Copolymers and cosmetic products comprising them

Abstract

The present invention aims to provide a copolymer that has both good dispersibility in water and high water repellency when formed into a coating film. A copolymer comprising: more than 20 mass% and less than 50 mass% of a structural unit represented by the following formula (1) in the copolymer; more than 0 mass% and less than 40 mass% of a structural unit represented by the following formula (2) in the copolymer; and a structural unit represented by the following formula (3).(1) (in the formula, R 1 ~R 3 each independently represents an optionally substituted linear or branched alkyl group having 1 to 30 carbons)(2) (in the formula, R 4 represents an optionally substituted alkylene group having 2 to 10 carbons, and m represents an integer of 1 to 30)(3) (in the formula, R 5 represents an optionally substituted linear or branched alkyl group having 1 to 30 carbons).

Description

Technical Field

[0001] This invention relates to copolymers and cosmetics containing them. Background Technology

[0002] Due to the diversity of preferences, the desired feel of cosmetics varies greatly. To meet these consumer demands, cosmetics exist in various formulations. Among them, water-based cosmetics and oil-in-water emulsion cosmetics (hereinafter also referred to as water-based cosmetics) have a continuous phase composed of water-based ingredients, and therefore have the following characteristics when used as cosmetics: (1) they can achieve a light, smooth spread and a refreshing feel; (2) they are relatively easy to manufacture; and (3) they are not easily affected by temperature.

[0003] On the other hand, various polymers are incorporated into cosmetics to impart various functions. For example, Lipidure (a registered trademark of Nichiyu Corporation) is known as an MPC polymer with methacryloyloxyethyl phosphocholine (hereinafter referred to as "MPC") as a repeating unit, which is excellent in terms of moisturizing properties, skin adhesion, and safety. MPC with phosphocholine groups is used as a biocompatible material with excellent moisturizing properties, and is used for example as an application agent for artificial organs, biological membranes, medical devices, drug delivery, and cosmetic ingredients. On the other hand, for organosilicon, which has the necessary characteristics of a cosmetic raw material such as physiological inactivity, very high safety, and stability, any organosilicon in both solid and liquid (silicone oil) forms has been used for various purposes in the cosmetic field. As cosmetics containing polymers with phosphocholine groups and polymers that have both the characteristics of organosilicon, for example, cosmetics containing polymers with polyorganosiloxane residues and phosphocholine groups have been proposed (Patent Documents 1-3).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2005 / 094758

[0007] Patent Document 2: Japanese Patent Application Publication No. 2018-24591

[0008] Patent Document 3: International Publication No. 2019 / 189608 Summary of the Invention

[0009] However, when the polymers disclosed in Patent Documents 1-3 are incorporated into systems containing water, it is difficult to achieve stable formulation. For example, in the case of cosmetics, aqueous components are often incorporated to obtain a moisturizing feel, resulting in a high demand for functional materials that can be stably formulated in aqueous systems. On the other hand, cosmetics also require durability against moisture such as sweat, necessitating the development of functional materials with high water-repellency when used in coatings.

[0010] Therefore, the object of the present invention is to provide a copolymer that combines good dispersibility in water with high water repellency when made into a coating.

[0011] In addition, another object of the present invention is to provide cosmetics with water resistance of the cosmetic film, suppression of secondary adhesion of cosmetics to masks, etc., good makeup retention, and high stability over time.

[0012] The present invention is a copolymer comprising: more than 20% by mass and less than 50% by mass of the structural unit shown in formula (1) below; more than 0% by mass and less than 40% by mass of the structural unit shown in formula (2) below; and the structural unit shown in formula (3) below.

[0013]

[0014] (where R is in the formula) 1 ~R 3 Each independently represents an alkyl group of 1 to 30 carbon atoms in either a straight or branched chain that may be substituted.

[0015]

[0016] (where R is in the formula) 4 (This indicates an alkylene group with 2 to 10 carbon atoms that may be substituted, where m represents an integer from 1 to 30.)

[0017]

[0018] (where R is in the formula) 5 (Refers to alkyl groups of 1 to 30 carbon atoms that are optionally substituted, either straight-chain or branched). Detailed Implementation

[0019] The embodiments of the present invention will be described below. It should be noted that the present invention is not limited to the embodiments described below. In this specification, the range “X~Y” includes both X and Y, meaning “X or more and Y or less”. Furthermore, unless otherwise stated, the operation and physical properties, etc., are measured at room temperature (20~25°C) and relative humidity 45~55%RH.

[0020] The present invention is a copolymer comprising: more than 20% by mass and less than 50% by mass of the structural unit of formula (1) in the copolymer; more than 0% by mass and less than 40% by mass of the structural unit of formula (2) in the copolymer; and the structural unit of formula (3).

[0021] The copolymers according to the present invention exhibit good dispersibility in water and high water repellency when formed into coatings.

[0022] The coating formed by the copolymer of the present invention exhibits high water repellency and high dispersibility in water. This balance between high water repellency and good dispersibility in water is achieved by setting the ratio of the structural units shown in formula (1) to those shown in formula (2) within a specific range of the present invention. The high water repellency is believed to be due to the fact that, with the configuration of the present invention, the structural units shown in formula (2), which are lipophilic components, tend to oriented outwards when the coating is formed. Furthermore, the good dispersibility in water is believed to be due to the fact that the structural units shown in formula (1) oriented outwards in water, forming micelles and dispersing in water. In the case of a binary polymer consisting of structural units shown in formula (1) and those shown in formula (2) without the structural units shown in formula (3), considering that the effects of the present invention cannot be achieved (for example, see comparative synthesis examples 1-5 described later), the structural units shown in formula (3) play an important role in controlling the orientation as described above. It should be noted that the speculative mechanism for achieving the effects of the present invention described above does not limit the scope of the present invention in any way.

[0023] The copolymers of the present invention will be described below.

[0024] [The structural unit shown in Equation (1)]

[0025]

[0026] In the formula, R 1 R 2 and R 3 Each can be independently represented as a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms.

[0027] Examples of alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 3-methylpentan-2-yl, 3-methylpentan-3-yl, 4-methylpentyl, 4-methylpentan-2-yl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylbutan-2-yl, n-heptyl, 1-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 1-(n-propyl)butyl, and 1,1-dimethyl... Pentyl, 1,4-dimethylpentyl, 1,1-diethylpropyl, 1,3,3-trimethylbutyl, 1-ethyl-2,2-dimethylpropyl, n-octyl, 2-ethylhexyl, 2-methylhexane-2-yl, 2,4-dimethylpentane-3-yl, 1,1-dimethylpentane-1-yl, 2,2-dimethylhexane-3-yl, 2,3-dimethylhexane-2-yl, 2,5-dimethylhexane-2-yl, 2,5-dimethylhexane-3-yl, 3,4-dimethylhexane-3-yl, 3,5-dimethylhexane-3-yl, 1-methylheptyl, 2-methylheptyl, 5-methylheptyl 2-Methylheptane-2-yl, 3-Methylheptane-3-yl, 4-Methylheptane-3-yl, 4-Methylheptane-4-yl, 1-Ethylhexyl, 2-Ethylhexyl, 1-Propylpentyl, 2-Propylpentyl, 1,1-Dimethylhexyl, 1,4-Dimethylhexyl, 1,5-Dimethylhexyl, 1-Ethyl-1-Methylpentyl, 1-Ethyl-4-Methylpentyl, 1,1,4-Trimethylpentyl, 2,4,4-Trimethylpentyl, 1-Isopropyl-1,2-Dimethylpropyl, 1,1,3,3-Tetramethylbutyl, n-Nonyl, 1-Methyloctyl, 6-Methyloctyl, 1-Ethyl Heptyl, 1-(n-butyl)pentyl, 4-methyl-1-(n-propyl)pentyl, 1,5,5-trimethylhexyl, 1,1,5-trimethylhexyl, 2-methyloctane-3-yl, n-decyl, 1-methylnonyl, 1-ethyloctyl, 1-(n-butyl)hexyl, 1,1-dimethyloctyl, 3,7-dimethyloctyl, n-undecyl, 1-methyldecyl, 1-ethylnonyl, n-dodecyl, 1-methylundecyl, n-tridecyl, n-tetradecyl, 1-methyltridecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, etc.

[0028] In this context, considering stability in aqueous systems, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. That is, in a suitable embodiment, R 1 ~R 3 Each of the components is independently a linear or branched alkyl group having 1 to 3 carbon atoms that may be optionally substituted, more preferably a substituted methyl group, and particularly preferably a (unsubstituted) methyl group.

[0029] Examples of substituents in straight-chain or branched alkyl groups having 1 to 30 carbon atoms include halogen atoms (F, Cl, Br, I), unsubstituted straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, unsubstituted straight-chain or branched alkenyl groups having 2 to 4 carbon atoms, unsubstituted cycloalkyl groups having 3 to 6 carbon atoms, hydroxyl groups, and amino groups. For alkyl groups having 1 to 30 carbon atoms, unsubstituted groups are preferred considering stability in aqueous systems. It should be noted that alkyl groups are not included in this list of substituents.

[0030] R 1 ~R 3 When the methyl group is used, the structural unit shown in formula (1) becomes a structural unit derived from 2-methacryloyloxyethyl phosphocholine (MPC) as shown in the following formula.

[0031]

[0032] The content of the structural unit shown in Formula (1) in the copolymer is more than 20% by mass and less than 50% by mass. When the content of the structural unit shown in Formula (1) is less than 20% by mass, the dispersibility in water is significantly reduced. In addition, when the content of the structural unit shown in Formula (1) is more than 50% by mass, the water repellency of the coating is significantly reduced. The content of the structural unit shown in Formula (1) in the copolymer is preferably 25 to 45% by mass, more preferably 25 to 40% by mass, and even more preferably more than 25% by mass and less than 40% by mass.

[0033] [The structural unit shown in equation (2)]

[0034]

[0035] In equation (2), R 4 R indicates an alkylene group having 2 to 10 carbon atoms that are optionally substituted. 4 Preferably, the alkylene group has a straight or branched chain with 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms, particularly preferably 2 to 3 carbon atoms, and most preferably trimethylene (-CH2CH2CH2-). Examples of alkylene groups with 2 to 10 carbon atoms include ethylene, propyleneene, trimethylene, tetramethylene, propyleneene, butylene, ethyl ethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene.

[0036] Examples of substituents present in alkylene groups having 2 to 10 carbon atoms include halogen atoms (F, Cl, Br, I), unsubstituted straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, unsubstituted straight-chain or branched alkenyl groups having 2 to 4 carbon atoms, unsubstituted cycloalkyl groups having 3 to 6 carbon atoms, hydroxyl groups, and amino groups. For alkylene groups having 2 to 10 carbon atoms, unsubstituted substituents are preferred considering the water repellency of the coating. It should be noted that alkyl groups are not included in this list of substituents.

[0037] In equation (2), m represents an integer from 1 to 30. When m is an integer greater than 31, the dispersion in water decreases. m is preferably an integer from 1 to 24, and examples include integers from 1 to 20, 1 to 18, 1 to 16, 1 to 12, 6 to 24, 6 to 20, 6 to 18, 6 to 16, 6 to 12, 8 to 24, 8 to 20, 8 to 16, 8 to 12, 8, 9, 10, 11, and 12. A suitable implementation is m = 11.

[0038] The content of the structural unit shown in Formula (2) in the copolymer is greater than 0% by mass and less than 40% by mass. When the content of the structural unit shown in Formula (1) is 40% by mass or more, the dispersibility in water is significantly reduced. When the content of the structural unit shown in Formula (2) is 0% by mass, the water repellency of the coating is significantly reduced. The content of the structural unit shown in Formula (2) in the copolymer is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and particularly preferably greater than 10% by mass and less than 30% by mass.

[0039] [The structural unit shown in equation (3)]

[0040]

[0041] In the formula, R 5 R indicates an alkyl group, either straight-chain or branched, with 1 to 30 carbon atoms, which may be optionally substituted. 5 When the number of carbon atoms is 31 or higher, its dispersibility in water decreases.

[0042] As an alkyl group having 1 to 30 carbon atoms, it is the same as that described in column (1) above. Among these, considering solubility in water, an alkyl group having 1 to 8 carbon atoms is preferred. That is, in a suitable embodiment, R... 5 The substituted alkyl group is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and even more preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, particularly preferably a n-butyl group, and most preferably an (unsubstituted) n-butyl group.

[0043] Examples of substituents in straight-chain or branched alkyl groups having 1 to 30 carbon atoms include halogen atoms (F, Cl, Br, I), unsubstituted straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, unsubstituted straight-chain or branched alkenyl groups having 2 to 4 carbon atoms, unsubstituted cycloalkyl groups having 3 to 6 carbon atoms, hydroxyl groups, and amino groups. For alkyl groups having 1 to 30 carbon atoms, unsubstituted groups are preferred, considering both stability in aqueous systems and makeup retention. It should be noted that alkyl groups are not included in this list of substituents.

[0044] The content of the structural unit shown in formula (3) in the copolymer is preferably 20 to 70% by mass, more preferably 30% by mass or more and less than 70% by mass, even more preferably 35 to 65% by mass, and particularly preferably 40 to 60% by mass. By keeping the content of the structural unit shown in formula (3) within this range, it is easy to further balance the water resistance and dispersibility in water of the formed coating.

[0045] [Other structural units]

[0046] The copolymer of the present invention may contain structural units other than those shown in formulas (1) to (3) (hereinafter also referred to as other structural units). However, in the present invention, from the viewpoint of balancing the water resistance and dispersibility in water of the formed coating, the content of other structural units in the copolymer is preferably less than 1% by mass, more preferably less than 0.5% by mass, and preferably substantially non-existent. Here, substantially non-existent means that the content of other structural units is preferably 0.01% by mass or less (lower limit 0% by mass), more preferably 0.001% by mass or less (lower limit 0% by mass), and particularly preferably 0% by mass. A suitable embodiment of the present invention is a copolymer composed of structural units shown in formulas (1) to (3).

[0047] [Weight-average molecular weight]

[0048] The weight-average molecular weight (Mw) of the copolymer of the present invention is not particularly limited as long as it achieves the purpose of the present invention, but is preferably 20,000 or more, more preferably 30,000 or more. By making the weight-average molecular weight at or above the above-mentioned lower limit, the water repellency of the coating is further improved. Furthermore, the weight-average molecular weight (Mw) of the copolymer of the present invention is not particularly limited as long as it achieves the purpose of the present invention, but is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 70,000 or less, and particularly preferably 60,000 or less. By making the weight-average molecular weight at or below the above-mentioned upper limit, the solubility in water is further improved, and the stability is further improved. The weight-average molecular weight (Mw) of the copolymer of the present invention is, for example, 20,000 to 100,000, and further examples include 20,000 to 80,000, 20,000 to 70,000, 30,000 to 70,000, and 30,000 to 60,000. The weight-average molecular weight of the copolymers of the present invention was calculated using the multi-angle light scattering method (MALS) with a multi-angle light scattering detector.

[0049] [Manufacturing Method]

[0050] The copolymers of the present invention, which include the structural units shown in formulas (1) to (3) as repeating units, can be obtained by polymerization in the presence of a solvent based on a known polymerization method. There are no particular limitations; for monomer compositions containing monomers used to form each structural unit, polymerization can be carried out in the presence of a free radical polymerization initiator. Examples of free radical polymerization initiators include, for instance, organic peroxides such as tert-butyl peroxynedecanoate, benzoyl peroxide, and lauroyl peroxide; azo compounds such as α,α'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(2-methylbutyronitrile); and persulfate-based polymerization initiators such as potassium persulfate and ammonium persulfate. These polymerization initiators can be used alone, or in combination of two or more. The amount of polymerization initiator used is typically 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of all monomers.

[0051] As a monomer used to form the structural unit of formula (1), for example, the monomer shown in the following formula can be listed.

[0052]

[0053] In the above formula, R 1 ~R 3 R in equation (1) 1 ~R 3 They have the same meaning.

[0054] As a monomer used to form the structural unit of formula (1), specifically, 2-methacryloyloxyethyl phosphocholine (MPC) as shown in the following formula can be listed.

[0055]

[0056] As a unit used to form the structural unit of formula (2), the following units can be listed as examples.

[0057]

[0058] In the above formula, R 4 R in equation (2) 4 The meanings are the same. Furthermore, in the above formula, m has the same meaning as m in formula (2). It should be noted that the monomer shown in the above formula is sometimes simply referred to as "SiMA".

[0059] As monomers used to form the structural unit of formula (3), alkyl methacrylates can be listed. Specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc. can be listed.

[0060] It should be noted that the content of each structural unit is consistent with the amount of each monomer added during the manufacturing stage. Furthermore, the content of each structural unit can be determined through NMR-based measurements and molecular weight determination.

[0061] Polymerization can be carried out under an inert gas atmosphere such as nitrogen. Furthermore, polymerization can be performed using solution polymerization, suspension polymerization, bulk polymerization, precipitation polymerization, etc. Solution polymerization is particularly preferred as it readily allows for the adjustment of the molecular weight of the resulting copolymer to an optimal range. Additionally, the copolymer of the present invention can be purified using known purification methods such as reprecipitation or dialysis. The copolymer of the present invention can be any of random copolymers or block copolymers; for example, the copolymer of the present invention is a random copolymer.

[0062] Examples of solvents used in the copolymer polymerization of the present invention include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; alcohols such as isopropanol, ethanol, and methanol; and water. One or more of these solvents may be used. Alternatively, polymerization may be carried out in alkane solvents such as light isoalkanes, isododecane, and isohexadecane.

[0063] The polymerization temperature of the copolymers of the present invention is not particularly limited as long as it falls within the temperature range that is commonly used by free radical polymerization initiators, and is typically carried out in the range of 40 to 120°C. The reaction temperature varies depending on the free radical polymerization initiator used, the type of monomer, and the reaction time, and is typically carried out for 2 to 24 hours. If the polymerization time is too short, the amount of residual monomer will be high and the yield will be low, which is not preferable.

[0064] [cosmetic]

[0065] The copolymer of the present invention (hereinafter also simply referred to as the copolymer) can be used as a raw material for manufacturing various cosmetics. That is, the present invention also provides cosmetics containing the copolymer. By including the copolymer in the cosmetic, water resistance to sweat, etc., is improved, and makeup retention is enhanced. Furthermore, by including the copolymer in the cosmetic, secondary adhesion of the cosmetic to masks, etc., can be suppressed. Moreover, by including the copolymer in the cosmetic, high stability over time is achieved. Details regarding how the above effects are achieved through the use of the copolymer of the present invention are not clear, but speculation is as follows.

[0066] The cosmetic of the present invention has high water resistance due to the inclusion of a copolymer with high water repellency. Furthermore, the cosmetic of the present invention has high makeup effect persistence (good makeup retention) due to the inclusion of the copolymer. This is believed to be because, by including a copolymer with high water repellency, the cosmetic film, as described above, not only has high water resistance, but also has a structure similar to the phospholipids of intercellular lipids shown in formula (1), and has the specific property of retaining bound water. Furthermore, by including the structural units of formulas (1) to (3) in a specific proportion, the polymer conformation becomes good, and the structural units shown in formula (1) are easily oriented towards the skin side, thus improving the skin affinity of the cosmetic. In addition, the cosmetic of the present invention can suppress the secondary adhesion of the cosmetic to masks, etc. This is believed to be because, in the copolymer of the present invention, the structural units shown in formula (1) have the specific property of retaining bound water; in addition, by including the structural units of formulas (1) to (3) in a specific proportion, the polymer conformation becomes good, and the structural units of formula (2), which have low friction and low adhesion (stickiness), are easily arranged on the outermost surface of the film. Furthermore, it is believed that because the copolymer has good dispersibility in water, it has high stability over time when incorporated into cosmetics.

[0067] Furthermore, by including copolymers in the cosmetics of the present invention, they also have a tactile feel that is neither burdensome during application nor burdensome over time.

[0068] The content of copolymers in cosmetics is appropriately set according to the desired feel and function, for example, 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, even more preferably 0.1 to 10% by mass, particularly preferably more than 0.5% by mass and less than 8% by mass, and particularly preferably 1 to 5% by mass.

[0069] Examples of cosmetic products include basic cosmetics such as toners, lotions, creams, serums, massage cosmetics, face masks, hand creams, body lotions, body creams, eye creams, and sunscreens; color cosmetics such as foundations and makeup bases; and hair cosmetics such as hair creams and hair waxes. Furthermore, regarding the physical form of cosmetics, examples include liquid, gel, lotion, cream, semi-solid, and solid cosmetics. Liquid cosmetics are preferred because they can incorporate a large amount of water-based ingredients.

[0070] The copolymer of the present invention exhibits good dispersibility in water, thus enabling stable formulation in aqueous systems. Furthermore, this stability is maintained even after prolonged periods. Therefore, as a dosage form for cosmetics, it is preferable to use a water-infused formulation, an aqueous system (including soluble types, powder-containing bilayer types), or an emulsion system (oil-in-water type, water-in-oil type, etc.), where the aqueous phase is the external phase, contributing to the overall stability of the system; therefore, an aqueous system or an oil-in-water emulsion system is more preferred.

[0071] Because the copolymer of the present invention exhibits good dispersibility in water, it is preferable that the cosmetic contains water. There are no particular limitations on the type of water used in cosmetics, including ordinary water, purified water, ion-exchanged water, thermal spring water, deep well water, lavender water, rose water, orange blossom water, and other plant-derived steam-distilled water. One type of water may be used alone, or two or more may be used in combination. The water content in the cosmetic is not particularly limited, but is preferably 20–99% by mass, more preferably 30–95% by mass, and even more preferably 40–95% by mass.

[0072] Cosmetics can be combined with a wide variety of ingredients commonly used in cosmetics. Common ingredients in cosmetics can be combined with oils, surfactants (anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants), thickeners (gelling agents, polymers), colorants, powders other than colorants, lower alcohols such as ethanol, polyols, UV absorbers, pH adjusters, antioxidants, metal chelating agents, preservatives, fragrances, and various pharmaceuticals, etc.

[0073] As oiling agents, examples include isododecane, isohexadecane, light-chain isoalkanes, liquid paraffin, squalane, squalene, α-olefin oligomers, polybutene, liquid isoalkanes, heavy liquid isoalkanes, polyisobutylene, hydrogenated polyisobutylene, rapeseed oil, avocado oil, almond oil, and apricot (PRUNUS) oil. Armeniaca seed oil, perilla seed oil, orange oil, olive oil, kiwi seed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, sage oil, soybean oil, tea tree seed oil, corn oil, rapeseed oil, evening primrose oil, camellia seed oil, peach kernel oil, coix seed oil, peanut oil, sunflower oil, grape seed oil, meadowfoam seed oil, rosemary leaf oil, jojoba seed oil, macadamia nut seed oil, lavender oil, rosehip oil, mink oil, and other animal and vegetable oils; tri-2-ethylhexanoic acid glyceride, isotriadecyl isononanoate, isonononyl isononanoate, 2-ethylhexanoic acid Hexadecyl ester, Isopropyl myristate, Isopropyl palmitate, 2-ethylhexyl palmitate, Octyl dodecyl myristate, Tricaprylyl glyceryl tris(caprylyl) / caprylyl triglyceride, Glyceryl stearate, Diisostearate, Triisostearate, Deca-polyglycerol isostearate (polyglycerol-10 deca-isostearate), Propylene glycol dicaprylyl ester, Neopentyl alcohol dicaprylyl ester, Polyglycerol triisostearate, Diisostearate malate, Neopentyl glycol di(ethylhexanoate), Polyglycerol-10 deca-isostearate, Pentaerythritol tetraisostearate, Pentaerythritol tetra(2-) Esters such as ethylhexanoate, pentaerythritol pentaisostearate, dialkyl carbonate, trimellitic acid triterpenoid, bis(diethoxydiethylene glycol cyclohexane 1,4-dicarboxylic acid ester, and di-linoleyl alcohol hydrogenated rosinate; fatty acids such as oleic acid, isostearic acid, and stearic acid; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol, 2-hexyldecanol, and cetyl alcohol; dimethylpolysiloxane (dimethicone), methyl polytrimethylsiloxane, methylphenyl polysiloxane, and octamethylcyclotetrasiloxane. Silicone oils such as oxanes, decamethylcyclopentasiloxanes, tetramethyltetrahydrocyclotetrasiloxanes, tetramethyltetraphenylcyclotetrasiloxanes, tetramethyltetratrifluoropropylcyclotetrasiloxanes, pentamethylpentatrifluoropropylcyclopentasiloxanes, polyether-modified methylpolysiloxanes, oil-modified methylpolysiloxanes, and polyvinylpyrrolidone-modified methylpolysiloxanes; fluorinated oils such as perfluoropolyethers, perfluorodecane, and perfluorooctane; lanolin derivatives such as acetylated lanolin, isopropyl lanolinate, and lanolin alcohol; and liquid oils such as 2-ethylhexyl p-methoxycinnamate and ethylhexyl salicylate, which are ultraviolet absorbers.Cocoa butter, shea butter, castor oil, hydrogenated castor oil, hydrogenated coconut oil, petrolatum, hydrogenated castor oil monostearate, hydrogenated castor oil monohydroxystearate, cholesterol hydroxystearate, dipentaerythritol fatty acid ester, N-lauroyl-L-glutamate di(octyldodecyl / cholesterol / betaine) ester, di(octyldodecyl / phytosterol / betaine)N-lauroyl-L-glutamate ester, phytosterol whole-leaved Australian styrax Nut seed oil fatty acid esters, (phytosterol / isostearyl / hexadecyl / stearyl / betaine) dimerized linoleic acid esters, and other paste-like oils; solid paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, stearic acid, betaine acid, hexadecyl palmitate, polyethylene glycol distearate, tris(betaine) glyceryl ester, cholesterol, phytosterols, stearyl-modified polysiloxanes, hardened oils, petrolatum, palm oil, and other solid oils. These oils can be used alone or in combination of two or more.

[0074] Examples of anionic surfactants include fatty acid soaps, acylglutamate salts, alkyl phosphates, polyoxyethylene lauryl ether phosphate, polyoxyethylene hexadecyl ether phosphate, polyoxyethylene stearyl ether phosphate, and polyoxyethylene alkyl phosphate. These anionic surfactants can be used alone or in combination of two or more.

[0075] Examples of nonionic surfactants include sorbitan fatty acid esters, fatty acid glycerides, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid glycerides, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene phytosterol ethers, polyoxyethylene cholesterol ethers, polyoxyethylene cholesterol ethers, polyoxyethylene-modified organopolysiloxanes, polyoxyethylene-alkyl co-modified organopolysiloxanes, alkanolamides, sugar ethers, and sugar amides. These nonionic surfactants can be used alone or in combination of two or more.

[0076] Examples of amphoteric surfactants include imidazoline-based surfactants (e.g., sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline, sodium 2-cocoyl-2-imidazoline hydroxide-1-carboxyethoxy2-sodium salt, etc.); betaine-based surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazoline betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amide betaine, sulfonate betaine, etc.); and phospholipids (e.g., lecithin, hydrogenated lecithin, etc.). It should be noted that sources of lecithin include soybeans and eggs.

[0077] Colorants are not specifically limited to shapes such as spherical, plate-like, spindle-shaped, or needle-like, or particle sizes such as smoky, microparticle, or pigment-grade, or particle structures such as porous or non-porous. Inorganic pigments, organic pigments, glitter pigments, and metals can be used. Specific examples of powders include white inorganic pigments such as titanium dioxide, zinc oxide, cerium oxide, and barium sulfate; colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, Prussian blue, ultramarine, and red lead; mica titanium; bismuth oxychloride; organic pigment-treated mica titanium; titanium dioxide-coated mica; titanium dioxide-coated synthetic phlogopite; titanium dioxide-coated bismuth oxychloride; iron oxide mica titanium; Prussian blue-treated mica titanium; carmine-treated mica titanium; fish scale foil; titanium dioxide-coated glass powder; polyethylene terephthalate-aluminum-epoxy laminated powder; polyethylene terephthalate-polyolefin laminated film powder; polyethylene terephthalate-polymethyl methacrylate laminated film powder and other resin laminated powders, as well as glitter pigments such as Red 201 and Red... Organic pigment powders such as No. 202, No. 205, No. 226, No. 228, No. 203, No. 204, No. 404, and No. 401; organic pigment powders such as No. 3, No. 104, No. 106, No. 205, No. 4, No. 5, No. 3, and No. 1, such as zirconium, barium, or aluminum lake pigment powders; or further, metal powders such as aluminum powder, gold powder, and silver powder; micronized titanium dioxide coated with mica titanium; micronized zinc oxide coated with mica titanium; barium sulfate coated with mica titanium; silicon dioxide containing titanium dioxide; and silicon dioxide containing zinc oxide, etc., as natural pigments, such as carmine acid, shellac acid, safflower pigment, flavonoids, and crocin, etc., can be used as needed, one or more of them. These can also be surface treated using one or more of the following: fluorine compounds, organosilicon compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants, etc.

[0078] As for powders other than colorants, any powder commonly used as a cosmetic ingredient is not particularly limited to shapes such as plate-like, spindle-shaped, or needle-like, particle sizes such as smoky or microparticle-sized, or particle structures such as porous or non-porous. Furthermore, powders other than colorants can include inorganic powders such as alumina, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, talc, kaolin, silicon dioxide, silicon carbide, and boron nitride; and organic powders such as magnesium stearate, zinc stearate, N-acyl lysine, nylon, polymethyl methacrylate, organopolysiloxane powders, and cellulose powders. One or more of these can be used. Additionally, one or more of these powders can be combined. For this surface treatment, oil treatment, organosilicon compound treatment, or water-soluble polymer treatment can also be performed.

[0079] Examples of gelling agents include dextrin caprylate, dextrin laurate, dextrin myristate, dextrin palmitate, dextrin palmitate / 2-ethylhexanoate, dextrin stearate, dextrin isostearate, dextrin palmitate / stearate, dextrin oleate, dextrin palmitate / hexyldecanoate, dextrin benzyl ester, dextrin coconut oil fatty acid ester, etc.; sucrose stearate, sucrose palmitate, etc.; oligofructose stearate, etc.; inulin stearate, etc.; dimethyl distearylamine lithium montmorillonite, dimethyl distearylamine bentonite, benzyl dimethyl distearylamine lithium montmorillonite, distearyl dimethylamine lithium montmorillonite, and di(octadecyl)dimethylammonium Organically modified bentonite, including salt-modified montmorillonite, octadecyl dimethyl benzyl ammonium salt-modified montmorillonite, and di(hexadecyl) dimethyl ammonium salt-modified montmorillonite; glycerol-based low-polyester gelling agents synthesized from glycerol, eicosanoic acid, and betaine acid (called glycerol (betaine acid / eicosanoic acid) esters); glycerol low-polyesters such as 2-ethyloctadecanoic acid glyceride, myristate tetradecanoic acid glyceride, palmitic acid eicosanoic acid glyceride, stearate hexadecanoic acid glyceride, isostearate eicosanoic acid glyceride, betaine octadecanoic acid glyceride, 2-ethylhexanoic acid dodecanoic acid glyceride, and oleic acid 2-ethyloctadecanoic acid glyceride; smoky anhydrous silica; and metal soaps such as aluminum isostearate, zinc stearate, and magnesium stearate. These gelling agents can be used alone or in combination of two or more.

[0080] Examples of water-soluble polymers include carrageenan, xanthan gum, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylene polymers, alkyl-modified carboxyethylene polymers, polyvinyl alcohol, polyvinylpyrrolidone, (sodium acrylate / sodium acryloyl dimethyl taurate) copolymers, and (PEG-240 / decyltetradecyl alcohol polyether-20 / HDI) copolymers; terpene resins; and organosilicon resins (e.g., graft copolymers of acrylic polymers and polydimethylsiloxane (acrylate / polydimethylsiloxane copolymers) (INCI name). (Meth)acrylate·(meth)acrylate alkyl ester copolymer (acrylate (ester) copolymer (INCI name)), trimethylsiloxysilicate, polymethylsilsesquioxane, hydrocarbon resins, vinyl acetate resins (e.g., polyvinyl acetate), rosin resins (e.g., pentaerythritol rosinate, pentaerythritol hydrogenated rosinate, hydrogenated glycerol dehydroabiate / tetrahydroabiate), acrylic resins (e.g., polyethyl acrylate, polybutyl methacrylate, acrylic / alkyl acrylate copolymer, alkyl acrylate / vinyl acetate copolymer), etc. It should be noted that even when the copolymers of this application are combined with water-soluble polymers, no precipitation due to thickening or polymer complex formation occurs, as confirmed in the following examples. In this respect, it is also possible to further include water-soluble polymers in cosmetics.

[0081] Examples of polyols include propylene glycol, 1,3-butanediol, dipropylene glycol, and tripropylene glycol. These polymers can be used individually or in combination of two or more.

[0082] Examples of UV absorbers include cinnamic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, phenylbenzimidazole derivatives, phenylbenzotriazole derivatives, and organosilicon derivatives. Specifically, examples include 2-ethylhexyl p-methoxycinnamate, octocrylene, polyorganosilicon-15, tert-butylmethoxydibenzoylmethane, ethylhexyl triazine, diethylaminohydroxybenzoyl benzoate, bis-ethylhexyloxyphenol methoxyphenyl triazine, oxybenzone, methylenebisbenzotriazolyl tetramethylbutylphenol, phenylbenzimidazole sulfonic acid, homosalate, and ethylhexyl salicylate. It should be noted that UV absorbers can also include oils.

[0083] As a method for manufacturing cosmetics, cosmetics can be obtained by dissolving the copolymer of the present invention in an aqueous system and emulsifying it as needed.

[0084] Example

[0085] The effects of the present invention will be illustrated by the following examples and comparative examples. In the examples, the terms "parts" or "%" are sometimes used, but unless otherwise stated, they represent "parts by mass" or "% by mass". Furthermore, unless otherwise stated, all operations are performed at room temperature (25°C).

[0086] [Synthesis Example 1]

[0087] 30.0g of 2-methacryloyloxyethyl phosphocholine (MPC, manufactured by Nippon Oil Co., Ltd.), organosilicon methacrylate (SiMA, manufactured by Shin-Etsu Chemical Co., Ltd.), and R in formula (2) 4 10.0 g of trimethylene glycol (m=11) and 60.0 g of butyl methacrylate (Blemmer BMA, manufactured by Nippon Oil Co., Ltd.) were placed in a four-necked flask and dissolved in 233.3 g of ethanol. Nitrogen gas was introduced for 30 minutes. Then, 2.0 g of tert-butyl peroxyneodecanate (PERBUTYL (Japanese registered trademark) ND (PB-ND), manufactured by Nippon Oil Co., Ltd.) was added as a polymerization initiator, and the polymerization reaction was carried out at 70°C for 6 hours. After polymerization, volatile components were removed by distillation under reduced pressure to obtain polymer powder. The molecular weight of the polymer was analyzed using the MALS method. The apparatus used was a multi-angle light scattering detector (DAWN HELEOS II 8+), and the medium was isopropanol. The weight-average molecular weight was 34,000.

[0088] [Synthesis Examples 2 to 4]

[0089] The polymer was prepared using the monomer types and amounts shown in Table 1 below, except following the same steps as in Synthesis Example 1.

[0090] [Comparative Examples of Synthesis 1 to 12]

[0091] The polymer was prepared using the monomer types and amounts shown in Table 1 below, except following the same steps as in Synthesis Example 1.

[0092] (Evaluation Method 1: Dispersibility in water)

[0093] 10g of the copolymer prepared in the synthesis examples or comparative examples was mixed in 90g of water, heated at 70°C for 2 hours, and then cooled to room temperature. The stability of the dispersion was visually confirmed. The results are shown in Table 1 below.

[0094] ○: Dissolves transparently

[0095] ×: Cloudy appearance, or polymer precipitation in the lower layer.

[0096] (Evaluation Method 2: Contact Angle of Coating)

[0097] A 10% by mass aqueous solution of the copolymer produced in the synthesis examples or comparative examples was prepared and film was formed using a 25 μm doctor blade. The static contact angle of water was determined using the droplet method. A value of 2 or higher was considered to indicate good water repellency. The results are shown in Table 1 below.

[0098] 5: Above 100°

[0099] 4: 80° or higher but less than 100°

[0100] 3: Above 60° and below 80°

[0101] 2: 50° or higher and below 60°

[0102] 1: Below 50°C

[0103] [Table 1]

[0104] Synthesis Example 1 30 10 60 White powder ○ 4 Synthesis Example 2 30 20 50 White powder ○ 5 Synthesis Example 3 30 30 40 White powder ○ 4 Synthesis Example 4 40 10 50 White powder ○ 3 Comparative Synthesis Example 1 90 10 0 White powder ○ 1 Comparative Synthesis Example 2 80 20 0 White powder ○ 1 Comparative Synthesis Example 3 70 30 0 White rubbery × - Comparative Synthesis Example 4 50 50 0 White rubbery × - Comparative Synthesis Example 5 30 70 0 White rubbery × - Comparative Synthesis Example 6 90 5 5 White powder ○ 1 Comparative Synthesis Example 7 80 10 10 White powder ○ 1 Comparative Synthesis Example 8 70 10 20 White powder ○ 1 Comparative Synthesis Example 9 50 10 40 White powder ○ 1 Comparative Synthesis Example 10 20 10 70 White powder × - Comparative Synthesis Example 11 10 10 80 White powder × - Comparative Synthesis Example 12 30 40 30 White powder × -

[0105] (Note) The ellipses in Table 1 have the following meanings.

[0106] MPC: 2-Methacryloyloxyethylphosphocholine (manufactured by NOF Corporation)

[0107] SiMA: Organosilicon methacrylate (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0108] BMA: Butyl methacrylate (Blemmer BMA, manufactured by NOF Corporation)

[0109] It should be noted that the molecular weight (Mw) of synthesis example 1 is 34,000, the molecular weight (Mw) of synthesis example 2 is 52,000, the molecular weight (Mw) of synthesis example 3 is 52,000, and the molecular weight (Mw) of synthesis example 4 is 55,000.

[0110] Based on the above results, the copolymers in the synthetic examples exhibit good dispersibility in water and high water repellency of the coating.

[0111] [Examples 1-5, Comparative Examples 1-5: Water-in-oil foundation]

[0112] Water-in-oil foundations with the composition shown in Table 2 (mass % relative to 100% of the total cosmetic product, and the same applies below) were prepared using the manufacturing method described below. The following evaluation methods and criteria were used to evaluate (i) the water resistance of the cosmetic film, (ii) the effect of preventing secondary adhesion of the cosmetic film, (iii) the absence of cosmetic collapse over time, (iv) the absence of a heavy feeling when applied, (v) the absence of a heavy feeling over time, and (vi) the stable compatibility of the polymer. The results are shown in Table 2.

[0113] [Manufacturing Method]

[0114] (1) Mix components 1-3 and 8-14 evenly and heat to 75°C.

[0115] (2) Mix components 7, 15-22 and 24-25 evenly and heat to 75°C.

[0116] (3) Add (1) to (2) and emulsify and cool.

[0117] (4) Use three rollers to process components 4-6, 23, and 26-30.

[0118] (5) Add (4) to (3) and disperse using a disperser.

[0119] (6) Add ingredients 31-32 to (5), and after defoaming, obtain an oil-in-water foundation.

[0120] [Evaluation Method]

[0121] (i) Water resistance of cosmetic films

[0122] After applying 10mg of each foundation liquid to a PMMA perforated plate (5×5cm), the plate was dried at room temperature for 30 minutes. The plate was then attached to a cylindrical plastic container, 100g of water was added, and the mixture was shaken for 1 minute. The collapse and lightening of the cosmetic film were then visually observed, and the water resistance was evaluated according to the following criteria.

[0123] (Judgment Criteria)

[0124] The cosmetic mask remained completely intact: ◎

[0125] The cosmetic film barely peeled off: 〇

[0126] Cosmetic mask peeling off: △

[0127] The cosmetic mask has severely peeled off: ×

[0128] (ii) Effect of preventing secondary adhesion of cosmetic film

[0129] After applying 10 mg of each foundation liquid to black artificial leather (5×5 cm), drying it at room temperature for 30 minutes, then placing a nonwoven fabric (5×5 cm) and then a metal plate (5×5 cm) on it, and pressing it with a hydraulic press at a pressure of 50 MPa, the effect of preventing secondary adhesion was evaluated based on the degree of color transfer to the nonwoven fabric according to the following judgment criteria.

[0130] (Judgment Criteria)

[0131] Not attached at all to the nonwoven fabric: ◎

[0132] The nonwoven fabric was almost unattached: 〇

[0133] Attached to nonwoven fabric: △

[0134] Severe adhesion on nonwoven fabrics: ×

[0135] (iii) No makeup sagging during application; (iv) No feeling of heaviness during application (the makeup has poor spreadability, and the skin is stretched due to rubbing); (v) No feeling of heaviness during application (the skin feels tight or feels blocked due to the makeup film).

[0136] Regarding the issue of makeup sagging over time for various foundations, a professional cosmetics evaluation team of 20 members visually observed changes on the entire face immediately after application and 6 hours later. For sagging without a makeup film, each member conducted a five-stage evaluation based on the following criteria, assigning scores to each stage. The average score from all evaluation team members was then used to determine the final assessment. Additionally, sensory evaluations were conducted immediately after application and 6 hours later, with each evaluation conducted in five stages based on the following criteria, assigning scores to each stage. The average score from all evaluation team members was then used to determine the final assessment.

[0137] (Evaluation Result): (Score)

[0138] Excellent: 5 stars

[0139] Good: 4 points

[0140] Average: 3 points

[0141] Slightly unsatisfactory: 2 points

[0142] Poor: 1 point

[0143] (Judgment Criteria): Judgment

[0144] Over 4.0: ◎

[0145] Above 3.0 and below 4.0: 〇

[0146] Above 2.0 and below 3.0: △

[0147] Below 2.0: ×

[0148] (vi) Stable coordination of polymers

[0149] After each foundation liquid was left to stand in a constant temperature bath at 5°C for one month, it was returned to room temperature to confirm whether there was any insolubility of the co-existing polymers.

[0150] (Judgment Criteria): Judgment

[0151] No polymer insolubility was observed at all: ◎

[0152] Polymer insolubility was observed: ×

[0153] [Table 2-1]

[0154] (quality%)

[0155] 1 stearic acid 1 1 1 1 1 1 1 1 1 1 2 Glyceryl stearate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 3 cetyl alcohol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 4 Sorbitan sesquioleate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 5 Polyoxyethylene (20) hydrogenated castor oil 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 6 Hydrogenated lecithin 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 7 Triethanolamine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 8 Liquid paraffin 3 3 3 3 3 3 3 3 3 3 9 decamethylcyclopentasiloxane 5 5 5 5 5 5 5 5 5 5 10 Dimethylpolysiloxane 3 3 3 3 3 3 3 3 3 3 11 2-Ethylhexyl p-methoxycinnamate 3 3 3 3 3 3 3 3 3 3 12 Diethylaminohydroxybenzoyl benzoate 1 1 1 1 1 1 1 1 1 1 13 bis-ethylhexyloxyphenol methoxyphenyl triazine 1 1 1 1 1 1 1 1 1 1 14 Trimethylsilyloxysilicate*1 3 15 Synthetic copolymers described in Example 1 3 16 Synthetic copolymers described in Example 2 3 8 0.5 17 Synthetic copolymers described in Example 3 3 18 Acrylic (ester) / VA copolymer*2 3 19 Polyvinyl acetate*3 3 20 Acrylic (ester) copolymers*4 3 21 Purified water margin margin margin margin margin margin margin margin margin margin

[0156] [Table 2-2]

[0157] 23 1,3-Butanediol 10 10 10 10 10 10 10 10 10 10 24 ethanol 3 3 3 3 3 3 3 3 3 3 2.5 Phenoxyethanol 1 1 1 1 1 1 1 1 1 1 26 micronized titanium dioxide 3 3 3 3 3 3 3 3 3 3 27 micronized zinc oxide 2 2 2 2 2 2 2 2 2 2 28 Titanium oxide 8 8 8 8 8 8 8 8 8 8 29 iron oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 30 talc 2 2 2 2 2 2 2 2 2 2 31 Globular cellulose 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 32 silicon dioxide 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

[0158]

[0159] *1: KF-9021 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

[0160] *2: VINYSOL 2140L (manufactured by Daido Chemical Industries)

[0161] *3: VINYBLAN GV-5651 (manufactured by Nissin Chemical Industries, Ltd.)

[0162] *4: COVACRYL MS11 WP (Made by Sensient)

[0163] As understood from the table above, the water-in-oil foundations of Examples 1-5 exhibited excellent performance in all aspects: (i) water resistance of the cosmetic film, (ii) prevention of secondary adhesion of the cosmetic film, (iii) no makeup sagging over time, (iv) no feeling of heaviness during application, (v) no feeling of heaviness over time, and (vi) stable polymer formulation. On the other hand, Comparative Example 1, which did not use the copolymer of the present invention, showed significantly poor results in aspects (i) to (iii). Comparative Example 2, which incorporated an oil-soluble silicone resin instead of the copolymer of the present invention, resulted in a feeling of heaviness during application or over time. Furthermore, Comparative Examples 3-5, which incorporated a water-soluble polymer instead of the copolymer of the present invention, showed poor results in the aspects of prevention of secondary adhesion and no makeup sagging. Additionally, a feeling of heaviness over time was observed.

[0164] [Example 6: Water-in-oil foundation]

[0165]

[0166]

[0167] *1: Shin-Etsu Chemical Industry Co., Ltd. KP-578

[0168] *2: Shin-Etsu Chemical Industry Co., Ltd. KF-6028P

[0169] *3: Shin-Etsu Chemical Industry Co., Ltd. KSP-102

[0170] *4: TOSPEARL2000B made by Momentive Materials Performance Japan Ltd.

[0171] [Manufacturing Method]

[0172] (1) Mix components 1-7, components 9 and 10, and process them with 3 rollers.

[0173] (2) Use a disperser to disperse components 8 and 11-20.

[0174] (3) Add (1) to (2) and disperse using a disperser.

[0175] (4) Mix and dissolve components 21 to 27.

[0176] (5) Add (4) to (3), emulsify and defoam, and then obtain an oil-in-water foundation.

[0177] The water-in-oil foundation of Example 6 is excellent in (i) the water resistance of the cosmetic film, (ii) the effect of preventing secondary adhesion of the cosmetic film, (iii) no makeup collapse over time, (iv) no burden when applying, (v) no burden over time, and (vi) the stable compatibility of the polymer.

[0178] [Example 7: Aqueous Substrate (with Powder Double Layer)]

[0179]

[0180]

[0181] *1: RHEOCRYSTA C-2SP (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.)

[0182] *2: EUSOLEX 232 (manufactured by Merck Performance Materials Ltd.)

[0183] *3: TOSPEARL2000B made by Momentive Materials Performance Japan Ltd.

[0184] *4: AEROSIL 200 (made by NIPPON AEROSIL CO., Ltd.)

[0185] [Manufacturing Method]

[0186] (1) After mixing components 1, 2, 8, 9 and components 13 to 20, process them with 3 rollers.

[0187] (2) Dissolve components 3-7 and components 10-12 evenly.

[0188] (3) Add (3) to (2), disperse with a disperser, and then degas to obtain an aqueous substrate.

[0189] The water-based substrate of Example 7 is excellent in (i) water resistance of the cosmetic film, (ii) prevention of secondary adhesion of the cosmetic film, (iii) no cosmetic collapse over time, (iv) no burden during application, (v) no burden over time, and (vi) stable compatibility of the polymer.

[0190] [Example 8: Water-in-oil sunscreen]

[0191]

[0192]

[0193] *1: SIMULGEL EG (manufactured by SEPPIC)

[0194] *2: Rheopearl ISK2 (manufactured by Chiba Flour Milling Co., Ltd.)

[0195] *3: Uvinul (registered trademark) MC80 (made by BASF)

[0196] *4: Tinosorb (registered trademark) S (manufactured by BASF)

[0197] *5: Uvinul (registered trademark) A PLUS (manufactured by BASF)

[0198] *6: PARSOL SLX (manufactured by DSM)

[0199] *7: CARBOPOL (registered trademark) 980 (made by Lubrizol Corporation)

[0200] *8: MZ-500 (manufactured by Tayca Corporation)

[0201] *9: KSP-102 manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0202] [Manufacturing Method]

[0203] (1) Mix components 6-8 and components 21-24 and process them with 3 rollers.

[0204] (2) Mix components 1-5 and components 9-12 evenly and heat to 75°C.

[0205] (3) Mix components 13 to 20 evenly and heat to 75°C.

[0206] (4) Add (2) to (3), emulsify and then cool.

[0207] (5) Add (1) to (4), disperse with a disperser, and then defoam to obtain an oil-in-water sunscreen.

[0208] The water-in-oil sunscreen of Example 8 is excellent in (i) the water resistance of the cosmetic film, (ii) the effect of preventing secondary adhesion of the cosmetic film, (iii) no cosmetic collapse over time, (iv) no burden when applying, (v) no burden over time, and (vi) the stable compatibility of the polymer.

[0209] This application is based on Japanese Patent Application No. 2021-109184, filed on June 30, 2021, the entire contents of which are incorporated herein by reference.

Claims

1. A copolymer comprising: more than 20% by mass and less than 50% by mass of structural units of formula (1) below; more than 0% by mass and less than 40% by mass of structural units of formula (2) below; and 20 to 70% by mass of structural units of formula (3) below. In the formula, R 1 ~R 3 Each independently represents an alkyl group, either straight-chain or branched, with 1 to 30 carbon atoms, which may be optionally substituted. In the formula, R 4 This indicates an alkylene group with 2 to 10 carbon atoms that are optionally substituted, and m represents an integer from 1 to 30. In the formula, R 5 It refers to an alkyl group with 1 to 30 carbon atoms that is optionally substituted, either straight or branched.

2. The copolymer according to claim 1, wherein the weight-average molecular weight (Mw) is 20,000 to 100,000.

3. The copolymer according to claim 1 or 2, wherein, The value of m is an integer from 8 to 16.

4. The copolymer according to claim 1 or 2, wherein, The R 1 ~R 3 Each is independently an alkyl group with 1 to 3 carbon atoms that is optionally substituted, either straight or branched.

5. The copolymer according to claim 1 or 2, wherein, The content of structural units other than those shown in formulas (1) to (3) in the copolymer is less than 1% by mass.

6. The copolymer according to claim 1 or 2, wherein, The R 5 The substituted alkyl group is a straight-chain or branched alkyl group having 1 to 8 carbon atoms.

7. A cosmetic product comprising any one of claims 1 to 6.

8. The cosmetic according to claim 7, wherein it is an aqueous or oil-in-water emulsion system.

9. The cosmetic product according to claim 7 or 8, wherein, The content of the copolymer is 0.01~20 by mass.

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