Esterification reaction product, method for producing esterification reaction product, and cosmetic

Abstract

An esterification reaction product obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer, the esterification reaction product having a weight average molecular weight of 6500 to 9000 and a dispersity of 1.40 to 1.65. A cosmetic contains the esterification reaction product. The esterification reaction product is manufactured by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0.

Description

Technical Field

[0001] This invention relates to esterification reaction products. In particular, it relates to esterification reaction products that combine good adhesion to the skin and other surfaces, ease of application and spreading, and excellent water resistance, powder dispersibility, film-forming properties, and water retention.

[0002] This application claims priority based on Japanese Patent Application No. 2024-52517, filed in Japan on March 27, 2024, the contents of which are incorporated herein by reference. Background Technology

[0003] In cosmetics such as sunscreens, skincare / haircare products, and makeup, oils are required to possess excellent moisturizing properties, skin adhesion, powder dispersibility, water resistance, and oxidative stability. Furthermore, they must have a pleasant texture and low skin irritation. In addition to these functions, recent years have seen a focus on environmental protection, with a growing demand for plant-based oils derived from plant-based alcohols and fatty acids.

[0004] Polyhydroxyalkanoates (PHA) are a type of cosmetic oil that uses plant-derived ingredients. PHAs are products of the esterification reaction of polyhydroxyalkanoates with alcohols. Depending on the degree of polymerization of the polyhydroxyalkanoates, the type of hydroxyalkanoates as monomers, and the type of alcohol, a wide variety of esterification products with different structures can be included. Among these diverse PHAs, substances with good moisturizing properties, good skin adhesion, good powder dispersibility, good water resistance, good oxidative stability, good feel, and good water retention are known. However, PHAs using plant-derived ingredients that possess all of the above functions have not yet been developed.

[0005] Examples of polyhydroxyalkanoates that utilize plant-derived raw materials include polyglycerol polyricinoleate, polyglycerol-3 polyricinoleate, polyglycerol-4 polyricinoleate, polyglycerol-5 polyricinoleate, polyglycerol-6 polyricinoleate, polyglycerol-10 polyricinoleate, and polyricinoleate (lauryl / myristyl) ester. These polyricinoleates exhibit excellent emulsifying properties and are primarily used as emulsifiers and dispersants (Patent Documents 1-5). However, they suffer from low water resistance and poor skin adhesion. Furthermore, the presence of double bonds in their structure leads to low oxidative stability.

[0006] In addition, examples of polyhydroxystearic acid esters that use plant-derived raw materials include: polyglycerol-4 diisostearate / polyhydroxystearate / sebacic acid ester, PEG-30 dihydroxystearic acid, dipentaerythritol tetra(behenic acid / polyhydroxystearic acid) ester, pentaerythritol (behenic acid / polyhydroxystearic acid) ester, polyglycerol-6 polyhydroxystearate, and polyglycerol-2 dihydroxystearate. Among these polyhydroxystearates, dipentaerythritol trihydroxystearate (Patent Documents 6-11) is particularly noteworthy for its excellent powder dispersibility, skin adhesion, water resistance, low skin irritation, oxidative stability, water retention, and moisturizing properties. However, dipentaerythritol trihydroxystearate has a very high viscosity and is sticky, making it difficult to spread and apply. Therefore, its use in cosmetics is limited, and its dosage in low-viscosity emulsified cosmetics and sunscreens is also limited. In addition, dipentaerythritol, the alcohol skeleton, is non-plant-based, which has led to a large demand for improvement from cosmetic manufacturers seeking more plant-based ingredients.

[0007] On the other hand, compared to pentaerythritol trihydroxystearate, polyglycerol-2-dihydroxystearate, as a type of polyhydroxystearate, has a relatively lower viscosity, higher powder dispersibility, and higher oxidative stability (Patent Documents 12-15). Therefore, polyglycerol-2-dihydroxystearate is suitable as an oil in cosmetics and has been widely used as a cosmetic raw material. However, polyglycerol-2-dihydroxystearate has high emulsifying properties and is mainly used as an emulsifier, but its water resistance and skin adhesion are insufficient.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2022-007717

[0011] Patent Document 2: Japanese Patent Application Publication No. 2022-072074

[0012] Patent Document 3: International Publication No. 2022 / 153928

[0013] Patent Document 4: International Publication No. 2023 / 032834

[0014] Patent Document 5: Japanese Patent Application Publication No. 2008-162932

[0015] Patent Document 6: Japanese Patent No. 6397891

[0016] Patent Document 7: Japanese Patent No. 4027157

[0017] Patent Document 8: Japanese Patent No. 5395325

[0018] Patent Document 9: Japanese Patent Application Publication No. 2023-107034

[0019] Patent Document 10: Japanese Patent No. 7373916

[0020] Patent Document 11: Japanese Patent Application Publication No. 2022-117486

[0021] Patent Document 12: Japanese Patent No. 3787353

[0022] Patent Document 13: Japanese Patent No. 7324217

[0023] Patent Document 14: Japanese Patent Publication No. 2001-524504

[0024] Patent Document 15: Japanese Patent No. 4109209 Summary of the Invention

[0025] The problem that the invention aims to solve

[0026] The purpose of this invention is to provide an esterification reaction product, which is a polyhydroxy stearate, that can take into account both skin adhesion and ease of application and spreading, and has good water resistance, powder dispersibility, film-forming properties and water retention.

[0027] In addition, the present invention aims to provide cosmetics containing the esterification reaction product.

[0028] In addition, the present invention aims to provide a method for manufacturing the esterification reaction product.

[0029] Problem Solving Methods

[0030] To solve the above problems, the inventors conducted in-depth research and found that by controlling the weight-average molecular weight and dispersibility of polyglycerol-2 dihydroxystearate, an esterification reaction product that balances skin adhesion and ease of application and spread, as well as good water resistance, powder dispersibility, film-forming properties and water retention can be obtained, thus completing the present invention.

[0031] That is, the present invention includes the following methods.

[0032] [1] An esterification product obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer.

[0033] The weight-average molecular weight of the esterification product is 6500-9000, preferably 6700-9000, more preferably 7000-9000, and even more preferably 7500-9000; the dispersity is 1.40-1.65, preferably 1.41-1.64, more preferably 1.41-1.56, even more preferably 1.41-1.52, and even more preferably 1.42-1.48.

[0034] [2] According to the esterification reaction product described in [1] above, wherein,

[0035] The average degree of polymerization of the above-mentioned 12-hydroxystearic acid polymer is 4.0~10.0.

[0036] [3] According to the esterification reaction product described in [2] above, wherein,

[0037] The above-mentioned esterification reaction product is obtained by esterifying 1.5 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 relative to 1.0 mole of diglyceride.

[0038] [4] According to the esterification reaction product described in [1] above, wherein,

[0039] The esterification reaction products mentioned above include at least two esterification reaction products obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer.

[0040] [5] According to the esterification reaction product described in [4] above, wherein,

[0041] The esterification reaction products mentioned above include:

[0042] The product of the first esterification reaction, and

[0043] Either the product of the second esterification reaction or the product of the third esterification reaction.

[0044] The product of the first esterification reaction described above is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0. Its weight-average molecular weight is 6500 to 9000, and its dispersion is 1.40 to 1.65.

[0045] The product of the second esterification reaction described above is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0. Its weight-average molecular weight is 4000-6000, and its dispersion is 1.35-1.50.

[0046] The product of the third esterification reaction mentioned above is obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0. Its weight-average molecular weight is 10,000 to 13,000 and its dispersion is 1.35 to 1.50.

[0047] [6] According to the esterification reaction product described in [5] above, wherein,

[0048] The product of the first esterification reaction described above is obtained by esterifying 1.5 to 2.4 moles of a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 relative to 1.0 mole of diglyceride.

[0049] The product of the second esterification reaction described above is obtained by esterifying 2.0 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0 with 1.0 mole of diglyceride.

[0050] The product of the third esterification reaction described above is obtained by esterifying 1.5 to 2.0 moles of 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with 1.0 mole of diglyceride.

[0051] [7] According to the esterification reaction product described in [4] above, wherein,

[0052] The esterification reaction products mentioned above include the second esterification reaction product and the third esterification reaction product.

[0053] The product of the second esterification reaction described above is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0. Its weight-average molecular weight is 4000-6000, and its dispersion is 1.35-1.50.

[0054] The product of the third esterification reaction mentioned above is obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0. Its weight-average molecular weight is 10,000 to 13,000 and its dispersion is 1.35 to 1.50.

[0055] [8] According to the esterification reaction product described in [7] above, wherein,

[0056] The product of the second esterification reaction described above is obtained by esterifying 2.0 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0 with 1.0 mole of diglyceride.

[0057] The product of the third esterification reaction described above is obtained by esterifying 1.5 to 2.0 moles of 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with 1.0 mole of diglyceride.

[0058] [9] A cosmetic product containing any one of the esterification reaction products described in any one of [1] to [8].

[0059]

[10] The cosmetic according to [9] above further contains one or more selected from ultraviolet scattering agents and ultraviolet absorbing agents.

[0060]

[11] The cosmetics described in [9] or

[10] above are sunscreen cosmetics, skin care / hair care cosmetics, or color cosmetics.

[0061]

[12] The cosmetic according to any one of [9] to

[11] above is an emulsified cosmetic.

[0062]

[13] A method for manufacturing an esterification reaction product, the method comprising:

[0063] Diglycerides are esterified with a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 to produce an esterification product with a weight average molecular weight of 6500 to 9000, preferably 6700 to 9000, more preferably 7000 to 9000, further preferably 7500 to 9000, and a dispersion of 1.40 to 1.65, preferably 1.41 to 1.64, more preferably 1.41 to 1.56, further preferably 1.41 to 1.52, and even more preferably 1.42 to 1.48.

[0064]

[14] According to the method for manufacturing the esterification reaction product described in

[13] above, wherein,

[0065] 12-hydroxystearic acid was heated to 100℃~250℃ while removing water to carry out the reaction, resulting in a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0~10.0. The 12-hydroxystearic acid polymer was then esterified with diglycerides.

[0066]

[15] A water resistance enhancer for cosmetics, comprising the esterification reaction product described in any one of [1] to [8] above.

[0067]

[16] A cosmetic adhesive enhancer comprising the esterification reaction product described in any one of [1] to [8] above.

[0068]

[17] A film-forming agent for a cosmetic, comprising the esterification reaction product described in any one of [1] to [8] above.

[0069]

[18] A hair cosmetic product for improving the fit of hair, comprising the esterification reaction product described in any one of [1] to [8] above.

[0070]

[19] Use of the esterification reaction product according to any one of the above [1] to [8] for improving the water resistance of cosmetics.

[0071]

[20] Use of the esterification reaction product according to any one of the above [1] to [8] for improving the adhesion of cosmetics.

[0072]

[21] Use of the esterification reaction product according to any one of the above [1] to [8] for improving the film-forming property of cosmetics.

[0073]

[22] Use of the esterification reaction product according to any one of the above [1] to [8] for improving the hair manageability feeling of hair cosmetics.

[0074]

[23] Use of the esterification reaction product according to any one of the above [1] to [8] for manufacturing cosmetics with improved water resistance.

[0075]

[24] Use of the esterification reaction product according to any one of the above [1] to [8] for manufacturing cosmetics with improved adhesion.

[0076]

[25] Use of the esterification reaction product according to any one of the above [1] to [8] for manufacturing cosmetics with improved film-forming property.

[0077]

[26] Use of the esterification reaction product according to any one of the above [1] to [8] for manufacturing hair cosmetics with improved hair manageability feeling.

[0078] Effects of the Invention

[0079] According to the present invention, it is possible to provide an esterification reaction product that balances adhesion to the skin and ease of spreading during application, and has good water resistance, powder dispersibility, film-forming property and water retention property, a cosmetic containing the esterification reaction product, and a method for producing the esterification reaction product. Detailed Description of the Embodiments

[0080] In the present invention and the specification of the present application, regarding numerical ranges, "A or more and B or less (A and B are real numbers satisfying A < B)" may be expressed as "A to B". For example, when described as "1 to 10 parts by mass", it refers to the range from 1 part by mass to 10 parts by mass, a numerical range including the lower limit (1 part by mass) and the upper limit (10 parts by mass), that is, "1 part by mass or more and 10 parts by mass or less".

[0081] In this invention and the specification of this application, "weight-average molecular weight (Mw)" refers to the average molecular weight taking into account the weight fraction of the molecule. "Number-average molecular weight (Mn)" refers to the average molecular weight per molecule. "Dispersion" refers to the value obtained by dividing the weight-average molecular weight (Mw) by the number-average molecular weight (Mn) (Mw / Mn). The closer the dispersion is to 1, the narrower the molecular weight distribution.

[0082] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the esterification reaction products can be determined by gel permeation chromatography. Specifically, this refers to the values ​​calculated by converting the values ​​from the standard polystyrene obtained based on a standard curve obtained by measuring the molecular weight of standard polystyrene. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the esterification reaction products in this embodiment can be determined using an ACQUITY Advanced Polymer Chromatography (APC) System (manufactured by Nihon Waters).

[0083] <Esterification reaction products>

[0084] A summary of the esterification reaction products of this embodiment will be provided.

[0085] The esterification product of this embodiment is obtained by esterifying diglyceride with a 12-hydroxystearic acid polymer, and has a weight-average molecular weight of 6500-9000 and a dispersion of 1.40-1.65. The esterification product of this embodiment is polyglycerol-2-dimeric hydroxystearate (the esterification product of polyhydroxystearic acid and diglyceride) with a weight-average molecular weight and dispersion within the above range. Therefore, it has good skin adhesion and spreadability, and can improve water resistance, powder dispersibility, and water retention. Furthermore, the esterification product of this embodiment has low viscosity, making it easy to handle and highly operable. Moreover, the absence of double bonds in its structure results in excellent oxidative stability.

[0086] The weight-average molecular weight of the esterification product in this embodiment only needs to be in the range of 6500 to 9000, preferably 6700 to 9000, more preferably 7000 to 9000, and even more preferably 7500 to 9000. Alternatively, the weight-average molecular weight of the esterification product in this embodiment is more preferably 6500 to 8000.

[0087] The dispersion of the esterification product in this embodiment only needs to be in the range of 1.40 to 1.65, preferably 1.41 to 1.64, more preferably 1.41 to 1.56, even more preferably 1.41 to 1.52, and even more preferably 1.42 to 1.48. Alternatively, the dispersion of the esterification product in this embodiment is more preferably 1.45 to 1.56.

[0088] As the esterification product of this embodiment, any esterification product with a weight-average molecular weight of 6500-9000 and a dispersity of 1.40-1.65 is acceptable. Preferably, the weight-average molecular weight is 6700-9000, more preferably 7000-9000, further preferably 7500-9000, and the dispersity is preferably 1.41-1.64, more preferably 1.41-1.56, further preferably 1.41-1.52, and even more preferably 1.42-1.48. Alternatively, as the esterification product of this embodiment, an esterification product with a weight-average molecular weight of 6800-7800 and a dispersity of 1.45-1.56 is more preferred.

[0089] The diglycerides used to produce the esterification product of this embodiment can be obtained from glycerol through a condensation reaction or the like. Alternatively, commercially available diglycerides can also be used as the raw material for producing the esterification product of this embodiment.

[0090] The polymer of 12-hydroxystearic acid used to manufacture the esterification reaction product of this embodiment preferably has an average degree of polymerization of 4.0 to 10.0.

[0091] 12-Hydroxystearic acid is a 12-hydroxystearic acid having one hydroxyl group in its molecule, and can be obtained, for example, by hydrogenating ricinoleic acid obtained from the hydrolysis of castor seed oil. Alternatively, commercially available 12-hydroxystearic acid can be used as a raw material for manufacturing the esterification reaction product of this embodiment.

[0092] The raw materials used to manufacture the esterification reaction product of this embodiment, namely diglycerides and 12-hydroxystearic acid polymer, are preferably plant-derived.

[0093] The esterification product of this embodiment is obtained by esterifying a polymer of 12-hydroxystearic acid with diglycerides. Preferably, the manufacturing method is carried out in two steps: a polymerization step of 12-hydroxystearic acid and an esterification step of the 12-hydroxystearic acid polymer with diglycerides. Hereinafter, this manufacturing method will be referred to as a "two-step reaction".

[0094] The polymerization reaction of 12-hydroxystearic acid can be carried out, for example, as described below.

[0095] 12-hydroxystearic acid is added to a reaction vessel, and an esterification reaction (polymerization reaction) is carried out for 5 to 30 hours with stirring in the presence or absence of acid, base, or other metal catalyst, preferably at 100°C to 250°C, more preferably at 150°C to 250°C, further preferably at 160°C to 240°C, and even more preferably at 190°C to 230°C.

[0096] To produce the esterification product of this embodiment, a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 is preferably used. When the average degree of polymerization is within the above range, esterification with diglycerides readily yields an esterification product with a weight-average molecular weight of 6500 to 9000 and a dispersion of 1.40 to 1.65. The average degree of polymerization of the 12-hydroxystearic acid polymer is more preferably 4.0 to 8.0, and even more preferably 5.0 to 7.0. To set the average degree of polymerization within the above range, the polymerization reaction of 12-hydroxystearic acid can be carried out by measuring the acid value of the reaction product. That is, the reaction product is sampled during the polymerization reaction of 12-hydroxystearic acid, and its acid value is measured to calculate the average degree of polymerization. The esterification reaction (polymerization reaction) is stopped when the desired average degree of polymerization is reached, thereby adjusting the average degree of polymerization.

[0097] In this application specification, "average degree of polymerization" refers to the number-average degree of polymerization calculated by acid value.

[0098] The hydroxyl value of the esterification product in this embodiment is preferably 0-180 mg KOH / g, more preferably 0-160 mg KOH / g, even more preferably 0-100 mg KOH / g, and even more preferably 0-90 mg KOH / g. In particular, the hydroxyl value of the esterification product in this embodiment is preferably 20-70 mg KOH / g, more preferably 20-60 mg KOH / g, even more preferably 25-55 mg KOH / g, and even more preferably 30-40 mg KOH / g. The hydroxyl value is determined according to the quasi-drug raw material specification 2021.

[0099] The acid value of the esterification product in this embodiment is preferably below 3 mg KOH / g, more preferably 0 to 3 mg KOH / g, and even more preferably 0.5 to 1.5 mg KOH / g. If the acid value exceeds 3 mg KOH / g, an unpleasant odor may sometimes be produced. The acid value is determined according to the quasi-drug raw material specification 2021.

[0100] The esterification product of the present invention can be obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer. By adjusting the feed ratio of diglycerol to 12-hydroxystearic acid polymer, the weight-average molecular weight and dispersion of the obtained esterification product can be adjusted to the desired range. The feed amount of 12-hydroxystearic acid polymer used in the esterification reaction is preferably 1.5 to 2.4 mol, more preferably 1.5 to 2.0 mol, relative to 1.0 mol of diglycerol.

[0101] The esterification reaction of diglycerol with 12-hydroxystearic acid polymer can be carried out, for example, as described below. Diglycerol and 12-hydroxystearic acid polymer are added to a reaction vessel, and the esterification reaction is carried out for 1 to 20 hours in an inactive organic solvent and / or gas at a temperature preferably 100°C to 250°C, more preferably 150°C to 250°C, further preferably 160°C to 240°C, and even more preferably 190°C to 230°C, while removing water generated as a byproduct, thereby obtaining the esterification product of diglycerol and 12-hydroxystearic acid polymer.

[0102] In the polymerization reaction of 12-hydroxystearic acid and the esterification reaction with diglycerides, catalysts may be used as needed. Examples of catalysts include acid catalysts, base catalysts, and metal catalysts. Examples of acid catalysts include sulfuric acid, hydrochloric acid, and trifluoroacetic acid; examples of base catalysts include sodium hydroxide, potassium hydroxide, and triethylamine; and examples of metal catalysts include alkali metals, alkaline earth metals, transition metals, or alkoxides. When using an acid catalyst, base catalyst, or metal catalyst, its amount relative to the total mass of the reactants is preferably about 0.001 to 1.0% by mass.

[0103] As the solvent mentioned above, solvents known in the field of organic chemistry for the esterification reaction of alcohols and fatty acids can be used.

[0104] After the reaction, known purification processes such as water washing, alkali deacidification, adsorption treatment, and distillation can remove the catalyst and unreacted raw materials. Furthermore, decolorization and deodorization treatments can further purify the obtained reactants.

[0105] The esterification reaction product of this embodiment may include at least two esterification reaction products obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer.

[0106] The weight-average molecular weight of the esterification reaction product in this embodiment is in the range of 6500 to 9000, and the dispersity is in the range of 1.40 to 1.65. By mixing two or more esterification reaction products (esterification reaction products of diglycerol and 12-hydroxystearic acid polymer) in which one or both of the weight-average molecular weight and dispersity are different from each other, it is also possible to produce an esterification product of diglycerol and 12-hydroxystearic acid polymer with a weight-average molecular weight of 6500 to 9000 and a dispersity of 1.40 to 1.65.

[0107] The weight average molecular weight of the esterification reaction product in this embodiment is in the range of 6500 to 9000 and the dispersion is in the range of 1.40 to 1.65. By mixing an esterification reaction product with a weight average molecular weight outside the range of 6500 to 9000 (the esterification reaction product of diglycerol and 12-hydroxystearic acid polymer) or an esterification reaction product with a dispersion of ...

[0108] Furthermore, regarding the esterification reaction product of this embodiment, by mixing two or more esterification reaction products with a weight average molecular weight outside the range of 6500 to 9000 (esterification reaction product of diglycerol and 12-hydroxystearic acid polymer) or esterification reaction products with a dispersity outside the range of 1.40 to 1.65 (esterification reaction product of diglycerol and 12-hydroxystearic acid polymer), it is also possible to produce an esterification product of diglycerol and 12-hydroxystearic acid polymer with a weight average molecular weight of 6500 to 9000 and a dispersity of 1.40 to 1.65.

[0109] The esterification reaction product of this embodiment includes the above-mentioned esterification reaction product with a weight average molecular weight of 6500-9000 and a dispersion of 1.40-1.65, obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0-10.0, as the first esterification reaction product.

[0110] The esterification reaction product of this embodiment may further include:

[0111] The second esterification product, obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0, has a weight average molecular weight of 4000-6000 and a dispersion of 1.35-1.50.

[0112] The third esterification product, with a weight average molecular weight of 10,000 to 13,000 and a dispersion of 1.35 to 1.50, is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0.

[0113] The product of the first esterification reaction is preferably obtained by esterifying 1.5 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 relative to 1.0 mole of diglyceride.

[0114] The product of the second esterification reaction is preferably obtained by esterifying 2.0 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mole of diglyceride.

[0115] The product of the third esterification reaction is preferably obtained by esterifying 1.5 to 2.0 moles of a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with 1.0 moles of diglycerides.

[0116] The weight-average molecular weight of the second esterification product obtained by esterifying the 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or more and less than 4.0 with diglycerides is only required to be in the range of 4,000 to 6,000, preferably 4,000 to 5,000, and more preferably 4,500 to 4,900.

[0117] The weight-average molecular weight of the third esterification product obtained by esterifying the 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with diglycerides is only required to be in the range of 10,000 to 13,000, preferably 10,500 to 12,500, and more preferably 11,000 to 12,000.

[0118] The dispersion of the second esterification product obtained by esterifying the 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or more and less than 4.0 with diglycerides is only required to be in the range of 1.35 to 1.50, preferably 1.35 to 1.48.

[0119] The dispersion of the third esterification product obtained by esterifying the 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with diglycerides is only required to be in the range of 1.35 to 1.50, preferably 1.37 to 1.40.

[0120] The weight-average molecular weight of the esterification product, which includes the first esterification product and the second or third esterification product, is 6,500 to 9,000, preferably 7,000 to 9,000, and more preferably 7,100 to 8,900.

[0121] The dispersion of the esterification product containing the first esterification product and the second or third esterification product is 1.40 to 1.65, preferably 1.41 to 1.64.

[0122] In the esterification reaction product containing the first esterification reaction product and the second or third esterification reaction product, the mass ratio of the first esterification reaction product to the second or third esterification reaction product (first esterification reaction product: second or third esterification reaction product) is not particularly limited as long as the weight average molecular weight and dispersion of the esterification reaction product containing the first esterification reaction product and the second or third esterification reaction product are within the above-mentioned range. For example, it is preferably 3:7 to 8:2.

[0123] In the case where the esterification reactants of this embodiment include the first esterification product and the second esterification product, the mass ratio of the first esterification product to the second esterification product (first esterification product: second esterification product) is not particularly limited as long as the weight average molecular weight and dispersion of the esterification reactants of this embodiment are within the above range. For example, it is preferably 7:3 to 9:1.

[0124] The weight-average molecular weight of the esterification product comprising the first esterification product and the second esterification product is 6,500 to 9,000, preferably 6,500 to 8,000, and more preferably 6,500 to 7,500.

[0125] The dispersion of the esterification product containing the first esterification product and the second esterification product is 1.40 to 1.65, preferably 1.40 to 1.45.

[0126] In the case where the esterification reaction product of this embodiment includes the first esterification reaction product and the third esterification reaction product, the mass ratio of the first esterification reaction product to the third esterification reaction product (first esterification reaction product: third esterification reaction product) is not particularly limited as long as the weight average molecular weight and dispersion of the esterification reaction product of this embodiment are within the above range. For example, it is preferably 2:8 to 4:6.

[0127] The weight-average molecular weight of the esterification product comprising the first esterification product and the third esterification product is 6,500 to 9,000, preferably 7,000 to 9,000, and more preferably 8,000 to 9,000.

[0128] The dispersion of the esterification product containing the first esterification product and the third esterification product is 1.40 to 1.65, preferably 1.50 to 1.65.

[0129] The first esterification product and the second or third esterification product can be produced independently via the above-described "two-step reaction".

[0130] As mentioned above, for the first esterification reaction product, 1.5 to 2.4 moles of 12-hydroxystearic acid polymer, obtained by adjusting the amount of 12-hydroxystearic acid and the reaction time to make the average degree of polymerization calculated by acid value 4.0 or more and 10.0 or less, are added to a reaction vessel relative to 1.0 mole of diglycerol. The esterification reaction is carried out for 1 to 20 hours in the presence of an inactive organic solvent and / or gas at a temperature preferably 100°C to 250°C, more preferably 150°C to 250°C, further preferably 160°C to 240°C, and even more preferably 190°C to 230°C, while removing water generated as a byproduct, thereby obtaining the esterification reaction product of diglycerol and 12-hydroxystearic acid polymer.

[0131] Similarly, 1.5 to 2.4 mol, preferably 2.0 to 2.4 mol, of 12-hydroxystearic acid polymer obtained by adjusting the amount of 12-hydroxystearic acid and the reaction time in such a way that the average degree of polymerization calculated by acid value is 3.0 or more and less than 4.0, is added to a reaction vessel relative to 1.0 mol of glycerol. In the presence of an inactive organic solvent and / or gas, at a temperature preferably 100°C to 250°C, more preferably 150°C to 250°C, further preferably 160°C to 240°C, and even more preferably 190°C to 230°C, an esterification reaction is carried out while removing water generated as a byproduct, thereby obtaining the second esterification reaction product.

[0132] Similarly, 1.5 to 2.4 mol, preferably 1.5 to 2.0 mol, of a 12-hydroxystearic acid polymer obtained by adjusting the amount of 12-hydroxystearic acid and the reaction time in such a way that the average degree of polymerization calculated by acid value is greater than 10.0 and less than 12.0, is added to a reaction vessel relative to 1.0 mol of glycerol. In the presence of an inactive organic solvent and / or gas, at a temperature preferably 100°C to 250°C, more preferably 150°C to 250°C, further preferably 160°C to 240°C, and even more preferably 190°C to 230°C, an esterification reaction is carried out while removing water generated as a byproduct, to obtain the third esterification reaction product.

[0133] Alternatively, the esterification reaction product of this embodiment preferably includes the second esterification reaction product and the third esterification reaction product described above.

[0134] The products of the second and third esterification reactions described above can be produced independently through the aforementioned two-step reaction.

[0135] The mass ratio of the second esterification product to the third esterification product (second esterification product: third esterification product) is not particularly limited as long as the weight average molecular weight and dispersion of the esterification product containing the second esterification product and the third esterification product are within the range described above. For example, it is preferably 0.5:9.5 to 2:8.

[0136] The weight-average molecular weight of the esterified product containing the second and third esterification products is 6,500 to 9,000, preferably 8,000 to 9,000.

[0137] The dispersion of the esterification reactant containing the second esterification reaction product and the third esterification reaction product is 1.40 to 1.65, preferably 1.40 to 1.45.

[0138] <Cosmetics>

[0139] The cosmetic of this embodiment contains the esterification reaction product of this embodiment as described above. Because it contains the esterification reaction product of this embodiment, the solid components such as pigments in the cosmetic of this embodiment have good dispersibility, high water resistance and water retention, and excellent skin adhesion and ease of application when applied to the skin.

[0140] The content of the esterification reaction product in this embodiment, relative to the total amount of cosmetics, is not particularly limited as long as it is sufficient to achieve the effects of improved physical properties brought about by the esterification reaction product, particularly improved skin adhesion, ease of application and spread, water resistance, and powder dispersibility. It can be appropriately set as a desired quality characteristic of the cosmetic. The content of the esterification reaction product relative to the total amount of the cosmetics in this embodiment is preferably 0.1 to 80.0% by mass, more preferably 1.0 to 80.0% by mass, further preferably 1.0 to 60.0% by mass, even more preferably 1.0 to 40.0% by mass, and particularly preferably 5.0 to 40.0% by mass. Alternatively, the content of the esterification reaction product relative to the total amount of the cosmetics in this embodiment is preferably 1.0 to 40.0% by mass.

[0141] The cosmetic product of this embodiment can have any appearance, such as transparent, semi-transparent, or emulsified (cloudy), and can also be in any form, such as liquid, cream, lotion, solid, or sol.

[0142] The cosmetic product of this embodiment is preferably an emulsified cosmetic product. When the cosmetic product of this embodiment is an emulsified cosmetic product, it can be either an O / W type emulsified cosmetic product or a W / O type emulsified cosmetic product.

[0143] The cosmetics described in this embodiment can be for external use only, and their uses are not limited. For example, the cosmetics described in this embodiment can be sunscreens, makeup products, or skin / hair care products. Examples of makeup products include: lipsticks, lip balms, lip glosses, lip stains, etc.; foundations, concealers, makeup primers, blushes, setting powders, etc.; eyebrow and eye makeup products such as eyebrow ink, eyeshadow, eyeliner, mascara, etc.; and nail polish, base coats, top coats, etc. Examples of skin / hair care products include: lotions, creams, serums, toners, hand creams, cleansing oils, facial cleansers, gels, balms, stick products, sprays, sols, sheet masks, shampoos, hair conditioners, hair pomades, etc. There are no particular restrictions on the manufacturing methods of these cosmetics; they can be manufactured using known methods.

[0144] The improved water resistance, skin adhesion, and ease of application resulting from the esterification reaction product of this embodiment make the cosmetic of this embodiment suitable as a component of cosmetics requiring high durability against sebum, sweat, and friction. Therefore, the cosmetic of this embodiment is preferably a sunscreen cosmetic or a color cosmetic.

[0145] In addition, the esterification reaction product of this embodiment can be used as a water resistance improver and a cosmetic adhesion improver.

[0146] Furthermore, the esterification reaction product of this embodiment has the effect of improving the film-forming properties of cosmetics and improving the hair adherence of hair cosmetics.

[0147] Therefore, the esterification reaction product of this embodiment can be used as a film-forming agent for cosmetics and a hair-fitting agent for hair cosmetics.

[0148] As the cosmetic of this embodiment, sunscreen cosmetics are particularly preferred. Sunscreen cosmetics are cosmetics containing one or more ingredients selected from ultraviolet scattering agents and ultraviolet absorbers as ingredients that impart sun protection function. Among the ingredients imparting sun protection function, the ultraviolet scattering agent is a powder. The esterification reaction product of this embodiment has high powder dispersibility; therefore, by incorporating it into sunscreen cosmetics, the ultraviolet scattering agent can be uniformly dispersed in the cosmetic, and when applied to the skin, a uniform ultraviolet scattering film can be formed on the skin, thus improving the ultraviolet protection effect. That is, even if the amount of ultraviolet scattering agent in the cosmetic is the same, it has the effect of increasing the SPF (Sun Protection Factor).

[0149] As sunscreen cosmetics, there are oil-in-water (W / O) cream-type sunscreen cosmetics. Other forms include oil-in-water (W / O) lotion-type sunscreen cosmetics, oil-in-water (W / O) multi-layered emulsion sunscreen cosmetics, water-in-oil (O / W) cream-type sunscreen cosmetics, and water-in-oil (O / W) lotion-type sunscreen cosmetics. The improved skin adhesion, ease of application and spread, water resistance, and powder dispersibility brought about by the esterification reaction product of this embodiment can be achieved when combined with any form of sunscreen cosmetic. Furthermore, as a cosmetic of this embodiment, it is preferable to contain one or more ultraviolet scattering agents; it can be a cosmetic containing one or more ultraviolet scattering agents and one or more ultraviolet absorbers; or it can be a cosmetic containing one or more ultraviolet absorbers but not containing ultraviolet scattering agents.

[0150] In addition to the esterification reaction product of this embodiment, the cosmetic of this embodiment may also incorporate various ingredients commonly used in cosmetics, as needed, without impairing the effects of the present invention. Such ingredients vary depending on the purpose and dosage form of the cosmetic, and examples include: oily ingredients, alcohols, polymer emulsions, thickeners, surfactants, pH adjusters, antioxidants, antioxidant auxiliaries, preservatives, inorganic salts, organic acid salts, metal ion blocking agents, powders, ultraviolet absorbers, moisturizers, extracts, vitamins, pigments, fragrances, and purified water, etc.

[0151] Examples of the aforementioned oily components include: hydrocarbons, waxes, fatty acid esters, triglycerides, fatty acids, higher alcohols, sterols, silicone oils, fluorinated oils and their derivatives. Specifically, examples include: castor oil, olive oil, avocado oil, palm oil, cocoa butter, liquid paraffin, branched-chain liquid paraffin, petrolatum, squalane, hydrogenated polyisobutylene, hydrogenated polydecene, lauric acid, myristic acid, palmitic acid, stearic acid, carnauba wax, candelilla wax, beeswax, sunflower wax, polyethylene wax, microcrystalline wax, ceresin, paraffin wax, propylene glycol di(caprylic / capric acid) ester, neopentyl glycol dicaprate, polyglycerol-6 caprylate, caprylic / capric triglyceride, triglyceride tri(ethylhexanoate), butyl stearate, ethylhexyl palmitate, cocoyl alcohol (caprylic / capric acid) ester, octyl (caprylic / capric acid) octyl ester, octyl dodecyl myristate, isopropyl myristate, isopropyl lanolinate, lanolin acid. Hexyl ester, diisopropyl adipate, diisopropyl sebacate, isotriadecyl isononanoate, isonononyl isononanoate, polyglycerol decaisostearate, 2-octyldodecyl alcohol, diisostearate malate, polyglycerol-2-triisostearate, polyglycerol-2-diisostearate, pentaerythritol pentaisostearate, pentaerythritol tetraisostearate, ethylene glycol distearate, trimethylolpropane triisostearate, hexa(hydroxystearic acid / stearic acid / rosin acid) dipentaerythritol, glycerol (ethylhexanoic acid / stearic acid / adipate) ester, oleyl alcohol, dimethyl polysiloxane, methylphenyl polysiloxane, dimethylcyclopolysiloxane, methylhydropolysiloxane, perfluoropolyether, dipentaerythritol hexahydroxy Stearates, pentaerythritol tetra(hydroxystearic acid / isostearic acid) ester, dipentaerythritol trihydroxystearate, mineral oil, cetyl ethylhexanoate, phenyl polytrimethylsiloxane, isododecane, cholesterol, phytosterols and other sterols; phytosterol sunflower seed oleate, phytosterol rice bran oleate, phytosterol macadamia nut oleate, phytosterol oleate, phytosterol isostearate, myristoyl methyl-β-alanine (phytosterol / decyltetradecanoyl) ester, lauroyl glutamate di(octyldodecanoyl / phytosterol / behenol) ester, lauroyl glutamate di(phytosterol / octyldodecanoyl) ester, di-linoleic acid di(isostearyl / phytosterol) ester, di-linoleic acid di-... Sterol derivatives such as oleyl alcohol bis(behenol / isostearyl / phytosterol) ester, dilinoleic acid (phytosterol / isostearyl / cetearyl alcohol / stearyl / behenol) ester, cholesterol macadamia oleate, cholesterol nonanoate, cholesterol oleate, dihydrocholesterol oleate, cholesterol stearate, cholesterol hydroxystearate, cholesterol butyrate, dihydrocholesterol butyrate, cholesterol hexyl dicarboxylate pullulan, and cholesterol lanolinate; silicones such as dimethyl silicone oil, cyclopentamethoxysiloxane, diphenylsiloxyphenyl polytrimethylsiloxane, cyclohexamethoxysiloxane, and cross-linked methyl polysiloxane; and perfluorobutyl ether, perfluorooctyltriethoxysilane, and perfluoropolymethylisopropyl.These oily ingredients can be used alone, or in combination of two or more.

[0152] Examples of the aforementioned alcohols include: methanol, ethanol, propanol, isopropanol, isobutanol, tert-butanol, cetyl alcohol (hexadecyl alcohol, palmitol), stearyl alcohol (octadecyl alcohol), isostearyl alcohol (isooctadecyl alcohol), oleyl alcohol, cetearyl alcohol, octyldodecyl alcohol, decyltetradecyl alcohol, hexyldecyl alcohol, squalene alcohol, behenyl alcohol, lauryl alcohol, lanolin alcohol, isostearyl alcohol, cetearyl alcohol, hydrogenated rapeseed oil alcohol, hydrogenated lanolin alcohol, and other monohydric alcohols; propylene glycol Alcohols such as 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, pentanediol, neopentanediol, isopentyl glycol, dipropylene glycol, glycerol, diglycerol, polyglycerol, polyethylene glycol, pentaerythritol, dipentaerythritol, sorbitol, and dehydrated sorbitol are among the polyols mentioned above. These alcohols can be used alone or in combination of two or more.

[0153] Examples of the aforementioned polymer emulsions include: alkyl acrylate copolymer emulsions, alkyl methacrylate polymer emulsions, alkyl acrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, acrylic / alkyl acrylate copolymer emulsions, methacrylic acid / alkyl methacrylate copolymer emulsions, alkyl acrylate / styrene copolymer emulsions, alkyl methacrylate / styrene copolymer emulsions, vinyl acetate polymer emulsions, polyvinyl acetate emulsions, vinyl acetate-containing copolymer emulsions, vinylpyrrolidone / styrene copolymer emulsions, and copolymer emulsions containing silicone. The polymer emulsions can be used alone or in combination of two or more.

[0154] The aforementioned thickeners can be natural water-soluble polymers, semi-synthetic water-soluble polymers, or synthetic water-soluble polymers. These thickeners can be used alone or in combination of two or more.

[0155] Examples of naturally occurring water-soluble polymers include: agar, glucomannan, gum arabic, astragalus gum, galactan, guar gum, locust bean gum, ark sylvestris gum, carrageenan, pectin, quince seed (marmelo), algal colloids (brown algae extract), and starches (rice, corn, potato, wheat), among other plant-based polymers; xanthan gum, dextran, succinosaccharide, pullulan, among other microbial polymers; and collagen, casein, albumin, and gelatin, among other animal-based polymers. These naturally occurring water-soluble polymers can be used alone or in combination of two or more.

[0156] Examples of semi-synthetic water-soluble polymers include: starch-based polymers such as carboxymethyl starch and methyl hydroxypropyl starch; cellulose-based polymers such as methyl cellulose, nitrocellulose, methyl hydroxypropyl cellulose, sodium cellulose sulfate, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, and powdered cellulose; and alginate-based polymers such as sodium alginate and propylene glycol alginate. These semi-synthetic water-soluble polymers can be used alone or in combination of two or more.

[0157] Examples of synthesized water-soluble polymers include: vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, acrylic copolymers, and carboxyvinyl polymers; polyoxyethylene polymers such as polyethylene glycol 20000, 40000, and 60000; copolymers of polyoxyethylene and polyoxypropylene; acrylic polymers such as sodium polyacrylate, ethyl polyacrylate, and polyacrylamide; polyethyleneimine; and cationic polymers. These synthesized water-soluble polymers can be used alone or in combination of two or more.

[0158] The surfactants mentioned above can be any of the following: anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and natural surfactants. These surfactants can be used alone or in combination of two or more.

[0159] Examples of anionic surfactants mentioned above include alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene lauryl ether phosphates. These anionic surfactants can be used alone or in combination of two or more.

[0160] Examples of cationic surfactants include primary amines, secondary amines, tertiary amine salts, and quaternary ammonium salts having aliphatic hydrocarbon groups. Cationic surfactants can be used alone or in combination of two or more.

[0161] Examples of amphoteric surfactants include sodium β-laurylaminopropionate, lauryl dimethylaminoacetic acid betaine, and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline betaine. Amphoteric surfactants can be used alone or in combination of two or more.

[0162] Examples of nonionic surfactants include: monoglycerides, sorbitol fatty acid esters, sucrose fatty acid esters, polyglycerol fatty acid esters, alkanolamides, amine oxides, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene propylene glycol monoglyceride esters, polyoxyethylene cured castor oil, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkyl glycosides, α-monoalkyl glycerol ethers, dimethyl polysiloxane / polyoxyalkylene copolymers, dimethyl polysiloxane / monoalkyl glycerol ether copolymers, sorbitan sesquiisostearate, etc. Nonionic surfactants can be used alone or in combination of two or more.

[0163] Examples of natural surfactants mentioned above include: lecithin, hydrogenated lecithin, hydroxylated lecithin, lysophosphatidylcholine, hydrogenated lysophosphatidylcholine, and other lecithin derivatives; saponins such as soybean saponins; sphingolipids, ceramides, etc. Examples of hydrogenated lecithin include: hydrogenated soybean lecithin, hydrogenated rapeseed lecithin, hydrogenated egg yolk lecithin, etc. Natural surfactants can be used alone or in combination of two or more.

[0164] Examples of pH adjusters mentioned above include: edemaic acid, disodium edemaate, citric acid, sodium citrate, sodium hydroxide, potassium hydroxide, and triethanolamine. pH adjusters can be used alone or in combination of two or more.

[0165] Examples of antioxidants mentioned above include: vitamin C derivatives and their salts, tocopherols and their derivatives and their salts, butylated hydroxytoluene, butylated hydroxyanisole, and gallic acid esters. Antioxidants can be used alone or in combination of two or more.

[0166] Examples of antioxidant auxiliaries mentioned above include: phosphoric acid, citric acid, maleic acid, malonic acid, succinic acid, fumaric acid, phosphatidylcholine, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid. These antioxidant auxiliaries can be used alone or in combination of two or more.

[0167] Examples of preservatives mentioned above include ethylhexylglycerin, phenoxyethanol, methylparaben, ethylparaben, and butylparaben. These preservatives can be used alone or in combination of two or more.

[0168] Examples of the aforementioned inorganic salts include sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, and magnesium sulfate. These inorganic salts can be used alone or in combination of two or more.

[0169] Examples of the aforementioned organic acid salts include citric acid, malic acid, tartaric acid and their salts, ascorbic acid and its salts, ascorbic acid derivatives and their salts, etc. These organic acid salts can be used alone or in combination of two or more.

[0170] Examples of metal ion blocking agents include disodium edetate, edetate salts, and hydroxyethylidene diphosphonic acid. Metal ion blocking agents can be used alone or in combination of two or more.

[0171] For example, extender pigments, coloring pigments, and pearlescent pigments can be used as the powder. The powder can be used alone or in combination of two or more. The powder content is preferably 0-50% by mass, more preferably 0-40% by mass, and even more preferably 0-30% by mass, relative to the overall cosmetic product of this embodiment.

[0172] Examples of extender pigments include: silicic acid, anhydrous silicic acid, magnesium silicate, aluminum silicate, barium silicate, calcium silicate, talc, sericite, mica, kaolin, clay, bentonite, montmorillonite, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, fluorapatite, hydroxyapatite, ceramic powder, and other inorganic pigments and their composite powders; organic powders composed of polyamide, polyester, polypropylene, polystyrene, polyurethane, nylon, organosilicon resin, vinyl resin, urea resin, phenolic resin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene / styrene copolymer, silk powder, cellulose, Nε-lauroyl-L-lysine, long-chain alkyl phosphate metal salts, N-mono-long-chain alkyl acyl basic amino acids, metal soaps, etc., and their composite powders; and composite powders of the above inorganic and organic powders. It should be noted that the particle shape of these powders can be any shape, such as spherical, plate-like, needle-like, granular, or irregular.

[0173] Examples of coloring pigments include: titanium dioxide, zinc oxide, iron oxide yellow, iron oxide red (iron oxide), iron oxide black, Prussian blue, ultramarine, chromium oxide, chromium hydroxide and other metal oxides; manganese violet, cobalt titanate and other metal complexes, as well as inorganic pigments such as carbon black; tar-based pigments, lake pigments and other organic pigments; carmine and other natural pigments.

[0174] Pearlescent pigments can be made by coating mica, synthetic phlogopite, etc., with colorants such as titanium dioxide, iron oxide, silicon dioxide, Prussian blue, chromium oxide, carmine, and organic pigments. These powders can be used after undergoing various surface treatments such as water-repellent treatment and water / oil-repellent treatment using common methods.

[0175] Among the aforementioned powders, powders with ultraviolet (UV) shielding effects, such as metal oxide powders, can also be used as UV scattering agents. There are no particular limitations on the type of metal oxide powder with UV shielding effects; examples include inorganic white pigments such as titanium dioxide, zinc oxide, zirconium oxide, and cerium oxide. Furthermore, surface-coated inorganic white pigments obtained by coating the surface of these metal oxide powders with fatty acid soaps such as aluminum hydroxide, aluminum stearate, and zinc palmitate, as well as fatty acids such as stearic acid, myristic acid, and palmitic acid, and fatty acid esters such as palmitic dextrin ester, can also be used as UV scattering agents. Preferably, surface-coated inorganic white pigments are obtained by coating metal oxide powders such as titanium dioxide with fatty acids such as aluminum hydroxide and / or stearic acid. When the cosmetic of this embodiment is a sunscreen cosmetic, one or more of these metal oxide powders and surface-coated inorganic white pigments can be used as UV scattering agents.

[0176] The shape of the metal oxide powder with UV-blocking effect is not particularly limited, and examples include spherical, needle-shaped, spindle-shaped, plate-shaped, and flake-shaped forms. To reduce surface activity, it can be treated with inorganic compounds such as silica or alumina. Furthermore, when the average particle size of the metal oxide powder is 10-100 nm, whitening when applied to the skin can be suppressed, which is therefore preferred.

[0177] Examples of ultraviolet absorbers mentioned above include: para-aminobenzoic acid (hereinafter referred to as PABA), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA octyl ester, and other benzoic acid-based ultraviolet absorbers; N-acetylanoaminobenzoic acid-3,3,5-trimethylcyclohexyl ester, and other anthranilic acid-based ultraviolet absorbers; and amyl salicylate, water... Salicylic acid-based UV absorbers include menthyl salicylate, homosalyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanol phenyl salicylate; octyl cinnamate, ethyl 4-isopropylcinnamate, methyl 2,5-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, methyl 2,4-diisopropylcinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), and p-methoxycinnamate. Cinnamon acid-based UV absorbers include 2-ethoxyethyl ester, cyclohexyl p-methoxycinnamate, ethyl α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-bis-p-methoxycinnamate; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. Benzyl-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylic acid ester, 2-hydroxy-4-n-octyloxybenzophenone, 4-hydroxy-3-carboxybenzophenone and other benzophenone-based ultraviolet absorbers; 3-(4'-methylbenzyl)-d,l-camphor, 3-benzyl-d,l-camphor, urocanic acid, ethyl urocanic acid, 2-phenyl-5-methylbenzo[…] Examples of UV absorbers include azoles, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dibenzylhydrazine, 4,4'-dimethoxydiphenylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornenyl)-3-pent-2-one, and 2,4,6-triphenylamino-p-(carbonyl-2'-ethylhexyl-1'-oxy)-1,3,5-triazine, 4-tert-butyl-4'-methoxydibenzoylmethane, etc. Among these, cinnamic acid-based UV absorbers, such as 2-ethylhexyl p-methoxycinnamate, are preferred. UV absorbers can be used alone or in combination of two or more. In the case that the cosmetic product in this embodiment is a sunscreen cosmetic product, the content of ultraviolet absorber is preferably more than 0% by mass and less than 10% by mass relative to the cosmetic product as a whole, more preferably more than 0% by mass and less than 2.0% by mass, and even more preferably more than 0% by mass and less than 1.0% by mass.

[0178] Examples of such moisturizers include: polyethylene glycol, propylene glycol, glycerin, 1,3-butanediol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucin sulfate, trichosamic acid, atelocollagen, cholesterol-12-hydroxystearate, sodium lactate, urea, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglyceride (EO)PO adduct, prickly pear extract, yarrow extract and sweet clover extract, raffinose, trehalose, polyoxyethylene methyl glucoside, betaine, etc. Moisturizers can be used alone or in combination of two or more.

[0179] Examples of the aforementioned extracts include plant extracts from aloe vera, witch hazel, *Hamamelis*, cucumber, tomato, apple, lemon, lavender, and rose. These extracts can be used alone or in combination of two or more.

[0180] Examples of the aforementioned vitamins include: vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin E, vitamin K and their derivatives, pantothenic acid and its derivatives, biotin, etc. These vitamins can be used alone or in combination of two or more.

[0181] Examples of such pigments include chlorophyll and beta-carotene. Pigments can be used alone or in combination of two or more.

[0182] Examples of the aforementioned fragrances include, for instance, plant-based fragrances such as rose oil, jasmine oil, and lavender oil, as well as synthetic fragrances such as limonene, citral, linalool, and eugenol. Fragrances can be used alone or in combination of two or more.

[0183] As a cosmetic product according to this embodiment, it is preferable to contain one or more of the ultraviolet scattering agents (metal oxide powders) and ultraviolet absorbers described above.

[0184] As the cosmetic of this embodiment, it is preferably a cosmetic containing one or more ultraviolet scattering agents. It can be a cosmetic containing one or more ultraviolet scattering agents and one or more ultraviolet absorbers, or it can be a cosmetic containing one or more ultraviolet absorbers but not containing ultraviolet scattering agents.

[0185] Example

[0186] The present invention will be described in further detail below through embodiments. The scope of the present invention is not necessarily limited to these embodiments. It should be noted that, in the following embodiments, unless otherwise stated, parts and % represent parts by mass or percentage by mass.

[0187] In the following experiments, the acid value and hydroxyl value of the esterification reaction products were determined in accordance with the quasi-drug raw material specification 2021.

[0188] <Determination of weight-average molecular weight (Mw) and dispersity (Mw / Mn)>

[0189] In the following experiments, the Mw and dispersity of the esterification products were determined using the ACQUITY Advanced Polymer Chromatography (APC) System (manufactured by Nihon Waters). Specifically, the determinations were performed using the following methods.

[0190] (Measurement conditions)

[0191] Measurement / Analysis Software: Empower3 (manufactured by Nihon Waters)

[0192] Detector: RI

[0193] Refractive index unit full scale: 500 μRIU

[0194] Column (Section 1): ACQUITY APC XT200 (4.6×150mm)

[0195] Column (Section 2): ACQUITY APC XT45 (4.6×150mm)

[0196] Column (3rd stage): ACQUITY APC XT45 (4.6×150 mm)

[0197] Solvent: Tetrahydrofuran (THF)

[0198] Flow rate: 0.6 mL / min

[0199] Concentration: 0.5 mg / mL

[0200] Column temperature: 40°C

[0201] Injection volume: 20 μL

[0202] <SPF Measurement>

[0203] In the following experiments, the SPF of the sunscreen cosmetics was measured using an SPF analyzer (product name "UV-2000S", manufactured by Lacsphere). This SPF analyzer is a measurement apparatus that complies with sunscreen evaluation test standards such as ISO 24443, Colipa Guideline, and FDA Final Rule. Specifically, the measurement was carried out by the following method.

[0204] Each test sample was placed in small dots on a respective different PMMA plate (product name "HELIOPLATE HD6", manufactured by HerioscreenLab, plate size: 5 cm × 5 cm). At this time, the test sample was placed in such a manner that the amount was 30.0 ± 0.2 mg per plate. Next, an appropriate amount of the test sample on the plate was rubbed evenly on a finger wearing a finger cot to remove excess clumps, and then quickly and uniformly spread over the entire plate with light force. The coated plate was allowed to stand for 30 minutes at room temperature in the dark. Then, the SPF values at 9 positions on the plate were measured using the SPF analyzer, and the average value thereof was taken as the SPF value of the test sample applied to the plate.

[0205] [SPF Value Evaluation Criteria]

[0206] A: SPF value is 40 or more.

[0207] B: SPF value is 25 or more and less than 40.

[0208] C: SPF value is 15 or more and less than 25.

[0209] D: SPF value is less than 15.

[0210] According to the above evaluation criteria, when the evaluation is A or B, the sunscreen cosmetic is judged to have excellent ultraviolet protection effect.

[0211] <Water Resistance Evaluation>

[0212] In the following experiments, the water resistance of sunscreen cosmetics was determined using the following methods.

[0213] A PMMA plate coated with the test sample was fixed in a 200 mL metal cup and placed in a constant-temperature water bath adjusted to 29–31°C, similar to the SPF determination described above. Next, a propeller-type agitator from Three-One Motor (manufactured by Shin-To Science Co., Ltd.) was placed inside the metal cup, and the plate was kept in a state of water flow generated by rotating the agitator at 100 rpm for 80 minutes, thus performing a water flow load test (water resistance test). After the test, the plate was gently removed from the metal cup and allowed to stand at room temperature in the dark for 30 minutes. Then, the SPF value of the plate was measured using an SPF analyzer in the same manner as described above.

[0214] Calculate what percentage the SPF value after the water resistance test is equivalent to the SPF value before the water resistance test, and use this value as the residual rate ([SPF value after water resistance test] / [SPF value before water resistance test]×100%).

[0215] [Evaluation criteria for water resistance]

[0216] A: The survival rate is over 70%.

[0217] B: The survival rate is above 60% but less than 70%.

[0218] C: The survival rate is above 50% but less than 60%.

[0219] D: Survival rate is less than 50%.

[0220] Based on the above evaluation criteria, sunscreen cosmetics rated A or B are judged to have excellent water resistance.

[0221] <Fitness Assessment>

[0222] In the following experiment, the adhesion of sunscreen cosmetics was determined using the following methods.

[0223] Four professional judges conducted a sensory evaluation of the skin's adhesion.

[0224] A pea-sized amount of sunscreen was placed on the back of the hand, spread with the index finger, and then the finger was moved perpendicular to the application area. Sensory evaluation was conducted based on the following three-level assessment. The sum of each reviewer's score was calculated to evaluate the adhesion of each sunscreen product.

[0225] [Evaluation Criteria for Each Reviewer]

[0226] 3 points: It has a tight fit.

[0227] 2 points: Slightly tight fit.

[0228] 1 point: No tightness.

[0229] [Evaluation criteria for the adhesion of sunscreen cosmetics]

[0230] A: The tightness score is 12-11.

[0231] B: The tightness score is 10-9.

[0232] C: The tightness score is 8-7.

[0233] D: The tightness score is 6-4.

[0234] Based on the above evaluation criteria, sunscreen cosmetics rated A or B are judged to have excellent adhesion.

[0235] <Evaluation of ease of application and spread>

[0236] In the following experiment, the ease of application and spread of sunscreen cosmetics was determined using the following methods.

[0237] Four professional judges conducted a sensory evaluation of the ease of application and spread on the skin.

[0238] A pea-sized amount of sunscreen was placed on the back of the hand, and a sensory evaluation was conducted based on the resistance and smoothness felt when spreading it horizontally with the index finger, using the following 3-level rating system. The sum of the scores from each reviewer was calculated to evaluate the ease of application and spread of each sunscreen.

[0239] [Evaluation Criteria for Each Reviewer]

[0240] 3 points: Easy to apply and spread.

[0241] 2 points: Slightly easy to apply and spread.

[0242] 1 point: Difficult to apply and spread.

[0243] [Evaluation Criteria for the Ease of Application and Spreading of Sunscreen Cosmetics]

[0244] A: The ease of application and spreading is rated 12-11.

[0245] B: Ease of application and spreading is rated 10-9.

[0246] C: Ease of application and spreading is rated 8-7.

[0247] D: Ease of application and spreading is rated 6-4.

[0248] Based on the above evaluation criteria, when rated A or B, it is judged as a sunscreen cosmetic with excellent ease of application and spread.

[0249] [Examples 1 and 6]

[0250] After obtaining 12-hydroxystearic acid polymers with an average degree of polymerization of 5.0–7.0 through polymerization of 12-hydroxystearic acid, 1.5–2.0 moles of the 12-hydroxystearic acid polymer were added relative to 1.0 mole of diglyceride for esterification, thereby synthesizing esterification products with different weight-average molecular weights and dispersities. The SPF and water resistance of O / W type sunscreens containing these products, as well as the SPF, water resistance, adhesion, and ease of application and spreading of W / O type sunscreens, were evaluated.

[0251] [Compare Examples 1 and 4]

[0252] After obtaining 12-hydroxystearic acid polymers with an average degree of polymerization greater than 3.0 and less than 4.0 through the polymerization of 12-hydroxystearic acid, 2.0–2.4 moles of the 12-hydroxystearic acid polymer were added relative to 1.0 mole of diglyceride for esterification, thereby synthesizing esterification products with different weight-average molecular weights and dispersities. The SPF and water resistance of O / W type sunscreens containing these products, as well as the SPF, water resistance, adhesion, and ease of application and spreading of W / O type sunscreens, were evaluated.

[0253] [Compare Examples 2 and 3]

[0254] After obtaining 12-hydroxystearic acid polymers with an average degree of polymerization greater than 10.0 and less than 12.0 through the polymerization of 12-hydroxystearic acid, 1.5–2.0 moles of the 12-hydroxystearic acid polymer were added relative to 1.0 mole of diglyceride for esterification, thereby synthesizing esterification products with different weight-average molecular weights and dispersities. The SPF and water resistance of O / W type sunscreens containing these products, as well as the SPF, water resistance, adhesion, and ease of application and spreading of W / O type sunscreens, were evaluated.

[0255] [Examples 2-5]

[0256] For the esterification products obtained through a two-step reaction involving the polymerization of 12-hydroxystearic acid and the esterification with diglycerides, two esterification products with different weight-average molecular weights and dispersities were mixed to obtain esterification products with weight-average molecular weights in the range of 6500–9000 and dispersities in the range of 1.40–1.65. The SPF and water resistance of O / W type sunscreens containing these products, and the SPF, water resistance, adhesion, and ease of application of W / O type sunscreens were evaluated.

[0257] [Comparative Example 5]

[0258] Using the same amounts of 12-hydroxystearic acid and diglycerides as in the synthesis of the esterification product of Example 1, but without polymerizing 12-hydroxystearic acid, the esterification product was synthesized by esterification of 12-hydroxystearic acid monomer and diglycerides (one-step reaction). The SPF and water resistance of O / W type sunscreens containing this product, as well as the SPF, water resistance, adhesion, and ease of application of W / O type sunscreens containing this product, were evaluated.

[0259] (1) Synthesis of esterification reaction products [Example 1 (two-step reaction)]

[0260] 12-hydroxystearic acid (manufactured by Kokura Synthetic Industries Co., Ltd., trade name: 12-hydroxystearic acid) was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to ensure that the average degree of polymerization calculated from the acid value reached the desired range (average degree of polymerization 5.0~7.0). The acid value of the obtained 12-hydroxystearic acid polymer was 33 mg KOH / g.

[0261] Next, 2.0 mol of the aforementioned 12-hydroxystearic acid polymer and 1.0 mol of diglycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name "Diglycerol 801") were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding an esterification product (the feed amount of 12-hydroxystearic acid polymer relative to 1.0 mol of diglycerol was 2.0 mol). The esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 7800, the dispersity was 1.45, the acid value was 1.0 mg KOH / g, and the hydroxyl value was 34.6 mg KOH / g.

[0262] (2) Synthesis of esterification reaction products [Example 6 (two-step reaction)]

[0263] 12-hydroxystearic acid, as used in Example 1, was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to achieve an average degree of polymerization of 5.0–7.0 based on the acid value. The acid value of the obtained 12-hydroxystearic acid polymer was 33 mg KOH / g.

[0264] Next, 1.5 mol of the 12-hydroxystearic acid polymer obtained above and 1.0 mol of diglycerol used in Example 1 were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding the esterification product (the amount of 12-hydroxystearic acid polymer relative to 1.0 mol of diglycerol was 1.5 mol). The obtained esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 6800, the dispersity was 1.52, the acid value was 1.0 mg KOH / g, and the hydroxyl value was 52.2 mg KOH / g.

[0265] (3) Synthesis of esterification reaction products [Comparative Example 1 (two-step reaction)]

[0266] 12-hydroxystearic acid, as used in Example 1, was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to ensure that the average degree of polymerization, calculated based on the acid value, reached 3.0 or higher but less than 4.0. The acid value of the obtained 12-hydroxystearic acid polymer was 65 mg KOH / g.

[0267] Next, 2.0 mol of the 12-hydroxystearic acid polymer obtained above and 1.0 mol of diglycerol used in Example 1 were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding an esterification product (the amount of 12-hydroxystearic acid polymer relative to 1.0 mol of diglycerol was 2.0 mol). The esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 4500, the dispersion was 1.48, the acid value was 0.5 mg KOH / g, and the hydroxyl value was 90.8 mg KOH / g.

[0268] (4) Synthesis of esterification reaction products [Comparative Example 2 (two-step reaction)]

[0269] 12-hydroxystearic acid, as used in Example 1, was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to ensure that the average degree of polymerization calculated from the acid value was greater than 10.0 and less than 12.0. The acid value of the obtained 12-hydroxystearic acid polymer was 17 mg KOH / g.

[0270] Next, 2.0 mol of the 12-hydroxystearic acid polymer obtained above and 1.0 mol of diglycerol used in Example 1 were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding an esterification product (the amount of 12-hydroxystearic acid polymer relative to 1.0 mol of diglycerol was 2.0 mol). The esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 12000, the dispersity was 1.37, the acid value was 1.5 mg KOH / g, and the hydroxyl value was 20.7 mg KOH / g.

[0271] (5) Synthesis of esterification reaction products [Comparative Example 3 (two-step reaction)]

[0272] 12-hydroxystearic acid, as used in Example 1, was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to ensure that the average degree of polymerization calculated from the acid value was greater than 10.0 and less than 12.0. The acid value of the obtained 12-hydroxystearic acid polymer was 17 mg KOH / g.

[0273] Next, 1.5 moles of the 12-hydroxystearic acid polymer obtained above and 1.0 mole of diglycerol used in Example 1 were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding the esterification product (the amount of 12-hydroxystearic acid polymer relative to 1.0 mole of diglycerol was 1.5 moles). The obtained esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 11000, the dispersity was 1.40, the acid value was 0.5 mg KOH / g, and the hydroxyl value was 25.7 mg KOH / g.

[0274] (6) Synthesis of esterification reaction products [Comparative Example 4 (two-step reaction)]

[0275] 12-hydroxystearic acid, as used in Example 1, was added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. A suitable amount of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid added and the reaction time were adjusted to ensure that the average degree of polymerization calculated from the acid value was greater than 3.0 and less than 4.0. The acid value of the obtained 12-hydroxystearic acid polymer was 65 mg KOH / g.

[0276] Next, 2.4 mol of the 12-hydroxystearic acid polymer obtained above and 1.0 mol of diglycerol used in Example 1 were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. The reaction was carried out at 210°C under a nitrogen flow to remove the generated water, yielding the esterification product (the amount of 12-hydroxystearic acid polymer added relative to 1.0 mol of diglycerol was 2.4 mol). The obtained esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 4900, the dispersion was 1.35, the acid value was 0.9 mg KOH / g, and the hydroxyl value was 75.4 mg KOH / g.

[0277] (7) Preparation of esterification products [Examples 2-5 (mixing of two reactants)]

[0278] By mixing two esterification reaction products obtained from Examples 1, 6 and Comparative Examples 1 to 4, an esterification product of diglycerol and 12-hydroxystearic acid polymer with a weight average molecular weight of 6500 to 9000 and a dispersion of 1.40 to 1.65 was prepared.

[0279] Specifically, the esterification product of Example 1 and the esterification product of Example 6 were mixed at a mass ratio of 5:5 to produce the esterification product of Example 2.

[0280] Similarly, the esterification reaction products of Examples 3-5 were prepared by mixing the two esterification reaction products according to the mass ratio shown in Table 1.

[0281] The weight-average molecular weight (Mw), dispersity, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the esterification reaction products obtained in Examples 2-5 are shown in Table 1.

[0282]

[0283] (8) Synthesis of esterification reaction products [Comparative Example 5]

[0284] 12.0 mol of 12-hydroxystearic acid and 1.0 mol of diglycerol, used in Example 1, were added to a 1L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and moisture separator. Then, appropriate amounts of catalyst and organic solvent were added, and the reaction was carried out at 210°C under a nitrogen flow to remove the generated water, producing an esterification product (12.0 mol of 12-hydroxystearic acid relative to 1.0 mol of diglycerol). The obtained esterification product was purified by adsorption, filtration, and deodorization. The weight-average molecular weight of the obtained esterification product was 6100, the dispersion was 1.30, the acid value was 0.8 mg KOH / g, and the hydroxyl value was 38.0 mg KOH / g.

[0285] The reaction here is a one-step reaction in which the polymerization of 12-hydroxystearic acid does not occur, but the polymerization of 12-hydroxystearic acid also occurs during the esterification reaction of 12-hydroxystearic acid with diglycerides. This reaction is referred to as the "one-step reaction".

[0286] In addition, commercially available polyglycerol-2 dihydroxystearate (product name "Dehymuls PGPH", manufactured by BASF) was used as Comparative Example 6, and its weight-average molecular weight, dispersibility, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) were determined. Dehymuls PGPH is a W / O type emulsifier with HLB=5.0.

[0287] In addition, commercially available pentaerythritol trihydroxystearate was used as Comparative Example 7, and its weight-average molecular weight, dispersity, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) were determined. The alcohol backbone of the commercially available pentaerythritol trihydroxystearate is pentaerythritol made from non-vegetable raw materials.

[0288] (2) Manufacturing of O / W type sunscreen cosmetics

[0289] Using the esterification reaction products of Examples 1-6 and Comparative Examples 1-7, respectively, O / W type sunscreen cosmetics were manufactured according to the formulations described in Table 2. Specifically, firstly, the oily component and the ultraviolet absorber were uniformly mixed to prepare mixture A. Separately, all remaining components were uniformly mixed to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as the sunscreen cosmetic.

[0290] In the tables of this application, "%" represents "mass %" and "%aq" represents the content (mass %) in the aqueous solution.

[0291]

[0292] Isotridecyl isononanoate: Product name "SALACOS 913", manufactured by Nissin Oriyo Group Co., Ltd.

[0293] Dimethyl silicone oil: Product name "KF-96A-10CS", manufactured by Shin-Etsu Chemical Co., Ltd.

[0294] Ethylhexyl methoxycinnamate (2-ethylhexyl p-methoxycinnamate): Product name "NOMCORT TAB", manufactured by Nissin Oriyo Group Co., Ltd.

[0295] Microparticle titanium dioxide (stearic acid treated): Product name "MT-500CST", manufactured by Tayca.

[0296] (Acrylic ester / alkyl acrylate (C10-30)) crosspolymer (2% aq.): Product name "PemulenTR-1", manufactured by Lubrizol)

[0297] Xanthan Gum: Product name "NOMCORT ZZ", manufactured by Nissin Oriyo Group Co., Ltd.

[0298] Glyceryl stearate: Product name "Lasemul 92 AE", manufactured by IQL.

[0299] (3) Evaluation of SPF value and water resistance of various sunscreen cosmetics

[0300] For each type of O / W sunscreen cosmetic, the SPF value and water resistance were investigated. The evaluation results, together with the weight-average molecular weight (Mw), dispersibility, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the esterification reaction products used as raw materials, are shown in Tables 3 to 5.

[0301]

[0302]

[0303]

[0304] As shown in Table 4, the sunscreen cosmetic (Comparative Example 6) using commercially available polyglycerol-2-dihydroxystearate as an emulsifier had a high initial SPF value, but insufficient water resistance. O / W type sunscreen cosmetics (Comparative Examples 1 and 4) using esterification products with a slightly higher weight-average molecular weight than Comparative Example 6 also exhibited low water resistance, and a tendency for the SPF to decrease as the weight-average molecular weight increased was observed. O / W type sunscreen cosmetics (Comparative Examples 2 and 3) using esterification products with a significantly increased weight-average molecular weight also had low water resistance. On the other hand, O / W type sunscreen cosmetics (Examples 1-6) using esterification products with a weight-average molecular weight in the range of 6500-9000 and a dispersity in the range of 1.40-1.65 all had sufficiently high initial SPF values ​​and excellent water resistance. The initial SPF value of the O / W type sunscreen cosmetic (Comparative Example 7) made from commercially available pentaerythritol trihydroxy stearate was also sufficiently high, and its water resistance was excellent.

[0305] As shown in Table 5, an esterification product was obtained in one step by using the same amount of 12-hydroxystearic acid and diglycerides in the polymerization process of 12-hydroxystearic acid. Compared with an O / W type sunscreen cosmetic (Example 1) that used the esterification product obtained by a two-step reaction of 12-hydroxystearic acid polymerization, the O / W type sunscreen cosmetic (Comparative Example 5) using this esterification product had a lower weight-average molecular weight and dispersion, and the molecular weight distribution changed. In addition, the initial SPF value and water resistance were lower.

[0306] (4) Manufacturing of W / O type sunscreen cosmetics

[0307] Using the esterification reaction products of Examples 1-6 and Comparative Examples 1-7, respectively, O / W type sunscreen cosmetics were manufactured according to the formulations described in Table 6. Specifically, firstly, the oily component and the ultraviolet absorber were uniformly mixed to prepare mixture A. Separately, all remaining components were uniformly mixed to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as the sunscreen cosmetic.

[0308]

[0309] Mineral oil: Product name "CARNATION", manufactured by Shima Trading Co., Ltd.

[0310] Ethylhexyl methoxycinnamate (2-ethylhexyl p-methoxycinnamate): Product name "NOMCORT TAB", manufactured by Nissin Oriyo Group Co., Ltd.

[0311] Particulate titanium dioxide (treated with aluminum hydroxide / stearic acid): Product name "MT-100TV", manufactured by Tayca.

[0312] Cetyl PEG / PPG-10 / 1 dimethyl silicone oil: Product name "ABIL EM 90", manufactured by Evonik Operations GmbH.

[0313] 3) Evaluation of SPF values ​​and water resistance of various sunscreen cosmetics

[0314] For each W / O type sunscreen cosmetic, SPF value, water resistance, adhesion, and ease of application and spread were investigated. The evaluation results, together with the weight-average molecular weight (Mw), dispersibility, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the esterification reaction products used as raw materials, are shown in Tables 7 and 8.

[0315]

[0316]

[0317] As shown in Table 7, the W / O type sunscreen cosmetic (Comparative Example 6) made from commercially available polyglycerol-2 dihydroxystearate used as an emulsifier had a high initial SPF value but insufficient water resistance.

[0318] Sunscreen cosmetics (Comparative Examples 1, 4, and 5) using esterification products with a slightly higher weight-average molecular weight than Comparative Example 6 and reduced dispersibility as raw materials exhibited improved water resistance, but their initial SPF values ​​decreased. In sunscreen cosmetics (Comparative Examples 2 and 3) using esterification products with a significantly increased weight-average molecular weight as raw materials, water resistance was improved. However, the skin-adhesion and spreadability of the W / O type sunscreen cosmetics of Comparative Examples 1-6 were not good. On the other hand, the W / O type sunscreen cosmetics (Examples 1-6) using esterification products with a weight-average molecular weight in the range of 6500-9000 and a dispersibility in the range of 1.40-1.65 as raw materials all had sufficiently high initial SPF values ​​and excellent water resistance. Furthermore, their skin-adhesion and spreadability were also good.

[0319] Although the initial SPF value, water resistance, and adhesion of the commercially available pentaerythritol trihydroxy stearate as raw material (Comparative Example 7) were very high, they were good, but the ease of application and spreading was poor.

[0320] Next, makeup, skincare, and haircare products were created and evaluated separately. The evaluation was conducted through sensory assessment. The methods for sensory assessment are described below.

[0321] Ten sensory evaluation judges used the cosmetics for sensory evaluation. The evaluation covered the following aspects: spreadability (how smoothly the cosmetic spreads on the skin or other application areas), film-forming properties (whether it forms a film after application), adhesion (whether it adheres well after application), durability (whether it retains its color despite sebum, sweat, and friction), makeup blending (whether it blends easily with smudged makeup), and adherence (whether hair adheres well to the skin after application of hair-related cosmetics). Each evaluation item was scored according to the following evaluation criteria.

[0322] Evaluation Criteria

[0323] 6 points: Very good.

[0324] 5 points: Good.

[0325] 4 points: Slightly better.

[0326] 3 points: Average.

[0327] 2 points: Slightly poor.

[0328] 1 point: Poor.

[0329] 0:00: Very bad.

[0330] In addition, the average score of the 10 sensory evaluation judges was calculated, and the evaluation was carried out according to the following evaluation criteria based on the value.

[0331] 5 points or above: A. Excellent.

[0332] 3 points or above but below 5 points: B Excellent.

[0333] A score of 1 or higher but less than 3: C. Neither good nor bad (average).

[0334] Less than 1 point: D (Poor).

[0335] Based on the above evaluation criteria, cosmetics are judged to have excellent effects in each evaluation item when rated A or B.

[0336] (5) Manufacturing of stick lipstick cosmetics

[0337] Stick-shaped lipstick cosmetics were manufactured using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 9. It should be noted that all figures in the table represent percentages by mass. Pigment was added to a portion of the oily component (B) and processed using a roller to prepare a pigment base. Then, all components and the pigment base were heated to dissolve and uniformly dispersed using a homogenizer. The dispersion was poured into a mold and quenched to obtain stick-shaped lipsticks. The results of sensory evaluations are shown in Table 10.

[0338]

[0339]

[0340] As shown in Table 10, the stick lipstick cosmetics made from the esterification reaction products of Examples 1 and 6 showed good results in terms of spreadability, adhesion, and durability. On the other hand, the stick lipstick cosmetics made from the esterification reaction products of Comparative Examples 3 to 6 did not achieve good results in at least one of the following: spreadability, adhesion, and durability.

[0341] (6) Manufacturing of W / O cream foundation

[0342] Using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, W / O cream foundations were manufactured according to the formulations described in Table 11. It should be noted that all figures in the table represent percentages by mass. Oily component (A), alcohol (A), UV absorber, surfactant, preservative (A), and pigment were mixed at 40°C to obtain mixture (A). On the other hand, alcohol (B), preservative (B), stabilizer, moisturizing component, and water were mixed at room temperature to obtain mixture (B). Mixture (B) was slowly added dropwise to mixture (A) while heating and stirring at 50°C, and the mixture was uniformly dispersed using a homogenizer and cooled to room temperature to obtain a W / O cream foundation. The results of sensory evaluations of each are shown in Table 12.

[0343]

[0344]

[0345] As shown in Table 12, the W / O cream foundations using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of spreadability, film-forming properties, and durability. On the other hand, the W / O cream foundations using the esterification reaction products of Comparative Examples 3 to 6 did not achieve good results in at least one of the following aspects: spreadability, film-forming properties, and durability.

[0346] (7) Manufacturing of O / W liquid foundation

[0347] O / W liquid foundations were manufactured using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 13. It should be noted that all figures in the table represent mass percent. Oily component (A) and alcohol (A) were heated and mixed at 80°C to obtain mixture (A). On the other hand, oily component (B) and pigment were heated and mixed at 80°C to obtain mixture (B). Aqueous thickener, alcohol (B), pH adjuster, preservative, and water were mixed at room temperature to obtain mixture (C). Mixture (B) was added to mixture (A) while heating and stirring at 80°C, and the mixture was uniformly dispersed using a homogenizer. Furthermore, mixture (C) was added in small amounts while uniformly dispersing using a homogenizer. The dispersion was cooled to room temperature to obtain O / W liquid foundations. The results of sensory evaluations of each are shown in Table 14.

[0348]

[0349]

[0350] As shown in Table 14, the O / W liquid foundations made from the esterification reaction products of Examples 1 and 6 showed good results in terms of spreadability, film-forming properties, and durability. On the other hand, the O / W liquid foundations made from the esterification reaction products of Comparative Examples 3 to 6 did not achieve good results in any of the aspects of spreadability, film-forming properties, and durability.

[0351] (8) Manufacturing of solid powder foundation

[0352] Solid powder foundations were manufactured using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 15. It should be noted that all figures in the table represent mass percent. Oily component (A) was heated and mixed at 50°C to obtain mixture (A). On the other hand, oily component (B) was mixed and dispersed with powder components, and the above mixture (A) was added and mixed to obtain mixture (B). The obtained mixture (B) was pulverized and compressed in a pan to obtain solid powder foundation. The results of sensory evaluations of each are shown in Table 16.

[0353]

[0354]

[0355] As shown in Table 16, the solid powder foundations using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of spreadability, adhesion, and durability. On the other hand, the solid powder foundations using the esterification reaction products of Comparative Examples 3 to 6 as raw materials did not achieve good results in at least one of the following: spreadability, adhesion, and durability.

[0356] (9) Emulsion manufacturing

[0357] Emulsions were prepared using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 17. It should be noted that all figures in the table represent percentages by mass. The oily components were heated and mixed at 80°C to obtain mixture (A). Meanwhile, the remaining raw materials were heated at 80°C, and mixture (A) was slowly added and mixed. The mixture was then cooled to room temperature to obtain an emulsion. The results of sensory evaluations of each are shown in Table 18.

[0358]

[0359]

[0360] As shown in Table 18, the emulsions using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of spreadability and film-forming properties. On the other hand, the emulsions using the esterification reaction products of Comparative Examples 3 to 6 as raw materials did not achieve good results in at least one of the aspects of spreadability and film-forming properties.

[0361] (10) Manufacturing of makeup remover

[0362] Makeup remover milks were manufactured using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 19. It should be noted that all figures in the table represent percentages by mass. The oily component, surfactant, and alcohol (A) were heated and mixed at 80°C to obtain mixture (A). The remaining raw materials were heated and mixed at 80°C, then slowly added to mixture (A) and mixed. After cooling to room temperature, the makeup remover milk was obtained. The results of sensory evaluations are shown in Table 20.

[0363]

[0364]

[0365] As shown in Table 20, the cleansing milks using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of makeup blending / spreadability. On the other hand, the cleansing milks using the esterification reaction products of Comparative Examples 3 to 6 did not achieve good results in any aspect of makeup blending / spreadability.

[0366] (11) Manufacturing of cleansing oil

[0367] Makeup remover oils were manufactured using the esterification products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 21. It should be noted that all figures in the table represent percentages by mass. The oily components and surfactants were heated and mixed at 80°C, then cooled to room temperature to obtain the makeup remover oils. The results of sensory evaluations are shown in Table 22.

[0368]

[0369]

[0370] As shown in Table 22, the cleansing oils using the esterification reaction products of Examples 1 and 6 as raw materials yielded good results in terms of makeup blending and spreadability. On the other hand, the cleansing oils using the esterification reaction products of Comparative Examples 3 to 6 as raw materials did not achieve good results in any aspect of makeup blending and spreadability.

[0371] (12) Manufacturing of hair conditioner (hair cosmetics)

[0372] Hair conditioners were manufactured using the esterification reaction products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 23. It should be noted that all figures in the table represent percentages by mass. The oily component was heated and mixed with alcohol (A) at 80°C to obtain mixture (A). Meanwhile, the remaining raw materials were heated and mixed at 80°C, and the aforementioned mixture (A) was slowly added and mixed. After cooling to room temperature, the hair conditioner was obtained. The results of sensory evaluations of each are shown in Table 24.

[0373]

[0374]

[0375] As shown in Table 24, the conditioners using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of film-forming properties / smoothing feel. On the other hand, the conditioners using the esterification reaction products of Comparative Examples 3 to 6 as raw materials did not achieve good results in at least one of the aspects of film-forming properties / smoothing feel.

[0376] (13) Manufacturing of hair oil (hair cosmetics)

[0377] Hair oils were manufactured using the esterification products of Examples 1, 6, and Comparative Examples 3-6, respectively, according to the formulations described in Table 25. It should be noted that all figures in the table represent percentages by mass. The oily components were mixed at room temperature to obtain the hair oils. The results of sensory evaluations of each are shown in Table 26.

[0378]

[0379]

[0380] As shown in Table 26, the hair oils using the esterification reaction products of Examples 1 and 6 as raw materials showed good results in terms of spreadability / comfort. On the other hand, the hair oils using the esterification reaction products of Comparative Examples 3 to 6 as raw materials did not achieve good results in at least one of the aspects of spreadability / comfort.

[0381] (14) Determination of water holding capacity

[0382] The esterification products of Examples 1 and 6 are ester compounds of 12-hydroxystearic acid polymer and polyol, which have excellent water retention.

[0383] It was compared with commercially available products such as dimeric pentaerythritol trimeric hydroxystearate (Comparative Example 7), lanolin, and cholesterol hydroxystearate.

[0384] The water-holding capacity test was conducted with reference to the British Pharmacopoeia (BP) method for determining the water content of lanolin, as described below.

[0385] Mix 1g of the test sample with 9g of petroleum jelly, and add purified water dropwise while vigorously stirring (200-300 rpm) in a constant temperature bath at 40℃. The endpoint is defined as the point where no more water can be incorporated, and the result is expressed as the percentage of water mass relative to the mass of the mixed sample. A higher value indicates higher water retention. The results of the water retention test are shown in Table 27.

[0386]

[0387] As shown in Table 27, the esterification products of Examples 1 and 6 showed good water retention even compared with dimeric pentaerythritol trimeric hydroxystearate (Comparative Example 7), lanolin, and cholesterol hydroxystearate, which are known to have high water retention.

[0388] Industrial applicability

[0389] According to the present invention, an esterification reaction product with good skin adhesion and ease of application and spreading, water resistance, powder dispersibility, film-forming properties and water retention, a cosmetic comprising the esterification reaction product, and a method for manufacturing the esterification reaction product can be provided.

Claims

1. An esterification product obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer, The weight-average molecular weights of the esterification products are 6500-9000 and the dispersity is 1.40-1.

65.

2. The esterification product according to claim 1, wherein, The average degree of polymerization of the 12-hydroxystearic acid polymer is 4.0 to 10.

0.

3. The esterification product according to claim 2, wherein, The esterification product is obtained by esterifying 1.5 to 2.4 moles of the 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 relative to 1.0 mole of diglyceride.

4. The esterification product according to claim 1, wherein, The esterification reaction product comprises at least two esterification reaction products obtained by esterifying diglycerides with a 12-hydroxystearic acid polymer.

5. The esterification product according to claim 4, wherein, The esterification product comprises: The product of the first esterification reaction, and Either the product of the second esterification reaction or the product of the third esterification reaction. The first esterification product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0, and has a weight-average molecular weight of 6500 to 9000 and a dispersion of 1.40 to 1.

65. The second esterification product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.

0. Its weight-average molecular weight is 4000-6000, and its dispersion is 1.35-1.

50. The third esterification product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0, and has a weight-average molecular weight of 10,000 to 13,000 and a dispersion of 1.35 to 1.

50.

6. The esterification product according to claim 5, wherein, The first esterification product is obtained by esterifying 1.5 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 relative to 1.0 mole of diglyceride. The second esterification product is obtained by esterifying 2.0 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0 with 1.0 mole of diglyceride. The third esterification product is obtained by esterifying 1.5 to 2.0 moles of a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with 1.0 mole of diglycerides.

7. The esterification product according to claim 4, wherein, The esterification reaction product includes a second esterification reaction product and a third esterification reaction product. The second esterification product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.

0. Its weight-average molecular weight is 4000-6000, and its dispersion is 1.35-1.

50. The third esterification product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0, and has a weight-average molecular weight of 10,000 to 13,000 and a dispersion of 1.35 to 1.

50.

8. The esterification product according to claim 7, wherein, The second esterification product is obtained by esterifying 2.0 to 2.4 moles of 12-hydroxystearic acid polymer with an average degree of polymerization of 3.0 or higher and less than 4.0 with 1.0 mole of diglyceride. The third esterification product is obtained by esterifying 1.5 to 2.0 moles of a 12-hydroxystearic acid polymer with an average degree of polymerization greater than 10.0 and less than 12.0 with 1.0 mole of diglycerides.

9. A cosmetic product comprising the esterification reaction product according to any one of claims 1 to 8.

10. The cosmetic according to claim 9, further comprising one or more selected from ultraviolet scattering agents and ultraviolet absorbing agents.

11. The cosmetic according to claim 9, wherein it is a sunscreen cosmetic, a skin care / hair care cosmetic, or a makeup cosmetic.

12. The cosmetic according to claim 9, wherein it is an emulsified cosmetic.

13. A method for producing an esterification reaction product, the method comprising: Diglycerides are esterified with a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0 to 10.0 to produce an esterification product with a weight average molecular weight of 6500 to 9000 and a dispersion of 1.40 to 1.

65.

14. The method for producing the esterification reaction product according to claim 13, wherein, 12-hydroxystearic acid was heated to 100℃~250℃ while removing water to carry out the reaction, resulting in a 12-hydroxystearic acid polymer with an average degree of polymerization of 4.0~10.

0. The 12-hydroxystearic acid polymer was then esterified with diglycerides.

15. A water resistance enhancer for cosmetics, comprising the esterification reaction product according to any one of claims 1 to 8.

16. A cosmetic adhesion enhancer comprising the esterification reaction product according to any one of claims 1 to 8.

17. A film-forming enhancer for cosmetics, comprising the esterification reaction product according to any one of claims 1 to 8.

18. A hair cosmetic product for improving hair conformability, comprising the esterification reaction product according to any one of claims 1 to 8.

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