Phenyl-containing silicone resin film-forming agent, preparation method therefor, and use thereof

Abstract

The present application provides a phenyl-containing organic silicone resin film-forming agent, a preparation method therefor, and a use thereof. The organic silicone resin film-forming agent comprises an organic silicone resin represented by general structural formula (I): (R1 3SiO0.5)a(R2SiO1.5)b(PhSiO1.5)c(SiO2)1 (I), wherein 0.2<a<1, 0≤b, and 0.1<c<1. In the present application, the organic silicone resin film-forming agent obtained by rationally adjusting the proportion of each unit and further introducing a phenyl group not only has excellent film-forming properties and flexibility, but also has excellent compatibility with organic substances containing a large number of hydrocarbon groups, such as natural oils. The organic silicone resin film-forming agent also exhibits excellent skin adhesion properties, is difficult to manually wipe off after being applied to the skin and formed into a film, has various properties that can meet the requirements of daily chemical products, and can be widely used in daily cosmetics, personal care products, or medical products.

Description

A phenyl-containing organosilicon resin film-forming agent, its preparation method and application Technical Field

[0001] This application relates to the field of film-forming agents, such as a phenyl-containing organosilicon resin film-forming agent, its preparation method, and its application. Background Technology

[0002] Film-forming materials can be used for surface protection or to apply therapeutic and cosmetic ingredients to the skin surface, finding wide application in cosmetics, personal care products, and medical products. Commonly used film-forming agents include acrylate resin film-forming agents, copolymers of various hydrocarbons, polyethylene copolymers, and silicone-modified acrylates. These film-forming agents generally have poor breathability, a poor feel, and poor compatibility with silicone oil systems. Silicone materials, on the other hand, have weak intermolecular forces and large free space, thus exhibiting superior breathability. Applying them to film-forming materials not only improves breathability but also enhances feel and water resistance.

[0003] In the prior art, patent CN115947942A discloses an MQ silicone resin with excellent film-forming and solubility, and its preparation method. This MQ silicone resin exhibits excellent film-forming properties and can be applied in the cosmetics field. However, the film formed by this MQ silicone resin is relatively hard and lacks flexibility, and it also suffers from poor compatibility with other cosmetic ingredients such as natural oils, as well as insufficient light transmittance. In the cosmetics field, however, people generally expect beauty products to be transparent and clear, and possess good softness.

[0004] Therefore, developing a film-forming agent with good light transmittance, softness and compatibility is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of the claims.

[0006] This application provides a phenyl-containing organosilicon resin film-forming agent. The phenyl-containing organosilicon resin film-forming agent provided in this application has the advantages of good flexibility, light transmittance, and good compatibility with other daily chemical components. While meeting various performance requirements, its cured film also has high toughness, a glossy surface, and excellent skin-adhesive properties.

[0007] This application also provides a method for preparing a phenyl-containing organosilicon resin film-forming agent.

[0008] This application also provides the application of the above-mentioned phenyl-containing organosilicon resin film-forming agent.

[0009] The specific technical solution is as follows:

[0010] In a first aspect, this application provides a phenyl-containing organosilicon resin film-forming agent, said organosilicon resin film-forming agent comprising an organosilicon resin having the structure shown in general formula (I): (R 1 3SiO 0.5 ) a (R 2 SiO 1.5 ) b (PhSiO 1.5 ) c (SiO2)1(Ⅰ); where R 1 Independently selected from substituted or unsubstituted C 1-10 alkyl, R 2 It is independently selected from one or two of methyl, ethyl, propyl, phenyl, and benzyl; the substituent is any one of alkyl, aryl, hydroxyl, and alkoxy; wherein, 0.2 < a < 1, for example, it can take values ​​of 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, etc.;

[0011] b ≥ 0; for example, it can take values ​​of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, etc.

[0012] 0.1 < c < 1, for example, it can take values ​​of 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, etc.

[0013] In one embodiment, in the general formula (Ⅰ), 0.5 ≤ a < 1.

[0014] In one embodiment, in the structural formula (Ⅰ), 0.6≤a≤0.8.

[0015] In one embodiment, in the general formula (Ⅰ), 0.2≤c≤0.6.

[0016] In one embodiment, in the general formula (Ⅰ), 0.4≤c≤0.6.

[0017] In one embodiment, the phenyl-containing organosilicon resin film-forming agent is obtained by hydrolysis-condensation reaction of a reaction system comprising the following components:

[0018] (A) Monofunctional silanes;

[0019] (B) Phenyl trifunctional silanes;

[0020] (C) Tetrafunctional silanes;

[0021] (D) Optional catalyst;

[0022] (E) Optional organic solvent;

[0023] (F) Water.

[0024] In one embodiment, the molar ratio between the monofunctional silane and the tetrafunctional silane is (0.5~1):1; for example, it can be 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, etc.

[0025] In one embodiment, the molar ratio between the monofunctional silane and the tetrafunctional silane is (0.6~0.8):1.

[0026] Under the above-mentioned preferred ratio, the silicone resin film-forming agent is not prone to gelation during the preparation process, and the film can maintain a soft and tough effect after formation.

[0027] In one embodiment, the molar ratio between the phenyl-containing trifunctional silane and the tetrafunctional silane is (0.2~1):1; for example, it can be 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, etc.

[0028] In one embodiment, the molar ratio between the phenyl-containing trifunctional silane and the tetrafunctional silane is (0.4~0.6):1.

[0029] Under the above-mentioned preferred ratio, the prepared organosilicon resin film-forming agent has good compatibility and does not become too hard after film formation.

[0030] In one embodiment, the molar ratio of water to total alkoxy groups in the reaction system is (0.5~3):1; for example, it can be 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8:1, 1.9, 2:1, 2.2, 2.3, 2.4, 2.5, 2.5:1, etc.

[0031] The total alkoxy groups in the reaction system refer to the sum of alkoxy groups contained in components (A), (B), and (C).

[0032] In one embodiment, the molar ratio of water to total alkoxy groups in the reaction system is (1~2):1.

[0033] This application uses water in the above-mentioned specific ratio for hydrolysis reaction, which can achieve better hydrolysis reaction effect.

[0034] In one embodiment, the amount of catalyst component (D) added is 1 to 5 parts, based on a total mass of 100 parts by mass of components (A), (B), and (C).

[0035] In one embodiment, based on a total mass of 100 parts by mass of components (A), (B), and (C), the amount of organic solvent added to component (E) is 25 to 50 parts.

[0036] In one embodiment, the monofunctional silane includes one or more of trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane.

[0037] In one embodiment, the phenyl trifunctional silane includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltrichlorosilane.

[0038] In one embodiment, the tetrafunctional silane includes tetraethyl orthosilicate and / or tetramethoxysilane.

[0039] In one embodiment, the catalyst includes a hydrolysis catalyst and a condensation catalyst.

[0040] In one embodiment, the hydrolysis catalyst comprises an acidic catalyst; the condensation catalyst comprises a basic catalyst.

[0041] Optionally, the acidic catalyst is selected from any one of concentrated hydrochloric acid, sulfuric acid, and organic acids.

[0042] Optionally, the alkaline catalyst comprises 5 wt% to 15 wt% of an aqueous solution of potassium hydroxide or 5 wt% to 15 wt% of an aqueous solution of sodium hydroxide.

[0043] Secondly, this application provides a method for preparing the above-mentioned organosilicon resin film-forming agent, the preparation method comprising the following steps:

[0044] S1. A reaction mixture is prepared by mixing a monofunctional silane, a phenyl-containing trifunctional silane, and a tetrafunctional silane. An optional catalyst and an optional solvent are added to the reaction mixture, and then water is added to carry out a hydrolysis reaction to obtain a hydrolysis reaction mixture.

[0045] S2. Separate the organic phase from the hydrolysis reaction mixture obtained in step S1, adjust the organic phase to the set pH, carry out a condensation reaction, and finally perform post-treatment to obtain a phenyl-containing organosilicon resin film-forming agent.

[0046] In one embodiment, step S1 specifically includes the following steps:

[0047] S11. At a first set temperature, water is added dropwise to the reaction mixture. After the addition is complete, reflux is performed at a second set temperature.

[0048] In one embodiment, the first set temperature is 20°C to 30°C.

[0049] In one embodiment, the dripping time is 1 hour to 5 hours.

[0050] In one embodiment, the second set temperature is 75°C to 85°C.

[0051] In one embodiment, the reflux time is 2h to 6h.

[0052] In one embodiment, step S2 includes the following post-processing steps: neutralization, water washing, filtration, and vacuum distillation.

[0053] In one embodiment, the set pH is 8-14; alternatively, it is 9-10.

[0054] In one embodiment, the temperature of the condensation reaction is 120°C to 180°C; alternatively, it is 130°C to 160°C.

[0055] Thirdly, this application provides the application of the above-mentioned phenyl-containing organosilicon resin film-forming agent or the phenyl-containing organosilicon resin film-forming agent prepared according to the above-mentioned preparation method in daily cosmetics, personal care products or medical products.

[0056] Compared with related technologies, this application has the following advantages:

[0057] 1. This application provides a phenyl-containing organosilicon resin film-forming agent, which comprises an organosilicon resin (R) having the general structural formula (Ⅰ). 1 3SiO 0.5 ) a (R 2 SiO 1.5 ) b (PhSiO 1.5 ) c(SiO2)1(Ⅰ), where 0.2 < a < 1; 0 ≤ b; 0.1 < c < 1. This application, through a reasonable combination of the proportions of each unit and the introduction of phenyl groups, yields an organosilicon resin film-forming agent that not only possesses excellent film-forming properties and softness, but also exhibits excellent compatibility with natural oils and other organic substances containing a large number of hydrocarbon groups. This organosilicon resin film-forming agent also possesses excellent skin-adhesive properties; once applied to the skin and forming a film, it is difficult to manually wipe off, and its various properties meet the requirements of daily chemical products.

[0058] 2. The phenyl-containing organosilicon resin film-forming agent provided in this application improves the light transmittance of the silicone resin by introducing phenyl groups, so that the resin film has good light transmittance and a very glossy surface after film formation. In addition, the phenyl groups increase the organic content of the silicone resin film-forming agent, making it compatible with other natural oils and other daily chemical components containing a large amount of hydrocarbon groups, and can be widely used in various daily chemical products.

[0059] 3. This application also provides a method for preparing a phenyl-containing organosilicon resin film-forming agent. This preparation method is simple, mild, and easy to control, and has broad application prospects.

[0060] After reading and understanding the accompanying diagrams and detailed descriptions, the other aspects can be understood. Attached Figure Description

[0061] The accompanying drawings are used to provide a further understanding of the technical solutions in this paper and form part of the specification. They are used together with the embodiments of this application to explain the technical solutions in this paper and do not constitute a limitation on the technical solutions in this paper.

[0062] Figure 1 is a schematic diagram of the synthesis route of a phenyl-containing organosilicon resin film-forming agent provided in an embodiment of this application. Detailed Implementation

[0063] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0064] The raw materials used in the embodiments of this application are all commonly used in the field and can be obtained through commercial channels.

[0065] This application does not impose any special restrictions on the neutralization, washing and filtration processes, and any technical solutions known to those skilled in the art can be used.

[0066] Example 1

[0067] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-1):

[0068] (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-1).

[0069] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0070] 48.6 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane, and 208.33 g of tetraethyl orthosilicate were sequentially added to a reaction vessel. Then, 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6 g of water was gradually added dropwise to the reaction vessel at 25°C over 2 hours. After the water addition was complete, the temperature was raised to 80°C, and the reaction was refluxed for 4 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The upper water layer was removed, and the organic layer was then treated with 25 wt% of [a specific ingredient / component]. The pH of the potassium hydroxide aqueous solution was adjusted to 9-10, and the temperature was raised to 150℃. The condensation reaction was carried out in a reactor equipped with a water separator for 3 hours. After the reaction was completed, the temperature was lowered to 60℃, and acetic acid with a molar amount of 1.5 times that of potassium hydroxide was added and stirred at room temperature for 1 hour. The mixture was washed once with water, with 300g of water added each time. The organic layer was allowed to stand, filtered, and heated to 120℃. A portion of the low-boiling substances was removed by vacuum distillation using an oil pump, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0071] Example 2

[0072] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-2):

[0073] (Me3SiO 0.5 ) 0.7 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-2).

[0074] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0075] 56.7g of hexamethyldisiloxane, 96.12g of phenyltriethoxysilane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel. Then, 160g of isododecane and 5.87g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0076] Example 3

[0077] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-3): (Me3SiO 0.5 ) 0.8 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1 (Ⅰ-3).

[0078] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0079] 64.8 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane, and 208.33 g of tetraethyl orthosilicate were sequentially added to a reaction vessel. Then, 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6 g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, yielding an MTQ organosilicon copolymer with a solid content of 50%. The formula for this product is (Me3SiO2). 0.5 ) 0.8 (PhSiO 1.5 ) 0.4 (SiO 2.0 1.

[0080] Example 4

[0081] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-4): (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.6 (SiO 2.0 )1 (Ⅰ-4).

[0082] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0083] 48.6 g of hexamethyldisiloxane, 144.18 g of phenyltriethoxysilane, and 208.33 g of tetraethyl orthosilicate were sequentially added to a reaction vessel. Then, 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6 g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, yielding an MTQ organosilicon copolymer with a solid content of 50%. The formula for this product is (Me3SiO2). 0.5 ) 0.6 (PhSiO 1.5 ) 0.6 (SiO 2.01.

[0084] Example 5

[0085] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-5):

[0086] (Me3SiO 0.5 ) 0.5 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1 (Ⅰ-5).

[0087] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0088] 40.5g of hexamethyldisiloxane, 96.12g of phenyltriethoxysilane, and 208.33g of tetraethyl orthosilicate were sequentially added to a reaction vessel. Then, 75g of isododecane and 12.1g of concentrated hydrochloric acid were added. Under nitrogen protection, 187.2g of water was gradually added dropwise to the reaction vessel at 20°C over 5 hours. After the water addition was complete, the temperature was raised to 85°C, and the reaction was refluxed for 2 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The upper water layer was removed, and the organic layer was then treated with 25wt% of [amount missing]. The pH was adjusted to 9-10 with a % potassium hydroxide aqueous solution, and the temperature was raised to 160℃. A condensation reaction was carried out in a reactor equipped with a water separator for 3 hours. After the reaction was completed, the temperature was lowered to 60℃, and acetic acid with a molar amount of 1.5 times that of potassium hydroxide was added and stirred at room temperature for 1 hour. The mixture was washed once with water, with 300g of water added each time. The organic layer was allowed to stand, filtered, and heated to 120℃. A portion of the low-boiling substances was removed by vacuum distillation using an oil pump, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0089] Example 6

[0090] This embodiment provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula (Ⅰ-6):

[0091] (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.2 (SiO 2.0 )1 (Ⅰ-6).

[0092] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0093] 48.6 g of hexamethyldisiloxane, 42.31 g of phenyltrichlorosilane, and 208.33 g of tetraethyl orthosilicate were sequentially added to a reaction vessel, followed by 160 g of isododecane. Then, under nitrogen protection, 187.2 g of water was gradually added dropwise to the reaction vessel at 30 °C over 1 hour. After the water addition was complete, the temperature was raised to 75 °C, and the reaction was refluxed for 6 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The upper water layer was removed, and the organic layer was then treated with 25 wt% potassium hydroxide. The pH of the aqueous solution was adjusted to 9-10, and the temperature was raised to 130℃. A condensation reaction was carried out in a reactor equipped with a water separator for 5 hours. After the reaction was completed, the temperature was lowered to 60℃, and acetic acid with a molar amount of 1.5 times that of potassium hydroxide was added and stirred at room temperature for 1 hour. The mixture was washed once with water, with 300g of water added each time. The organic layer was allowed to stand, filtered, and heated to 120℃. A portion of the low-boiling substances was removed by vacuum distillation using an oil pump, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0094] Comparative Example 1

[0095] This comparative example provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula: (Me3SiO 0.5 )1(PhSiO 1.5 ) 0.4 (SiO 2.0 1.

[0096] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0097] 81g of hexamethyldisiloxane, 96.12g of phenyltriethoxysilane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel, followed by 160g of isododecane and 5.87g of concentrated hydrochloric acid. Then, under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0098] Comparative Example 2

[0099] Comparative Example 2 provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula: (Me3SiO 0.5 ) 0.2 (PhSiO 1.5 ) 0.4 (SiO 2.0 1.

[0100] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0101] 16.2g of hexamethyldisiloxane, 96.12g of phenyltriethoxysilane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel. Then, 160g of isododecane and 5.87g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, to obtain a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0102] Comparative Example 3

[0103] This comparative example provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula: (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 )1(SiO 2.0 1.

[0104] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0105] 48.6g of hexamethyldisiloxane, 240.3g of phenyltriethoxysilane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel. Then, 160g of isododecane and 5.87g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50%.

[0106] Comparative Example 4

[0107] This comparative example provides a phenyl-containing organosilicon resin film-forming agent having the following general structural formula: (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.1 (SiO 2.0 1.

[0108] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps:

[0109] 48.6g of hexamethyldisiloxane, 24.03g of phenyltriethoxysilane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel. Then, 160g of isododecane and 5.87g of concentrated hydrochloric acid were added. Under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, resulting in a phenyl-containing organosilicon resin film-forming agent with a solid content of 50wt%.

[0110] Comparative Example 5

[0111] This comparative example provides an organosilicon resin film-forming agent having the following general structural formula: (Me3SiO) 0.5 ) 0.6 (SiO 2.0 1.

[0112] This comparative example provides a method for preparing an organosilicon resin film-forming agent, comprising the following steps:

[0113] 48.6g of hexamethyldisiloxane and 208.33g of tetraethyl orthosilicate were added sequentially to a reaction vessel, followed by 160g of isododecane and 5.87g of concentrated hydrochloric acid. Then, under nitrogen protection, 93.6g of water was gradually added dropwise to the reaction vessel over 2 hours. The other steps were the same as in Example 1 above, thus preparing a commercially available silicone resin film-forming agent with a solid content of 50wt%.

[0114] Performance testing and characterization:

[0115] The silicone resin film-forming agents obtained in the above examples and comparative examples were subjected to various performance tests:

[0116] Comparative Example 2 was already gelled during preparation, so it could not be tested.

[0117] Film-forming properties: 2g of the silicone resin film-forming agents obtained in Examples 1-6 and Comparative Examples 1-5 were dropped onto a tetrafluoroethylene plate and cured at 105°C for 3 hours. The film-forming properties of the cured silicone resin film-forming agents were evaluated, and the film-forming properties were divided into 1-5 grades according to the quality of the coating film formed. Grade 5 was the best, indicating that the formed coating film was continuous and without cracks; Grade 1 was the worst, indicating that the formed coating film had many cracks.

[0118] Flexibility: The phenyl-containing organosilicon resin film-forming agents obtained in Examples 1-6 and Comparative Examples 1-5 were tested according to the national standard GB / T1731-2020 "Test Method for Flexibility of Paint Film and Putty Film". The test results were divided into 1-3 grades. When the test result was ≤1mm, the flexibility was grade 3; when the test result was 1-3mm, the flexibility was grade 2; and when the test result was greater than 3mm, the flexibility was grade 1.

[0119] Compatibility: The phenyl-containing silicone resin film-forming agents obtained in Examples 1-6 and Comparative Examples 1-5 were mixed with natural oils (triglycerides) at a mass ratio of 1:1 to obtain film-forming agent mixtures. After standing for 24 hours, the transparency of the film-forming agent mixture was observed. The test results were divided into 1-5 grades according to the transparency of the film-forming agent mixture, where grade 5 was colorless and transparent, grade 4 was slightly white and turbid but without layering lines, grade 3 was white and turbid but without layering lines, grade 2 was white and turbid with slight layering lines, and grade 1 was white and turbid with obvious dividing lines.

[0120] The test results obtained from the above performance tests are shown in Table 1.

[0121]

[0122] As shown in Table 1, the phenyl-containing organosilicon resin film-forming agents provided in Examples 1-4 of this application have excellent film-forming properties (level 4 or above) and high flexibility (level 2 or above), while also having good compatibility with natural oils (level 4 or above).

[0123] The film-forming properties and flexibility of the silicone resin film-forming agents obtained in Comparative Examples 1 and 3 could not be tested because the silicone resin film-forming agents obtained in Comparative Examples 1 and 3 were oily and could hardly form a film.

[0124] As can be seen from the comparison of Example 1, Comparative Example 1 and Comparative Example 2, when the amount of monofunctional silane M added is too large, the molecular weight of the resulting silicone resin film-forming agent is too low and cannot form a film; while when the amount of monofunctional silane M added is too small, the resulting silicone resin film-forming agent gels during the preparation process and cannot yield an applicable product.

[0125] As can be seen from Example 1, Comparative Example 3, and Comparative Example 4, the trifunctional silane T containing phenyl Ph When the amount added is too small, the resulting silicone resin film-forming agent contains too few organic groups, T Ph The performance cannot be demonstrated; while the trifunctional silane T containing phenyl groups... Ph When too much is added, the overall structure and properties of the resulting silicone resin film-forming agent are more inclined towards silicone oil, resulting in a poor film-forming agent or even the inability to form a film.

[0126] Comparative Example 5 yielded a traditional MQ silicone resin. A comparison of Example 1 and Comparative Example 5 shows that the MQ silicone resin obtained in Comparative Example 5 is prone to cracking after film formation, and its flexibility and compatibility are also poor. In contrast, the properties of Examples 1-4 are superior to those of the MQ silicone resin obtained in Comparative Example 5. This is because the MQ silicone resin has too few organic groups, resulting in properties that are more like inorganic substances, leading to higher hardness after film formation. This application addresses this by incorporating a certain amount of T into the MQ resin. Ph This makes the resin more "organic" and improves its compatibility with natural oils and other organic substances containing a large number of hydrocarbon groups. Furthermore, T... Ph The introduction of [a specific ingredient] can significantly increase its toughness without drastically reducing its hardness.

[0127] The above description of the disclosed embodiments enables those skilled in the art to make or use this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A phenyl-containing organosilicon resin film-forming agent, wherein, The organosilicon film-forming agent comprises an organosilicon resin having the structure shown in general formula (I): (R 1 3SiO 0.5 ) a (R 2 SiO 1.5 ) b (PhSiO 1.5 ) c (SiO2)1(Ⅰ); Among them, R 1 Independently selected from substituted or unsubstituted C 1-10 alkyl, R 2 The components are independently selected from one or two of methyl, ethyl, propyl, phenyl, and benzyl; the substituents are any one of alkyl, aryl, hydroxyl, and alkoxy; wherein 0.2 < a < 1; b ≥ 0; 0.1 < c < 1.

2. The organosilicon resin film-forming agent according to claim 1, wherein, In the general formula (Ⅰ) of the structure, 0.5 ≤ a < 1.

3. The organosilicon resin film-forming agent according to claim 2, wherein, In the general formula (Ⅰ) of the structure, 0.6≤a≤0.

8.

4. The organosilicon resin film-forming agent according to claim 1, wherein in the general structural formula (Ⅰ), 0.2≤c≤0.

6.

5. The organosilicon resin film-forming agent according to claim 4, wherein in the general structural formula (Ⅰ), 0.4≤c≤0.

6.

6. The organosilicon resin film-forming agent according to claim 1, wherein, The silicone resin film-forming agent is obtained by hydrolysis and condensation reaction of a reaction system comprising the following components: (A) Monofunctional silanes; (B) Phenyl trifunctional silanes; (C) Tetrafunctional silanes; (D) Optional catalyst; (E) Optional organic solvent; (F) Water.

7. The organosilicon resin film-forming agent according to claim 6, wherein, The molar ratio between the monofunctional silane and the tetrafunctional silane is (0.5~1):1; Optionally, the molar ratio between the monofunctional silane and the tetrafunctional silane is (0.6~0.8):

1.

8. The organosilicon resin film-forming agent according to claim 1, wherein, The molar ratio between the phenyl-containing trifunctional silane and the tetrafunctional silane is (0.2~1):1; Optionally, the molar ratio between the phenyl-containing trifunctional silane and the tetrafunctional silane is (0.4~0.6):1; Optionally, the molar ratio of water to total alkoxy groups in the reaction system is (0.5~3):1; Optionally, the molar ratio of water to total alkoxy groups in the reaction system is (1~2):1; Optionally, based on a total mass of 100 parts by mass of components (A), (B), and (C), the amount of catalyst component (D) added is 1 to 5 parts; Optionally, based on a total mass of 100 parts by mass of components (A), (B), and (C), the amount of organic solvent added to component (E) is 25 to 50 parts.

9. The organosilicon resin film-forming agent according to claim 1, wherein, The monofunctional silanes include one or more of trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane; Optionally, the phenyl trifunctional silane includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltrichlorosilane; Optionally, the tetrafunctional silane includes tetraethyl orthosilicate and / or tetramethoxysilane; Optionally, the catalyst includes a hydrolysis catalyst and a condensation catalyst; Optionally, the hydrolysis catalyst includes an acidic catalyst; the condensation catalyst includes a basic catalyst. Optionally, the organic solvent includes one or more of isododecane, isotridecane, dimethyl silicone oil with a viscosity of 1-100 cps, and cyclic organopolysiloxane.

10. A method for preparing an organosilicon resin film-forming agent according to any one of claims 1-9, comprising the following steps: S1. A reaction mixture is prepared by mixing a monofunctional silane, a phenyl-containing trifunctional silane, and a tetrafunctional silane. An optional catalyst and an optional solvent are added to the reaction mixture, and then water is added to carry out a hydrolysis reaction to obtain a hydrolysis reaction mixture. S2. Separate the organic phase from the hydrolysis reaction mixture obtained in step S1, adjust the organic phase to the set pH, carry out a condensation reaction, and finally perform post-treatment to obtain a phenyl-containing organosilicon resin film-forming agent.

11. The preparation method according to claim 10, wherein, In step S1, the hydrolysis reaction specifically includes the following steps: S11. At a first set temperature, water is added dropwise to the reaction mixture. After the addition is complete, reflux is performed at a second set temperature.

12. The preparation method according to claim 11, wherein, The first set temperature is 20℃~30℃.

13. The preparation method according to claim 11, wherein, The dripping time is 1 hour to 5 hours; Optionally, the second set temperature is 75℃~85℃; Optionally, the reflux time is 2h to 6h.

14. The preparation method according to claim 10, characterized in that, In step S2, the post-processing includes neutralization, water washing, filtration, and vacuum distillation. Optionally, the set pH value is 8-14; optionally, it is 9-10. Optionally, the temperature of the condensation reaction is 120℃~180℃; or optionally 130~160℃.

15. The use of the phenyl-containing organosilicon resin film-forming agent according to any one of claims 1-9 or the phenyl-containing organosilicon resin film-forming agent prepared according to the preparation method according to any one of claims 10-14 in daily cosmetics, personal care products or medical products.

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