Phenyl-containing organic silicon resin film-forming agent as well as preparation method and application thereof

Abstract

The invention provides a phenyl-containing organic silicon resin film-forming agent as well as a preparation method and application thereof. The organic silicon resin film-forming agent comprises organic silicon resin as shown in a structural general formula (I): (R13SiO0.5) a (R2SiO1.5) b (PhSiO1.5) c (SiO2) 1 (I), wherein a is greater than 0.2 and less than 1; b > = 0; 0.1 < c < 1. According to the organic silicon resin film-forming agent disclosed by the invention, by reasonably matching the proportion of each unit and introducing a phenyl group, the obtained organic silicon resin film-forming agent not only has excellent film-forming property and flexibility, but also has excellent compatibility with natural grease and other organic matters containing a large number of alkyl groups. In addition, the organic silicon resin film-forming agent also has excellent skin-attaching performance and is difficult to wipe manually after being coated on the skin to form a film, various performances can meet the requirements of daily chemical products, and the organic silicon resin film-forming agent can be widely applied to daily cosmetics, personal care products or medical products.

Description

Technical Field

[0001] The present invention relates to the field of film-forming agents, and more specifically to a phenyl-containing organic silicone resin film-forming agent and a preparation method and application thereof. Background Art

[0002] Film-forming materials can be used for surface protection or to apply therapeutic and cosmetic ingredients to the skin surface. They are widely used in cosmetics, personal care products, medical products and other products. Commonly used film-forming agents include acrylic resin film-forming agents, copolymers of various hydrocarbons, polyethylene copolymers, silicone-modified acrylates and other types. These film-forming agents have average air permeability, poor hand feel, and poor compatibility in silicone oil systems. Silicone materials have weak intermolecular forces and large free space, so they have better air permeability. Applying them to film-forming materials can not only improve air permeability, but also improve hand feel and water resistance.

[0003] In the prior art, the patent with publication number CN115947942A discloses an MQ silicone resin with excellent film-forming property and solubility and a preparation method thereof. The MQ silicone resin has excellent film-forming property and can be applied in the field of cosmetics. However, the MQ silicone resin is relatively hard and not flexible after film formation, and has disadvantages such as poor compatibility with other cosmetic ingredients such as natural oils and fats, and insufficient light transmittance. In the field of cosmetics, people generally expect beauty products to be transparent and bright in appearance and have good softness.

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

[0005] In view of this, the object of the present invention is to provide a phenyl-containing organosilicon resin film-forming agent. The phenyl-containing organosilicon resin film-forming agent provided by the present invention has the advantages of good flexibility, light transmittance and good compatibility with other daily chemical ingredients. While meeting various performance requirements, the cured film also has high toughness, glossy surface, and excellent skin-adhesive properties.

[0006] Another object of the present invention is to provide a method for preparing a phenyl-containing organosilicon resin film-forming agent.

[0007] Another object of the present invention is to provide application of the above-mentioned phenyl-containing organosilicon resin film-forming agent.

[0008] In order to achieve the above purpose, the specific technical solution is as follows: In a first aspect, the present invention provides a phenyl-containing organosilicon resin film-forming agent, wherein the organosilicon resin film-forming agent comprises an organosilicon resin having a general structural formula (I): (R 13SiO 0.5 ) a (R 2 SiO 1.5 ) b (PhSiO 1.5 ) c (SiO2)1(Ⅰ);wherein, R 1 Independently selected from substituted or unsubstituted C 1-10 The alkyl group, R 2 is independently selected from one or two of methyl, ethyl, propyl, phenyl and benzyl; the substituted substituent is any one of alkyl, aryl, hydroxyl and alkoxy; wherein 0.2<a<1, for example, the values ​​may be 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.; b≥0; for example, the value can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, etc.; 0.1<c<1, for example, the values ​​can be 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.

[0009] Preferably, in the general structural formula (I), 0.5≤a<1.

[0010] Preferably, in the general structural formula (I), 0.6≤a≤0.8.

[0011] Preferably, in the general structural formula (I), 0.2≤c≤0.6.

[0012] Preferably, in the general structural formula (I), 0.4≤c≤0.6.

[0013] Preferably, the phenyl-containing organosilicon resin film-forming agent is obtained by subjecting a reaction system comprising the following components to a hydrolysis condensation reaction: (A) Monofunctional silane; (B) phenyl-containing trifunctional silane; (C) tetrafunctional silane; (D) optionally a catalyst; (E) optionally an organic solvent; (F) Water.

[0014] Preferably, the molar ratio of the monofunctional silane to the tetrafunctional silane is (0.5-1):1; for example, it may 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.

[0015] More preferably, the molar ratio between the monofunctional silane and the tetrafunctional silane is (0.6-0.8):1.

[0016] Under the above preferred ratio, the organic silicone resin film-forming agent is not easy to gel during the preparation process, and can maintain a soft and tough effect after film formation.

[0017] Preferably, 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.

[0018] More preferably, the molar ratio between the phenyl-containing trifunctional silane and the tetrafunctional silane is (0.4-0.6):1.

[0019] Under the above preferred ratio, the prepared organic silicone resin film-forming agent has good compatibility and will not be too hard after film formation.

[0020] Preferably, the molar ratio of the water to the 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.

[0021] The total alkoxy groups in the reaction system refer to the total of the alkoxy groups contained in the components (A), (B) and (C).

[0022] More preferably, the molar ratio of the water to the total alkoxy groups in the reaction system is (1-2):1.

[0023] The present invention adopts the water in the above specific ratio to carry out the hydrolysis reaction, which can achieve a better hydrolysis reaction effect.

[0024] Preferably, the amount of the catalyst of component (D) added is 1 to 5 parts by weight based on 100 parts by weight of the total weight of the component (A), the component (B) and the component (C).

[0025] Preferably, based on 100 parts by mass of the total mass of the component (A), the component (B) and the component (C), the amount of the organic solvent added as the component (E) is 25 to 50 parts by mass.

[0026] Preferably, the monofunctional silane includes one or more of trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane and hexamethyldisilazane.

[0027] Preferably, the phenyl-containing trifunctional silane includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane and phenyltrichlorosilane.

[0028] Preferably, the tetrafunctional silane includes ethyl orthosilicate and / or tetramethoxysilane.

[0029] Preferably, the catalyst includes a hydrolysis catalyst and a condensation catalyst.

[0030] More preferably, the hydrolysis catalyst comprises an acidic catalyst; and the condensation catalyst comprises a basic catalyst.

[0031] More preferably, the acidic catalyst is selected from any one of concentrated hydrochloric acid, sulfuric acid, and organic acid.

[0032] Further preferably, the alkaline catalyst comprises 5 wt % to 15 wt % of a potassium hydroxide aqueous solution or 5 wt % to 15 wt % of a sodium hydroxide aqueous solution.

[0033] In a second aspect, the present invention provides a method for preparing the above-mentioned organosilicon resin film-forming agent, the preparation method comprising the following steps: S1. A monofunctional silane, a phenyl-containing trifunctional silane and a tetrafunctional silane are mixed to obtain a reaction mixture, 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 a set pH, perform a condensation reaction, and finally perform post-treatment to obtain a phenyl-containing organic silicone resin film-forming agent.

[0034] Preferably, in step S1, the hydrolysis reaction specifically comprises the following steps: S11. Add water dropwise to the reaction mixture at the first set temperature, and after the addition is complete, reflux at the second set temperature.

[0035] Preferably, the first set temperature is 20°C-30°C.

[0036] Preferably, the dropping time is 1 h to 5 h.

[0037] Preferably, the second set temperature is 75°C-85°C.

[0038] Preferably, the reflux time is 2h~6h.

[0039] Preferably, in step S2, the post-treatment includes neutralization, water washing, filtration, and reduced pressure distillation. Preferably, the set pH is 8-14; more preferably 9-10.

[0040] Preferably, the temperature of the condensation reaction is 120°C to 180°C; more preferably 130°C to 160°C.

[0041] In a third aspect, the present invention provides the use 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.

[0042] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention provides a phenyl-containing organic silicone resin film-forming agent, which comprises an organic silicone resin (R 1 3SiO 0.5 ) a (R 2 SiO 1.5 ) b (PhSiO 1.5 ) c (SiO2)1 (I), wherein 0.2<a<1; 0≤b; 0.1<c<1. The present invention introduces phenyl groups by reasonably matching the ratio of each unit, and the obtained silicone resin film-forming agent not only has excellent film-forming property and softness, but also has excellent compatibility with organic substances containing a large number of hydrocarbon groups such as natural oils and fats. The silicone resin film-forming agent also has excellent skin-fitting properties. After being applied on the skin to form a film, it is difficult to be manually wiped off. Various properties can meet the requirements of daily chemical products and can be widely used in daily chemical products.

[0043] 2. The phenyl-containing silicone resin film-forming agent provided by the present invention improves the light transmittance of the silicone resin by introducing a phenyl group, so that the resin has good light transmittance after film formation, and the surface after film formation is very glossy. In addition, the phenyl group increases the organic content of the silicone resin film-forming agent, so that it has good compatibility with other daily chemical components containing a large amount of hydrocarbon groups such as other natural oils and fats, and can be widely used in various daily chemical products.

[0044] 3. The present invention also provides a method for preparing a phenyl-containing organosilicon resin film-forming agent. The preparation method has simple process, mild conditions, easy control, and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The schematic diagram is a synthetic route of the phenyl-containing organosilicon resin film-forming agent of the present invention. DETAILED DESCRIPTION

[0046] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] The raw materials used in the present invention are all commonly used raw materials in the art and can be obtained through commercial channels.

[0048] The present invention has no special limitation on the neutralization, washing and filtering processes, and the technical solutions well known to those skilled in the art can be adopted. Example 1

[0049] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-1): (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-1).

[0050] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: Take 48.6g hexamethyldisiloxane, 96.12g phenyltriethoxysilane and 208.33g ethyl orthosilicate and add them to the reactor in sequence, then add 160g isododecane and 5.87g concentrated hydrochloric acid, then under nitrogen protection, gradually add 93.6g water to the reactor at 25°C within 2h, after the water is added, the temperature is raised to 80°C, and the reaction is refluxed for 4h; after the reaction is completed, the reaction is allowed to stand and the layers are separated, the upper water layer is removed, and the organic layer is taken and 25wt% is added The pH value of the aqueous potassium hydroxide solution is adjusted to 9-10, the temperature is raised to 150°C, and the condensation reaction is carried out in a reactor equipped with a water separation device for 3 hours; after the reaction, the temperature is lowered to 60°C, and acetic acid with a molar amount of 1.5 times that of potassium hydroxide is added, and stirred at room temperature for 1 hour; the mixture is washed with water once, and the amount of water added each time is 300g; the organic layer is allowed to stand, filtered, and heated to 120°C. The low-boiling substances are removed by oil pump vacuum distillation to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50wt%. Example 2

[0051] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-2): (Me3SiO 0.5 ) 0.7 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-2).

[0052] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 56.7 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 hours under nitrogen protection. The other steps were consistent with the above Example 1 to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50 wt%. Example 3

[0053] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-3): (Me3SiO 0.5 ) 0.8 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-3).

[0054] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 64.8 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to a reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 h under nitrogen protection. The other steps were consistent with those in Example 1 above to obtain a MTQ silicone resin copolymer with a solid content of 50%. The product was expressed as (Me3SiO 0.5 ) 0.8 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1. Example 4

[0055] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-4): (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.6 (SiO 2.0 )1(Ⅰ-4).

[0056] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 48.6 g of hexamethyldisiloxane, 144.18 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to a reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 h under nitrogen protection. The other steps were consistent with those in Example 1 above to obtain a MTQ silicone resin copolymer with a solid content of 50%. The product was expressed as (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.6 (SiO 2.0 )1. Example 5

[0057] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-5): (Me3SiO 0.5 ) 0.5 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1(Ⅰ-5).

[0058] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: Take 40.5g hexamethyldisiloxane, 96.12g phenyltriethoxysilane and 208.33g ethyl orthosilicate and add them to the reactor in sequence, then add 75g isododecane and 12.1g concentrated hydrochloric acid, then add 187.2g water to the reactor gradually at 20°C within 5h under nitrogen protection, after the water is added, the temperature is raised to 85°C, and the reaction is refluxed for 2h; after the reaction is completed, the layers are allowed to stand, the upper water layer is separated, and 25wt% of the organic layer is added % potassium hydroxide aqueous solution to adjust the pH to 9-10, heat to 160°C, and carry out condensation reaction in a reactor equipped with a water separation device for 3 hours; after the reaction, cool to 60°C, add acetic acid with a molar amount of 1.5 times that of potassium hydroxide, and stir at room temperature for 1 hour; wash once with water, and the amount of water added each time is 300g; take the organic layer, let it stand, filter, heat to 120°C, and distill with an oil pump under reduced pressure to remove part of the low-boiling substances, to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50wt%. Example 6

[0059] This embodiment provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula (I-6): (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.2 (SiO 2.0 )1(Ⅰ-6).

[0060] This embodiment provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: Take 48.6g hexamethyldisiloxane, 42.31g phenyltrichlorosilane and 208.33g ethyl orthosilicate and add them to the reactor in sequence, then add 160g isododecane, and then gradually add 187.2g water to the reactor at 30°C within 1h under nitrogen protection. After the water is added, the temperature is raised to 75°C and refluxed for 6h. After the reaction is completed, stand and separate, remove the upper water layer, take the organic layer and add 25wt% potassium hydroxide The pH of the aqueous solution is adjusted to 9-10, the temperature is raised to 130°C, and the condensation reaction is carried out in a reactor equipped with a water separation device for 5 hours; after the reaction is completed, the temperature is lowered to 60°C, acetic acid with a molar amount of 1.5 times that of potassium hydroxide is added, and stirred at room temperature for 1 hour; the mixture is washed with water once, and the amount of water added each time is 300 g; the organic layer is allowed to stand, filtered, and heated to 120°C. Part of the low-boiling substances are removed by oil pump vacuum distillation to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50wt%.

[0061] Comparative Example 1 This comparative example provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula: (Me3SiO 0.5 )1(PhSiO 1.5 )0.4 (SiO 2.0 )1.

[0062] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 81 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 hours under nitrogen protection. The other steps were consistent with the above Example 1 to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50 wt%.

[0063] Comparative Example 2 This comparative example provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula: (Me3SiO 0.5 ) 0.2 (PhSiO 1.5 ) 0.4 (SiO 2.0 )1.

[0064] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 16.2 g of hexamethyldisiloxane, 96.12 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 h under nitrogen protection. The other steps were consistent with the above Example 1 to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50 wt%.

[0065] Comparative Example 3 This comparative example provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula: (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 )1(SiO 2.0 )1.

[0066] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 48.6 g of hexamethyldisiloxane, 240.3 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 hours under nitrogen protection. The other steps were consistent with the above Example 1 to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50%.

[0067] Comparative Example 4 This comparative example provides a phenyl-containing organic silicone resin film-forming agent having the following structural formula: (Me3SiO 0.5 ) 0.6 (PhSiO 1.5 ) 0.1 (SiO 2.0 )1.

[0068] This comparative example provides a method for preparing a phenyl-containing organosilicon resin film-forming agent, comprising the following steps: 48.6 g of hexamethyldisiloxane, 24.03 g of phenyltriethoxysilane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 hours under nitrogen protection. The other steps were consistent with the above Example 1 to obtain a phenyl-containing silicone resin film-forming agent with a solid content of 50 wt%.

[0069] Comparative Example 5 This comparative example provides a silicone resin film-forming agent having the following structural formula: (Me3SiO 0.5 ) 0.6 (SiO 2.0 )1.

[0070] This comparative example provides a method for preparing a silicone resin film-forming agent, comprising the following steps: 48.6 g of hexamethyldisiloxane and 208.33 g of ethyl orthosilicate were added to the reactor in sequence, and then 160 g of isododecane and 5.87 g of concentrated hydrochloric acid were added. Then, 93.6 g of water was gradually added dropwise to the reactor within 2 hours under nitrogen protection. The other steps were consistent with the above-mentioned Example 1 to prepare a silicone resin film-forming agent with a solid content of 50 wt% commonly used on the market.

[0071] Performance testing and characterization: The organosilicon resin film-forming agents obtained in the above examples and comparative examples were subjected to various performance tests: Comparative Example 2 had already gelled during preparation and therefore could not be tested.

[0072] Film-forming property: 2 g of each of the organic silicone resin film-forming agents obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were respectively added dropwise onto a tetrafluoroethylene plate and dried at 105°C for 3 h for curing. The film-forming property of the cured organic silicone resin film-forming agent was evaluated and classified into grades 1 to 5 according to the quality of the formed coating, wherein grade 5 is the best, indicating that the formed coating is continuous and has no cracks; grade 1 is the worst, indicating that the formed coating has more cracks.

[0073] Flexibility: The silicone resin film-forming agents obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were tested in accordance with the national standard GB / T1731-2020 "Determination of Flexibility of Paint Films and Putty Films", and the test results were divided into 1 to 3 levels. When the test result is ≤1mm, the flexibility is level 3; when the test result is 1 to 3mm, the flexibility is level 2; when the test result is greater than 3m, the flexibility is level 1.

[0074] Compatibility: The silicone resin film-forming agents obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were respectively mixed with natural oils (triglycerides) at a mass ratio of 1:1 to obtain a film-forming agent mixture. After standing for 24 hours, the film-forming agent mixture was observed to see whether it was transparent. The test results were divided into 1 to 5 levels according to the transparency of the film-forming agent mixture, wherein level 5 was colorless and transparent, level 4 was slightly white turbid but without delamination lines, level 3 was white turbid but without delamination lines, level 2 was white turbid with slight delamination lines, and level 1 was white turbid with obvious demarcation lines.

[0075] The test results obtained from the above performance test are shown in Table 1.

[0076] Table 1 Test data of the silicone resin film-forming agent provided in Examples 1 to 6 and Comparative Examples 1 to 5

[0077] As can be seen from Table 1, the phenyl-containing silicone resin film-forming agent provided in Examples 1 to 6 of the present invention has excellent film-forming property (above grade 4) and high flexibility (above grade 2), and has good compatibility with natural oils and fats (above grade 4).

[0078] The film-forming property and softness of the organic silicone resin film-forming agents obtained in Comparative Examples 1 and 3 could not be tested because the organic silicone resin film-forming agents obtained in Comparative Examples 1 and 3 were in an oily state and could hardly form a film.

[0079] By comparing Example 1 with Comparative Examples 1 and 2, it can be seen that when the amount of monofunctional silane M added is too much, the molecular weight of the obtained silicone resin film-forming agent is too low and it is impossible to form a film; and when the amount of monofunctional silane M added is too little, the obtained silicone resin film-forming agent gels during the preparation process and no product that can be used can be obtained.

[0080] It can be seen from Example 1 and Comparative Examples 3 and 4 that the trifunctional silane T containing phenyl Ph When the amount added is too small, the obtained silicone resin film-forming agent contains too few organic groups, T Ph The performance of the phenyl-containing trifunctional silane T Ph When the amount added is too much, the overall structural performance of the obtained silicone resin film-forming agent is more inclined to silicone oil, resulting in a poor film-forming agent or even no film-forming ability.

[0081] Comparative Example 5 obtains a conventional MQ organic silicone resin. As can be seen from the comparison between Example 1 and Comparative Example 5, the MQ organic silicone resin obtained in Comparative Example 5 is prone to cracking after film formation, and has poor flexibility and compatibility. However, the performances of Examples 1-4 are all superior to the MQ silicone resin obtained in Comparative Example 5. The reason is that the MQ silicone resin has too few organic groups, which results in its performance being biased towards inorganic substances, and the hardness after film formation is high. The present invention achieves this by adding a certain amount of T Ph , making the resin move from "inorganic" to "organic", improving its compatibility with organic substances containing a large number of hydrocarbon groups such as natural oils and fats, and T Ph The introduction of can greatly increase its toughness without significantly reducing its hardness.

[0082] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be 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 the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A phenyl-containing organosilicon resin film-forming agent, characterized in that: The organic silicone resin film-forming agent comprises an organic silicone resin having a general structural 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 The alkyl group, R 2 One or two independently selected from methyl, ethyl, propyl, phenyl and benzyl; the substituted substituent is any one of alkyl, aryl, hydroxyl and alkoxy; wherein 0.2<a<1; b≥0; 0.1<c<1.

2. The organic silicone resin film-forming agent according to claim 1, characterized in that: In the general structural formula (I), 0.5≤a<1; Preferably, in the general structural formula (I), 0.6≤a≤0.8; Preferably, in the general structural formula (I), 0.2≤c≤0.6; Preferably, in the general structural formula (I), 0.4≤c≤0.

6.

3. The organic silicone resin film-forming agent according to claim 1, characterized in that: The organic silicone resin film-forming agent is obtained by subjecting a reaction system including the following components to a hydrolysis condensation reaction: (A) Monofunctional silane; (B) phenyl-containing trifunctional silane; (C) tetrafunctional silane; (D) optionally a catalyst; (E) optionally an organic solvent; (F) Water.

4. The organic silicone resin film-forming agent according to claim 3, characterized in that: The molar ratio between the monofunctional silane and the tetrafunctional silane is (0.5 to 1): 1; Preferably, the molar ratio between the monofunctional silane and the tetrafunctional silane is (0.6-0.8):

1.

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

6. The organic silicone resin film-forming agent according to claim 1, characterized in that: The monofunctional silane includes one or more of trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane and hexamethyldisilazane; Preferably, the phenyl-containing trifunctional silane includes one or more of phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltrichlorosilane; Preferably, the tetrafunctional silane includes ethyl orthosilicate and / or tetramethoxysilane; Preferably, the catalyst comprises a hydrolysis catalyst and a condensation catalyst; More preferably, the hydrolysis catalyst comprises an acidic catalyst; the condensation catalyst comprises a basic catalyst; Preferably, the organic solvent includes one or more of isododecane, isotridecane, dimethyl silicone oil with a viscosity of 1 to 100 cps, and cyclic organopolysiloxane.

7. A method for preparing the organosilicon resin film-forming agent according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: S1. A monofunctional silane, a phenyl-containing trifunctional silane and a tetrafunctional silane are mixed to obtain a reaction mixture, 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 a set pH, perform a condensation reaction, and finally perform post-treatment to obtain a phenyl-containing organic silicone resin film-forming agent.

8. The preparation method according to claim 7, characterized in that: In step S1, the hydrolysis reaction specifically comprises the following steps: S11. adding water dropwise to the reaction mixture at a first set temperature, and after completion of the addition, refluxing at a second set temperature; Preferably, the first set temperature is 20°C to 30°C; Preferably, the dropping time is 1h~5h; Preferably, the second set temperature is 75°C to 85°C; Preferably, the reflux time is 2h~6h.

9. The preparation method according to claim 7, characterized in that: In step S2, the post-treatment includes neutralization, water washing, filtration, and reduced pressure distillation steps; Preferably, the set pH is 8 to 14; more preferably 9 to 10; Preferably, the temperature of the condensation reaction is 120°C to 180°C; more preferably 130°C to 160°C.

10. Use of the phenyl-containing organosilicon resin film-forming agent according to any one of claims 1 to 6 or the phenyl-containing organosilicon resin film-forming agent prepared by the preparation method according to any one of claims 7 to 9 in daily cosmetics, personal care products or medical products.

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