Silicon-based material, method of preparation and use thereof in silicone leather

Abstract

The present invention provides a silicon-based material, a preparation method and its application in silicone leather. The silicon-based material of the present invention is prepared from raw materials in parts by weight including 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 preparing 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 contains siloxane groups. The linear coupling agent has a structure as shown below. The present invention obtains a silicon-based material by using a linear coupling agent and hand feeling powder of a specific structure and compounding them with raw materials such as silicone rubber base. Its application in silicone leather can effectively improve the hand feel, anti-fouling performance, wear resistance and mechanical strength.

Description

TECHNICAL FIELD

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

[0002] Organic silicon leather is a kind of artificial leather made of organic silicon material. It combines the unique properties of organic silicon material and the appearance and touch of traditional leather, and is widely used in clothing, footwear, furniture, automotive interiors, electronic products and other fields. Organic silicon leather is attracting more and more attention due to its excellent physical properties, environmental characteristics and sustainability. With the continuous progress of technology and the maturation of the market, organic silicon leather is expected to become one of the mainstream artificial leather materials in the future.

[0003] The surface layer material of organic silicon leather is the core material of leather compound, which provides touch, wear resistance, stain resistance, weather resistance and other functions. Invention patent CN 115895268 A discloses an anti-tearing silicone leather and its preparation process and application, which provides good mechanical properties, but is limited by the inherent properties of silicone material, and its touch and stain resistance cannot reach the level of conventional leather.

[0004] In order to achieve good hand feeling, silicone products often need to be sprayed with hand feeling oil, but the wear resistance is not ideal. In the leather field, wear resistance is one of the important indicators. Silicone leather has followed the formula idea of hand feeling oil and developed a series of surface treatment agents adding hand feeling powder substances, which has improved the hand feeling of leather to some extent, but the wear resistance, scratch resistance and stain resistance are not as expected. The current technology is difficult to achieve the unity of good hand feeling and mechanical properties. Good hand feeling requires more hand feeling powder substances and dense cross-linked structure (high hardness), which causes the film layer to be brittle. Correspondingly, the performance of wear resistance, scratch resistance and stain resistance will decrease. Therefore, it is an urgent need in the industry to develop a material that can improve the wear resistance of leather while maintaining good hand feeling and stain resistance. SUMMARY

[0005] The purpose of the present application is to provide a silicon-based material, a preparation method and application thereof in organic silicon leather. The present application uses a linear coupling agent with a specific structure and hand feeling powder and is compounded with silicone rubber-based glue and other raw materials to obtain a silicon-based material. The application of the silicon-based material in organic silicon leather can effectively improve the hand feeling, stain resistance, wear resistance and mechanical strength.

[0006] To achieve the above object, the present application provides a kind of silicon-based materials in the first aspect, and the preparation raw material includes 100 parts of silicone rubber base glue, 1 part ~ 5 parts linear coupling agent, 10 parts ~ 30 parts hand powder, 1 part ~ 10 parts hydrogen-containing silicone oil, 0.025 parts ~ 1 parts inhibitor and 20 parts ~ 100 parts organic solvent, wherein the preparation raw material of silicone rubber base glue includes 100 parts of end-vinyl side-vinyl silicone oil, 20 parts ~ 60 parts white carbon black, 4 parts ~ 12 parts hexamethyl disilazane and 0.5 parts ~ 1 parts water, hydrogen-containing silicone oil is selected from at least one of trimethyl silyl end-capped hydrogen-containing silicone oil and hydrogen-containing MQ resin, hand powder has rough structure and has siloxane group, linear coupling agent has the structure as shown in the following:

[0007]

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

[0009] Compared with prior art, the present application can give good hardness to the silicon-based material by using end-vinyl side-vinyl silicone oil with trimethyl silyl end-capped hydrogen-containing silicone oil and / or hydrogen-containing MQ resin, and ensure its good mechanical properties such as tear and tensile strength. On this basis, the present application further introduces hand powder with rough structure and siloxane group and linear coupling agent with specific structure, wherein the rough structure of hand powder gives it high specific surface area, which can effectively improve the surface roughness of the silicon-based material after vulcanization, so as to give it smooth hand feeling and anti-fouling effect on the basis of ensuring good mechanical properties; the linear coupling agent contains both methoxysilyl group and silicon-hydrogen bond, which can react with siloxane group on the surface of hand powder through methoxysilyl group, and also can react with vinyl in silicone rubber base glue through silicon-hydrogen bond, so as to connect hand powder to the silicon-based material through chemical bond, improve the compatibility of hand powder and silicon-based material, ensure the stability of its structure, and thus significantly improve the overall mechanical strength, wear resistance, smooth hand feeling and anti-fouling effect of the silicon-based material.

[0010] As a preferred technical solution, the hand powder of the present application is silicone elastomer powder, and the particle size Dv50 of the hand powder is 0.5 μm ~ 5 μm.

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

[0012] As a preferred technical scheme, the viscosity of the end-vinyl side-vinyl silicone oil is 80000 mPa·s-200000 mPa·s, and the mass content of the vinyl is 0.2%-0.6%.

[0013] As a preferred technical scheme, the inhibitor is at least one selected from acetylenic alcohol compounds, hydrocarbon-based siloxane compounds and maleate compounds, and the organic solvent is selected from alkane compounds.

[0014] As a preferred technical scheme, 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-400 cm 2 / g.

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

[0016] (1) mixing end-vinyl side-vinyl silicone oil, white carbon black, hexamethyl disilazane and water to obtain a silicone rubber-based glue;

[0017] (2) mixing the silicone rubber-based glue, a linear coupling agent, a hand feel powder, hydrogen-containing silicone oil, an inhibitor and an organic solvent uniformly, and then filtering to obtain the silicon-based material.

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

[0019] As a preferred technical scheme, the method comprises uniformly mixing the platinum-gold catalyst, the solvent and the silicon-based material to form a mixture with a viscosity of 500 mPa·s-5000 mPa·s, coating the mixture on the surface of the silicone leather and solidifying to form a surface treatment layer with a thickness of 3 μm-10 μm.

[0020] As a preferred technical scheme, the method comprises uniformly mixing the platinum-gold catalyst, the solvent and the silicon-based material to form a mixture with a viscosity of 2000 mPa·s-10000 mPa·s, coating the mixture on the surface of the release paper and solidifying to form a surface layer with a thickness of 20 μm-100 μm. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 It is a scanning electron microscope diagram of the hand feel powder A in the embodiment of the present application.

[0022] Figure 2 It is a scanning electron microscope diagram of the hand feel powder B in the comparative example of the present application. DETAILED DESCRIPTION

[0023] The application provides a silicon-based material, and raw materials for preparing the silicon-based material include 100 parts of a silicone rubber base glue, 1-5 parts of a linear coupling agent, 10-30 parts of a hand feel powder, 1-10 parts of a hydrogen-containing silicone oil, 0.025-1 part of an inhibitor and 20-100 parts of an organic solvent.

[0024] The viscosity of the end-vinyl side-vinyl silicone oil is 80000-200000 mpa·s, and the viscosity of the end-vinyl 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, 200000 mpa·s, for example. The mass content of the vinyl group is 0.2%-0.6%, and the mass content of the vinyl group can be, but is not limited to, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, for example. The application can effectively ensure the mechanical properties of the silicon-based material by using the end-vinyl side-vinyl silicone oil with a viscosity of 80000-200000 mpa·s and a mass content of the vinyl group of 0.2%-0.6%. The end-vinyl side-vinyl silicone oil of the application refers to a silicone oil in which the vinyl group is located at both ends and side chains of a polysiloxane segment. It should be noted that the source of the end-vinyl side-vinyl silicone oil is not particularly limited in the application, and the end-vinyl side-vinyl silicone oil can be purchased on the market or prepared according to a conventional method known to those skilled in the art. The end-vinyl side-vinyl silicone oil with a mass content of the vinyl group of 0.25% and a viscosity of 100000 mpa·s is taken as an example, and the structural formula thereof can be as shown below:

[0025]

[0026] The weight part of the 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 or 60 parts. The white carbon black can be fumed white carbon black, and the specific surface area of the fumed white carbon black is 200-400 cm 2 / g, and in some technical solutions, the specific surface area of the fumed white carbon black is 200-350 cm 2 / g. 2 / g, and in some technical solutions, the specific surface area of the fumed white carbon black is 200-350 cm 2 / g, in some embodiments, the specific surface area of the fumed silica is 220 cm 2 / g~340 cm 2 / g. For example, the specific surface area of the fumed silica can be, but is not limited to, 200 cm 2 / g, 220 cm 2 / g, 240 cm 2 / g, 260 cm 2 / g, 280 cm 2 / g, 300 cm 2 / g, 320 cm 2 / g, 340 cm 2 / g, 360 cm 2 / g, 380 cm 2 / g, 400 cm 2 / g. The fumed silica with a specific surface area of 200 cm 2 / g~400 cm 2 / g can effectively improve the wear resistance of the silicon-based material. The weight fraction of hexamethyldisilazane can be, but is not limited to, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts. Hexamethyldisilazane can effectively improve the processing performance of the silicone rubber-based glue. The weight fraction of water can be, but is not limited to, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part.

[0027] The weight fraction 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, 5 parts. The linear coupling agent of the present application has the following structure:

[0028]

[0029] Wherein, m+n+p+2=12~40, and n+p>=1.5m, p>=2, x=2~5. By controlling the segment length of the linear coupling agent in the range, the present application effectively avoids the phenomenon of gelation caused by the instability of the structure due to the too long molecular chain segment, or the situation that the good functional group loading effect cannot be achieved due to the too short molecular chain segment, thereby affecting the performance effect. The linear coupling agent of the present application contains methoxy silicon group and silicon hydrogen bond, which can react with the feel powder and the side vinyl silicone oil with terminal vinyl respectively, and as an intermediate bridge, the feel powder and the side vinyl silicone oil with terminal vinyl are connected together, thereby improving the overall structural stability of the silicon-based material of the present application, and further ensuring the wear resistance, stain resistance and hand feeling performance effect of the silicon-based material. It should be noted that the present application does not have special restrictions on the source of the linear coupling agent, which can be purchased on the market or prepared according to the conventional method known to those skilled in the art. As an example, the preparation of the linear coupling agent of the present application can include mixing hydrogen-containing silicone oil, vinyl trimethoxysilane and platinum catalyst and then heating to prepare. Wherein, the hydrogen-containing silicone oil and the vinyl trimethoxysilane are mixed according to 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 heating reaction temperature can be but is not limited to 60℃, and the heating reaction time can be but is not limited to 6h.

[0030] The weight fraction of the feel powder of the present application can be but is not limited to 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts. The feel powder of the present application is a silicone elastomer powder, which has a rough structure and has siloxane groups. The particle size Dv50 of the feel powder is 0.5um~5um, as an example, the particle size Dv50 of the feel powder can be but is not limited to 0.5um, 1um, 2um, 3um, 4um, 5um. The feel powder of the present application has a rough structure and has siloxane groups, which can chemically react with the linear coupling agent to improve the compatibility with the silicone-based material system of the present application, thereby ensuring the stain resistance effect and smooth hand feeling. It should be noted that the present application does not have special restrictions on the source of the feel powder, which can be purchased on the market or prepared according to the conventional method known to those skilled in the art. As an example, the feel powder can be purchased from Guangzhou Rongda Chemical Co., Ltd., model 3900, but not limited to this.

[0031] The weight fraction of the hydrogen-containing silicone oil of the present application 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, 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 20 mPa·s to 200 mPa·s, in some technical solutions, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 20 mPa·s to 185 mPa·s, in some technical solutions, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 50 mPa·s to 145 mPa·s, in some technical solutions, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil is 80 mPa·s to 105 mPa·s. As an example, the viscosity of the trimethylsilyl-terminated hydrogen-containing silicone oil can be, but is not limited to, 20 mPa·s, 40 mPa·s, 60 mPa·s, 80 mPa·s, 100 mPa·s, 20 mPa·s, 20 mPa·s, 20 mPa·s, 20 mPa·s, 200 mPa·s. The mass content of active hydrogen of the trimethylsilyl-terminated hydrogen-containing silicone oil is greater than or equal to 0.75%. The mass content of active hydrogen of the hydrogen-containing MQ resin is greater than or equal to 0.45%. It should be noted that the present application does not have special restrictions on the source of the hydrogen-containing silicone oil, which can be purchased on the market or prepared according to the conventional method familiar to those skilled in the art. Taking the trimethylsilyl-terminated hydrogen-containing silicone oil with a viscosity of 80 mPa·s as an example, its structural formula can be as follows:

[0032]

[0033] The weight fraction of the inhibitor of the present application can be, but is not limited to, 0.025 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part. The inhibitor is selected from at least one of acetylenic alcohol compounds, hydrocarbyl siloxane compounds and maleate compounds. Specifically, the acetylenic alcohol compounds can be, but are not limited to, at least one of 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynyl-1-cyclohexanol and 3-phenyl-1-butyne-3-ol. The hydrocarbyl siloxane compounds can be, but are not limited to, methyl vinyl cyclosiloxane. The maleate compounds can be, but are not limited to, at least one of dimethyl maleate, diethyl maleate, diphenyl maleate, diallyl maleate, di(2-methoxyethyl) maleate.

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

[0035] The application provides a preparation method of a silicon-based material, comprising the following steps: (1) mixing end-vinyl side-vinyl silicone oil, white carbon black, hexamethyldisilazane and water to obtain a silicone rubber base glue; and (2) mixing the silicone rubber base glue, a linear coupling agent, a hand feel powder, hydrogen-containing silicone oil, an inhibitor and an organic solvent uniformly, and then filtering to obtain the silicon-based material. In the filtering, a filter screen mesh size of 200-400 is used.

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

[0037] Specifically, the method comprises the following steps: uniformly mixing a platinum gold catalyst, a solvent and the silicon-based material to form a mixture with a viscosity of 500-5000 mPa·s, coating the mixture on the surface of the silicone leather, and curing to form a surface treatment layer with a thickness of 3-10 μm. The platinum gold catalyst can be a Karstedt catalyst with a platinum element content of 3-20 ppm, the curing temperature can be 120-170 ℃, and the curing time can be 1-10 min.

[0038] Specifically, the method comprises the following steps: uniformly mixing a platinum gold catalyst, a solvent and the silicon-based material to form a mixture with a viscosity of 2000-10000 mPa·s, coating the mixture on the surface of the release paper, and curing to form a surface layer with a thickness of 20-100 μm. The platinum gold catalyst can be a Karstedt catalyst with a platinum element content of 3-20 ppm, the curing temperature can be 120-170 ℃, and the curing time can be 1-10 min.

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

[0040] To better illustrate the purposes, technical solutions and beneficial effects of the application, the application will be further described below in combination with specific examples. It should be noted that the following implementation of the method is a further explanation of the application and should not be regarded as a limitation of the application.

[0041] In the examples and comparative examples of the application, the liquid silicone rubber is purchased from Dongguan Zheng'an Silicone Technology Co., Ltd., and the model number is GA-2960A / B; the hand feel powder A is purchased from Guangzhou Rongda Chemical Co., Ltd., and the model number is 3900, and the morphology structure is as shown in Figure 1The rough structure is formed by nanometer microspheres. The hand feel powder B is purchased from Yongqi Material Technology (Shanghai) Co., Ltd. and its model is R300. The morphology structure is shown in Figure 2B. Figure 2 The rest of the raw materials not described herein can be obtained from ordinary market or prepared according to the conventional preparation method in the art.

[0042] Example 1

[0043] The present embodiment provides a preparation method of a silicon-based material, comprising the steps of:

[0044] (1) 100 parts by weight of a terminal-vinyl side-vinyl silicone oil (vinyl mass 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 glue;

[0045] (2) 100 parts by weight of the silicone rubber base glue, 4 parts by weight of a 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), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, mass content of active hydrogen is 0.75%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered through a 200-400 mesh filter to obtain a silicon-based material.

[0046] Example 2

[0047] The present embodiment provides a preparation method of a silicon-based material, comprising the steps of:

[0048] (1) 100 parts by weight of a terminal-vinyl side-vinyl silicone oil (vinyl mass 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 glue;

[0049] (2) 100 parts by weight of the silicone rubber base glue, 4 parts by weight of a 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), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, mass content of active hydrogen is 0.75%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered through a 200-400 mesh filter to obtain a silicon-based material.

[0050] Example 3

[0051] The present example provides a preparation method of a silicon-based material, comprising the steps of:

[0052] (1) mixing 100 parts by weight of a terminal-vinyl side-vinyl silicone oil (vinyl mass 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 to obtain a silicone rubber base glue;

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

[0054] Example 4

[0055] The present example provides a preparation method of a silicon-based material, comprising the steps of:

[0056] (1) mixing 100 parts by weight of a terminal-vinyl side-vinyl silicone oil (vinyl mass 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 to obtain a silicone rubber base glue;

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

[0058] Example 5

[0059] The present example provides a preparation method of a silicon-based material, comprising the steps of:

[0060] (1) 100 parts by weight of a terminal vinyl side vinyl silicone oil (vinyl mass 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 were mixed to obtain a silicone rubber base rubber;

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

[0062] Example 6

[0063] The present embodiment provides a method for preparing a silicone base material, comprising the steps of:

[0064] (1) 100 parts by weight of a terminal vinyl side vinyl silicone oil (vinyl mass 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 were mixed to obtain a silicone rubber base rubber;

[0065] (2) 100 parts by weight of the silicone rubber base rubber, 4 parts by weight of a linear coupling agent (x = 2, p = 5, n = 25, m = 8, m + n + p + 2 = 40), 20 parts by weight of a hand feel powder A (Dv50 is 1 μm), 5 parts by weight of a trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa-s, mass content of active hydrogen is 0.75%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered using a 200-400 mesh filter to obtain a silicone base material.

[0066] Example 7

[0067] The present embodiment provides a method for preparing a silicone base material, comprising the steps of:

[0068] (1) 100 parts by weight of a terminal vinyl side vinyl silicone oil (vinyl mass 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 were mixed to obtain a silicone rubber base rubber;

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

[0070] Example 8

[0071] The present example provides a method for preparing a silicone-based material, comprising the steps of:

[0072] (1) 100 parts by weight of the vinyl-terminated vinyl silicone oil (mass content of vinyl is 0.4%, viscosity is 100000 mPa-s), 25 parts by weight of the fumed silica (specific surface area is 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 the silicone rubber base, 4 parts by weight of the linear coupling agent (x = 2, p = 4, n = 20, m = 14, m + n + p + 2 = 40), 20 parts by weight of the hand powder A (Dv50 is 1 μm), 3 parts by weight of the hydrogen-containing MQ resin (mass content of active hydrogen is 0.45%), and 0.5 parts by weight of methylvinylcyclosiloxane are uniformly mixed in a planetary mixer, diluted with 80 parts of isododecane, and filtered with a 200-400 mesh filter to obtain the silicone-based material.

[0074] Example 9

[0075] The present example provides a method for preparing a silicone-based material, comprising the steps of:

[0076] (1) 100 parts by weight of the vinyl-terminated vinyl silicone oil (mass content of vinyl is 0.4%, viscosity is 100000 mPa-s), 25 parts by weight of the fumed silica (specific surface area is 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;

[0077] (2) 100 parts by weight of the silicone rubber base, 4 parts by weight of the linear coupling agent (x = 2, p = 4, n = 20, m = 14, m + n + p + 2 = 40), 20 parts by weight of the feel powder A (Dv50 = 1 μm), 9 parts by weight of the trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity = 100 mPa-s, mass content of active hydrogen = 0.75%), and 0.8 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed in a planetary mixer, diluted with 50 parts of isododecane, and 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 silicone-based material, comprising the steps of:

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

[0081] (2) 100 parts by weight of the silicone rubber base, 20 parts by weight of the feel powder B (Dv50 = 3 μm), 5 parts by weight of the hydrogen-containing silicone oil (active hydrogen located at both ends and side chains of the siloxane segment, viscosity = 30 mPa-s, mass content of active hydrogen = 0.45%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered through 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 silicone-based material, comprising the steps of:

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

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

[0086] Comparative Example 3

[0087] The present comparative example provides a method for preparing a silicone-based material, comprising the steps of:

[0088] (1) 100 parts by weight of the vinyl-terminated silicone oil (mass content of vinyl group is 0.06%, viscosity is 100000 mPa-s), 40 parts by weight of the fumed silica (specific surface area is 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 the silicone rubber base, 4 parts by weight of the linear coupling agent (x = 2, p = 4, n = 20, m = 14, m + n + p + 2 = 40), 20 parts by weight of the feel powder A (Dv50 is 1 μm), 5 parts by weight of the trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa-s, mass content of active hydrogen is 0.75%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered with a 200-400 mesh filter to obtain the silicone-based material.

[0090] Comparative Example 4

[0091] The present comparative example provides a method for preparing a silicone-based material, comprising the steps of:

[0092] (1) 100 parts by weight of the vinyl-terminated silicone oil (mass content of vinyl group is 0.06%, viscosity is 100000 mPa-s), 40 parts by weight of the fumed silica (specific surface area is 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 the silicone rubber base, 4 parts by weight of the linear coupling agent (x = 2, p = 4, n = 20, m = 14, m + n + p + 2 = 40), 20 parts by weight of the hand powder A (Dv50 is 1 μm), 5 parts by weight of the hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, viscosity is 30 mPa-s, mass content of active hydrogen is 0.45%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered with a 200-400 mesh filter to obtain the silicone base material.

[0094] Comparative Example 5

[0095] The present comparative example provides a method for preparing a silicone base material, comprising the steps of:

[0096] (1) 100 parts by weight of the vinyl-terminated and vinyl- side silicone oil (mass content of vinyl is 0.4%, viscosity is 100000 mPa-s), 40 parts by weight of the fumed silica (specific surface area is 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 the silicone rubber base, 4 parts by weight of the linear coupling agent (x = 2, p = 4, n = 20, m = 14, m + n + p + 2 = 40), 20 parts by weight of the hand powder A (Dv50 is 1 μm), 10 parts by weight of the hydrogen-containing silicone oil (active hydrogen is located at both ends and side chains of the siloxane segment, viscosity is 30 mPa-s, mass content of active hydrogen is 0.25%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and filtered with a 200-400 mesh filter to obtain the silicone base material.

[0098] Comparative Example 6

[0099] The present comparative example provides a method for preparing a silicone base material, comprising the steps of:

[0100] (1) 100 parts by weight of the vinyl-terminated and vinyl- side silicone oil (mass content of vinyl is 0.4%, viscosity is 100000 mPa-s), 40 parts by weight of the fumed silica (specific surface area is 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 glue, 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 B (Dv50 is 3 μm), 5 parts by weight of trimethylsilyl-terminated hydrogen-containing silicone oil (viscosity is 100 mPa·s, mass content of active hydrogen is 0.75%), and 0.025 parts by weight of 1-ethynyl-1-cyclohexanol are uniformly mixed in a planetary mixer, diluted with 100 parts of isododecane, and then filtered with a 200-400 mesh filter to obtain a silicone-based material.

[0102] Liquid silicone rubber (Zheng'an Silicone, model GA-2960A / B) is coated on a release paper with a thickness of 100 μm, cured at 120°C for 10 min; then liquid silicone rubber (Zheng'an Silicone, model GA-2960A / B) is coated with a thickness of 80 μm, 200 gram weight non-woven fabric is overlaid thereon, 500 Pa pressure is applied for 10 s, and cured at 120°C for 10 min, and after the release paper is removed, a silicone leather is obtained. 5 ppm Karstedt catalyst, isododecane, and silicone-based material (one of the silicone-based materials obtained in Examples 1-9 and Comparative Examples 1-6) are uniformly mixed to form a mixture with a viscosity of 500 mPa·s, the mixture is coated on 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] 5 ppm Karstedt catalyst, isododecane, and silicone-based material (one of the silicone-based materials obtained in Examples 1-9 and Comparative Examples 1-6) are uniformly mixed to form a mixture with a viscosity of 10000 mPa·s, the mixture is coated on the surface of the release paper and cured at 120°C for 10 min to form a surface layer with a thickness of 20 μm. Then liquid silicone rubber (Zheng'an Silicone, model GA-2960A / B) is coated on the surface of the surface layer with a thickness of 100 μm, cured at 120°C for 10 min; then liquid silicone rubber (Zheng'an Silicone, model GA-2960A / B) is coated with a thickness of 80 μm, 200 gram weight non-woven fabric is overlaid thereon, 500 Pa pressure is applied for 10 s, and cured at 120°C for 10 min, and after the release paper is removed, a silicone leather is obtained. The surface layer of the silicone leather is subjected to mechanical property, wear resistance, stain resistance, and hand feel tests, the test methods are as follows, and the test results are shown in Table 1.

[0104] Wear resistance test method: GB / T 20991-2007 "Leather wear resistance test method - Martindale method".

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

[0106] Tensile strength test method (Mpa): tested according to GB / T 528-2009.

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

[0108] Stain resistance test method: using oily pen line, after solvent volatilization, using paper towel to wipe, scoring 10 for complete erasing, scoring 0 for complete non-erasing.

[0109] Hand feeling: scoring 10 for dry and smooth hand feeling, scoring 0 for sticky and strong resistance hand feeling.

[0110] Table 1 Performance test results of examples 1-9 and comparative examples 1-6

[0111]

[0112] Please refer to Table 1, from the performance test results of examples 1-9 and comparative examples 1-6, it can be known that, lacking any one or several of the end-vinyl side-vinyl silicone oil, linear coupling agent, hand feeling powder A and hydrogen-containing silicone oil disclosed in the application, or replacing any one or several of the end-vinyl side-vinyl silicone oil, linear coupling agent, hand feeling powder A and hydrogen-containing silicone oil disclosed in the application with others, will affect the mechanical properties, wear resistance, hand feeling and stain resistance of the surface layer formed by the silicone-based material, and it is difficult to simultaneously consider the mechanical properties, wear resistance, stain resistance and hand feeling effect.

[0113] The end-vinyl side-vinyl silicone oil, trimethyl silyl-terminated hydrogen-containing silicone oil and / or hydrogen-containing MQ resin used in the application can give the silicone-based material good hardness and ensure its good mechanical properties such as tear and tensile strength. On this basis, the application 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 high specific surface area, which can effectively improve the surface roughness of the vulcanized silicone-based material, so as to give it a smooth hand feeling and stain resistance effect on the basis of 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 groups in the silicone rubber-based glue through the silicon-hydrogen bonds contained therein, thereby connecting the hand feeling powder to the silicone-based material through a chemical bond, improving the compatibility of the hand feeling powder and the silicone-based material, ensuring the stability of its structure, and thereby significantly improving the overall mechanical strength, wear resistance, smooth hand feeling and stain resistance effect of the silicone-based material.

[0114] It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it is not limited to the listed in the embodiments, and those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the essence and scope of the technical solutions of the present application.

Claims

1. Silicon-based material, characterized in that In parts by weight, the preparation raw materials include 100 parts of silicone rubber base, 1 part to 5 parts of linear coupling agent, 10 parts to 30 parts of hand feeling powder, 1 part to 10 parts of hydrogenated silicone oil, 0.025 parts to 1 part of inhibitor and 20 parts to 100 parts of organic solvent. The preparation raw materials of the silicone rubber base include 100 parts of vinyl-terminated and vinyl-side silicone oil, 20 parts to 60 parts of white carbon black, 4 parts to 12 parts of hexamethyldisilazane and 0.5 parts 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 contains siloxane groups. The linear coupling agent has the structure shown below: Wherein, m+n+p+2=12-40, n+p≥1.5m, p≥2, x=2-5, and the linear coupling agent contains both methoxysilyl groups and silicon-hydrogen bonds.

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 an active hydrogen content of greater than or equal to 0.75% by mass. The hydrogen-containing MQ resin has an active hydrogen content of greater than or equal to 0.45% by mass.

4. The silicon-based material according to claim 1, characterized in that The viscosity of the vinyl-terminated and side-vinyl silicone oil is 80,000 mPa·s to 200,000 mPa·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: Including steps: (1) mixing the vinyl-terminated and vinyl-side 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 a silicon-based material in silicone leather, characterized in that: The silicon-based material is used as a surface treatment layer or surface layer of silicone leather. 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 preparation method of the silicon-based material according to claim 7.

9. The use of the silicon-based material in silicone 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, applying the mixture to 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 uniformly mixing a platinum catalyst, a solvent and the silicon-based material 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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