Modified film-forming agent and preparation method thereof

Abstract

The present application relates to a modified film-forming agent and a preparation method thereof, the modified film-forming agent being a reaction product of an ultraviolet absorber monomer and a film-forming agent monomer, the ultraviolet absorber monomer being an ultraviolet absorber having an ester group, a carboxyl group and / or a hydroxyl group, and the film-forming agent monomer being a film-forming agent having a hydroxyl group, an ester group and / or a carboxyl group. According to the modified film-forming agent, through chemical combination of the film-forming agent and the sun-screening agent, the modified film-forming agent has the function of absorbing ultraviolet rays, and the problem of skin damage caused by small molecular weight of a traditional sun-screening agent is solved.

Description

Technical Field

[0001] This invention relates to the field of cosmetic additives, and more specifically to a modified film-forming agent for cosmetics and its preparation method. Background Technology

[0002] Film-forming agents are key ingredients in cosmetics, imparting moisturizing, waterproofing, and setting properties. They help fix makeup and skincare products, enhancing their durability and adhesion. They also provide waterproofing and sweatproofing, protecting cosmetics from external damage. Furthermore, they can refine product texture, even filling in fine lines, and improving the overall makeup effect.

[0003] Generally speaking, film-forming agents themselves have no effect on UV absorption. Therefore, cosmetics that need to provide some sun protection usually also contain a certain amount of sunscreen agents to increase the product's SPF (Sun Protection Factor). However, traditional sunscreen agents such as benzotriazoles and benzophenones, due to their small molecular weight, can easily penetrate the skin when directly applied to cosmetics, posing a risk of skin damage.

[0004] There is a need in this field for film-forming agents with sun protection functions in order to obtain cosmetics with good safety and sun protection effects. Summary of the Invention

[0005] To address the aforementioned problems, this invention proposes a film-forming agent with sun protection effect and its preparation method, in order to obtain a cosmetic with good safety and sun protection effect. In a first aspect, this application relates to a modified film-forming agent, which is a reaction product of an ultraviolet absorber monomer and a film-forming agent monomer, wherein the ultraviolet absorber monomer is an ultraviolet absorber having ester, carboxyl, and / or hydroxyl groups, and the film-forming agent monomer is a film-forming agent having hydroxyl, ester, and / or carboxyl groups.

[0006] Preferably, the modified film-forming agent is a product of the ultraviolet absorber monomer and the film-forming agent monomer through transesterification or esterification.

[0007] In some embodiments, the ultraviolet absorber monomer is selected from ultraviolet absorbers containing hydroxyl groups, ultraviolet absorbers containing ester groups, or ultraviolet absorbers containing carboxyl groups; Preferably, the ultraviolet absorber monomer is selected from one or more of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid or salicylic ester ultraviolet absorbers, cinnamic acid or cinnamic ester ultraviolet absorbers, p-aminophenyl ester ultraviolet absorbers, triazine ultraviolet absorbers, and cyanopropionate ultraviolet absorbers.

[0008] The benzotriazole-based ultraviolet absorber has a compound of formula I. (I) In Equation I, R1-R4 are each independently hydrogen or C. 1-6 alkyl; At least one of R5-R8 is an ester structure or a hydroxyl or carboxyl group, and the remainder is hydrogen or C. 1-6 Alkyl group, preferably at least one of 3-benzotriazol-5-tert-butyl-4-hydroxyphenyl propionate; more preferably methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate; The benzophenone-based ultraviolet absorber is selected from diethylaminohydroxybenzoyl benzoate (CAS: 302776-68-7); The salicylic acid or salicylic ester ultraviolet absorber is selected from compounds having the structure of formula II. (II) In Equation II, R a Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; Preferably, the salicylic acid or salicylic acid ester ultraviolet absorber is selected from one or more of the following: methyl salicylate, homosalate (CAS: 118-56-9), isooctyl salicylate (CAS: 118-60-5), 4-tert-butylphenyl salicylate (CAS: 87-18-3), and phenyl o-hydroxybenzoate (CAS: 118-55-8); The cinnamic acid or cinnamic ester ultraviolet absorber is selected from compounds having the structure of Formula III. (III) In Equation II, R b Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; Preferably, the cinnamic acid or cinnamic ester ultraviolet absorber is selected from at least one of isoamyl methoxycinnamate or ethylhexyl methoxycinnamate.

[0009] The para-aminobenzoic esters are selected from one or more of 2-ethylhexyl 4-aminobenzoic acid (CAS: 26218-04-2), PEG-25 para-aminobenzoic acid (CAS: 116242-27-4), and glyceryl para-aminobenzoate (CAS: 136-44-7); The triazine ultraviolet absorber is selected from at least one of bis(ethylhexyloxyphenol)methoxyphenyltriazine (CAS: 187393-00-6) and 4,4',4”-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate tri(2-ethylhexyl) ester (CAS: 88122-99-0); The cyanopropionate ultraviolet absorber is selected from at least one of the following: etorizine (CAS: 5232-99-5), octocrylene (CAS: 6197-30-4), and 2-ethylhexyl-2-cyano-3-(4-methoxyphenyl)-3-phenylacrylate (CAS: 947753-66-4); Preferably, the carboxyl-containing ultraviolet absorber is selected from salicylic acid or cinnamic acid ultraviolet absorbers.

[0010] Preferably, the ultraviolet absorber monomer having an ester group is selected from one or more of p-aminophenyl ester (PABA) ultraviolet absorbers, benzyl camphor cinnamic acid ester ultraviolet absorbers, salicylate ultraviolet absorbers, and cinnamic acid ester ultraviolet absorbers. Preferably, the ultraviolet absorber monomer with an ester group is selected from one or more of 2-ethylhexyl 4-aminobenzoate (CAS No.: 26218-04-2), PEG-25 PABA, octocrylene, etorylene, 2-ethylhexyl-2-cyano-3-(4-methoxyphenyl)-3-phenylacrylate, methyl salicylate, humosalilate, isooctyl salicylate, isoamyl p-methoxycinnamate, and ethylhexyl p-methoxycinnamate.

[0011] In some embodiments, the ultraviolet absorber monomer is an ultraviolet absorber monomer with an ester group, which is further modified with a polyol or hydrolyzed before reacting with the film-forming agent monomer.

[0012] In some embodiments, polyol modification includes: reacting the ester-containing ultraviolet absorber monomer with a polyol in the presence of a first catalyst to obtain a polyol-modified ultraviolet absorber monomer. Preferably, the polyol is C2-C 10 The polyol, and / or the molar ratio of the polyol to the UV absorber monomer having an ester group is 1.5-5.0:1.0; and / or the first catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide.

[0013] In some embodiments, the hydrolysis treatment includes: hydrolyzing the ester-containing ultraviolet absorber monomer in the presence of a second catalyst to obtain a hydrolyzed ultraviolet absorber monomer. Preferably, the second catalyst is selected from one or more of sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid.

[0014] In some embodiments, the film-forming agent monomer is selected from one or more of benzoate film-forming agents, acrylic copolymer film-forming agents, polyurethane film-forming agents, vinyl polymer film-forming agents, polyvinyl alcohol film-forming agents, and polyvinylpyrrolidone polymer film-forming agents; Preferably, the benzoate film-forming agent is selected from sucrose benzoate, benzoic acid and C8–C 13 One or more monoesters formed from long-chain fatty alcohols; Acrylic copolymer film-forming agents are selected from acrylic (ester) / polydimethylsiloxane copolymer (KP545), acrylic (ester) / octylacrylamide copolymer (DERMACRYL 79 Polymer), acrylic (ester) / C 12-22 Alkyl methacrylate copolymer (Allianz OPT polymer); The polyvinyl alcohol film-forming agent is selected from one or more of polyvinyl alcohol EG-05C and polyvinyl alcohol EG-40C; Polyurethane film-forming agents are selected from products such as polyurethane-35; vinyl polymer film-forming agents are selected from the Antaron series. Polyvinylpyrrolidone (PVP) polymer film-forming agents are selected from the Luvitec series or the Polycar series, such as Luvitec... ® VMA-570P\Polycar ® 10.

[0015] Secondly, this application also relates to a method for preparing a modified film-forming agent, comprising: The ultraviolet absorber monomer and the film-forming agent monomer are reacted in the presence of a catalyst. The ultraviolet absorber monomer has ester, carboxyl and / or hydroxyl groups, and the film-forming agent monomer has hydroxyl, ester and / or carboxyl groups. The catalyst is selected from esterification catalysts or transesterification catalysts.

[0016] In some embodiments, the reaction is carried out in the presence of a phase transfer agent selected from any one of benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, and tetrabutylammonium bisulfate.

[0017] In some embodiments, the ultraviolet absorber monomer is an ultraviolet absorber monomer with an ester group, and the ultraviolet absorber monomer with an ester group is further modified with a polyol or hydrolyzed before reacting with the film-forming agent monomer. Preferably, the polyol modification includes: reacting the ultraviolet absorber monomer with the ester group with a polyol in the presence of a first catalyst to obtain a polyol-modified ultraviolet absorber monomer; Preferably, the polyol is C2-C 10 The polyol, and / or the molar ratio of the polyol to the UV absorber monomer having an ester group is 1.5-5.0:1.0; and / or the first catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide. Preferably, the polyol modification is carried out in an aromatic solvent, and preferably, the aromatic solvent is selected from toluene or xylene.

[0018] Preferably, the hydrolysis treatment includes: hydrolyzing the ultraviolet absorber monomer with ester groups in the presence of a second catalyst to obtain a hydrolyzed ultraviolet absorber monomer; Preferably, the second catalyst is selected from one or more of sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; Preferably, the hydrolysis treatment is carried out in an aromatic solvent, and preferably, the aromatic solvent is selected from toluene or xylene.

[0019] In some embodiments, the mass ratio of the polyol-modified UV absorber monomer or the hydrolyzed UV absorber monomer to the film-forming agent monomer is 1.0-7.0:1.0. The esterification catalyst is selected from one or more of sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; The transesterification catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide. The reaction between the polyol-modified ultraviolet absorber monomer or the hydrolyzed ultraviolet absorber monomer and the film-forming agent monomer is carried out in an aromatic solvent, preferably, the aromatic solvent is selected from toluene or xylene.

[0020] In some embodiments, the ultraviolet absorber monomer is an ultraviolet absorber monomer having hydroxyl or carboxyl groups. The modified film-forming agent is obtained by reacting the ultraviolet absorber monomer having hydroxyl or carboxyl groups with the film-forming agent monomer in an aromatic solvent in the presence of a catalyst. Preferably, the mass ratio of the ultraviolet absorber monomer having hydroxyl or carboxyl groups to the film-forming agent monomer is 1.0-7.0:1.0.

[0021] Thirdly, this application relates to a cosmetic composition comprising the modified film-forming agent of the first aspect of this application or the modified film-forming agent obtained by the method of the second aspect of this application.

[0022] The modified film-forming agent of this application, through the chemical combination of the film-forming agent and the sunscreen agent, enables the modified film-forming agent to absorb ultraviolet rays, and solves the problem of skin damage caused by the small molecular weight of traditional sunscreen agents. Attached Figure Description

[0023] Figure 1 This is the UV absorption spectrum of polyurethane-35. Figure 2 This is the UV absorption spectrum of the modified film-forming agent S31 obtained in this embodiment. Figure 3 The image shows the UV absorption spectrum of Carbomer 934. Figure 4 This is the UV absorption spectrum of the modified film-forming agent S32 obtained in this embodiment. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention in any way.

[0025] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments.

[0026] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0027] This invention "C1-C 12 "Straight-chain or branched alkyl or cycloalkyl" includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, isobutyl (i-Bu), tert-butyl (t-Bu), isopentyl, tert-pentyl, neopentyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 2,3,3-trimethylbutyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 2,5-dimethylhexyl, 2,2,3 -Trimethylpentyl, 2,3,4-trimethylpentyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 2,2-dimethylheptyl, 3,3-diethylpentyl, 2,2,3,3-tetramethylbutyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 2,2-dimethyloctyl, 3,3-dimethyloctyl, 2,3,5-trimethylheptyl, methylcyclopentyl (C6), 1,2-dimethylcyclohexyl (C8), isopropylcyclohexyl (C9), tert-butylcyclohexyl (C10), 1-methyl-1-ethylcyclopentyl (C8), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl.

[0028] In a first aspect, this application relates to a modified film-forming agent, which is a reaction product of an ultraviolet absorber monomer and a film-forming agent monomer, wherein the ultraviolet absorber monomer has an ester group, a carboxyl group and / or a hydroxyl group, and the film-forming agent monomer has a hydroxyl group, an ester group and / or a carboxyl group.

[0029] The modified film-forming agent of this application has a sun protection effect because it incorporates a portion from the ultraviolet absorber monomer; and because of its larger molecular weight, it avoids the risks associated with small molecule ultraviolet absorber monomers, thus possessing better safety and sun protection properties, and can replace sunscreens used in conventional cosmetic compositions or reduce their dosage.

[0030] The ultraviolet absorber monomer used in this application has ester, carboxyl, and / or hydroxyl groups, while the film-forming agent monomer used in this application has hydroxyl, ester, and / or carboxyl groups. The two can be linked together by forming an ester group. It should be noted that, in order to form an ester group, the ultraviolet absorber monomer and the film-forming agent monomer used in this application cannot simultaneously have only hydroxyl groups or only carboxyl groups. When the ultraviolet absorber monomer used in this application has hydroxyl groups, the film-forming agent monomer used in this application needs to have ester and / or carboxyl groups; when the ultraviolet absorber monomer used in this application has carboxyl groups, the film-forming agent monomer used in this application needs to have ester and / or hydroxyl groups; and vice versa.

[0031] In some embodiments, the ultraviolet absorber monomer is selected from one or more of hydroxyl-containing ultraviolet absorbers, ester-containing ultraviolet absorbers, and carboxyl-containing ultraviolet absorbers.

[0032] In some embodiments, the ultraviolet absorber monomer is selected from one or more of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid or salicylic ester ultraviolet absorbers, cinnamic acid or cinnamic ester ultraviolet absorbers, p-aminophenyl ester ultraviolet absorbers, triazine ultraviolet absorbers, and cyanopropionate ultraviolet absorbers.

[0033] For example, benzotriazole UV absorbers can be benzotriazole UV absorbers having the following formula. In this case, R1-R4 are each independently hydrogen or C. 1-6 alkyl; At least one of R5-R8 is an ester structure or a hydroxyl or carboxyl group, and the remainder is hydrogen or C. 1-6 alkyl; In some specific embodiments, the benzotriazole-based ultraviolet absorber is selected from 3-benzotriazole-5-tert-butyl-4-hydroxyphenyl propionate, which can be selected from esters or mixed esters formed by reacting 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionic acid with C1-C18 straight-chain or straight-chain alcohols. For example, it can be selected from methyl 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate (CAS: 84268-33-7), ethyl 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate, propyl 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate, etc.

[0034] For example, the benzophenone-based ultraviolet absorber is selected from diethylaminohydroxybenzoyl benzoate (CAS: 302776-68-7); In some embodiments, the ultraviolet absorber monomer can be a carboxyl-containing ultraviolet absorber, such as salicylic acid or cinnamic acid ultraviolet absorbers.

[0035] In some embodiments, the ultraviolet absorber monomer can be an ester-containing ultraviolet absorber, which can be selected from one or more of p-aminophenyl ester (PABA) ultraviolet absorbers, cyanopropionate ultraviolet absorbers, salicylate ultraviolet absorbers, and cinnamic acid ester ultraviolet absorbers.

[0036] For example, p-aminophenyl ester (PABA) type ultraviolet absorbers can be selected from one or more of 2-ethylhexyl 4-aminobenzoate (CAS No.: 26218-04-2) and PEG-25 PABA (CAS No.: 116242-27-4).

[0037] The salicylic acid or salicylic ester ultraviolet absorber is selected from compounds having the structure of formula II. (II) In Equation II, R a Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; Preferably, the salicylic acid or salicylic acid ester ultraviolet absorber is selected from one or more of the following: methyl salicylate, homosalate (CAS: 118-56-9), isooctyl salicylate (CAS: 118-60-5, 4-tert-butylphenyl salicylate, and phenyl o-hydroxybenzoate). The cinnamic acid or cinnamic ester ultraviolet absorber is selected from compounds having the structure of Formula III. (III) In Equation III, Rb Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; For example, cinnamic acid ester ultraviolet absorbers may be selected from one or more of isoamyl p-methoxycinnamate (CAS: 71617-10-2) and ethylhexyl p-methoxycinnamate (CAS: 5466-77-3).

[0038] For example, cyanopropionate UV absorbers can be selected from one or more of the following: octocrylene, eostocrylene, solarstay® S1 (2-ethylhexyl-2-cyano-3-(4-methoxyphenyl)-3-phenylacrylate (947753-66-4)).

[0039] The triazine ultraviolet absorber is selected from at least one of bis(ethylhexyloxyphenol)methoxyphenyltriazine (CAS: 187393-00-6) and 4,4',4”-(1,3,5-triazine-2,4,6-trimethyltriimino)tribenzoate tri(2-ethylhexyl) ester (CAS: 88122-99-0).

[0040] In some embodiments, the ultraviolet absorber monomer is an ultraviolet absorber monomer with an ester group, which is further modified with a polyol or hydrolyzed before reacting with the film-forming agent monomer.

[0041] In some embodiments, the hydrolysis treatment includes: hydrolyzing the ester-containing ultraviolet absorber monomer in the presence of a second catalyst (ester hydrolysis catalyst) to obtain a hydrolyzed ultraviolet absorber monomer.

[0042] The second catalyst (ester hydrolysis catalyst) typically used in this hydrolysis process can be selected from sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid.

[0043] In some embodiments, the hydrolysis treatment can be carried out in an aromatic solvent such as toluene or xylene. For example, an ester-containing UV absorber monomer is added to an aromatic solvent such as toluene, a second catalyst (ester hydrolysis catalyst) such as sulfuric acid and water are added, the temperature is raised, and the mixture is washed repeatedly with deionized water. The solvent such as toluene is removed under reduced pressure to obtain a hydrolyzed UV absorber monomer with a carboxyl group.

[0044] In some embodiments, polyol modification includes reacting the ester-containing ultraviolet absorber monomer with a polyol in the presence of a first catalyst to obtain a polyol-modified ultraviolet absorber monomer.

[0045] In some embodiments, the polyol is C2-C. 10The polyol is selected from polyols such as ethylene glycol, glycerol, pentaerythritol, and pentanediol. In some embodiments, the molar ratio of the polyol to the ester-group-containing UV absorber monomer is 1.5-5.0:1.0, for example, 1.2-5.0:1.0. In some embodiments, the first catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide.

[0046] In some embodiments, polyol modification can be carried out in aromatic solvents such as toluene or xylene. For example, an ester-group UV absorber monomer and a polyol, along with a transesterification catalyst such as tetrabutyl titanate, are added to an aromatic solvent such as toluene. The transesterification reaction is carried out under reflux conditions, followed by multiple water washings with deionized water, and the solvent and alcohol are removed under reduced pressure to obtain a polyol-modified UV absorber monomer.

[0047] In some embodiments, polyol modification includes: hydrolyzing the ester-containing UV absorber monomer first, followed by adding a polyol for esterification. The hydrolysis can be performed as described above to obtain a hydrolyzed UV absorber monomer containing a carboxyl group. The polyol can be C2-C... 10 Polyols, such as ethylene glycol, glycerol, pentaerythritol, and pentanediol, are used in the esterification reaction, which is carried out in the presence of an esterification catalyst (such as sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid). Modification with polyols allows UV absorber monomers with ester groups to form intermediates with active hydroxyl groups, facilitating subsequent reactions with film-forming agent monomers.

[0048] In some embodiments, the film-forming agent monomer is selected from one or more of benzoate film-forming agents, acrylic copolymer film-forming agents, polyurethane film-forming agents, vinyl polymer film-forming agents, polyvinyl alcohol film-forming agents, and polyvinylpyrrolidone polymer film-forming agents.

[0049] For example, benzoic acid ester film-forming agents can be sucrose benzoate, as well as monoesters formed by benzoic acid and fatty alcohols with C8–C13 chain lengths, such as 2-ethylhexyl benzoate, isononyl benzoate, and isodecanyl benzoate.

[0050] For example, acrylic copolymer film-forming agents can be selected from acrylic (ester) / polydimethylsiloxane copolymer (KP545), acrylic (ester) / octylacrylamide copolymer (DERMACRYL 79 Polymer), and acrylic (ester) / C12-22 alkanol methacrylate copolymer (Allianz OPT polymer); The acrylate / C12-22 alkanol methacrylate copolymer is preferably at least one of carbomer 934, carbomer 940, carbomer 941, carbomer ETD 2020, carbomer AQUA SF-1, and carbomer Ultraz 20.

[0051] For example, polyvinyl alcohol film-forming agents can be selected from polyvinyl alcohol EG-05C (Mitsubishi Chemical) and polyvinyl alcohol EG-40C (Mitsubishi Chemical), etc. Polyurethane film-forming agents are selected from products such as polyurethane-35; vinyl polymer film-forming agents are selected from the Antaron series, such as Antaron V216. Polyvinylpyrrolidone (PVP) polymer film-forming agents are selected from the Luvitec series or the Polycar series, such as Luvitec... ® VMA-570P\Polycar ® 10.

[0052] Secondly, this application provides a method for preparing a modified film-forming agent, comprising: The ultraviolet absorber monomer and the film-forming agent monomer are reacted in the presence of a catalyst. The ultraviolet absorber monomer has ester, carboxyl and / or hydroxyl groups, and the film-forming agent monomer has hydroxyl, ester and / or carboxyl groups. The catalyst is selected from esterification catalysts or transesterification catalysts.

[0053] In some embodiments, the UV absorber monomer is a UV absorber monomer having an ester group. As mentioned above, for UV absorber monomers having an ester group, they may be further modified with a polyol or hydrolyzed before reacting with the film-forming agent monomer. The polyol modification and hydrolysis methods can be carried out as described above and will not be repeated here.

[0054] The ultraviolet absorber monomer can be one or more of the following: benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid or salicylic ester ultraviolet absorbers, cinnamic acid or cinnamic ester ultraviolet absorbers, p-aminophenyl ester ultraviolet absorbers, triazine ultraviolet absorbers, and cyanopropionate ultraviolet absorbers. These ultraviolet absorbers can be the ultraviolet absorbers described above, and will not be repeated here.

[0055] Ultraviolet absorber monomers modified with polyols or treated with hydrolysis can react with film-forming agent monomers to obtain modified film-forming agents.

[0056] The reaction between the polyol-modified or hydrolyzed ultraviolet absorber monomer and the film-forming agent monomer is carried out in an aromatic solvent, preferably selected from toluene or xylene. In some embodiments, the mass ratio of the polyol-modified or hydrolyzed ultraviolet absorber monomer to the film-forming agent monomer is 1.0-7.0:1.0, for example, 6.0:1.0, 5.0:1.0, 4.0:1.0, 3.0:1.0, etc.

[0057] In some embodiments, the catalyst may be an esterification catalyst, such as one or more selected from sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. In some embodiments, the catalyst may be a transesterification catalyst, such as one or more selected from tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide.

[0058] In some embodiments, the reaction can be carried out in the presence of a phase transfer agent, which may be selected from any one of benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, and tetrabutylammonium bisulfate.

[0059] In some embodiments, the ultraviolet absorber monomer is an ultraviolet absorber monomer having hydroxyl or carboxyl groups, and the ultraviolet absorber monomer having hydroxyl or carboxyl groups is reacted with the film-forming agent monomer in an aromatic solvent in the presence of a catalyst to obtain the modified film-forming agent. Preferably, the mass ratio of the ultraviolet absorber monomer having hydroxyl or carboxyl groups to the film-forming agent monomer is 1.0-7.0:1.0, for example, it can be 6.0:1.0, 5.0:1.0, 4.0:1.0, 3.0:1.0, etc.

[0060] In some embodiments, the film-forming agent monomer is selected from one or more of benzoate film-forming agents, acrylic copolymer film-forming agents, polyurethane film-forming agents, vinyl polymer film-forming agents, polyvinyl alcohol film-forming agents, and polyvinylpyrrolidone polymer film-forming agents. Specific details are as described above and will not be repeated here.

[0061] The preparation method described in this application allows the reaction to be carried out at reflux temperature. After the reaction, simple steps such as washing with water, filtration, and drying are performed to obtain the final modified film-forming agent with sun protection function. Moreover, this modified film-forming agent has a relatively large molecular weight, avoiding the risk of skin damage caused by conventional small-molecule sunscreens that easily penetrate the skin.

[0062] Thirdly, this application also relates to a cosmetic composition comprising the modified film-forming agent of the first aspect of this application or the modified film-forming agent obtained by the method of the second aspect of this application.

[0063] Cosmetic compositions typically contain a base component, including water, oily ingredients, and emulsifiers, as well as functional components such as moisturizers, sunscreens, and film-forming agents. The modified film-forming agent of this application combines the functions of both a film-forming agent and a sunscreen, and can replace conventional sunscreens or reduce the amount of conventional sunscreens used.

[0064] The present application will be further described in detail below through embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0065] Example 1 27.7g of elequiline, 60ml of toluene, 2g of concentrated sulfuric acid and 10ml of water were added to a reaction flask, heated to 80-90℃ and kept at this temperature for 6-8 hours. When the elequiline content was found to be less than 0.5%, the reaction was completed. Water was added for washing, and after washing until neutral, toluene was removed to obtain 19.32g of intermediate S11.

[0066] 19.32g of intermediate S11 and 25g of polyurethane-35 were added to a reactor, along with 50ml of xylene, 2.5g of p-toluenesulfonic acid, and 0.2g of tetrabutylammonium bromide. The mixture was subjected to a reduced pressure reflux reaction at 80-90℃ for 10 hours. After washing with pure water, the mixture was filtered at 80-90℃ to obtain 38.92g of modified film-forming agent S31.

[0067] Figure 1 This is the UV absorption spectrum of polyurethane-35. Figure 2 The UV absorption spectrum of the modified film-forming agent S31 obtained in this embodiment shows that the modified film-forming agent S31 has UV absorption.

[0068] Example 2 25g of methyl ester-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionic acid and 15.0g of pentylene glycol were added to a reactor, along with 50mL of toluene and 1.5g of tetrabutyl titanate. The mixture was refluxed at 100-110℃. Methanol was collected during the reaction. After 7-8 hours, the 1120 content was found to be less than 1%, indicating the end of the reaction. 50mL of water was added for washing, and this washing was repeated twice to remove toluene and unreacted pentylene glycol, yielding 20.1g of intermediate S12.

[0069] 20.1g of intermediate S12 and 40g of carbomer 934 were added to a reactor, along with 80mL of toluene, 1.0g of tetraisopropyl titanate, and 0.1g of tetrabutylammonium hydrogen sulfate. The mixture was heated to reflux and reacted for 8 hours. Samples were taken for testing, and after passing the test, 50mL of water was added for washing. This process was repeated twice. The mixture was then filtered at 70-80℃ and dried to obtain 55.18g of modified film-forming agent S32.

[0070] Figure 3 The image shows the UV absorption spectrum of Carbomer 934. Figure 4 The UV absorption spectrum of the modified film-forming agent S32 obtained in this embodiment shows that the modified film-forming agent S32 has UV absorption.

[0071] Example 3 30g of diethylaminohydroxybenzoylhexyl benzoate, 70mL of xylene, 1.5g of sulfuric acid, and 20mL of water were added to a four-necked flask. The mixture was heated to 90-100℃ and kept at that temperature for 8-10 hours. When the content of diethylaminohydroxybenzoylhexyl benzoate was less than 0.5%, the hydrolysis reaction was considered complete. The mixture was cooled, and the insoluble matter was filtered out to obtain intermediate 1. The insoluble matter was added back to the four-necked flask, along with 14g of pentaerythritol, 100mL of xylene, and 2.0g of sulfuric acid. The mixture was refluxed under reduced pressure at 110-120℃ to remove water. When the content of intermediate 1 was less than 0.5%, the reaction was considered complete. The mixture was washed with water until neutral, and the xylene was removed. The mixture was cooled to 50-60℃, and 60mL of methanol was added to crystallize the mixture, yielding 24.5g of S13.

[0072] 24.5g of intermediate S13 and 50g of Polycarb were added. ® 10 was added to the reactor, along with 80 mL of xylene, 1.3 g of tetraisobutyl titanate, and 0.1 g of tetrabutylammonium bromide. The mixture was heated to reflux and reacted for 6-8 hours. Samples were taken for testing. After passing the test, 50 mL of water was added for washing. This process was repeated twice. The mixture was then filtered at 40-50 °C and dried to obtain 62.4 g of modified film-forming agent S33.

[0073] Test Example 1: Verification of Sunscreen Efficacy The modified film-forming agents obtained in the above examples were formulated into products according to Table 1 below, and the sun protection factor (SPF) was measured (refer to ISO 24443). The results are shown in Table 2.

[0074] Table 1

[0075] Table 2

[0076] Note: The film-forming agents used in the test examples and comparative examples listed in Tables 1, 2, and 3 of this invention are as follows: a- Test Example 1 uses the modified film-forming agent S31 prepared in Example 1; b - Comparative Example 1 used the unmodified film-forming agent polyurethane-35; c-Test Example 2 uses the modified film-forming agent S32 prepared in Example 2; d-Comparative Example 2 used the unmodified film-forming agent Carbomer 934.

[0077] 2. Film-forming performance test Water resistance testing was conducted according to the "Cosmetic Safety Technical Specifications": For sunscreens formulated according to Table 1, a 40-minute water resistance test was performed as follows: 1. Apply sunscreen to the skin test area and wait 15-30 minutes or as per the label instructions.

[0078] 2. Subjects engaged in moderate activity in the water or in a water flow with moderate rotation for 20 minutes.

[0079] 3. Let the water cool for 20 minutes (do not wipe the test area with a towel).

[0080] 4. After entering the water, engage in moderate activity for 20 minutes.

[0081] 5. After finishing water activities, wait for the skin to dry (do not rub the test area with a towel) before measuring SPF.

[0082] The results are shown in Table 3.

[0083] Table 3

[0084] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A modified film-forming agent, which is a reaction product of a UV absorber monomer and a film-forming agent monomer, wherein, The ultraviolet absorber monomer is an ultraviolet absorber having ester, carboxyl, and / or hydroxyl groups, and the film-forming agent monomer is a film-forming agent having hydroxyl, ester, and / or carboxyl groups.

2. The modified film-forming agent according to claim 1, characterized in that, The ultraviolet absorber monomer is selected from one or more of the following: benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylic acid or salicylic ester ultraviolet absorbers, cinnamic acid or cinnamic ester ultraviolet absorbers, p-aminophenyl ester ultraviolet absorbers, triazine ultraviolet absorbers, and cyanopropionate ultraviolet absorbers.

3. The modified film-forming agent according to claim 2, characterized in that, The benzotriazole-based ultraviolet absorber has a compound of formula I. （I） In Equation I, R1-R4 are each independently hydrogen or C. 1-6 alkyl; At least one of R5-R8 is an ester structure or a hydroxyl or carboxyl group, and the remainder is hydrogen or C. 1-6 Alkyl group, preferably at least one of 3-benzotriazol-5-tert-butyl-4-hydroxyphenyl propionate; more preferably methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate; And / or, The benzophenone-based ultraviolet absorber is selected from 2-diethylaminohydroxybenzoyl benzoate; And / or, The salicylic acid or salicylic ester ultraviolet absorber is selected from compounds having the structure of formula II. (II) In Equation II, R a Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; Preferably, the salicylic acid or salicylic acid ester ultraviolet absorber is selected from one or more of the following: methyl salicylate, homosalate, isooctyl salicylate, 4-tert-butylphenyl salicylate, and phenyl o-hydroxybenzoate. And / or, The cinnamic acid or cinnamic ester ultraviolet absorber is selected from compounds having the structure of Formula III. (III) In Equation III, R b Selected from H or C1-C 12 Straight-chain or branched alkyl or cycloalkyl groups; Preferably, the cinnamic acid or cinnamic ester ultraviolet absorber is selected from at least one of isoamyl methoxycinnamate or ethylhexyl methoxycinnamate; And / or, The para-aminobenzoic esters are selected from one or more of 2-ethylhexyl 4-aminobenzoic acid, PEG-25 para-aminobenzoic acid, and glyceryl para-aminobenzoate. And / or, The triazine ultraviolet absorber is selected from at least one of bis(ethylhexyloxyphenol)methoxyphenyltriazine and 4,4',4”-(1,3,5-triazine-2,4,6-triyltriimino)tribenzoate tri(2-ethylhexyl) ester; And / or, The cyanopropionate ultraviolet absorber is selected from at least one of itolithrin, octocrylene, and 2-ethylhexyl-2-cyano-3-(4-methoxyphenyl)-3-phenylacrylate.

4. The modified film-forming agent according to claim 1, characterized in that, The film-forming agent monomer is selected from one or more of the following: benzoic acid ester film-forming agents, acrylic acid copolymer film-forming agents, polyurethane film-forming agents, vinyl polymer film-forming agents, polyvinyl alcohol film-forming agents, and polyvinylpyrrolidone polymer film-forming agents; Preferably, the benzoate film-forming agent is selected from sucrose benzoate, benzoic acid and C8–C 13 One or more monoesters formed from long-chain fatty alcohols; acrylic copolymer film-forming agents are selected from acrylic (ester) / polydimethylsiloxane copolymers, acrylic (ester) / octylacrylamide copolymers, acrylic (ester) / C 12-22 Alkyl methacrylate copolymers; polyvinyl alcohol film-forming agents selected from one or more of polyvinyl alcohol EG-05C and polyvinyl alcohol EG-40C; polyurethane film-forming agents selected from polyurethane-35; vinyl polymer film-forming agents selected from the Antaron series; polyvinylpyrrolidone polymer film-forming agents selected from the Luvitec series or Polycar series.

5. The modified film-forming agent according to any one of claims 1-4, characterized in that, When the ultraviolet absorber monomer is an ultraviolet absorber monomer with an ester group, the ultraviolet absorber monomer with an ester group is further modified with a polyol or hydrolyzed before reacting with the film-forming agent monomer.

6. The modified film-forming agent according to claim 5, characterized in that, Polyol modification includes: reacting the ultraviolet absorber monomer with an ester group with a polyol in the presence of a first catalyst to obtain a polyol-modified ultraviolet absorber monomer; Preferably, the polyol is C2-C 10 The polyol, and / or the molar ratio of the polyol to the UV absorber monomer having an ester group is 1.5-5.0:1.0; and / or the first catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide. And / or, The hydrolysis treatment includes: hydrolyzing the ultraviolet absorber monomer with ester groups in the presence of a second catalyst to obtain a hydrolyzed ultraviolet absorber monomer; Preferably, the second catalyst is selected from one or more of sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid.

7. A method for preparing a modified film-forming agent, characterized in that, include: The ultraviolet absorber monomer and the film-forming agent monomer are reacted in the presence of a catalyst. The ultraviolet absorber monomer has ester, carboxyl and / or hydroxyl groups, and the film-forming agent monomer has hydroxyl, ester and / or carboxyl groups. The catalyst is selected from esterification catalysts or transesterification catalysts.

8. The method according to claim 7, characterized in that, The reaction is carried out in the presence of a phase transfer agent, which is selected from any one or more of benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, and tetrabutylammonium hydrogen sulfate. Preferably, the esterification catalyst is selected from one or more of sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; The transesterification catalyst is selected from one or more of tetraisopropyl titanate, tetrabutyl titanate, sodium acetate, potassium hydroxide, potassium acetate, and aluminum triisopropoxide.

9. A modified film-forming agent obtained by the method of any one of claims 7-8.

10. A cosmetic composition comprising a modified film-forming agent according to any one of claims 1-6 or a modified film-forming agent obtained by any one of claims 7-8.

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