Organic silicon modified oil-soluble dye as well as preparation method and application thereof

Abstract

The invention relates to the technical field of makeup raw materials, and particularly discloses an organic silicon modified oil-soluble dye as well as a preparation method and application thereof. The organic silicon modified oil-soluble dye comprises a dye and organic silicon resin grafted on the dye, the preparation method comprises the following steps: stirring preparation raw materials of T, Q, D and M structural units, acetic acid and a catalyst I for reaction to obtain a reaction solution; and carrying out post-treatment on the reaction liquid to obtain the organic silicon resin. Mixing organic silicon resin, a polar organic solvent I and a catalyst II to obtain an organic silicon resin mixture; mixing a dye and a polar organic solvent II, adding the mixture into the organic silicon resin mixture, and continuously stirring for reaction to obtain a reaction solution; and carrying out post-treatment on the reaction liquid to obtain the organic silicon modified oil-soluble dye. The organic silicon modified oil-soluble dye disclosed by the invention has good compatibility and stability in oily cosmetics, is good in film forming effect and excellent in makeup maintaining effect, is not easy to remain after makeup removal, and has relatively wide applicability.

Description

Technical Field

[0001] This application relates to the field of color cosmetic raw material technology, and more specifically, it relates to an organosilicon-modified oil-soluble dye, its preparation method, and its application. Background Technology

[0002] In the cosmetics industry, colorants are the core raw materials for achieving product color expression. They are mainly divided into soluble dyes and pigments that are insoluble in the medium used. Dyes can dissolve in a specified solvent, using the solvent as a medium to color the object being dyed.

[0003] Based on their solubility, dyes are classified into water-soluble dyes and oil-soluble dyes. Unlike insoluble pigments, which color through microparticles that cover and reflect specific light, dyes dissolve at the molecular level, allowing the medium itself to become colored, exhibiting many unique advantages. For example, they offer exceptional transparency and a clear, sheer finish, as well as superior vibrancy and color intensity. In particular, because oil-soluble dyes can alter the color of the medium while largely maintaining its original texture, they possess excellent skin feel and blendability. Makeup products containing these oil-soluble dyes often have better spreadability, a smoother and lighter feel, and adhere better to the skin, avoiding the powdery and adherent feeling commonly found in pigment-based products.

[0004] Although oil-soluble dyes have the advantages mentioned above, in the cosmetic manufacturing process, various raw materials are heated to dissolve and then cooled to room temperature before being discharged. During this process, although the solubility of oil-soluble dye molecules increases after heating, the solubility decreases after cooling. This may cause recrystallization, precipitation, or the formation of ultrafine aggregates invisible to the naked eye, leading to problems such as sedimentation and uneven color in cosmetics. Summary of the Invention

[0005] To improve the temperature stability of oil-soluble dyes, this application provides an organosilicon-modified oil-soluble dye, its preparation method, and its application.

[0006] In a first aspect, this application provides an organosilicon-modified oil-soluble dye, employing the following technical solution: An organosilicon-modified oil-soluble dye comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: ; Where Dye is a dye and R is methyl or phenyl; Organosilicon resin is prepared by condensation reaction of raw materials including M structural units, D structural units, Q structural units and T structural units. a represents the equivalent amount of raw materials used to prepare the M-structure unit; b represents the equivalent amount of raw materials used to prepare the D-structure unit. c represents the equivalent amount of raw materials used to prepare the Q-structure unit; d represents the equivalent amount of raw materials used to prepare the T-structure unit. The ratio of a, b, c, d is (0.5~3):(2~50):(0~3):1.

[0007] In silicone resins, the M-structure unit is a monofunctional end-capping unit that controls the overall molecular weight, preventing the formation of excessively large cross-linked networks that could negatively impact the overall solubility of the material. The difunctional D-structure unit extends the flexible silicon chain, significantly improving solubility. Increasing the number of D-structure units also improves the film-forming flexibility of the final product; however, excessive D-structure units weaken film-forming properties. The Q-structure unit is a tetrafunctional cross-linking unit that enhances the rigidity of the film-forming material but limits the improvement in solubility. The trifunctional T-structure unit is generally constructed using siloxane coupling agent molecules with suitable functional groups, acting as a link between dye molecules and the silicone resin. To further increase solubility, structural units with lipophilic functional groups can also be introduced during synthesis. By controlling the composition and ratio of the structural units in the silicone resin, silicone resins with different solubilities and film-forming properties can be synthesized.

[0008] By adopting the above technical solution, water-soluble dye molecules that meet the requirements of cosmetics are transformed into oil-soluble dyes loaded with organosilicon resins, expanding the range of selectable oil-soluble dyes. Simultaneously, it changes the traditional mode of oil-soluble dyes dissolving in solvent systems in small molecule form. Based on organosilicon resins, polymer dyes link small molecule dyes through polymer chains, enhancing the overall compatibility and stability of the dyes, reducing dye migration, and allowing the color to be removed along with the polymer during makeup removal. The overall properties of polymer-type oil-soluble dyes largely depend on the composition of the loaded organosilicon resin. The ratio of the organosilicon resin can be adjusted according to requirements to regulate properties such as stability, solubility, and film-forming properties, facilitating the control of product performance in subsequent application formulations.

[0009] Preferably, the raw materials for preparing the T-structure unit in the organosilicon resin include any one of aminosilane coupling agents, mercaptosilane coupling agents, and alkylsilane coupling agents.

[0010] Preferably, the raw materials for preparing the Q structural unit in the organosilicon resin include tetraethyl orthosilicate or sodium silicate.

[0011] Preferably, the raw materials for preparing the D-structure unit in the organosilicon resin include any one of dimethyldimethoxysiloxane, hydroxyl polydimethylsiloxane, and diphenyldimethoxysilane.

[0012] Preferably, the raw materials for preparing the M structural unit in the organosilicon resin include hexamethyldisiloxane or hexaphenyldisiloxane.

[0013] One mol of hexamethyldisiloxane can generate 2 mol of M units in the reaction. By adopting the above technical solution and selecting the above-mentioned raw materials to prepare oil-soluble organosilicon resin, not only can water-soluble dyes be converted into oil-soluble dyes, but some advantages of organosilicon resins can also be retained, achieving a good combination of dye molecules and film-forming agents, and obtaining special cosmetic raw materials with high stability, good film-forming properties, high durability, good color migration resistance, and excellent water and oil repellency.

[0014] Secondly, this application provides a method for preparing organosilicon-modified oil-soluble dyes, using the following technical solution: A method for preparing an organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: The raw materials for preparing T-structure units, Q-structure units, D-structure units, and M-structure units are mixed, and then acetic acid is added. The mixture is stirred for 0.5–1 h to obtain a mixture. Catalyst I was added to the mixture and stirred at 60–80 °C for 4–8 h to obtain a reaction solution; the reaction solution was then post-treated to obtain an organosilicon resin. S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin and polar organic solvent I, the mixture is stirred at 60-120℃ for 0.5-2 hours, and then catalyst II is added to obtain an organosilicon resin mixture. The dye and polar organic solvent II are mixed and then added to the organosilicon resin mixture. The mixture is stirred and reacted for 8-12 hours to obtain a reaction solution. The reaction solution is then post-treated to obtain an organosilicon-modified oil-soluble dye.

[0015] By adopting the above technical solution, the raw materials for preparing each structural unit are first mixed with acetic acid. Acetic acid can be used as a reaction solvent and provide an acidic environment, so that the reaction system can be uniformly mass-transferred, which is conducive to the condensation reaction under the catalysis of catalyst I to obtain an oil-soluble organosilicon resin with a structure similar to MQ resin.

[0016] Secondly, after mixing the dye and polar organic solvent II, slowly add it dropwise to the organosilicon resin mixture to avoid obvious phase separation. After the addition is completed in 1 hour, continue heating to facilitate the coupling reaction between the dye and the amino or mercapto groups introduced in the organosilicon resin and the sulfonic acid groups in the dye molecules, thus completing the connection between the dye molecules and the organosilicon resin.

[0017] Finally, the reaction was stopped by cooling. The oil-soluble dye product was extracted using an ethyl acetate / water system, thoroughly washed with water to remove water-soluble dye residue, the solvent was removed under reduced pressure, and then dried in a vacuum oven at 80°C for 12–16 hours to obtain the target oil-soluble dye molecule. The preparation method described in this application is simple in procedure and easy to operate, making it suitable for large-scale production.

[0018] Preferably, in the preparation of the S1 organosilicon resin, the equivalent ratio of the raw materials for preparing the T structural unit, the raw materials for preparing the Q structural unit, the raw materials for preparing the D structural unit, and the raw materials for preparing the M structural unit is 1:(0~3):(2~50):(0.5~3).

[0019] Because water-soluble dye molecules have compatibility issues with oil-soluble organosilicon resins, the above-mentioned technical solution involves adding the raw materials for preparing D-structure units and M-structure units as necessary raw materials to obtain oil-soluble organosilicon resins. By controlling the amount of raw materials added for each structure unit, the resulting oil-soluble organosilicon resins have good compatibility with dye molecules. After grafting onto dye molecules, the resulting organosilicon-modified oil-soluble dyes exhibit excellent film-forming properties and solubility.

[0020] Meanwhile, during the research and production process, it was found that the D-structural unit is indispensable in the construction of this type of organosilicon resin; otherwise, an insoluble solid pigment product cannot be obtained, and oil solubility cannot be guaranteed. However, it should not be introduced in excess, otherwise the product will exhibit the form of a viscous, non-film-forming oily liquid.

[0021] The presence of Q-structure units increases the overall crosslinking degree of the silicone resin. Although it reduces the solubility of the product, it plays a role in regulating the film-forming texture of the product and can be added according to the product performance requirements.

[0022] When additional solubility is required, extra oil-soluble functional groups can be introduced into the M and T structural units. For example, triisopropylchlorosilane can be used to replace hexamethyldisiloxane in the construction of the M unit; in addition to the necessary siloxane coupling agent, octyltrimethoxysilane or dodecyltrimethoxysilane, which have additional lipophilic chains, can be introduced into the T unit to participate in the reaction.

[0023] Preferably, in the S2 organosilicon resin grafted dye, the mass ratio of dye to organosilicon resin is 1:(5-20).

[0024] By adopting the above technical solution, appropriately increasing the amount of dye grafting can improve the overall color concentration of the dye and enhance its color development ability. However, excessive addition of dye will lead to an increase in the degree of cross-linking of the material and a significant decrease in solubility, so the ratio is limited to a mass range of 1:(5-20).

[0025] Preferably, the catalyst I comprises any one of concentrated hydrochloric acid, sulfuric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.

[0026] By employing the above technical solutions, the catalytic reactions of inorganic acid salts, acids, and sulfuric acid are rapid and vigorous, requiring control of the addition rate. They can also be quickly removed by alkali washing after the reaction. Organic acids trifluoroacetic acid and trifluoromethanesulfonic acid exhibit good overall compatibility with the reaction system, resulting in mild and stable catalytic reactions; however, there is a risk of residue buildup during post-processing.

[0027] Preferably, the catalyst II comprises triethylamine or triethanolamine.

[0028] Preferably, the polar organic solvent I includes any one of tetrahydrofuran, ethylene glycol dimethyl ether, and N,N-dimethylformamide.

[0029] Preferably, the polar organic solvent II includes any one of water, ethanol, and tetrahydrofuran.

[0030] Secondly, this application provides an application of organosilicon-modified oil-soluble dyes, employing the following technical solution: Application of an organosilicon-modified oil-soluble dye in color cosmetics.

[0031] By adopting the above technical solution, the organosilicon-modified oil-soluble dye of this application has good compatibility and stability with oil-based makeup formulations, and can endow oil-based makeup with excellent film-forming properties, durability, color migration resistance and excellent waterproof and oil-repellent properties, greatly expanding the range of makeup color options and having a wide range of applicability.

[0032] In summary, this application has the following beneficial effects: 1. This application synthesizes a film-forming, performance-designable oil-soluble dye by chemically grafting water-soluble dyes onto oil-soluble organosilicon resins. The oil-soluble organosilicon resins are used to convert the dyes from water-soluble to water-soluble while retaining some of the advantages of organosilicon resins. This achieves a good combination of dye molecules and film-forming agents, and synthesizes a special color cosmetic raw material with excellent stability, film-forming properties, durability, color migration resistance, and excellent water and oil repellency. 2. In this application, by controlling the composition and ratio of the structural units of silicone resin, oil-soluble polymers with different solubility and film-forming properties can be synthesized, which is beneficial to improving the applicability of oil-soluble polymers in the field of color cosmetics. 3. This application modifies water-soluble dye molecules through reasonable modification, transforming them into dyes that are well-compatible with oil-based solvents. These dyes can be applied in the field of color cosmetics, greatly expanding the range of color options available for color cosmetics. Attached Figure Description

[0033] Figure 1 This is the infrared spectrum of the organosilicon-modified oil-soluble dye in Example 1 of this application; Figure 2 This is the infrared spectrum of the organosilicon-modified oil-soluble dye in Example 2 of this application; Figure 3 This is the infrared spectrum of the organosilicon-modified oil-soluble dye in Example 3 of this application. Detailed Implementation

[0034] The present application will be further described in detail below with reference to the accompanying drawings and embodiments.

[0035] Example Example 1

[0036] An organosilicon-modified oil-soluble dye comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: ; Dye is pigment CI 16035, and the silicone resin is composed of T structural units, Q structural units, D structural units and M structural units, where R is methyl, a=2, b=4, c=1 and d=1.

[0037] The preparation method of the above-mentioned organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: Hexamethyldisiloxane (14.7g), dimethyldimethoxysiloxane (43.4g), tetraethyl orthosilicate (18.8g), and aminopropyltriethoxysiloxane (20.0g) were mixed, and acetic acid (120ml) was added. The mixture was stirred for 0.5h to obtain a mixture.

[0038] Catalyst I (sulfuric acid, 2 ml) was added to the mixture and stirred at 80 °C for 8 h to obtain a reaction solution. The reaction solution was first cooled to room temperature, and then neutralized to neutrality by adding 12% sodium bicarbonate solution. Finally, it was extracted three times with ethyl acetate, and the organic phases collected three times were combined and washed with saturated brine. The washed organic phase was collected and the solvent was removed by vacuum. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain organosilicon resin (M2D4QT).

[0039] S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin (30g) and polar organic solvent I (tetrahydrofuran, 100ml), the mixture was stirred at 60℃ for 1h, and then catalyst II (triethylamine, 3g) was added to obtain an organosilicon resin mixture.

[0040] The dye (chroma key CI 16035, 5g) and polar organic solvent II (tetrahydrofuran, 50ml) were mixed and then added to the organosilicon resin mixture at a flow rate of 1ml / min. After the addition was complete, the reaction was stirred for 12h to obtain the reaction solution. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The three organic phases were combined and washed three times each with water and saturated brine. The aqueous phase was nearly colorless. The washed organic phase was collected, and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80℃ for 12h to obtain the oil-soluble dye. Figure 1 It can be seen that the oil-soluble dye is the organosilicon-modified oil-soluble dye shown in Example 1. Example 2

[0041] An organosilicon-modified oil-soluble dye comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: ; Dye is pigment CI 16035. The silicone resin is composed of T structural units, Q structural units, D structural units and M structural units, where R is methyl, a=2, b=16, c=0.5 and d=1.

[0042] The preparation method of the above-mentioned organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: Hexamethyldisiloxane (14.7 g), hydroxydimethylpolysiloxane (average molecular weight 800, 82.1 g), tetraethyl orthosilicate (9.91 g) and aminopropyltriethoxysiloxane (20.0 g) were mixed, and then acetic acid (150 ml) was added. The mixture was stirred for 0.5 h to obtain a mixture.

[0043] Catalyst I (sulfuric acid, 2 ml) was added to the mixture, and the mixture was stirred at 80 °C for 6 h to obtain a reaction solution. The reaction solution was first cooled to room temperature, then neutralized to neutrality with 12% sodium bicarbonate solution. Finally, the mixture was extracted three times with ethyl acetate. The three organic phases were combined and washed with saturated brine. The washed organic phase was collected, and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain the organosilicon resin (M2D). 16 Q 0.5 T).

[0044] S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin (30g) and polar organic solvent I (tetrahydrofuran, 100ml), the mixture was stirred at 60℃ for 1h, and then catalyst II (triethylamine, 3g) was added to obtain an organosilicon resin mixture.

[0045] The dye (chroma key CI 16035, 5g) and polar organic solvent II (tetrahydrofuran, 50ml) were mixed and then added to the organosilicon resin mixture at a flow rate of 1ml / min. After the addition was complete, the reaction was stirred for 12h to obtain the reaction solution. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The three organic phases were combined and washed three times each with water and saturated brine. The aqueous phase was nearly colorless. The washed organic phase was collected, and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80℃ for 12h to obtain the oil-soluble dye. Figure 2 It can be seen that the oil-soluble dye is the organosilicon-modified oil-soluble dye shown in Example 2. Example 3

[0046] An organosilicon-modified oil-soluble dye comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: ; Dye is color pigment CI 20470, and the silicone resin is composed of T1 structural unit, T2 structural unit, D structural unit and M structural unit, where R is methyl, a=2, b=4, c=1 and d=1.

[0047] The preparation method of the above-mentioned organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: Triisopropylchlorosilane (34.8 g), dimethyldimethoxysiloxane (43.4 g), octyltrimethoxysilane (24.9 g) and mercaptopropyltrimethoxysilane (17.4 g) were mixed, and then acetic acid (150 ml) was added. The mixture was stirred for 0.5 h to obtain a mixture.

[0048] Catalyst I (trifluoromethanesulfonic acid, 2 ml) was added to the mixture, and the mixture was stirred at 80 °C for 6 h to obtain a reaction solution. The reaction solution was first cooled to room temperature, and then neutralized to neutrality by adding 12% sodium bicarbonate solution. Finally, the mixture was extracted three times with ethyl acetate, and the three organic phases were combined and washed with saturated brine. The washed organic phase was collected, and the solvent was removed by vacuum drying. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain the organosilicon resin (MD2Q). 0.5 T).

[0049] S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin (30g) and polar organic solvent I (DMF, 100ml), the mixture was stirred at 120℃ for 1h, and then catalyst II (triethanolamine, 3g) was added to obtain an organosilicon resin mixture.

[0050] The dye (chroma key CI 20470, 5 g) and polar organic solvent II (ethanol, 50 ml) were mixed and then added to the organosilicon resin mixture at a flow rate of 1 ml / min. After the addition was complete, the reaction was stirred for 12 h to obtain the reaction solution. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The three organic phases were combined and washed three times each with water and saturated brine. The aqueous phase was nearly colorless. The washed organic phase was collected, and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain the oil-soluble dye. Figure 3 It can be seen that the oil-soluble dye is the organosilicon-modified oil-soluble dye shown in Example 3.

[0051] The raw materials used in the preparation methods of organosilicon-modified oil-soluble dyes in Examples 1-3 are shown in the table below.

[0052]

[0053] Comparative Example Comparative Example 1 An organosilicon-modified oil-soluble dye, differing from Example 1 in that it comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: ; Dye is color pigment CI 20470. The silicone resin is composed of T structural units, Q structural units, D structural units and M structural units, where R is methyl, a=2, b=1 and d=1.

[0054] The preparation method of the above-mentioned organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: Hexamethyldisiloxane (14.7g), tetraethyl orthosilicate (18.8g), and aminopropyltriethoxysiloxane (21.3g) were mixed, and then acetic acid (100ml) was added. The mixture was stirred for 0.5h to obtain a mixture.

[0055] Catalyst I (sulfuric acid, 2 ml) was added to the mixture and stirred at 80 °C for 6 h to obtain a reaction solution. The reaction solution was first cooled to room temperature, and then neutralized to neutrality by adding 12% sodium bicarbonate solution. Finally, it was extracted three times with ethyl acetate, and the organic phases collected three times were combined and washed with saturated brine. The washed organic phase was collected and the solvent was removed by vacuum drying. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain organosilicon resin (M2QT).

[0056] S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin (30g) and polar organic solvent I (DMF, 100ml), the mixture was stirred at 120℃ for 1h, and then catalyst II (triethanolamine, 3g) was added to obtain an organosilicon resin mixture.

[0057] The dye (chroma key CI 20470, 5 g) and polar organic solvent II (ethanol, 50 ml) were mixed and then added to the organosilicon resin mixture at a flow rate of 1 ml / min. After the addition was complete, the mixture was stirred for 12 h to obtain a reaction solution. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The three organic phases were combined and washed three times each with water and saturated brine. The aqueous phase was nearly colorless. The washed organic phase was collected and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain a solid grafted product.

[0058] Because the organosilicon-modified oil-soluble dye prepared in Comparative Example 2 lacks D structural units and has excessive crosslinking, it is difficult to dissolve and therefore cannot be used in subsequent performance comparisons.

[0059] Comparative Example 2 An organosilicon-modified oil-soluble dye comprises a dye and an organosilicon resin grafted onto the dye; its structural formula is shown below: .

[0060] Dye is pigment CI 16035, and the silicone resin is composed of T structural units, Q structural units, D structural units and M structural units, where R is phenyl, a=2, b=4, c=1 and d=1.

[0061] The preparation method of the above-mentioned organosilicon-modified oil-soluble dye includes the following steps: Preparation of S1 silicone resin: Hexaphenyldisiloxane (48.3g), diphenyldimethoxysilane (88.3g), tetraethyl orthosilicate (18.8g) and aminopropyltriethoxysiloxane (20g) were mixed, and acetic acid (100ml) was added. The mixture was stirred for 0.5h to obtain a mixture.

[0062] Catalyst I (sulfuric acid, 2 ml) was added to the mixture and stirred at 80 °C for 6 h to obtain a reaction solution. The reaction solution was first cooled to room temperature, and then neutralized to neutrality by adding 12% sodium bicarbonate solution. Finally, it was extracted three times with ethyl acetate, and the organic phases collected three times were combined and washed with saturated brine. The washed organic phase was collected and the solvent was removed by vacuum drying. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain organosilicon resin (M2D4QT-Ph).

[0063] S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin (30g) and polar organic solvent I (DMF, 100ml), the mixture was stirred at 120℃ for 1h, and then catalyst II (triethanolamine, 3g) was added to obtain an organosilicon resin mixture.

[0064] The dye (chroma key CI 20470, 2.5 g) and polar organic solvent II (ethanol, 50 ml) were mixed and then added to the organosilicon resin mixture at a flow rate of 1 ml / min. After the addition was complete, the mixture was stirred for 12 h to obtain a reaction solution. The reaction solution was cooled to room temperature and extracted three times with ethyl acetate. The three organic phases were combined and washed three times each with water and saturated brine. The aqueous phase was nearly colorless. The washed organic phase was collected and the solvent was removed under reduced pressure. The concentrate was collected and dried in a vacuum oven at 80 °C for 12 h to obtain a solid grafted product. Performance testing

[0065] The dyes prepared in the examples and comparative examples were subjected to stability, solubility, and film-forming properties tests, and the test methods are as follows: Stability test: The dyes prepared in Examples 1-3 and Comparative Example 2 were respectively mixed with cyclopentadimethylsiloxane, isododecane, isononyl isononanoate, and dimethyl silicone oil (10cSt) to prepare 25% mass fraction solutions. The solutions were first stirred and mixed at 80°C for 15 min, and then stored at -15°C and 55°C for 4 weeks. The solutions were then visually inspected to see if they separated into layers, changed color, or precipitated.

[0066] Solubility test: The dye was prepared into a 25% mass mixture with cyclopentadimethylsiloxane, isododecane, caprylic / capric triglyceride, dimethyl silicone oil (10cSt), and dimethyl silicone oil (100cSt). The mixture was stirred at 80°C for 15 min and then allowed to return to room temperature. The solubility of the dye in the mixture was then visually inspected.

[0067] Film-forming property test: The dye and isododecane were prepared into a 25% mass fraction solution, stirred and mixed at 80℃ for 15 min, and then brought to room temperature. The solution was then applied to the skin surface and allowed to stand and dry for 10 min. The appearance of the formed film was visually inspected to see if it was uniform and smooth, and to assess the feel of the film (hard, soft, tough, sticky), as well as the elasticity, durability, and integrity of the film after standing for 1 hour.

[0068] Performance test results: (1) Stability of dyes prepared in Examples 1-3 and Comparative Example 2

[0069] Data analysis of the table above shows that the dyes prepared in Examples 1-3, after being dissolved in conventional solvents by heating, and stored at -15°C and 55°C for 4 weeks, did not exhibit stratification or discoloration, maintaining good stability. However, the dye prepared in Comparative Example 2 showed low-temperature stratification in isododecane and isononyl isononanoate. This indicates that in the organosilicon-modified oil-soluble dyes of this application, the R in the D structural unit is a methyl group, which can improve the stability of organosilicon-modified oil-soluble dyes in oil-based formulation systems.

[0070] (2) Solubility

[0071] Data analysis of the table above shows that the dyes prepared in Examples 1-3, due to modification with organosilicon resin, exhibit good solubility in conventional oil-based formulation systems. In particular, the dye prepared in Example 3, by introducing additional lipophilic groups, can increase its solubility without significantly altering the proportions of the raw materials used in each structural unit.

[0072] Compared to the dyes prepared in Examples 1-3, the dye in Comparative Example 2 was insoluble in conventional oil-based formulation systems. This indicates that the D-structural unit in the organosilicon-modified oil-soluble dye of this application can improve the solubility of the organosilicon-modified oil-soluble dye in oil-based formulation systems. The reason for this is likely that the D-structural unit extends the flexible silicon chain, significantly affecting the dye's solubility in oil-based formulation systems. However, the D-structural unit should not be introduced in excessive amounts; otherwise, the synthesized dye will exhibit the form of a viscous, non-film-forming oily liquid.

[0073] Compared to the dyes prepared in Examples 1-3, the dye in Comparative Example 3 is partially insoluble in conventional oil-based formulation systems. This indicates that in the organosilicon-modified oil-soluble dyes of this application, the R in the D structural unit is a methyl group, which can improve the solubility of the organosilicon-modified oil-soluble dyes in oil-based formulation systems.

[0074] (3) Film-forming properties

[0075] Data analysis of the table above shows that the dyes prepared in Examples 1 to 3 can all form uniform and glossy films.

[0076] Compared to Example 3, the membrane in Example 1 has poorer elasticity. Compared to Examples 1 and 2, the membrane in Example 3 has higher durability. This may be because in Example 1, the Q and T ratios are higher, resulting in a higher overall degree of cross-linking and a harder membrane with poorer elasticity and generally lower durability. In Example 2, the D ratio is significantly increased, enhancing the membrane structure's variability and improving its elasticity. In Example 3, due to the introduction of additional alkyl chain modifications, the flexible segments maintain the characteristics of a soft membrane, improving overall toughness and skin adhesion while maintaining a certain degree of cross-linking.

[0077] Compared to the dyes prepared in Examples 1-3, the dye prepared in Comparative Example 2 formed a film with unevenness and weak gloss. This indicates that in the organosilicon-modified oil-soluble dyes of this application, the R in the D structural unit is methyl, which can improve the film-forming properties of organosilicon-modified oil-soluble dyes in oil-based formulation systems. The reason for this may be that while phenyl silicone oil plays a relatively important role in improving film gloss and refractive index in current applications, the high gloss of phenyl silicone oil depends on good film-forming properties, and uneven aggregation states cannot demonstrate this advantage.

[0078] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. An organosilicon-modified oil-soluble dye, characterized in that, It includes dyes and silicone resins grafted onto the dyes; its structural formula is shown below: ； Where Dye is a dye and R is methyl or phenyl; Organosilicon resin is prepared by condensation reaction of raw materials including M structural units, D structural units, Q structural units and T structural units. a represents the equivalent amount of raw materials used to prepare the M-structure unit; b represents the equivalent amount of raw materials used to prepare the D-structure unit. c represents the equivalent amount of raw materials used to prepare the Q-structure unit; d represents the equivalent amount of raw materials used to prepare the T-structure unit. The ratio of a, b, c, d is (0.5~3):(2~50):(0~3):

1.

2. The organosilicon-modified oil-soluble dye according to claim 1, characterized in that, The raw materials for preparing the T-structure unit in the organosilicon resin include any one of aminosilane coupling agents, mercaptosilane coupling agents, and alkylsilane coupling agents.

3. The organosilicon-modified oil-soluble dye according to claim 1, characterized in that, In the organosilicon resin, the raw materials for preparing the Q structural unit include tetraethyl orthosilicate or sodium silicate.

4. The organosilicon-modified oil-soluble dye according to claim 1, characterized in that, In the organosilicon resin, the raw materials for preparing the D structural unit include any one of dimethyldimethoxysiloxane or hydroxyl polydimethylsiloxane and diphenyldimethoxysilane.

5. The organosilicon-modified oil-soluble dye according to claim 1, characterized in that, In the organosilicon resin, the raw materials for preparing the M structural unit include hexamethyldisiloxane or hexaphenyldisiloxane.

6. The method for preparing the organosilicon-modified oil-soluble dye according to any one of claims 1 to 5, characterized in that, Includes the following steps: Preparation of S1 silicone resin: The raw materials for preparing T-structure units, Q-structure units, D-structure units, and M-structure units are mixed, and then acetic acid is added. The mixture is stirred for 0.5–1 h to obtain a mixture. Catalyst I was added to the mixture and stirred at 60–80 °C for 4–8 h to obtain a reaction solution; the reaction solution was then post-treated to obtain an organosilicon resin. S2 Organosilicon Resin Grafted Dye: After mixing organosilicon resin and polar organic solvent I, the mixture is stirred at 60-120℃ for 0.5-2 hours, and then catalyst II is added to obtain an organosilicon resin mixture. The dye and polar organic solvent II are mixed and then added to the organosilicon resin mixture. The mixture is stirred and reacted for 8-12 hours to obtain a reaction solution. The reaction solution is then post-treated to obtain an organosilicon-modified oil-soluble dye.

7. The method for preparing organosilicon-modified oil-soluble dyes according to claim 6, characterized in that, In the preparation of the S1 organosilicon resin, the equivalent ratio of the raw materials for preparing the T structural unit, the Q structural unit, the D structural unit, and the M structural unit is 1:(0~3):(2~50):(0.5~3).

8. The method for preparing organosilicon-modified oil-soluble dyes according to claim 6, characterized in that, In the S2 organosilicon resin grafted dye, the mass ratio of dye to organosilicon resin is 1:(5-20).

9. The method for preparing organosilicon-modified oil-soluble dyes according to claim 6, characterized in that, Catalyst I includes any one of concentrated hydrochloric acid, sulfuric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.

10. The application of the organosilicon-modified oil-soluble dye according to any one of claims 1 to 5, characterized in that, Applications in makeup.

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