A silicone-modified polyurethane film-forming agent, and a method for preparing and using the same

Abstract

The application discloses a kind of organic silicon modified polyurethane film forming agent and its preparation method and application.The preparation method includes the following steps: preparing dispersed phase, continuous phase and water phase respectively;Dispersed phase is added to continuous phase for shearing emulsification, and O / O type emulsion is obtained;Then, water phase is added and heated to react, and the organic silicon modified polyurethane film forming agent is prepared.The organic silicon modified polyurethane film forming agent containing active ingredients is prepared by using specific process, which is suitable for oil-based formula system.The active ingredients are loaded in the organic silicon modified polyurethane matrix, which can ensure excellent film forming performance, improve the ability of anti-makeup removal, realize uniform anchoring of active ingredients in makeup film, continuously exert the efficacy of active ingredients, effectively inhibit oxidation and further prolong the makeup effect, and provide an effective new strategy for improving the long-lasting makeup effect of foundation product.

Description

Technical Field

[0001] This invention relates to the field of organosilicon materials technology, specifically to an organosilicon-modified polyurethane film-forming agent, its preparation method, and its application. Background Technology

[0002] Base makeup products (such as liquid foundation, cream foundation, and concealer) commonly face problems like makeup fading, dullness, and short wear time due to factors such as sebum secretion, sweat, friction, and oil oxidation. One of the core demands of consumers for base makeup products is "long-lasting wear," requiring the makeup to remain intact, vibrant, and without patchiness or dullness for several hours. Currently, adding film-forming agents is a common method to improve makeup staying power. These agents primarily utilize the formation of a continuous film on the skin's surface to effectively fix makeup particles and enhance resistance to migration, water, and friction. Polyurethane film-forming agents have been used in some color cosmetic products due to their excellent film-forming continuity, flexibility, and skin affinity. However, traditional polyurethane film-forming agents are mostly water-based polyurethanes, which usually have problems such as slow film-forming speed and poor initial water resistance. Moreover, due to the significant difference between their polarity and oil-based systems, they have poor compatibility in oil-based formulations, making it difficult to achieve uniform dispersion and effective film formation. This greatly limits their application in oil-based makeup products such as liquid foundation, cream foundation, and concealer.

[0003] On the other hand, unsaturated fatty acids in the base of foundation products are prone to auto-oxidation upon contact with air and light, leading to darkening and dulling of the color, thus affecting the makeup effect. To address this, some studies have focused on adding antioxidant active ingredients to the formula, utilizing their ability to scavenge lipid peroxidation free radicals to inhibit base oxidation and extend makeup wear. However, directly added active ingredients lack effective retention and protection mechanisms; after makeup application, these active ingredients are easily washed away or transferred by sweat, sebum, or daily friction on the skin's surface, making it difficult for them to continuously exert their antioxidant effect on the makeup surface. This results in limited improvement in makeup wear and unsatisfactory performance in practical applications.

[0004] Therefore, the present invention aims to develop a polyurethane film-forming agent suitable for oil-based makeup formulations to meet the usage needs of makeup products that seek long-lasting makeup effects. Summary of the Invention

[0005] To overcome the shortcomings of the existing technology, the present invention aims to provide a method for preparing a silicone-modified polyurethane film-forming agent, which can obtain a silicone-modified polyurethane containing active ingredients. This method is suitable for oil-based formulation systems. By loading the active ingredients into the silicone-modified polyurethane matrix, while ensuring excellent film-forming performance and improving makeup resistance, the active ingredients are uniformly anchored in the makeup film and can continuously exert their active ingredient effects, effectively inhibiting oxidation and further prolonging the makeup effect. This provides an effective new strategy for improving the long-lasting makeup effect of base makeup products.

[0006] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a method for preparing an organosilicon-modified polyurethane film-forming agent, comprising the following steps: S1. Hydroxy silicone oil and diisocyanate are subjected to a prepolymerization reaction to obtain an organosilicon-modified polyurethane prepolymer. After the reaction is completed, a polar aprotic solvent is added, followed by the addition of cosmetic active ingredients. After uniform dispersion, a dispersed phase is obtained. S2. Dissolve and disperse the emulsifier in isododecane to obtain a continuous phase; S3. Dissolve a water-soluble chain extender containing amino or hydroxyl groups in water to form the aqueous phase; S4. The dispersed phase is added to the continuous phase for shear emulsification to obtain an O / O type emulsion; then the aqueous phase is added and the temperature is raised to react. After the reaction is completed, the organosilicon-modified polyurethane film-forming agent is prepared.

[0007] Further, in step S1, the hydroxyl silicone oil is selected from at least one of single-terminated diol hydroxyl silicone oil and double-terminated monool hydroxyl silicone oil.

[0008] The single-terminal diol hydroxyl silicone oil has the structure shown in formula (1): Equation (1); The dual-terminated monool hydroxyl silicone oil has the structure shown in formula (2): Equation (2); In formulas (1) and (2), a, b, j, and k are each positive integer greater than or equal to 1; n1, n2, m1, and m2 are each 2 or 3; R1 and R2 are each selected from any one of alkyl groups with 1-22 carbon atoms, aryl groups with 6-18 carbon atoms, and polymer chains with a number average molecular weight of 500-2000, wherein the polymer chain is any one of polyether, polyester, or polyacrylate. Preferably, R1 and R2 are each independently selected from any one of methyl, ethyl, heptyl, octyl, phenyl, polyether, polyester, and polyacrylate with a number average molecular weight of 500-2000.

[0009] Preferably, the number-average molecular weight of the hydroxyl silicone oil is 500-10000 g / mol; Further, in step S1, the diisocyanate is selected from at least one of aliphatic diisocyanates and aromatic diisocyanates.

[0010] The aliphatic diisocyanate is preferably selected from at least one of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, and methylcyclohexane diisocyanate.

[0011] The aromatic diisocyanate is preferably selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, dimethyl terephthalic diisocyanate, isophthalic diisocyanate, and 1,5-naphthalene diisocyanate. Further, in step S1, the polar aprotic solvent is a solvent that does not react with isocyanate monomers. Preferably, the polar aprotic solvent is selected from at least one of dimethyl carbonate, dimethylformamide, and dimethylacetamide, more preferably dimethyl carbonate.

[0012] Further, in step S1, the cosmetic active ingredient is selected from fat-soluble active ingredients with antioxidant functions. Preferably, the cosmetic active ingredient is selected from at least one of vitamin E, vitamin E derivatives, β-carotene, ferulic acid, coenzyme Q10, lipoic acid, or gallic acid esters; more preferably, the cosmetic active ingredient is selected from vitamin E.

[0013] Furthermore, in step S1, the molar ratio of -NCO to -OH in the prepolymerization reaction system is (1.4-2.6):1.

[0014] Furthermore, in step S1, the mass percentage content of the polar aprotic solvent in the dispersed phase is 15%-50%, and the mass percentage content of the cosmetic active ingredient is 10%-25%.

[0015] Furthermore, in step S1, the temperature of the prepolymerization reaction is 60-130°C, and the reaction time is 1-6 hours. Preferably, the reaction is carried out in an inert gas atmosphere.

[0016] Preferably, the hydroxyl silicone oil is subjected to high-temperature vacuum dehydration treatment before the reaction. The dehydration treatment conditions are: temperature 90~110℃, vacuum degree -0.01~-0.09MPa, and dehydration treatment time 1~3h.

[0017] Furthermore, in step S1, the prepolymerization system also includes a diol chain extender. Preferably, the diol chain extender is selected from aliphatic diols having 4-12 carbon atoms; more preferably, it is at least one selected from 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 3-methyl-1,5-pentanediol.

[0018] Furthermore, the molar ratio of the diol chain extender to the isocyanate is 1:(2-5).

[0019] Further, in step S2, the emulsifier is selected from polyether-modified silicone emulsifiers. Preferably, the HLB value of the polyether-modified silicone emulsifier is 3-6.

[0020] Furthermore, the mass ratio of the emulsifier to isododecane is 1:(2-9).

[0021] Further, in step S3, the water-soluble chain extender is selected from at least one of aliphatic diamines and aliphatic diols.

[0022] The aliphatic diamine is preferably at least one of isophorone diamine and ethylenediamine.

[0023] The aliphatic diol is preferably at least one of butanediol and propylene glycol.

[0024] Preferably, the water-soluble chain extender in the aqueous phase has a mass percentage content of 1%-10%.

[0025] Further, in step S4, the mass ratio of the dispersed phase, the continuous phase, and the aqueous phase is 1:(1.5-4):(0.05-0.25).

[0026] Furthermore, in step S4, the shearing speed for high-speed shear emulsification is 2500-4000 rpm.

[0027] Furthermore, in step S4, the reaction temperature is 40-50℃ and the reaction time is 3-7h.

[0028] Furthermore, in step S4, after the reaction is complete, isododecane can be added to reach the required solid content as needed.

[0029] In a second aspect, the present invention provides an organosilicon-modified polyurethane film-forming agent, which is prepared by the preparation method described in the first aspect.

[0030] Furthermore, the solid content of the organosilicon-modified polyurethane film-forming agent of the present invention is 15%-80%.

[0031] Thirdly, this invention provides the application of the aforementioned silicone-modified polyurethane film-forming agent in cosmetics. The cosmetics may be, for example, oil-based cosmetics such as foundation, cream foundation, concealer, and lip gloss.

[0032] Fourthly, the present invention provides a cosmetic composition comprising the silicone-modified polyurethane film-forming agent described in the second aspect.

[0033] The present invention has the following beneficial effects: This invention prepares a silicone-modified polyurethane film-forming agent containing active ingredients using a specific process. This agent exhibits good compatibility with oil-based cosmetic formulations, enabling uniform dispersion and rapid film formation. It effectively fixes makeup particles and significantly enhances makeup resistance. Simultaneously, by loading the active ingredients into a silicone-modified polyurethane matrix, the active ingredients are uniformly anchored and distributed within the makeup film during use. This continuously scavenges lipid peroxidation free radicals on the makeup surface, effectively inhibiting color darkening and dulling of base makeup products caused by oxidation. This significantly prolongs the makeup's staying power and maintains a bright complexion, providing an effective new strategy for improving the long-lasting effect of base makeup products. Attached Figure Description

[0034] Figure 1 This is a schematic diagram illustrating the effect of applying foundation in Example 1. The left image is a photo before applying foundation, and the right image is a photo after applying foundation. Figure 2 This is a schematic diagram illustrating the effect of using the lip gloss in Example 2. Detailed Implementation

[0035] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0036] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0037] Unless otherwise specified, room temperature or normal temperature in the embodiments of the present invention refers to 25±1℃. Example 1

[0038] This embodiment provides an organosilicon-modified polyurethane film-forming agent, the preparation method of which is as follows (the following component amounts are by weight): (1) Add 50 parts of hydroxyl silicone oil (double-terminated monool hydroxyl silicone oil, number average molecular weight of 1500 g / mol, Silok-8812F2) to the reaction vessel, and slowly heat it to 100°C while stirring. Then turn on the vacuum dehydration system for 1 hour and the vacuum degree is -0.09 MPa. After the vacuum dehydration is completed, add 18.5 parts of isophorone diisocyanate at 100°C, turn on the nitrogen protection system, heat it to 110°C and keep it at the temperature for 4 hours. After the reaction is completed, add 40 parts of dimethyl carbonate and 16 parts of vitamin E. After dispersing evenly, disperse phase I is obtained. (2) Stir 85 parts of isododecane and 15 parts of emulsifier (polyether modified silicone emulsifier, SiCare2216F) until completely dissolved and homogeneous to obtain continuous phase I; (3) Mix 3 parts of ethylenediamine and 32.5 parts of deionized water and stir until homogeneous to obtain aqueous phase I; (4) 60 parts of continuous phase I were transferred to a high-speed shear emulsifier and stirred at 3000 rpm. Then, 35 parts of dispersed phase I were added while stirring. After the dispersed phase was added, it was sheared and emulsified at 3000 rpm for 10 min to obtain an O / O type emulsion. The emulsion was then transferred to a reaction vessel equipped with a heating and stirring device. 5 parts of aqueous phase I were slowly added while stirring at 400 rpm. After the addition was completed, the temperature was raised to 45°C and kept at that temperature for 5 h. After the reaction was completed, organosilicon modified polyurethane film-forming agent I was prepared with a solid content of about 33%. Example 2

[0039] This embodiment provides an organosilicon-modified polyurethane film-forming agent, the preparation method of which is as follows (the following component amounts are by weight): (1) Add 70 parts of hydroxyl silicone oil (double-terminated monool hydroxyl silicone oil, number average molecular weight of 1800 g / mol, Silok-8812F4) to the reaction vessel, and slowly heat it to 110°C while stirring. Then turn on the vacuum dehydration system for 3 hours and the vacuum degree is -0.07 MPa. After the vacuum dehydration is completed, add 10 parts of terephthalic diisocyanate at 60°C, turn on the nitrogen protection system, and keep the reaction at 60°C for 1 hour. After the reaction is completed, add 34 parts of dimethyl carbonate and 19 parts of vitamin E. After the mixture is evenly dispersed, dispersed phase II is obtained. (2) Stir 85 parts of isododecane and 15 parts of emulsifier (polyether modified silicone emulsifier, SiCare2216F) until completely dissolved and homogeneous to obtain continuous phase II; (3) Mix 1 part ethylenediamine and 38 parts deionized water evenly to obtain aqueous phase II; (4) 60 parts of continuous phase II were transferred to a high-speed shear emulsifier and stirred at 3000 rpm. Then, 35 parts of dispersed phase II were added while stirring. After the dispersed phase was added, it was sheared and emulsified at 3000 rpm for 10 min to obtain an O / O type emulsion. The emulsion was then transferred to a reaction vessel equipped with a heating and stirring device. 5 parts of aqueous phase II were slowly added while stirring at 400 rpm. After the addition was completed, the temperature was raised to 45°C and kept at that temperature for 5 h. After the reaction was completed, organosilicon modified polyurethane film-forming agent II was prepared with a solid content of about 33%. Example 3

[0040] This embodiment provides an organosilicon-modified polyurethane film-forming agent, the preparation method of which is as follows (the following component amounts are by weight): (1) Add 60 parts of hydroxyl silicone oil (double-terminated monool hydroxyl silicone oil, number average molecular weight of 4500 g / mol, Silok-8814F4) to the reaction vessel, and slowly heat it to 100°C while stirring. Then turn on the vacuum dehydration system for 3 hours and the vacuum degree is -0.08 MPa. After the vacuum dehydration is completed, add 30.6 parts of isophorone diisocyanate and 5 parts of 1,4-butanediol at 110°C. Turn on the nitrogen protection system and heat it to 130°C for 6 hours. After the reaction is completed, add 24 parts of dimethyl carbonate and 23 parts of vitamin E. After dispersing evenly, dispersed phase III is obtained. (2) Mix 85 parts of isododecane and 15 parts of emulsifier (polyether modified silicone emulsifier, SiCare2216F) and stir until completely dissolved and homogeneous to obtain continuous phase III; (3) Mix 3 parts of ethylenediamine and 46 parts of deionized water and stir until homogeneous to obtain aqueous phase III; (4) 60 parts of continuous phase III were transferred to a high-speed shear emulsifier and stirred at 3000 rpm. Then, 35 parts of dispersed phase III were added while stirring. After the dispersed phase was added, the mixture was sheared and emulsified at 3000 rpm for 10 min to obtain an O / O type emulsion. The emulsion was then transferred to a reaction vessel equipped with a heating and stirring device. 4 parts of aqueous phase III were slowly added while stirring at 400 rpm. The temperature was raised to 45°C and kept at that temperature for 5 h. After the reaction was completed, 12 parts of isododecane were added to prepare organosilicon modified polyurethane film-forming agent III with a solid content of about 33%. Example 4

[0041] This embodiment provides an organosilicon-modified polyurethane film-forming agent, the preparation method of which is as follows (the following component amounts are by weight): (1) Add 60 parts of hydroxyl silicone oil (double-terminated monool hydroxyl silicone oil, number average molecular weight of 1000 g / mol, Silok-8802) to the reaction vessel, and slowly heat it to 100°C while stirring. Then turn on the vacuum dehydration system for 3 hours and the vacuum degree is -0.08 MPa. After the vacuum dehydration is completed, add 24 parts of hexamethylene diisocyanate and 3.5 parts of 1,6-hexanediol at 100°C, turn on the nitrogen protection system, heat it to 110°C and keep it at the temperature for 4 hours. After the reaction is completed, add 29 parts of dimethyl carbonate and 21 parts of vitamin E. After dispersing evenly, disperse phase IV is obtained. (2) Mix 85 parts of isododecane and 15 parts of emulsifier (polyether modified silicone emulsifier, SiCare2216F) and stir until completely dissolved and homogeneous to obtain continuous phase IV; (3) Mix 2.3 parts of ethylenediamine and 42 parts of deionized water and stir until homogeneous to obtain aqueous phase IV; (4) 60 parts of continuous phase IV were transferred to a high-speed shear emulsifier and stirred at 3000 rpm. Then, 35 parts of dispersed phase IV were added while stirring. After the dispersed phase was added, the mixture was sheared and emulsified at 3000 rpm for 10 min to obtain an O / O type emulsion. The emulsion was then transferred to a reaction vessel equipped with a heating and stirring device. 5 parts of aqueous phase IV were slowly added while stirring at 400 rpm. The temperature was raised to 45°C and kept at that temperature for 5 h. After the reaction was completed, 12 parts of isododecane were added to prepare organosilicon modified polyurethane film-forming agent IV with a solid content of about 33%.

[0042] Comparative Example 1 This comparative example provides an organosilicon-modified polyurethane film-forming agent. The difference between its preparation method and that of Example 1 is that vitamin E is not added in step (1), and the remaining steps are the same as those of Example 1. An organosilicon-modified polyurethane film-forming agent V without vitamin E is prepared.

[0043] Comparative Example 2 This comparative example provides an organosilicon-modified polyurethane film-forming agent, which is prepared as follows (the following component amounts are by weight): Take 100 parts of organosilicon-modified polyurethane film-forming agent V of Comparative Example 1, add 16 parts of vitamin E, and stir at 500 rpm for 30 minutes at room temperature to disperse vitamin E in the film-forming agent, thereby preparing organosilicon-modified polyurethane film-forming agent VI.

[0044] Comparative Example 3 This comparative example provides a polyurethane film-forming agent, the preparation method of which differs from that of Example 1 only in that 50 parts of hydroxyl silicone oil are replaced with 33 parts of PTMEG-1000 (Korean PTG) in step (1), and the remaining steps are the same as those in Example 1; a non-silicone modified polyurethane film-forming agent VII is prepared.

[0045] Relevant performance tests: 1. Vitamin E loading rate determination Accurately weigh 1g of sample, add 10mL of ethanol to break the emulsion, centrifuge at 10000r / min for 20 minutes, then take the supernatant and determine the free vitamin E content by high performance liquid chromatography (HPLC); loading rate (%) = (total vitamin E content - free vitamin E content) / total vitamin E content × 100%.

[0046] 2. Storage stability test The film-forming agent sample was placed in a 40℃ constant temperature incubator for accelerated storage for 4 weeks. The vitamin E loading rate of the sample before and after accelerated storage was tested, and the loading retention rate was calculated. Load retention rate = Loading rate before accelerated storage / Loading rate after accelerated storage × 100%.

[0047] 3. Film-forming performance test The film-forming agent sample to be tested was uniformly coated onto a transparent polyester film substrate (wet film thickness approximately 100 μm) and dried at room temperature for 24 hours to form a film. The appearance and continuity of the film were observed; and the film adhesion level was tested according to the cross-cut adhesion test method of standard GB / T 9286-2021.

[0048] 4. Sweat resistance test The film-formed sample was immersed in artificial sweat (prepared according to the preparation method of acidic test solution in GB / T 3922) and shaken at 37℃ and 100 r / min. Samples were taken at 0h and 24h, and the vitamin E content in the film at 0h and 24h was measured and the retention rate was calculated. The method for testing vitamin E content is as follows: cut a quantitative membrane (10cm×10cm) and grind it into fragments, add hexane / isopropanol (9:1 mass ratio) solvent and sonicate for 30 minutes, let it stand and take the supernatant, and determine it by high performance liquid chromatography (HPLC).

[0049] Retention rate (%) = C 24h / C 0h ×100%; C 0h The vitamin E content in the membrane sampled at 0h; C 24h The content of vitamin E in the membrane sampled over 24 hours.

[0050] The performance test results are shown in Table 1.

[0051] Table 1 Performance test results of the film-forming agents in Examples 1-4 and Comparative Examples 1-3

[0052] The results above show that the method of the present invention can prepare an organosilicon-modified polyurethane film-forming agent containing active ingredients, which can achieve stable loading of active ingredients and has excellent film-forming properties. The film is continuous and transparent with high adhesion (reaching level 1-3).

[0053] Application Example 1 The film-forming agent from Example 1 was used to prepare a liquid foundation, and the liquid foundation formulation is shown in Table 2.

[0054] Table 2 Foundation formulation for Application Example 1 (by mass percentage)

[0055] Preparation steps: S1. After accurately weighing all the raw materials of component A, put them into the grinding equipment and grind them thoroughly until the system is completely homogeneous and free of particles; then add component B and homogenize at a high speed of 3000 rpm for 5 minutes until the system is homogeneous; then add component C, continue homogenizing, heat to 75℃ to obtain the oil phase, and keep it warm for later use. S2. After accurately weighing each component of the aqueous phase, mix them in a mixing tank, stir at 200 rpm and heat to 75°C to completely dissolve sodium chloride, glycerol and butanediol to obtain the aqueous phase, and keep it warm for later use; S3. While stirring, slowly add the aqueous phase dropwise to the oil phase. After the addition is complete, homogenize and emulsify at a high speed of 3000 rpm for 4 minutes. After emulsification, cool to 45°C, add the preservative, and stir evenly at 200 rpm to prepare the finished foundation liquid.

[0056] Apply an appropriate amount of foundation to the back of your hand. It is easy to spread and blends quickly and evenly. After application, it forms a film quickly, adheres to the skin without caking, and provides natural coverage. See results for usage effects. Figure 1 .

[0057] After applying foundation, the back of the hand was subjected to a water spray test. The surface was hydrophobic and the makeup did not smudge, demonstrating high water resistance. After applying oil, the makeup did not smudge easily, demonstrating high oil resistance.

[0058] Comparative Application Example 1 The only difference from Application Example 1 is that the film-forming agent of Comparative Example 1 is used for the oil phase C component. The rest is the same as Application Example 1, and the finished liquid foundation is prepared.

[0059] Comparative Application Example 2 The only difference from Application Example 1 is that the film-forming agent of Comparative Example 2 is used for the oil phase C component. The rest is the same as Application Example 1, and the finished liquid foundation is prepared.

[0060] Comparative Application Example 3 The only difference from Application Example 1 is that the film-forming agent of Comparative Example 3 is used for the oil phase C component; otherwise, the same as Application Example 1 is used to prepare the finished liquid foundation.

[0061] Comparative Application Example 4 The only difference from Application Example 1 is that component C is not added to the oil phase; otherwise, it is the same as Application Example 1, and the finished liquid foundation is prepared.

[0062] The foundation prepared in Application Example 1 and Comparative Application Examples 1-4 were tested for their makeup-holding performance. The test methods are as follows: 1. Friction-based makeup retention test The foundation sample was tested at 2 mg / cm³. 2 Apply the product evenly to a PMMA plate and allow it to air dry for 10 minutes to form a makeup film. Using a rubbing fastness tester, apply a certain pressure to the surface of the makeup film (the rubbing head is a dry cotton cloth with a load of 500g) and perform reciprocating rubbing (speed 30 times / min, number of rubbing cycles 30 times).

[0063] (1) Use a colorimeter to measure the L*a*b* values ​​of the makeup film area before and after rubbing, and calculate the total color difference value ΔE. The smaller the ΔE value, the stronger the anti-makeup removal ability.

[0064] (2) Weigh the changes in mass of the PMMA plate before and after friction, and calculate the coating peeling rate (%).

[0065] 2. Anti-dullness test The foundation sample was tested at 2 mg / cm³. 2 Apply the mixture evenly to a PMMA plate and place it in a simulated sunlight aging chamber (irradiance of 0.55 W / m²). 2 The paint film was continuously irradiated for 4 hours at a wavelength of 340nm, a blackboard temperature of 45±2℃, and a relative humidity of 50±5%. Before and after irradiation, the L*a*b* values ​​of the paint film area were measured, and the total color difference value ΔE and the change in b value (Δb) were calculated. The larger the ΔE and Δb values, the more severe the yellowing / dulling of the paint film.

[0066] The test results are shown in Table 3.

[0067] Table 3. Test results of makeup holding performance in Application Example 1 and Comparative Application Examples 1-4

[0068] The results above show that the film-forming agent of the present invention has good compatibility with the oil-based cosmetic formulation system, can be evenly dispersed and achieve rapid film formation, effectively fix makeup particles, and significantly improve the ability to resist makeup removal; at the same time, the active ingredients in the film-forming agent can continuously remove lipid peroxidation free radicals on the makeup surface, effectively inhibit the color darkening and dulling of the base makeup product caused by oxidation, thereby significantly prolonging the makeup effect of the base makeup product.

[0069] Application Example 2 The film-forming agent of Example 1 was used to prepare lip gloss, and the lip gloss formulation is shown in Table 4.

[0070] Table 4. Lip gloss formulation for Application Example 2 (by weight percentage)

[0071] Preparation steps: After accurately weighing all the raw materials of phase A, put them into a beaker and heat them to 85°C until they are completely dissolved. Then add the raw materials of phase B and keep them at 85°C while stirring evenly. Then add the raw materials of phase C and stir evenly. Grind the mixture three times with a three-roll mill until the material is fine and uniform. After the material cools down to 45°C, add phase D and stir evenly to prepare the finished lip gloss.

[0072] Apply an appropriate amount of lip gloss to the back of your hand. It spreads easily and forms a film quickly; the film feels light and adheres well to the skin, with excellent color retention and anti-migration properties, preventing smudging and fading. See results for usage effects. Figure 2 .

Claims

1. A method for preparing an organosilicon-modified polyurethane film-forming agent, characterized in that, Includes the following steps: S1. Hydroxy silicone oil and diisocyanate are subjected to a prepolymerization reaction to obtain an organosilicon-modified polyurethane prepolymer. After the reaction is completed, a polar aprotic solvent is added, followed by the addition of cosmetic active ingredients. After uniform dispersion, a dispersed phase is obtained. The molar ratio of -NCO to -OH in the prepolymerization reaction system is (1.4-2.6):1; The active ingredients in the cosmetics are selected from fat-soluble active ingredients with antioxidant functions; The dispersed phase contains 15%-50% by mass of polar aprotic solvent and 10%-25% by mass of cosmetic active ingredients. S2. Dissolve and disperse the emulsifier in isododecane to obtain a continuous phase; S3. Dissolve a water-soluble chain extender containing amino or hydroxyl groups in water to form the aqueous phase; S4. The dispersed phase is added to the continuous phase for shear emulsification to obtain an O / O type emulsion; then the aqueous phase is added and the temperature is raised to react. After the reaction is completed, the organosilicon-modified polyurethane film-forming agent is prepared.

2. The preparation method according to claim 1, characterized in that, In step S1, the hydroxyl silicone oil is selected from at least one of single-terminated diol hydroxyl silicone oil and double-terminated monool hydroxyl silicone oil; The single-terminal diol hydroxyl silicone oil has the structure shown in formula (1): Equation (1); The dual-terminated monool hydroxyl silicone oil has the structure shown in formula (2): Equation (2); In formulas (1) and (2), a, b, j, and k are each positive integer greater than or equal to 1; n1, n2, m1, and m2 are each 2 or 3; R1 and R2 are each selected from any one of alkyl groups with 1-22 carbon atoms, aryl groups with 6-18 carbon atoms, and polymer chains with a number average molecular weight of 500-2000, wherein the polymer chain is any one of polyether, polyester, or polyacrylate. The number-average molecular weight of the hydroxyl silicone oil is 500-10000 g / mol; The diisocyanate is selected from at least one of aliphatic diisocyanates and aromatic diisocyanates; the aliphatic diisocyanate is selected from at least one of hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, and methylcyclohexane diisocyanate; the aromatic diisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophenyl diisocyanate, and 1,5-naphthalene diisocyanate. The polar aprotic solvent is selected from at least one of dimethyl carbonate, dimethylformamide, and dimethylacetamide; The active ingredient in the cosmetic is selected from at least one of vitamin E, beta-carotene, coenzyme Q10, or gallic acid esters.

3. The preparation method according to claim 1, characterized in that, In step S1, the temperature of the prepolymerization reaction is 60℃-130℃, and the reaction time is 1-6h.

4. The preparation method according to claim 1, characterized in that, In step S1, the prepolymerization system also includes a diol chain extender; the diol chain extender is selected from aliphatic diols with 4-12 carbon atoms; the molar ratio of the diol chain extender to the diisocyanate is 1:(2-5).

5. The preparation method according to claim 1, characterized in that, In step S2, the emulsifier is selected from polyether-modified silicone emulsifier; the HLB value of the polyether-modified silicone emulsifier is 3-6; and the mass ratio of the emulsifier to isododecane is 1:(2-9).

6. The preparation method according to claim 1, characterized in that, In step S3, the water-soluble chain extender is selected from aliphatic diamines or aliphatic diols; the aliphatic diamine is selected from at least one of isophorone diamine and ethylenediamine; the aliphatic diol is selected from at least one of butanediol and propylene glycol; and the mass percentage of the water-soluble chain extender in the aqueous phase is 1%-10%.

7. The preparation method according to claim 1, characterized in that, In step S4, the mass ratio of the dispersed phase, continuous phase, and aqueous phase is 1:(1.5-4):(0.05-0.25); the shearing speed for shear emulsification is 2500-4000 rpm; the reaction temperature is 40-50℃; and the reaction time is 3-7 h.

8. An organosilicon-modified polyurethane film-forming agent, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

9. The organosilicon-modified polyurethane film-forming agent according to claim 8, characterized in that, The solid content of the organosilicon-modified polyurethane film-forming agent is 15%-80%.

10. A cosmetic composition, characterized in that, Includes the organosilicon-modified polyurethane film-forming agent as described in claim 8.

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