A quick-drying organosiloxane-polyurethane film-forming agent, a method for preparing the same, and a cosmetic

Abstract

The application provides a quick-drying organosiloxane-polyurethane film-forming agent, a preparation method thereof and a cosmetic, and relates to the cosmetic field. The raw materials of the quick-drying organosiloxane-polyurethane film-forming agent include a hydroxyl-containing polysiloxane, a polyisocyanate, a crosslinking agent, a blocking agent and a volatile oil substance. The molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 1-4:1. The molar ratio of the polyisocyanate to the crosslinking agent is 3-8:1. The mass ratio of the polyisocyanate to the blocking agent is 5-10:1. The mass of the volatile oil substance accounts for 65-75% of the total mass of the raw materials. The quick-drying organosiloxane-polyurethane film-forming agent overcomes the common tight and rigid defects of commercially available silicone resins, and has outstanding performance in the aspects of use feeling, fit and film-forming property. Finally, the beneficial effects of high stability, refreshing skin feeling, quick film-forming, long-acting makeup, uniform makeup effect and the like are achieved.

Description

Technical Field

[0001] This application relates to the field of cosmetics, and more particularly to a fast-drying organosiloxane-polyurethane film-forming agent, its preparation method, and cosmetics. Background Technology

[0002] Film-forming agents are functional materials that can form continuous, uniform, and stable thin films on substrate surfaces through physical or chemical means. They can alter interfacial properties and impart specific functions or provide protection to the substrate, making them key components in coatings, adhesives, and composite materials. Film-forming agents are also widely used in daily chemical products, including lipsticks, mascaras, foundations, sunscreens, hairsprays, and nail polishes. However, the performance requirements for film-forming agents in the daily chemical industry differ significantly from those in other fields. Besides focusing on the physicochemical properties of the film after formation (such as flexibility, water / sweat resistance, and breathability), user experience and sensory attributes must also be considered, including skin feel (such as silky smoothness and non-stickiness), texture, odor, ease of removal (such as removal with warm water), and safety (non-irritating). Film-forming agents can impart various functions to daily chemical products, such as moisturizing, sun protection, sweat and water resistance, styling, smudge-proof properties, and increased shine. In formulation design, the synergistic effect of film-forming agents with other components such as moisturizers, sunscreens, and pigments is increasingly valued to achieve a balance between lightweight breathability and long-lasting makeup. Although the amount of film-forming agent added to the formulation is small, it largely determines the final user experience and efficacy of the product, serving as a key bridge connecting "ingredients" and "experience".

[0003] Organosilicon film-forming agents are widely used as functional ingredients in color cosmetics, UV-protective cosmetics, and hair care cosmetics due to their excellent film-forming ability and resistance to water, sweat, and sebum. Currently, phenyl organosilicon resins with high phenyl content and organopolysiloxane polymers modified with long-chain alkyl, polyether, or polyglycerol chains have been developed on the market to further improve the water resistance, sweat resistance, durability, and gloss of products. MQ silicone film-forming agents have good film-forming properties and are one of the most widely used film-forming agents in daily chemical products. They are often used in setting sprays, sunscreens, and other products to provide waterproof, breathable, and makeup-setting effects. However, the film formed by MQ film-forming agents is relatively brittle, has uneven thickness, and its adhesion is easily affected by oil components, resulting in insufficient product spreadability, skin adherence, and durability. Furthermore, organosilicon resins with high phenyl content or long-chain alkyl modification have poor compatibility with organosilicon or alkane-based oily components.

[0004] In formulation practice, the compatibility of film-forming agents with other components in the formulation is crucial, especially with silicone oils. Organosilicon film-forming agents (such as silicone resins) have good compatibility with silicone oils, forming uniform and transparent films, but poor compatibility with alkane oils. Commercially available polyurethane-modified and acrylate-modified organosilicon film-forming agents, while combining the excellent skin feel of organosilicon with the film-forming strength of polyurethane or acrylate and exhibiting good compatibility with alkane oils, do not have ideal compatibility with silicone oils. This is particularly true when compounded with volatile, low-viscosity silicone oils (such as cyclopentamethoxysiloxane, polydimethylsiloxane, etc.), where problems such as precipitation, turbidity, layering, or uneven film formation are prone to occur. Volatile low-viscosity silicone oils are widely used as solvents or skin feel modifiers in daily chemical products, providing a refreshing and fast-evaporating user experience. However, poor compatibility between them and film-forming agents can lead to decreased product stability, white spots or uneven film formation during application, and ultimately affect the final makeup effect and sensory quality.

[0005] In summary, while existing silicone resins modified with high phenyl content or long-chain alkyl groups, as well as polyurethane and acrylate-modified silicone film-forming agents, can improve film strength, water and sweat resistance, and long-lasting makeup effects, their compatibility with volatile, low-viscosity silicone oils is generally poor. In actual formulations, when these film-forming agents are compounded with commonly used refreshing skin-feel modifiers, stability problems such as precipitation, turbidity, layering, or uneven film formation easily occur. Currently, commercially available modified silicone film-forming agents struggle to simultaneously achieve good compatibility with low-viscosity silicone oils, a refreshing user experience, and long-lasting film-forming performance, becoming a significant technical bottleneck restricting the optimization of daily chemical product formulations.

[0006] Therefore, there is an urgent need to develop a novel modified film-forming agent that has good compatibility with volatile, low-viscosity silicone oil and also possesses excellent film-forming properties. Summary of the Invention

[0007] The purpose of this application is to provide a fast-drying organosiloxane-polyurethane film-forming agent, its preparation method, and cosmetics, in order to solve the problems of precipitation, turbidity, layering, and uneven film formation that easily occur when existing polyurethane organosilicone film-forming agents are compounded.

[0008] To achieve the above objectives, the first aspect of this application provides a fast-drying organosiloxane-polyurethane film-forming agent, the raw materials of which include hydroxyl-containing polysiloxane, polyisocyanate, crosslinking agent, capping agent, and volatile oil substances; The molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 1-4:1; The molar ratio of the polyisocyanate to the crosslinking agent is 3-8:1; The mass ratio of the polyisocyanate to the capping agent is 5-10:1; The volatile oils account for 65-75% of the total mass of the raw materials.

[0009] Optionally, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The crosslinking agent includes a polyol; the polyol includes at least one of glycerol, trimethylolethane, trimethylolpropane, tri(hydroxymethyl)aminomethane, pentaerythritol, sorbitol, and mannitol; (2) The capping agent includes a small molecule alcohol, which includes at least one of methanol, ethanol, isopropanol, and n-butanol; (3) The volatile oils include volatile silicone oils and / or volatile organic oils.

[0010] Optionally, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The volatile silicone oil includes at least one of dimethyl silicone oil, decamethylcyclopentasiloxane, cyclohexylsiloxane, and methyl polytrimethylsiloxane; (2) The volatile organic oil includes at least one of light isoparaffin, isododecane, light liquid isoparaffin and butyl acetate.

[0011] Optionally, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The polyisocyanate includes one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and arylaliphatic polyisocyanates; The functionality of the polyisocyanate is ≥2; (2) The hydroxyl-containing polysiloxane includes at least one compound with the following structural formula: , R1 and R2 are each independently selected from any one of unsubstituted alkylene, ether, arylene, and alkoxy groups; the number of carbon atoms in R1 and R2 are each independently 1-10; n is an integer from 1 to 50; m is an integer from 1 to 80; and f is an integer from 6 to 20.

[0012] Optionally, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The polyisocyanate comprises 4,4' Dicyclohexylmethane diisocyanate, 1,4 Cyclohexane diisocyanate, trimethyl 1,6 One or more of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, and toluene diisocyanate; (2) The hydroxyl-containing polysiloxane includes double-terminated monohydroxyl-terminated polysiloxane and / or polyethylene glycol polydimethylsiloxane.

[0013] Optionally, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The mass percentage of the monomer units formed by hydroxyl polysiloxane in the fast-drying organosiloxane-polyurethane film-forming agent is 70%-90%; (2) The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent is 100-2000 mm. 2 / s; (3) The weight average molecular weight of the fast-drying organosiloxane-polyurethane film-forming agent is 10kDa-50kDa.

[0014] A second aspect of this application provides a method for preparing the aforementioned fast-drying organosiloxane-polyurethane film-forming agent, comprising: Under a nitrogen atmosphere, hydroxyl-containing polysiloxane and polyisocyanate are mixed and reacted to obtain a prepolymer. The prepolymer, crosslinking agent, catalyst, and some volatile oil substances are mixed and subjected to a second reaction to obtain a reactant. The reactant and a capping agent are mixed and subjected to a capping reaction to obtain a semi-finished product. The semi-finished product is cooled to room temperature and then mixed with another portion of volatile oils, swollen, and purified to obtain a fast-drying organosiloxane-polyurethane film-forming agent.

[0015] Optionally, the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The temperature of the first reaction is 50°C. 70℃, for 1-5 hours; (2) The temperature of the second reaction is 55-65℃ and the time is 0.5-3h; (3) The temperature of the end-capping reaction is 40°C. 60℃, time is 0.5-1h.

[0016] Optionally, the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The catalyst includes an organometallic catalyst, which includes stannous octoate and / or bismuth neodecanoate; (2) The mass of the catalyst accounts for 0.01%-0.05% of the mass of the prepolymer; (3) At the beginning of the second reaction, the mass ratio of the volatile oil to the prepolymer is 0.3-3:1; (4) The purification includes vacuum distillation, wherein the temperature of the vacuum distillation is 55-65℃; (5) The R value in the reaction system of the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent is 1.0-1.2.

[0017] A third aspect of this application provides a cosmetic product comprising the aforementioned fast-drying organosiloxane-polyurethane film-forming agent.

[0018] Compared with the prior art, the beneficial effects of this application include: The fast-drying organosiloxane-polyurethane film-forming agent provided in this application has polyurethane as the main structure and introduces polysiloxane segments and cross-linking structures. This design gives it both excellent adhesion and flexibility, enabling it to form an extremely thin soft film, thereby giving the product good extensibility, durability and skin-feel. At the same time, this fast-drying organosiloxane-polyurethane film-forming agent overcomes the common defects of tightness and stiffness of commercially available silicone resins, and performs outstandingly in terms of user experience, adherence and film-forming properties. Ultimately, it achieves the beneficial effects of high stability, refreshing skin feel, fast film formation, long-lasting makeup and even makeup effect.

[0019] The preparation method of the fast-drying organosiloxane-polyurethane film-forming agent provided in this application is simple, has low energy consumption in the preparation process, does not require the use of toxic acetone reagents for dilution, and has good economic benefits.

[0020] The cosmetics provided in this application have good skin adhesion and moisturizing properties. Attached Figure Description

[0021] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0022] Figure 1 Comparison of coating states formed by the fast-drying organosiloxane-polyurethane film-forming agent and MQ resin film-forming agent provided in Example 1 after being placed at room temperature for 24 hours (the left side is the coating state formed by the organosilicone modified polyurethane film-forming agent provided in Example 1 after baking at 70°C for 2 hours, and the right side is the coating state formed by the MQ resin film-forming agent after baking at 70°C for 2 hours). Detailed Implementation

[0023] First, the solution provided in this application will be explained in more detail as follows: The first aspect of this application provides a fast-drying organosiloxane-polyurethane film-forming agent, the raw materials of which include hydroxyl-containing polysiloxane, polyisocyanate, crosslinking agent, capping agent, and volatile oil substances; The molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 1-4:1; Optionally, the molar ratio of the isocyanate group in the polyisocyanate to the hydroxyl group in the hydroxyl-containing polysiloxane can be any value between 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 or 1-4:1; It should be noted that if the molar ratio of isocyanate groups in polyisocyanates to hydroxyl groups in hydroxyl-containing polysiloxanes is less than 1:1 or greater than 4:1, the synthesized prepolymer will have a smaller molecular weight, which is not conducive to further chain extension reactions. Preferably, the molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 1-3:1; More preferably, the molar ratio of the isocyanate group in the polyisocyanate to the hydroxyl group in the hydroxyl-containing polysiloxane is 1-2:1; The molar ratio of the polyisocyanate to the crosslinking agent is 3-8:1; It should be noted that adding too little crosslinking agent will result in a small molecular weight of the product, while adding too much will cause the reaction to be too fast and promote product gelation; preferably, the molar ratio of the polyisocyanate to the crosslinking agent is 3-7:1; More preferably, the molar ratio of the polyisocyanate to the crosslinking agent is 4-7:1; The mass ratio of the polyisocyanate to the capping agent is 5-10:1; Optionally, the mass ratio of polyisocyanate to capping agent can be any value between 5:1, 6:1, 7:1, 8:1, 9:1, 10:1 or 5:10:1; It should be noted that too little capping agent will result in NCO residue, while adding too much will lead to raw material waste; The volatile oils account for 65-75% of the total mass of the raw materials.

[0024] Optionally, the volatile oil content may be any value between 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, or 65-75% of the total mass of the raw materials.

[0025] It should be noted that adding too much volatile oil will reduce the viscosity of the product. When used in cosmetics, the amount added needs to be increased. Adding too little may result in incomplete dissolution or even excessively high viscosity, making it inconvenient to handle.

[0026] It should also be noted that the mechanism of fast-drying organosiloxane-polyurethane film-forming agents is as follows: the molecular weight of the fast-drying organosiloxane-polyurethane film-forming agent is extended / cross-linked polymerized to a certain extent. At the same time, the glass transition temperature of the fast-drying organosiloxane-polyurethane film-forming agent is higher than body temperature. After the solvent evaporates, the polymer can form a dry film on the skin. Otherwise, it will be sticky. In addition, the proportion of silicon units in the polymer cannot be too low, otherwise the adhesion will be too low.

[0027] In some embodiments, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The crosslinking agent includes a polyol; the polyol includes at least one of glycerol, trimethylolethane, trimethylolpropane, tri(hydroxymethyl)aminomethane, pentaerythritol, sorbitol, and mannitol; (2) The capping agent includes a small molecule alcohol, which includes at least one of methanol, ethanol, isopropanol, and n-butanol; (3) The volatile oils include volatile silicone oils and / or volatile organic oils.

[0028] In some embodiments, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The volatile silicone oil includes at least one of dimethyl silicone oil, decamethylcyclopentasiloxane, cyclohexylsiloxane, and methyl polytrimethylsiloxane; (2) The volatile organic oil includes at least one of light isoparaffin, isododecane, light liquid isoparaffin and butyl acetate.

[0029] In some embodiments, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The polyisocyanate includes one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and arylaliphatic polyisocyanates; The functionality of the polyisocyanate is ≥2; (2) The hydroxyl-containing polysiloxane includes at least one compound with the following structural formula: , R1 and R2 are each independently selected from any one of unsubstituted alkylene, ether, arylene, and alkoxy groups; the number of carbon atoms in R1 and R2 are each independently 1-10; n is an integer from 1 to 50; m is an integer from 1 to 80; and f is an integer from 6 to 20.

[0030] Optionally, the number of carbon atoms in R1 and R2 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or any integer between 1 and 10, n can be 1, 5, 10, 20, 30, 40, 50 or any integer between 1 and 50, m can be 1, 5, 10, 20, 30, 40, 50, 60, 70, 80 or any integer between 1 and 80, and f can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any integer between 6 and 20.

[0031] In some embodiments, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The polyisocyanate comprises 4,4' Dicyclohexylmethane diisocyanate, 1,4 Cyclohexane diisocyanate, trimethyl 1,6 One or more of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, and toluene diisocyanate; Preferably, the polyisocyanate includes isophorone diisocyanate (IPDI). It should be noted that polymers obtained by reacting isophorone diisocyanate (IPDI) as a raw material are widely used in cosmetic raw materials. Secondly, IPDI has moderate reactivity and can be catalyzed at relatively low temperatures. In addition, its structure after reacting with hydroxyl-containing silicone oil has good compatibility with volatile oils. (2) The hydroxyl-containing polysiloxane includes double-terminated monohydroxyl-terminated polysiloxane and / or polyethylene glycol polydimethylsiloxane.

[0032] In some embodiments, the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The mass percentage of the monomer units formed by hydroxyl polysiloxane in the fast-drying organosiloxane-polyurethane film-forming agent is 70%-90%; Optionally, the mass percentage of monomer units formed by hydroxyl polysiloxane in the fast-drying organosiloxane-polyurethane film-forming agent can be any value between 70%, 75%, 80%, 85%, 90%, or 70-90%. (2) The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent is 100-2000 mm. 2 / s; Optionally, the viscosity of the fast-drying organosiloxane-polyurethane film-forming agent can be 100 mm. 2 / s, 200 mm 2 / s, 400mm 2 / s, 600 mm2 / s, 800 mm 2 / s, 1000 mm 2 / s, 1200 mm 2 / s, 1400 mm 2 / s, 1600 mm 2 / s, 1800 mm 2 / s, 2000 mm 2 / s or 100-2000 mm 2 Any value between / s; (3) The weight average molecular weight of the fast-drying organosiloxane-polyurethane film-forming agent is 10kDa-50kDa.

[0033] Optionally, the weight-average molecular weight of the fast-drying organosiloxane-polyurethane film-forming agent can be any value between 10 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa, or 10 kDa-50 kDa.

[0034] A second aspect of this application provides a method for preparing the aforementioned fast-drying organosiloxane-polyurethane film-forming agent, comprising: Under a nitrogen atmosphere, hydroxyl-containing polysiloxane and polyisocyanate are mixed and reacted to obtain a prepolymer. It should be noted that when hydroxyl-containing polysiloxanes and polyisocyanates undergo urethane esterification, the resulting prepolymer has a linear structure with NCO reactive groups at the end. The prepolymer, crosslinking agent, catalyst, and some volatile oil substances are mixed and subjected to a second reaction to obtain a reactant. The reactant and a capping agent are mixed and subjected to a capping reaction to obtain a semi-finished product. It is worth noting that during the second reaction, the prepolymer did not precipitate or separate at 25°C, indicating that it has good solubility in volatile oils and is particularly suitable for use in color cosmetics. The second reaction involves the prepolymer and crosslinking agent undergoing further chain extension and crosslinking under the action of a catalyst. The addition of some volatile oils reduces the viscosity of the system, which further increases the molecular weight of the reactants and prevents the reaction from being too fast and completely gelling and solidifying. It should also be noted that the addition of the end-capping agent is to terminate the further reaction of the chain-extended prepolymer. The end-capping agent undergoes a carbamate reaction with the remaining NCO in the prepolymer, making the final product non-reactive. The semi-finished product is cooled to room temperature and mixed with another part of volatile oil substances, swollen, and purified to obtain a fast-drying organosiloxane-polyurethane film-forming agent.

[0035] It is important to note that this application uses hydroxyl-containing polysiloxanes and reacts them with polyisocyanates under specific ratios and processes. Simultaneously, the proportion of crosslinking agents must be controlled, and end-capping is essential to obtain a composition with the desired molecular weight and low viscosity. Otherwise, the product will not only be highly viscous but also prone to gelation. Furthermore, highly volatile oils must be used as solvents and diluents during polymerization; otherwise, the product will have poor compatibility and is prone to precipitation upon further dilution or dilution with other oils. The proportion of hydroxyl-containing polysiloxanes must be within a defined range, and the ratio of polyisocyanates to hydroxyl-containing polysiloxanes (reactive silicone oils) must also be within a certain range; otherwise, compatibility and stability issues will arise.

[0036] In some embodiments, the method for preparing the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The temperature of the first reaction is 50°C. 70℃, for 1-5 hours; Optionally, the temperature of the first reaction can be any value between 50°C, 60°C, 70°C or 50-70°C, and the time can be any value between 1h, 2h, 3h, 4h, 5h or 1-5h. (2) The temperature of the second reaction is 55-65℃ and the time is 0.5-3h; Optionally, the temperature of the second reaction can be any value between 55℃, 60℃, 65℃ or 55-65℃, and the time can be any value between 0.5h, 1h, 2h, 3h or 0.5-3h. (3) The temperature of the end-capping reaction is 40°C. 60℃, time is 0.5-1h.

[0037] Optionally, the temperature of the capping reaction can be any value between 40°C, 50°C, 60°C or 40-60°C, and the time can be any value between 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h or 0.5-1 h.

[0038] In some embodiments, the method for preparing the fast-drying organosiloxane-polyurethane film-forming agent satisfies at least one of the following conditions: (1) The catalyst includes an organometallic catalyst, which includes stannous octoate and / or bismuth neodecanoate; (2) The mass of the catalyst accounts for 0.01%-0.05% of the mass of the prepolymer; Optionally, the mass of the catalyst accounts for any value between 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, or 0.01-0.05% of the mass of the prepolymer; (3) At the beginning of the second reaction, the mass ratio of the volatile oil to the prepolymer is 0.3-3:1; Optionally, the mass ratio of volatile oils to prepolymer can be 0.3:1, 0.5:1, 1:1, 2:1, 3:1, or any value between 0.3 and 3:1; (4) The purification includes vacuum distillation, wherein the temperature of the vacuum distillation is 55-65℃; Optionally, the temperature for vacuum distillation can be any value between 55°C, 60°C, 65°C, or 55-65°C; (5) The R value in the reaction system of the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent is 1.0-1.2.

[0039] Optionally, the R value in the reaction system of the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent can be any value between 1, 1.1, 1.2 or 1-1.2.

[0040] A third aspect of this application provides a cosmetic product comprising the aforementioned fast-drying organosiloxane-polyurethane film-forming agent.

[0041] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0042] Example 1 The first aspect of this embodiment provides a fast-drying organosiloxane-polyurethane film-forming agent, comprising the following raw materials: Volatile oily substances: Methyl polytrimethylsiloxane, purchased from Anhui Aiyota Silicone Oil Co., Ltd., model IOTA 9229; Hydroxyl-containing polysiloxane: PEG-10 polydimethylsiloxane and hydroxypropyl-terminated silicone oil (mass ratio 10:7), wherein the PEG-10 polydimethylsiloxane was purchased from Shin-Etsu Chemical, model KF6017, with a molecular weight of approximately 2000; and the hydroxypropyl-terminated silicone oil was purchased from Shin-Etsu Chemical, Japan, model KF6001. Polyisocyanate: Isophorone diisocyanate, abbreviated as IPDI; Crosslinking agent: trimethylolpropane; Capping agent: ethanol.

[0043] The molar ratio between the isocyanate group in the polyisocyanate and the hydroxyl group in the hydroxyl-containing polysiloxane is 1.25:1. The molar ratio of polyisocyanate to crosslinking agent is 6.5:1; the R value is 1.05, and the remaining active hydrogen is made up with end-capping agent, with a mass ratio of polyisocyanate to end-capping agent of 8:1. Volatile oils account for 70% of the total mass of the raw materials.

[0044] The second aspect of this embodiment provides a method for preparing a fast-drying organosiloxane-polyurethane film-forming agent, as detailed below: S1. IPDI was mixed with hydroxyl-containing polysiloxane after dehydration under reduced pressure at 100℃, and then pre-stirred and polymerized in a closed reactor under nitrogen. The temperature was raised to 60℃ and the reaction was carried out for 3.5 hours to obtain the prepolymer. S2. The prepolymer obtained in S1 is mixed with trimethylolpropane, a portion of methyl polytrimethylsiloxane and stannous octoate catalyst (stannous octoate accounts for 0.05% of the mass of the prepolymer), wherein the mass ratio of the prepolymer to methyl polytrimethylsiloxane is 1:1. After the reaction is continued at 65°C for 2 hours, ethanol end-capping agent is added for end-capping to obtain organosiloxane-polyurethane film-forming agent. S3. Cool to room temperature, mix the remaining methyl polytrimethylsiloxane with the organosiloxane-polyurethane film-forming agent, swell for 10 hours, and distill under reduced pressure to obtain the fast-drying organosiloxane-polyurethane film-forming agent.

[0045] The mass percentage of monomer units formed by hydroxyl-containing polysiloxanes in the fast-drying organosiloxane-polyurethane film-forming agent is 86%.

[0046] The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was tested to be 320 mm. 2 / s, weight-average molecular weight Mw=32570Da.

[0047] Example 2 The first aspect of this embodiment provides a fast-drying organosiloxane-polyurethane film-forming agent, comprising the following raw materials: Volatile oily substances: methyl polytrimethylsiloxane; Polyisocyanate: IPDI; Hydroxyl-containing polysiloxane: Dihydroxyethyl polydimethylsiloxane (molecular weight 2000, hydroxyl content 1.7wt%). Crosslinking agent: glycerol; End-capping agent: methanol; The catalyst is stannous octoate.

[0048] The molar ratio between the isocyanate group in the polyisocyanate and the hydroxyl group in the hydroxyl-containing polysiloxane is 1.5:1. The molar ratio of polyisocyanate to crosslinking agent is 5:1; the R value is 1.05, and the remaining active hydrogen is made up with methanol end-capping agent, with a mass ratio of polyisocyanate to end-capping agent of 8:1. Volatile oils account for 70% of the total mass of the raw materials.

[0049] The second aspect of this embodiment provides a method for preparing a fast-drying organosiloxane-polyurethane film-forming agent, as detailed below: S1. IPDI was mixed with hydroxyl-containing polysiloxane after dehydration under reduced pressure at 100℃, and then pre-stirred and polymerized in a closed reactor under nitrogen. The temperature was raised to 65℃ and the reaction was carried out for 3.5 hours to obtain the prepolymer. S2. The prepolymer obtained in S1 is mixed with a crosslinking agent, some volatile oils and a catalyst, stannous octoate (stannous octoate accounts for 0.05% of the mass of the prepolymer), wherein the mass ratio of the prepolymer to methyl polytrimethylsiloxane is 1:1. After the reaction is continued at 65°C for 2 hours, a capping agent is added for capping to obtain an organosiloxane-polyurethane film-forming agent. S3. Cool to room temperature, mix the remaining volatile oils with the organosiloxane-polyurethane film-forming agent, swell for 10 hours, and then distill under reduced pressure to obtain the fast-drying organosiloxane-polyurethane film-forming agent.

[0050] The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was tested to be 460 mmHg. 2 / s, weight-average molecular weight Mw=46520Da.

[0051] Example 3 The first aspect of this embodiment provides a fast-drying organosiloxane-polyurethane film-forming agent, comprising the following raw materials: Volatile oils: 0.65cst dimethyl silicone oil, purchased from DOW manufacturer, model XIAMETER PMX-200 Silicone Fluid 0.65CST; Polyisocyanate: 4,4' Dicyclohexylmethane diisocyanate, abbreviated as HMDI; Hydroxyl-containing polysiloxane: Dihydroxyethyl polydimethylsiloxane (molecular weight 2000, hydroxyl content 1.7wt%). Crosslinking agent: mannitol; Capping agent: ethanol; The catalyst is stannous octoate.

[0052] The molar ratio between the isocyanate group in the polyisocyanate and the hydroxyl group in the hydroxyl-containing polysiloxane is 1.5:1. The molar ratio of polyisocyanate to crosslinking agent is 5:1; the R value is 1.05, and the remaining active hydrogen is made up with methanol end-capping agent, with a mass ratio of polyisocyanate to end-capping agent of 8:1. Volatile oils account for 70% of the total mass of the raw materials.

[0053] The second aspect of this embodiment provides a method for preparing a fast-drying organosiloxane-polyurethane film-forming agent, as detailed below: S1. HMDI is mixed with hydroxyl-containing polysiloxane that has been dehydrated under reduced pressure at 100℃, and then pre-stirred and polymerized in a closed reactor under nitrogen. The temperature is raised to 65℃ and the reaction is carried out for 3.5 hours to obtain the prepolymer. S2. The prepolymer obtained in S1 is mixed with a crosslinking agent, some volatile oils and a catalyst, stannous octoate (stannous octoate accounts for 0.05% of the mass of the prepolymer), wherein the mass ratio of the prepolymer to methyl polytrimethylsiloxane is 1:1. After the reaction is continued at 65°C for 2 hours, a capping agent is added for capping to obtain an organosiloxane-polyurethane film-forming agent. S3. Cool to room temperature, mix the remaining volatile oils with the organosiloxane-polyurethane film-forming agent, swell for 10 hours, and then distill under reduced pressure to obtain the fast-drying organosiloxane-polyurethane film-forming agent.

[0054] Tests showed that the viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was 120 mm. 2 / s, weight-average molecular weight Mw=46826Da.

[0055] Comparative Example 1 The difference between the raw materials and those in Example 1 is that the molar ratio between the isocyanate group in the polyisocyanate and the hydroxyl group in the hydroxyl-containing polysiloxane is 5:1; and the molar ratio between the polyisocyanate and the crosslinking agent is 10:1.

[0056] The difference between the preparation method and Example 1 is that the temperature in step S1 is 45°C, the temperature in step S2 is 70°C, and the swelling time in step S3 is 10h.

[0057] The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was tested to be 480 mmHg. 2 / s, weight-average molecular weight Mw=41052Da.

[0058] Comparative Example 2 The difference from Example 1 is that trimethylolpropane is not added.

[0059] Tests showed that the viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was 80 mm. 2 / s, weight-average molecular weight Mw=11510Da.

[0060] Comparative Example 3 The raw materials differ from those in Example 1 as follows: the hydroxyl-containing polysiloxane is replaced with dihydroxy-terminated polydimethylsiloxane and polypropylene glycol (PPG, molecular weight 2000, hydroxyl content 1.7wt%) in a mass ratio of 1:1; the crosslinking agent trimethylolpropane is replaced with mannitol; and the volatile oily substance is replaced with decamethylcyclopentasiloxane. The molar ratio between the isocyanate group in the polyisocyanate and the hydroxyl group in the hydroxyl-containing polysiloxane is 1.5:1; and the molar ratio between the polyisocyanate and the crosslinking agent is 5:1.

[0061] The difference between the preparation method and Example 1 is that the temperature in step S1 is 65°C.

[0062] Tests showed that the viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was 120 mm. 2 / s, weight-average molecular weight Mw=11532Da.

[0063] Comparative Example 4 The difference from Example 1 is that volatile oily substances such as methyl polytrimethylsiloxane are not added in step S2, but all volatile oily substances are added in step S3.

[0064] The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was tested to be 630 mmHg. 2 / s, weight-average molecular weight Mw=56813Da.

[0065] Comparative Example 5 The difference from Example 1 is that no end-capping agent is added in step S2 for end-capping.

[0066] Tests showed that the viscosity of the fast-drying organosiloxane-polyurethane film-forming agent was 650 mm. 2 / s, weight-average molecular weight Mw=68420Da.

[0067] In this application, the organosiloxane-polyurethane film-forming agents and MQ resin film-forming agents (purchased from DOWSIL, model MQ1600) prepared in Examples 1-3 and Comparative Examples 1-5 were coated onto test plates and cured into films at 70°C for 2 hours. The film-forming state of the organosiloxane-polyurethane film-forming agents and MQ film-forming agents was then observed, and the composition state and film-forming properties were recorded. The specific test data are shown in Table 1.

[0068] Room temperature surface drying time: Surface drying time is an indicator of the initial curing time of a material surface, specifically the time required for the material surface to lose its tackiness and form a "skin" or dry film. Judgment criteria: Generally, the absence of paint or adhesive residue when lightly touching the material surface with a finger (no adhesion upon touch) is used as the criterion for judging the completion of surface drying. The organosiloxane-polyurethane film-forming agents and MQ resin film-forming agents prepared in Examples 1-3 and Comparative Examples 1-3 were applied to the same thickness using a scraper applicator and dried in a constant temperature and humidity test chamber at 25°C.

[0069] Table 1 Film Formation Test

[0070] In addition, the coating states formed by the fast-drying organosiloxane-polyurethane film-forming agent and the MQ resin film-forming agent provided in Example 1 after being left at room temperature for 24 hours are compared as follows: Figure 1 As shown, where, Figure 1 The left side (marked as a) shows the coating state of the silicone-modified polyurethane film-forming agent provided in Example 1 after baking at 70°C for 2 hours. Figure 1 The right side (marked as b) shows the coating state formed by the MQ resin film-forming agent after baking at 70°C for 2 hours.

[0071] From Table 1 and Figure 1 As can be seen, the organosilicon-modified polyurethane film-forming agent obtained in this application embodiment has good film-forming properties and extensibility. As shown in Comparative Example 4, without the addition of volatile oily substances in step S2, the final product is unstable and difficult to dissolve completely.

[0072] This application also tested the compatibility of the organosiloxane-polyurethane film-forming agents prepared in the above examples and comparative examples with common cosmetic ingredients. The test method was as follows: 3g of the sample to be tested in the examples or comparative examples was taken and mixed with the test solvent at mass ratios of 1:9, 5:5, and 9:1, respectively. The mixture was heated in a water bath at 60°C, and the appearance of the mixture was observed and recorded.

[0073] The results of the above compatibility tests are shown in Table 2.

[0074] Table 2 Compatibility Test Results

[0075] Note: C = compatible; M = miscible; NC = incompatible.

[0076] To further test the usability of the organosiloxane-polyurethane film-forming agents prepared in Examples 1-3 and Comparative Examples 1-5, this application also conducted adhesion and application sensory tests on each agent by a trained evaluation panel of 10 people according to the following methods: Adhesion: After the film-forming agent is applied to the arm and forms a film, observe the amount of residue that comes off when rubbed with a finger. The residue is rated from 1 to 5, where 5 points represents good adhesion, 4 points represents a small area of ​​peeling off, 3 points represents a moderate area of ​​peeling off, 2 points represents a lot of peeling off, and 1 point represents severe peeling off.

[0077] Adhesion: After the obtained film-forming agent was applied to the arm for 6 hours, the durability was evaluated by the area of ​​film-forming agent peeling off. The film-forming agent was rated from 1 to 5 according to the area of ​​peeling off, where 5 points means that there is no obvious difference between the film-forming agent and when it was first applied, 4 points means that the peeling area is small, 3 points means that the peeling area is moderate, 2 points means that there is a lot of peeling off, and 1 point means that the peeling off is severe.

[0078] Application Sensation: Rate the application feel and moisturizing feel, and assign a score of 1 to 10 based on the quality of the application feel and moisturizing feel, where 1 point represents the worst, 5 points represent the average, and 10 points represent the best.

[0079] The above scores were calculated by summing the total scores given by the evaluation team and averaging them. The results are shown in Table 3.

[0080] Table 3 User Experience Evaluation

[0081] The film-forming agent obtained in Example 1 has excellent film-forming properties and superior adhesion / durability and skin feel.

[0082] This application also tested the hydrophobic, perspiration-repellent, and oleophobic properties of the organosiloxane-polyurethane film-forming agents prepared in the above examples and comparative examples. The test method was as follows: a 30% sample solution (Examples 1-3, Comparative Examples 1-5, MQ resin) was uniformly coated onto a glass slide with a thickness of 25 μm using a coating applicator. After the solution on the glass slide dried and formed a film, a contact angle meter was used to measure the static contact angle of deionized water, artificial sweat, and artificial sebum as contact liquids, respectively, by dropping them onto the glass slide. Images were acquired after 5 μL of contact liquid had been dropped for 1 second, and the waterproof contact angle of each sample was analyzed by the droplet shape to study its hydrophobic, perspiration-repellent, and oleophobic properties. According to the contact angle principle, the higher the contact angle when the contact liquid contacts the interface, the better the hydrophobic, perspiration-repellent, or oleophobic properties of the sample. Artificial sweat conforms to ISO / TR10271 standard, and its specific formula is as follows: sodium chloride (7.5g / L), lactic acid (1.14g / L), urea (1 g / L). The specific formula of artificial sebum is as follows: fatty acids (17%), triglycerides (44.7%), monowax esters / jojoba oil (25%), squalene (12.4%).

[0083] The results of the above hydrophobic, perspiration-repellent, and oleophobic tests are shown in Table 4.

[0084] Table 4 Hydrophobic, sweat-repellent, and oleophobic tests

[0085] Analysis: The samples in Examples 1-3 exhibit significant hydrophobic / sweat-repellent effects, and their anti-sebum effect is significantly better than that of the comparative example and MQ resin. This demonstrates that the film-forming agent of the present invention possesses excellent hydrophobic, sweat-repellent, and oleophobic properties.

[0086] As can be seen from the above tests, the film-forming agents prepared in Examples 1-3 of the present invention have good film-forming properties, better surface drying time than the comparative examples, excellent film-forming properties, excellent adhesion / durability and skin feel, good compatibility with most silicone oils and alkane oils, and excellent hydrophobic, sweat-repellent and oleophobic properties.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0088] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A fast-drying organosiloxane-polyurethane film-forming agent, characterized in that, Its raw materials include hydroxyl-containing polysiloxanes, polyisocyanates, crosslinking agents, end-capping agents, and volatile oils; The molar ratio of isocyanate groups in the polyisocyanate to hydroxyl groups in the hydroxyl-containing polysiloxane is 1-4:1; The molar ratio of the polyisocyanate to the crosslinking agent is 3-8:1; The mass ratio of the polyisocyanate to the capping agent is 5-10:1; The volatile oils account for 65-75% of the total mass of the raw materials.

2. The fast-drying organosiloxane-polyurethane film-forming agent according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The crosslinking agent includes a polyol; the polyol includes at least one of glycerol, trimethylolethane, trimethylolpropane, tri(hydroxymethyl)aminomethane, pentaerythritol, sorbitol, and mannitol; (2) The capping agent includes a small molecule alcohol, which includes at least one of methanol, ethanol, isopropanol, and n-butanol; (3) The volatile oils include volatile silicone oils and / or volatile organic oils.

3. The fast-drying organosiloxane-polyurethane film-forming agent according to claim 2, characterized in that, At least one of the following conditions must be met: (1) The volatile silicone oil includes at least one of dimethyl silicone oil, decamethylcyclopentasiloxane, cyclohexylsiloxane, and methyl polytrimethylsiloxane; (2) The volatile organic oil includes at least one of light isoparaffin, isododecane, light liquid isoparaffin and butyl acetate.

4. The fast-drying organosiloxane-polyurethane film-forming agent according to claim 1, characterized in that, At least one of the following conditions must be met: (1) The polyisocyanate includes one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and arylaliphatic polyisocyanates; The functionality of the polyisocyanate is ≥2; (2) The hydroxyl-containing polysiloxane includes at least one compound with the following structural formula: , R1 and R2 are each independently selected from any one of unsubstituted alkylene, ether, arylene, and alkoxy groups; the number of carbon atoms in R1 and R2 are each independently 1-10; n is an integer from 1 to 50; m is an integer from 1 to 80; and f is an integer from 6 to 20.

5. The fast-drying organosiloxane-polyurethane film-forming agent according to claim 4, characterized in that, At least one of the following conditions must be met: (1) The polyisocyanate comprises 4,4' Dicyclohexylmethane diisocyanate, 1,4 Cyclohexane diisocyanate, trimethyl 1,6 One or more of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, isophorone diisocyanate, and toluene diisocyanate; (2) The hydroxyl-containing polysiloxane includes double-terminated monohydroxyl-terminated polysiloxane and / or polyethylene glycol polydimethylsiloxane.

6. The fast-drying organosiloxane-polyurethane film-forming agent according to any one of claims 1-5, characterized in that, At least one of the following conditions must be met: (1) The mass percentage of the monomer units formed by hydroxyl polysiloxane in the fast-drying organosiloxane-polyurethane film-forming agent is 70%-90%; (2) The viscosity of the fast-drying organosiloxane-polyurethane film-forming agent is 100-2000 mm. 2 / s; (3) The weight average molecular weight of the fast-drying organosiloxane-polyurethane film-forming agent is 10kDa-50kDa.

7. A method for preparing a fast-drying organosiloxane-polyurethane film-forming agent as described in any one of claims 1-6, characterized in that, include: Under a nitrogen atmosphere, hydroxyl-containing polysiloxane and polyisocyanate are mixed and reacted to obtain a prepolymer. The prepolymer, crosslinking agent, catalyst, and some volatile oil substances are mixed and subjected to a second reaction to obtain a reactant. The reactant and a capping agent are mixed and subjected to a capping reaction to obtain a semi-finished product. The semi-finished product is cooled to room temperature and then mixed with another portion of volatile oils, swollen, and purified to obtain a fast-drying organosiloxane-polyurethane film-forming agent.

8. The preparation method of the fast-drying organosiloxane-polyurethane film-forming agent according to claim 7, characterized in that, At least one of the following conditions must be met: (1) The temperature of the first reaction is 50°C. 70℃, for 1-5 hours; (2) The temperature of the second reaction is 55-65℃ and the time is 0.5-3h; (3) The temperature of the end-capping reaction is 40°C. 60℃, time is 0.5-1h.

9. The method for preparing the fast-drying organosiloxane-polyurethane film-forming agent according to claim 7 or 8, characterized in that, At least one of the following conditions must be met: (1) The catalyst includes an organometallic catalyst, which includes stannous octoate and / or bismuth neodecanoate; (2) The mass of the catalyst accounts for 0.01%-0.05% of the mass of the prepolymer; (3) At the beginning of the second reaction, the mass ratio of the volatile oil to the prepolymer is 0.3-3:1; (4) The purification includes vacuum distillation, wherein the temperature of the vacuum distillation is 55-65℃; (5) The R value in the reaction system of the preparation method of the fast-drying organosiloxane-polyurethane film-forming agent is 1.0-1.

2.

10. A cosmetic product, characterized in that, Includes the fast-drying organosiloxane-polyurethane film-forming agent according to any one of claims 1-6.

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