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

Abstract

This esterification reaction product is obtained by esterifying diglycerin and a 12-hydroxystearic acid polymer. The esterification reaction product has a weight-average molecular weight of 6500-9000 and a degree of dispersion of 1.40-1.65. The cosmetic contains the esterification reaction product. The esterification reaction product is produced by esterifying diglycerin and a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0-10.0.

Description

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

[0001] The present invention relates to an esterification reaction product. In particular, the present invention relates to an esterification reaction product that exhibits both excellent adhesion to skin and ease of spreadability, and also excellent water resistance, powder dispersibility, film-forming properties, and water holding ability. This application claims priority based on Japanese Patent Application No. 2024-52517, filed on March 27, 2024, the contents of which are incorporated herein by reference.

[0002] The functions of oils used in cosmetics such as sunscreen cosmetics (sunscreen cosmetics), skin care cosmetics, hair care cosmetics, and makeup cosmetics must be excellent in terms of moisturizing properties, adhesion to skin, powder dispersibility, water resistance, and oxidation stability, and further, they must have a good feel to the touch and be low in skin irritation. In addition to these functions, due to recent interest in environmental considerations, there is a demand for plant-derived oils obtained from plant-derived alcohols and fatty acids.

[0003] Polyhydroxy fatty acid esters are examples of cosmetic oils that use plant-derived raw materials. Polyhydroxy fatty acid esters are esterification reaction products of polyhydroxy fatty acids and alcohols, and include a wide variety of esterification reaction products with different structures depending on factors such as the degree of polymerization of the polyhydroxy fatty acid, the type of hydroxy fatty acid monomer, and the type of alcohol. Among these diverse polyhydroxy fatty acid esters, some are known to have good moisturizing properties, good skin adhesion, good powder dispersibility, good water resistance, good oxidation stability, good texture, and good water-holding properties. However, no polyhydroxy fatty acid esters that use plant-derived raw materials and possess all of these functions have yet been developed.

[0004] Examples of polyhydroxy fatty acid esters using plant-derived raw materials include polyricinoleate esters such as polyglyceryl polyricinoleate, polyglyceryl-3 polyricinoleate, polyglyceryl-4 polyricinoleate, polyglyceryl-5 polyricinoleate, polyglyceryl-6 polyricinoleate, polyglyceryl-10 polyricinoleate, and lauryl / myristyl polyricinoleate. These polyricinoleate esters have excellent emulsifying properties and are primarily used as emulsifiers and dispersants (Patent Documents 1 to 5), but have problems such as poor water resistance and poor adhesion to skin, and further, poor oxidative stability due to the presence of double bonds in their structure.

[0005] Further, examples of polyhydroxy fatty acid esters using plant-derived raw materials include polyhydroxystearic acid esters such as polyglyceryl-4 (diisostearate / polyhydroxystearic acid / sebacic acid), PEG-30 dipolyhydroxystearate, dipentaerythrityl tetra(behenic acid / polyhydroxystearate), pentaerythrityl (behenic acid / polyhydroxystearate), polyglyceryl-6 polyhydroxystearate, and polyglyceryl-2 dipolyhydroxystearate. Among these polyhydroxystearic acid esters, dipentaerythrityl tri-polyhydroxystearate is particularly excellent in terms of powder dispersibility, skin adhesion, water resistance, low skin irritation, oxidation stability, water-holding ability, and moisturizing properties (Patent Documents 6 to 11). However, dipentaerythrityl tri-polyhydroxystearate is an oily agent that is very viscous, sticky, and difficult to spread, and therefore its use in cosmetics is limited, and the amount of incorporation into low-viscosity emulsion cosmetics and sunscreen formulations has also been limited. In addition, because the alcohol skeleton of dipentaerythritol is non-plant-based, there have been many requests for improvements from cosmetic manufacturers seeking more plant-based ingredients.

[0006] On the other hand, polyglyceryl-2 dipolyhydroxystearate, a type of polyhydroxystearic acid ester, has relatively low viscosity, high powder dispersibility, and high oxidation stability compared to dipentaerythrityl tripolyhydroxystearate (Patent Documents 12 to 15). Therefore, polyglyceryl-2 dipolyhydroxystearate is suitable as an oil agent for cosmetics and is often used as a cosmetic ingredient. However, polyglyceryl-2 dipolyhydroxystearate also has high emulsifying function and is mainly used as an emulsifier, and its water resistance and adhesion to skin are insufficient.

[0007] Japanese Patent Application Laid-Open No. 2022-007717 Japanese Patent Application Laid-Open No. 2022-072074 International Publication No. 2022 / 153928 International Publication No. 2023 / 032834 Japanese Patent Application Laid-Open No. 2008-162932 Japanese Patent No. 6397891 Japanese Patent No. 4027157 Japanese Patent No. 5395325 Japanese Patent Application Laid-Open No. 2023-107034 Japanese Patent No. 7373916 Japanese Patent Application Laid-Open No. 2022-117486 Japanese Patent No. 3787353 Japanese Patent No. 7324217 Japanese Patent Publication No. 2001-524504 Japanese Patent No. 4109209

[0008] An object of the present invention is to provide an esterification reaction product of a polyhydroxystearic acid ester that exhibits both good adhesion to skin and good spreadability, and that has good water resistance, powder dispersibility, film-forming properties, and water holding capacity. Another object of the present invention is to provide a cosmetic containing the esterification reaction product. Another object of the present invention is to provide a method for producing the esterification reaction product.

[0009] As a result of intensive investigations to solve the above problems, the present inventors have found that by controlling the weight-average molecular weight and dispersity of polyglyceryl-2-dipolyhydroxystearate, an esterification reaction product can be obtained that satisfies both good adhesion to skin and good spreadability, and that has good water resistance, powder dispersibility, film-forming properties, and water holding ability, and have completed the present invention.

[0010] That is, the present invention includes the following aspects: [1] An esterification reaction product obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer, wherein the esterification reaction product has a weight-average molecular weight of 6,500 to 9,000, preferably 6,700 to 9,000, more preferably 7,000 to 9,000, and even more preferably 7,500 to 9,000, and a polydispersity 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 still more preferably 1.42 to 1.48. [2] The esterification reaction product according to item [1] above, wherein the 12-hydroxystearic acid polymer has an average degree of polymerization of 4.0 to 10.0. [3] The esterification reaction product according to [2] above, which is an esterification reaction product obtained by esterifying 1.5 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 with 1.0 mol of diglycerol. [4] The esterification reaction product according to [1] above, which contains at least two esterification reaction products obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer.[5] The esterification reaction product comprises: a first esterification reaction product; and one of a second esterification reaction product and a third esterification reaction product; the first esterification reaction product is obtained by esterifying diglycerol and a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0, and has a weight-average molecular weight of 6,500 to 9,000 and a polydispersity of 1.40 to 1.65; and the second esterification reaction product is obtained by esterifying diglycerol and a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0, and has a weight-average molecular weight of 4,000 to 6,000 and a polydispersity of 1.35 to 1.50; The esterification reaction product according to [4] above, wherein the third esterification reaction product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and not more than 12.0, and has a weight-average molecular weight of 10,000 to 13,000 and a polydispersity of 1.35 to 1.50. [6] The esterification reaction product according to [5], wherein the first esterification reaction product is obtained by esterifying 1.5 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 with 1.0 mol of diglycerol; the second esterification reaction product is obtained by esterifying 2.0 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mol of diglycerol; and the third esterification reaction product is obtained by esterifying 1.5 to 2.0 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with 1.0 mol of diglycerol.[7] The esterification reaction product according to [4], wherein the esterification reaction product comprises a second esterification reaction product and a third esterification reaction product, wherein the second esterification reaction product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0, and has a weight-average molecular weight of 4,000 to 6,000 and a dispersity of 1.35 to 1.50, and the third esterification reaction product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less, and has a weight-average molecular weight of 10,000 to 13,000 and a dispersity of 1.35 to 1.50. [8] The esterification reaction product according to [7], wherein the second esterification reaction product is obtainable by esterifying 2.0 to 2.4 mols of a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mol of diglycerol, and the third esterification reaction product is obtainable by esterifying 1.5 to 2.0 mols of a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with 1.0 mol of diglycerol. [9] A cosmetic comprising the esterification reaction product according to any one of [1] to [8].

[10] The cosmetic according to [9], further comprising one or more agents selected from the group consisting of an ultraviolet scattering agent and an ultraviolet absorber.

[11] The cosmetic according to [9] or

[10] , which is a sunscreen cosmetic, a skin care / hair care cosmetic, or a makeup cosmetic.

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

[11] , which is an emulsion cosmetic.

[13] A method for producing an esterification reaction product, comprising esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0, to produce an esterification reaction product having a weight-average molecular weight of 6,500 to 9,000, preferably 6,700 to 9,000, more preferably 7,000 to 9,000, even more preferably 7,500 to 9,000, and a dispersity 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 still more preferably 1.42 to 1.48.

[14] A method for producing the esterification reaction product of

[13] above, comprising heating 12-hydroxystearic acid to 100°C to 250°C and reacting while removing water to obtain a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0, and then esterifying the 12-hydroxystearic acid polymer with diglycerin.

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

[16] An adhesion improver for cosmetics, comprising the esterification reaction product of any one of [1] to [8] above.

[17] A film-forming property improver for cosmetics, comprising the esterification reaction product of any one of [1] to [8] above.

[18] An agent for improving hair manageability in hair cosmetics, comprising the esterification reaction product of any one of [1] to [8] above.

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

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

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

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

[23] Use of the esterification reaction product according to any one of [1] to [8] above for producing a cosmetic having improved water resistance.

[24] Use of the esterification reaction product according to any one of [1] to [8] above for producing a cosmetic having improved adhesion.

[25] Use of the esterification reaction product according to any one of [1] to [8] above for producing a cosmetic preparation that improves film-forming properties.

[26] Use of the esterification reaction product according to any one of [1] to [8] above for producing a hair cosmetic preparation that improves hair manageability.

[0011] The present invention can provide an esterification reaction product that satisfies both good adhesion to skin and good spreadability, and that has good water resistance, powder dispersibility, film-forming properties, and water holding ability; a cosmetic containing the esterification reaction product; and a method for producing the esterification reaction product.

[0012] In the present invention and the specification of this application, a numerical range of "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 it is written as "1 to 10 parts by mass," it means a numerical range from 1 part by mass to 10 parts by mass that includes 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."

[0013] In the present invention and the present specification, "weight average molecular weight (Mw)" means the average molecular weight taking into account the weight fraction in the molecule. "Number average molecular weight (Mw)" means the average molecular weight per molecule. "Dispersity" means the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). The closer the dispersity is to 1, the narrower the molecular weight distribution.

[0014] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the esterification reaction product can be measured by gel permeation chromatography. Specifically, these values ​​are determined in terms of standard polystyrene based on a calibration 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 product of this embodiment can be measured using an ACQUITY Advanced Polymer Chromatography (APC) system (manufactured by Nihon Waters).

[0015] <Esterification Reaction Product> An overview of the esterification reaction product of this embodiment will be described. The esterification reaction product of this embodiment is an esterification reaction product obtained by esterifying diglycerin and a 12-hydroxystearic acid polymer, and has a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65. The esterification reaction product of this embodiment is polyglyceryl-2 dipolyhydroxystearate (an esterification reaction product of polyhydroxystearic acid and diglyceryl) having a weight-average molecular weight and dispersity within the above ranges. Therefore, the esterification reaction product of this embodiment exhibits good adhesion to skin and good spreadability, and can improve water resistance, powder dispersibility, and water holding ability. Furthermore, the esterification reaction product of this embodiment has a relatively low viscosity, making it easy to handle and highly manageable. Furthermore, the absence of double bonds in the structure results in excellent oxidation stability.

[0016] The weight-average molecular weight of the esterification reaction product of this embodiment may be within a range of 6,500 to 9,000, preferably 6,700 to 9,000, more preferably 7,000 to 9,000, and even more preferably 7,500 to 9,000. Alternatively, the weight-average molecular weight of the esterification reaction product of this embodiment is more preferably 6,500 to 8,000.

[0017] The dispersity of the esterification reaction product of this embodiment may be within a 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 still more preferably 1.42 to 1.48. Alternatively, the dispersity of the esterification reaction product of this embodiment is more preferably 1.45 to 1.56.

[0018] The esterification reaction product of this embodiment may be any esterification reaction product having a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65, and is preferably an esterification reaction product having a weight-average molecular weight of preferably 6,700 to 9,000, more preferably 7,000 to 9,000, even more preferably 7,500 to 9,000, and a dispersity of preferably 1.41 to 1.64, more preferably 1.41 to 1.56, even more preferably 1.41 to 1.52, and still more preferably 1.42 to 1.48. Alternatively, the esterification reaction product of this embodiment is more preferably an esterification reaction product having a weight-average molecular weight of 6,800 to 7,800 and a dispersity of 1.45 to 1.56.

[0019] The diglycerol used to produce the esterification reaction product of this embodiment can be obtained by a condensation reaction or the like using glycerol as a raw material. Alternatively, commercially available diglycerol may be used as a raw material to produce the esterification reaction product of this embodiment.

[0020] The 12-hydroxystearic acid polymer used to produce the esterification reaction product of this embodiment preferably has an average degree of polymerization of 4.0 to 10.0. 12-hydroxystearic acid is 12-hydroxystearic acid having one hydroxyl group in the molecule, and can be obtained, for example, by hydrogenating ricinoleic acid obtained by hydrolyzing castor seed oil. Commercially available 12-hydroxystearic acid may also be used as a raw material for producing the esterification reaction product of this embodiment.

[0021] The raw materials for diglycerin and 12-hydroxystearic acid polymer used to produce the above-described esterification reaction product of this embodiment are both preferably derived from plants.

[0022] The esterification reaction product of this embodiment is obtained by esterifying a 12-hydroxystearic acid polymer with diglycerin, and is preferably produced in two steps: a step of polymerizing 12-hydroxystearic acid and a step of esterifying the 12-hydroxystearic acid polymer with diglycerin. Hereinafter, this production method will be referred to as a "two-step reaction."

[0023] The polymerization reaction of 12-hydroxystearic acid can be carried out, for example, as follows: 12-hydroxystearic acid is charged into a reaction vessel and subjected to an esterification reaction (polymerization reaction) with stirring in the presence or absence of an acid, alkali, or other metal catalyst, preferably at a temperature of 100°C to 250°C, more preferably 150°C to 250°C, even more preferably 160°C to 240°C, and still more preferably 190°C to 230°C, for 5 to 30 hours.

[0024] To produce the esterification reaction product of this embodiment, it is preferable to use a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0. When the average degree of polymerization is within the above range, esterification with diglycerin readily yields an esterification reaction product having a weight-average molecular weight of 6,500 to 9,000 and a polydispersity 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. The average degree of polymerization can be adjusted to the above range by measuring the acid value of the reaction product during the polymerization reaction of 12-hydroxystearic acid. That is, the reaction product is sampled during the polymerization reaction of 12-hydroxystearic acid, and the average degree of polymerization is calculated by measuring the acid value. The esterification reaction (polymerization reaction) can be stopped when the desired average degree of polymerization is reached, thereby adjusting the average degree of polymerization. In this specification, the term "average degree of polymerization" refers to the number-average degree of polymerization calculated from the acid value.

[0025] The hydroxyl value of the esterification reaction product of this embodiment is preferably 0 to 180 mgKOH / g, more preferably 0 to 160 mgKOH / g, even more preferably 0 to 100 mgKOH / g, and even more preferably 0 to 90 mgKOH / g. In particular, the hydroxyl value of the esterification reaction product of this embodiment is preferably 20 to 70 mgKOH / g, more preferably 20 to 60 mgKOH / g, even more preferably 25 to 55 mgKOH / g, and even more preferably 30 to 40 mgKOH / g. The hydroxyl value is measured in accordance with the Standards for Quasi-drug Ingredients 2021.

[0026] The acid value of the esterification reaction product of this embodiment is preferably 3 mgKOH / g or less, more preferably 0 to 3 mgKOH / g, and even more preferably 0.5 to 1.5 mgKOH / g. If the acid value exceeds 3 mgKOH / g, an odor may be generated. The acid value is measured in accordance with the Standards for Quasi-drug Ingredients 2021.

[0027] The esterification reaction product of the present invention is obtained by esterifying diglycerin and a 12-hydroxystearic acid polymer. By adjusting the charge ratio of diglycerin to 12-hydroxystearic acid polymer, the weight-average molecular weight and polydispersity of the resulting esterification reaction product can be adjusted within desired ranges. The charge amount of the 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, per 1.0 mol of diglycerin.

[0028] The esterification reaction of diglycerol and 12-hydroxystearic acid polymers can be carried out, for example, as follows: Diglycerol and 12-hydroxystearic acid polymers are placed in a reaction vessel and the esterification reaction is carried out in an inert organic solvent and / or gas at a temperature of preferably 100°C to 250°C, more preferably 150°C to 250°C, even more preferably 160°C to 240°C, and even more preferably 190°C to 230°C for 1 to 20 hours while removing by-product water, to obtain an esterification reaction product of diglycerol and 12-hydroxystearic acid polymers.

[0029] A catalyst may be used, if necessary, in the polymerization reaction of 12-hydroxystearic acid and the esterification reaction with diglycerin. Examples of the catalyst include acid catalysts, alkali catalysts, and metal catalysts. Examples of acid catalysts include sulfuric acid, hydrochloric acid, and trifluoroacetic acid. Examples of alkali catalysts include sodium hydroxide, potassium hydroxide, and triethylamine. Examples of metal catalysts include simple alkali metals, alkaline earth metals, and transition metals, as well as alkoxides. When an acid catalyst, alkali catalyst, or metal catalyst is used as the catalyst, the amount used is preferably about 0.001 to 1.0% by mass relative to the total mass of the reaction raw materials. As the solvent, solvents known per se in the field of organic chemistry that are used in esterification reactions of alcohols and fatty acids can be used.

[0030] After the reaction, the catalyst and unreacted raw materials can be removed by known purification treatments such as washing with water, alkali deoxidation, adsorption treatment, and distillation. Furthermore, the obtained reaction product can be further purified by decolorization and deodorization treatment.

[0031] The esterification reaction product of the present embodiment can include at least two esterification reaction products obtained by esterifying diglycerol and 12-hydroxystearic acid polymer.

[0032] The esterification reaction product of this embodiment has a weight-average molecular weight in the range of 6,500 to 9,000 and a dispersity in the range of 1.40 to 1.65. However, by mixing two or more esterification reaction products (esterification reaction products of diglycerol and 12-hydroxystearic acid polymers) having different weight-average molecular weights or dispersities, an esterification product of diglycerol and 12-hydroxystearic acid polymers having a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65 can also be produced.

[0033] The esterification reaction product of this embodiment has a weight-average molecular weight in the range of 6,500 to 9,000 and a dispersity in the range of 1.40 to 1.65. However, an esterification reaction product of diglycerin and 12-hydroxystearic acid polymer having a weight-average molecular weight of 6,500 to 9,000 and a dispersity in the range of 1.40 to 1.65 can also be produced by mixing an esterification reaction product having a weight-average molecular weight outside of the range of 6,500 to 9,000 (esterification reaction product of diglycerin and 12-hydroxystearic acid polymer) or an esterification reaction product having a dispersity outside of the range of 1.40 to 1.65 (esterification reaction product of diglycerin and 12-hydroxystearic acid polymer) with an esterification reaction product having a weight-average molecular weight in the range of 6,500 to 9,000 and a dispersity in the range of 1.40 to 1.65 (esterification reaction product of diglycerin and 12-hydroxystearic acid polymer).

[0034] Furthermore, the esterification reaction product of this embodiment can also be produced as an esterification reaction product of diglycerin and 12-hydroxystearic acid polymer having a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65 by mixing two or more kinds of esterification reaction products (esterification reaction products of diglycerin and 12-hydroxystearic acid polymers) having a weight-average molecular weight outside the range of 6,500 to 9,000 or a dispersity outside the range of 1.40 to 1.65 (esterification reaction products of diglycerin and 12-hydroxystearic acid polymers).

[0035] The esterification reaction product of this embodiment may include: a first esterification reaction product obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0, and having a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65; a second esterification reaction product obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0, and having a weight-average molecular weight of 4,000 to 6,000 and a dispersity of 1.35 to 1.50; or a third esterification reaction product obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 but not more than 12.0, and having a weight-average molecular weight of 10,000 to 13,000 and a dispersity of 1.35 to 1.50.

[0036] The first esterification reaction product is preferably obtained by esterifying 1.5 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 with 1.0 mol of diglycerol. The second esterification reaction product is preferably obtained by esterifying 2.0 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mol of diglycerol. The third esterification reaction product is preferably obtained by esterifying 1.5 to 2.0 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with 1.0 mol of diglycerol.

[0037] The weight-average molecular weight of the second esterification reaction product obtained by esterifying the 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with diglycerin may be within a range of 4,000 to 6,000, preferably 4,000 to 5,000, and more preferably 4,500 to 4,900. The weight-average molecular weight of the third esterification reaction product obtained by esterifying the 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with diglycerin may be within a range of 10,000 to 13,000, preferably 10,500 to 12,500, and more preferably 11,000 to 12,000.

[0038] The dispersity of the second esterification reaction product obtained by esterifying the 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with diglycerin is within the range of 1.35 to 1.50, preferably 1.35 to 1.48.The dispersity of the third esterification reaction product obtained by esterifying the 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with diglycerin is within the range of 1.35 to 1.50, preferably 1.37 to 1.40.

[0039] The weight-average molecular weight of the esterification reaction product comprising the first esterification reaction product and the second or third esterification reaction product is 6,500 to 9,000, preferably 7,000 to 9,000, and more preferably 7,100 to 8,900. The polydispersity of the esterification reaction product comprising the first esterification reaction product and the second or third esterification reaction product is 1.40 to 1.65, and preferably 1.41 to 1.64.

[0040] In the esterification reaction product comprising 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 dispersity of the esterification reaction product comprising the first esterification reaction product and the second or third esterification reaction product are within the above-described ranges. However, it is preferably, for example, 3:7 to 8:2.

[0041] When the esterification reaction product of this embodiment contains the first esterification reaction product and the second esterification reaction product, the mass ratio of the first esterification reaction product to the second esterification reaction product (first esterification reaction product:second esterification reaction product) is not particularly limited as long as the weight-average molecular weight and polydispersity of the esterification reaction product of this embodiment are within the above-mentioned ranges. However, for example, it is preferably 7:3 to 9:1. The weight-average molecular weight of the esterification reaction product containing the first esterification reaction product and the second esterification reaction product is 6,500 to 9,000, preferably 6,500 to 8,000, and more preferably 6,500 to 7,500. The polydispersity of the esterification reaction product containing the first esterification reaction product and the second esterification reaction product is 1.40 to 1.65, and preferably 1.40 to 1.45.

[0042] When 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 polydispersity of the esterification reaction product of this embodiment are within the above-mentioned ranges. However, for example, it is preferably 2:8 to 4:6. The weight-average molecular weight of the esterification reaction product including the first esterification reaction product and the third esterification reaction product is 6,500 to 9,000, preferably 7,000 to 9,000, and more preferably 8,000 to 9,000. The polydispersity of the esterification reaction product including the first esterification reaction product and the third esterification reaction product is 1.40 to 1.65, and preferably 1.50 to 1.65.

[0043] The first esterification reaction product and the second or third esterification reaction product can each be independently produced by the above-mentioned "two-step reaction." The first esterification reaction product is obtained by charging 1.5 to 2.4 moles of a 12-hydroxystearic acid polymer, obtained by adjusting the amount of 12-hydroxystearic acid charged and the reaction time so that the average degree of polymerization, as calculated from the acid value, is 4.0 to 10.0, into a reaction vessel relative to 1.0 mole of diglycerin, and performing an esterification reaction in the presence of an inert organic solvent and / or gas at preferably 100°C to 250°C, more preferably 150°C to 250°C, even more preferably 160°C to 240°C, and still more preferably 190°C to 230°C, for 1 to 20 hours while removing by-product water, thereby obtaining an esterification reaction product of diglycerin and a 12-hydroxystearic acid polymer. Similarly, a reaction vessel is charged with 1.5 to 2.4 mol, preferably 2.0 to 2.4 mol, of a 12-hydroxystearic acid polymer obtained by adjusting the amount of 12-hydroxystearic acid charged and the reaction time so that the average degree of polymerization calculated from the acid value would be 3.0 or more and less than 4.0, and the polymer is subjected to an esterification reaction in the presence of an inert organic solvent and / or gas, preferably at a temperature of 100°C to 250°C, more preferably 150°C to 250°C, even more preferably 160°C to 240°C, and still more preferably 190°C to 230°C, while removing by-product water, to obtain a second esterification reaction product. Similarly, a 12-hydroxystearic acid polymer obtained by adjusting the amount of 12-hydroxystearic acid charged and the reaction time so that the average degree of polymerization calculated from the acid value is more than 10.0 and not more than 12.0 is charged in an amount of 1.5 to 2.4 mol, preferably 1.5 to 2.0 mol, per 1.0 mol of glycerin into a reaction vessel and subjected to an esterification reaction in the presence of an inert organic solvent and / or gas preferably at a temperature of 100°C to 250°C, more preferably 150°C to 250°C, further preferably 160°C to 240°C, still more preferably 190°C to 230°C, while removing by-product water, to obtain a third esterification reaction product.

[0044] Alternatively, the esterification reaction product of this embodiment preferably contains the second esterification reaction product and the third esterification reaction product. The second esterification reaction product and the third esterification reaction product can each be independently produced by the "two-step reaction." The mass ratio of the second esterification reaction product to the third esterification reaction product (second esterification reaction product:third esterification reaction product) is not particularly limited as long as the weight-average molecular weight and dispersity of the esterification reaction product containing the second esterification reaction product and the third esterification reaction product fall within the above-mentioned ranges. For example, the mass ratio is preferably 0.5:9.5 to 2:8. The weight-average molecular weight of the esterification reaction product containing the second esterification reaction product and the third esterification reaction product is 6,500 to 9,000, preferably 8,000 to 9,000. The polydispersity of the esterification reaction product including the second esterification reaction product and the third esterification reaction product is 1.40 to 1.65, and preferably 1.40 to 1.45.

[0045] <Cosmetic> The cosmetic of this embodiment contains the esterification reaction product of this embodiment. Because the cosmetic of this embodiment contains the esterification reaction product of this embodiment, the cosmetic of this embodiment has good dispersibility of solid components such as pigments, high water resistance and water holding capacity, and when applied to the skin, has excellent adhesion to the skin and ease of spreadability.

[0046] The content of the esterification reaction product of this embodiment relative to the total amount of the cosmetic of this embodiment is not particularly limited, as long as the esterification reaction product exhibits the effects of improving physical properties, particularly the effects of improving adhesion to skin, ease of application, water resistance, powder dispersibility, etc., and can be appropriately set in consideration of the desired quality characteristics of the cosmetic. The content of the esterification reaction product relative to the total amount of the cosmetic of this embodiment is preferably 0.1 to 80.0 mass%, more preferably 1.0 to 80.0 mass%, even more preferably 1.0 to 60.0 mass%, still more preferably 1.0 to 40.0 mass%, and particularly preferably 5.0 to 40.0 mass%. Alternatively, the content of the esterification reaction product relative to the total amount of the cosmetic of this embodiment is preferably 1.0 to 40.0 mass%.

[0047] The cosmetic of this embodiment may have any appearance, be it transparent, translucent, or emulsion (opaque), and may take any form, such as liquid, cream, emulsion, solid, or aerosol. The cosmetic of this embodiment is preferably an emulsion cosmetic. When the cosmetic of this embodiment is an emulsion cosmetic, it may be an O / W type emulsion cosmetic or a W / O type emulsion cosmetic.

[0048] The cosmetic of this embodiment may be a cosmetic for external use, and its application is not limited. For example, the cosmetic of this embodiment may be a sunscreen cosmetic, a makeup cosmetic, or a skin care / hair care cosmetic. Examples of makeup cosmetics include lip cosmetics such as lipstick, lip balm, lip gloss, and lip color; base makeup cosmetics such as foundation, concealer, makeup base, blush, and face powder (finishing powder); eyebrow cosmetics such as eyebrow makeup, eye shadow, eyeliner, and mascara; and nail cosmetics such as nail enamel, base coat, and top coat. Examples of skin care / hair care cosmetics include emulsions, creams, serums, lotions, hand creams, cleansing oils, facial cleansers, gels, balms, sticks, sprays, aerosols, sheet masks, shampoos, rinses, conditioners, and hair oils. There are no particular limitations on the method for producing these cosmetics, and they can be produced by known methods.

[0049] The esterification reaction product of this embodiment has the effects of improving water resistance, adhesion to skin, and ease of spreadability, making the cosmetic of this embodiment suitable as a component of cosmetics that require high resistance to sebum, sweat, and rubbing. Therefore, the cosmetic of this embodiment is preferably a sunscreen cosmetic or a makeup cosmetic. The esterification reaction product of this embodiment can be used as a water resistance improver for cosmetics or an adhesion improver for cosmetics. Furthermore, the esterification reaction product of this embodiment has the effect of improving the film-forming properties of cosmetics and improving the manageability of hair cosmetics. Therefore, the esterification reaction product of this embodiment can be used as a film-forming property improver for cosmetics or an agent for improving hair manageability of hair cosmetics.

[0050] The cosmetic of this embodiment is particularly preferably a sunscreen cosmetic. A sunscreen cosmetic is a cosmetic that contains one or more components selected from the group consisting of ultraviolet scattering agents and ultraviolet absorbers as a component that imparts sunscreen function. Of the components that impart sunscreen function, the ultraviolet scattering agent is in the form of a powder. Because the esterification reaction product of this embodiment has high powder dispersibility, by incorporating it into a sunscreen cosmetic, the ultraviolet scattering agent is uniformly dispersed in the cosmetic, and a uniform ultraviolet scattering film is formed on the skin when applied to the skin, thereby improving the ultraviolet protection effect. In other words, even if the amount of ultraviolet scattering agent in the cosmetic is the same, there is an effect of increasing the SPF (sun protection factor).

[0051] Sunscreen cosmetics may take the form of a water-in-oil (W / O) cream sunscreen cosmetic, a water-in-oil (W / O) emulsion sunscreen cosmetic, a water-in-oil (W / O) multi-layer emulsion sunscreen cosmetic, an oil-in-water (O / W) cream sunscreen cosmetic, or an oil-in-water (O / W) emulsion sunscreen cosmetic. The effects of the esterification reaction product of this embodiment on improving skin adhesion, ease of application, water resistance, and powder dispersibility are exhibited regardless of the form of sunscreen cosmetic in which it is incorporated. Furthermore, the cosmetic of this embodiment is preferably a cosmetic containing one or more ultraviolet scattering agents, and may be a cosmetic containing one or more ultraviolet scattering agents and one or more ultraviolet absorbers, or may be a cosmetic containing one or more ultraviolet absorbers but not an ultraviolet scattering agent.

[0052] The cosmetic of this embodiment may contain, as needed, various components commonly used in cosmetics in addition to the esterification reaction product of this embodiment, provided that the effects of the present invention are not impaired. While such components vary depending on the intended use and formulation of the cosmetic, examples include oil components, alcohols, polymer emulsions, thickeners, surfactants, pH adjusters, antioxidants, antioxidant aids, preservatives, inorganic salts, organic acid salts, sequestering agents, powders, ultraviolet absorbers, moisturizers, extracts, vitamins, colorants, fragrances, and purified water.

[0053] Examples of the oily component include hydrocarbons, waxes, fatty acid esters, triglycerides, fatty acids, higher alcohols, sterols, silicone oils, fluorine-based oils, and derivatives thereof. Specific examples include castor oil, olive oil, avocado oil, palm oil, cacao oil, liquid paraffin, liquid branched paraffin, petrolatum, squalane, hydrogenated polyisobutene, hydrogenated polydecene, lauric acid, myristic acid, palmitic acid, stearic acid, carnauba wax, candelilla wax, beeswax, sunflower wax, polyethylene wax, microcrystalline wax, ceresin wax, paraffin wax, di(caprylic / capric)propanediol, neopentyl glycol dicaprate, oleic acid, sorbitan isopropyl alcohol ... Polyglyceryl-6 Cutacaprylate, Caprylic / Capric Triglyceride, Triethylhexanoin, Butyl Stearate, Ethylhexyl Palmitate, Coco-Caprylate / Caprate, Caprylyl Caprylate / Caprate, Octyldodecyl Myristate, Isopropyl Myristate, Isopropyl Lanolinate, Hexyl Lanolinate, Diisopropyl Adipate, Diisopropyl Sebacate, Isotridecyl Isononanoate, Isononyl Isononanoate, Decaisostearyl Polyglyceryl Tristearate, 2-Octyldodecanol, Diisostearyl Malate, Polyglyceryl-2 Triisostearate, Polyglyceryl-2 Diisostearate, Dipentaerythrityl Pentaisostearate, Dipentaerythrityl Tetraisostearate, Pentaerythrityl Tetraisostearate, Ethylene Glycol Distearate, Trimethylolpropane Triisostearate, Dipentaerythrityl Hexa(hydroxystearate / stearic acid / rosinate), (Ethyl Hexahydroxystearate / hexastearic acid / hexarosinate), Glyceryl xanthate / stearate / adipic acid, oleyl alcohol, dimethylpolysiloxane, methylphenylpolysiloxane, dimethylcyclopolysiloxane, methylhydrogenpolysiloxane, perfluoropolyether, dipentaerythrityl hexahydroxystearate, dipentaerythrityl tetrahydroxystearate / isostearate, dipentaerythrityl tripolyhydroxystearate, mineral oil, cetyl ethylhexanoate, phenyl trimethicone,Isododecane, cholesterol, sterols such as phytosterol, sunflower seed oil fatty acid phytosteryl, rice bran oil fatty acid phytosteryl, macadamia nut fatty acid phytosteryl, oleate, phytosteryl isostearate, myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl), lauroyl glutamate di(octyldodecyl / phytosteryl / behenyl), lauroyl glutamate di(phytosteryl / octyldodecyl), dimer dilinoleate di(isostearyl / phytosteryl), dimer dilinoleyl dimer dilinoleate bis(behenyl / isostearyl / phytosteryl), dimer dilinoleate (phytosteryl / isostearyl / phytosteryl), Examples of oily ingredients include sterol derivatives such as oleic acid, glycerin, glycerin, glycerin (isostearyl / cetyl / stearyl / behenyl), cholesteryl macadamiate, cholesteryl nonanoate, cholesteryl oleate, dihydrocholesteryl oleate, cholesteryl stearate, cholesteryl hydroxystearate, cholesteryl butyrate, dihydrocholesteryl butyrate, cholesteryl hexyldicarbamate pullulan, and cholesteryl lanolinate; silicones such as dimethicone, cyclopentasiloxane, diphenylsiloxyphenyl trimethicone, cyclohexasiloxane, and crosslinked methylpolysiloxane; methyl perfluorobutyl ether, perfluorooctyltriethoxysilane, and perfluoropolymethylisopropyl. These oily ingredients may be used alone or in combination of two or more.

[0054] Examples of the alcohol include methanol, ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol, cetanol (cetyl alcohol, palmityl alcohol), stearyl alcohol (octadecyl alcohol), isostearyl alcohol (isooctadecanol), oleyl alcohol, cetostearyl alcohol, octyldodecanol, decyltetradecanol, hexyldecanol, batyl alcohol, behenyl alcohol, lauryl alcohol, lanolin alcohol, isostearyl alcohol, cetearyl alcohol, hydrogenated rapeseed oil alcohol, and water. and polyhydric alcohols such as propylene glycol (1,2-propanediol), 1,3-propanediol, 1,3-butylene glycol (1,3-butanediol), pentylene glycol (1,2-pentanediol), neopentylene glycol (2,2-dimethyl-1,3-propanediol), isoprene glycol (3-methyl-1,3-butanediol), dipropylene glycol, glycerin, diglycerin, polyglycerin, polyethylene glycol, pentaerythritol, dipentaerythritol, sorbitol, and sorbitan. The above alcohols may be used alone or in combination of two or more.

[0055] Examples of the polymer emulsion include alkyl acrylate copolymer emulsion, alkyl methacrylate polymer emulsion, alkyl acrylate copolymer emulsion, alkyl methacrylate copolymer emulsion, acrylic acid / alkyl acrylate copolymer emulsion, methacrylic acid / alkyl methacrylate copolymer emulsion, alkyl acrylate / styrene copolymer emulsion, alkyl methacrylate / styrene copolymer emulsion, vinyl acetate polymer emulsion, polyvinyl acetate emulsion, vinyl acetate-containing copolymer emulsion, vinylpyrrolidone / styrene copolymer emulsion, silicone-containing copolymer emulsion, etc. The polymer emulsions may be used alone or in combination of two or more.

[0056] The thickener may be a natural water-soluble polymer, a semi-synthetic water-soluble polymer, or a synthetic water-soluble polymer. These thickeners may be used alone or in combination of two or more.

[0057] Examples of natural water-soluble polymers include plant-based polymers such as agar, glucomannan, gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, quince seed (quince), algae colloid (cassow extract), and starch (rice, corn, potato, wheat), microbial polymers such as xanthan gum, dextran, succinoglucan, and pullulan, and animal polymers such as collagen, casein, albumin, and gelatin. The above-mentioned natural water-soluble polymers may be used alone or in combination of two or more.

[0058] Examples of semi-synthetic water-soluble polymers include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, cellulose-based polymers such as methylcellulose, nitrocellulose, methylhydroxypropyl cellulose, sodium cellulose sulfate, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose and cellulose powder, and alginic acid-based polymers such as sodium alginate and propylene glycol alginate. The above-mentioned semi-synthetic water-soluble polymers may be used alone or in combination of two or more.

[0059] Examples of synthetic water-soluble polymers include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, acrylic acid copolymers, and carboxyvinyl polymers, polyoxyethylene polymers such as polyethylene glycol 20,000, 40,000, and 60,000, polyoxyethylene-polyoxypropylene copolymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide, polyethyleneimine, and cationic polymers. The above synthetic water-soluble polymers may be used alone or in combination of two or more.

[0060] The surfactant may be any of anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and natural surfactants, and these surfactants may be used alone or in combination of two or more.

[0061] Examples of the anionic surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene lauryl ether phosphate, etc. The anionic surfactants may be used alone or in combination of two or more.

[0062] Examples of the cationic surfactant include primary, secondary, and tertiary amine salts and quaternary ammonium salts each having an aliphatic hydrocarbon group. The cationic surfactants may be used alone or in combination of two or more.

[0063] Examples of the amphoteric surfactant include sodium β-laurylaminopropionate, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, etc. The amphoteric surfactants may be used alone or in combination of two or more.

[0064] Examples of the nonionic surfactants include monoglycerides, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, alkanolamides, amine oxides, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol mono-fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, alkyl saccharides, α-monoalkylglyceryl ethers, dimethylpolysiloxane-polyoxyalkylene copolymers, dimethylpolysiloxane-monoalkylglyceryl ether copolymers, sorbitan sesquiisostearate, etc. The nonionic surfactants may be used alone or in combination of two or more.

[0065] Examples of the natural surfactants include lecithins such as lecithin, hydrogenated lecithin, hydroxylated lecithin, lysolecithin, and hydrogenated lysolecithin; saponins such as soybean saponin; sphingoglycolipids; and ceramides. Examples of hydrogenated lecithins include hydrogenated soybean phospholipids, hydrogenated rapeseed phospholipids, and hydrogenated egg yolk phospholipids. The natural surfactants may be used alone or in combination of two or more.

[0066] Examples of the pH adjuster include edetic acid, edetate disodium, citric acid, sodium citrate, sodium hydroxide, potassium hydroxide, triethanolamine, etc. The pH adjusters may be used alone or in combination of two or more.

[0067] Examples of the antioxidant include vitamin C and derivatives thereof and salts thereof, tocopherols and derivatives thereof and salts thereof, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc. The antioxidants may be used alone or in combination of two or more.

[0068] Examples of the antioxidant aids include phosphoric acid, citric acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid, etc. The antioxidant aids may be used alone or in combination of two or more.

[0069] Examples of the preservatives include ethylhexylglycerin, phenoxyethanol, methylparaben, ethylparaben, butylparaben, etc. The preservatives may be used alone or in combination of two or more.

[0070] Examples of the inorganic salt include sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, etc. The inorganic salts may be used alone or in combination of two or more.

[0071] Examples of the organic acid salts include citric acid, malic acid, tartaric acid, and salts thereof, ascorbic acid and salts thereof, ascorbic acid derivatives and salts thereof, etc. The organic acid salts may be used alone or in combination of two or more.

[0072] Examples of the sequestering agent include disodium edetate, edetate salts, hydroxyethanediphosphonic acid, etc. The sequestering agents may be used alone or in combination of two or more.

[0073] The powder may be, for example, an extender pigment, a color pigment, or a pearl pigment. The powder may be used alone or in combination of two or more. The content of the powder in the cosmetic of this embodiment relative to the total cosmetic is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and even more preferably 0 to 30% by mass.

[0074] Examples of extender pigments include inorganic pigments such as silicic acid, silicic acid anhydride, 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, and ceramic powder, and composite powders thereof; organic powders such as polyamide, polyester, polypropylene, polystyrene, polyurethane, nylon, silicone resin, vinyl resin, urea resin, phenolic resin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene-styrene copolymer, silk powder, cellulose, Nε-lauroyl-L-lysine, long-chain alkyl phosphate metal salt, N-mono long-chain alkyl acyl basic amino acid, and metal soap, and composite powders thereof; and composite powders of the above-mentioned inorganic powders and organic powders. The particle shape of these powders may be any shape such as spherical, plate-like, needle-like, granular, or irregular.

[0075] Examples of coloring pigments include metal oxides such as titanium oxide, zinc oxide, yellow iron oxide, red iron oxide (iron oxide), black iron oxide, iron blue, ultramarine, chromium oxide, and chromium hydroxide; metal complexes such as manganese violet and cobalt titanate; inorganic pigments such as carbon black; organic pigments such as tar-based dyes and lake pigments; and natural pigments such as carmine.

[0076] As the pearl pigment, there can be used pearl pigments obtained by coating mica, synthetic phlogopite, etc. with a colorant such as titanium oxide, iron oxide, silicon oxide, Prussian blue, chromium oxide, carmine, organic pigments, etc. These powders may be subjected to various surface treatments such as water repellency treatment and water / oil repellency treatment by a conventional method before use.

[0077] Among the above powders, powders having an ultraviolet shielding effect, such as metal oxide powders, can also be used as ultraviolet scattering agents. Metal oxide powders having an ultraviolet shielding effect are not particularly limited, and examples include inorganic white pigments such as titanium oxide, zinc oxide, zirconium oxide, and cerium oxide. Surface-coated inorganic white pigments obtained by coating the surface of these metal oxide powders with aluminum hydroxide, aluminum stearate, zinc palmitate, and other fatty acid soaps, fatty acids such as stearic acid, myristic acid, and palmitic acid, and fatty acid esters such as dextrin palmitate can also be used as ultraviolet scattering agents. Among these, surface-coated inorganic white pigments obtained by coating metal oxide powders such as titanium oxide with aluminum hydroxide and / or fatty acids such as stearic acid are preferred. 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 ultraviolet scattering agents.

[0078] The shape of the metal oxide powder having the UV-shielding effect is not particularly limited, and examples thereof include spherical, needle-like, spindle-like, plate-like, and flaky shapes. The powder may be treated with an inorganic compound such as silica or alumina to reduce its surface activity. Furthermore, it is more preferable for the metal oxide powder to have an average particle size of 10 to 100 nm, since this prevents the powder from appearing white when applied to the skin.

[0079] Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers such as para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, and N,N-dimethyl PABA octyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; amyl salicylate, menthyl salicylate, homomenthyl salicylate, and octyl salicylate; salicylic acid-based ultraviolet absorbers such as octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), cinnamic acid-based ultraviolet absorbers such as 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-di-para-methoxycinnamate; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2 benzophenone-based ultraviolet absorbers such as ',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, and 4-hydroxy-3-carboxybenzophenone;Examples of such an ester include 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, 2,4,6-trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)1,3,5-triazine, and 4-tert-butyl-4'-methoxydibenzoylmethane. Among these, cinnamic acid-based ultraviolet absorbers such as 2-ethylhexyl-p-methoxycinnamate are preferred. The ultraviolet absorbers may be used alone or in combination of two or more. When the cosmetic of this embodiment is a sunscreen cosmetic, the content of the ultraviolet absorber relative to the entire cosmetic is preferably more than 0% by mass and not more than 10% by mass, more preferably more than 0% by mass and not more than 2.0% by mass, and even more preferably more than 0% by mass and not more than 1.0% by mass.

[0080] Examples of the humectants include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, urea, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO)PO adduct, Rosa asiatica extract, Achillea millefolium extract, Melilot extract, raffinose, trehalose, polyoxyethylene methyl glucoside, betaine, etc. The humectants may be used alone or in combination of two or more.

[0081] Examples of the extract include plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, tomato, apple, lemon, lavender, rose, etc. The extracts may be used alone or in combination of two or more.

[0082] Examples of the vitamins include vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin E, vitamin K and derivatives thereof, pantothenic acid and derivatives thereof, biotin, etc. The vitamins may be used alone or in combination of two or more.

[0083] Examples of the pigment include chlorophyll, β-carotene, etc. The pigment may be used alone or in combination of two or more kinds.

[0084] Examples of the fragrance include plant-derived fragrances such as rose oil, jasmine oil, and lavender oil, and synthetic fragrances such as limonene, citral, linalool, and eugenol. The fragrances may be used alone or in combination of two or more.

[0085] The cosmetic of this embodiment preferably contains one or more selected from the group consisting of the ultraviolet scattering agent (metal oxide powder) and the ultraviolet absorber. The cosmetic of this embodiment preferably contains one or more ultraviolet scattering agents, and may contain one or more ultraviolet scattering agents and one or more ultraviolet absorbers, or may contain one or more ultraviolet absorbers but no ultraviolet scattering agents.

[0086] The present invention will be described in more detail below with reference to examples. It goes without saying that the scope of the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass or % by mass unless otherwise specified.

[0087] In the following experiments, the acid value and hydroxyl value of the esterification reaction products were measured in accordance with the Standards for Quasi-drug Ingredients 2021.

[0088] <Measurement of Weight Average Molecular Weight (Mw) and Dispersity (Mw / Mn)> In the following experiments, the Mw and dispersity of the esterification reaction product were measured using an ACQUITY Advanced Polymer Chromatography (APC) system (manufactured by Nihon Waters Co., Ltd.). Specifically, the measurements were performed by the following method.

[0089] (Measurement conditions) Measurement and analysis software: Empower3 (manufactured by Nihon Waters) Detector: RI Refractive index unit full scale: 500 μRIU Column (first stage): ACQUITY APC XT200 (4.6 × 150 mm) Column (second stage): ACQUITY APC XT45 (4.6 × 150 mm) Column (third stage): ACQUITY APC XT45 (4.6 × 150 mm) Solvent: tetrahydrofuran (THF) Flow rate: 0.6 mL / min Concentration: 0.5 mg / mL Column temperature: 40°C Injection volume: 20 μL

[0090] <SPF Measurement> In the following experiments, the SPF of the sunscreen cosmetics was measured using an SPF analyzer (product name "UV-2000S", manufactured by Lacsphere). The SPF analyzer is a measuring device 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.

[0091] The test samples were each placed in the form of a small spot on a separate PMMA plate (product name "HELIOPLATE HD6", manufactured by HelioscreenLab, plate size: 5 cm x 5 cm). At this time, the test sample was placed so that 30.0 ± 0.2 mg of the test sample was placed per plate. Next, an appropriate amount of the test sample on the plate was rubbed onto a finger wearing a finger cot to remove excess bulk, and then quickly and evenly spread over the entire plate with light pressure. After application, the plate was left to stand at room temperature in a dark place for 30 minutes. Thereafter, the SPF values ​​of nine spots on the plate were measured using an SPF analyzer, and the average value was taken as the SPF value of the test sample applied to the plate.

[0092] [SPF Value Evaluation Criteria] A: SPF value is 40 or more. B: SPF value is 25 or more and less than 40. C: SPF value is 15 or more and less than 25. D: SPF value is less than 15. When a product was rated A or B according to the above evaluation criteria, it was determined that the sunscreen cosmetic had excellent UV protection effect.

[0093] <Water Resistance Evaluation> In the following experiments, the water resistance of sunscreen cosmetics was measured by the following method. A PMMA plate, on whose surface a test sample had been applied in the same manner as in the SPF measurement described above, was fixed to a 200 mL metal mug and placed in a thermostatic water bath adjusted to 29 to 31°C. Next, a propeller-type stirring blade attached to a Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) was placed in the metal mug, and the stirring blade was rotated at a rotation speed of 100 rpm to generate a water flow, and the test was held for 80 minutes to conduct a water flow load test (water resistance test). After the test, the plate was gently removed from the metal mug and allowed to stand at room temperature in a dark place for 30 minutes. The SPF value of the plate was then measured using an SPF analyzer in the same manner as described above.

[0094] The percentage of the SPF value after the water resistance test that corresponded to the SPF value before the water resistance test was calculated, and this value was taken as the residual rate ([SPF value after the water resistance test] / [SPF value before the water resistance test]×100%).

[0095] [Evaluation criteria for water resistance] A: Residual rate is 70% or more. B: Residual rate is 60% or more and less than 70%. C: Residual rate is 50% or more and less than 60%. D: Residual rate is less than 50%. When a sunscreen cosmetic was rated A or B according to the above evaluation criteria, it was determined that the sunscreen cosmetic had excellent water resistance.

[0096] <Adhesion Evaluation> In the following experiments, the adhesion of the sunscreen cosmetics was measured using the following method. Four expert panelists performed a sensory evaluation of the adhesion on the skin. A soybean-sized amount of the sunscreen cosmetics was placed on the back of the hand, spread with the index finger, and then the finger was moved perpendicular to the applied area to perform a sensory evaluation based on the following three-level rating system. The panelists' evaluation scores were calculated to evaluate the adhesion of each sunscreen cosmetic.

[0097] [Evaluation criteria for each panelist] 3 points: Good adhesion 2 points: Slight adhesion 1 point: No adhesion

[0098] [Evaluation criteria for adhesion of sunscreen cosmetics] A: Adhesion is 12 to 11 points. B: Adhesion is 10 to 9 points. C: Adhesion is 8 to 7 points. D: Adhesion is 6 to 4 points. When a sunscreen cosmetic was rated A or B according to the above evaluation criteria, it was determined that the sunscreen cosmetic had excellent adhesion effect.

[0099] <Evaluation of Ease of Spreading> In the following experiments, the ease of spreading of sunscreen cosmetics was measured using the following method. Four expert panelists conducted a sensory evaluation of the ease of spreading on the skin. A soybean-sized amount of sunscreen cosmetics was placed on the back of the hand, and the sunscreen cosmetics were spread horizontally with the index finger. The sensory evaluation was based on the resistance and slipperiness felt when the sunscreen cosmetics were spread horizontally using the index finger, and rated on a three-point scale as follows. The evaluation scores of each panelist were calculated to evaluate the ease of spreading of each sunscreen cosmetic.

[0100] [Evaluation criteria for each panelist] 3 points: Easy to spread. 2 points: Somewhat easy to spread. 1 point: Difficult to spread.

[0101] [Evaluation criteria for ease of spreading of sunscreen cosmetics] A: Ease of spreading is 12 to 11 points. B: Ease of spreading is 10 to 9 points. C: Ease of spreading is 8 to 7 points. D: Ease of spreading is 6 to 4 points. When a sunscreen cosmetic was rated A or B according to the above evaluation criteria, it was determined that the sunscreen cosmetic had excellent ease of spreading.

[0102] Examples 1 and 6: 12-hydroxystearic acid polymers having an average degree of polymerization of 5.0 to 7.0 were obtained by polymerization of 12-hydroxystearic acid, and then 1.5 to 2.0 mol of the 12-hydroxystearic acid polymer was added to 1.0 mol of diglycerin for esterification to synthesize esterification reaction products with different weight-average molecular weights and polydispersities. The SPF and water resistance of O / W sunscreen cosmetics containing these polymers, and the SPF, water resistance, adhesion, and spreadability of W / O sunscreen cosmetics were evaluated.

[0103] Comparative Examples 1 and 4: 12-hydroxystearic acid polymers having an average degree of polymerization of 3.0 or more and less than 4.0 were obtained by polymerization of 12-hydroxystearic acid, and then esterification was performed by adding 2.0 to 2.4 mol of the 12-hydroxystearic acid polymer to 1.0 mol of diglycerin to synthesize esterification reaction products with different weight-average molecular weights and polydispersities. The SPF and water resistance of O / W sunscreen cosmetics containing these polymers, and the SPF, water resistance, adhesion, and spreadability of W / O sunscreen cosmetics were evaluated.

[0104] Comparative Examples 2 and 3: 12-hydroxystearic acid polymers having an average degree of polymerization of more than 10.0 and not more than 12.0 were obtained by polymerization of 12-hydroxystearic acid, and then esterification was performed by adding 1.5 to 2.0 mol of the 12-hydroxystearic acid polymer to 1.0 mol of diglycerin to synthesize esterification reaction products with different weight-average molecular weights and polydispersities. The SPF and water resistance of O / W sunscreen cosmetics containing these polymers, and the SPF, water resistance, adhesion, and spreadability of W / O sunscreen cosmetics were evaluated.

[0105] Examples 2 to 5 Esterification reaction products obtained by a two-step reaction consisting of a polymerization step of 12-hydroxystearic acid and a esterification step with diglycerin were mixed to obtain two esterification reaction products having different weight-average molecular weights and / or dispersities, thereby obtaining esterification reaction products having weight-average molecular weights in the range of 6,500 to 9,000 and dispersities in the range of 1.40 to 1.65. The SPF and water resistance of O / W sunscreen cosmetics containing these products, and the SPF, water resistance, adhesion, and spreadability of W / O sunscreen cosmetics were evaluated.

[0106] Comparative Example 5 An esterification reaction product was synthesized by esterifying 12-hydroxystearic acid alone with diglycerin without carrying out a polymerization reaction of 12-hydroxystearic acid, using the same amounts of 12-hydroxystearic acid and diglycerin as used in the synthesis of the esterification reaction product in Example 1 (one-step reaction). The SPF and water resistance of an O / W sunscreen cosmetic containing this, as well as the SPF, water resistance, adhesion, and spreadability of a W / O sunscreen cosmetic containing this were evaluated.

[0107] (1) Synthesis of Esterification Reaction Product [Example 1 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and water remover was charged with 12-hydroxystearic acid (trade name: 12-hydroxystearic acid, manufactured by Kokura Synthetic Industries, Ltd.), and an appropriate amount of catalyst and organic solvent were added. A reaction was conducted at 210°C under a nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid charged and the reaction time were adjusted so that the average degree of polymerization, calculated from the acid value, was within the desired range (average degree of polymerization: 5.0 to 7.0). The acid value of the resulting 12-hydroxystearic acid polymer was 33 mgKOH / g.

[0108] Next, 2.0 mol of the 12-hydroxystearic acid polymer prepared as described above and 1.0 mol of diglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name "Diglycerin 801") were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 2.0 mol per 1.0 mol of diglycerin). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization treatment. The resulting esterification reaction product had a weight-average molecular weight of 7,800, a polydispersity of 1.45, an acid value of 1.0 mgKOH / g, and a hydroxyl value of 34.6 mgKOH / g.

[0109] (2) Synthesis of Esterification Reaction Product [Example 6 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet, and water remover was charged with the 12-hydroxystearic acid used in Example 1, and an appropriate amount of catalyst and organic solvent were added. A reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid charged and the reaction time were adjusted so that the average degree of polymerization, calculated from the acid value, was within the range of 5.0 to 7.0. The acid value of the resulting 12-hydroxystearic acid polymer was 33 mgKOH / g.

[0110] Next, 1.5 mol of the 12-hydroxystearic acid polymer obtained as described above and 1.0 mol of the diglycerol used in Example 1 were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 1.5 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization. The resulting esterification reaction product had a weight-average molecular weight of 6,800, a polydispersity of 1.52, an acid value of 1.0 mgKOH / g, and a hydroxyl value of 52.2 mgKOH / g.

[0111] (3) Synthesis of Esterification Reaction Product [Comparative Example 1 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and water remover was charged with the 12-hydroxystearic acid used in Example 1, and an appropriate amount of catalyst and organic solvent were added. A reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid charged and the reaction time were adjusted so that the average degree of polymerization, calculated from the acid value, might be 3.0 or more and less than 4.0. The acid value of the resulting 12-hydroxystearic acid polymer was 65 mgKOH / g.

[0112] Next, 2.0 mol of the 12-hydroxystearic acid polymer prepared as described above and 1.0 mol of the diglycerol used in Example 1 were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 2.0 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization. The resulting esterification reaction product had a weight-average molecular weight of 4,500, a polydispersity of 1.48, an acid value of 0.5 mgKOH / g, and a hydroxyl value of 90.8 mgKOH / g.

[0113] (4) Synthesis of Esterification Reaction Product [Comparative Example 2 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and water remover was charged with the 12-hydroxystearic acid used in Example 1, and an appropriate amount of catalyst and organic solvent were added. A reaction was conducted at 210°C under a nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid charged and the reaction time were adjusted so that the average degree of polymerization, calculated from the acid value, might be more than 10.0 and 12.0 or less. The acid value of the resulting 12-hydroxystearic acid polymer was 17 mgKOH / g.

[0114] Next, 2.0 mol of the 12-hydroxystearic acid polymer prepared as described above and 1.0 mol of the diglycerol used in Example 1 were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 2.0 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization. The resulting esterification reaction product had a weight-average molecular weight of 12,000, a polydispersity of 1.37, an acid value of 1.5 mgKOH / g, and a hydroxyl value of 20.7 mgKOH / g.

[0115] (5) Synthesis of Esterification Reaction Product [Comparative Example 3 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and water remover was charged with the 12-hydroxystearic acid used in Example 1, and an appropriate amount of catalyst and organic solvent were added. A reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the amount of 12-hydroxystearic acid charged and the reaction time were adjusted so that the average degree of polymerization, calculated from the acid value, might be more than 10.0 and 12.0 or less. The acid value of the resulting 12-hydroxystearic acid polymer was 17 mgKOH / g.

[0116] Next, 1.5 mol of the 12-hydroxystearic acid polymer obtained as described above and 1.0 mol of the diglycerol used in Example 1 were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 1.5 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization. The resulting esterification reaction product had a weight-average molecular weight of 11,000, a polydispersity of 1.40, an acid value of 0.5 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g.

[0117] (6) Synthesis of Esterification Reaction Product [Comparative Example 4 (Two-Step Reaction)] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, and water remover was charged with the 12-hydroxystearic acid used in Example 1, and an appropriate amount of catalyst and organic solvent were added. A reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give a 12-hydroxystearic acid polymer. The acid value of the reaction product was measured over time, and the charged amount of 12-hydroxystearic acid and the reaction time were adjusted so that the average degree of polymerization calculated from the acid value might be 3.0 or more and less than 4.0. The acid value of the resulting 12-hydroxystearic acid polymer was 65 mgKOH / g.

[0118] Next, 2.4 mol of the 12-hydroxystearic acid polymer prepared as described above and 1.0 mol of the diglycerol used in Example 1 were placed in a 1-L four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a water remover, and a reaction was carried out at 210°C under nitrogen gas flow with removing generated water to give an esterification reaction product (the charged amount of 12-hydroxystearic acid polymer was 2.4 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption treatment, filtration, and deodorization. The resulting esterification reaction product had a weight-average molecular weight of 4900, a polydispersity of 1.35, an acid value of 0.9 mgKOH / g, and a hydroxyl value of 75.4 mgKOH / g.

[0119] (7) Production of Esterification Products [Examples 2 to 5 (Mixing of Two-Step Reaction Products)] Esterification products of diglycerin and 12-hydroxystearic acid polymers having weight-average molecular weights of 6,500 to 9,000 and dispersities of 1.40 to 1.65 were produced by mixing two of the esterification reaction products obtained in Examples 1 and 6 and Comparative Examples 1 to 4. Specifically, the esterification reaction product of Example 2 was produced by mixing the esterification reaction product of Example 1 and the esterification reaction product of Example 6 in a mass ratio of 5:5. Similarly, the esterification reaction products of Examples 3 to 5 were produced by mixing two esterification reaction products in the mass ratios shown in Table 1. The weight-average molecular weights (Mw), dispersities, acid values ​​(mg KOH / g), and hydroxyl values ​​(mg KOH / g) of the obtained esterification reaction products of Examples 2 to 5 are shown in Table 1.

[0120]

[0121] (8) Synthesis of Esterification Reaction Product [Comparative Example 5] A 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet, and water separator was charged with 12.0 mol of the 12-hydroxystearic acid used in Example 1 and 1.0 mol of diglycerin. An appropriate amount of catalyst and organic solvent were then added, and the mixture was reacted at 210°C under a nitrogen stream while removing the generated water to produce an esterification reaction product (the amount of 12-hydroxystearic acid charged was 12.0 mol per 1.0 mol of diglycerin). The resulting esterification reaction product was purified by adsorption treatment, filtration treatment, and deodorization treatment. The resulting esterification reaction product had a weight-average molecular weight of 6,100, a polydispersity of 1.30, an acid value of 0.8 mgKOH / g, and a hydroxyl value of 38.0 mgKOH / g.

[0122] The reaction here is a reaction carried out in one step in which the polymerization reaction of 12-hydroxystearic acid is not carried out, but rather the polymerization reaction of 12-hydroxystearic acid is also carried out when the esterification reaction of 12-hydroxystearin with diglycerin is carried out, and is hereinafter referred to as a "one-step reaction."

[0123] Furthermore, commercially available polyglyceryl-2 dipolyhydroxystearate (product name "Dehymuls PGPH", manufactured by BASF) was used as Comparative Example 6, and its weight-average molecular weight, dispersity, acid value (mg KOH / g), and hydroxyl value (mg KOH / g) were measured. Dehymuls PGPH is a W / O type emulsifier with an HLB of 5.0. In addition, commercially available dipentaerythrityl tri-polyhydroxystearate was used as Comparative Example 7, and its weight-average molecular weight, dispersity, acid value (mg KOH / g), and hydroxyl value (mg KOH / g) were measured. Commercially available dipentaerythrityl tri-polyhydroxystearate is dipentaerythritol whose alcohol skeleton is made from a non-vegetable raw material.

[0124] (2) Production of O / W Sunscreen Cosmetics Using the esterification reaction products of Examples 1 to 6 and Comparative Examples 1 to 7, O / W sunscreen cosmetics were produced according to the formulations shown in Table 2. Specifically, first, the oily component and the UV absorber were mixed uniformly to prepare mixture A. Separately, all remaining components were mixed uniformly to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as a sunscreen cosmetic. In the tables of this specification, "%" indicates "% by mass," and "% aq" indicates the content (% by mass) in the aqueous solution.

[0125]

[0126] Isotridecyl isononanoate: Product name "Salacos 913", manufactured by The Nisshin Oillio Group, Ltd. Dimethicone: Product name "KF-96A-10CS", manufactured by Shin-Etsu Chemical Co., Ltd. Ethylhexyl methoxycinnamate (2-ethylhexyl-p-methoxycinnamate): Product name "Nomcoat TAB", manufactured by The Nisshin Oillio Group, Ltd. Fine particle titanium dioxide (treated with stearic acid): Product name "MT-500CST", manufactured by Teika Corporation (Acrylates / alkyl acrylate (C10-30)) crosspolymer (2% aq.): Product name "Pemulen TR-1", manufactured by Lubrizol Co., Ltd. Xanthan gum: Product name "Nomcoat ZZ", manufactured by The Nisshin Oillio Group, Ltd. Glyceryl stearate: Product name "Lasemul 92 AE", manufactured by IQL Corporation

[0127] (3) Evaluation of SPF Value and Water Resistance of Each Sunscreen Cosmetic The SPF value and water resistance of each O / W sunscreen cosmetic were examined. The evaluation results are shown in Tables 3 to 5, along with the weight-average molecular weight (Mw), dispersity, acid value (mg KOH / g), and hydroxyl value (mg KOH / g) of the esterification reaction products used as raw materials.

[0128]

[0129]

[0130]

[0131] As shown in Table 4, the sunscreen cosmetic (Comparative Example 6) made from commercially available polyglyceryl-2 dipolyhydroxystearate used as an emulsifier had a high initial SPF value but insufficient water resistance. O / W sunscreen cosmetics (Comparative Examples 1 and 4) made from esterification reaction products with slightly higher weight-average molecular weights than those of Comparative Example 6 also had poor water resistance, and a tendency for the SPF to decrease as the weight-average molecular weight increased was observed. O / W sunscreen cosmetics (Comparative Examples 2 and 3) made from esterification reaction products with significantly higher weight-average molecular weights also had poor water resistance. On the other hand, the O / W sunscreen cosmetics (Examples 1 to 6) made from esterification reaction products with weight-average molecular weights in the range of 6,500 to 9,000 and dispersities in the range of 1.40 to 1.65 all had sufficiently high initial SPF values ​​and excellent water resistance. The oil-in-water sunscreen cosmetic (Comparative Example 7) made from commercially available dipentaerythrityl tripolyhydroxystearate as a raw material also had a sufficiently high initial SPF value and excellent water resistance.

[0132] As shown in Table 5, the O / W sunscreen cosmetic preparation (Comparative Example 5) which used an esterification reaction product obtained in a one-step reaction by polymerizing 12-hydroxystearic acid using the same amounts of 12-hydroxystearic acid and diglycerol showed lower weight-average molecular weight and polydispersity, and a change in molecular weight distribution, compared to the O / W sunscreen cosmetic preparation (Example 1) which used an esterification reaction product obtained in a two-step reaction by polymerizing 12-hydroxystearic acid. Furthermore, the initial SPF value and water resistance were also low.

[0133] (4) Production of W / O-Type Sunscreen Cosmetics Using the esterification reaction products of Examples 1 to 6 and Comparative Examples 1 to 7, O / W-type sunscreen cosmetics were produced according to the formulations shown in Table 6. Specifically, first, the oily component and the ultraviolet absorber were mixed uniformly to prepare mixture A. Separately, all of the remaining components were mixed uniformly to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as a sunscreen cosmetic.

[0134]

[0135] Mineral oil: product name "CARNATION", manufactured by Shima Trading Co., Ltd. Ethylhexyl methoxycinnamate (2-ethylhexyl-p-methoxycinnamate): product name "Nomcoat TAB", manufactured by Nisshin Oillio Group Co., Ltd. Fine particle titanium dioxide (treated with aluminum hydroxide and stearic acid): product name "MT-100TV", manufactured by Teika Co., Ltd. Cetyl PEG / PPG-10 / 1 dimethicone: product name "ABIL EM 90", manufactured by Evonik Operations GmbH

[0136] 3) Evaluation of SPF value and water resistance of each sunscreen cosmetic Each W / O type sunscreen cosmetic was examined for SPF value, water resistance, adhesion, and ease of spread. The evaluation results, including the weight-average molecular weight (Mw), dispersity, acid value (mg KOH / g), and hydroxyl value (mg KOH / g) of the esterification reaction products used as raw materials, are shown in Tables 7 and 8.

[0137]

[0138]

[0139] As shown in Table 7, the W / O type sunscreen cosmetic (Comparative Example 6) made from commercially available polyglyceryl-2 dipolyhydroxystearate used as an emulsifier had a high initial SPF value but insufficient water resistance. The sunscreen cosmetics (Comparative Examples 1, 4, and 5) made from esterification reaction products with slightly higher weight-average molecular weights and lower dispersities than those of Comparative Example 6 had improved water resistance but lower initial SPF values. The sunscreen cosmetics (Comparative Examples 2 and 3) made from esterification reaction products with significantly higher weight-average molecular weights had improved water resistance. However, the W / O type sunscreen cosmetics of Comparative Examples 1 to 6 did not have good adhesion to the skin or good spreadability. On the other hand, the W / O type sunscreen cosmetics (Examples 1 to 6) made from esterification reaction products with weight-average molecular weights in the range of 6,500 to 9,000 and dispersities in the range of 1.40 to 1.65 all had sufficiently high initial SPF values ​​and excellent water resistance. In addition, the adhesiveness to the skin and ease of spreading were also good. The W / O type sunscreen cosmetic (Comparative Example 7) made from commercially available dipentaerythrityl tripolyhydroxystearate as a raw material had very high initial SPF value, water resistance, and adhesiveness, but was not easy to spread.

[0140] Next, makeup, skin care, and hair care cosmetics were prepared and each was evaluated. The evaluation was carried out by sensory evaluation. The sensory evaluation method is as follows. Sensory evaluation of cosmetics: Ten sensory evaluation panelists used each cosmetic and assigned scores for each evaluation item according to the following evaluation criteria for spreadability (whether the cosmetic spreads smoothly on the application site such as the skin), film-forming properties (whether there is a film-forming feel after use), adhesion (whether there is a feeling of adhesion after use), durability (whether the makeup is maintained against sebum, sweat, rubbing, etc.), makeup compatibility (whether it is easy to adapt to makeup stains), and manageability (whether the hair is manageable after use of the hair cosmetic). Evaluation criteria: 6 points: very good. 5 points: good. 4 points: fairly good. 3 points: average. 2 points: somewhat poor. 1 point: poor. 0 point: very poor.

[0141] In addition, the average scores of the 10 sensory evaluation panelists were calculated, and the values ​​were evaluated according to the following evaluation criteria: 5 points or more: A - Very excellent; 3 points or more but less than 5 points: B - Excellent; 1 point or more but less than 3 points: C - Neither good nor bad; Less than 1 point: D - Poor. When a cosmetic was rated A or B according to the above evaluation criteria, it was determined that the cosmetic had excellent effects in each evaluation item.

[0142] (5) Production of Stick-Type Lipstick Cosmetics Stick-type lipstick cosmetics were produced using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6 according to the formulations shown in Table 9. All figures in the table represent mass %. A pigment was added to a portion of the oil component (B) and treated with a roller to prepare a pigment base. All components and the pigment base were then heated and dissolved, and then uniformly dispersed using a homomixer. The dispersion was poured into a mold and rapidly cooled to obtain stick-type lipsticks. The results of sensory evaluation of each lipstick are shown in Table 10.

[0143]

[0144]

[0145] As shown in Table 10, the stick-type 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-type lipstick cosmetics made from the esterification reaction products of Comparative Examples 3 to 6 did not show good results in terms of spreadability, adhesion, or durability.

[0146] (6) Production of W / O Cream Foundation Using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, W / O cream foundations were produced according to the formulations shown in Table 11. All figures in the table represent mass %. Oil component (A), alcohol (A), UV absorber, surfactant, preservative (A), and pigment were heated and mixed at 40°C to obtain mixture (A). Meanwhile, alcohol (B), preservative (B), stabilizer, moisturizing component, and water were mixed at room temperature to obtain mixture (B). While heating and stirring mixture (A) at 50°C, mixture (B) was slowly added dropwise, and the mixture was uniformly dispersed using a homomixer and cooled to room temperature to obtain a W / O cream foundation. The results of sensory evaluation of each foundation are shown in Table 12.

[0147]

[0148]

[0149] As shown in Table 12, the W / O cream foundations made from the esterification reaction products of Examples 1 and 6 exhibited favorable results in terms of spreadability, film-forming ability, and durability. On the other hand, the W / O cream foundations made from the esterification reaction products of Comparative Examples 3 to 6 did not exhibit favorable results in terms of spreadability, film-forming ability, or durability.

[0150] (7) Production of O / W Liquid Foundation Using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, O / W liquid foundations were produced according to the formulations shown in Table 13. All figures in the table represent mass %. Oil component (A) and alcohol (A) were heated and mixed at 80°C to obtain mixture (A). Meanwhile, oil component (B) and pigment were heated and mixed at 80°C to obtain mixture (B). A water-based thickener, alcohol (B), pH adjuster, preservative, and water were mixed at room temperature to obtain mixture (C). While heating and stirring mixture (A) at 80°C, mixture (B) was added, and the mixture was uniformly dispersed using a homomixer. Mixture (C) was then added in small portions and uniformly dispersed using a homomixer. The dispersions were cooled to room temperature to obtain O / W liquid foundations. The results of sensory evaluation of each of the foundations are shown in Table 14.

[0151]

[0152]

[0153] As shown in Table 14, the O / W liquid foundations made from the esterification reaction products of Examples 1 and 6 exhibited favorable results in terms of spreadability, film-forming ability, 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 exhibit favorable results in any of the spreadability, film-forming ability, and durability.

[0154] (8) Production of Solid Powder Foundation Solid powder foundations were produced according to the formulations shown in Table 15 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, respectively. All numbers in the table represent mass %. Oil component (A) was heated and mixed at 50°C to obtain mixture (A). Separately, oil component (B) and powder component were mixed and dispersed, and the mixture (A) was added and mixed to obtain mixture (B). The obtained mixture (B) was pulverized and compression-molded into a dish to obtain solid powder foundations. The results of sensory evaluation of each foundation are shown in Table 16.

[0155]

[0156]

[0157] As shown in Table 16, the solid powder foundations made from the esterification reaction products of Examples 1 and 6 exhibited favorable results in terms of spreadability, adhesion, and durability. On the other hand, the solid powder foundations made from the esterification reaction products of Comparative Examples 3 to 6 did not exhibit favorable results in terms of spreadability, adhesion, or durability.

[0158] (9) Production of Emulsions Emulsions were produced according to the formulations shown in Table 17 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, respectively. All numbers in the table represent mass %. The oily components were heated and mixed at 80°C to obtain mixture (A). Meanwhile, the remaining raw materials were heated to 80°C, and mixture (A) was gradually added thereto and mixed, followed by cooling to room temperature to obtain emulsions. The results of sensory evaluation of each emulsion are shown in Table 18.

[0159]

[0160]

[0161] As shown in Table 18, the emulsions made from the esterification reaction products of Examples 1 and 6 exhibited favorable results in terms of spreadability and film-forming properties. On the other hand, the emulsions made from the esterification reaction products of Comparative Examples 3 to 6 did not exhibit favorable results in terms of either spreadability or film-forming properties.

[0162] (10) Production of Cleansing Cream Using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, cleansing creams were produced according to the formulations shown in Table 19. All numbers in the table represent 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, and this was gradually added to and mixed with mixture (A), followed by cooling to room temperature to obtain cleansing creams. The results of sensory evaluation of each cleansing cream are shown in Table 20.

[0163]

[0164]

[0165] As shown in Table 20, the cleansing creams made from the esterification reaction products of Examples 1 and 6 showed good results in terms of makeup blending and spreadability. On the other hand, the cleansing creams made from the esterification reaction products of Comparative Examples 3 to 6 did not show good results in terms of makeup blending and spreadability.

[0166] (11) Production of Cleansing Oils Cleansing oils were produced using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6 according to the formulations shown in Table 21. All figures in the table represent mass %. The oily component and surfactant were heated and mixed at 80°C and then cooled to room temperature to obtain cleansing oils. The results of sensory evaluation of each cleansing oil are shown in Table 22.

[0167]

[0168]

[0169] As shown in Table 22, the cleansing oils made from the esterification reaction products of Examples 1 and 6 showed good results in terms of makeup blendability and spreadability. On the other hand, the cleansing oils made from the esterification reaction products of Comparative Examples 3 to 6 did not show good results in either terms of makeup blendability or spreadability.

[0170] (12) Production of Conditioner (Hair Cosmetic) Conditioners were produced according to the formulations shown in Table 23 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, respectively. All numbers in the table represent mass %. The oily component and alcohol (A) were heated and mixed at 80°C to obtain mixture (A). Meanwhile, the remaining raw materials were heated and mixed at 80°C, and the mixture (A) was gradually added and mixed thereto, followed by cooling to room temperature to obtain conditioners. The results of sensory evaluation of each conditioner are shown in Table 24.

[0171]

[0172]

[0173] As shown in Table 24, the conditioners made from the esterification reaction products of Examples 1 and 6 exhibited favorable results in terms of film-forming ability and manageability. On the other hand, the conditioners made from the esterification reaction products of Comparative Examples 3 to 6 did not exhibit favorable results in terms of either film-forming ability or manageability.

[0174] (13) Production of Hair Oil (Hair Cosmetic) Hair oils were produced according to the formulations shown in Table 25 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6. All numbers in the table represent mass %. The oily components were mixed at room temperature to obtain hair oils. The results of sensory evaluation of each product are shown in Table 26.

[0175]

[0176]

[0177] As shown in Table 26, the hair oils made from the esterification reaction products of Examples 1 and 6 showed good results in terms of spreadability and manageability. On the other hand, the hair oils made from the esterification reaction products of Comparative Examples 3 to 6 did not show good results in terms of spreadability or manageability.

[0178] (14) Measurement of Water Holding Capacity The esterification reaction products of Examples 1 and 6 were ester compounds of 12-hydroxystearic acid polymer and polyhydric alcohol, and had excellent water holding capacity. They were compared with commercially available products such as dipentaerythrityl tri-polyhydroxystearate (Comparative Example 7), lanolin, and cholesteryl hydroxystearate.

[0179] The water holding capacity test was carried out as follows, with reference to the lanolin water content measurement method of the British Pharmacopoeia (BP). 1 g of the test sample and 9 g of petrolatum were mixed and vigorously stirred (200-300 rpm) in a constant temperature bath at 40°C while adding purified water dropwise. The end point was the point at which all the water could be added, and the end point was expressed as a percentage of the mass of water relative to the mass of the mixed sample. The higher this value, the higher the water holding capacity of the sample. The results of the water holding capacity test are shown in Table 27.

[0180]

[0181] As shown in Table 27, the esterification reaction products of Examples 1 and 6 showed good water holding ability even when compared with dipentaerythrityl tri-polyhydroxystearate (Comparative Example 7), lanolin, and cholesteryl hydroxystearate, which are known to have high water holding ability.

[0182] The present invention can provide an esterification reaction product that has good adhesion to skin, good spreadability, water resistance, powder dispersibility, film-forming properties, and water holding property, a cosmetic containing the esterification reaction product, and a method for producing the esterification reaction product.

Claims

1. An esterification reaction product obtained by esterifying diglycerin and 12-hydroxystearic acid polymer, wherein the esterification reaction product has a weight-average molecular weight of 6,500 to 9,000 and a polydispersity of 1.40 to 1.

65.

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

0.

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

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

5. The esterification reaction product comprises a first esterification reaction product and one of a second esterification reaction product and a third esterification reaction product, wherein the first esterification reaction product is obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 and has a weight-average molecular weight of 6,500 to 9,000 and a dispersity of 1.40 to 1.65, and the second esterification reaction product is obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 and has a weight-average molecular weight of 4,000 to 6,000 and a dispersity of 1.35 to 1.

50.

5. The esterification reaction product according to claim 4, wherein the third esterification reaction product is obtained by esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and not more than 12.0, and has a weight-average molecular weight of 10,000 to 13,000 and a polydispersity of 1.35 to 1.

50.

6. The esterification reaction product according to claim 5, wherein the first esterification reaction product is obtained by esterifying 1.5 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 with 1.0 mol of diglycerol; the second esterification reaction product is obtained by esterifying 2.0 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mol of diglycerol; and the third esterification reaction product is obtained by esterifying 1.5 to 2.0 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with 1.0 mol of diglycerol.

7. The esterification reaction product according to claim 4, wherein the esterification reaction product comprises a second esterification reaction product and a third esterification reaction product; the second esterification reaction product is obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0, and has a weight-average molecular weight of 4,000 to 6,000 and a polydispersity of 1.35 to 1.50; and the third esterification reaction product is obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less, and has a weight-average molecular weight of 10,000 to 13,000 and a polydispersity of 1.35 to 1.

50.

8. The esterification reaction product according to claim 7, wherein the second esterification reaction product is obtained by esterifying 2.0 to 2.4 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or more and less than 4.0 with 1.0 mol of diglycerol, and the third esterification reaction product is obtained by esterifying 1.5 to 2.0 mol of a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and 12.0 or less with 1.0 mol of diglycerol.

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

10. The cosmetic preparation according to claim 9, further comprising one or more members selected from the group consisting of ultraviolet scattering agents and ultraviolet absorbing agents.

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

12. The cosmetic according to claim 9, which is an emulsion cosmetic.

13. A method for producing an esterification reaction product, comprising esterifying diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0 to produce an esterification reaction product having a weight-average molecular weight of 6,500 to 9,000 and a polydispersity of 1.40 to 1.

65.

14. The method for producing an esterification reaction product according to claim 13, comprising heating 12-hydroxystearic acid to 100°C to 250°C and reacting while removing water to obtain 12-hydroxystearic acid polymers having an average degree of polymerization of 4.0 to 10.0, and then esterifying the 12-hydroxystearic acid polymers with diglycerin.

15. A cosmetic water resistance improver comprising the esterification reaction product according to any one of claims 1 to 8.

16. An adhesion improver for cosmetics, comprising the esterification reaction product according to any one of claims 1 to 8.

17. A cosmetic film-forming improver comprising the esterification reaction product according to any one of claims 1 to 8.

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

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