbon black, hexamethyldisilazane and water to obtain a silicone rubber base; (2) uniformly mixing a silicone rubber base, a linear coupling agent, a hand-feeling powder, a hydrogen-containing silicone oil, an inhibitor and an organic solvent, and filtering to obtain a silicon-based material. The mesh number of the filter used for filtration is 200 to 400 meshes.

[0036] The present invention also provides an application of a silicon-based material in silicone leather, wherein the silicon-based material is used as a surface treatment layer or surface layer of the silicone leather, and the silicon-based material is the aforementioned silicon-based material or a silicon-based material prepared according to the aforementioned method for preparing the silicon-based material.

[0037] Specifically, the process includes uniformly mixing a platinum catalyst, a solvent, and a silicon-based material to form a mixture with a viscosity of 500mPa·s to 5000mPa·s, applying the mixture to the surface of the organic silicon leather and curing it to form a surface treatment layer with a thickness of 3μm to 10μm. The platinum catalyst may be a Custer catalyst with a platinum content of 3ppm to 20ppm, the curing temperature may be 120℃ to 170℃, and the curing time may be 1min to 10min.

[0038] Specifically, the process includes uniformly mixing a platinum catalyst, a solvent, and a silicon-based material to form a mixture with a viscosity of 2000mPa·s to 10000mPa·s, coating the mixture on the surface of a release paper, and curing the mixture to form a surface layer with a thickness of 20μm to 100μm, wherein the platinum catalyst may be a Custer catalyst with a platinum content of 3ppm to 20ppm, the curing temperature may be 120°C to 170°C, and the curing time may be 1min to 10min.

[0039] The solvent may be selected from alkane solvents, including but not limited to isododecane, 180# solvent oil, 190# solvent oil, 200# solvent oil, and the like.

[0040] In order to better illustrate the purpose, technical scheme and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the following implementation method is a further explanation of the present invention and should not be used as a limitation of the present invention.

[0041] In the embodiments and comparative examples of the present invention, liquid silicone rubber was purchased from Dongguan Zhengan Organic Silicone Technology Co., Ltd., model GA-2960A / B; hand feel powder A was purchased from Guangzhou Rongda Chemical Co., Ltd., model 3900, and its morphology and structure are as follows Figure 1As shown, it has a rough structure composed of nano-scale microsphere clusters; the hand feel powder B was purchased from Yongqi Material Technology (Shanghai) Co., Ltd., model R300, and its morphology and structure are as shown Figure 2 As shown, it is a smooth sphere. The other raw materials not described here can be obtained from common commercial sources or prepared according to conventional preparation methods in the art.

[0042] Example 1

[0043] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0044] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0045] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0046] Example 2

[0047] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0048] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.6%, viscosity 80000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0049] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0050] Example 3

[0051] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0052] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.2%, viscosity 200000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0053] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0054] Example 4

[0055] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0056] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0057] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=3, n=7, m=0, m+n+p+2=12), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0058] Example 5

[0059] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0060] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0061] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=5, n=25, m=8, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0062] Example 6

[0063] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0064] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0065] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=14, m=10, m+n+p+2=30), 30 parts by weight of hand powder A (Dv50 is 0.5 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0066] Example 7

[0067] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0068] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0069] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=14, m=10, m+n+p+2=30), 10 parts by weight of hand powder A (Dv50 is 5 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 25 mPa·s, and the mass content of active hydrogen is 1.5%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0070] Example 8

[0071] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0072] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 25 parts by weight of fumed silica (specific surface area 280 cm 2 / g), 12 parts by weight of hexamethyldisilazane, and 0.5 parts by weight of water are mixed to obtain a silicone rubber base;

[0073] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand feel powder A (Dv50 is 1 μm), 3 parts by weight of hydrogenated MQ resin (mass content of active hydrogen is 0.45%) and 0.5 parts by weight of methylvinylcyclotetrasiloxane are mixed uniformly in a planetary mixer, 80 parts of isododecane is added for dilution, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0074] Example 9

[0075] This embodiment provides a method for preparing a silicon-based material, comprising the steps of:

[0076] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 55 parts by weight of fumed silica (specific surface area 350 cm 2 / g), 5 parts by weight of hexamethyldisilazane, and 1 part by weight of water are mixed to obtain a silicone rubber base;

[0077] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 9 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.8 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 50 parts of isododecane is added for dilution, and then filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0078] Comparative Example 1

[0079] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0080] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.06%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0081] (2) 100 parts by weight of silicone rubber base, 20 parts by weight of hand powder B (Dv50 is 3 μm), 5 parts by weight of hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, the viscosity is 30 mPa·s, and the mass content of active hydrogen is 0.45%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and the mixture is filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0082] Comparative Example 2

[0083] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0084] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.06%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0085] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder B (Dv50 is 3 μm), 5 parts by weight of hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, the viscosity is 30 mPa·s, and the mass content of active hydrogen is 0.45%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added to dilute the mixture, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0086] Comparative Example 3

[0087] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0088] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.06%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0089] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0090] Comparative Example 4

[0091] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0092] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0093] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 5 parts by weight of hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, the viscosity is 30 mPa·s, and the mass content of active hydrogen is 0.45%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added to dilute the mixture, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0094] Comparative Example 5

[0095] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0096] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0097] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder A (Dv50 is 1 μm), 10 parts by weight of hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, the viscosity is 30 mPa·s, and the mass content of active hydrogen is 0.25%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added for dilution, and the mixture is filtered through a 200-400 mesh filter to obtain a silicone-based material.

[0098] Comparative Example 6

[0099] This comparative example provides a method for preparing a silicon-based material, comprising the steps of:

[0100] (1) 100 parts by weight of vinyl-terminated silicone oil (vinyl content 0.4%, viscosity 100000 mPa·s), 40 parts by weight of fumed silica (specific surface area 200 cm 2 / g), 8 parts by weight of hexamethyldisilazane, and 0.8 parts by weight of water are mixed to obtain a silicone rubber base;

[0101] (2) 100 parts by weight of silicone rubber base, 4 parts by weight of linear coupling agent (x=2, p=4, n=20, m=14, m+n+p+2=40), 20 parts by weight of hand powder B (Dv50 is 3 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, and the mass content of active hydrogen is 0.75%) and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are mixed uniformly in a planetary mixer, 100 parts of isododecane is added to dilute, and then filtered using a 200-400 mesh filter to obtain a silicone-based material.

[0102] Liquid silicone rubber (Zhengan silicone, model GA-2960A / B) was coated on release paper with a thickness of 100 μm and cured at 120°C for 10 min; then liquid silicone rubber (Zhengan silicone, model GA-2960A / B) was coated with a thickness of 80 μm, a 200 g non-woven fabric was overlapped with it, a pressure of 500 Pa was applied for 10 s, and it was cured at 120°C for 10 min. After removing the release paper, silicone leather was obtained. 5 ppm of Custer catalyst, isomeric dodecane, and silicon-based substrate (one of the silicon-based materials prepared in Examples 1 to 9 and Comparative Examples 1 to 6) were mixed uniformly to form a mixture with a viscosity of 500 mPa·s, and the mixture was applied to the surface of the silicone leather and cured at 120°C for 10 min to form a surface treatment layer with a thickness of 3 μm.

[0103] 5ppm of Custer catalyst, isomeric dodecane, and silicon-based material (one of the silicon-based materials obtained in Examples 1 to 9 and Comparative Examples 1 to 6) were mixed evenly to form a mixture with a viscosity of 10000mPa·s, and the mixture was applied to the surface of the release paper and cured at 120°C for 10min to form a surface layer with a thickness of 20μm. Then, liquid silicone rubber (Zhengan silicone, model GA-2960A / B) was applied to the surface of the surface layer with a thickness of 100μm and cured at 120°C for 10min; liquid silicone rubber (Zhengan silicone, model GA-2960A / B) was applied again with a thickness of 80μm, and a 200g non-woven fabric was overlapped therewith, a pressure of 500Pa was applied for 10s, and cured at 120°C for 10min, and the release paper was removed to obtain silicone leather. The surface layer of the silicone leather was tested for mechanical properties, wear resistance, stain resistance and feel, and the test method was as follows, and the test results are shown in Table 1.

[0104] Abrasion resistance test method: GB / T 20991-2007 "Test method for abrasion resistance of leather-Martindale method".

[0105] Hardness test method (Shore A): obtained by referring to GB / T 531.1-2008 test, the test piece is obtained by heating and molding without adding diluent.

[0106] Tensile strength test method (Mpa): obtained by referring to GB / T 528-2009 test.

[0107] Tear strength test method (kN / m): obtained by referring to GB / T 529-2008 test.

[0108] Stain resistance test method: Use an oil-based pen to draw a line, and wipe it with a paper towel after the solvent evaporates. If it can be completely erased, the score is 10, and if it cannot be erased at all, the score is 0.

[0109] Feel: A score of 10 indicates a dry and smooth feel; a score of 0 indicates a sticky or obstructive feel.

[0110] Table 1 Performance test results of Examples 1 to 9 and Comparative Examples 1 to 6

[0111]

[0112] Please refer to Table 1 for details. It can be seen from the performance test results of Examples 1 to 9 and Comparative Examples 1 to 6 that the lack of any one or more of the vinyl-terminated side vinyl silicone oil, linear coupling agent, hand feeling powder A and hydrogen-containing silicone oil disclosed in the present invention, or the replacement of any one or more of the vinyl-terminated side vinyl silicone oil, linear coupling agent, hand feeling powder A and hydrogen-containing silicone oil disclosed in the present invention with others will affect the mechanical properties, wear resistance, hand feeling and anti-fouling properties of the surface layer formed by the silicon-based material, and it is difficult to take into account its mechanical properties, wear resistance, anti-fouling properties and hand feeling effects at the same time.

[0113] The present invention can give good hardness to silicon-based materials and ensure good mechanical properties such as tear and tensile strength by using end-vinyl side-vinyl silicone oil in combination with trimethylsilyl-terminated hydrogen silicone oil and / or hydrogen-containing MQ resin. On this basis, the present invention further introduces a hand-feeling powder with a rough structure and a siloxane group and a linear coupling agent with a specific structure, wherein the rough structure of the hand-feeling powder gives the hand-feeling powder a higher specific surface area, thereby effectively improving the surface roughness of the silicon-based material after vulcanization, so that it can give it a smooth feel and anti-fouling effect on the basis of ensuring good mechanical properties; the linear coupling agent contains methoxysilyl groups and silicon-hydrogen bonds at the same time, which can react with the siloxane groups on the surface of the hand-feeling powder through the methoxysilyl groups, and can also react with the vinyl in the silicone rubber base through the silicon-hydrogen bonds it contains, so that the hand-feeling powder is connected to the silicon-based material in the form of chemical bonding, thereby improving the compatibility of the hand-feeling powder with the silicon-based material, ensuring the stability of its structure, and thus significantly improving the overall mechanical strength, wear resistance, smooth feel and anti-fouling effect of the silicon-based material.

[0114] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. Silicon-based material, characterized in that: In parts by weight, the raw materials for preparation include 100 parts of silicone rubber base, 1 to 5 parts of linear coupling agent, 10 to 30 parts of hand feeling powder, 1 to 10 parts of hydrogenated silicone oil, 0.025 to 1 part of inhibitor and 20 to 100 parts of organic solvent. The raw materials for preparation of the silicone rubber base include 100 parts of vinyl-terminated side vinyl silicone oil, 20 to 60 parts of white carbon black, 4 to 12 parts of hexamethyldisilazane and 0.5 to 1 part of water. The hydrogenated silicone oil is selected from at least one of trimethylsilyl-terminated hydrogenated silicone oil and hydrogenated MQ resin. The hand feeling powder has a rough structure and has a siloxane group. The linear coupling agent has the structure shown below: Among them, m+n+p+2=12~40, and n+p≥1.5m, p≥2, x=2~5.

2. The silicon-based material according to claim 1, characterized in that: The hand-feeling powder is organic silicone elastic powder, and the particle size Dv50 of the hand-feeling powder is 0.5 μm to 5 μm.

3. The silicon-based material according to claim 1, characterized in that: The trimethylsilyl-terminated hydrogen-containing silicone oil has a viscosity of 20 mPa·s to 200 mPa·s and a mass content of active hydrogen of greater than or equal to 0.75%, and the mass content of active hydrogen of the hydrogen-containing MQ resin is greater than or equal to 0.45%.

4. The silicon-based material according to claim 1, characterized in that: The viscosity of the vinyl-terminated and side-vinyl silicone oil is 80000mpa·s to 200000mpa·s, and the mass content of vinyl is 0.2% to 0.6%.

5. The silicon-based material according to claim 1, characterized in that: The inhibitor is selected from at least one of acetylenic alcohol compounds, hydrocarbon siloxane compounds and maleate compounds, and the organic solvent is selected from alkane compounds.

6. The silicon-based material according to claim 1, characterized in that The white carbon black is fumed white carbon black, and the specific surface area of ​​the fumed white carbon black is 200 cm 2 / g~400cm 2 / g.

7. The method for preparing a silicon-based material according to any one of claims 1 to 6, characterized in that: Includes steps: (1) mixing the vinyl-terminated and vinyl-pendent silicone oil, the white carbon black, the hexamethyldisilazane and the water to obtain a silicone rubber base; (2) The silicone rubber base, the linear coupling agent, the hand-feeling powder, the hydrogenated silicone oil, the inhibitor and the organic solvent are uniformly mixed and then filtered to obtain a silicone-based material.

8. Application of silicon-based materials in silicone leather, characterized in that: The silicon-based material is used as a surface treatment layer or surface layer of silicone leather, and the silicon-based material is the silicon-based material according to any one of claims 1 to 6 or the silicon-based material prepared by the method for preparing the silicon-based material according to claim 7.

9. The use of the silicon-based material in organic silicon leather according to claim 8, characterized in that: The method comprises uniformly mixing a platinum catalyst, a solvent and the silicon-based material to form a mixture with a viscosity of 500mPa·s to 5000mPa·s, coating the mixture on the surface of the organic silicon leather and curing the mixture to form the surface treatment layer with a thickness of 3μm to 10μm.

10. The use of the silicon-based material in silicone leather according to claim 8, characterized in that: The method comprises mixing a platinum catalyst, a solvent and the silicon-based material uniformly to form a mixture with a viscosity of 2000mPa·s to 10000mPa·s, coating the mixture on the surface of the release paper and curing the mixture to form the surface layer with a thickness of 20μm to 100μm.

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