Cosmetic film-forming agent as well as preparation method and application thereof
The polymer film-forming agent prepared by reacting soluble polysaccharides with halogenated organosilicones solves the shortcomings of cosmetic film-forming agents in terms of durability, flexibility, gloss, and skin feel, and achieves excellent film-forming effect.
Patent Information
- Application Number
- CN202511882736.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-12
- Publication Date
- 2026-01-30
AI Technical Summary
Existing cosmetic film-forming agents cannot meet the needs of the market and consumers in terms of film-forming durability, flexibility, film gloss, and skin feel.
A polymer film-forming agent was prepared by silanizing soluble polysaccharides with halogenated organosilanes. The polymer has a specific structure and molecular weight range, which ensures the cohesive strength and flexibility of the film. The water resistance and gloss of the film are improved by the synergistic effect of the branched structure and degree of substitution.
It achieves excellent film-forming durability, flexibility, high gloss and comfortable skin feel of cosmetic film-forming agents, and solves the shortcomings of existing film-forming agents in terms of durability, flexibility, gloss and skin feel.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of daily-use cosmetics, and particularly relates to a cosmetic film-forming agent, a preparation method and application thereof. BACKGROUND
[0002] Film-forming agents are a class of chemical substances that form a continuous film on the surface of an object through solution evaporation or molecular cross-linking. Film-forming agents in cosmetics can be divided into water-soluble film-forming agents and hydrophobic film-forming agents according to their solubility. After drying, they can form a film on the skin, hair or nails. Film-forming agents can impart moisturizing, sunscreen, sweat-resistant, waterproofing, styling and other functions to cosmetic products. Common oil-soluble film-forming agents include polyvinylpyrrolidone / hexadecene copolymer, trimethylsiloxy silicate, acrylic resin and dimethylsiloxane copolymer, etc.; common water-soluble film-forming agents include acrylic acid salt / octyl acrylamide copolymer, polyvinylpyrrolidone, polyvinyl alcohol, acrylic acid copolymer, etc.
[0003] With the increasing diversification and functionality of cosmetic products, the demand for cosmetic film-forming agents is increasing. However, the performance of existing film-forming agents in terms of film-forming durability, film-forming flexibility, film gloss and skin feel cannot meet the needs of the market and consumers. SUMMARY
[0004] The present application provides a cosmetic film-forming agent, a preparation method and application thereof. The cosmetic film-forming agent has excellent film-forming durability, flexibility, high gloss and comfortable skin feel.
[0005] In a first aspect, the present application provides the use of a polymer as a cosmetic film-forming agent, wherein the polymer is prepared by a silyl etherification reaction of a soluble polysaccharide and a halogenated organosilane. The polymer has a structure represented by formula (I): (I), wherein A comprises a soluble polysaccharide residue, the weight average molecular weight of the soluble polysaccharide is 3000 Da to 18000 Da; R1, R2 and R3 are each independently selected from one of C1-C22 alkyl, C6-C12 aryl ring group, C1-C22 halogenated alkyl and C6-C12 halogenated aryl ring group; and at least one of R1, R2 and R3 is C8-C22 alkyl containing a branch; and n is an average degree of substitution, selected from a natural number of 1 to 3.
[0006] In any embodiment of the present application, R1, R2 and R3 are each independently selected from C1-C22 alkyl or phenyl; and at least one of R1, R2 and R3 is C8-C22 alkyl containing a branch.
[0007] In any embodiment of this application, the C8-C22 alkyl group containing the branch is selected from the structure shown in one of formulas (II-1) to (II-5): (II-1) (II-2) (II-3) (II-4) (II-5)
[0008] In any embodiment of this application, the weight-average molecular weight of the soluble polysaccharide is 8000 Da to 12000 Da; optionally, the soluble polysaccharide includes at least one of inulin, maltodextrin and soluble starch.
[0009] In any embodiment of this application, at least one of R1, R2, and R3 is a C8-C12 alkyl group containing branches.
[0010] In any embodiment of this application, the soluble polysaccharide is maltodextrin, the weight average molecular weight of the soluble polysaccharide is 8000 Da ~ 12000 Da, at least one of R1, R2, and R3 is a C8 ~ C12 alkyl group containing branches, and n is 1.8 ~ 2.2, preferably 2.
[0011] Secondly, this application provides a method for preparing a cosmetic film-forming agent, comprising the following steps: dissolving soluble polysaccharide and triethylamine in N,N-dimethylformamide to obtain a premix; adding a haloorganosilane to the premix and reacting to obtain a crude product; purifying the crude product to obtain the cosmetic film-forming agent; wherein the molar ratio of soluble polysaccharide, triethylamine and haloorganosilane is 1:4:2.
[0012] In any embodiment of this application, the soluble polysaccharide includes at least one selected from inulin, maltodextrin, and soluble starch; optionally, the weight-average molecular weight of the soluble polysaccharide is 3000 Da to 18000 Da; optionally, the haloorganosilanes have the structure shown in formula (II): (II) X is selected from at least one of Cl, Br and I, and R1, R2 and R3 are each independently selected from one of C1~C22 alkyl, C6~C12 aryl, C1~C22 haloalkyl and C6~C12 haloaryl; and at least one of R1, R2 and R3 is a C8~C22 alkyl containing a branch.
[0013] In any embodiment of this application, in the step of adding a haloorganosilane to a premixed solution and reacting to obtain a crude product, the reaction temperature is 0°C to 25°C and the reaction time is 18h to 24h. Optionally, the step of purifying the crude product to obtain a cosmetic film-forming agent includes mixing the crude product with water and extracting it with ethyl acetate to obtain a crude extract, and concentrating the crude extract under reduced pressure to obtain the cosmetic film-forming agent.
[0014] Thirdly, this application provides a cosmetic film-forming agent, which is prepared according to the preparation method described in the second aspect, and the cosmetic film-forming agent has the structure shown in formula (I): (I), where, A includes soluble polysaccharide residues, and the weight-average molecular weight of the soluble polysaccharide is 3000 Da to 18000 Da; R1, R2, and R3 are each independently selected from one of C1-C22 alkyl, C6-C12 aromatic alkyl, C1-C22 haloalkyl, and C6-C12 haloaromatic alkyl; and at least one of R1, R2, and R3 is a C8-C22 alkyl group containing a branch; n is the average degree of substitution, selected from a natural number from 1 to 3.
[0015] This application uses a polymer with a specific structure as a film-forming agent in cosmetics. The soluble polysaccharide backbone with a specific weight-average molecular weight of 3000-18000 Da in the polymer ensures that the film has the necessary cohesive strength and continuity, laying the foundation for durability. At least one of R1, R2, and R3 is a branched C8-C22 alkyl group, which effectively inhibits the tight stacking of molecular chains through its large steric hindrance, giving the film excellent flexibility to prevent cracking. At the same time, its hydrophobicity and smoothness jointly improve the water resistance durability and surface gloss. In addition, the average degree of substitution of 1-3 can balance the skin affinity of polysaccharides and the excellent sensory properties of organosilicones, so that the film is firm but not rigid, thus bringing a light and comfortable skin feel. Detailed Implementation
[0016] To make the purpose, technical solution, and beneficial technical effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the implementation details described in this specification are merely for illustrative purposes and are not intended to limit the scope of this application.
[0017] For simplicity, this application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form a range not explicitly stated; and any lower limit can be combined with other lower limits to form a range not explicitly stated, just as any upper limit can be combined with any other upper limit to form a range not explicitly stated. Furthermore, although not explicitly stated, every point or individual value between the endpoints of the range is included within that range. Therefore, each point or individual value can be used as its own lower or upper limit and combined with any other point or individual value or with other lower or upper limits to form a range not explicitly stated.
[0018] It should be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0019] Unless otherwise stated, the values of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this application). Unless otherwise stated, the test temperature for all parameters mentioned in this application is 25°C and the test pressure is standard atmospheric pressure.
[0020] The foregoing description of this application is not intended to describe every disclosed implementation or method. Instead, the following description provides more specific examples of exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments, which can be used in various combinations. The examples listed are representative only and should not be construed as exhaustive.
[0021] In view of the deficiencies in the prior art, this application provides a cosmetic film-forming agent, its preparation method and application. The prepared cosmetic film-forming agent has excellent film-forming durability, flexibility, high gloss and comfortable skin feel.
[0022] The first aspect of this application provides an application of a polymer as a film-forming agent in cosmetics, wherein the polymer is prepared by a silanization reaction of a soluble polysaccharide with a halogenated organosilane; The polymer has the structure shown in formula (Ⅰ): (I), wherein A includes soluble polysaccharide residues, the weight average molecular weight of which is 3000 Da to 18000 Da; R1, R2, and R3 are each independently selected from one of C1 to C22 alkyl, C6 to C12 aromatic alkyl, C1 to C22 haloalkyl, and C6 to C12 haloaromatic alkyl; and at least one of R1, R2, and R3 is a C8 to C22 alkyl containing a branch; n is the average degree of substitution, selected from a natural number from 1 to 3.
[0023] In some embodiments, the cosmetic film-forming agent is a polysaccharide silyl etherification derivative formed by the silyl etherification reaction between the hydroxyl groups in the soluble polysaccharide structure and the halogen atoms in the haloorganosilanes.
[0024] As an example, the weight-average molecular weight of soluble polysaccharides can be 3000 Da, 4000 Da, 5000 Da, 6000 Da, 7000 Da, 8000 Da, 9000 Da, 10000 Da, 11000 Da, 12000 Da, 13000 Da, 14000 Da, 15000 Da, 16000 Da, 17000 Da, or 18000 Da.
[0025] n refers to the average number of hydroxyl groups substituted by silylation on each glycoside repeating unit in a soluble polysaccharide. For example, n can be 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0.
[0026] The polymer contains soluble polysaccharides with a weight-average molecular weight between 3000 Da and 18000 Da. Its moderate molecular chain length provides sufficient cross-linking sites to ensure membrane stability while avoiding the stiffness caused by excessively large molecules. R1, R2, and R3 are each independently selected from C1-C22 alkyl groups, C6-C12 aromatic ring groups, etc., with at least one being a branched C8-C22 alkyl group. The branched structure reduces intermolecular forces, improving the membrane's spreadability and flexibility. The synergistic effect of groups with different carbon chain lengths and structures enhances the adhesion between the membrane and the skin, and imparts a good gloss to the membrane. n is 1-3. The average degree of substitution is within a range that balances the hydrophilicity of polysaccharides with the hydrophobicity of halogenated organosilicones. This avoids problems such as poor film formation and sweat resistance caused by excessively low substitution, or sticky skin feel caused by excessively high substitution. The synergistic effect of these three factors allows the polymer to simultaneously possess excellent film formation durability, flexibility, high gloss, and comfortable skin feel as a cosmetic film-forming agent.
[0027] In some embodiments, R1, R2, and R3 are each independently selected from C1 to C22 alkyl or phenyl groups; and at least one of R1, R2, and R3 is a C8 to C22 alkyl group containing branches.
[0028] The hydrophobicity of C1-C22 alkyl or phenyl groups enhances the adhesion between the film and the skin surface, reduces damage to the film from external environments (such as sweat and moisture), and improves film durability. The branched structure of C8-C22 alkyl groups breaks up the tight packing of molecular chains, reducing intermolecular forces and making the film more flexible under stress, thus giving it excellent flexibility and preventing cracking or peeling due to dryness or external forces. Simultaneously, the regular structure of C1-C22 alkyl or phenyl groups synergistically with the spatial arrangement of branched C8-C22 alkyl groups reduces surface roughness, improves light reflection uniformity, and enhances the film's gloss. Furthermore, the presence of branches prevents the sticky feel caused by excessive aggregation of long-chain alkyl groups, and the appropriate length of C1-C22 alkyl groups further contributes to this effect. Alkyl or phenyl compounds can enable the film to form a thin, smooth coating on the skin surface, ultimately achieving the effect of film-forming agents with excellent film-forming durability, flexibility, high gloss, and comfortable skin feel.
[0029] In some embodiments, the branched C8-C22 alkyl group is selected from the structure shown in one of formulas (II-1) to (II-5): (II-1) (II-2) (II-3) (II-4) (II-5)
[0030] The specific branched structures of formulas (II-1) to (II-5) can form appropriate steric hindrance between the molecular chains of the film-forming agent, which not only avoids the brittleness of the film layer caused by excessively dense molecular packing, but also enhances the stability of the film layer structure through the synergistic effect between the branches, reduces the damage to the film layer caused by sweat and water penetration, and improves the film-forming durability. At the same time, these specific branches can break the rigid arrangement of molecular chains, allowing the film layer to flexibly stretch with the deformation of the skin during skin movement, effectively preventing cracking or peeling, and giving it excellent flexibility. In addition, the regular spatial configuration of the branches of formulas (II-1) to (II-5) can reduce the surface roughness of the film layer, improve the uniformity of light reflection, and thus enhance the high gloss of the film layer. Moreover, this type of branched structure can reduce the stickiness caused by the aggregation of long-chain alkyl groups, so that the film layer forms a thin and smooth covering layer on the skin surface. Combined with its hydrophobicity and skin compatibility, the film-forming agent achieves the effect of excellent film-forming durability, flexibility, high gloss and comfortable skin feel.
[0031] In some embodiments, the weight-average molecular weight of the soluble polysaccharide is 8000 Da to 12000 Da; optionally, the soluble polysaccharide includes at least one of inulin, maltodextrin and soluble starch.
[0032] 8000Da~12000Da The weight-average molecular weight ensures that the polysaccharide molecular chain length is within a moderate range. This provides sufficient reaction sites to form stable silane bonds with haloorganosilanes, constructing a robust film framework to enhance film-forming durability. It also avoids the problems of film stiffness caused by excessively long molecular chains or easy film breakage caused by excessively short chains. Inulin, maltodextrin, and soluble starch themselves have good water solubility and biocompatibility. After silane etherification, the hydroxyl groups in their molecular structure retain moderate hydrophilicity to ensure the film adheres well to the skin. The introduced organosilicon segments enhance the film's flexibility, preventing cracking after drying. At the same time, the natural molecular regularity of these polysaccharides improves the smoothness of the film surface, helping to uniformly reflect light and enhance high gloss. Their mild properties and moderate molecular weight work together to avoid the film forming a heavy, sticky feeling on the skin surface, achieving a light, smooth, and comfortable skin feel. This gives the film-forming agent excellent film-forming durability, flexibility, high gloss, and comfortable skin feel.
[0033] In some embodiments, at least one of R1, R2, and R3 is a C8-C12 alkyl group containing branches.
[0034] As an example, at least one of R1, R2, and R3 is a C8-C12 alkyl group containing branches.
[0035] The C8-C12 carbon chain length offers both suitable hydrophobicity and skin compatibility, further enhancing the adhesion between the film and the skin surface, reducing the erosion of the film by sweat and external moisture, and improving film durability. It also avoids the problem of a thick film caused by the aggregation of long-chain alkyl groups. The branched structure breaks up the tight packing between molecular chains, reducing intermolecular forces and allowing the film to deform flexibly during skin activity, effectively preventing cracking or peeling after drying and providing excellent flexibility. Simultaneously, the regular spatial configuration and moderate molecular volume of the C8-C12 branched alkyl groups further reduce surface roughness, improve light reflection uniformity, and achieve high gloss. Furthermore, this length of branched chain avoids the easy dissolution of the film due to insufficient hydrophobicity of short-chain alkyl groups and prevents the sticky feeling caused by long-chain alkyl groups, allowing the film to form a thin and smooth covering layer on the skin surface. This results in a film-forming agent with excellent film durability, flexibility, high gloss, and a comfortable feel.
[0036] In some embodiments, the soluble polysaccharide is maltodextrin, the weight-average molecular weight of the soluble polysaccharide is 8000 Da to 12000 Da, at least one of R1, R2, and R3 is a C8 to C12 alkyl group containing branches, and n is 1.8 to 2.2, preferably 2.
[0037] Maltodextrin with a weight-average molecular weight of 8000 Da to 12000 Da forms the structural basis of the film-forming agent, possessing both cohesive strength and flexibility. On the one hand, maltodextrin within this weight-average molecular weight range can provide a solid cohesive framework through sufficient interchain entanglement, ensuring film durability; on the other hand, it avoids excessive rigidity of the polymer chain, thus ensuring the flexibility and conformability of the film layer. At least one of R1, R2, and R3 is a C8 to C12 alkyl group containing branches. Its moderate chain length and branched structure endow the film layer with good hydrophobicity and durability, while avoiding the stiffness caused by excessively long alkyl groups, effectively improving flexibility and smooth gloss. The n value is controlled at 1.8 to 2.2, ensuring that each sugar unit is grafted with an average of about two organosilicon side chains, which enables the biocompatibility of polysaccharides and the excellent skin feel of organosilicon to achieve a perfect synergy. This ensures both the continuity and strength of the film layer, while avoiding the stiffness caused by excessive cross-linking, ultimately achieving high gloss and a comfortable skin feel.
[0038] The second aspect of this application provides a method for preparing a cosmetic film-forming agent, comprising the following steps: dissolving soluble polysaccharide and triethylamine in N,N-dimethylformamide to obtain a premix; adding a haloorganosilane to the premix and reacting to obtain a crude product; purifying the crude product to obtain the cosmetic film-forming agent; wherein the molar ratio of soluble polysaccharide, triethylamine and haloorganosilane is 1:4:2.
[0039] Soluble polysaccharides, triethylamine, and haloorganosilanes were dissolved in N,N-dimethylformamide at a molar ratio of 1:4:2, followed by reaction and purification. Excess triethylamine effectively neutralized the hydrogen halides generated during the reaction, preventing their inhibition of the silanization reaction. Simultaneously, it ensured efficient binding of the haloorganosilanes to the hydroxyl groups of the soluble polysaccharides, avoiding poor film durability due to excessively low substitution and sticky skin feel due to excessively high substitution. This ensured stable and controllable substitution of the silanization groups in the product. N,N-dimethylformamide, as an excellent solvent, allowed for uniform dispersion of the raw materials, reducing incomplete local reactions and resulting in uneven product structure. Subsequent purification removed unreacted raw materials and byproducts, preventing impurities from affecting film smoothness and imparting high gloss and a comfortable skin feel (preventing stickiness or roughness).
[0040] In some embodiments, the soluble polysaccharide includes at least one of inulin, maltodextrin, and soluble starch; optionally, the weight-average molecular weight of the soluble polysaccharide is 3000 Da to 18000 Da. Alternatively, the haloorganosilanes have the structure shown in formula (II): (II) X is selected from at least one of Cl, Br and I, and R1, R2 and R3 are each independently selected from one of C1~C22 alkyl, C6~C12 aryl, C1~C22 haloalkyl and C6~C12 haloaryl; and at least one of R1, R2 and R3 is a C8~C22 alkyl containing a branch.
[0041] Soluble polysaccharides such as inulin, maltodextrin, or soluble starch are selected, and their biocompatibility brings a comfortable skin feel to the membrane. Controlling their weight-average molecular weight within the range of 3000 Da to 18000 Da balances the cohesive strength and chain flexibility of the film, ensuring excellent durability and flexibility. Simultaneously, the aforementioned halogenated organosilanes with specific structures, especially those containing specific branched C8-C22 alkyl groups, effectively prevent excessively dense molecular chain packing through steric hindrance, thereby significantly enhancing the membrane's flexibility and crack resistance. The enrichment of this hydrophobic group on the membrane surface further imparts high gloss and a refreshing skin feel to the membrane. X being Cl, Br, or I ensures efficient silylation, ultimately resulting in a film-forming agent that combines excellent film-forming durability, flexibility, high gloss, and a comfortable skin feel.
[0042] In some embodiments, in the step of adding a haloorganosilane to the premixed solution and reacting to obtain a crude product, the reaction temperature is 0°C to 25°C and the reaction time is 18h to 24h. Optionally, the step of purifying the crude product to obtain a cosmetic film-forming agent includes mixing the crude product with water and extracting it with ethyl acetate to obtain a crude extract, and concentrating the crude extract under reduced pressure to obtain the cosmetic film-forming agent.
[0043] As an example, the reaction temperature can be 0℃, 2℃, 4℃, 6℃, 8℃, 10℃, 12℃, 14℃, 16℃, 18℃, 20℃, 21℃, 22℃, 23℃, 24℃, or 25℃.
[0044] As an example, the reaction time can be 18h, 19h, 20h, 21h, 22h, 23h, or 24h.
[0045] As an example, the number of extractions can be 1, 2, or 3.
[0046] A third aspect of this application provides a cosmetic film-forming agent, which is prepared according to the preparation method described in the second aspect, and has the structure shown in formula (I): (I), wherein A includes soluble polysaccharide residues, the weight average molecular weight of which is 3000 Da to 18000 Da; R1, R2, and R3 are each independently selected from one of C1 to C22 alkyl, C6 to C12 aromatic alkyl, C1 to C22 haloalkyl, and C6 to C12 haloaromatic alkyl; and at least one of R1, R2, and R3 is a C8 to C22 alkyl containing a branch; n is the average degree of substitution, selected from a natural number from 1 to 3.
[0047] Example The following embodiments describe the disclosure of this application in more detail. These embodiments are for illustrative purposes only, as various modifications and variations will be apparent to those skilled in the art within the scope of the disclosure of this application. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.
[0048] The sources of some of the reagents used in Examples 1-9 and Comparative Examples 1-13 are as follows: 1. The inulin in Example 1 was purchased from Shandong Baolingbao, 1 kg / bag; the halogenated organosilane in Example 1 was purchased from Ron Reagent, 25 mL / bottle.
[0049] 2. The soluble starch in Example 2 was purchased from Shandong Hecheng, 1 kg / bag; the halogenated organosilane in Example 2 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0050] 3. The maltodextrin in Example 3 was purchased from Shandong Hecheng, 1 kg / bag; the halogenated organosilicon in Example 3 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0051] 4. The inulin in Example 4 was purchased from Shandong Baolingbao, 1 kg / bag; the halogenated organosilicon in Example 4 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0052] 5. The soluble starch in Example 5 was purchased from Shandong Hecheng, 1 kg / bag; the halogenated organosilane in Example 5 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0053] 6. The maltodextrin in Example 6 was purchased from Shandong Hecheng (1 kg / bag); the halogenated organosilicon in Example 6 was purchased from Bid Pharmaceutical (25 mL / bottle).
[0054] 7. The maltodextrin in Example 7 was purchased from Shandong Hecheng, 1 kg / bag; the halogenated organosilicon in Example 7 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0055] 8. The maltodextrin in Example 8 was purchased from Shandong Hecheng, 1 kg / bag; the halogenated organosilicon in Example 8 was purchased from Bid Pharmaceutical, 25 mL / bottle.
[0056] 9. The inulin in Comparative Example 1 was purchased from Shandong Baolingbao, 1 kg / bag.
[0057] 10. The maltodextrin in Comparative Example 2 was purchased from Shandong Hecheng, 1 kg / bag.
[0058] 11. The halogenated organosilanes in Comparative Example 3 were purchased from Titan Technology, 25 mL / bottle. 12. The halogenated organosilanes in Comparative Example 4 were purchased from Titan Technology, 25 mL / bottle.
[0059] 13. The halogenated organosilicones in Comparative Example 5 were purchased from Titan Technology, 25 mL / bottle.
[0060] 14. The β-cyclodextrin in Comparative Example 6 was purchased from Shandong Baolingbao, 1 kg / bag.
[0061] 15. The soluble starch in Comparative Example 7 was purchased from Shandong Hecheng, 1 kg / bag.
[0062] 16. The prantosaccharide in Comparative Example 8 was purchased from Roquette, France, 1 kg / bag.
[0063] 17. The maltodextrin in Comparative Example 9 was purchased from Roquette, France, 1 kg / bag.
[0064] 18. The inulin in Comparative Example 10 was purchased from Shandong Baolingbao, 1 kg / bag.
[0065] 19. The halogenated organosilanes in Comparative Example 11 were purchased from Titan Technology, 25 mL / bottle.
[0066] 20. The halogenated organosilanes in Comparative Example 12 were purchased from Titan Technology, 25 mL / bottle.
[0067] 21. The halogenated organosilanes in Comparative Example 13 were purchased from Titan Technology, 25 mL / bottle.
[0068] It should be noted that the term C1~C22 alkyl in this invention includes methyl, ethyl, C3 straight / branched alkyl, C4 straight / branched alkyl, C5 straight / branched alkyl, C6 straight / branched alkyl, C7 straight / branched alkyl, C8 straight / branched alkyl, C9 straight / branched alkyl, C10 straight / branched alkyl, C11 straight / branched alkyl, C12 straight / branched alkyl, C13 straight / branched alkyl, C14 straight / branched alkyl, C15 straight / branched alkyl, C16 straight / branched alkyl, C17 straight / branched alkyl, C18 straight / branched alkyl, C19 straight / branched alkyl, C20 straight / branched alkyl, C21 straight / branched alkyl, and C22 straight / branched alkyl.
[0069] The term C6-C12 aromatic ring group as used in this invention includes C6 aromatic ring group (phenyl), C7 aromatic ring group, C8 aromatic ring group, C9 aromatic ring group, C10 aromatic ring group, C11 aromatic ring group, and C12 aromatic ring group. It can be understood as referring to a carbocyclic hydrocarbon group containing 6-12 carbon atoms, composed of one or more fused rings, wherein at least one ring is an aromatic ring. Examples of aryl groups include, but are not limited to: phenyl, naphthyl, 1,2,3,4-tetrahydronaphthyl, indenyl, indenyl, azulel, preferably phenyl and naphthyl, with phenyl being the most preferred.
[0070] The term C1-C22 haloalkyl as used herein refers to an alkyl group as defined herein in which one or more hydrogen atoms, for example 1, 2, 3, 4, 5, or 6 hydrogen atoms, are replaced by halogen atoms, and when more than one hydrogen atom is replaced by a halogen atom, the halogen atoms may be the same or different from each other. C1-C22 haloalkyl refers to an alkyl group having 1-22 carbon atoms in which one or more hydrogen atoms, for example 1, 2, 3, 4, 5, or 6 hydrogen atoms, are replaced by halogen atoms. Examples of haloalkyl groups include, but are not limited to, -CX3, -CHX2, -CH2X, -CH2CX3, -CH(CX3)2, etc., where X is selected from at least one of Cl, Br, and I.
[0071] The term C6-C12 haloaryl group as used in this invention refers to an aromatic ring group as defined herein in which one or more hydrogen atoms, for example 1, 2, 3, 4, 5, or 6 hydrogen atoms, are replaced by halogen atoms, and when more than one hydrogen atom is replaced by a halogen atom, the halogen atoms may be the same or different from each other. C6-C12 haloaryl group refers to an aromatic ring group having 6-12 carbon atoms in which one or more hydrogen atoms, for example 1, 2, 3, 4, 5, or 6 hydrogen atoms, are replaced by halogen atoms. Examples of haloaryl groups include, but are not limited to, -(C6H4)-X, -(C6H3)-X2, -(C6H2)-X3, -(C6H)-X4, -C6X5, etc., where X is selected from at least one of Cl, Br, and I.
[0072] Example 1 Example 1 of this application provides a cosmetic film-forming agent. The cosmetic film-forming agent is a polysaccharide silanized derivative formed by the silanization reaction of hydroxyl groups in a soluble polysaccharide structure with a haloorganosilane. The specific preparation method of the cosmetic film-forming agent includes: S1, soluble polysaccharide inulin and triethylamine are dissolved in N,N-dimethylformamide to obtain a premixed solution, wherein the weight average molecular weight of the soluble polysaccharide is 3000 Da, and the average number n (average degree of substitution) of hydroxyl groups substituted by silyl etherification on each glycoside unit in the soluble polysaccharide is 2. S2, add a haloorganosilane to the premix at 0~25℃. The reaction was carried out at 25°C for 18-24 hours to obtain a crude product, wherein the molar ratio of soluble polysaccharide, triethylamine and haloorganosilanes was 1:4:2. S3. The crude product is purified by pouring the reaction solution after the reaction in step S2 into water and extracting it three times with ethyl acetate. The organic phase is concentrated under reduced pressure to remove the solvent, and the cosmetic film-forming agent is obtained.
[0073] The proton NMR data are shown below: 1 HNMR (CDCl) 3, 600HMz):&5.50-3.12(m,7H),1.82-1.72(m,4H),1.56-1.48(m,16H),1.38-1.31(m,1 6H),1.29-1.25(m,8H),1.20-1.16(m,16H),1.03-0.86(m,12H),0.08-0.01(m,24H).
[0074] Example 2 Example 2 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that... The soluble polysaccharide was adjusted to soluble starch; the weight-average molecular weight of the soluble polysaccharide was adjusted to 15000 Da.
[0075] Example 3 Example 3 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that... The soluble polysaccharide was adjusted to maltodextrin; the weight-average molecular weight of the soluble polysaccharide was adjusted to 8000 Da; the halogenated organosilanes were adjusted to... .
[0076] Example 4 Example 4 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that... The weight-average molecular weight of the soluble polysaccharide inulin was adjusted to 5000 Da; the halogenated organosilanes were adjusted to... .
[0077] Example 5 Example 5 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 4, the only difference being that... The soluble polysaccharide was adjusted to soluble starch; the weight-average molecular weight of the soluble polysaccharide was adjusted to 18000 Da.
[0078] Example 6 Example 6 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 4, the only difference being that... The soluble polysaccharide was adjusted to maltodextrin; the weight-average molecular weight of the soluble polysaccharide was adjusted to 12000 Da; the halogenated organosilanes were adjusted to... .
[0079] Example 7 Example 7 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that... The soluble polysaccharide was adjusted to maltodextrin; the weight-average molecular weight of the soluble polysaccharide was adjusted to 8000 Da.
[0080] The proton NMR data are shown below: 1 HNMR (CDCl) 3, 600HMz):&5.56-3.34(m,7H),1.66-1.58(m,16H),1.38-1.31(m,32H),1.29 -1.21(m,8H),1.18-1.12(m,16H),1.03-0.86(m,12H),0.09-0.01(m,24H).
[0081] Example 8 Example 8 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 4, except that the soluble polysaccharide is adjusted to maltodextrin and the weight-average molecular weight of the soluble polysaccharide is adjusted to 12000 Da.
[0082] The proton NMR data are shown below: 1 HNMR (CDCl) 3, 600HMz):&5.59-3.40(m,7H),1.66-1.58(m,16H),1.38-1.31(m,56H),1.29 -1.21(m,9H),1.18-1.12(m,20H),1.03-0.86(m,12H),0.09-0.01(m,24H).
[0083] Example 9 Example 9 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 3, the only difference being that the halogenated organosilane is adjusted to... .
[0084] Comparative Example 1 Comparative Example 1 of this application provides a cosmetic film-forming agent, which is a soluble polysaccharide inulin, wherein the weight average molecular weight of the soluble polysaccharide is 3000 Da.
[0085] This is equivalent to the polysaccharide in Example 1 that was not modified with organosilicon.
[0086] Comparative Example 2 Comparative Example 2 of this application provides a cosmetic film-forming agent, which is a soluble polysaccharide maltodextrin, wherein the weight average molecular weight of the soluble polysaccharide is 8000 Da.
[0087] This is equivalent to the polysaccharide in Example 3 that was not modified with organosilicon.
[0088] Comparative Example 3 Comparative Example 3 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that the halogenated organosilane is adjusted to... .
[0089] Comparative Example 4 Comparative Example 4 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that the halogenated organosilane is adjusted to... .
[0090] Comparative Example 5 Comparative Example 5 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, the only difference being that the halogenated organosilane is adjusted to... .
[0091] Comparative Example 6 Comparative Example 6 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that the soluble polysaccharide is adjusted to β-cyclodextrin and the weight-average molecular weight of the soluble polysaccharide is adjusted to 1135 Da.
[0092] Comparative Example 7 Comparative Example 7 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that the soluble polysaccharide is adjusted to soluble starch and the weight-average molecular weight of the soluble polysaccharide is adjusted to 30,000 Da.
[0093] Comparative Example 8 Comparative Example 8 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that the soluble polysaccharide is adjusted to pran polysaccharide; and the weight-average molecular weight of the soluble polysaccharide is adjusted to 100,000 Da.
[0094] Comparative Example 9 Comparative Example 9 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that the soluble polysaccharide is changed to maltodextrin; the weight-average molecular weight of the soluble polysaccharide is adjusted to 8000 Da, and the average degree of substitution n is 0.5.
[0095] Comparative Example 10 Comparative Example 10 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that the average degree of substitution n is adjusted to 0.8.
[0096] Comparative Example 11 Comparative Example 11 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that R3 in the haloorganosilanes is changed to a C24 branched alkyl group. .
[0097] Comparative Example 12 Comparative Example 12 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 1, except that R3 in the haloorganosilanes is adjusted to a partially methoxylated form. .
[0098] Comparative Example 13 Comparative Example 13 of this application provides a cosmetic film-forming agent, the preparation method of which is similar to that of Example 9, except that R1 in the haloorganosilanes is adjusted to pyrene- , .
[0099] Performance testing The performance of the cosmetic film-forming agents prepared in Examples 1-9 and Comparative Examples 1-13 was tested: 1. Stability observation: After the product is left at room temperature for 48 hours, observe whether a pungent odor is produced (indicating product instability) or swelling occurs.
[0100] 2. Oil solubility test: Dissolve the product in isododecane and observe whether it dissolves completely.
[0101] 3. Film-forming property test: Using a wire bar coater, the product was evenly coated onto a black glass slide, with the wet film thickness controlled at 50-100 μm. The slide was then dried and cured for 10 minutes at a temperature of 23±2℃ and a relative humidity of 50±5%, and the film formation was observed.
[0102] 4. Anti-crystallization test The product was placed in a humid environment at room temperature for more than 7 days to observe whether crystallization occurred.
[0103] 5. Film gloss test Using a wire bar coater, an appropriate amount of product is evenly coated onto a black glass slide, with the wet film thickness controlled at 50-100μm. The film is then dried and cured for 10 minutes at a temperature of 23±2℃ and a relative humidity of 50±5%. A visual comparison method is used to compare the sample film with a standard gloss level card under natural light. The gloss level is determined by observing the intensity of the reflected light with the naked eye, with gloss scores ranging from 1 to 6 from low to high.
[0104] 6. Membrane flexibility test Using a bar coater, apply an appropriate amount of product evenly onto white cardstock. Dry and cure for 10 minutes at a temperature of 23±2℃ and a relative humidity of 50±5%. Bend the cardstock for 10 seconds and then restore it to its original position. Observe the degree of film cracking and whether the film has oil cracks: no cracks+++, slight cracks++, broken+.
[0105] 7. Film-forming durability test Using a bar coater, an appropriate amount of product is evenly coated onto a black glass slide, with the wet film thickness controlled at 50-100 μm. The slide is then dried and cured for 10 minutes at a temperature of 23±2℃ and a relative humidity of 50±5%. After 1, 4, and 6 hours, the slide is washed with water containing facial cleanser. If any residue remains, it indicates that the film-forming durability test at that time has passed.
[0106] 8. Film-forming skin feel test The volunteer evaluation method involved 10 volunteers applying the products of the examples and comparative examples to different parts of both arms and describing the smoothness, roughness, stickiness, and waxiness of the film. If more than half of the volunteers gave the same description, it was recorded as the evaluation result.
[0107] The experimental results are shown in Tables 1 and 2.
[0108] Table 1 Table 2 Examples 1-9 of this application use a weight-average molecular weight of 300. A 18000 Da soluble polysaccharide can be silanized with a haloorganosilane containing a specific branched structure to synthesize a cosmetic film-forming agent that combines excellent film-forming durability, flexibility, high gloss, and a comfortable skin feel. The 3000 Da~18000 Da weight-average molecular weight soluble polysaccharide backbone provides a suitable chain length and cohesive strength, ensuring both film continuity and structural stability while avoiding the film stiffness caused by high molecular weight. , , At least one of them is a branched C8-C22 alkyl group, whose steric hindrance effectively inhibits the tight packing of molecular chains, significantly improving the flexibility and crack resistance of the film. At the same time, its hydrophobic structure enhances the water resistance and surface gloss. The average degree of substitution of 1-3 can balance the skin affinity of polysaccharides and the sensory advantages of organosilicones, so that the film has both strength and a light and comfortable feel. Compared with comparative examples 1-13, the cosmetic film-forming agents with specific structures prepared in Examples 1-9 of this application show significant advantages in terms of film-forming durability, flexibility, gloss and skin feel. Among them, the film gloss of Examples 7-8 is the best, with a score as high as 6 points.
Claims
1. Use of a polymer as a film-forming agent for a cosmetic product, characterized in that, The polymer is prepared by silylation reaction of a soluble polysaccharide and a halogenated organosilane; The polymer has a structure shown in formula (I): (I), wherein, A comprises a soluble polysaccharide residue, and the soluble polysaccharide has a weight average molecular weight of 3000 Da to 18000 Da; R1, R2, and R3 are each independently selected from one of C1-C22 alkyl, C6-C12 aryl ring group, C1-C22 halogenated alkyl, and C6-C12 halogenated aryl ring group; and at least one of R1, R2, and R3 is C8-C22 alkyl containing a branch. n is an average substitution degree, and is a natural number selected from 1 to 3.
2. Use according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from C1-C22 alkyl or phenyl; and at least one of R1, R2, and R3 is C8-C22 alkyl containing a branch.
3. Use according to claim 1, characterized in that, The C8-C22 alkyl containing a branch is selected from one of structures shown in formulae (II-1) to (II-5): (II-1), (II-2), (II-3), (II-4), (I-5).
4. Use according to claim 1, characterized in that, The soluble polysaccharide has a weight average molecular weight of 8000 Da to 12000 Da. Optionally, the soluble polysaccharide comprises at least one of inulin, maltodextrin, and soluble starch.
5. The use according to claim 1, characterized in that, At least one of R1, R2, and R3 is C8-C12 alkyl containing a branch.
6. Use according to claim 1, characterized in that, The soluble polysaccharide is maltodextrin, the soluble polysaccharide has a weight average molecular weight of 8000 Da to 12000 Da, at least one of R1, R2, and R3 is C8-C12 alkyl containing a branch, and n is 1.8 to 2.2, preferably 2.
7. A method for preparing a cosmetic film former, characterized by, The method comprises the following steps: The soluble polysaccharide and triethylamine are dissolved in N,N-dimethylformamide to obtain a premix solution; The halogenated organosilane is added to the premix solution, and a reaction is performed to obtain a crude product; The crude product is purified to obtain the cosmetic film former; The molar ratio of the soluble polysaccharide, the triethylamine, and the halogenated organosilane is 1:4:
2.
8. The production method according to claim 7, characterized by, The soluble polysaccharide comprises at least one of inulin, maltodextrin, and soluble starch. Optionally, the soluble polysaccharide has a weight average molecular weight of 3000 Da to 18000 Da. Optionally, the halogenated organosilane has a structure shown in formula (II): (II), X is selected from at least one of Cl, Br, and I, R1, R2, R3are each independently selected from one of C1-C22alkyl, C6-C12aromatic ring group, C1-C22haloalkyl, and C6-C12haloaromatic ring group; and at least one of R1, R2, R3is a C8-C22alkyl group comprising a branch.
9. The preparation method according to claim 7, characterized in that, In the step of adding the halogenated organosilane to the premix solution and performing a reaction to obtain a crude product, the reaction temperature is 0°C to 25°C, and the reaction time is 18 h to 24 h. Optionally, the step of purifying the crude product to obtain the cosmetic film former comprises mixing the crude product with water and extracting with ethyl acetate to obtain a crude extract, and performing a reduced-pressure concentration treatment on the crude extract to obtain the cosmetic film former.
10. A cosmetic film former characterized by, The cosmetic film former is prepared according to the preparation method of any one of claims 7 to 9, and has a structure shown in formula (I): (I), wherein, A comprises a soluble polysaccharide residue, and the soluble polysaccharide has a weight average molecular weight of 3000 Da to 18000 Da; R1, R2, R3are each independently selected from one of C1-C22alkyl, C6-C12aromatic ring group, C1-C22halogenated alkyl, and C6-C12halogenated aromatic ring group; and at least one of R1, R2, R3is C8-C22alkyl containing a branch; n is an average degree of substitution, and is a natural number selected from 1 to 3.