Liquid silicone rubber feel treatment agent and its preparation method and application

Abstract

The present invention relates to the technical field of liquid silicone rubber feel treatment agent, and more specifically, to a liquid silicone rubber feel treatment agent and a preparation method and application thereof. The liquid silicone rubber feel treatment agent, by mass, comprises raw materials including 80-100 parts of vinyl silicone oil, 10-20 parts of polydimethylsilicone oil, 10-20 parts of reinforcing filler, 5-15 parts of modified hydrogen-containing silicone oil A, 2-6 parts of modified hydrogen-containing silicone oil B, 0.1-0.5 parts of platinum catalyst, and 0.01-0.1 parts of inhibitor. The liquid silicone rubber feel treatment agent provided by the present invention has good feel, wear resistance, scratch resistance, and stain resistance, and can prevent silicone leather from mildewing in a hot and humid environment, and has good adhesion to silicone leather.

Description

Technical Field

[0001] The invention relates to the technical field of liquid silicone rubber hand-feel treatment agents, and more specifically, to a liquid silicone rubber hand-feel treatment agent and a preparation method and application thereof. Background Art

[0002] Silicone leather is an artificial leather material made of silicone rubber, which is widely used in furniture (such as sofas, chairs), car interiors, handbags, shoes, clothing and other fields.

[0003] In order to improve the feel and tactile experience of silicone leather and increase its functionality (for example, improving its weather resistance and adhesion), coating a feel agent / treatment agent on its surface is a commonly used method. For example, the Chinese patent with publication number CN110591526A discloses a two-component feel rubber paint, which includes the following components by weight: component A: 25-35 parts of polyester resin, 2-4 parts of elastic agent, 2-4 parts of feel agent, 0.2-0.4 parts of leveling agent, 5-7 parts of matting powder, 0.5-1.2 parts of anti-settling agent, 40-55 parts of combined solvent, 0.1-0.2 parts of dibutyltin dilaurate; polyester resin includes 18-22 parts of F520 polyaspartic acid ester and 7-13 parts of modified polyester resin; component B: 30-45 parts of isocyanate curing agent; the rubber paint of this technical solution has good weather resistance and adhesion. However, the above technical solution contains organic solvents, which are not environmentally friendly and not only cause environmental pollution but also damage the health of producers.

[0004] The Chinese patent with the authorization publication number CN115058138B discloses a water-based rubber treatment agent, the components and weight proportions of which are as follows: carboxymethyl cellulose: 100 parts; complex fluoride: 1-10 parts; nano oxide: 3-12 parts; permanganate: 0.2-1.0 parts; acrylic acid: 0.1-1 parts; hydroxyethyl cellulose: 0.1-0.5 parts; thickener: 0.5-1.5 parts; sealant: 0.5-1.5 parts; the nano oxide is a compound system of nano titanium dioxide and nano silicon dioxide in a mass ratio of 2:1. This technical solution has good stain resistance and wear resistance, as well as excellent hydrolysis resistance, wear resistance and weather resistance. However, there is a large amount of carboxymethyl cellulose in this technical solution, which has high moisture sensitivity and is prone to microbial growth in a humid environment, which may lead to the growth of mold, and its application in furniture is potentially harmful.

[0005] With the improvement of people's living standards and quality of life, consumers have higher and higher requirements for the functionality of silicone leather for furniture in addition to the feel, including wear resistance, scratch resistance, stain resistance, etc. In addition, in recent years, high temperature weather has continued to exist, and the south has been in a hot and humid environment for a long time, and silicone leather is prone to mold. Therefore, it is of great significance to provide a silicone rubber feel treatment agent that has good feel, wear resistance, scratch resistance, stain resistance, and can prevent silicone leather from mold in a hot and humid environment. Summary of the invention

[0006] The present invention aims to provide a liquid silicone rubber hand-feel treatment agent and a preparation method and application thereof in view of the deficiencies in the prior art. The provided liquid silicone rubber hand-feel treatment agent has good hand feel, wear resistance, scratch resistance, and stain resistance, while being able to prevent silicone leather from mildewing in a hot and humid environment, and has good adhesion to silicone leather.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] The first aspect of the present invention provides a liquid silicone rubber feel treatment agent, wherein the raw materials include, by weight, 80-100 parts of vinyl silicone oil, 10-20 parts of polydimethyl silicone oil, 10-20 parts of reinforcing filler, 5-15 parts of modified hydrogen-containing silicone oil A, 2-6 parts of modified hydrogen-containing silicone oil B, 0.1-0.5 parts of platinum catalyst, and 0.01-0.1 parts of inhibitor;

[0009] The preparation method of the modified hydrogenated silicone oil A comprises the following steps: under nitrogen protection conditions, side chain hydrogenated silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene are mixed, reacted at 70-80° C. for 1-2 hours, and toluene is removed after the reaction is completed to obtain the modified hydrogenated silicone oil A;

[0010] The preparation method of the modified hydrogen-containing silicone oil B comprises the following steps: under nitrogen protection conditions, side chain hydrogen-containing silicone oil, allyl glycidyl ether and an isopropanol solution containing chloroplatinic acid are mixed, reacted at 70-80° C. for 4-5 hours, and after the reaction is completed, the isopropanol is removed to obtain an intermediate; the intermediate, curcumin, chitosan and N,N-dimethylformamide are mixed, reacted at 80-100° C. for 4-6 hours, and after the reaction is completed, the N,N-dimethylformamide is removed to obtain the modified hydrogen-containing silicone oil B.

[0011] The present invention creatively adopts POSS-vinyl heptaoctyl caged polysilsesquioxane to modify the end-chain hydrogenated silicone oil to obtain a modified hydrogenated silicone oil A, which improves the scratch resistance of the liquid silicone rubber hand treatment agent while also improving the stain resistance and mildew resistance. The inventor speculates that: POSS-vinyl heptaoctyl caged polysilsesquioxane is grafted onto the molecular chain of the end-chain hydrogenated silicone oil through chemical bonds, thereby avoiding the agglomeration of POSS-vinyl heptaoctyl caged polysilsesquioxane and weakening the interaction between the molecular chains of the end-chain hydrogenated silicone oil, so that the silicone leather can better disperse the stress when subjected to external force, reduce the local stress concentration, and thus improve the scratch resistance; at the same time, the presence of POSS-vinyl heptaoctyl caged polysilsesquioxane enables the liquid silicone rubber hand treatment agent to form a micro-nano rough surface on the surface of the silicone leather, and the micro-nano rough structure can reduce the attachment of macro pollutants and reduce the attachment and growth of mold on the surface of the silicone leather.

[0012] The inventors also found that if POSS-vinyl heptauctyl caged polysilsesquioxane is used to modify the liquid silicone rubber feel treatment agent during the preparation process of the liquid silicone rubber feel treatment agent, the overall performance of the obtained feel treatment agent is poor. The inventors speculate that this is because POSS-vinyl heptauctyl caged polysilsesquioxane and vinyl silicone oil competitively react with the terminal side chain hydrogen-containing silicone oil, and the reaction is uncontrollable, resulting in a decrease in the performance of the liquid silicone rubber feel treatment agent.

[0013] The present invention creatively introduces curcumin and chitosan into the structure of side chain hydrogenated silicone oil. The hydrogenated silicone oil modified by curcumin and chitosan can prevent the degradation or loss of curcumin and chitosan over time. Meanwhile, the present inventor unexpectedly finds that the synergistic effect of curcumin, chitosan and side chain hydrogenated silicone oil not only improves the mildew resistance and durability of the liquid silicone rubber hand-feel treatment agent, but also improves the hand feel and adhesion of the liquid silicone rubber hand-feel treatment agent. The present inventor speculates that the introduction of curcumin and chitosan makes the hydrophilic end branching degree of the modified hydrogenated silicone oil B high, reduces the surface tension of the liquid silicone rubber hand-feel treatment agent, and the liquid silicone rubber hand-feel treatment agent can better penetrate into the tiny pores of silicone leather, thereby improving the adhesion and hand feel of the liquid silicone rubber hand-feel treatment agent.

[0014] In some preferred embodiments, the vinyl silicone oil is a vinyl-terminated polydimethylsiloxane, including vinyl silicone oil A and vinyl silicone oil B; the mass ratio of the vinyl silicone oil A to the vinyl silicone oil B is (5-8):1.

[0015] In some preferred embodiments, the vinyl silicone oil A has a vinyl content of 0.1-0.3 wt % and a viscosity of 1000-20000 mPa·s.

[0016] Preferably, the vinyl content of the vinyl silicone oil A is 0.18 wt % and the viscosity is 5000 mPa·s. In some preferred embodiments, the vinyl content of the vinyl silicone oil B is 0.4-0.7 wt % and the viscosity is 250-500 mPa·s.

[0017] Preferably, the vinyl content of the vinyl silicone oil B is 0.55 wt % and the viscosity is 300 mPa·s.

[0018] In some preferred embodiments, the viscosity of the polydimethylsilicone oil is 190-350 mPa·s, preferably 200±10 mPa·s.

[0019] In some preferred embodiments, the mass ratio of the terminal side chain hydrogen-containing silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene is (5-8): (0.08-0.12): (0.03-0.07): (30-50).

[0020] Preferably, the mass ratio of the terminal side chain hydrogen-containing silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene is 6:0.1:0.05:40.

[0021] In some preferred embodiments, the hydrogen content of the terminal side chain hydrogen-containing silicone oil is 0.2-0.3 wt % and the viscosity is 90-120 mPa·s.

[0022] Preferably, the hydrogen content of the terminal side chain hydrogen-containing silicone oil is 0.28 wt % and the viscosity is 105±15 mPa·s.

[0023] In some preferred embodiments, the side chain hydrogen-containing silicone oil has a hydrogen content of 0.18-0.36 wt % and a viscosity of 60-100 mPa·s.

[0024] Preferably, the side chain hydrogen-containing silicone oil has a hydrogen content of 0.25 wt % and a viscosity of 85±15 mPa·s.

[0025] In some preferred embodiments, the molar ratio of the silicon-hydrogen bonds in the side chain hydrogen-containing silicone oil to the double bonds in allyl glycidyl ether is 1:(1.1-1.3), preferably 1:1.2.

[0026] In some preferred embodiments, the concentration of chloroplatinic acid in the isopropanol solution containing chloroplatinic acid is 0.1-0.2 wt %, preferably 0.15 wt %.

[0027] In some preferred embodiments, the mass ratio of the isopropanol solution containing chloroplatinic acid to the side chain hydrogen-containing silicone oil is (3-5):1, preferably 4:1.

[0028] In some preferred embodiments, the mass ratio of allyl glycidyl ether, curcumin, chitosan and N,N-dimethylformamide is 1:(2-3):(2-3):(20-30), preferably 1:2.5:2.5:25.

[0029] In some preferred embodiments, the reinforcing filler includes zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA (polymethyl methacrylate) micropowder; the mass ratio of the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA micropowder is 1:(3-5), preferably 1:4.

[0030] In some preferred embodiments, the preparation method of the zinc ricinoleate modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol comprises the following steps: dispersing Zn-MOF-74 in water, adding nitrogen-containing heterocyclic phenol alcohol, stirring at 25-30°C for 6-10 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol; adding Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol to zinc ricinoleate, stirring at 25-30°C for 4-6 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol.

[0031] The inventors found that although the introduction of modified hydrogen-containing silicone oil A and modified hydrogen-containing silicone oil B improved the mildew resistance of the liquid silicone hand treatment agent, the long-term mildew resistance of silicone leather under high temperature and high humidity conditions was poor. When zinc ricinoleate-modified Zn-MOF-74@ nitrogen-containing heterocyclic phenol alcohol was added, not only the wear resistance of the liquid silicone hand treatment agent was improved, but also the silicone leather could be free from mildew under long-term high temperature and high humidity conditions. The present invention speculates that it is because Zn-MOF-74 encapsulates nitrogen-containing heterocyclic phenol alcohols, and zinc ricinoleate coats Zn-MOF-74, and the obtained zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohols can be evenly distributed in the system, thereby improving the wear resistance of the liquid feel treatment agent. At the same time, the surface of zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohols is hydrophobic, which can not only realize the gradual release of zinc ions and nitrogen-containing heterocyclic phenol alcohols of Zn-MOF-74, but also avoid Zn-MOF-74 and nitrogen-containing heterocyclic phenol alcohols from agglomerating and decomposing too quickly under high temperature and high humidity, thereby working together with the modified hydrogen-containing silicone oil B to realize that the silicone leather also has good mildew resistance under long-term high temperature and high humidity conditions.

[0032] The inventors further found that PMMA micropowder and zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol not only improve the wear resistance of the liquid feel treatment agent through synergistic action, but also improve the feel and stain resistance. The inventors speculate that this is because PMMA micropowder, while improving the hardness of the liquid feel treatment agent, works together with zinc ricinoleate on the surface of Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol to further reduce the surface energy of the liquid feel treatment agent, thereby improving the feel and stain resistance of the feel treatment agent.

[0033] In some preferred embodiments, the mass ratio of Zn-MOF-74, nitrogen-containing heterocyclic phenol alcohol and water is 1:(3-5):(90-110), preferably 1:4:100.

[0034] In some preferred embodiments, the mass ratio of the Zn-MOF-74@ nitrogen-containing heterocyclic phenol alcohol to zinc ricinoleate is 1:(3-5), preferably 1:4.

[0035] In some preferred embodiments, the pore size of the Zn-MOF-74 is 1-2 nm.

[0036] In some preferred embodiments, the nitrogen-containing heterocyclic phenol alcohol includes 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol; the mass ratio of 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol is (1-3): (1-3): (1-3), preferably 2:2:1.

[0037] In some preferred embodiments, the average particle size of the PMMA powder is 8-12 μm, preferably 10 μm.

[0038] In some preferred embodiments, the platinum content of the platinum catalyst is 1500-5000 ppm, preferably 3000 ppm.

[0039] In some preferred embodiments, the inhibitor is selected from at least one of methyl butynol, ethynyl cyclohexanol, and polyvinyl polysiloxane, preferably ethynyl cyclohexanol.

[0040] The second aspect of the present invention provides a method for preparing the above-mentioned liquid silicone rubber hand-feel treatment agent, comprising the following steps:

[0041] Mix vinyl silicone oil, polydimethyl silicone oil and reinforcing filler evenly, add modified hydrogen-containing silicone oil A, modified hydrogen-containing silicone oil B and inhibitor and mix evenly, then add platinum catalyst and mix evenly to obtain the product.

[0042] The third aspect of the present invention provides the use of the liquid silicone rubber hand-feel treatment agent in the surface treatment of silicone leather.

[0043] Beneficial effects:

[0044] 1. The present invention creatively adopts POSS-vinyl heptaoctyl caged polysilsesquioxane to modify the end-side chain hydrogen-containing silicone oil to obtain a modified hydrogen-containing silicone oil A, which improves the scratch resistance of the liquid silicone rubber hand treatment agent while also improving the stain resistance and mildew resistance.

[0045] 2. The present invention creatively introduces curcumin and chitosan into the structure of side chain hydrogenated silicone oil. The curcumin and chitosan modified hydrogenated silicone oil can prevent curcumin and chitosan from being degraded or lost over time. Meanwhile, the curcumin, chitosan and side chain hydrogenated silicone oil not only improve the mildew resistance and durability of the liquid silicone rubber hand treatment agent through synergistic effect, but also improve the hand feel and adhesion of the liquid silicone rubber hand treatment agent.

[0046] 3. The invention adds zinc ricinoleate to modify Zn-MOF-74@ nitrogen-containing heterocyclic phenol alcohol, which not only improves the wear resistance of the liquid silicone hand treatment agent, but also prevents the silicone leather from getting moldy under long-term high temperature and high humidity conditions.

[0047] 4. The PMMA micropowder of the present invention and the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol not only improve the wear resistance of the liquid hand-feel treatment agent through synergistic effect, but also improve the hand feel and stain resistance. DETAILED DESCRIPTION

[0048] In order to better explain the present invention, the following will combine the examples in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. The embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0049] In the following examples, unless otherwise specified, the operating methods used are all conventional operating methods, the equipment used are all conventional equipment, and the raw materials used are all commercially available.

[0050] Example 1

[0051] Liquid silicone rubber feel treatment agent, calculated by mass, the raw materials include 90 parts of vinyl silicone oil, 15 parts of polydimethyl silicone oil, 15 parts of reinforcing filler, 10 parts of modified hydrogen-containing silicone oil A, 4 parts of modified hydrogen-containing silicone oil B, 0.3 parts of platinum catalyst, and 0.05 parts of inhibitor.

[0052] The preparation method of the modified hydrogenated silicone oil A comprises the following steps: under nitrogen protection conditions, side chain hydrogenated silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene are mixed and reacted at 75° C. for 1.5 hours, and toluene is removed after the reaction is completed to obtain the modified hydrogenated silicone oil A;

[0053] The mass ratio of the terminal side chain hydrogen silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene is 6:0.1:0.05:40.

[0054] The terminal side chain hydrogen-containing silicone oil has a hydrogen content of 0.28 wt % and a viscosity of 105±15 mPa·s, and is purchased from Jiangsu Kexing New Materials Co., Ltd., model: DSH-28.

[0055] The POSS-vinyl heptaoctyl caged polysilsesquioxane was purchased from Jiangsu Kexing New Materials Co., Ltd., model: DSH-25.

[0056] The preparation method of the modified hydrogen-containing silicone oil B comprises the following steps: under nitrogen protection conditions, side chain hydrogen-containing silicone oil, allyl glycidyl ether and an isopropanol solution containing chloroplatinic acid are mixed, reacted at 75° C. for 4.5 hours, and after the reaction is completed, the isopropanol is removed to obtain an intermediate; the intermediate, curcumin, chitosan and N,N-dimethylformamide are mixed, reacted at 90° C. for 5 hours, and after the reaction is completed, the N,N-dimethylformamide is removed to obtain the modified hydrogen-containing silicone oil B;

[0057] The side chain hydrogen-containing silicone oil has a hydrogen content of 0.25 wt % and a viscosity of 85±15 mPa·s, and is purchased from Jiangsu Kexing New Materials Co., Ltd., model: SH-25.

[0058] The molar ratio of the silicon-hydrogen bond in the side chain hydrogen-containing silicone oil to the double bond in the allyl glycidyl ether is 1:1.2.

[0059] The concentration of chloroplatinic acid in the isopropanol solution containing chloroplatinic acid is 0.15 wt %.

[0060] The mass ratio of the isopropanol solution containing chloroplatinic acid to the side chain hydrogen-containing silicone oil is 4:1.

[0061] The mass ratio of the allyl glycidyl ether, curcumin, chitosan and N,N-dimethylformamide is 1:2.5:2.5:25.

[0062] The curcumin was purchased from Dalian Meilun Biotechnology Co., Ltd., catalog number: MB2147.

[0063] The chitosan was purchased from Dalian Meilun Biotechnology Co., Ltd., item number: MB5782-1.

[0064] The vinyl silicone oil is a vinyl-terminated polydimethylsiloxane, including vinyl silicone oil A and vinyl silicone oil B; the mass ratio of the vinyl silicone oil A to the vinyl silicone oil B is 6:1.

[0065] The vinyl silicone oil A has a vinyl content of 0.18 wt % and a viscosity of 5000 mPa·s and is purchased from Jiangsu Kexing New Materials Co., Ltd., model: V-5000.

[0066] The vinyl silicone oil B has a vinyl content of 0.55 wt % and a viscosity of 300 mPa·s and is purchased from Jiangsu Kexing New Materials Co., Ltd., model: V-300.

[0067] The viscosity of the polydimethylsilicone oil is 200±10 mPa·s, and it is purchased from Anhui Aiyota Silicone Oil Co., Ltd., model 201-200.

[0068] The reinforcing filler includes zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA micropowder; the mass ratio of the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA micropowder is 1:4.

[0069] The preparation method of zinc ricinoleate modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol comprises the following steps: dispersing Zn-MOF-74 in water, adding nitrogen-containing heterocyclic phenol alcohol, stirring at 25°C for 8 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol; adding Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol to zinc ricinoleate, stirring at 25°C for 5 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol.

[0070] The mass ratio of the Zn-MOF-74, nitrogen-containing heterocyclic phenol alcohol and water is 1:4:100.

[0071] The mass ratio of the Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol to zinc ricinoleate is 1:4.

[0072] The pore size of the Zn-MOF-74 is 1-2 nm, and it was purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.

[0073] The nitrogen-containing heterocyclic phenol alcohol comprises 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol; the mass ratio of the 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol is 2:2:1.

[0074] The PMMA powder has an average particle size of 10 μm and is purchased from Soken Chemical (Suzhou) Co., Ltd., model: MX-1000F.

[0075] The platinum content of the platinum catalyst is 3000 ppm, and it is purchased from Jiangsu Kexing New Materials Co., Ltd., model: XAT-Pt030.

[0076] The inhibitor is ethynyl cyclohexanol.

[0077] The preparation method of the liquid silicone rubber feel treatment agent comprises the following steps:

[0078] Mix vinyl silicone oil, polydimethyl silicone oil and reinforcing filler evenly, add modified hydrogen-containing silicone oil A, modified hydrogen-containing silicone oil B and inhibitor and mix evenly, then add platinum catalyst and mix evenly to obtain the product.

[0079] Example 2

[0080] The only difference from Implementation 1 is that the raw materials of the liquid silicone rubber feel treatment agent, calculated by mass, include 80 parts of vinyl silicone oil, 10 parts of polydimethyl silicone oil, 10 parts of reinforcing filler, 5 parts of modified hydrogen-containing silicone oil A, 2 parts of modified hydrogen-containing silicone oil B, 0.1 parts of platinum catalyst, and 0.01 parts of inhibitor; the rest are the same.

[0081] Example 3

[0082] The only difference from Example 1 is that the raw materials of the liquid silicone rubber feel treatment agent, calculated by mass, include 100 parts of vinyl silicone oil, 20 parts of polydimethyl silicone oil, 20 parts of reinforcing filler, 15 parts of modified hydrogen-containing silicone oil A, 6 parts of modified hydrogen-containing silicone oil B, 0.5 parts of platinum catalyst, and 0.1 parts of inhibitor; the rest are the same.

[0083] Comparative Example 1

[0084] The difference from Example 1 is that in the preparation method of modified hydrogenated silicone oil A, the terminal side chain hydrogenated silicone oil is replaced by side chain hydrogenated silicone oil, the side chain hydrogenated silicone oil has a hydrogen content of 0.25 wt %, a viscosity of 70±20 mPa·s, purchased from Jiangsu Kexing New Materials Co., Ltd., model: DSH-25; the rest are the same.

[0085] Comparative Example 2

[0086] The difference from Example 1 is that the preparation method of modified hydrogenated silicone oil A comprises the following steps: mixing terminal side chain hydrogenated silicone oil and POSS-vinyl heptaoctyl caged polysilsesquioxane in a mass ratio of 6:0.1; the rest are the same.

[0087] Comparative Example 3

[0088] The difference from Example 1 is that the preparation method of modified hydrogen-containing silicone oil B comprises the following steps: mixing side chain hydrogen-containing silicone oil, allyl glycidyl ether, curcumin, and chitosan; the molar ratio of the silicon-hydrogen bond in the side chain hydrogen-containing silicone oil to the double bond in allyl glycidyl ether is 1:1.2; the mass ratio of allyl glycidyl ether, curcumin, chitosan and N,N-dimethylformamide is 1:2.5:2.5:25; and the rest are the same.

[0089] Comparative Example 4

[0090] The difference from Example 1 is that in the preparation method of modified hydrogen-containing silicone oil B, curcumin is replaced by catechins of equal mass, which are purchased from Dalian Meilun Biotechnology Co., Ltd., item number: MB6626-1; the rest are the same.

[0091] Comparative Example 5

[0092] The difference from Example 1 is that in the preparation method of modified hydrogen-containing silicone oil B, chitosan is replaced by curcumin of equal mass; the rest are the same.

[0093] Comparative Example 6

[0094] The difference from Example 1 is that the ricinoleate zinc modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol is replaced with PMMA powder of the same mass; the rest are the same.

[0095] Comparative Example 7

[0096] The difference from Example 1 is that PMMA powder is replaced by fumed silica, purchased from Guangzhou Jingyi New Materials Co., Ltd., model: TS-530; the rest are the same.

[0097] Comparative Example 8

[0098] The difference from Example 1 is that the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol is replaced by Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol; the rest are the same.

[0099] Application Examples

[0100] The liquid silicone rubber feel treatment agent of Examples 1-3 and Comparative Examples 1-8 was sprayed on the silicone leather at a spraying amount of 4 kg / cm 2 , and then vulcanized at 80°C for 5 minutes. The silicone leather was tested as follows. The results are shown in Table 1:

[0101] 1. Hand feel: A total of 20 volunteers aged 18-40, including 10 males and 10 females, were selected as the evaluation team. Each person touched the silicone leather treated with the liquid silicone rubber hand feel treatment agent of Examples 1-3 and Comparative Examples 1-8, and the evaluation levels of all the evaluators in the evaluation team were calculated by arithmetic average, and the result was retained to one decimal place as the hand feel level; the evaluation level was divided into four levels: Level 1 was poor; Level 2 was average; Level 3 was relatively satisfactory; and Level 4 was very satisfactory.

[0102] 2. Abrasion resistance: Use a dust-free cloth dipped in alcohol, apply a 500g weight and rub 50 times / min, observe and record the time it takes for damage to occur, in seconds;

[0103] 3. Scratch resistance: Use a five-finger scratch tester to rub the surface of the silicone leather back and forth once under a pressure of 10N to observe whether the surface of the silicone leather is damaged. If there is no damage, it is recorded as qualified; if there is damage, it is recorded as unqualified.

[0104] 4. Stain resistance: Oil pen test method, use an oil pen to draw an × on the surface, then use a dust-free cloth to wipe it once, and observe whether there is any residue on the surface of the silicone leather. If there is no residue, it is marked as qualified, and if there is residue, it is marked as unqualified.

[0105] 5. Adhesion: Use a grid marker to draw 100 squares on the surface of the silicone leather. The size of the square is 1m×1m. Use 3M's 250 tape to smooth the oil coating. Quickly peel it off at a 60-degree angle to observe whether there is any shedding at the edge of the scratch. If there is no shedding, it is 5B. If the shedding amount is between 0-5%, it is 4B. If it is between 5-15%, it is 3B. If it is between 15-35%, it is 2B. If it is between 35-65%, it is 1B. If it is above 65%, it is 0B.

[0106] 6. Room temperature mildew resistance: Place the silicone leather at 25±2℃ for 6 months and observe whether there is mildew on the surface. If there is no mildew, it is qualified; if there is mildew, it is unqualified.

[0107] 7. High temperature and high humidity mildew resistance: Place the silicone leather under the conditions of 85±5% relative humidity and 35±2℃ temperature for 6 months, and observe whether there is mildew on the surface of the silicone leather. If there is no mildew, it is qualified; if there is mildew, it is unqualified.

[0108] Table 1 Performance test results of liquid silicone rubber hand-feel treatment agents of Examples 1-3 and Comparative Examples 1-8

[0109]

[0110] It can be seen from Table 1 that:

[0111] The silicone leather treated with the liquid silicone rubber feel treatment agent of Examples 1-3 has good feel, wear resistance, scratch resistance, stain resistance, adhesion, mildew resistance at room temperature and mildew resistance at high temperature and high humidity;

[0112] Comparative Example 1 Since the end-side chain hydrogen-containing silicone oil is replaced with the side hydrogen silicone oil in the preparation method of the modified hydrogen-containing silicone oil A, the scratch resistance, stain resistance and high temperature and high humidity corrosion resistance of the silicone leather treated with the obtained liquid silicone rubber hand treatment agent are unqualified;

[0113] Comparative Example 2: Since the end-side chain hydrogenated silicone oil and POSS-vinyl heptaoctyl caged polysilsesquioxane were directly mixed without grafting, the silicone leather treated with the liquid silicone rubber feel treatment agent was unqualified in terms of feel, wear resistance, decreased adhesion, stain resistance, normal temperature corrosion resistance, and high temperature and high humidity corrosion resistance;

[0114] In Comparative Example 3, since the side chain hydrogen silicone oil, allyl glycidyl ether, curcumin and chitosan were directly mixed without grafting, the hand feel and adhesion of the silicone leather treated with the liquid silicone rubber hand treatment agent were reduced, and the room temperature anticorrosion and high temperature and high humidity anticorrosion properties were unqualified;

[0115] Comparative Example 4 Since curcumin was replaced with catechins of equal mass in the preparation method of modified hydrogen-containing silicone oil B, the room temperature anticorrosion and high temperature and high humidity anticorrosion properties of the obtained liquid silicone rubber feel treatment agent were unqualified;

[0116] Comparative Example 5 Since chitosan is replaced with curcumin of equal mass in the preparation method of modified hydrogen-containing silicone oil B, the room temperature anticorrosion and high temperature and high humidity anticorrosion of the obtained liquid silicone rubber feel treatment agent are unqualified;

[0117] In Comparative Example 6, since the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol was replaced with PMMA micropowder of equal mass, the hand feel and wear resistance of the silicone leather treated with the liquid silicone rubber hand treatment agent were reduced, and the scratch resistance, room temperature corrosion resistance, and high temperature and high humidity corrosion resistance were unqualified;

[0118] In Comparative Example 7, PMMA powder was replaced with fumed silica, so the hand feel and wear resistance of the silicone leather treated with the liquid silicone rubber hand treatment agent were reduced, and the high temperature and high humidity corrosion resistance was unqualified;

[0119] In Comparative Example 8, since the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol is replaced by Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol, the hand feel and wear resistance of the silicone leather treated with the obtained liquid silicone rubber hand treatment agent are reduced, and the stain resistance and high temperature and high humidity corrosion resistance are unqualified.

[0120] The above description is only a specific embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent transformation made by the present invention, or directly or indirectly applied in other related technical fields, is also included in the patent protection scope of the present invention.

Claims

1. Liquid silicone rubber feel treatment agent, characterized in that: By mass, the raw materials include 80-100 parts of vinyl silicone oil, 10-20 parts of polydimethyl silicone oil, 10-20 parts of reinforcing filler, 5-15 parts of modified hydrogen-containing silicone oil A, 2-6 parts of modified hydrogen-containing silicone oil B, 0.1-0.5 parts of platinum catalyst, and 0.01-0.1 parts of inhibitor; The preparation method of the modified hydrogenated silicone oil A comprises the following steps: under nitrogen protection conditions, side chain hydrogenated silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene are mixed, reacted at 70-80° C. for 1-2 hours, and toluene is removed after the reaction is completed to obtain the modified hydrogenated silicone oil A; The preparation method of the modified hydrogen-containing silicone oil B comprises the following steps: under nitrogen protection conditions, mixing side chain hydrogen-containing silicone oil, allyl glycidyl ether and an isopropanol solution containing chloroplatinic acid, reacting at 70-80° C. for 4-5 hours, and removing isopropanol after the reaction to obtain an intermediate; mixing the intermediate, curcumin, chitosan and N,N-dimethylformamide, reacting at 80-100° C. for 4-6 hours, and removing N,N-dimethylformamide after the reaction to obtain the modified hydrogen-containing silicone oil B; The reinforcing filler includes zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA micropowder; the mass ratio of the zinc ricinoleate-modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and PMMA micropowder is 1:(3-5).

2. The liquid silicone rubber feel treatment agent according to claim 1, characterized in that: The vinyl silicone oil is a vinyl-terminated polydimethylsiloxane, including vinyl silicone oil A and vinyl silicone oil B; the mass ratio of the vinyl silicone oil A to the vinyl silicone oil B is (5-8):1; the vinyl content of the vinyl silicone oil A is 0.1-0.3wt%, and the viscosity is 1000-20000mPa·s; the vinyl content of the vinyl silicone oil B is 0.4-0.7wt%, and the viscosity is 250-500mPa·s.

3. The liquid silicone rubber feel treatment agent according to claim 2, characterized in that: The mass ratio of the terminal side chain hydrogen-containing silicone oil, POSS-vinyl heptaoctyl caged polysilsesquioxane, di(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum and toluene is (5-8): (0.08-0.12): (0.03-0.07): (30-50).

4. The liquid silicone rubber feel treatment agent according to claim 3, characterized in that: The mass ratio of allyl glycidyl ether, curcumin, chitosan and N,N-dimethylformamide is 1:(2-3):(2-3):(20-30).

5. The liquid silicone rubber feel treatment agent according to claim 4, characterized in that: The preparation method of zinc ricinoleate modified Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol comprises the following steps: dispersing Zn-MOF-74 in water, adding nitrogen-containing heterocyclic phenol alcohol, stirring at 25-30° C. for 6-10 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol; adding Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol to zinc ricinoleate, stirring at 25-30° C. for 4-6 hours, and centrifuging and drying to obtain Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol.

6. The liquid silicone rubber feel treatment agent according to claim 5, characterized in that: The mass ratio of the Zn-MOF-74, nitrogen-containing heterocyclic phenol alcohol and water is 1:(3-5):(90-110); the mass ratio of the Zn-MOF-74@nitrogen-containing heterocyclic phenol alcohol and zinc ricinoleate is 1:(3-5).

7. The liquid silicone rubber hand-feel treatment agent according to claim 6, characterized in that: The nitrogen-containing heterocyclic phenol alcohol comprises 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol; the mass ratio of the 2-hydroxypyridine, 8-hydroxyquinoline zinc and phenol is (1-3): (1-3): (1-3).

8. The method for preparing the liquid silicone rubber hand-feel treatment agent according to any one of claims 1 to 7, characterized in that: The following steps are involved: Vinyl silicone oil, polydimethyl silicone oil and reinforcing filler are mixed evenly, modified hydrogen-containing silicone oil A, modified hydrogen-containing silicone oil B and inhibitor are added and mixed evenly, and then platinum catalyst is added and mixed evenly to obtain the product.

9. Use of the liquid silicone rubber feel treatment agent according to any one of claims 1 to 7 in silicone leather surface treatment.

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