Organic silicon modified acrylic acid and / or acrylate film-forming agent and preparation method thereof

Abstract

The invention relates to the field of cosmetics, and particularly discloses an organic silicon modified acrylic acid and / or acrylate film-forming agent and a preparation method thereof. A is an acrylic monomer, B is a functional monomer, C and D are vinyl modified polyhedral oligomeric silsesquioxane, a is equal to 100 to 10000, m is equal to 1 to 1000, b is equal to 0 to 10000, and n is equal to 1 to 1000. The film-forming agent integrates the respective advantages of an acrylic acid and / or acrylate film-forming agent and an organic silicon film-forming agent, has good water resistance and oil resistance, can uniformly form a film, and effectively considers the flexibility and toughness of the formed film; and in addition, good performance is shown in a water-based system, and the application range of an organic silicon modified polymer material in a film-forming agent is greatly widened.

Description

Technical Field

[0001] The present application relates to the field of cosmetics, specifically, to the field of film-forming agent technology, and more specifically, it relates to an organic silicon-modified acrylic acid and / or acrylate resin film-forming agent and a preparation method thereof. Background Art

[0002] In cosmetic products, the use of film formers can form a thin film structure. Based on the different structures and performance characteristics of the film former materials themselves, the products can be endowed with anti-sweat, anti-oil, setting, long-lasting, anti-scratch, anti-migration and other properties, which are important factors affecting the makeup lasting effect. The development of film formers mainly involves extensive research and exploration of new polymer materials, and targeted regulation of the structure, molecular weight, hydrophilicity and lipophilicity of polymer materials to meet the actual needs of different categories of cosmetic products.

[0003] The film formers currently used in cosmetics can be roughly divided into two categories: water-based film formers and oil-based film formers, depending on the system in which they are used. Among them, acrylic acid and / or acrylate copolymers are one of the earlier used water-based film former materials, with good film-forming softness, strong ductility, excellent aging resistance and light performance, and in actual use, the additional selection of different monomer copolymers can greatly enrich its product performance. It is widely used in many products such as eyeliner, mascara, foundation, etc., with a wide range of application scenarios.

[0004] Among oily film formers, in addition to traditional hydrophobic polymer materials, siloxane and its derivatives have also been widely used in cosmetic products in recent years. Silicone film formers have excellent characteristics such as waterproof, oil-resistant, heat-resistant, weather-resistant and chemical-resistant, which can effectively improve the sensory properties of products and have gradually developed into a mature film former category. In addition, organic polymer materials modified with siloxane have also been used in recent years, and chemically modified silicone materials also better match the actual needs of cosmetics to a certain extent.

[0005] However, through practical application, people have found that both types of film formers have their own problems. The acrylic acid and / or acrylate film formers are too soft and have weak water and oil resistance, which affects the makeup lasting effect. The silicone film formers have problems such as uneven film formation and easy formation of resin aggregates after solvent evaporation, which makes the film prone to cracks. Although silicone-modified organic polymer materials have achieved excellent improvement effects, they are currently limited to the field of oily film formers and have a narrow application range. Summary of the invention

[0006] In order to solve the above technical problems, the present application provides a silicone-modified acrylic acid and / or acrylic acid ester film-forming agent and a preparation method thereof.

[0007] In the first aspect, the present application provides an organosilicon-modified acrylic acid and / or acrylic acid ester film-forming agent, which adopts the following technical solution: An organic silicon modified acrylic acid and / or acrylic acid ester film-forming agent, the film-forming agent has the structural formula: A is an acrylic monomer, B is a functional monomer, C and D are vinyl-modified cage-type polysilsesquioxanes, a=100-10000, m=1-1000, b=0-10000, and n=1-1000.

[0008] By adopting the above technical scheme, the present application designs a composite film-forming agent of acrylic acid and / or acrylate modified with a cage-like organosilicon structure. The composite film-forming agent takes polyacrylic acid and / or acrylate structure as the main body, and combines the advantages of acrylic acid and / or acrylate film-forming agents and organosilicon film-forming agents to complement each other. Specifically, the participation of organosilicon resin is used to improve the relatively insufficient waterproofness and oil resistance of acrylic acid and / or acrylate film-forming agents, and increase the effect of makeup holding and durable anti-falling; and the separation and series effect of acrylic monomers between organosilicon resin units is used to make the film formation of the composite film-forming agent more uniform, effectively taking into account the softness and toughness of the film. In addition, the composite film-forming agent shows good performance in water-based systems, which greatly broadens the application scope of organosilicon-modified polymer materials in film-forming agents.

[0009] At the same time, the present application introduces a silicone unit that forms a cage-like structure, which can selectively adsorb some components in the cosmetic formula according to its different spatial sizes. The small-sized spatial structure can adsorb some small molecule solvents, play a certain sustained release role in the process of film formation, adjust the dynamics of the film formation process, regulate the uniformity and continuity of the formed film, and reduce the dryness caused by too fast film formation; the larger-sized spatial structure can provide a relatively stable dispersion environment for the particle dispersed components in the cosmetic formula, such as color powder, and reduce the excessive aggregation of dispersed particles or leakage in the film-forming state and other undesirable phenomena.

[0010] Preferably, the number of vinyl groups in the vinyl-modified cage-type polysilsesquioxane is ≤3.

[0011] By adopting the above technical scheme, the present application optimizes the number of vinyl groups in a single cage-type polysilsesquioxane. When the number of vinyl groups is 1, the cage-type polysilsesquioxane is connected to the main chain to play the role of side chain modification and end-capping. When the number of vinyl groups is greater than 1, the cage-type polysilsesquioxane can be further connected to other groups as a cross-linking group after being connected to the main chain, and participate in the construction of the polymer. However, if the number of vinyl groups in the cage-type polysilsesquioxane is too large, there is a possibility of excessive cross-linking, which will cause gelation and have an adverse effect on the dissolution and processing properties of the film-forming agent.

[0012] Preferably, the raw materials used for the vinyl-modified cage-type polysilsesquioxane include siloxane monomers and vinyl siloxane. By weight percentage, the siloxane monomers include 85-100% trifunctional siloxane monomers, 0-10% difunctional siloxane monomers, and 0-5% monofunctional siloxane monomers.

[0013] Preferably, by weight percentage, the siloxane monomer includes 85% trifunctional siloxane monomer, 10% difunctional siloxane monomer, and 5% monofunctional siloxane monomer.

[0014] By adopting the above technical scheme, the vinyl-modified cage-type polysilsesquioxane of the present application is mainly realized by T-type silicone resin, and the cage-like silicone molecules are formed by condensation between trifunctional siloxane monomers, and then the sites that can be further polymerized are extended outward through the vinyl group, and finally the synthesis of the polymer is realized. Since the internal pores of the cage-type polysilsesquioxane prepared by only using trifunctional siloxane monomers for reaction are small, it is easy to form a gel-like product that is difficult to use in cosmetic products, so the present application further introduces difunctional siloxane monomers and monofunctional siloxane monomers.

[0015] The difunctional siloxane monomer can expand the O-Si-O ring that forms the pores and increase the porosity; the monofunctional siloxane monomer can be used as a capping agent to limit the unlimited extension of the organosilicon structural unit, thereby controlling the overall spatial size of the organosilicon molecule. However, when introducing the difunctional siloxane monomer and the monofunctional siloxane monomer, the integrity of the organosilicon structural unit should also be ensured, that is, an organosilicon cage with a distinct body structure is obtained to avoid the formation of linear or simply branched oligomers due to excessive addition of difunctional siloxane monomers or monofunctional siloxane monomers.

[0016] Experiments have shown that when the proportion of trifunctional siloxane monomers is 85%, the proportion of difunctional siloxane monomers is 10%, and the proportion of monofunctional siloxane monomers is 5%, the pore size of cage-type polysilsesquioxane can be expanded to 20-40nm, and the molecular weight can be controlled at 3000-4000, which not only ensures that the cage-type polysilsesquioxane can modify the structure of polyacrylic acid and / or acrylate, but also enables the film-forming agent to have sufficient solubility and processing properties.

[0017] Optionally, the acrylic monomer includes one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, isooctyl acrylate, and isodecyl acrylate.

[0018] Preferably, the acrylic monomer comprises methacrylic acid and hydroxyethyl acrylate in a weight ratio of 1:(1-1.5).

[0019] Through the above technical scheme, the present application further selects a mixture of methacrylic acid and hydroxyethyl acrylate with good hydrophilicity as monomers for constructing the main chain of acrylic acid and / or acrylate, and together with the silicone molecules, regulates the hydrophilic and lipophilic properties of the film-forming agent to a certain extent, so that the film-forming agent can be suitable for water-based systems.

[0020] Optionally, the functional monomer is one of styrene, vinyl pyrrolidone, vinyl alcohol and acrylonitrile.

[0021] Through the above technical scheme, the present application can also select suitable tool components, such as styrene, vinyl pyrrolidone, vinyl alcohol, acrylonitrile, etc., when preparing the film-forming agent according to the required properties of the film-forming agent, and the process of their participation in the copolymerization reaction is a conventional preparation method well known to technicians in this field.

[0022] In a second aspect, the present application provides a method for preparing a silicone-modified acrylic acid and / or acrylic acid ester film-forming agent, which adopts the following technical scheme: A method for preparing an organosilicon-modified acrylic acid and / or acrylic acid ester film-forming agent comprises the following steps: S1. At a temperature of 25-80° C., reacting a siloxane monomer and a vinyl siloxane under the action of an acid catalyst for 4-8 hours, and then neutralizing, extracting, distilling under reduced pressure, and drying to obtain a vinyl-modified cage-type polysilsesquioxane; S2. At a temperature of 70-80°C, the vinyl-modified cage-type polysilsesquioxane and acrylic monomer are reacted under the action of an initiator for 4-6 hours, and then subjected to reduced pressure distillation, precipitation, filtration, washing and drying to obtain an organosilicon-modified acrylic acid and / or acrylate film-forming agent.

[0023] Through the above technical scheme, the first step of the present application is to dissolve the siloxane monomer and vinyl siloxane in a molar ratio of 1: (0.05-0.25) in a polar solvent, and then add an acid catalyst dropwise while stirring at a certain temperature to react, neutralize the reaction solution, extract the organic phase, and distill under reduced pressure to remove the solvent and unreacted siloxane, and obtain a vinyl-modified cage-type polysilsesquioxane after drying, wherein the theoretical number of vinyl groups is 1-3. Among them, the polar solvent is one of tetrahydrofuran, ethylene glycol dimethyl ether, and N,N-nitrosodimethylamine. The acid catalyst is an inorganic acid or an organic acid, specifically one of concentrated hydrochloric acid, sulfuric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.

[0024] In the second step of the present application, the vinyl-modified cage-type polysilsesquioxane obtained in step S1 is dissolved in an organic solvent, and the acrylic monomer and initiator are also dissolved in an organic solvent, and then the solution containing the acrylic monomer and the initiator is slowly added dropwise into the solution containing the vinyl-modified cage-type polysilsesquioxane, and a free radical polymerization reaction is carried out at a certain temperature to obtain an organosilicon-modified acrylic acid and / or acrylate film-forming agent. In this step, functional monomers such as styrene, vinyl pyrrolidone, vinyl alcohol, and acrylonitrile can also be added to participate in the copolymerization reaction. Among them, the organic solvent used in the present application is n-heptane, and the initiator is azobisisobutyronitrile. Other conventional organic solvents and initiators used in the art can also achieve the same effect.

[0025] Preferably, in step S1, the reaction temperature is 40-80°C.

[0026] Preferably, in step S1, the reaction temperature is 60°C.

[0027] Through the above technical scheme, the present application further optimizes the reaction temperature of siloxane monomers and vinyl siloxanes, and can obtain vinyl-modified cage-type polysilsesquioxanes with more suitable molecular sizes. If the temperature is too high, the molecular weight of the vinyl-modified cage-type polysilsesquioxane is too large and does not have sufficient dissolution and processing properties, but if the temperature is too low, there may be a problem that the modification effect on the film-forming agent is not obvious. Experiments have shown that when the reaction temperature is 60°C, the molecular weight and spatial size of the obtained vinyl-modified cage-type polysilsesquioxane are most moderate, and on the basis of ensuring a good modification effect, it also has good dissolution and processing properties.

[0028] In summary, this application has the following beneficial technical effects: 1. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent of the present application combines the advantages of acrylic acid and / or acrylic acid ester film-forming agents and silicone film-forming agents, and has good water resistance and oil resistance, and can form a uniform film, effectively taking into account the softness and toughness of the film; 2. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent of the present application exhibits good performance in an aqueous system, greatly broadening the application scope of silicone-modified polymer materials in film-forming agents. DETAILED DESCRIPTION

[0029] The present application is further described in detail below with reference to the embodiments.

[0030] Material Source Unless otherwise specified, the raw materials used in this application are all commercially available products.

[0031] Example 1 A method for preparing an organosilicon-modified acrylic acid and / or acrylic acid ester film-forming agent comprises the following steps: S1. 100 mmol of methyltrimethoxysilane and 5 mmol of 1,3-divinyltetramethyldisiloxane were dissolved in 100 mL of tetrahydrofuran, and then 40 mL of acid catalyst (20 mL of concentrated hydrochloric acid, 20 mL of trifluoromethanesulfonic acid) was added dropwise to the system at a rate of 1 mL / min while stirring at a temperature of 25°C. After the addition was completed, the reaction was allowed to proceed for 4 hours, and then the reaction solution was neutralized with a saturated sodium carbonate solution. The organic phase was extracted with petroleum ether, and the solvent and unreacted siloxane were removed by distillation under reduced pressure, and then dried in vacuo to obtain a vinyl-modified cage-type polysilsesquioxane; S2. The vinyl-modified cage-type polysilsesquioxane obtained in step S1 is dissolved in 100 mL of n-heptane, preheated to 70°C, 50 mmol of methacrylic acid, 50 mmol of isodecyl acrylate and 3 mmol of azobisisobutyronitrile are dissolved in 30 mL of n-heptane, and added dropwise at a rate of 2 mL / min to the solution containing the vinyl-modified cage-type polysilsesquioxane to react for 4 hours, and then the solvent is removed by reduced pressure distillation, and the product is precipitated with methanol and water, the product is collected by filtration and washed with a small amount of methanol, and dried to obtain an organosilicon-modified acrylic acid and / or acrylate film-forming agent.

[0032] Example 2 A method for preparing an organosilicon-modified acrylic acid and / or acrylic acid ester film-forming agent comprises the following steps: S1. 100 mmol of methyltrimethoxysilane and 25 mmol of 1,3-divinyltetramethyldisiloxane were dissolved in 100 mL of ethylene glycol dimethyl ether, and then 40 mL of acid catalyst (20 mL of concentrated hydrochloric acid, 20 mL of trifluoromethanesulfonic acid) was added dropwise to the system at a rate of 1 mL / min while stirring at a temperature of 25°C. After the addition was completed, the reaction was allowed to proceed for 8 hours, and then the reaction solution was neutralized with a saturated sodium carbonate solution. The organic phase was extracted with petroleum ether, and the solvent and unreacted siloxane were removed by distillation under reduced pressure, and then dried in vacuo to obtain a vinyl-modified cage-type polysilsesquioxane; S2. The vinyl-modified cage-type polysilsesquioxane obtained in step S1 is dissolved in 100 mL of n-heptane, preheated to 80°C, 25 mmol of methacrylic acid, 25 mmol of isodecyl acrylate and 3 mmol of azobisisobutyronitrile are dissolved in 30 mL of n-heptane, and added dropwise at a rate of 2 mL / min to the solution containing the vinyl-modified cage-type polysilsesquioxane to react for 6 hours, and then the solvent is removed by reduced pressure distillation, and the product is precipitated with methanol and water, the product is collected by filtration and washed with a small amount of methanol, and dried to obtain an organosilicon-modified acrylic acid and / or acrylate film-forming agent.

[0033] Comparative Example 1 The difference from Example 1 is that in step S2, a linear organic silicon unit, namely vinyl silicone oil, is used to replace the vinyl-modified cage-type polysilsesquioxane for reaction. The specific reaction process is as follows: Vinyl silicone oil was dissolved in 100 mL of n-heptane and preheated to 80°C. 50 mmol of methacrylic acid, 50 mmol of isodecyl acrylate and 3 mmol of azobisisobutyronitrile were dissolved in 30 mL of n-heptane and added dropwise at a rate of 2 mL / min to a solution containing vinyl-modified cage-type polysilsesquioxane to react for 6 hours. The solvent was then removed by reduced pressure distillation, and the product was precipitated with methanol and water. The product was collected by filtration and washed with a small amount of methanol. After drying, a linear silicone-modified acrylic acid and / or acrylate film-forming agent with a molecular weight of about 4000 was obtained.

[0034] Comparative Example 2 The difference from Example 1 is that in step S1, the molar ratio of methyltrimethoxysilane to 1,3-divinyltetramethyldisiloxane is 1:0.5, wherein methyltrimethoxysilane is 100 mmol, and 1,3-divinyltetramethyldisiloxane is 50 mmol, and the rest is the same as Example 1.

[0035] Performance Testing The film-forming agents prepared in Examples 1-2 and Comparative Examples 1-2 and commercially available acrylic resins (acrylic resin 5000STY purchased from DAITOSOL, acrylic resin Carfil 9120NP purchased from Wanhua Chemical), and silicone resins (silicone resin MQ-1600SolidResin purchased from DOWSIL, silicone resin MQ-1640FlakeResin purchased from DOWSIL) were tested for relevant properties, and the results are shown in Table 1. The relevant performance tests include tactile properties, water resistance, oil resistance, film flexibility, film integrity, and anti-wiping ability. Among them, tactile properties, film flexibility, and film integrity are the subjective feelings of the film-forming agent after being applied to the skin. Water resistance: After the film-forming agent is applied on the skin and is completely dry, rinse with water at the same flow rate for 3 minutes and observe the shedding situation. If it is high, there is no shedding; if it is weak, there is obvious shedding. Oil resistance: Apply the film-forming agent on a glass slide and then soak it in a beaker containing isododecane. If it is high, there is no obvious shedding; if it is medium, there is partial dissolution and shedding. Anti-wiping ability: The skin is coated evenly, and after the film layer is completely dry, rinse with water according to the test conditions and rub it with the fingertips 10 times. If it is high, there is no obvious shedding; if it is medium, there is partial shedding; if it is poor, there is obvious shedding.

[0036] Table 1 Performance test results As can be seen from Table 1, compared with acrylic resin film-forming agents, the composite film-forming agent of the present application has been significantly improved in terms of water resistance, making up for the relatively insufficient water resistance and oil resistance of acrylic resin; compared with silicone resin film-forming agents, the composite film-forming agent of the present application has good film softness and toughness. Experimental data show that the acrylic acid and / or acrylate composite film-forming agent modified with cage-like silicone structure prepared in the present application combines the advantages of acrylic resin film-forming agents and silicone resin film-forming agents, and has good makeup holding, durable and anti-falling effects, and can form a uniform film without cracks. In addition, the composite film-forming agent of the present application can be used in water-based systems, greatly broadening the application scope of silicone-modified polymer materials in film-forming agents.

[0037] The difference between Comparative Example 1 and Example 1 is that a linear silicone structure is used for modification. As can be seen from Table 1, Comparative Example 1 is significantly inferior to Example 1 in terms of tactile properties, water resistance and anti-wiping ability. This indicates that the present application introduces silicone units forming a cage structure, which selectively adsorb some components in the cosmetic formula according to their different spatial sizes, thereby improving the modification effect of the silicone structure on the polyacrylic acid and / or acrylate main chain, thereby improving the various properties of the film-forming agent.

[0038] The difference between Comparative Example 2 and Example 1 is that the vinyl content in the vinyl-modified cage-type polysilsesquioxane is different. The theoretical number of vinyl groups in the vinyl-modified cage-type polysilsesquioxanes prepared in Examples 1-2 of the present application is 1-3, while the theoretical number of vinyl groups in the vinyl-modified cage-type polysilsesquioxane prepared in Comparative Example 2 is greater than 3. As can be seen from Table 1, Comparative Example 2 is significantly inferior to Example 1 in terms of tactile properties, film flexibility and film integrity. This indicates that when the number of vinyl groups is greater than 3, gelation will occur due to excessive cross-linking, and the film-forming agent cannot be evenly applied, thereby affecting the film flexibility and integrity.

[0039] To further demonstrate the effect of reaction temperature on the molecular size of vinyl-modified cage-type polysilsesquioxane, the applicant uses the following Examples 3-5 together with Example 1 for illustration.

[0040] Example 3 The difference from Example 1 is that in step S1, the reaction temperature is 40° C., and the rest is prepared in exactly the same manner as in Example 1 to obtain vinyl-modified cage-type polysilsesquioxane.

[0041] Example 4 The difference from Example 1 is that in step S1, the reaction temperature is 60° C., and the rest is prepared in exactly the same manner as in Example 1 to obtain vinyl-modified cage-type polysilsesquioxane.

[0042] Example 5 The difference from Example 1 is that in step S1, the reaction temperature is 80° C., and the rest is prepared in exactly the same manner as in Example 1 to obtain vinyl-modified cage-type polysilsesquioxane.

[0043] Performance Testing The molecular weight and pore size of the vinyl-modified cage-type polysilsesquioxane prepared in Example 1 and Examples 3-5 were detected, and then the final film-forming agent was mixed with the same color paste to form a film, and then immersed in isododecane to observe the stability of the film. The results are shown in Table 2.

[0044] Table 2 Molecular size results project Reaction temperature (℃) Molecular weight Pore ​​size (nm) Performance Example 1 25 589 3 Membrane dissolution Example 3 40 1632 8 Membrane dissolution Example 4 60 3511 12 Started to fall off after 4 hours Example 5 80 6982 22 24h film intact viscosity is too high As can be seen from Table 2, the reaction temperature has a certain influence on the molecular weight and pore size of the vinyl-modified cage-type polysilsesquioxane. Compared with Example 1, Examples 3-5 further optimize the reaction temperature at 40-80°C, which can further improve the molecular weight of the vinyl-modified cage-type polysilsesquioxane and expand the pore size, but when the temperature reaches 80°C, the molecular weight and pore size increase to a greater extent, making the film-forming agent with a higher viscosity and stronger oil resistance, which is not conducive to dissolution processing. If the temperature is further increased on this basis, it does not have sufficient dissolution processing performance. Therefore, the experimental results show that Example 4 further controls the reaction temperature to 60°C, which can make the vinyl-modified cage-type polysilsesquioxane have a moderate molecular weight and pore size, thereby ensuring a good modification effect and also having good dissolution processing performance.

[0045] On the basis of Example 4, the applicant further uses the following Examples 6-8 to further demonstrate the influence of siloxane monomers on the molecular size of vinyl-modified cage-type polysilsesquioxane.

[0046] Example 6 The difference from Example 4 is that: in step S1, dimethyldimethoxysilane is also added and dissolved in tetrahydrofuran together with methyltrimethoxysilane and 1,3-divinyltetramethyldisiloxane, wherein the amount of methyltrimethoxysilane is 95 mmol, the amount of dimethyldimethoxysilane is 5 mmol, and the amount of 1,3-divinyltetramethyldisiloxane is 5 mmol. The rest is prepared in exactly the same manner as in Example 4 to obtain a vinyl-modified cage-type polysilsesquioxane.

[0047] Example 7 The difference from Example 4 is that in step S1, dimethyldimethoxysilane is also added and dissolved in tetrahydrofuran together with methyltrimethoxysilane and 1,3-divinyltetramethyldisiloxane, wherein the amount of methyltrimethoxysilane is 90 mmol, the amount of dimethyldimethoxysilane is 10 mmol, and the amount of 1,3-divinyltetramethyldisiloxane is 5 mmol. The rest is prepared in exactly the same manner as in Example 4 to obtain a vinyl-modified cage-type polysilsesquioxane.

[0048] Example 8 The difference from Example 4 is that: in step S1, dimethyldimethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane and 1,3-divinyltetramethyldisiloxane are also added and dissolved in tetrahydrofuran, wherein the amount of methyltrimethoxysilane is 85 mmol, the amount of dimethyldimethoxysilane is 10 mmol, the amount of methyltrimethoxysilane is 5 mol, and the amount of 1,3-divinyltetramethyldisiloxane is 5 mmol, and the rest is prepared in exactly the same manner as in Example 4 to obtain a vinyl-modified cage-type polysilsesquioxane.

[0049] Performance Testing The molecular weight and pore size of the vinyl-modified cage-type polysilsesquioxane prepared in Example 4 and Examples 6-8 were detected, and then the final film-forming agent was mixed with the same color paste to form a film, and then immersed in isododecane to observe the stability of the film. The results are shown in Table 3.

[0050] Table 3 Molecular size results As can be seen from Table 3, the selection and ratio of siloxane monomers with different functionalities have a certain influence on the molecular weight and pore size of the vinyl-modified cage-type polysilsesquioxane. When the difunctional siloxane monomer is further introduced into Examples 6-7, the pore size of the vinyl-modified cage-type polysilsesquioxane is increased, which indicates that the difunctional siloxane monomer can expand the O-Si-O ring that forms the pores and increase the porosity, but it will increase the molecular weight of the vinyl-modified cage-type polysilsesquioxane, which is not conducive to dissolution processing; when the monofunctional siloxane monomer is further introduced into Example 8, compared with Example 7, the porosity is further increased and the molecular weight is reduced, which indicates that the monofunctional siloxane monomer can be used as a capping agent to limit the infinite extension of the organosilicon structural unit, thereby controlling the overall spatial size of the organosilicon molecule. Therefore, the experimental results show that when the proportion of trifunctional siloxane monomers is 85%, the proportion of difunctional siloxane monomers is 10%, and the proportion of monofunctional siloxane monomers is 5%, it can ensure that the cage-type polysilsesquioxane can modify the polyacrylic acid and / or acrylate structure, and at the same time enable the film-forming agent to have sufficient solubility and processing properties.

[0051] In summary, by optimizing the reaction temperature and the selection and ratio of siloxane monomers with different functionalities, the pore size of cage-type polysilsesquioxane can be further expanded to 20-40 nm, and the molecular weight can be controlled between 3000-4000, which not only ensures that the cage-type polysilsesquioxane can modify the structure of polyacrylic acid and / or acrylate, but also enables the film-forming agent to have sufficient solubility and processing properties.

[0052] In order to further verify the effects of the molecular size of vinyl-modified cage-type polysilsesquioxane and the monomers of acrylic acid and / or acrylate main chain on the performance of the film-forming agent in the aqueous system, the applicant further uses the following Examples 9-12 for illustration.

[0053] Example 9 The difference from Example 3 is that in step S2, the acrylic monomer dissolved in the solvent together with the initiator is 50 mmol methacrylic acid and 50 mmol hydroxyethyl acrylate, and the rest is prepared by the same method as Example 3 to prepare the film-forming agent.

[0054] Example 10 The difference from Example 4 is that in step S2, the acrylic monomer dissolved in the solvent together with the initiator is 50 mmol methacrylic acid and 50 mmol hydroxyethyl acrylate, and the rest is prepared by the same method as Example 4 to prepare the film-forming agent.

[0055] Embodiment 11 The difference from Example 5 is that in step S2, the acrylic monomer dissolved in the solvent together with the initiator is 50 mmol methacrylic acid and 50 mmol hydroxyethyl acrylate, and the rest is prepared by the same method as Example 5 to prepare the film-forming agent.

[0056] Example 12 The difference from Example 4 is that in step S2, the acrylic monomer dissolved in the solvent together with the initiator is 50 mmol methacrylic acid and 75 mmol hydroxyethyl acrylate, and the rest is prepared by the same method as Example 4 to prepare the film-forming agent.

[0057] Performance Testing The overall molecular weight and emulsion particle size of the film-forming agents prepared in Example 3 and Examples 9-12 were detected, and a film was evenly applied on the skin. After the film layer was completely dried, it was rinsed with water according to the test conditions and rubbed with the fingertips 10 times. The results are shown in Table 4.

[0058] Table 4 Performance test results The difference between Example 9 and Example 3 is that the acrylic monomer is selected differently. Example 9 selects a more hydrophilic acrylic monomer, so it has better solubility in water and stronger hydrophilicity. By comparing the data between Examples 9-12, it can be seen that smaller organic silicon structural units and longer hydrophilic segments are conducive to the film-forming agent forming a stable emulsion dispersion in the water phase, but the water and oil resistance after film formation requires that the organic silicon unit cannot be too small. In practice, the molecular weight of the organic silicon unit is controlled at 2000-4000, which can show good water resistance and makeup holding performance on the film surface.

[0059] The embodiments of this specific implementation method are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. An organosilicon-modified acrylic acid and / or acrylic acid ester film-forming agent, characterized in that: The film-forming agent structural formula is: A is an acrylic monomer, B is a functional monomer, C and D are vinyl-modified cage-type polysilsesquioxanes, a=100-10000, m=1-1000, b=0-10000, and n=1-1000.

2. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 1, characterized in that: The vinyl number in the vinyl-modified cage-type polysilsesquioxane is ≤3.

3. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 2, characterized in that: The raw materials used for the vinyl modified cage polysilsesquioxane include siloxane monomers and vinyl siloxane. By weight percentage, the siloxane monomers include 85-100% trifunctional siloxane monomers, 0-10% difunctional siloxane monomers, and 0-5% monofunctional siloxane monomers.

4. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 3, characterized in that: By weight percentage, the siloxane monomer includes 85% of trifunctional siloxane monomer, 10% of difunctional siloxane monomer, and 5% of monofunctional siloxane monomer.

5. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 1, characterized in that: The acrylic monomer includes one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, and isooctyl acrylate.

6. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 5, characterized in that: The acrylic monomer includes methacrylic acid and hydroxyethyl acrylate in a weight ratio of 1:(1-1.5).

7. The silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 1, characterized in that: The functional monomer is one of styrene, vinyl pyrrolidone, vinyl alcohol and acrylonitrile.

8. A method for preparing the silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 1, characterized in that: The following steps are involved: S1. At a temperature of 25-80° C., reacting a siloxane monomer and a vinyl siloxane under the action of an acid catalyst for 4-8 hours, and then neutralizing, extracting, distilling under reduced pressure, and drying to obtain a vinyl-modified cage-type polysilsesquioxane; S2. At a temperature of 70-80°C, the vinyl-modified cage-type polysilsesquioxane and acrylic monomer are reacted under the action of an initiator for 4-6 hours, and then subjected to reduced pressure distillation, precipitation, filtration, washing and drying to obtain an organosilicon-modified acrylic acid and / or acrylate film-forming agent.

9. The method for preparing a silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 8, characterized in that: In the step S1, the reaction temperature is 40-80°C.

10. The method for preparing a silicone-modified acrylic acid and / or acrylic acid ester film-forming agent according to claim 9, characterized in that: In the step S1, the reaction temperature is 60°C.

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