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

Abstract

The esterification reaction product is obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer, and has a weight-average molecular weight of 6,500 to 9,000 and a polydispersity of 1.40 to 1.65. A cosmetic contains the esterification reaction product. The esterification reaction product is produced by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0.

Description

[Technical Field]

[0001] The present invention relates to an esterification reaction product. In particular, the present invention relates to an esterification reaction product that exhibits both good adhesion to skin and good spreadability, and is also excellent in 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. [Background technology]

[0002] The oils used in cosmetics such as sunscreen cosmetics (sunscreen cosmetics), skin care cosmetics, hair care cosmetics, and makeup cosmetics must have excellent moisturizing properties, adhesion to the skin, powder dispersibility, water resistance, and oxidation stability, as well as a pleasant feel and low skin irritation. In addition to these functions, with recent interest in environmental considerations, there is a demand for plant-derived oils derived 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 made from plant-derived materials include polyricinoleic acid 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 polyricinoleic acid esters have excellent emulsifying properties and are primarily used as emulsifiers and dispersants (Patent Documents 1 to 5), but suffer from 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 tetrabehenate / polyhydroxystearate, pentaerythrityl (behenate / polyhydroxystearate), polyglyceryl-6 polyhydroxystearate, and polyglyceryl-2 dipolyhydroxystearate. Among these polyhydroxystearic acid esters, dipentaerythrityl tripolyhydroxystearate 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 tripolyhydroxystearate is an oily agent that is very viscous, sticky, and difficult to spread, so its use in cosmetics is limited, and its incorporation amount in 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 additive in 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 the skin are insufficient. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2022-007717 [Patent Document 2] Japanese Patent Publication No. 2022-072074 [Patent Document 3] International Publication No. 2022 / 153928 [Patent Document 4] International Publication No. 2023 / 032834 [Patent Document 5] Japanese Patent Application Laid-Open No. 2008-162932 [Patent Document 6] Patent No. 6397891 [Patent Document 7] Patent No. 4027157 [Patent Document 8] Patent No. 5395325 [Patent Document 9] Japanese Patent Application Publication No. 2023-107034 [Patent Document 10] Patent No. 7373916 [Patent Document 11] Japanese Patent Publication No. 2022-117486 [Patent Document 12] Patent No. 3787353 [Patent Document 13] Patent No. 7324217 [Patent Document 14] Special Publication No. 2001-524504 [Patent Document 15] Patent No. 4109209 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide an esterification reaction product of a polyhydroxystearic acid ester that satisfies both good adhesion to the 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 preparation containing the esterification reaction product. Another object of the present invention is to provide a method for producing the esterification reaction product. [Means for solving the problem]

[0009] As a result of intensive investigations aimed at solving the above-mentioned 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 the 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 diglycerin and 12-hydroxystearic acid polymer, The esterification reaction product has a weight average molecular weight of 6500 to 9000, preferably 6700 to 9000, more preferably 7000 to 9000, and even more preferably 7500 to 9000, 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. [2] The esterification reaction product according to [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, wherein the 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. [4] The esterification reaction product according to item [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 a first esterification reaction product; and either a second esterification reaction product or a third esterification reaction product; 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 polydispersity of 1.40 to 1.65; 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 greater 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 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. The esterification reaction product according to [4] above. [6] 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 per 1.0 mol of diglycerol; The esterification reaction product according to item [5] above, wherein 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 not more than 12.0 per 1.0 mol of diglycerol. [7] 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 diglycerol with a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or greater 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 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. The esterification reaction product according to [4] above. [8] The second esterification reaction product is a mixture of 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 per 1.0 mol of diglycerol. of obtained by esterification, The esterification reaction product according to item [7], wherein 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 not more than 12.0 per 1.0 mol of diglycerol. [9] A cosmetic preparation comprising the esterification reaction product according to any one of [1] to [8] above.

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

[11] The cosmetic according to [9] or

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

[12] The cosmetic preparation according to any one of the above [9] to

[11] , which is an emulsion cosmetic preparation.

[13] Esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0, A method for producing an esterification reaction product, comprising producing an esterification reaction product having a weight-average molecular weight of 6500 to 9000, preferably 6700 to 9000, more preferably 7000 to 9000, and even more preferably 7500 to 9000, 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.

[14] A method for producing the esterification reaction product according to

[13] above, comprising heating 12-hydroxystearic acid to 100°C to 250°C and reacting it while removing water to give 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 diglycerol.

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

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

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

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

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

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

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

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

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

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

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

[26] Use of the esterification reaction product according to any one of [1] to [8] above for the production of hair cosmetics with improved cohesiveness of hair. [Effect of the Invention]

[0011] According to the present invention, it is possible to provide an esterification reaction product having both good adhesion to the skin and ease of spreading, and having good water resistance, powder dispersibility, film-forming property and water retention property, a cosmetic containing the esterification reaction product, and a method for producing the esterification reaction product. [Modes for Carrying Out the Invention]

[0012] In the present invention and this specification, for a numerical range, "A or more and B or less (A and B are real numbers satisfying A < B)" may be expressed as "A to B". For example, when described as "1 to 10 parts by mass", it means a numerical range from 1 part by mass to 10 parts by mass, including the lower limit value (1 part by mass) and the upper limit value (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 this 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 with 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 exhibits good skin adhesion and spreadability, and can improve water resistance, powder dispersibility, and water holding capacity. 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 provides excellent oxidation stability.

[0016] The weight-average molecular weight of the esterification reaction product of this embodiment may be in the 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 polydispersity 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 polydispersity 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 preferably has a weight-average molecular weight of 6,700 to 9,000, more preferably 7,000 to 9,000, even more preferably 7,500 to 9,000, and a dispersity of 1.41 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 polymer of 12-hydroxystearic acid used to produce the esterification reaction product of the present embodiment preferably has an average degree of polymerization of 4.0 to 10.0. 12-hydroxystearic acid has one hydroxyl group in the molecule and can be obtained, for example, by hydrogenating ricinoleic acid obtained by hydrolyzing castor seed oil. Alternatively, commercially available 12-hydroxystearic acid may 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 an esterification reaction (polymerization reaction) is carried out 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 even 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. Specifically, 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 the present 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 Quasi-drug Ingredients Standards 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, odor may be generated. The acid value is measured in accordance with the Quasi-drug Ingredients Standards 2021.

[0027] The esterification reaction product of the present invention is obtained by esterifying diglycerin and a 12-hydroxystearic acid polymer. The weight-average molecular weight and polydispersity of the resulting esterification reaction product can be adjusted within desired ranges by adjusting the charging ratio of diglycerin to 12-hydroxystearic acid polymer. The charging 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 between diglycerol and a 12-hydroxystearic acid polymer can be carried out, for example, as follows: Diglycerol and a 12-hydroxystearic acid polymer 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 a 12-hydroxystearic acid polymer.

[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 substances or alkoxides of alkali metals, alkaline earth metals, and transition metals. 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, any solvent known per se in the field of organic chemistry, which is used in the esterification reaction of alcohol and fatty acid, 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 of 6,500 to 9,000 and a dispersity 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 of 6,500 to 9,000 and a dispersity 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 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 of 6,500 to 9,000 and a dispersity of 1.40 to 1.65 (esterification reaction product of diglycerin and 12-hydroxystearic acid polymer).

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

[0035] The esterification reaction product of the present embodiment is 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 index 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 greater and less than 4.0, and having a weight-average molecular weight of 4,000 to 6,000 and a polydispersity of 1.35 to 1.50; or The polymer may further comprise a third esterification reaction product obtained by esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of more than 10.0 and not more than 12.0, and having a weight-average molecular weight of 10,000 to 13,000 and a polydispersity 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 not more than 12.0 with 1.0 mol of diglycerol.

[0037] 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 has a weight-average molecular weight of 4,000 to 6,000, preferably 4,000 to 5,000, and more preferably 4,500 to 4,900. 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 not more than 12.0 with diglycerin may have a weight-average molecular weight of 10,000 to 13,000, preferably 10,500 to 12,500, and more preferably 11,000 to 12,000.

[0038] The polydispersity 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, and 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 not more than 12.0 with diglycerin is within the range of 1.35 to 1.50, and preferably 1.37 to 1.40.

[0039] The weight-average molecular weight of the esterification reaction product containing 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 containing 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-mentioned ranges. However, it is preferably, for example, 3:7 to 8:2.

[0041] When the esterification reaction product of this embodiment includes 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 fall within the above-mentioned ranges. However, for example, the mass ratio 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 fall within the above-mentioned ranges. However, for example, the mass ratio is preferably 2:8 to 4:6. The weight-average molecular weight of the esterification reaction product containing 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 containing 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 produced independently by the above-described "two-step reaction." As described above, 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, calculated from the acid value, is 4.0 or more and 10.0 or less, 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 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 reaction vessel is charged with 1.5 to 2.4 mol, preferably 1.5 to 2.0 mol, of a 12-hydroxystearic acid polymer obtained by adjusting the amount of 12-hydroxystearic acid charged and the reaction time so that the average degree of polymerization calculated from the acid value would be more than 10.0 and not more than 12.0, and the resulting polymer is subjected to 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, 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 produced independently 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 the polydispersity of the esterification reaction product containing the second esterification reaction product and the third esterification reaction product are within the above-mentioned ranges. However, 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, and preferably 8,000 to 9,000. The polydispersity of the esterification reaction product containing 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] <Cosmetics> The cosmetic preparation of this embodiment contains the esterification reaction product of this embodiment. Because the cosmetic preparation of this embodiment contains the esterification reaction product of this embodiment, the cosmetic preparation 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 weight 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 weight 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%, even 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 weight of the cosmetic of this embodiment is preferably 1.0 to 40.0 mass%.

[0047] The cosmetic material of this embodiment may have any appearance, such as transparent, translucent, or emulsion (opaque), and may take any form, such as liquid, cream, emulsion, solid, or aerosol. The cosmetic of the present embodiment is preferably an emulsion cosmetic. When the cosmetic of the present 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 intended use 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 application, making the cosmetic of this embodiment suitable as a component of cosmetics that require high durability against sebum, sweat, and rubbing. For this reason, the cosmetic of this embodiment is preferably a sunscreen cosmetic or a makeup cosmetic. The esterification reaction product of this embodiment can also be used as a water resistance improver or an adhesion improver for cosmetics. Furthermore, the esterification reaction product of the present embodiment has the effect of improving the film-forming properties of cosmetics and improving the manageability of hair produced by hair cosmetics. Therefore, the esterification reaction product of this embodiment can be used as a film-forming property improver in cosmetics and as a hair manageability improver in 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 enhancing the ultraviolet protection effect. In other words, even if the amount of ultraviolet scattering agent in the cosmetic remains the same, the sun protection factor (SPF) can be increased.

[0051] Sunscreen cosmetics may take the form of water-in-oil (W / O) cream sunscreen cosmetics, water-in-oil (W / O) emulsion sunscreen cosmetics, water-in-oil (W / O) multi-layer emulsion sunscreen cosmetics, oil-in-water (O / W) cream sunscreen cosmetics, or oil-in-water (O / W) emulsion sunscreen cosmetics. 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 UV scattering agents, and may be a cosmetic containing one or more UV scattering agents and one or more UV absorbers, or may be a cosmetic containing one or more UV absorbers but no UV scattering agents.

[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 acid)propanediol, neopentyl glycol dicaprate, octyl palmitate ... Polyglyceryl-6 Caprylate, 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, Decaisostearin Polyglyceryl Triisostearate, 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 / rosin acid), (Ethylhexanoate / Glyceryl stearate / adipate, 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 phytosteryl, myristoyl methyl-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 Sterol derivatives such as oleic acid (glyceryl / cetyl / stearyl / behenyl), macadamia nut fatty acid cholesteryl, cholesteryl nonanoate, cholesteryl oleate, dihydrocholesteryl oleate, cholesteryl stearate, cholesteryl hydroxystearate, cholesteryl butyrate, dihydrocholesteryl butyrate, cholesteryl hexyldicarbamate pullulan, and lanolin fatty acid cholesteryl; dimethicone, cyclopentasiloxane, diphenylsiloxyphenyl trimethicone, cyclohexasiloxane, silicones such as crosslinked methylpolysiloxane; methyl perfluorobutyl ether, perfluorooctyltriethoxysilane, and perfluoropolymethylisopropyl. These oily components 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 emulsions, alkyl methacrylate polymer emulsions, alkyl acrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, acrylic acid-alkyl acrylate copolymer emulsions, methacrylic acid-alkyl methacrylate copolymer emulsions, alkyl acrylate-styrene copolymer emulsions, alkyl methacrylate-styrene copolymer emulsions, vinyl acetate polymer emulsions, polyvinyl acetate emulsions, vinyl acetate-containing copolymer emulsions, vinylpyrrolidone-styrene copolymer emulsions, silicone-containing copolymer emulsions, 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, and 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 its derivatives and salts, tocopherols and its derivatives and salts, dibutylhydroxytoluene, butylhydroxyanisole, and 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 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, as well as composite powders thereof; organic powders such as polyamide, polyester, polypropylene, polystyrene, polyurethane, nylon, silicone resin, vinyl resin, urea resin, phenolic resin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene-styrene copolymer, silk powder, cellulose, Nε-lauroyl-L-lysine, long-chain alkyl phosphate metal salts, N-mono long-chain alkyl acyl basic amino acids, and metal soaps, as well as composite powders thereof; and composite powders of the above inorganic 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, Prussian 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 in which mica, synthetic phlogopite, etc. are coated with colorants 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 and water / oil repellency by conventional methods 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 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 anionic surfactants 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 moisturizer 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 japonica extract, Achillea millefolium extract, Melilot extract, raffinose, trehalose, polyoxyethylene methyl glucoside, betaine, etc. The moisturizers 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 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 absorbing agent. The cosmetic of the present embodiment is preferably a cosmetic containing one or more types of UV scattering agents, and may be a cosmetic containing one or more types of UV scattering agents and one or more types of UV absorbers, or may be a cosmetic containing one or more types of UV absorbers but no UV scattering agents. [Example]

[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 subsequent experiments, the acid value and hydroxyl value of the esterification reaction product were measured in accordance with the Raw Material Specifications for Quasi-Drugs 2021.

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

[0089] (Measurement Conditions) Measurement and analysis software: Empower3 (manufactured by Waters Japan) 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 subsequent experiments, the SPF of the sunscreen cosmetic was measured using an SPF analyzer (product name "UV-2000S", manufactured by Lacsphere). The SPF analyzer is a measuring device that conforms to the ISO24443, Colipa Guideline, FDA Final Rule, etc., which are the sunscreen evaluation test standards. Specifically, the measurement was performed 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 HerioscreenLab, plate size: 5 cm x 5 cm). At this time, the test sample was placed so that 30.0 ± 0.2 mg of 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 the plate was quickly and evenly spread with light pressure over the entire plate. After application, the plate was left to stand at room temperature in a dark place for 30 minutes. The SPF values ​​of nine spots on the plate were then measured using an SPF analyzer, and the average value was used as the SPF value of the test sample applied to the plate.

[0092] [SPF value evaluation criteria] A: The SPF value is 40 or higher. B: SPF value is 25 or more but less than 40. C: SPF value is 15 or more but less than 25. D: SPF value is less than 15. In accordance with the above evaluation criteria, a sunscreen cosmetic product was judged to have excellent UV protection effect when rated A or B.

[0093] <Water resistance evaluation> In the following experiments, the water resistance of the 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 29-31°C. A propeller-type stirring blade attached to a Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) was then placed in the metal mug, and the stirring blade was rotated at 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 SPF value after the water resistance test was calculated as a percentage of the SPF value before the water resistance test, 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] [Water resistance evaluation criteria] A: The survival rate is 70% or more. B: The residual rate is 60% or more but less than 70%. C: Residual rate is 50% or more but 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 cosmetic was measured by the following method. The adhesiveness on the skin was evaluated by a sensory panel of four experts. A soybean-sized amount of sunscreen cosmetic was placed on the back of the hand, spread with the index finger, and then the finger was moved perpendicular to the applied area for a sensory evaluation based on the following three-point scale. The scores of each panelist were calculated to evaluate the adhesion of each sunscreen cosmetic.

[0097] [Evaluation criteria for each panelist] 3 points: Adhesion is good. 2 points: Somewhat adhesive. 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. In the above evaluation criteria, a sunscreen cosmetic that received a rating of A or B was determined to have excellent adhesion effect.

[0099] <Easy to spread> In the following experiments, the ease of spreading of the sunscreen cosmetic was measured by the following method. The ease of spreading on the skin was evaluated by a sensory panel of four experts. A soybean-sized amount of sunscreen cosmetic was placed on the back of the hand, and the sunscreen cosmetic was spread horizontally with the index finger. Sensory evaluation was performed based on the resistance and slipperiness felt when the sunscreen cosmetic was spread using the following three-level scale. The scores of each panelist were totaled to evaluate the ease of spreading of each sunscreen cosmetic.

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

[0101] [Evaluation criteria for ease of spreading 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 the sunscreen cosmetic was rated A or B based on the above evaluation criteria, it was determined that the sunscreen cosmetic was excellent in terms of ease of spreading.

[0102] [Examples 1 and 6] Esterification products with different weight-average molecular weights and polydispersities were synthesized by polymerizing 12-hydroxystearic acid to obtain 12-hydroxystearic acid polymers with an average degree of polymerization of 5.0 to 7.0. The polymers were then esterified in an amount of 1.5 to 2.0 mol per 1.0 mol of diglycerin. The SPF and water resistance of oil-in-water sunscreen cosmetics containing these polymers were evaluated, as were the SPF, water resistance, adhesion, and spreadability of water-in-oil sunscreen cosmetics.

[0103] [Comparative Examples 1 and 4] Esterification products with different weight-average molecular weights and polydispersities were synthesized by polymerizing 12-hydroxystearic acid to obtain 12-hydroxystearic acid polymers with an average degree of polymerization of 3.0 or more but less than 4.0. Esterification products with different weight-average molecular weights and polydispersities were then synthesized by adding 2.0 to 2.4 moles of 12-hydroxystearic acid polymer to 1.0 mole of diglycerol. The SPF and water resistance of oil-in-water sunscreen cosmetics containing these polymers were evaluated, and the SPF, water resistance, adhesion, and spreadability of water-in-oil sunscreen cosmetics were evaluated.

[0104] [Comparative Examples 2 and 3] Esterification products with different weight-average molecular weights and polydispersities were synthesized by polymerizing 12-hydroxystearic acid to obtain 12-hydroxystearic acid polymers with an average degree of polymerization of more than 10.0 and not more than 12.0. The polymers were then esterified in 1.5 to 2.0 moles per 1.0 mole of diglycerin. The SPF and water resistance of oil-in-water sunscreen cosmetics containing these polymers were evaluated, as were the SPF, water resistance, adhesion, and spreadability of water-in-oil sunscreen cosmetics.

[0105] [Examples 2 to 5] Esterification reaction products obtained by a two-step reaction consisting of a polymerization step of 12-hydroxystearic acid and an esterification step with diglycerol were mixed to obtain two esterification reaction products having different weight-average molecular weights and / or dispersities, thereby obtaining esterification reaction products having a weight-average molecular weight within the range of 6500 to 9000 and a dispersity within the range of 1.40 to 1.65. The SPF and water resistance of O / W sunscreen cosmetics containing the same were evaluated, 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 (one-step reaction) 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. 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, and water separator was charged with 12-hydroxystearic acid (Kokura Synthetic Industries, Ltd., trade name: 12-hydroxystearic acid), and an appropriate amount of catalyst and organic solvent were added. A reaction was carried out at 210°C under a nitrogen stream while removing generated water to produce 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 Pharmaceutical Co., Ltd., trade name "Diglycerin 801") were placed in a 1-L four-neck flask equipped with a stirrer, thermometer, nitrogen gas inlet, and water remover. The reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give an esterification reaction product (2.0 mol of 12-hydroxystearic acid polymer per 1.0 mol of diglycerin). The resulting esterification reaction product was purified by adsorption, filtration, and deodorization. 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 conducted at 210°C under a nitrogen gas flow while 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 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, thermometer, nitrogen gas inlet, and water remover. The 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 1.5 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption, 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, 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 stream while 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, would 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, thermometer, nitrogen gas inlet, and water remover. The reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give an esterification reaction product (2.0 mol of 12-hydroxystearic acid polymer was charged per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption, 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, 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 while 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 more than 10.0 and less than 12.0. 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, thermometer, nitrogen gas inlet, and water remover. The reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give an esterification reaction product (2.0 mol of 12-hydroxystearic acid polymer was charged per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption, 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, 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 while 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 more than 10.0 and less than 12.0. 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 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, thermometer, nitrogen gas inlet, and water remover. The 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 1.5 mol per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption, 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, 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 stream while 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, would 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, thermometer, nitrogen gas inlet, and water remover. The reaction was carried out at 210°C under a nitrogen gas flow with removing generated water to give an esterification reaction product (2.4 mol of 12-hydroxystearic acid polymer was charged per 1.0 mol of diglycerol). The resulting esterification reaction product was purified by adsorption, 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) Preparation of esterified products [Examples 2 to 5 (mixing of two-stage reaction products)] An esterification 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 was 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 1 and the esterification reaction product of Example 6 were mixed in a mass ratio of 5:5 to produce the esterification reaction product of Example 2. Similarly, the two esterification reaction products were mixed in the mass ratios shown in Table 1 to produce the esterification reaction products of Examples 3 to 5. The weight average molecular weight (Mw), dispersity, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the obtained esterification reaction products of Examples 2 to 5 are shown in Table 1.

[0120] [Table 1]

[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 reaction was carried out at 210°C under a nitrogen stream while removing the generated water to produce an esterification reaction product (12.0 mol of 12-hydroxystearic acid was charged per 1.0 mol of diglycerin). The resulting esterification reaction product was purified by adsorption, filtration, and deodorization. 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 one-step reaction in which the polymerization reaction of 12-hydroxystearic acid is not carried out, but rather the polymerization reaction of 12-hydroxystearic acid is carried out during the esterification reaction of 12-hydroxystearin with diglycerin, and is hereinafter referred to as the "one-step reaction."

[0123] In addition, 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 (mgKOH / g), and hydroxyl value (mgKOH / 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 (mgKOH / g), and hydroxyl value (mgKOH / g) were measured. Commercially available dipentaerythrityl tri-polyhydroxystearate is dipentaerythritol whose alcohol skeleton is made from a non-vegetable raw material.

[0124] (2) Manufacturing of O / W type 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 uniformly mixed to prepare mixture A. Separately, all remaining components were uniformly mixed to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as a sunscreen cosmetic. In the tables of this specification, "%" indicates "% by mass" and "% aq" indicates the content (% by mass) in the aqueous solution.

[0125] [Table 2]

[0126] Isotridecyl isononanoate: Product name "Salacos 913", manufactured by Nisshin Oillio Group 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 Nisshin Oillio Group Fine particle titanium dioxide (stearic acid treated): Product name "MT-500CST", manufactured by Teika Co., Ltd. (Acrylates / C10-30 alkyl acrylate) crosspolymer (2% aq.): Product name "Pemulen TR-1", manufactured by Lubrizol Xanthan gum: Product name: Nomcoat ZZ, manufactured by Nisshin Oillio Group Glyceryl stearate: Product name "Lasemul 92 AE", manufactured by IQL

[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 composition were examined. The evaluation results are shown in Tables 3 to 5, along with the weight-average molecular weight (Mw), dispersity, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the esterification reaction products used as raw materials.

[0128] [Table 3]

[0129] [Table 4]

[0130] [Table 5]

[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 O / W sunscreen cosmetic (Comparative Example 7) made from commercially available dipentaerythrityl tri-polyhydroxystearate 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) that used an esterification reaction product obtained in a one-stage reaction involving the polymerization of 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) that used an esterification reaction product obtained in a two-stage reaction involving the polymerization of 12-hydroxystearic acid. Furthermore, the initial SPF value and water resistance were also low.

[0133] (4) Manufacturing of W / O type 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 6. Specifically, first, the oily component and the UV absorber were uniformly mixed to prepare mixture A. Separately, all remaining components were uniformly mixed to prepare mixture B. Next, mixture A and mixture B were mixed and emulsified, and the resulting emulsion was used as a sunscreen cosmetic.

[0134] [Table 6]

[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 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 The SPF value, water resistance, adhesion, and spreadability of each W / O sunscreen cosmetic composition were examined. The evaluation results, including the weight-average molecular weight (Mw), dispersity, acid value (mgKOH / g), and hydroxyl value (mgKOH / g) of the esterification reaction products used as raw materials, are shown in Tables 7 and 8.

[0137] [Table 7]

[0138] [Table 8]

[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. 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 showed improved water resistance but lower initial SPF values. Sunscreen cosmetics (Comparative Examples 2 and 3) made from esterification reaction products with significantly higher weight-average molecular weights showed improved water resistance. However, the W / O type sunscreen cosmetics of Comparative Examples 1 to 6 did not have good adhesion to skin and ease of spread. 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 very good water resistance. In addition, they also showed good adhesion to skin and ease of spread. A commercially available W / O type sunscreen cosmetic made from dipentaerythrityl tripolyhydroxystearate (Comparative Example 7) had very high initial SPF value, water resistance, and adhesion, but was not easy to spread.

[0140] Next, makeup, skin care, and hair care cosmetics were prepared and evaluated. The evaluation was carried out by sensory evaluation. The sensory evaluation method was as follows. Sensory evaluation of cosmetics Ten sensory evaluation panelists used each cosmetic product and assigned scores to each evaluation item in accordance with the following evaluation criteria for sensory evaluation of spreadability (whether the cosmetic spreads smoothly onto the application site such as the skin), film-forming ability (whether there is a film-like feeling 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 product). Evaluation criteria 6 points: Very good. 5 points: Good. 4 points: Fairly good. 3 points: Normal. 2 points: Somewhat poor. 1 point: Bad. 0 points: Very bad.

[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 above: A Excellent. 3 or more but less than 5 points: B Excellent. 1 point or more but less than 3 points: C Neither. Less than 1 point :D Poor. In the above evaluation criteria, if a cosmetic was rated A or B, it was determined that the cosmetic had excellent effects in each evaluation item.

[0142] (5) Manufacturing of stick-type lipstick cosmetics Stick-type lipstick cosmetics were produced according to the formulations shown in Table 9 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 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 a stick-type lipstick. The results of sensory evaluation of each product are shown in Table 10.

[0143] [Table 9]

[0144] [Table 10]

[0145] As shown in Table 10, the stick-type lipstick cosmetics made from the esterification reaction products of Examples 1 and 6 showed favorable 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 favorable results in terms of spreadability, adhesion, or durability.

[0146] (6) Manufacturing of W / O cream foundation W / O cream foundations were produced according to the formulations shown in Table 11 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6, respectively. 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] [Table 11]

[0148] [Table 12]

[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) Manufacturing 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-based component (A) and alcohol (A) were heated and mixed at 80°C to obtain mixture (A). Meanwhile, oil-based 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. Sensory evaluation of each of the foundations is shown in Table 14.

[0151] [Table 13]

[0152] [Table 14]

[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 terms of spreadability, film-forming ability, or durability.

[0154] (8) Manufacturing of 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] [Table 15]

[0156] [Table 16]

[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) Manufacturing 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 the mixture (A) was gradually added and mixed thereto, followed by cooling to room temperature to obtain emulsions. The results of sensory evaluation of each emulsion are shown in Table 18.

[0159] [Table 17]

[0160] [Table 18]

[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) Manufacturing of cleansing cream Cleansing creams were produced according to the formulations shown in Table 19 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, 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] [Table 19]

[0164] [Table 20]

[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 blendability 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 blendability or spreadability.

[0166] (11) Manufacturing of cleansing oil Cleansing oils were produced according to the formulations shown in Table 21 using the esterification reaction products of Examples 1 and 6 and Comparative Examples 3 to 6. 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] [Table 21]

[0168] [Table 22]

[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 any of the aspects of makeup blendability and spreadability.

[0170] (12) Manufacture of conditioners (hair cosmetics) 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] [Table 23]

[0172] [Table 24]

[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) Manufacture of hair oil (hair cosmetics) 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 oil are shown in Table 26.

[0175] [Table 25]

[0176] [Table 26]

[0177] As shown in Table 26, the hair oils made from the esterification reaction products of Examples 1 and 6 showed favorable 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 favorable 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 polymers and polyhydric alcohols, and had excellent water-holding properties. Comparison was made with commercially available products of dipentaerythrityl tri-polyhydroxystearate (Comparative Example 7), lanolin, and cholesteryl hydroxystearate.

[0179] The water holding 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 Vaseline were mixed and vigorously stirred (200-300 rpm) in a 40°C thermostatic bath while adding purified water dropwise. The end point was the point at which all the water could be added, and the percentage of the mass of water relative to the mass of the mixed sample was expressed. 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] [Table 27]

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

[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, The esterification reaction products each have a weight average molecular weight of 6,500 to 9,000 and a polydispersity of 1.40 to 1.

65.

2. 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. 3. The esterification reaction product according to claim 2, wherein the esterification reaction product is obtained by esterifying 1.5 to 2.4 mol of the 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 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 is a first esterification reaction product; and either a second esterification reaction product or a third esterification reaction product; the first esterification reaction product is obtained by esterifying diglycerol 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 polydispersity of 1.40 to 1.65; 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 greater 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; 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 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 per 1.0 mol of diglycerol; 6. The esterification reaction product according to claim 5, wherein 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 not more than 12.0 with 1.0 mol of diglycerol.

7. 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 diglycerol and a 12-hydroxystearic acid polymer having an average degree of polymerization of 3.0 or greater 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; 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.

8. 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 per 1.0 mol of diglycerol; 8. The esterification reaction product according to claim 7, wherein 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 not more than 12.0 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 at least one selected from the group consisting of an ultraviolet scattering agent and an ultraviolet absorbing agent.

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. esterifying diglycerin with a 12-hydroxystearic acid polymer having an average degree of polymerization of 4.0 to 10.0; A method for producing an esterification reaction product, comprising producing 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 it 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 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 property 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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