USOO7632957B2

(12) United States Patent (10) Patent No.: US 7,632,957 B2 Yamato et al. (45) Date of Patent: Dec. 15, 2009

(54) ESTERIFICATION REACTION PRODUCTS JP 49-02O341 A 2, 1974 AND COSMETIC PRODUCTS JP 52-48613 * 4, 1977 JP 52-048613. A 4, 1977 (75) Inventors: Yoshihito Yamato, Yokohama (JP): JP 53-127841 A 8, 1978 Yukiko Oi, Yokohama (JP); Masaaki JP 54-1099.17 A 8, 1978 Fujisawa, Yokohama (JP) JP 54-049337 A 4f1979 JP 54-1099.17 * 8, 1979 73) AssigSS19. Thee Nisshin Oillio Group, Ltd., TTokyo JP 55-057509 A 4f1980 JP 56-108739 A 8, 1981 (JP) JP 56-115740 * 9/1981 *) NotOt1Ce: Subjubject to anyy d1Sclaimer,disclai theh term off thithis JP 56-115740 A 9, 1981 patent is extended or adjusted under 35 JP 61-056113 A 3, 1986 JP 64-090025 A 4f1989 U.S.C. 154(b) by 118 days. JP 05-331023. A 12/1993 JP O7-008781 A 1, 1995 (21) Appl. No.: 11/883,116 JP O7-223.925 A 8, 1995 JP 10-067889 A 3, 1998 (22) PCT Filed: Jan. 26, 2006 JP 10-120833. A 5, 1998 (86). PCT No.: PCT/UP2OO6/3O1212 JP 10-273.433. A 10, 1998 JP 2000-095666 A 4/2000 JP 2000-290232 * 10/2000 S371 (c)(1), JP 2000-290232 A 10, 2000 (2), (4) Date: Jul. 26, 2007 JP 2003-104843. A 4/2003 JP 2003-212747. A T 2003 (87) PCT Pub. No.: WO2006/080389 JP 2004-33.1573. A 11, 2004 PCT Pub. Date: Aug. 3, 2006 WO WOO3,O15741 A1 2, 2003

(65) Prior Publication Data OTHER PUBLICATIONS US 2008/0260663 A1 Oct. 23, 2008 U.S. Appl. No. 1 1/883,089, filed Jul. 26, 2007, Confirmation No. (30) Foreign Application Priority Data 94.71. Y.Yamato et al. “The characteristic of a new water holding material, Jan. 28, 2005 (JP) ------2005-021095 and application to cosmetics”. Fragrance Journal, vol. 33, pp. 53-59 - - - - - 2005-170370 (2005) (Chemical Abstracts, abstract only). Jun. 10, 2005 (JP) Sep. 2, 2005 (JP) ------2005-255.030 Keshoshin-Jiten (Cosmetic Dictionary), Maruzen, p. 8 (2003). Oct. 13, 2005 (JP) ------PCT/JP2005/018856 English language International Preliminary Report on Patentability PCT/IB/373 (one page) and PCT/ISA/237 (3 pages) issued Jul. 31, (51) Int. Cl. 2007 in International Application PCT/JP2006/301212. C07C 59/00 (2006.01) * cited by examiner (52) U.S. Cl...... 554/213; 424/59: 424/61; 424/70.1 Primary Examiner Deborah D Carr (58) Field of Classification Search ...... 554/213; (74) Attorney, Agent, or Firm Frishauf, Holtz, Goodman & 424/59, 61, 70.1 Chick, P.C. See application file for complete search history. (57) ABSTRACT (56) References Cited U.S. PATENT DOCUMENTS An esterification reaction product obtained by esterifying dipentaerythritol and a 12-hydroxy Stearic acid polymer and 3,890,358 A 6, 1975 Hutchison et al. 5,840,943 A 11, 1998 Ansmann et al. having a hydroxyl value of 20 to 70 mg KOH/g and an acid 20040191282 A1 9/2004 Fujino et al. value of 3 mg KOH/g or less. The esterification reaction 2005, 011821.0 A1 6, 2005 Kachi et al. product has a high-water holding property and a pigment dispersing property. FOREIGN PATENT DOCUMENTS DE 4420 S16 A1 12/1995 11 Claims, 7 Drawing Sheets

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Éd is 30 trioctanoin 20 10 Production Example 1 EEEDa-a LLL L O 5 10 15 20 25 30 35 40 45 50 Time (hr) US 7,632,957 B2 1. 2 ESTERIFICATION REACTION PRODUCTS also have waterproof-film-forming abilities and non-dyeing AND COSMETIC PRODUCTS properties at certain degrees, it is desired to further improve these properties. This application is the United States national phase appli In addition, the ester compounds disclosed in Patent Docu cation of International Application PCT/JP2006/301212 filed ments 8 and 9 are emulsifying agents and do not have film Jan. 26, 2006. forming ability, which oils do. Furthermore, the amounts of these esters used in cosmetic products may be restricted TECHNICAL FIELD depending on types of the cosmetic products. Patent Document 1: Japanese Unexamined Patent Publica The present invention relates to esterification reaction 10 tion No. 52-48613 products. Specifically, the present invention relates to esteri Patent Document 2: Japanese Unexamined Patent Publica fication reaction products having good adhesion to skin and tion No. 54-109917 being excellent in waterproof-film-forming ability, pigment Patent Document 3: Japanese Unexamined Patent Publica dispersing properties, water-holding properties, non-dyeing tion No. 55-57509 properties, and long-term stability. 15 Patent Document 4: Japanese Unexamined Patent Publica The present invention also relates to cosmetic products tion No. 56-57509 containing the esterification reaction products. Patent Document 5: Japanese Unexamined Patent Publica tion No. 56-108739 BACKGROUND ART Patent Document 7: Japanese Unexamined Patent Publica tion No. 05-331023 Cosmetic products have been conventionally used for Patent Document 9: Japanese Unexamined Patent Publica imparting good appearance to skin or the like. In addition, tion No. 2000-290232 cosmetic products are used for protecting skin from drying by Patent Document 6: Japanese Unexamined Patent Publica preventing transpiration of moisture from the skin and further 25 tion No. 64-90025 conditioning the skin as well as giving good appearance to Patent Document 8: Japanese Unexamined Patent Publica skin or the like. tion No. 07-8781 Natural oils such as lanolin and castor oil and synthetic Non-Patent Document 1: Keshohin-Jiten (Cosmetic Dictio ester oils having water-holding ability have been widely used nary), Maruzen, published on Dec. 15, 2003 (Heisei 15) as raw materials for obtaining cosmetic products which can 30 prevent skin from drying and condition skin. In particular, DISCLOSURE OF INVENTION water-in-oil-type cosmetic products coat a skin surface with an oil film and have higher affinity to skin compared to oil Problems to be Solved by the Invention in-water-type cosmetic products, and are therefore widely used as cosmetic products that can prevent skin from drying 35 An object of the present invention is therefore to provide an and condition skin. esterification reaction product having good adhesion to, for Conventionally, lanolin has been widely used as an oil of example, skin and being excellent in waterproof-film-form natural origin. Lanolin is derived from wool fat and has high ing ability, pigment-dispersing properties, water-holding affinity, adhesion, and humectant properties to skin. Further properties, non-dyeing properties, and long-term stability. more, lanolin is excellent in water-holding and emulsifying 40 Further, an object of the present invention is to provide an properties. Therefore, lanolin has been widely used in basic esterification reaction product which can be used for manu cosmetics, makeup cosmetics, and many other cosmetic facturing cosmetic products (oil-in-water-type emulsion cos products (refer to, for example, Non-Patent Document 1). metic products and water-in-oil-type emulsion cosmetic However, the use of raw materials derived from animals is products) which can contain a large amount of water (and decreasing because of the recently occurred mad cow disease 45 polyols) and are good in water-retaining stability and long problems, and it is significantly decreased to directly use term stability. animal-derived raw materials in cosmetic products. In addi Further, an object of the present invention is to provide a tion, natural products such as lanolin and castor oil have cosmetic product having good adhesion to skin or the like and problems that a constant quality cannot be readily obtained being excellent in waterproof-film-forming ability, pigment and prices widely fluctuate. Thus, they are not stable raw 50 dispersing properties, softness, moisturizing properties, materials in the quality and price. water-holding properties, non-dyeing properties, and long Consequently, instead of natural oils, synthetic ester oils term stability. have been recently used. For example, ester compounds of Further, an object of the present invention is to provide a 12-hydroxy Stearic acid and polyols (refer to, for example, 55 cosmetic product excellent in adhesion to, for example, skin Patent Documents 1 to 4) and ester compounds of 12-hydrox or hair, emollient effects, and long-lasting makeup effects. yStearic acid polymers and polyols (refer to, for example, Patent Documents 5 to 9) have been developed. The synthetic Means for Solving the Problem ester oils disclosed in these Patent Documents can impart water-holding properties to products containing these oils. 60 The present inventors have conducted intensive studies to However, water-in-oil-type cosmetic products prepared achieve the above-mentioned objects and have found the fact using the ester compounds disclosed in Patent Documents 1 that the above-mentioned objects can be achieved by using a to 7 have unstable water-holding states, and thereby the long specific esterification reaction product. Thus, the present term stability and the pigment-dispersing properties of the invention has been accomplished. cosmetic products may be deteriorated. Furthermore, though 65 The present invention provides an esterification reaction cosmetic products prepared using the ester compounds dis product obtained by esterifying dipentaerythritol and a closed in Patent Documents 1 to 7 can well adhere to skin and 12-hydroxyStearic acid polymer. The esterification reaction US 7,632,957 B2 3 4 product has a hydroxyl value of 20 to 70 mg KOH/g and an Glycyrrhiza glabra extract, Gardenia florida extract, Sasa acid value of 3 mg KOH/g or less. Veitchii extract, Gentiana extract, Clammellia sinensis The present invention also provides a cosmetic product extract, Symphytum officinale leaf extract, Perilla ocymoides containing Such an esterification reaction product. leaf extract, Lithospermum erythrorhizone root extract, Lin den extract, Spiraea ulmaria extract, Paeonia albiflora root ADVANTAGEOUSEFFECT OF THE INVENTION extract, Lonicera japonica extract, Salvia officinalis extract, Hedera helix extract, Sambucus nigra flower extract, Achillea According to the present invention, an esterification reac millefolium extract, Swertia japonica extract, Mulberry root tion product excellent in properties for holding water and extract, Calendula officinalis flower extract, Eriobotrya dispensing, for example, a pigment is provided. 10 japonica leaf extract, Prunus persica leaf extract, Centaurea By using the above-mentioned esterification reaction prod cyanus flower extract, Saxifrage sarmentosa extract, Mog uct, oil-in-water-type and water-in-oil-type emulsion cos wort extract, Lactuca Scariola sativa extract, Anthemis nobilis metic products containing a large amount of water (and/or a flower extract, and Sanguisorba officinalis root extract. In the polyol) and having high water-retaining and long-term sta present invention, the above-mentioned inorganic salts, bilities can be provided. In the present invention, the high 15 organic salts, water-soluble agents, and animal or plant water-holding properties of the esterification reaction product extracts may be used alone or in a combination of two or more can be confirmed that a water-holding material composed of thereof. the esterification reaction product and water at a mass ratio of By using the esterification reaction product according to 7:3 shows no endothermic peak due to water at about 0°C. in the present invention, a cosmetic product having good adhe differential scanning calorimetry. Furthermore, the cosmetic sion to, for example, skin and excellent waterproof-film product according to the present invention can hold not only forming ability, pigment-dispersing properties, softness, a large amount of water but also water-soluble polyols such as moisturizing properties, water-holding properties, non-dye glycerin, which do not have compatibility to water. In the ing properties, and long-term stability can be provided. present invention, the term “polyol’ means glycerin and poly In addition, by using the esterification reaction product mers thereof glycols such as polyethylene glycol, propylene 25 according to the present invention, a cosmetic product excel glycol, and 1,3-butylene glycol; and saccharides such as Xyli lent in adhesion to, for example, skin or hair, emollient tol, Sorbitol, and maltitol. In addition, products containing the effects, and long-lasting makeup effects can be provided. esterification reaction product according to the present inven tion can hold not only water but also aqueous Solutions dis BRIEF DESCRIPTION OF THE DRAWINGS Solving, for example, inorganic salts, organic salts, water 30 soluble agents, or animal or plant extracts therein. FIG. 1 is a graph showing the results of water-holding Specifically, examples of the inorganic salts include sodium property test 2 of the esterification reaction product obtained chloride, potassium chloride, calcium chloride, magnesium in Production Example 1. chloride, sodium sulfate, magnesium sulfate, Sodium carbon FIG. 2 is a graph showing the results of water-holding ate, sodium hydrogen carbonate, and sodium phosphate. 35 property test 2 of the esterification reaction product obtained Examples of the organic salts include Sodium citrate, sodium in Production Example 2. malate, sodium gluconate, Sodium lactate, Sodium Succinate, FIG. 3 is a graph showing the results of water-holding and Sodium tartrate. Examples of the water-soluble agents property test 2 of the esterification reaction product obtained include skin-lightening agents. Examples of the skin-lighten in Production Example 3. ing agents include ascorbic acid and/or derivatives thereof, 40 FIG. 4 is a graph showing the results of water-holding Such as L-ascorbic acid glucoside, L-ascorbic acid-2-phos property test 2 of liquid lanolin. phate ester, L-ascorbic acid-3-phosphate ester, L-ascorbic FIG. 5 is a graph showing the results of water-holding acid-6-phosphate ester, L-ascorbic acid-2-polyphosphate property test 2 of cholesteryl hydroxystearate. ester, L-ascorbic acid-2-sulfate ester, L-ascorbic acid-2- FIG. 6 is a graph showing the results of water-holding palmitate ester, L-ascorbic acid-6-palmitate ester, L-ascorbic 45 acid-2-Stearate ester, L-ascorbic acid-6-stearate ester, property test 2 of diisoStearyl malate. L-ascorbic acid-2,6-dibutyl ester, L-ascorbic acid-2,6-di FIG. 7 is a graph showing the evaluation results of oxida palmitate ester, and salts thereof. Examples of the salts tive stability (CDM test). include sodium salts, potassium salts, magnesium salts, cal BEST MODE FOR CARRYING OUT THE cium salts, barium salts, ammonium salts, monoethanola 50 mine salts, diethanolamine salts, triethanolamine salts, INVENTION monoisopropanolamine salts, and triisopropanolamine salts. Other examples of the skin-lightening agent include arbutin, First, the esterification reaction product according to the kojic acid, and glutathione. Examples of water-soluble agent present invention will now be described. include anti-inflammatory agents. Examples of the anti-in 55 The esterification reaction product of the present invention flammatory agents include glycyrrhizinic acid derivatives is obtained by esterifying dipentaerythritol and a 12-hydrox and allantoin. Examples of the animal or plant extracts ystearic acid polymer and has a hydroxyl value of 20 to 70 mg include Nettle leaf extract, Siberian ginseng extract, Phello KOHAg and an acid value of 3 mg KOH/g or less. dendron bark extract, Coffea Arabica extract, White birch The dipentaerythritol used for manufacturing the esterifi extract, Mentha piperita extract, Thymus extract, Tea extract, 60 cation reaction product of the present invention may be a Hamamelis extract, Isodonis japonica extract, Coltsfoot commercially available one. For example, dipentaerythritol extract, Vitis vinifera leaf extract, Humulus lupulus extract, available from KOEI PERSTOP Co., Ltd. under the trade Horse chestnut extract, Melissa officinalis extract, Acerola name “di-Pentalit' can be used. extract, Rose fruit extract, Actinidia chinensis fruit extract, The 12-hydroxystearic acid polymer used for manufactur Arnica extract, Scutellaria baicalensis root extract, Coptis 65 ing the esterification reaction product of the present invention rhizome extract, Lamium album extract, Cattail extract, Cha is a polymer of 12-hydrocystearic acid having one hydroxyl momilla recutita extract, Artemisia capillaris flower extract, group in the molecule. For example, the 12-hydrocystearic US 7,632,957 B2 5 6 acid polymer can be obtained by polymerizing 12-hydroxyS As described above, the esterification reaction product of tearic acid given by hydrogenating ricinoleic acid obtained by the present invention is obtained by esterifying dipentaeryth hydrolysis of castor oil. ritol and a 12-hydroxyStearic acid polymer. The polymerization of 12-hydroxy Stearic acid is a reaction The charging amount of the 12-hydroxyStearic acid poly foresterifying a hydroxyl group or carboxyl group of a 12-hy 5 merused foresterification reaction is preferably 1 to 6 moles, more preferably 1.5 to 5 moles, and most preferably 2 to 4 droxyStearic acid molecule with a carboxyl group or hydroxyl moles on the basis of 1 mole of dipentaerythritol for adjusting group of another 12-hydroxyStearic acid molecule, namely, the hydroxyl value to the above-mentioned range and reduc intermolecular esterification. ing the amount of unreacted dipentaerythritol. The polymerization of 12-hydroxy Stearic acid can be con 10 The appearance, viscosity, and water-holding properties ducted, for example, as follows: can be provided to the resulting ester composition by thus 12-HydroxyStearic acid is charged in a reaction vessel and adjusting the charging ratio. is stirred foresterification reaction (polymerization reaction) The esterification of dipentaerythritol and a 12-hydroxys at 180 to 220° C. for 5 to 30 hours in the presence or absence tearic acid polymer is specifically conducted as follows: of an acid, alkali, or other metal catalyst, preferably, in an 15 dipentaerythritol and a 12-hydroxy Stearic acid polymer are organic solvent and/or gas which are inactive to the reaction. put into a reaction vessel and are subjected to esterification in The 12-hydroxy Stearic acid may be a commercially avail an inactive organic solvent and/or gas at 200 to 220° C. for 1 able one. For example, 12-hydroxy Stearic acid manufactured to 20 hours. Then, the reaction mixture is purified to obtain an by Kokura Synthetic Industies, Ltd. under the trade name esterification reaction product of dipentaerythritol and the “12-Hydro acid (HP), “Hydroxystearic Acid manufactured 12-hydroxyStearic acid polymer. by Kawaken Fine Chemicals Co., Ltd., and “Hydrogenated In the above-mentioned esterification reaction, a catalyst Castor Oil Fatty Acid manufactured by NOF Corp. can be may be used according to need. Examples of the catalyst used. include acid catalysts and alkoxides of alkaline earth metals. 12-HydroxyStearic acid polymers having a polymerization These catalysts are preferably used at an amount of about degree of 2 to 12 are preferably used for manufacturing the 25 0.001 to 1.0% by mass to of the total mass of reaction raw esterification reaction product of the present invention. A materials. 12-hydroxy Stearic acid polymer having a polymerization After the reaction, the catalyst and unreacted raw materials degree in this range can improve water-holding properties, can be removed by conducting known purification treatment dispersibility, adhesion, waterproof-film-forming ability, and Such as washing with water, alkali deacidification, or absorp non-dyeing properties. The polymerization degree is more 30 tive treatment. In addition, the resulting reactant product can preferably 4 to 12, and most preferably 6 to 12. The average be further purified by conducting bleaching and deodorizing. polymerization degree can be adjusted within the above-men Thus, an esterification reaction product can be obtained as tioned range by carrying out the polymerization reaction of a colorless or light yellow transparent odorless liquid. The 12-hydroxy Stearic acid while measuring acid value of the resulting esterification reaction product can be used as an reaction product. That is, the average polymerization degree 35 ingredient of cosmetic products described below. can be readily adjusted to the above-mentioned range by Next, cosmetic products according to the present invention sampling a reaction product during the progress of the poly will be described. merization reaction of 12-hydroxyStearic acid, measuring The cosmetic products of the present invention contain the acid value of the sampled reaction product, calculating aver esterification reaction product of the present invention. age polymerization degree from the acid value, and terminat 40 The application and formulation of the cosmetic products ing the esterification reaction (polymerization reaction) at the of the present invention are not especially limited. Examples point that gives the desired average polymerization degree is of the cosmetic products include lip cosmetics, foundation, obtained. emollient cream, milky lotion, makeup bases, hair cream, shampoo, hair rinse, hair conditioners, hand cream, serum, The hydroxyl value of esterification reaction product of the 45 eyebrow and eye cosmetics, nail cosmetics, and Sunscreen present invention is 20 to 70 mg KOH/g, preferably 20 to 60 cosmetics. mg KOH/g, more preferably 25 to 50 mg KOH/g, and most These cosmetic products can be manufactured by known preferably 30 to 40 mg KOH/g. When the hydroxyl value is methods without any particular limitation. lower than 20 mg KOH/g, the desired water-holding proper The cosmetic products according to the present invention ties and dispersibility cannot be achieved. On the contrary, 50 contain the above-mentioned esterification reaction product. when the hydroxyl value is higher than 70 mg KOH/g, the Thereby, adhesion, waterproof-film-forming, pigment-dis manufacturing becomes difficult. When the hydroxyl value is persing, and non-dyeing properties are imparted to, in par lower than 20 mg KOH/g, the manufacturing becomes also ticular, makeup cosmetics among the above-mentioned cos difficult. The hydroxyl value of the esterification reaction metic products, e.g., lip cosmetics, makeup bases, product can be adjusted to the above-mentioned range by, for 55 foundation, eyebrow and eye cosmetics, and nail cosmetics. example, controlling the ratio of dipentaerythritol or a 12-hy In the makeup bases and the foundation (liquid foundation, droxyStearic acid polymer. powder foundation, Stick-type foundation, and cream foun The acid value of the esterification reaction product of the dation), the waterproof-film-forming ability reduces rough present invention is 3 mg KOH/g or less and preferably 0 to 3 ness of skin to allow foundation fit better and also imparts mg KOH/g. When the acid value is higher than 3 mg KOH/g, 60 softening and moisturizing effects. odor may occur. In addition, the cosmetic products according to the present The acid value of the esterification reaction product can be invention are improved in resistance to sebum, perspiration, adjusted to the above-mentioned range by Sampling a reaction and rubbing. Thereby, the finish of makeup can last for a long product during the progress of the esterification reaction, time. Therefore, the present invention can be applied to Sun measuring acid value of the sampled reaction product, and 65 screen agents. In lip cosmetics (lip rouge, lip gloss, and lip terminating the esterification reaction at the point that gives balm), eyebrow and eye cosmetics (eyeliner, mascara, eye the desired acid value. shadow, and eye pencil), and nail cosmetics (nail enamel, US 7,632,957 B2 7 8 base coat, and top coat), uniform cosmetic films can be main product to the emulsion. In particular, the effect can be further tained for a long time by the excellent adhesion properties. In enhanced by adding an organic modified clay mineral to the addition, the coloring is improved by the excellent pigment emulsion. Such water-in-oil-type (W/O type) emulsion dispersing properties (coloring agent-dispersing properties). includes, for example, (a) an esterification reaction product, In general, a lip cosmetic product containing a dye may cause (b) an organic modified clay mineral, (c) oil, and (d) water. troubles (chapping, drying, allergy, darkening, and so on) by The contents of the respective ingredients of Such emulsion dyeing skin or mucous membrane. However, in the lip cos are preferably (a) 1 to 30% by mass, (b) 0.01 to 10% by mass, metic products containing the esterification reaction product (c) 10 to 80% by mass, and (d) 10 to 80% by mass, and more of the present invention, the makeup lasts for a long time preferably (a) 1 to 20% by mass, (b) 0.1 to 5% by mass, (c) 15 without dying skin or lip by the dyes contained in the cos 10 to 80% by mass, and (d) 20 to 80% by mass to the total amount metic products, and Smudges of the cosmetic products are less of the emulsion. This water-in-oil type (W/O type) emulsion caused. Furthermore, emulsion-type lip cosmetic products can be widely applied to emulsion cosmetic products such as can be readily prepared. In addition, effects of moisturizing cream, milky lotion, and aerosol, and is particularly Suitable and conditioning lip can be imparted to cosmetic products by for Sunscreen cosmetics and moisturizing cream. blending a moisturizing agent, an inorganic salt, an organic 15 The cosmetic products according to the present invention salt, a water-soluble agent, oran animal or plant extract to the may contain various ingredients generally used in cosmetic cosmetic products. Similarly, moisturizing effect can be products, according to need, in the range that does not impair imparted to cake-type and oil-type foundation by blending a the effects of the present invention. moisturizing agent, an inorganic salt, an organic salt, a water Such ingredients are properly selected based on use and soluble agent, or an animal or plant extract to the foundation. formulation of the cosmetic product, and examples of the Furthermore, the esterification reaction product of the present ingredients include oil ingredients, aqueous ingredients, invention can be blended to oil phases of oil-in-water-type polymer emulsions, anionic Surfactants, cationic Surfactants, emulsion cosmetic products. amphoteric Surfactants, oleophilic nonionic Surfactants, In particular, Sunscreen cosmetic products having a long hydrophilic nonionic Surfactants, natural Surfactants, mois acting effect, excellent adhesion to skin, and film-forming 25 turizing agents, thickeners, preservatives, powdery ingredi feeling can be obtained by blending the esterification reaction ents, pigments, pH-adjusters, antioxidants, ultraviolet product of the present invention thereto. Examples of the absorbers, perfumes, dyes, sequestering agents, and purified formulation of the Sunscreen cosmetic include water-in-oil Water. type (W/O type) sunscreen cream, water-in-oil-type (W/O Examples of the oil ingredients include carbon hydrides type) sunscreen milky lotion, water-in-oil-type (W/O type) 30 Such as liquid paraffin, heavy liquidisoparaffin, Solid paraffin, sunscreen multi-phase emulsion, oil-in-water-type (O/W C-olefin oligomer, squalane, Vaseline, polyisobutylene, poly type) sunscreen cream, and oil-in-water-type (O/W type) sun butene, montan wax, ceresin wax, microcrystalline wax, screen milky lotion. polyethylene wax, and Fisher-Tropsch wax; fats and oils such In addition, since the esterification reaction product of the as olive oil, castor oil, jojoba oil, mink oil, and macademianut present invention is excellent in pigment-dispersing proper 35 oil; waxes such as beeswax, candelilla wax, spermaceti wax, ties, inorganic pigments can be uniformly dispersed in Sun candelilla wax, carnauba wax, and Japan wax, esters such as screen cosmetic products by blending the esterification reac cetyl 2-ethylhexanoate, cetyl isooctanoate, isopropyl tion product to the cosmetic products. Therefore, a uniform myristate, isopropyl palmitate, octyldodecyl myristate, film of an inorganic pigment is formed on skin by applying polyglyceryl diisoStearate, polyglyceryl trisoStearate, dig the cosmetic product onto the skin, and thereby the ultraviolet 40 lyceryl triisoStearate, polyglyceryl tetraisoStearate, diglyc preventing effect can be enhanced. In other words, the SPF eryl tetraisostearate, trioctanoin, diisoStearyl malate, neopen (Sun Protection Factor) of the cosmetic product can be tyl glycol dioctanoate, propylene glycol didecanoate, enhanced by the same amount of the inorganic pigment. Fur cholesterol fatty acid ester, isopropyl myristate, glyceryl ther, the high water-holding properties of the esterification monostearate, glycerin fatty acid ester eicosadioate conden reaction product of the present invention can improve the 45 sate, dextrin palmitate, dextrin myristate, and dextrin fatty stability of W/O type emulsions, and thereby water-in-oil acid ester, fatty acids Such as Stearic acid, lauric acid, myristic type (W/O type) emulsions excellent in the long-term stabil acid, behenic acid, isostearic acid, and oleic acid; higher ity can be obtained by blending the esterification reaction alcohols such as Stearyl alcohol, cetyl alcohol, lauryl alcohol, product to the emulsions. Thus, Sunscreen cosmetic products oleyl alcohol, isostearyl alcohol, behenyl alcohol, stearyl having a long-acting effect, excellent adhesion to skin, and 50 alcohol, octyldodecanol, and isohexadecyl alcohol; silicones film-forming feeling and further having excellent ultraviolet Such as low-polymerized dimethylpolysiloxane, high-poly preventing effect and long-term stability can be obtained by merized dimethylpolysiloxane, methylphenylpolysiloxane, blending the above-mentioned ester compound to the Sun decamethylcyclopentasiloxane, octamethylcyclotetrasilox screen cosmetic products. ane, polyether-modified polysiloxane, polyoxyalkylene? The content of the esterification reaction product of the 55 alkylmethylpolysiloxane/methylpolysiloxane copolymer, present invention in a cosmetic product varies depending on and alkoxy-modified polysiloxane; fluorinated oils such as the formulation of the cosmetic product, but is preferably 0.1 perfluorodecane, perfluorooctane, and perfluoropolyether; to 80% by mass, more preferably 1 to 80% by mass, more amino acid ester oils such as N-acylglutamic acid Such as preferably 1 to 60% by mass, more preferably 1 to 40% by Stearoylglutamic acid, and di(cholesteryl or phytosterol/be mass, and most preferably 5 to 40% by mass for further 60 henyl/octyldodecyl) N-lauroyl-L-glutamate; and lanolin improving the feelings of use Such as adhesion, waterproof derivatives such as lanolin, liquid lanolin, lanolin acetate, film-forming, and moisturizing. liquidlanolin acetate, isopropyllanolate, and lanolin alcohol. The esterification reaction product of the present invention These oil ingredients may be used alone or in a combination is excellent in the water-holding properties and thereby has an of two or more thereof. effect of enhancing the stability of W/O emulsion. Therefore, 65 Examples of the aqueous ingredients include lower alco water-in-oil-type (W/O type) emulsion having long-term sta hols such as ethyl alcohol and butyl alcohol; glycols such as bility can be obtained by blending the esterification reaction propylene glycol. 1,3-butylene glycol, dipropylene glycol, US 7,632,957 B2 9 10 and polyethylene glycol; glycerols such as glycerin, diglyc taine, and Sulfobetaine. These amphoteric Surfactants may be erin, and polyglycerin; and plant extracts such as aloe Vera, used alone or in a combination of two or more thereof. witch hazel, hammamelis, cucumber, tomato, apple, lemon, Examples of the oleophilic nonionic Surfactants include lavender, and rose. These aqueous ingredients may be used Sorbitan fatty acid esters such as Sorbitan monooleate, Sorbi alone or in a combination of two or more thereof. tan monoisostearate, Sorbitan monolaurate, Sorbitan mono Examples of the polymer emulsions include alkyl acrylate palmitate, Sorbitan monostearate, Sorbitan sesquioleate, Sor copolymer emulsion, alkyl methacrylate polymer emulsion, bitan trioleate, diglycerolsorbitan penta-2-ethylhexylate, and alkyl acrylate copolymer emulsion, alkyl methacrylate diglycerolsorbitan tetra-2-ethylhexylate; Sucrose fatty acid copolymer emulsion, acrylic acid/alkyl acrylate copolymer esters; glyceryl fatty acids such as glyceryl monocottonseed emulsion, methacrylic acid/alkyl methacrylate copolymer 10 fatty acid, glyceryl monoerucate, glyceryl sesquioleate, glyc emulsion, alkyl acrylate/styrene polymer emulsion, alkyl eryl monoStearate, glyceryl C.C.'-oleate pyroglutamate, and methacrylate/styrene copolymer emulsion, vinyl acetate glyceryl monostearate; polyglyceryl fatty acid esters such as polymer emulsion, polyvinyl acetate emulsion, vinyl acetate diglyceryl monoisoStearate and diglyceryl diisoStearate; pro containing copolymer emulsion, vinylpyrrolidone/styrene pylene glycol fatty acid esters such as propylene glycol copolymer emulsion, and silicone-containing copolymer 15 monostearate; hydrogenated castor oil derivatives; and glyc emulsion. These polymer emulsions may be used alone or in erin alkylethers. These oleophilic nonionic Surfactants may a combination of two or more thereof. be used alone or in a combination of two or more thereof. Examples of the hydrophilic nonionic Surfactants include Examples of the anionic Surfactants include soap base POE-sorbitan fatty acid esters such as POE-sorbitan materials; fatty acid soap Such as sodium laurate and sodium monooleate, POE-sorbitan monostearate, POE-Sorbitan palmitate; higher alkyl Sulfate esters such as Sodium lauryl monoolate, and POE-sorbitan tetraoleate; POE-sorbitol fatty sulfate and potassium lauryl sulfate; alkyl ether sulfate esters acid esters such as POE-sorbitol monolaurate, POE-sorbitol such as triethanolamine polyoxyethylene (POE) laurylether monooleate, POE-sorbitol pentaoleate, and POE-sorbitol sulfate and sodium POE laurylether sulfate; N-acylsarcosi monostearate; POE-glycerin fatty acid esters such as POE nates Such as Sodium lauroylsarcosinate; higher fatty acid 25 glycerin monostearate, POE-glycerin monoisoStearate, and amide sulfonates such as sodium N-myristoyl-N-methyl tau POE-glycerin triisostearate; POE-fatty acid esters such as rate, sodium coconut fatty acid methyl taurate, and sodium POE-monooleate, POE-distearate, POE-monodioleate, and lauryl methyl taurate; phosphate esters such as sodium POE ethylene glycol distearate; POE-alkyl ethers such as POE oleylether phosphate and POE stearylether phosphate; sulfo lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behe Succinates such as di-2-ethylhexyl Sodium SulfoSuccinate, 30 nyl ether, POE-2-octyldodecyl ether, and POE-cholestanol Sodium monolauroyl monoethanolamide polyoxyethylene ether; pluronic types such as Pluronic; POE/POP alkyl ethers Sulfo Succinate, and sodium lauryl polypropylene glycol sul such as POE/POP-cetyl ether, POE/POP-2-decyltetradecyl foSuccinate; alkylbenzenesulfonates such as sodium linear ether, POE/POP-monobutyl ether, POE/POP-hydrogenated dodecylbenzene sulfonate, triethanolamine linear dodecyl lanolin, and POE/POP-glycerin ether; tetra POE/tetra POP benzene Sulfonate, and linear dodecylbenzenesulfonic acid; 35 ethylenediamine polymers such as Tetronic; POE-castor oil N-acylglutamates such as monosodium N-lauroyl glutamate, hydrogenated castor oil derivatives such as POE-castor oil, disodium N-Stearoyl glutamate, and monosodium N-myris POE-hydrogenated castor oil, POE-hydrogenated castor oil toyl-L-glutamate; higher fatty acid ester Sulfate esters such as monoisoStearate, POE-hydrogenated castor oil triisoStearate, Sodium hydrogenated coconut fatty acid glyceryl Sulfate; Sul POE-hydrogenated castor oil monopyroglutamate monoisos fated oils such as Turkey red oil; POE alkyl ether carboxy 40 tearate diester, and POE-hydrogenated castor oil maleate; lates; POE alkylallyl ether carboxylate: C-olefin sulfonates: POE-beeswax/lanolin derivatives such as POE-sorbitol bees higher fatty acid ester Sulfonates; secondary alcohol Sulfate wax; alkanol amides such as coconut oil fatty acid diethano esters; higher fatty acid alkylolamide Sulfate esters; sodium lamide, lauric acid monoethanolamide, and fatty acid isopro lauroyl monoethanolamide Succinate; di-triethanolamine panolamide; POE-propylene glycol fatty acid esters; POE N-palmitoylaspartate; and sodium caseinate. These anionic 45 alkylamines; POE-fatty acid amides; sucrose fatty acid Surfactants may be used alone or in a combination of two or esters; POE-nonylphenyl formaldehyde polymers; alky more thereof. lethoxydimethylamine oxides; and trioleyl phosphate. These Examples of the cationic Surfactants include alkyltrim hydrophilic nonionic Surfactants may be used alone or in a ethylammonium salts such as Stearyltrimethylammonium combination of two or more thereof. chloride and lauryltrimethylammonium chloride; dialky 50 Examples of the natural Surfactants include lecithins such ldimethylammonium salts such as distearyldimethylammo as soybean phospholipid, hydrogenated Soybean phospho nium chloride; alkylpyridinium salts such as poly(N,N'-dim lipid, yolk phospholipid, and hydrogenated yolk phospho ethyl-3,5-methylenepiperidinium)chloride and lipid; and Soybean Saponin. These natural Surfactants may be cetylpyridinium chloride; alkyl quaternary ammonium salts; used alone or in a combination of two or more thereof. alkyldimethylbenzylammonium salts; alkylisoquinolinium 55 Examples of the moisturizing agents include polyethylene salts; dialkylmorpholinium salts; POE alkylamines; alky glycol, propylene glycol, glycerin, 1,3-butylene glycol, Xyli lamine salts; polyamine fatty acid derivatives; amyl alcohol tol, sorbitol, maltitol, chondroitin sulfuric acid, hyaluronic fatty acid derivatives; benzalkonium chloride; and benzetho acid, mucoitin Sulfuric acid, caronic acid, atherocollagen, nium chloride. These cationic Surfactants may be used alone cholesteryl-12-hydroxy Stearate, Sodium lactate, urea, bile or in a combination of two or more thereof. 60 acid salts, d1-pyrrolidone carboxylic acid salts, short-chain Examples of the amphoteric Surfactants include imidazo soluble collagen, diglycerol (EO) PO adducts, Rosa rox line amphoteric Surfactants such as Sodium 2-undecyl-N,N. burghii extracts, Achillea millefolium extracts, and Melilotus N-(hydroxyethylcarboxymethyl)-2-imidazoline and 2-co officinalis extracts. These moisturizing agents may be used coyl-2-imidazoliniumhydroxide-1-carboxyethyloxy 2 alone or in a combination of two or more thereof. Sodium salt; and betaine Surfactants such as 2-heptadecyl-N- 65 Examples of the thickeners include gum Arabic, carrag carboxymethyl-N-hydroxyethylimidazolinium betaine, lau eenan, karayagum, tragacanth gum, carob gum, quince seeds ryldimethylaminoacetic acid betaine, alkylbetaine, amidobe (marmelo), casein, dextrin, gelatin, sodium pectate, sodium US 7,632,957 B2 11 12 alginate, methylcellulose, ethylcellulose, CMC, hydroxyeth gallic acid ester. These antioxidants may be used alone or in a ylcellulose, hydroxypropylcellulose, PVA, PVM, PVP. combination of two or more thereof. Sodium polyacrylate, carboxyvinyl polymer, locust bean Examples of the ultraviolet absorbers include benzoate gum, guar gum, tamarind gum, dialkyldimethylammonium ultraviolet absorbers such as p-aminobenzoic acid (hereinaf cellulose Sulfate, Xanthan gum, magnesium aluminum sili ter referred to as PABA), PABA monoglycerin ester, N.N- cate, bentonite, hectorite, quaternary ammonium cation dipropoxy PABAethyl ester, N,N-diethoxy PABAethyl ester, modified bentonite, quaternary ammonium cation-modified N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl hectorite, and decaglycerin fatty acid ester eicosadioate con ester, and N,N-dimethyl PABA octyl ester; anthranilic acid densate. These thickeners may be used alone or in a combi ultraviolet absorbers such as homomethyl-N-acetyl anthra nation of two or more thereof. 10 nilate: Salicylic acid ultraviolet absorbers such as amyl sali Examples of the preservatives include methylparaben, eth cylate, menthyl salicylate, homomethyl salicylate, octyl sali ylparaben, and butylparaben. These preservatives may be cylate, phenyl salicylate, benzyl salicylate, and p-isopropanol used alone or in a combination of two or more thereof. phenyl salicylate; cinnamic acid ultraviolet absorbers such as Examples of the powdery ingredients include inorganic octyl cinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-di powder Such as talc, kaolin, mica, sericite, white mica, gold 15 isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, mica, synthetic mica, red mica, black mica, rithia mica, Ver methyl-2,4-diisopropylcinnamate, propyl-p-methoxycin micurite, magnesium carbonate, calcium carbonate, alumi namate, isopropyl-p-methoxycinnamate, isoamyl-p-meth num silicate, barium silicate, calcium silicate, magnesium oxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p- silicate, strontium silicate, tungstate metal salts, magnesium, methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, silica, Zeolite, barium Sulfate, calcined calcium Sulfate (cal cyclohexyl-p-methoxycinnamate, ethyl-O-cyano-B-phenyl cined gypsum), calcium phosphate, fluorine apatite, cinnamate, 2-ethylhexyl-O-cyano-B-phenylcinnamate, and hydroxyapatite, ceramic powder, metallic Soap (zinc glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate; myristate, calcium palmitate, and aluminum Stearate), and benzophenone ultraviolet absorbers such as 2,4-dihydroxy boron nitride; organic powder Such as polyamide resin pow benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, der (nylon powder), polyethylene powder, methyl poly 25 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2.2',4,4-tet methacrylate powder, polystyrene powder, copolymer resin rahydroxybenzophenone, 2-hydroxy-4-methoxybenzophe powder of Styrene and acrylic acid, benzoguanamine resin none, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hy powder, poly(ethylene tetrafluoride) powder, and cellulose droxy-4-methoxybenzophenone-5-Sulfonate, powder. These powder ingredients may be used alone or in a 4-phenylbenzophenone, 2-ethylhexyl-4-phenylbenzophe combination of two or more thereof. 30 none-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, Examples of the pigments include inorganic white pig and 4-hydroxy-3-carboxybenzophenone; 3-(4-methylben ments such as titanium dioxide and Zinc oxide (including fine Zylidene)-d.l-camphor, 3-benzylidene-d.l-camphor; uro particles of titanium dioxide or Zinc oxide which are used as canic acid; ethyl urocanate ester, 2-phenyl-5-methylbenzox ultraviolet-scattering agents and Surface-coated inorganic azole; 2,2'-hydroxy-5-methylphenylbenzotriazole: 2-(2- white pigments given by coating the Surfaces of the particles 35 hydroxy-5'-t-octylphenyl)benzotriazole: 2-(2-hydroxy-5'- with fatty acid soap Such as aluminum Stearate or Zinc palmi methylphenyl)benzotriazole; dibenZalazine; tate; fatty acid Such as Stearic acid, myristic acid, or palmitic dianisoylmethane: 4-methoxy-4-t-butyldibenzoylmethane: acid; or fatty acid ester Such as dextrin palmitate); inorganic 5-(3.3-dimethyl-2-norbornylidene)-3-pentan-2-one; 2.4.6- red pigments such as iron oxide (bengara) and iron titanate; trianilino-p-(carbo-2'-ethylhexyl-1'-oxy)1,3,5-triazine; and inorganic brown pigments such as Y-iron oxide; inorganic 40 4-tert-butyl-4'-methoxydibenzoylmethane. These ultraviolet yellow pigments such as yellow iron oxide and yellow ocher; absorbers may be used alone or in a combination of two or inorganic black pigments such as black iron oxide, carbon more thereof. black, and titanium Suboxide; inorganic violet pigments such Examples of the dyes include chlorophyll and B-carotene. as mango violet and cobalt violet; inorganic green pigments These dyes may be used alone or in a combination of two or Such as chromium oxide, chromium hydroxide, and cobalt 45 more thereof. titanate; inorganic blue pigments such as ultramarine blue and Examples of the perfumes include plant perfumes such as iron blue; pearl pigments such as titanium oxide-coated mica, rose oil, jasmine oil, and lavender oil; and synthetic perfumes titanium oxide-coated bismuth oxychloride, titanium oxide Such as limonene, citral, linalool, and eugenol. These per coated talc, colored titanium oxide-coated mica, bismuth fumes may be used alone or in a combination of two or more oxychloride, and argentine film; metal powderpigments such 50 thereof. as aluminum powder and copper powder, organic pigments Examples of the sequestering agents include disodium ede such as Red Nos. 201, 202, 204, 205, 220, 226, 228, and 405, tate, edetic acid salts, and hydroxyethane diphosphonate. Orange Nos. 203 and 204, Yellow Nos. 205 and 401, and Blue These sequestering agents may be used alone or in a combi nation of two or more thereof. No. 404, and organic pigments such as Zirconium, barium, 55 and aluminum lakes of Red Nos. 3, 104, 106, 227, 230, 401, and 505, Orange No. 205, Yellow Nos. 4, 5, 202, and 203, EXAMPLES Green No. 3, and Blue No. 1. These pigments may be used alone or in a combination of two or more thereof. The present invention will now be further described in Examples of the pH-adjusters include edetic acid, diso 60 detail with reference to Examples. However, it is apparent dium edetate, citric acid, Sodium citrate, Sodium hydroxide, that the present invention is not limited to the Examples. In potassium hydroxide, and triethanolamine. These pH-adjust the following Examples, the terms part(s) and % denote ers may be used alone or in a combination of two or more part(s) by mass and% by mass, respectively, unless otherwise thereof. specified. Examples of the antioxidants include vitamin C, its deriva 65 Further, the acid value and hydroxyl value of esterification tives, and salts thereof, tocopherol, its derivatives, and salts reaction products were measured according to an old edition thereof: dibutylhydroxy toluene; butylhydroxy anisole; and of the Japanese Standards of Cosmetic Ingredients. US 7,632,957 B2 13 14 Production Example 1 After the completion of the reaction, the catalyst was removed by filtration. Then, the reaction product was A 1 liter tetra-neck flask equipped with a stirrer, a tempera bleached with activated clay and deodorized by blowing ture gauge, a nitrogen gas inlet tube, and a moisture separator steam under reduced pressure to obtain 325 g of an esterifi was charged with 483 g of 12-hydroxyStearic acid (manufac cation reaction product as a semisolid (paste) at room tem tured by Kawaken Fine Chemicals Co., Ltd. under the trade perature. name HydroxyStearic Acid), and tin chloride as a catalyst at a The obtained esterification reaction product had an acid concentration of 0.1% to the total charged amount and xylol value of 1.2 mg KOH/g and a hydroxyl value of 123 mg as a reflux solventata concentration of 5% to the total charged KOH/g. amount were added thereto. The resulting mixture was heated 10 to 200° C. for 15 hours while removing produced water under Production Example 4 a nitrogen gas flow to obtain a 12-hydroxyStearic acid poly mer. The obtained polymer had an acid value of 33 mg KOH/ A 1 liter tetra-neck flask equipped with a stirrer, a tempera g. The average polymerization degree calculated from the ture gauge, a nitrogen gas inlet tube, and a moisture separator acid value was 6 to confirm that the obtained product was a 15 was charged with 442 g of a 12-hydroxy Stearic acid polymer hexamer of 12-hydroxy Stearic acid. (acid value: 33 mg KOH/g, hexamer) prepared by the same Then, a 1 liter tetra-neck flask equipped with a stirrer, a procedure as in Production Example 1 and 43 g of dipen temperature gauge, a nitrogen gas inlet tube, and a moisture taerythritol (manufactured by KOEI PERSTOP Co., Ltd. separator was charged with 477 g of the thus obtained 12-hy under the trade name “di-Pentalit”). The resulting mixture droxystearic acid polymer (acid value: 33 mg KOH/g, hex was subjected to reaction at 210°C. while removing produced amer) and 17 g of dipentaerythritol (manufactured by KOEI water under a nitrogen gas flow until the acid value of the PERSTOP Co., Ltd. under the trade name “di-Pentalit”). The product was reduced to 1 mg KOHg or less. resulting mixture was subjected to reaction at 210°C. while After the completion of the reaction, the product was sepa removing produced water under a nitrogen gas flow until the rated from the unreacted dipentaerythritol, and a targetesteri acid value of the product was reduced to 1 mg KOH/g or less. 25 fication reaction product having a hydroxyl value of about After the completion of the reaction, the catalyst was 100 mg KOH/g was not obtained. removed by filtration. Then, the reaction product was bleached with activated clay and deodorized by blowing Production Example 5 steam under reduced pressure to obtain 340 g of an esterifi cation reaction product as a viscous liquid at room tempera 30 An esterification reaction product (330 g), which was a ture. The obtained esterification reaction product had an acid Viscous liquid at room temperature, was obtained by the same value of 0.5 mg KOH/g and a hydroxyl value of 35 mg procedure as in Production Example 1, except that the amount KOH/g. of the 12-hydroxystearic acid polymer (acid value: 33 mg KOH?g, hexamer) obtained by the same procedure as in Pro Production Example 2 35 duction Example 1 was 462g and the amount of dipentaeryth ritol (manufactured by KOEI PERSTOP Co., Ltd. under the A 12-hydroxystearic acid polyer was obtained by the same trade name “di-Pentalit) was 29 g. The obtained esterifica procedure as in Production Example 1, except that 487 g of tion reaction product had an acid value of 0.4 mg KOHIg and 12-hydroxystearic acid, manufactured by Kokura Synthetic a hydroxyl value of 44 mg. KOH/g. Industies, Ltd. under the trade name “12-Hydro acid (HP), 40 was used and the reaction was conducted for 18 hours. The Production Example 6 obtained polymer was measured for its acid value. The acid value was 19 mg KOH.g., and the average polymerization A 12-hydroxy Stearic acid polymer (acid value: 33 mg degree calculated from the acid value was 10 to confirm that KOH?g, hexamer) was obtained by the same procedure as in the obtained product was a decamer. 45 Production Example 1, except that 12-hydroxystearic acid Then, 344 g of an esterification reaction product was manufactured by Kokura Synthetic Industies, Ltd., under the obtained by the same procedure as in Production Example 1, trade name “12-Hydro acid (HP)' was used instead of 12-hy except that 478 g of the thus obtained 12-hydroxystearic acid droxystearic acid (manufactured by Kawaken Fine Chemi polymer (acid value: 19 mg KOH/g, decamer) and 13 g of cals Co., Ltd. under the trade name Hydroxystearic Acid). dipentaerythritol were used. The obtained esterification reac 50 Then, 338 g of an esterification reaction product, which tion product had an acid value of 0.2 mg KOH/g and a was a viscous liquid at room temperature, was obtained by the hydroxyl value of 31 mg KOH/g. same procedure as in Production Example 1, except that the amount of the obtained 12-hydroxy Stearic acid polymer was Production Example 3 475 g and that the amount of dipentaerythritol (manufactured 55 by KOEI PERSTOP Co., Ltd. under the trade name “di A 1 liter tetra-neck flask equipped with a stirrer, a tempera Pentalit) was 16 g. The obtained esterification reaction prod ture gauge, a nitrogen gas inlet tube, and a moisture separator uct had an acid value of 0.9 mg KOH/g and a hydroxyl value was charged with 413 g of 12-hydroxyStearic acid (manufac of 52 mg KOH/g. tured by Kawaken Fine Chemicals Co., Ltd. under the trade The esterification reaction products obtained in Production name Hydroxystearic Acid) and 87 g of dipentaerythritol 60 Examples 1 to 3 were evaluated as described below. Table 1 (manufactured by KOEI PERSTOP Co., Ltd. under the trade shows the results of evaluations (1), (3), and (4), Table 2 name “di-Pentalit”), and tin chloride as a catalyst at a con shows the results of evaluations (5) and (6), FIGS. 1 to 6 show centration of 0.1% to the total charged amount and Xylol as a the results of evaluation (2), and FIG. 7 shows the results of reflux solvent at a concentration of 5% to the total charged evaluation (7). In addition, by way of comparison, evaluations amount were added thereto. The resulting mixture was sub 65 (1) to (4) were conducted using liquid lanolin, cholesteryl jected to reaction at 210°C. for 20 hours while removing hydroxystearate (manufactured by The Nisshin OilliO produced water under a nitrogen gas flow. Group, Ltd. under the trade name Salacos HS), or diisostearyl US 7,632,957 B2 15 16 malate (manufactured by The Nisshin OilliO Group, Ltd. (5) Non-Dyeing Property Test under the trade name Cosmol 222). Furthermore, by way of A dye (Red No. 218) is dissolved in a sample to prepare a comparison, evaluations (5) and (6) were conducted using dye mixture containing 0.5% by mass of the dye. This dye liquid lanolin, polyglyceryl trisoStearate (manufactured by mixture is applied to the upper arm of a subject. After 3 hours, The Nisshin OilliO Group, Ltd. under the trade name: Cos- 5 the applied dye is wiped away with cotton. The skin is mol 43V), or diisostearyl malate (manufactured by The Nis observed under a microscope (x100) for observing the shin OilliO Group, Ltd. under the trade name Cosmol 222). amount of the dye remaining on the skin. Furthermore, by way of comparison, evaluation (7) was con The portion of skin applied with the dye is observed under ducted using liquidlanolin, trioctanoin (manufactured by The a microscope (x100), and the samples are classified into the Nisshin OilliO Group, Ltd. under the trade name T.I.O), 10 following levels according to visual observation. polyglyceryl triisostearate (manufactured by The Nisshin OilliO Group, Ltd. under the trade name Cosmol 43V), or O: skin is not dyed with dye disostearyl malate (manufactured by The Nisshin OilliO A: skin is slightly dyed with dye Group, Ltd. under the trade name Cosmol 222). X: skin is dyed with dye (1) Water-Holding Property Test 1 15 In this evaluation, a smaller amount of the dye remaining The water-holding property test of esterification reaction on the skin means better non-dyeing properties. products is conducted with reference to the lanolin water (6) Water Resistant Ability (Waterproof-Film-Forming Abil retention value test in British Pharmacopoeia (BP) as follows: ity) A measurement sample (1 g) and Vaseline (9 g) are mixed and vigorously stirred (200 to 300 rpm) in a thermostat cham A sample is dissolved in chloroform to prepare a sample ber at 40°C. while dropwise adding purified water thereto. Solution containing 10% by mass of the sample. The prepared The point when water is no longer being received is deter sample solution is applied onto a washed glass plate. Then, mined as the end-point and is expressed as a percentage of the solvent is removed to form a film, and one drop of distilled mass of water to mass of the mixture. A higher value means water is dropped onto the formed film. The contact angle better water-holding properties of the sample. 25 between the film surface and the water droplet is measured. After the measurement, the film is washed with flowing tap (2) Water-Holding Property Test 2 water (25 mL/s, 1 minute). The water resistant ability is A measurement sample and water are mixed at a mass ratio evaluated by comparing the contact angles before and after of 7:3 and are vigorously stirred (500 rpm, 3 minutes) in a the washing. A Smaller difference in the contact angle before thermostatic chamber at 70° C. to obtain a water-holding 30 and after the washing means better water resistant ability. Substance. The obtained water-holding Substance is analyzed with a differential scanning calorimeter (device name “DSC (7). Oxidative Stability (CDM Test) 6200, manufactured by Seiko Instruments Inc.). That is, the A sample is subjected to a CDM test (Standard oils and fats temperature of the water-holding Substance is raised at a rate analyzing test method: 120°C., Air: 20 L/hr) to evaluate the of 2°C./min in the range from -15° C. to 45° C. to obtain a 35 oxidative stability. In the test, changes of the dielectric con differential scanning calorimetry curve, and the curve is con stants are measured over time using a Rancimat type device firmed whether an endothermic peak due to water at around 0° (manufactured by Metrohm). In the CDM test, a sample C. is present or not. When this endothermic peak is not exhibiting less increase in the dielectric constant with the observed, the water-holding properties are judged to be good. lapse of time means to be excellent in oxidative stability. (3) Water-Retaining Property Test 40 A measurement sample (1 g) and Vaseline (9 g) are mixed TABLE 1 and vigorously stirred (500 rpm, 3 minutes) in a thermostat (1) Water- (3) Water- 4) Dispersibility chamber at 40° C. while dropwise adding 10 g of purified water thereto (the ratio of purified water to the mixture of 45 holding retaining Wetting sample and Vaseline was 1:1). When the sample become properties properties point Fluid point smooth, 10 g of the sample is uniformly applied onto a Petri (% by mass) (% by mass) (% by mass) (% by mass) Production 740 O.8 1 2 dish so as to have a thickness of 0.5 to 1.5 mm and then put in Example 1 athermostat chamber at 40°C. with the lid off. After 24 hours, Production S8O O.9 1 2 the sample is taken out from the chamber. The mass after the 50 Example 2 still standing is measured, and the reduced mass after the Production 150 8.2 2 5 standing is calculated and is expressed as a percentage to the Example 3 Liquid lanolin 350 2.1 3 5 mass of the applied sample. A lower value means better Cholesteryl 320 1.9 2 9 water-retaining properties of the sample. hydroxystearate Diisostearyl 200 3.0 3 22 (4) Dispersibility Test 55 A sample (4 g) and titanium oxide (20g) are mixed, and malate then octyl palmitate (manufactured by The Nisshin OilliO Group, Ltd. under the trade name Salacos P-8) is gradually The followings were confirmed by the results shown in added thereto. The point when the mixture become uniform Table 1. Liquid lanolin, cholesteryl hydroxystearate, and dii as a whole is determined as the wetting point, and the point 60 SoStearyl malate were not excellent in water-holding proper when the mixture starts to flow by tilting the whole mixture is ties, water-retaining properties, and dispersibility. The esteri determined as the fluid point. The amounts of octyl palmitate fication reaction product prepared in Production Example 3, added until to reach the respective points are measured and which did not contain 12-hydroxyStearic acid polymers and used as the wetting point value and the fluid point value. had a hydroxyl value outside the range of esterification reac A lower wetting point value or a smaller difference 65 tion products according of the present invention, was inferior between the wetting point value and the fluid point value in water-holding properties, water-retaining properties, and means higher pigment-dispersing properties of the sample. dispersibility. On the other hand, the esterification reaction US 7,632,957 B2 17 18 products prepared in Production Examples 1 and 2 were The evaluation results of oxidative stability are shown in excellent in the water-holding properties, water-retaining FIG. 7. FIG. 7 is a graph showing the evaluation results of properties, and dispersibility. oxidative stability (CDM test). The horizontal axis represents The results of water-holding test 2 are shown in FIGS. 1 to elapsed time and the vertical axis represents dielectric con 6. FIG. 1 is a graph showing the results of water-holding 5 stant. As shown in FIG. 7, the dielectric constant of the esteri fication reaction product prepared in Production Example 1 property test 2 of the esterification reaction product obtained did not substantially vary with the lapse of time. Thus, it was in Production Example 1. As shown in FIG. 1, in the esteri confirmed that the esterification reaction product was very fication reaction product prepared in Production Example 1, excellent in oxidative stability. In addition, the esterification an endothermic peak due to water at around 0°C. was not 10 reaction product did not have changes in the color tone and detected. This means that the esterification reaction product odor before and after the test, and thus it was confirmed that prepared in Production Example 1 has an ability to hold a the esterification reaction product was also excellent in ther large amount of water as fine particles and is also stable mal stability. In other compounds used in this test, the dielec against temperature change. tric constant increased with the lapse of time, and therefore it FIG. 2 is a graph showing the results of water-holding 15 was confirmed that the oxidative stability of these compounds property test 2 of the esterification reaction product obtained was inferior to that of the esterification reaction product pre in Production Example 2. As shown in FIG. 2, in the esteri pared in Production Example 1. Furthermore, though it is not fication reaction product prepared in Production Example 2. shown in the figure, the esterification reaction product pre an endothermic peak due to water at around 0°C. was not pared in Production Example 2 also had the same oxidative detected. This means that the esterification reaction product 20 stability as that of the product in Production Example 1. prepared in Production Example 2 has an ability to hold a Then, cosmetic products were produced and were each large amount of water as fine particles and is also stable evaluated. The evaluation of the cosmetic products was con against temperature change. ducted by sensory evaluation as follows: FIG. 3 is a graph showing the results of water-holding Sensory Evaluation of Cosmetic Product property test 2 of the esterification reaction product obtained 25 Each cosmetic product was used by ten sensory evaluation in Production Example 3. As shown in FIG. 3, in the esteri panelists and evaluated for the following items: spread fication reaction product prepared in Production Example 3, (whether or not the cosmetic product is Smoothly spread on, an endothermic peak due to water at around 0° C. was for example, skin), moisturizing feeling (whether or not the detected. This means that the esterification reaction product cosmetic product moisturizes, for example, skin), gloss prepared in Production Example 3 does not have an ability to 30 (whether or not the cosmetic product imparts natural gloss to, hold a large amount of water as fine particles and is also not for example, hair), softness (whether or not the cosmetic stable against temperature change. product imparts softness to skin, hair, or the like), film-form FIGS. 4 to 6 are graphs showing the results of water ing feeling (whether or not film-forming feeling is obtained holding property test 2 of liquid lanolin, cholesteryl hydrox after application of the cosmetic product), adhesion (whether yStearate, and diisoStearyl malate, respectively. As shown in 35 or not adhesiveness is obtained after application of the cos FIGS. 4 to 6, in each of these compounds, an endothermic metic product), conditioning feeling (whether or not the cos peak due to water at around 0°C. was detected. This means metic product imparts well-conditioning feeling to hair), din that these compounds cannot hold a large amount of water as giness (whether or not the cosmetic product is well clung to fine particles and are also not stable against temperature eyelashes), Smoothness (whether or not the cosmetic product change. 40 has smoothness upon application), curling feeling (whether or not the cosmetic product well curls eyelashes), tautness TABLE 2 (whether or not the cosmetic product imparts tautness to the applied portion), shine (whether or not the cosmetic products Water resistant ability imparts shine of the applied portion), effective length (difference in 45 (whether or not the makeup lasts for a long time after appli Dyeing properties contact angle ()) cation), color development (whether or not the cosmetic Production Example 1 O 4.3 product develops bright color at the applied portion), impact Production Example 2 O 4.5 resistance (whether or not the makeup is maintained against Production Example 3 A 1.7 touching), cleansing properties (whether or not the cleansing Liquid lanolin X 32.5 50 Polyglyceryl trilisostearate A 21.O ability is good), and hardness (whether or not the cosmetic Diisostearyl malate X 47.4 product such as lip rouge has sufficient hardness). Each evalu ation item was evaluated and was given an evaluation score The followings were confirmed by the results shown in according to the following evaluation criteria. Table 2. The esterification reaction products prepared in Pro 55 Evaluation Criteria duction Examples 1 and 2 were excellent in the non-dyeing Score 6: very excellent properties and had an effect to suppress the adhesion of dyes Score 5: excellent to skin. In addition, the difference in the contact angle Score 4: very good between the film surface and the water droplet before and Score 3: good after washing was Small in each of the esterification reaction products prepared in Production Examples 1 and 2, compared 60 Score 2: bad to those in liquid lanolin, polyglyceryl triisoStearate, and Score 1: poor disoStearyl malate. This means that these esterification reac Score 0: very poor tion products are excellent in water resistance. In other words, In addition, the average scores of the 10 sensory evaluation the esterification reaction products prepared in Production 65 panelists were calculated and the cosmetic products were Examples 1 and 2 are excellent in the non-dyeing properties evaluated based on the average scores according to the fol and water resistance. lowing evaluation criteria. US 7,632,957 B2 19 20 Scoresc5: ©(very excellent) taste and odor were not felt. Furthermore, it was confirmed 5>Scoresc3: O (excellent) that the Stick-type lip rouge of Example 1 reduced Smudges. 3>Scorele1: A (borderline) Example 2 and Comparative Example 3 1>Score: X (particularly poor) Production of Paste-Type Lip Rouge Example 1, Comparative Examples 1 and 2 Paste-type lip rouge having the formula shown in Table 5 was produced by the following process. Production of Stick-Type Lip Rouge Raw materials 1 to 12 were uniformly mixed and melted by 10 heating, and then raw materials 13 to 16 were added thereto. The resulting mixture was uniformly mixed and then put into Stick-type lip rouge having the formula shown in Table 3 a container to obtain paste-type lip rouge. The lip rouge was was produced by the following process. In the Examples sensorily evaluated. Table 6 shows the results. shown below, the unit of numerals in Tables is “96 by mass'. 15 Raw materials 3 to 5 were added to a part of raw material TABLE 5 11, and the mixture was treated with a roller to prepare a Comparative pigment part. Raw material 6 was dissolved in a part of raw Raw material Example 2 Example 3 material 11 to prepare a dye part. Raw material or 2 was mixed 1. Esterification reaction product 1O.O with raw materials 7 to 15. The resulting mixture was melted (Production Example 2) by heating, and then the pigment part and the dye part were 2. Lanolin 1O.O added thereto. The resulting mixture was uniformly dispersed 3. 12-Hydroxystearic acid 1.O 1.O 4. Dextrin fatty acid ester 3.0 3.0 with a homomixer. The resulting dispersion was poured into 5. Dimethyldichlorosilane treated fumed silica 1.O 1.O a mold and then rapidly cooled to obtain Stick-type lip rouge. 6. Aluminum isostearate 1.O 1.O 25 7. Heavy liquid isoparaffin 2S.O 2S.O The lip rouge was sensorily evaluated. Table 4 shows the 8. Diglyceryl tetraisostearate 2O.O 2O.O results. 9. Propylene glycol dicaprate 1O.O 1O.O 10. Antioxidant O.1 O.1 TABLE 3 11.2-Hydroxy-4-methoxybenzophenone O.1 O.1 12. Diisostearyl malate balance balance 30 13. Red No. 202 O.2 O.2 Comparative Comparative 14. Yellow No. 4 1.2 1.2 Raw material Example 1 Example 1 Example 2 15. Titanium oxide 3.0 3.0 16. Black iron oxide O.2 O.2 1. Esterification reaction 11.0 Tota 1OO.O 1OO.O product (Production Example 2) 2. Liquid lanolin 11.O 35 3. Titanium dioxide S.O S.O S.O 4. Red No. 201 O.6 O.6 O6 TABLE 6 5. Red No. 202 1.O 1.O 1.O 6. Red No. 223 O.2 O.2 O.2 Sensory test Example 2 Comparative Example 3 7. Candelilla wax 9.O 9.0 9.0 40 Effective length (3) A 8. Solid paraffin 8.0 8.O 8.0 Color development (3) O 9. Beewax S.O S.O S.O Adhesion (6) A 10. Carnauba wax S.O S.O S.O Film-forming feeling (6) A 11. Castor oil 2S.O 2S.O 36.0 12. Cetyl 2-ethylhexanoate 2O.O 2O.O 2O.O 13. Isopropyl myristic acid ester 1O.O 1O.O 1O.O 45 The followings were confirmed by the results shown in 14. Antioxidant O.1 O.1 O.1 Table 6. 15. Perfume O.1 O.1 O.1 It was recognized that the paste-type lip rouge of Example 2 was excellent in the color development of the pigment, Total 1OO.O 1OO.O 1OOO adhesion, and film-forming feeling (uniformity of cosmetic film) and maintained makeup for a long time. In addition, the 50 paste-type lip rouge of Example 2 was Superior to the paste type lip rouge of Comparative Example 3 in all the color TABLE 4 development, adhesion, and film-forming feeling. The Comparative Comparative makeup also lasted for a longer time. Sensory test Example 1 Example 1 Example 2 55 Example 3 and Comparative Example 4 Spread (6) (6) A Moisturizing feeling (6) O O Production of Stick-Type Lip Balm Containing Gloss (3) O A Glycerin

The followings were confirmed by the results shown in 60 Glycerin-containing Stick-type lip balm having the for Table 4. mula shown in Table 7 was produced by the following pro CCSS, It was recognized that the Stick-type lip rouge of Example All raw materials were mixed and melted by heating, and 1 was Smoothly spread on lips, imparted natural gloss to the then uniformly dispersed with a homomixer to obtain a dis lips, and had a moisturizing effect. In addition, the Stick-type 65 persion. The resulting dispersion was poured into a mold and lip rouge of Example 1 had excellent effects compared to the then rapidly cooled to obtain glycerin-containing Stick-type Stick-type lip rouge of Comparative Examples 1 and 2, and lip balm. US 7,632,957 B2 21 22 The glycerin-containing material in Table 7 was prepared as follows: TABLE 9 The esterification reaction product prepared in Production Example 1 and Vaseline were mixed at a mass ratio of esteri Raw material Example 4 Comparative Example 5 fication reaction product:Vaseline=1:9 (mass ratio). This 5 1. Vitamin C derivative- 1.1 mixture was stirred while dropwise adding glycerin thereto containing material 2. Esterification reaction product S.O up to an amount ten times the mixture to obtain a glycerin (Production Example 1) containing material. The results of sensory evaluation are 3. Liquid lanolin S.O shown in Table 8. 4. Vitamin C derivative aqueous 1.O 10 Solution TABLE 7 5. Celesin 8.0 8.0 6. Candelilla wax 1O.O 1O.O Raw material Example 3 Comparative Example 4 7. Microcrystalline wax 4.0 4.0 8. Dipentaerythrityl 1O.O 1O.O 1. Glycerin-containing material 1.1 (hydroxyStearatestearatefrosinate) 2. Esterification reaction product S.O 15 9. Diisostearyl malate 17.0 17.0 (Production Example 1) 10. Trioctanoin 1O.O 1O.O 3. Liquid lanolin S.O 11. Polyglyceryl trilisostearate balance balance 4. Glycerin 1.O Total 1OOO 1OOO 5. Ceresin 6.O 6.O 6. Candelilla wax 1O.O 1O.O 7. Microcrystalline wax 4.0 4.0 2O 8. Dipentaerythrityl 1O.O 1O.O TABLE 10 (hydroxyStearatestearatefrosinate) 9. Castor oil 17.0 17.0 Sensory test Example 4 Comparative Example 5 10. Trioctanoin 1S.O 1S.O 11. Polyglyceryl trilisostearate balance balance Moisturizing feeling (3) X Total 1OOO 1OOO Spread (3) X 25 Gloss (6) X Hardness (6) X

TABLE 8 The followings were confirmed by the results shown in Sensory test Example 3 Comparative Example 4 30 Table 10. Moisturizing feeling (6) A It was recognized that the vitamin C derivative-containing Spread (8) A Stick-type lip rouge of Example 4 was excellent in the mois Gloss (3) O turizing feeling, Smoothly spread on lips, imparted natural The followings were confirmed by the results shown in 35 gloss to the lips, and also had sufficient hardness. In addition, Table 8. these effects of the vitamin C derivative-containing stick-type It was recognized that the glycerin-containing stick-type lip rouge of Example 4 were higher than those of the stick lip balm of Example 3 was excellent in the moisturizing type lip rouge of Comparative Example 5. Furthermore, taste feeling, Smoothly spread on lips, and imparted natural gloss and odor were not felt. to the lips. In addition, the glycerin-containing stick-type lip 0 balm of Example 3 was superior to the stick-type lip balm of Example 5 and Comparative Example 6 Comparative Example 4 in all the moisturizing feeling, spread, and gloss. Furthermore, taste and odor were not felt. Production of Liquid Foundation (O/W Type) Example 4 and Comparative Example 5 45 Liquid foundation (O/W type) having the formula shown in Production of Stick-Type Lip Rouge Containing Table 11 was produced by the following process. Vitamin C Derivative Raw material 18 was dispersed in raw material 10, and then raw materials 19 and 20 were added thereto. The resulting Vitamin C derivative-containing Stick-type lip rouge hav- 50 mixture was treated with a homomixer at 70° C., and then the ing the formula shown in Table 9 was produced by the fol remaining aqueous ingredients (raw materials 11 and 12) lowing process. were added thereto. The resulting mixture was thoroughly All raw materials were mixed and melted by heating, and mixed to prepare an aqueous phase. Then, powder ingredients then uniformly dispersed with a homomixer to obtain a dis (raw materials 13 to 17) were sufficiently mixed and pulver persion. The resulting dispersion was poured into a mold and 55 ized and then added to the aqueous phase while stirring. The then rapidly cooled to obtain vitamin C derivative-containing Stick-type lip rouge. mixture was treated with a homomixer at 70° C. The vitamin C derivative-containing material in Table 9 At the same time, raw material 1 or 2 and oil ingredients was prepared as follows: (raw materials 3 to 8) were dissolved by heating at 70 to 80° The esterification reaction product prepared in Production 60 C. to prepare an oil phase. Then, this oil phase was gradually Example 1 and Vaseline were mixed at a mass ratio of esteri added to the aqueous phase containing the powder ingredi fication reaction product:Vaseline=1:9 (mass ratio). This ents. The resulting mixture was treated with a homomixer at mixture was stirred while dropwise adding a 20% magne 70° C. and then cooled to 45°C. while stirring, and then raw sium-L-ascorbyl-phosphate aqueous solution thereto up to an material 9 was added thereto. After cooling to room tempera amount tentimes the mixture to obtainavitamin C derivative- 65 ture, the cooled mixture was deaerated and put in a container containing material. The results of sensory evaluation are to obtain liquid foundation (O/W type). The results of sensory shown in Table 10. evaluation are shown in Table 12. US 7,632,957 B2 23 24

TABLE 11 TABLE 13-continued Comparative Comparative Raw material Example 5 Example 6 Raw material Example 6 Example 7 1. Esterification reaction product 1.5 3. Trioctanoin 2O.O 2O.O (Production Example 1) 4. Dimethyl polysiloxane (20 cs) 1.O 1.O 2. Cholesteryl hydroxystearate 1.5 5. Octamethylcyclotetrasiloxane S.O S.O 3. Squalane 3.0 3.0 6. Squalane S.O S.O 4. Liquid paraffin 3.0 3.0 7. Cetyl 2-ethylhexanoate 2.0 2.O 5. Dimethyl polysiloxane O.2 O.2 10 8. Polyether-modified polysiloxane 3.0 3.0 6. Stearic acid 2.5 2.5 9. Sorbitan sesquioleate 1.O 1.O 7. Sorbitan sesquioleate 1.O 1.O 10. Titanium oxide 7.0 7.0 8. Cetyl alcohol O.S O.S 11. Zinc oxide 4.0 4.0 9.1% Sodium hydroxide aqueous solution 1.3 1.3 12. Talc 4.7 4.7 10.1% Carboxyvinyl polymer aqueous solution S.O S.O 13. Mica 2.0 2.O 11. 1,3-Butylene glycol 8.0 8.0 15 14. Red iron oxide O.2 O.2 12. Triethanolamine 0.7 0.7 15. Yellow iron oxide 1.6 1.6 13. Talc 3.0 3.0 16. Black iron oxide O.2 O.2 14 Titanium dioxide S.O S.O 17. Nylon powder 2.0 2.O 15. Bengara O.S O.S 18. Titanated mica 2.0 2.O 16. Yellow iron oxide 1.4 1.4 19. Ethyl alcohol S.O S.O 17. Black iron oxide O.1 O.1 20. Glycerin S.O S.O 18. Bentonite O.S O.S 21. Antioxidant O.1 O.1 19. Preservative O.1 O.1 22. Moisturizing agent O.1 O.1 20. Purified water 62.7 62.7 23. Perfume O.1 O.1 24. Purified water balance balance Total 1OOO 1OOO Total 1OOO 1OO.O 25

TABLE 12 TABLE 1.4 Sensory test Example 5 Comparative Example 6 Sensory test Example 6 Comparative Example 7 Film-forming feeling (3) A 30 Effective length (3) A Adhesion (3) O Adhesion O A Moisturizing feeling (3) (3) Spread (3) O Softness O O Film-forming feeling (3) A

The followings were confirmed by the results shown in 35 The followings were confirmed by the results shown in Table 12. Table 14. It was recognized that the liquid foundation (O/W type) of It was recognized that the foundation (W/O type) of Example 5 well adhered to skin and moisturized and softened Example 6 was excellent in adhesion to skin, spread, and the skin. It was confirmed that the liquid foundation (O/W film-forming feeling (uniformity of cosmetic film), and the type) of Example 5 was superior to the liquid foundation 40 makeup was maintained for a long time. In addition, it was (O/W type) of Comparative Example 6 in all the film-forming confirmed that the foundation (W/O type) of Example 6 was superior to the foundation (W/O type) of Comparative feeling, adhesion, moisturizing feeling, and softness. Example 7 in all the adhesion, spread, and film-forming feel Example 6 and Comparative Example 7 ing. Furthermore, the makeup was maintained for a longer 45 time. Production of Foundation (W/O Type) Example 7 and Comparative Example 8 Foundation (W/O type) having the formula shown in Table 13 was produced by the following process. Production of Solid Powder Foundation 50 Raw materials 1 to 9 were mixed and melted by heating and Solid powder foundation having the formula shown in then cooled to 40°C., and then raw materials 10 to 18 were Table 15 was produced by the following process. added to thereto. The resulting mixture was dispersed with a Raw materials 1 to 4 were mixed and heated to 50° C. to homomixer to obtain mixture (A). At the same time, raw obtain mixture (A). At the same time, raw materials 5 to 13 materials 19 to 24 were uniformly mixed and dissolved to were mixed and dispersed and were then mixed with mixture obtain mixture (B). Then, mixture (B) was added to mixture 55 (A) to obtain mixture (B). The resulting mixture (B) was (A), and the resulting mixture was emulsified with a homo pulverized and compression molded into a plate to obtain mixer to obtain foundation (W/O type). The results of sensory solid powder foundation. The results of sensory evaluation evaluation are shown in Table 14. are shown in Table 16.

TABLE 13 60 TABLE 1.5 Comparative Comparative Raw material Example 6 Example 7 Raw material Example 7 Example 8 1. Esterification reaction product 1O.O 1. Esterification reaction product 1O.O (Production Example 1) 65 (Production Example 1) 2. Diisostearyl malate 1O.O 2. Liquid lanolin 1O.O US 7,632,957 B2

TABLE 15-continued TABLE 1.8 Comparative Sensory test Example 8 Comparative Example 9 Raw material Example 7 Example 8 Effective length (6) O 3. Dimethyl polysiloxane 2.0 2.0 Adhesion (3) O 4. Squalane S.O S.O Film-forming feeling (3) A 5. Polystyrene 2.0 2.0 6. Titanium oxide S.O S.O 7. Bengara O.S O.S The followings were confirmed by the results shown in 8. Yellow iron oxide 1.2 1.2 10 Table 18. 9. Black iron oxide O.1 O.1 10. Sericite SO.O SO.O It was recognized that the solid face powder of Example 11. Mica 2O.O 2O.O was excellent in adhesion to skin, film-forming feeling (uni 12. Talc 3.7 3.7 13. Preservative O.S O.S formity of cosmetic film), and the makeup was maintained for 15 a long time. In addition, it was confirmed that the Solid face Total 1OOO 1OOO powder of Example 8 was superior to the solid face powder of Comparative Example 9 in both the adhesion and film-form ing feeling. Furthermore, the makeup was maintained for a longer time. TABLE 16 Sensory test Example 7 Comparative Example 8 Example 9 and Comparative Example 10 Effective length (6) A Adhesion (6) O Production of Powder Cake Foundation (Using Film-forming feeling (3) A Water) 25 Powder cake foundation having the formula shown in The followings were confirmed by the results shown in Table 19 was produced by the following process. Table 16. Raw materials 8 to 15 were mixed and dispersed to obtain It was recognized that the solid powder foundation of mixture (A). At the same time, raw materials 1 to 6 were Example 7 was excellent in adhesion to skin, film-forming 30 mixed under heating to 50° C. to obtain mixture (B). Then, feeling (uniformity of cosmetic film), and the makeup was mixture (B) and raw material 7 were added to mixture (A), maintained for a long time. In addition, it was confirmed that and the resulting mixture was uniformly mixed to obtain the solid powder foundation of Example 7 was superior to the mixture (C). Then, the resulting mixture (C) was pulverized solid powder foundation of Comparative Example 8 in both and compression molded into a plate to obtain powder cake the adhesion and film-forming feeling. Furthermore, the 35 foundation. The results of sensory evaluation are shown in makeup was maintained for a longer time. Table 20.

Example 8 and Comparative Example 9 TABLE 19 Production of Solid Face Powder Comparative 40 Raw material Example 9 Example 10 Solid face powder having the formula shown in Table 17 1. Esterification reaction product S.O was produced by the following process. (Production Example 1) 2. Diisostearyl malate S.O Raw materials 6 to 10 were mixed and dispersed to obtain 3. POE-sorbitan monooleate (20 E.O.) 1.O 1.O mixture (A). Raw materials 1 to 5 were added to mixture (A), 45 4. Trioctanoin 4.0 4.0 and the resulting mixture was uniformly mixed to obtain 5. Dimethyl polysiloxane S.O S.O 6. Dipropylene glycol 3.0 3.0 mixture (B). The resulting mixture (B) was pulverized and 7. Perfume O.1 O.1 compression molded into a plate to obtain Solid face powder. 8. Silicone-treated talc. SO.O SO.O The results of sensory evaluation are shown in Table 18. 9. Fluorine-treated sericite? 17.1 17.1 10. Titanated mica 2.0 2.0 50 11. Bengara O.S O.S TABLE 17 12. Yellow iron oxide 2.0 2.0 13. Black iron oxide O.3 O.3 Comparative 14. Boron nitride powder S.O S.O Raw material Example 8 Example 9 15. Nylon powder S.O S.O 1. Esterification reaction product 1O.O 55 (Production Example 2) Total 1OO.O 1OOO 2. Esterification reaction product 1O.O (Production Example 3) 3. Dimethyl polysiloxane 1.O 1.O 4. Liquid paraffin S.O S.O TABLE 20 5. Dipentaerythrite fatty acid ester O.S O.S 6. Preservative O.S O.S 60 Sensory test Example 9 Comparative Example 10 7. Iron oxide titanated mica 2O.O 2O.O 8. Sericite 55.5 55.5 Effective length (3) A 9. Red No. 202 O.S O.S Adhesion O A 10. Spherical silica 7.0 7.0 Spread (3) A

Total 1OOO 1OOO 65 In Table 19, the raw material indicated by * 1 was treated with 5% by weight of methylhydrogen polysiloxane, and the US 7,632,957 B2 27 28 raw material indicated by *2 was treated with 5% by weight of a perfluoroalkyl phosphate ester diethanolamine salt. TABLE 23 The followings were confirmed by the results shown in Table 20. Comparative Raw material Example 11 Example 12 It was recognized that the powder cake foundation of 5 Example 9 well adhered and spread on skin, and the makeup 1. Esterification reaction product 7.0 was maintained for a long time. In addition, these effects of (Production Example 1) the powder cake foundation of Example 9 were higher than 2. Diisostearyl malate 7.0 3. Sorbitan tristearate O.OS O.OS those of the powder cake foundation of Comparative 4. POE-Sorbitan trioleate (20 E.O.) O.1 O.1 Example 10. Furthermore, the makeup was maintained for a 10 5. Stearic acid 0.4 0.4 longer time. 6. IsoStearic acid O.S O.S 7. Red No. 226 1.O 1.O Example 10 and Comparative Example 11 8. Silicone-treated bengara 1.O 1.O 9. Silicone-treated titanium oxide O.S O.S Production of Powder Eye Color 10. Silicone-treated titanated mica S.O S.O 15 11. Silicone-treated talc. 3.0 3.0 12. Methyl polymethacrylate spherical 2.0 2.0 Powder eye color having the formula shown in Table 21 powder was produced by the following process. 13. Ethyl alcohol S.O S.O Raw materials 3 to 8 were uniformly mixed and dispersed 14. Triethanolamine O.8 O.8 15. Glycerin 3.0 3.0 to obtain mixture (A), and raw materials 1 and 2 were added 16. Polyethylene glycol (400) 3.0 3.0 to mixture (A). The resulting mixture was pulverized to 17. Preservative O.1 O.1 obtain powder eye color. The results of sensory evaluation are 18. Purified water balance balance shown in Table 22. Total 1OOO 1OOO

TABLE 21 In Table 23, the raw material indicated by * was treated Comparative 25 with 5% by weight of dimethyl polysiloxane. Raw material Example 10 Example 11 1. Esterification reaction product 1O.O TABLE 24 (Production Example 1) 2. Diisostearyl malate 1O.O Sensory test Example 11 Comparative Example 12 3. Sericite 12.9 12.9 30 4. Mica 3O.O 3O.O Effective length (6) A Adhesion (3) A 5. Red No. 202 2.O 2.O 6. Titanated mica 40.O 40.O Film-forming feeling (3) A 7. Nylon powder S.O S.O 8. Preservative O.1 O.1 35 The followings were confirmed by the results shown in Total 1OO.O 1OOO Table 24. It was recognized that the eye color of Example 11 was excellent in adhesion and film-forming feeling (uniformity of cosmetic film), and the makeup was maintained for a long TABLE 22 time. In addition, the eye color of Example 11 was superior to 40 the eye color of Comparative Example 12 in both the adhesion Sensory test Example 10 Comparative Example 11 and film-forming feeling. Furthermore, the makeup was Effective length (3) A maintained for a longer time. Adhesion (6) O Spread O A Example 12 and Comparative Example 13 45 The followings were confirmed by the results shown in Production of Mascara (O/W Type) Table 22. It was recognized that the powder eye color of Example Mascara (O/W type) having the formula shown in Table 25 well adhered and spread on skin, and the makeup was main was produced by the following process. tained for a longtime. In addition, these effects of the powder 50 Raw materials 1 to 9 were dissolved by heating, and raw eye color of Example 10 were higher than those of the powder materials 10 to 12 were added thereto. The resulting mixture eye color of Comparative Example 11. Furthermore, the was uniformly mixed to obtain mixture (A). At the same time, makeup was maintained for a longer time. raw materials 13 to 21 were uniformly mixed to obtain mix Example 11 and Comparative Example 12 ture (B). Then, mixture (B) was added to mixture (A), and the 55 resulting mixture was emulsified to obtain mascara (O/W Production of Eye Color type). The results of sensory evaluation are shown in Table 26. Eye color having the formula shown in Table 23 was pro TABLE 25 duced by the following process. 60 Comparative Raw materials 1 to 6 were mixed and dissolved to obtain Raw material Example 12 Example 13 mixture (A). Raw materials 13 to 18 were heated to 80° C. 1. Esterification reaction product 3.0 and raw materials 7 to 12 were added thereto. The resulting (Production Example 1) mixture was dispersed with a homomixer to obtain a disper 2. Lanolin 3.0 sion (B). Then, dispersion (B) was added to mixture (A), and 3. Stearic acid 2.0 2.O the resulting mixture was treated with a homomixer and then 65 4. Carnauba wax 4.0 4.0 cooled to obtain eye color. The results of sensory evaluation 5. Beeswax 6.O 6.0 are shown in Table 24. US 7,632,957 B2

TABLE 25-continued TABLE 27-continued Comparative Comparative Raw material Example 12 Example 13 Raw material Example 13 Example 14 6. Cetyl alcohol 1.O 1.O 8. Preservative O.1 O.1 7. Glyceryl monostearate 1.O 1.O 9. Purified water balance balance 8. POE-sorbitan monooleate (20 E.O.) 1.5 1.5 Total 1OO.O 1OO.O 9. Sorbitan sesquioleate O.S O.S 10. Blue No. 1 1.O 1.O 11. Yellow No. 4 1.O 1.O 10 12. Iron oxide-coated titanated mica S.O S.O 13. Silica 2.5 2.5 TABLE 28 14. Triethanolamine 1.1 1.1 Sensory test Example 13 Comparative Example 14 15. 1,3-Butylene glycol 1O.O 1O.O 16. Polyvinyl acetate emulsion 1S.O 1S.O Clinginess (3) A 17. Nylon fiber 4.0 4.0 15 Smoothness (3) O 18. Carboxyvinyl polymer O.2 O.2 Curling feeling (3) O 19. Preservative O.1 O.1 Tautness (6) A 20. Beauty ingredient O.1 O.1 21. Purified water balance balance Total 1OOO 1OO.O The followings were confirmed by the results shown in 20 Table 28. It was recognized that the mascara of Example 13 readily TABLE 26 clung to eyelashes and was Smooth, and tautness and curling feeling were obtained. In addition, these effects of the mas Sensory test Example 12 Comparative Example 13 cara of Example 13 were higher than those of the mascara in Effective length (6) A 25 Comparative Example 14. Furthermore, no odor was felt. Adhesion (6) A Film-forming feeling (3) O Example 14 and Comparative Example 15 Impact resistance (3) A Production of Eyeliner (O/W Type) The followings were confirmed by the results shown in 30 Table 26. Eyeliner (O/W type) having the formula shown in Table 29 It was recognized that the mascara (O/W type) of Example WS produced by the following process. 12 was excellent in adhesion to skin, film-forming feeling Raw materials 1 to 5 were dissolved by heating, and raw (uniformity of cosmetic film), and impact resistance, and the materials 6 and 7 were added thereto. The resulting mixture makeup was maintained for a long time. In addition, the WS uniformly mixed to obtain m1Xture (A). At the same time, mascara (O/W type) of Example 12 was superior to the mas- raw materials 8 to 14 were uniformly mixed to obtain mixture cara (O/W type) of Comparative Example 13 in all the adhe- (B). Then, mixture (B) was added to mixture (A), and the Sion, film-forming feeling, and impact resistance. Further- resulting mixture was emulsified to obtain eyeliner (OW more,s the makeup was maintained for a longer time type). The results of sensory evaluation are shown in Table 30. 40 Example 13 and Comparative Example 14 TABLE 29 Comparative Production of Mascara Raw material Example 14 Example 15 Mascara having the formula shown in Table 27 was pro- E" product O.S duced by the following process. 2. Diisostearyl malate O.S Raw material 6 was added to raw material 9. The resulting 3. Stearic acid 1.O 1.O mixture was dispersed with a homomixer, and raw material 5 S. th 8. 8. was added thereto. The resulting mixture was heated to and 6. is tarate 1.0 1.0 maintained at 70° C. (phase A). Other raw materials were 50 7. Red No. 202 1.O 1.O mixed and heated to 70° C. (phase B). Phase A was added to 8. 1,3-Butylene glycol S.O S.O phase B, and the mixture was uniformly dispersed and emul- 9. St. list lsi O.2 O.2 sified to obtain mascara. The results of sensory evaluation are 10.11. AlkylTitanated acrylate mica copolymer emulsion 1O.O 1O.O shown in Table 28. ss 12. Perfume O.1 O.1 13. Preservative O.1 O.1 TABLE 27 14. Purified water balance balance Tota 1OOO 1OOO Comparative Raw material Example 13 Example 14 1. Esterification reaction product 8.0 60 TABLE 30 (Production Example 2) 2. Lanolin 8.0 Sensory test Example 14 Comparative Example 15 3. Paraffin wax 8.0 8.0 4. Light isoparaffin 3O.O 3O.O Effective length (6) O 5. Alkyl acrylate copolymer emulsion 3O.O 3O.O Film-forming feeling (3) A 6. Iron oxide 1O.O 1O.O 65 Color development (3) A 7. Sorbitan sesquioleate 4.0 4.0 US 7,632,957 B2 31 32 The followings were confirmed by the results shown in the film-forming feeling and color development. Further Table 30. more, the makeup was maintained for a longer time. It was recognized that the eyeliner (O/W type) of Example 14 was excellent in film-forming feeling (uniformity of cos Example 16 and Comparative Example 17 metic film) and color development, and the makeup was maintained for a long time. In addition, the eyeliner (O/W Production of Eyebrow (O/W Type) type) of Example 14 was superior to the eyeliner (O/W type) of Comparative Example 15 in both the film-forming feeling Eyebrow (O/W type) having the formula shown in Table 33 and color development. Furthermore, the makeup was main 10 was produced by the following process. tained for a longer time. Raw materials 1 to 7 were dissolved by heating, and raw material 8 was added thereto. The resulting mixture was Example 15 and Comparative Example 16 uniformly mixed to obtain mixture (A). At the same time, raw materials 9 to 13 were uniformly mixed to obtain mixture (B). Production of Eyeshadow (O/W Type) 15 Then, mixture (B) was added to mixture (A), and the resulting mixture was emulsified to obtain eyebrow (O/W type). The Eyeshadow (O/W type) having the formula shown in Table results of sensory evaluation are shown in Table 34. 31 was produced by the following process. TABLE 33 Raw materials 1 to 7 were dissolved by heating, and raw Comparative materials 8 and 9 were added thereto. The resulting mixture Raw material Example 16 Example 17 was uniformly mixed to obtain mixture (A). At the same time, 1. Esterification reaction product 1O.O raw materials 10 to 15 were uniformly mixed to obtain mix (Production Example 1) ture (B). Then, mixture (B) was added to mixture (A), and the 25 2. Diisostearyl malate 1O.O resulting mixture was emulsified to obtain eyeshadow (O/W 3. Stearic acid 3.0 3.0 4. Cetyl alcohol 2.0 2.0 type). The results of sensory evaluation are shown in Table 32. 5. Ethylene glycol monostearate O.S O.S 6. Glyceryl monostearate O.S O.S TABLE 31 7. Sucrose fatty acid ester 1.5 1.5 30 8. Black iron oxide 1.O 1.O Comparative 9. 1,3-Butylene glycol S.O S.O Raw material Example 15 Example 16 10. Sodium hydroxide O.2 O.2 11. Preservative O.1 O.1 1. Esterification reaction product 40.0 12. Alkyl acrylate copolymer emulsion 1O.O 1O.O (Production Example 2) 13. Purified water balance balance Total 1OOO 1OOO 2. Diisostearyl malate 40.O 35 3. Stearic acid 1.5 1.5 4. Cetyl alcohol 1.O 1.O 5. POE-sorbitan monooleate (20 E.O.) O.S O.S 6. Glyceryl monostearate O.S O.S TABLE 34 7. Sorbitan sesquioleate O.S O.S 8. Yellow No. 205 1.O 1.O 40 Sensory test Example 16 Comparative Example 17 9. Red No. 226 1.O 1.O Effective length A 10. Dipropylene glycol S.O S.O Film-forming feeling A 11. Carboxyvinyl polymer O.1 O.1 Color development O 12. Triethanolamine O.8 O.8 13. Titanium oxide-treated synthetic 1O.O 1O.O phlogopite 45 The followings were confirmed by the results shown in 14. Preservative O.1 O.1 Table 34. 15. Purified water balance balance It was recognized that the eyebrow (O/W type) of Example Tota 1OOO 1OO.O 16 was excellent in film-forming feeling (uniformity of cos 50 metic film) and color development, and the makeup was maintained for a long time. In addition, the eyebrow (O/W TABLE 32 type) of Example 16 was superior to the eyebrow (O/W type) Sensory test Example 15 Comparative Example 16 of Comparative Example 17 in both the film-forming feeling and color development. Furthermore, the makeup was main Effective length A 55 Film-forming feeling O tained for a longer time. Color development O Example 17 and Comparative Example 18 The followings were confirmed by the results shown in Production of Eyegloss (Paste Type) Table 32. 60 It was recognized that the eyeshadow (O/W type) of Eyegloss (paste type) having the formula shown in Table Example 15 was excellent in film-forming feeling (unifor was produced by the following process. mity of cosmetic film) and color development, and the Raw materials 1 to 10 were uniformly mixed and dissolved makeup was maintained for a long time. In addition, the 65 by heating to obtain a mixture. Then, the mixture was put into eyeshadow (O/W type) of Example 15 was superior to the a container to obtain eyegloss (paste type). The results of eyeshadow (O/W type) of Comparative Example 16 in both sensory evaluation are shown in Table 36. US 7,632,957 B2

TABLE 35 TABLE 38

Comparative Sensory test Example 18 Comparative Example 19 Raw material Example 17 Example 18 1. Esterification reaction product 1O.O Effective length A (Production Example 1) Adhesion O A 2. Liquid lanolin S.O 1O.O Spread O 3. Polybutene S.O 1O.O 4. Glyceryl (behenate? eicosadioate) 2.O 2.0 10 5. Sucrose fatty acid ester 3.0 3.0 6. Organic modified bentonite 2.O 2.0 The followings were confirmed by the results shown in 7. Diisostearyl malate 1O.O 1O.O Table 38. 8. 2-Ethylhexyl p-methoxycinnamate O.1 O.1 It was recognized that the powder cheek rouge of Example 9. Antioxidant O.1 O.1 15 10. Trioctanoin balance balance 18 well adhered and spread on skin, and the makeup was Total 1OO.O 1OOO maintained for a long time. In addition, the powder cheek rouge of Example 18 was Superior to the powder cheek rouge of Comparative Example 19 in both the adhesion and spread. TABLE 36 Furthermore, the makeup was maintained for a longer time. Sensory test Example 17 Comparative Example 18 Example 19 and Comparative Example 20 Effective length A Gloss O O Production of Base Coat Film-forming feeling A 25 Base coat having the formula shown in Table 39 was pro The followings were confirmed by the results shown in duced by the following process. Table 36. Raw materials 1 to 5 were uniformly mixed to obtain It was recognized that the eyegloss (paste type) of Example 30 mixture (A). Then, raw materials 6 to 8 were added to mixture 17 was excellent in gloss and film-forming feeling (unifor (A), and the resulting mixture was uniformly mixed to obtain mity of cosmetic film), and the makeup was maintained for a base coat. The results of sensory evaluation are shown in long time. In addition, the eyegloss (paste type) of Example Table 40. 17 was Superior to the eyegloss (paste type) of Comparative Example 18 in both the gloss and film-forming feeling. Fur 35 TABLE 39 thermore, the makeup was maintained for a longer time. Comparative Raw material Example 19 Example 20 Example 18 and Comparative Example 19 1. Esterification reaction product S.O 40 (Production Example 1) 2. Diisostearyl malate S.O Production of Powder Cheek Rouge 3. Isopropyl alcohol 5.5 5.5 4. Butyl acetate 3S.O 3S.O Powder cheek rouge having the formula shown in Table 37 5. Ethyl acetate 3O.O 3O.O was produced by the following process. 6. Alkyl acrylateistyrene copolymer 6.5 6.5 45 7. Sucrose benzoate ester 13.0 13.0 Raw materials 3 to 8 were uniformly mixed and dispersed 8. Toluene sulfonamide resin S.O S.O to obtain mixture (A). Then, raw materials 1 and 2 were added Total 1OOO 1OOO to mixture (A), and the resulting mixture was pulverized and compression molded into a plate to obtain powder cheek 50 rouge. The results of sensory evaluation are shown in Table TABLE 40 38. Sensory test Example 19 Comparative Example 20 TABLE 37 Effective length O Gloss O A Comparative 55 Film-forming feeling A Raw material Example 18 Example 19 1. Esterification reaction product 7.0 (Production Example 2) The followings were confirmed by the results shown in 2. Liquid lanolin 7.0 Table 40. 3. Talc 6O.O 6O.O 4. Mica 10.9 10.9 60 Base coats are applied to nails previous to the application 5. Red No. 226 2.O 2.0 6. Boron nitride powder 1S.O 1S.O of manicure products and planarize the nail Surfaces to allow 7. Nylon powder S.O S.O the manicure products to spread well. It was recognized that 8. Preservative O.1 O.1 the base coat of Example 19 improved the gloss and film Total 1OO.O 1OOO 65 forming feeling of a manicure product, and Such effects were maintained for a long time. In addition, the base coat of Example 19 was superior to the base coat of Comparative US 7,632,957 B2 35 Example 20 in both the gloss and film-forming feeling. Fur thermore, the gloss was maintained for a longer time. TABLE 43 Comparative Example 20 and Comparative Example 21 Raw material Example 21 Example 22 1. Esterification reaction product S.O Production of Top Coat (Production Example 1) 2. Castor oil S.O 3. Nitrocellulose 1O.O 1O.O Top coat having the formula shown in Table 41 was pro 4. Alkyd resin 1O.O 1O.O duced by the following process. 10 5. Ethyl acetate 2SO 2SO 6. Butyl acetate 40.O 40.O Raw materials 1 to 5 were uniformly mixed to obtain 7. Ethyl alcohol S.O S.O mixture (A). Then, raw materials 6 to 9 were added to mixture 8. Titanium oxide-coated mica 2.0 2.0 9. Red No. 202 1.O 1.O (A), and the resulting mixture was uniformly mixed to obtain 10. Black iron oxide 1.O 1.O top coat. The results of sensory evaluation are shown in Table 15 11. Yellow iron oxide O.S O.S 42. 12. Red No. 228 O.S O.S Total 1OOO 1OOO TABLE 41 Comparative Raw material Example 20 Example 21 TABLE 44 1. Esterification reaction product 8.0 (Production Example 2) Sensory test Example 21 Comparative Example 22 2. Esterification reaction product 8.0 (Production Example 3) Clinginess O Smoothness A 3. Isopropyl alcohol S.O S.O 25 4. Butyl acetate 3S.O 3S.O Shine A 5. Ethyl acetate 3O.O 3O.O Adhesion A 6. Alkyl acrylateistyrene copolymer 3.0 3.0 7. Sucrose benzoate ester 7.0 7.0 8. Toluene sulfonamide resin 2.O 2.0 The followings were confirmed by the results shown in 9. Nitrocellulose 1O.O 1O.O 30 Table 44. It was recognized that the nail enamel of Example 21 Total 1OO.O 1OOO readily clung to nails, was excellent in smoothness and shine, reduced the roughness of nails, and showed good adhesion. In addition, the effects of the nail enamel of Example 21 were TABLE 42 35 higher than those of the nail enamel of Comparative Example 22. Sensory test Example 20 Comparative Example 21 Effective length O Example 22 and Comparative Example 23 Shine O A Adhesion O 40 Production of Cleansing Cream The followings were confirmed by the results shown in Cleansing cream having the formula shown in Table 45 was Table 42. produced by the following process. Top coats are applied on manicure products to improve the Raw materials 1 to 8 were mixed and dissolved by heating shine of the manicure products and keep the effects of the 45 to 70° C. to obtain mixture (A). At the same time, raw mate manicure products. It was recognized that the top coat of rials 9 to 13 were mixed and heated to 70° C. to obtain mixture (B). Mixture (A) was gradually added to mixture (B) while Example 20 applied on a manicure product improved the stirring at 70° C. for saponification reaction. After the shine of the manicure product and kept the effects of the completion of the Saponification reaction, the mixture was manicure product for a long time. In addition, it was recog 50 nized that the top coat of Example 20 was superior to the top cooled while stirring to obtain cleansing cream. The results of coat of Comparative Example 21 in improvement of the shine sensory evaluation are shown in Table 46. and adhesion. Furthermore, the shine was maintained for a TABLE 45 longer time. 55 Comparative Example 21 and Comparative Example 22 Raw material Example 22 Example 23 1. Esterification reaction product 1.O Production of Nail Enamel (Production Example 2) 2. Polyglyceryl-2 trilisostearate 1.O 3. Lauric acid S.O S.O Nail enamel having the formula shown in Table 43 was 60 4. Myristic acid 1O.O 1O.O 5. Palmitic acid 1O.O 1O.O produced by the following process. 6. Stearic acid S.O S.O Raw materials 7 and 4 were mixed to raw material 1 or 2, 7. Oleyl alcohol 1.5 1.5 8. High-polymerized dimethylpolysiloxane O.1 O.1 and the resulting mixture was kneaded well. Then, other raw 9. Glycerin 18.0 18.0 materials were added thereto, and the resulting mixture was 65 10. Potassium hydroxide 6.O 6.0 uniformly dispersed to obtain nail enamel. The results of 11. Preservative O.S O.S sensory evaluation are shown in Table 44. US 7,632,957 B2 37 38 cleansing oil of Example 23 were higher than those of the TABLE 45-continued cleansing oil of Comparative Example 24. Comparative Raw material Example 22 Example 23 Example 24 and Comparative Example 25 12. Perfume O.1 O.1 13. Purified water balance balance Production of Cleansing Cream Total 1OOO 1OO.O Cleansing cream having the formula shown in Table 49 was 10 produced by the following process. TABLE 46 Raw materials 1 to 9 were dissolved by heating and uni formly mixed to obtain mixture (A). At the same time, raw Sensory test Example 22 Comparative Example 23 materials 10 to 15 were heated and uniformly mixed to obtain Softness A mixture (B). Mixture (B) was added to mixture (A) at 80°C. Moisturizing properties O 15 for emulsification and then cooled to obtain cleansing cream. Creaminess A Cleansing properties O The results of sensory evaluation are shown in Table 50. TABLE 49 The followings were confirmed by the results shown in Comparative Table 46. Raw materia Example 24 Example 25 It was recognized that the cleansing cream of Example was 1. Esterification reaction product 8.0 excellent in cleansing properties, and softened, moisturized, (Production Example 2) and smoothened skin. Furthermore, these effects of the 2. Esterification reaction product 8.0 (Production Example 3) cleansing cream of Example 22 were higher than those of the 25 3. Stearic acid S.O S.O cleansing cream of Comparative Example 23. 4. Cetyl alcohol 2.0 2.0 5. Sorbitan sesquioleate 1.O 1.O 6. POE-sorbitan monooleate (20 E.O.) 2.0 2.0 Example 23 and Comparative Example 24 7. Dimethyl polysiloxane O.S O.S 8. Squalane 1S.O 1S.O 30 9. Trioctanoin S.O S.O Preparation of Cleansing Oil 10. Glycerin S.O S.O 11. 1,3-Butylene glycol 1O.O 1O.O 12. Sodium hydroxide 0.7 0.7 Cleansing oil having the formula shown in Table 47 was 13. Preservative O.S O.S produced by the following process. 14. Perfume O.1 O.1 35 15. Purified water balance balance Raw materials 1 to 7 were uniformly mixed to obtain Total 1OOO 1OOO cleansing oil. The results of sensory evaluation are shown in Table 48. TABLE 50 TABLE 47 40 Comparative Sensory test Example 24 Comparative Example 25 Raw material Example 23 Example 24 Softness A Moisturizing properties O 1. Esterification reaction product 3.0 Smoothness A (Production Example 1) Cleansing properties A 2. Liquid lanolin 3.0 45 3. Trioctanoin 2O.O 2O.O 4. Cetyl 2-ethylhexanoate 32.O 32.O 5. Liquid paraffin 40.9 40.9 The followings were confirmed by the results shown in 6. POE-Sorbit tetraoleate (30 E.O.) 4.0 4.0 Table 50. 7. Perfume O.1 O.1 50 It was recognized that the cleansing cream of Example 24 Total 1OO.O 1OOO was excellent in cleansing properties, and softened, moistur ized, and smoothened skin. Furthermore, these effects of the cleansing cream of Example 24 were higher than those of the cleansing cream of Comparative Example 25. TABLE 48 55 Sensory test Example 23 Comparative Example 24 Example 25 and Comparative Example 26 Softness O Production of Lotion Moisturizing properties O Creaminess A Cleansing properties O 60 Lotion having the formula shown in Table 51 was produced by the following process. The followings were confirmed by the results shown in Raw materials 1 to 4 were uniformly mixed and dissolved to obtain mixture (A). At the same time, raw materials 5 to 9 Table 48. were uniformly mixed and dissolved to obtain mixture (B). It was recognized that the cleansing oil of Example 23 was 65 Then, mixture (A) was added to mixture (B) while stirring to excellent in cleansing properties, and softened, moisturized, obtain lotion. The results of sensory evaluation are shown in and smoothened skin. Furthermore, these effects of the Table 52. US 7,632,957 B2 40 The followings were confirmed by the results shown in TABLE 51 Table 54. It was recognized that the serum of Example 26 was well Comparative spread on skin and softened it, and moisturized the skin for a Raw material Example 25 Example 26 long time. In addition, these effects of the serum of Example 1. Esterification reaction product O.S 26 were higher than those of the serum of Comparative (Production Example 2) Example 27. 2. Liquid lanolin O.S 3. Ethyl alcohol S.O S.O 4. POE-hydrogenated castor oil (60 E.O.) 1.O 1.O Example 27 and Comparative Example 28 5. Glycerin 3.0 3.0 10 6. 1,3-Butylene glycol 1O.O 1O.O Production of Milky Lotion 7. Alkyl-modified carboxyvinyl polymer O.O1 O.O1 8. Preservative O.S O.S 9. Purified water balance balance Milky lotion having the formula shown in Table 55 was Total 1OOO 1OO.O produced by the following process. 15 Raw materials 1 to 6 were mixed and dissolved at 80°C. to obtain mixture (A). At the same time, raw materials 7 to 12 TABLE 52 were mixed and heated to 80° C. and were added to mixture (A). The resulting mixture was treated with a homomixer and Sensory test Example 25 Comparative Example 26 then cooled to obtain milky lotion. The results of sensory Softness A evaluation are shown in Table 56. Moisturizing properties O Smoothness O A TABLE 55 Comparative The followings were confirmed by the results shown in Raw material Example 27 Example 28 Table 52. 25 It was recognized that the lotion of Example 25 softened, 1. Esterification reaction product 1O.O moisturized, and Smoothened skin. Furthermore, these (Production Example 1) 2. Lanolin 1O.O effects of the lotion of Example 25 were higher than those of 3. Liquid paraffin 2O.O 2O.O the lotion of Comparative Example 26. 4. Cetyl alcohol O.S O.S 30 5. Stearoyl glutamate 1.O 1.O Example 26 and Comparative Example 27 6. Glyceryl monostearate 3.0 3.0 7. Dipropylene glycol 1O.O 1O.O 8. Glycerin S.O S.O Production of Serum 9. Carboxyvinyl polymer O.OS O.OS 10. Preservative O.1 O.1 Serum having the formula shown in Table 53 was produced 35 11. Sodium hydroxide proper quantity proper quantity by the following process. 12. Purified water balance balance Raw materials 1 to 5 were mixed and dissolved to obtain Total 1OO.O 1OO.O mixture (A). Raw materials 6 to 11 were mixed and heated to 80° C. to obtain mixture (B). Mixture (B) was added to mixture (A), and the resulting mixture was treated with a TABLE 56 homomixer and then cooled to obtain serum. The results of 40 sensory evaluation are shown in Table 54. Sensory test Example 27 Comparative Example 28 Spread A TABLE 53 Moisturizing properties O Softness A Comparative 45 Raw material Example 26 Example 27 1. Esterification reaction product 2.O The followings were confirmed by the results shown in (Production Example 1) Table 56. 2. Trioctanoin 2.0 It was recognized that the milky lotion of Example 27 was 3. Sorbitan sesquioleate O.1 O.1 50 well spread on and softened skin and moisturized the skin for 4. POE-sorbitan monooleate (20 E.O.) O.S O.S 5. Cetyl 2-ethylhexanoate S.O S.O a long time. Furthermore, these effects of the milky lotion of 6. Ethyl alcohol 1O.O 1O.O Example 27 were higher than those of the milky lotion of 7. Dipropylene glycol 1O.O 1O.O Comparative Example 28. 8. Glycerin 1O.O 1O.O 9. Perfume O.1 O.1 10. Preservative O.1 O.1 55 Example 28 and Comparative Example 29 11. Purified water balance balance Total 1OO.O 1OOO Production of Emollient Cream (W/O Type) Emollient cream (W/O type) having the formula shown in 60 Table 57 was produced by the following process. TABLE 54 Raw material 1 and raw material 2 or 3 were mixed at room Sensory test Example 26 Comparative Example 27 temperature to obtain mixture (A). At the same time, raw Spread O materials 4 to 8 were uniformly dissolved while heating to 80° Moisturizing properties A C., and then mixture (A) was gradually added thereto and Softness A 65 uniformly dispersed to obtain mixture (B). Then, raw mate rials 9 and 10 were heated to 70° C. and were added to mixture (B) while emulsifying the mixture with a homomixer. Then, US 7,632,957 B2 41 deaeration, filtration, and cooling were conducted to obtain emollient cream (W/O type). The results of sensory evalua TABLE 60 tion are shown in Table 58. Sensory test Example 29 Comparative Example 30 TABLE 57 Moisturizing properties O Adhesion A Comparative Softness O O Raw material Example 28 Example 29 Film-forming feeling A 1.1% Sodium alginate aqueous solution 1O.O 1O.O 2. Esterification reaction product 3.0 10 (Production Example 1) The followings were confirmed by the results shown in 3. Esterification reaction product 3.0 Table 60. (Production Example 3) It was recognized that the vitamin C derivative-containing 4. Ceresin 1.O 1.O cream of Example 29 well moistured, adhered to, and soft 5. Beeswax 2.0 2.0 ened skin and that film-forming feeling was maintained for a 6. Vaseline S.O S.O 7. Squalane 32.O 32.O 15 long time, and that these effects of the vitamin C derivative 8. Liquid paraffin 1O.O 1O.O containing cream of Example 29 were higher than those of the 9. Glycerin 2.0 2.0 Vitamin C derivative-containing cream of Comparative 10. Purified water 3S.O 3S.O Example 30. Total 1OO.O 1OOO Example 30 and Comparative Example 31 Production of Eye Cream TABLE 58 Eye cream having the formula shown in Table 61 was Sensory test Example 28 Comparative Example 29 25 produced by the following process. Spread Raw materials 1 to 8 were mixed and dissolved at 80°C. to Moisturizing properties O obtain mixture (A). Then, raw materials 9 to 14 were mixed Softness O and heated to 80° C. and then added to mixture (A). The resulting mixture was treated with a homomixer and then The followings were confirmed by the results shown in 30 cooled to obtain eye cream. The results of sensory evaluation Table 58. are shown in Table 62. It was recognized that the effects of spread, moisturizing properties, and softness were imparted to the emollient cream TABLE 61 of Example 28 and the emollient cream of Comparative Comparative Example 29, and these effects of the emollient cream of 35 Raw material Example 30 Example 31 Example 28 were higher than those of the cleansing cream of 1. Esterification reaction product 1.5 Comparative Example 29. (Production Example 2) 2. Polybutene 1.5 Example 29 and Comparative Example 30 3. Sorbitan tristearate O.OS O.OS 40 4. POE-Sorbitan trioleate (20 E.O.) O.1 O.1 5. Di (phytosteryl behenylfoctyldodecyl) O.S O.S Production of Vitamin C Derivative-Containing N-lauroyl-L-glutamate Cream 6. Microcrystalline wax O.S O.S 7. Stearyl alcohol 2.5 2.5 8. Dimethyl polysiloxane O.S O.S Vitamin C derivative-containing cream having the formula 9. Dipropylene glycol S.O S.O shown in Table 59 was produced by the following process. 45 10. Glycerin S.O S.O Raw materials 1 to 3 were uniformly mixed to obtain 11. Sodium alginate O.1 O.1 12. Preservative O.1 O.1 mixture (A). At the same time, raw materials 4 to 9 were 13. Perfume O.1 O.1 uniformly mixed to obtain mixture (B). Then, mixture (B) 14. Purified water balance balance was added to mixture (A) and emulsified to obtain vitamin C Total 1OOO 1OO.O derivative-containing cream. The results of sensory evalua 50 tion are shown in Table 60.

TABLE 59 TABLE 62 Sensory test Example 30 Comparative Example 31 Example Comparative 55 Raw material 29 Example 30 Spread A Moisturizing feeling A 1. Esterification reaction product S.O (Production Example 1) Softness A 2. Organic modified hectorite 1.5 1.5 3. Trioctanoin 2S.O 3O.O 4. Magnesium-L-ascorbyl-phosphate 3.0 3.0 60 The followings were confirmed by the results shown in 5. Sodium citrate 1.O 1.O Table 62. 6. 1,3-Butylene glycol 3.0 3.0 It was recognized that the eye cream of Example 30 was 7. Preservative O.S O.S well spread on and softened skin and that moisturizing feeling 8. Perfume O.1 O.1 9. Purified water balance balance was maintained for a long time. Furthermore, it was con Total 1OOO 1OO.O 65 firmed that these effects of the eye cream of Example 30 were higher than those of the eye cream of Comparative Example 31. US 7,632,957 B2 43 44 Example 31 and Comparative Example 32 TABLE 65 Production of Conditioning Shampoo Comparative Raw material Example 32 Example 33 Conditioning shampoo having the formula shown in Table 1. Esterification reaction product 3.0 63 was produced by the following process. (Production Example 2) Raw material 8 was added to raw material 12, and the 2. Diisostearyl malate 3.0 mixture was heated to 70° C. while stirring, and other raw 3. Cetyl 2-ethylhexanoate 1O.O 1O.O 4. Liquid paraffin 9.0 9.O materials were added thereto. The resulting mixture was 10 5. Methylphenylpolysiloxane 3.0 3.0 stirred and dissolved, and then cooled to obtain conditioning 6. Alkyl-modified carboxyvinyl polymer O.1 O.1 shampoo. The results of sensory evaluation are shown in 7. Carboxymethyl cellulose O.S O.S Table 64. 8. Triethanolamine O.1 O.1 9. Propylene glycol 1O.O 1O.O 10. Preservative 1.O 1.O TABLE 63 15 11. Perfume O.1 O.1 12. Purified water balance balance Comparative Total 1OOO 1OO.O Raw material Example 31 Example 32 1. Esterification reaction product 2.5 (Production Example 2) 2. Diisostearyl malate 2.5 TABLE 66 3. Lauryl polyoxyethylene (3) sulfate 1O.O 1O.O ester triethanolamine salt Sensory test Example 32 Comparative Example 33 (30% aqueous solution) Softness A 4. Lauryl polyoxyethylene (3) sulfate 2O.O 2O.O Moisturizing feeling O ester sodium salt (30% aqueous solution) Gloss A 5. Lauryl Sulfate ester sodium salt S.O S.O 25 (30% aqueous solution) Conditioning feeling O 6. Lauroyl diethanolamide 3.0 3.0 7. Lauryldimethylaminoacetic acid betaine 7.0 7.0 (30% aqueous solution) The followings were confirmed by the results shown in 8. Cationated cellulose O.2 O.2 Table 66. 9. Perfume O.1 O.1 30 10. Preservative O.2 O.2 It was recognized that the cuticle-protecting gel of 11. Sequestering agent, pH-adjuster 1.O 1.O Example 32 well softened and moistured hair and imparted 12. Purified water S1.O 51.0 gloss and conditioning feeling to the hair. Furthermore, these Total 1OO.O 1OOO effects of the cuticle-protecting gel of Example 32 were 35 higher than those of the cuticle-protecting gel of Comparative Example 33. TABLE 64 Example 33 and Comparative Example 34 Sensory test Example 31 Comparative Example 32 Moisturizing feeling O 40 Production of Hair Rinse Gloss O O Softness O Conditioning feeling A Hair rinse having the formula shown in Table 67 was pro duced by the following process.

45 Raw materials 1 to 5 were uniformly mixed and dissolved The followings were confirmed by the results shown in to obtain mixture (A). At the same time, raw materials 6 to 9 Table 64. and 11 were uniformly mixed and dissolved to obtain mixture It was recognized that the conditioning shampoo of Example 31 imparted moisturizing feeling, gloss, softness, (B). Then, mixture (A) and mixture (B) were heated to 80°C. and conditioning feeling to hair. In addition, it was confirmed The mixture (A) was added to mixture (B) at 80° C. for that these effects of the conditioning shampoo of Example 31 50 emulsification, and then raw material 10 was mixed thereto to were higher than those of the conditioning shampoo of Com obtain hair rinse. The results of sensory evaluation are shown parative Example 32. in Table 68. TABLE 67 Example 32 and Comparative Example 33 55 Comparative Production of Cuticle-protecting Gel Raw material Example 33 Example 34 1. Esterification reaction product 1.5 Cuticle-protecting gel having the formula shown in Table (Production Example 1) 65 was produced by the following process. 2. Liquid lanolin 1.5 60 3. Cetyl 2-ethylhexanoate 1O.O 1O.O Raw materials 1 to 5 were uniformly mixed to obtain 4. Isononyl isononanoate S.O S.O mixture (A). At the same time, raw materials 6 to 10 and 12 5. Behenyl alcohol 3.0 3.0 6. Distearyldimethylammonium chloride 2.5 2.5 were uniformly mixed to obtain mixture (B). Then, mixtures 7. Highly polymerized methylpolysiloxane 2.0 2.O (A) and (B) were mixed while adding mixture (A) to mixture emulsion (B), and then raw material 11 was added thereto. The resulting 65 8. Hydroxyethyl cellulose O.2 O.2 mixture was uniformly mixed to obtain cuticle-protecting gel. 9. Preservative 1.O 1.O The results of sensory evaluation are shown in Table 66. US 7,632,957 B2 46 The followings were confirmed by the results shown in TABLE 67-continued Table 70. It was recognized that the hair conditioner of Example well Comparative softened and moistured hair and imparted gloss and condi Raw material Example 33 Example 34 tioning feeling to the hair. Furthermore, these effects of the 10. Perfume O.1 O.1 hair conditioner of Example 34 were higher than those of the 11. Purified water balance balance Total 1OOO 1OO.O hair conditioner of Comparative Example 35. Example 35 and Comparative Example 36 TABLE 68 10 Production of Hair Cream Sensory test Example 33 Comparative Example 34 Softness A Hair cream having the formula shown in Table 71 was Moisturizing feeling O produced by the following process. Gloss O A 15 Raw materials 1 to 5 were uniformly mixed and dissolved Conditioning feeling A to obtain mixture (A). Raw materials 6 to 10 and 12 were uniformly mixed and dissolved to obtain mixture (B). Then, The followings were confirmed by the results shown in mixture (A) and mixture (B) were heated to 80°C., and then Table 68. mixture (B) was added to mixture (A) at 80° C. for emulsifi It was recognized that the hair rinse of Example 33 well cation. Then, raw material 11 was added thereto, and the softened and moistured hair and imparted gloss and condi resulting mixture was cooled to obtain hair cream. The results tioning feeling to the hair. Furthermore, these effects of the of sensory evaluation are shown in Table 72. hair rinse of Example 33 were higher than those of the hair rinse of Comparative Example 34. TABLE 71 25 Comparative Example 34 and Comparative Example 35 Raw material Example 35 Example 36 Production of Hair Conditioner 1. Esterification reaction product 3.0 (Production Example 1) 30 2. Esterification reaction product 3.0 Hair conditioner having the formula shown in Table 69 was (Production Example 3) produced by the following process. 3. Dimethyl polysiloxane S.O S.O 4. Liquid paraffin 9.0 9.0 Raw materials 1 to 7 were uniformly mixed and dissolved 5. Cetyl 2-ethylhexanoate 13.0 13.0 to obtain mixture (A). At the same time, raw materials 8 to and 6. Behenyl alcohol 4.0 4.0 13 were uniformly mixed and dissolved to obtain mixture (B). 7. POE-oleyl ether 1.O 1.O Then, mixture (A) and mixture (B) were heated to 80°C., and 35 8. Propylene glycol 7.0 7.0 then mixture (A) was added to mixture (B) at 80° C. for 9. Pyrrollidone carboxylate sodium salt O.S O.S 10. Preservative O.S O.S emulsification. Then, raw material 12 was mixed thereto to 11. Perfume O.1 O.1 obtain hair conditioner. The results of sensory evaluation are 12. Purified water balance balance shown in Table 70. Total 1OOO 1OOO 40 TABLE 69 Comparative TABLE 72 Raw material Example 34 Example 35 Sensory test Example 35 Comparative Example 36 1. Esterification reaction product 2.O 45 (Production Example 2) Softness A 2. Diisostearyl malate 2.0 Moisturizing feeling O 3. Trioctanoin 3.0 3.0 Gloss O A 4. Methylphenylpolysiloxane 1.O 1.O Conditioning feeling A 5. Dimethyl polysiloxane 2.O 2.0 6. Stearyl alcohol 1.O 1.O 50 7. Cetyl alcohol O.S O.S The followings were confirmed by the results shown in 8. Cetyltrimethylammonium chloride 1.O 1.O 9. 1,3-Butylene glycol 7.0 7.0 Table 72. 10. Cationated cellulose O.2 O.2 It was recognized that the hair cream of Example 35 well 11. Preservative 1.O 1.O softened and moistured hair and imparted gloss and condi 12. Perfume O.1 O.1 55 tioning feeling to the hair. Furthermore, these effects of the 13. Purified water balance balance hair cream of Example 35 were higher than those of the hair Total 1OO.O 1OOO cream of Comparative Example 36. Example 36 and Comparative Example 37 TABLE 70 60 Production of Hair Wax Sensory test Example 34 Comparative Example 35 Softness O Hair wax having the formula shown in Table 73 was pro Moisturizing feeling O Gloss A duced by the following process. Conditioning feeling A 65 Raw materials 1 to 9 were uniformly mixed and dissolved to obtain mixture (A). At the same time, raw materials 10, 11, 13, and 14 were uniformly mixed and dissolved to obtain US 7,632,957 B2 47 48 mixture (B). Then, mixture (A) and mixture (B) were heated to 80°C., and then mixture (A) was added to mixture (B) at TABLE 75-continued 80° C. for emulsification. Then, raw material 12 was mixed thereto to obtain hair wax. The results of sensory evaluation Comparative are shown in Table 74. Raw material Example 37 Example 38 3. Stearic acid-treated titanium oxide 1O.O 1O.O TABLE 73 microparticle 4. Decamethylcyclopentasiloxane 1S.O 1S.O Comparative 5. 2-Ethylhexyl p-methoxycinnamate S.O S.O Raw material Example 36 Example 37 6. Neopentylglycol dicaprate 9.8 9.8 10 7. Trimethoxycinnamic acid 2.0 2.O 1. Esterification reaction product 2.0 8. Cetyl dimethicone copolyol 3.0 3.0 (Production Example 2) 9. POE-sorbitan monooleate (20 E.O.) O.2 O.2 2. Diisostearyl malate 2.0 10. Sorbitan sesquioleate O.8 O.8 3. Candelilla wax 3.0 3.0 11. Nylon powder 2.0 2.O 4. Paraffin wax 1O.O 1O.O 12. Perfume O.1 O.1 5. Polyoxyethylene (10) oleyl alcohol 3.0 3.0 15 13. Ethyl alcohol S.O S.O 6. Steary alcohol O.S O.S 14. Sodium chloride O.1 O.1 7. Liquid paraffin 8.0 8.O 15. 1,3-Butylene glycol S.O S.O 8. Squalane 8.0 8.O 16. Purified water balance balance 9. Glycerin fatty acid ester eicosadioate 1.O 1.O Total 1OOO 1OO.O condensate 10. 1,3-Butylene glycol S.O S.O 11. Sodium hydroxide O.1 O.1 12. Perfume O.1 O.1 TABLE 76 13. Decaglycerin fatty acid ester eicosadioate O.S O.S condensate Sensory test Example 37 Comparative Example 38 14. Purified water balance balance Total 1OOO 1OO.O Effective length A 25 Adhesion A Film-forming feeling O

TABLE 74 The followings were confirmed by the results shown in Sensory test Example 36 Comparative Example 37 30 Table 76. Softness O It was recognized that the multi-phase emulsion Sunscreen Moisturizing feeling O (W/O type) of Example 37 was excellent in adhesion to skin Gloss A and film-forming feeling (uniformity of cosmetic film), and Conditioning feeling X the makeup was maintained for a long time. The multi-phase 35 emulsion sunscreen (W/O type) of Example 37 was excellent The followings were confirmed by the results shown in in both the adhesion and the film-forming feeling compared Table 74. to those of the multi-phase emulsion sunscreen (W/O type) of It was recognized that the hair wax of Example 36 well Comparative Example 38, and the makeup was maintained softened and moistured hair and imparted gloss and condi for a longer time. tioning feeling to the hair. Furthermore, these effects of the 40 hair wax of Example 36 were higher than those of the hair wax Example 38 and Comparative Example 39 of Comparative Example 37. Production of Sunscreen Cream (O/W Type) Example 37 and Comparative Example 38 45 Sunscreen cream (O/W type) having the formula shown in Production of Multi-Phase Emulsion Sunscreen Table 77 was produced by the following process. (W/O Type) Raw materials 1 to 11 were heated to 70° C. and uniformly mixed to obtain mixture (A). At the same time, raw materials Multi-phase emulsion sunscreen (W/O type) having the 13 to 17 were heated to 70° C. and uniformly mixed to obtain formula shown in Table 75 was produced by the following 50 mixture (B). Then, mixture (B) was added to mixture (A), and process. the resulting mixture was emulsified. The resulting emulsion Raw materials 1 to 12 were uniformly mixed to obtain was cooled to room temperature, and then raw material 12 mixture (A). At the same time, raw materials 13 to 16 were was mixed thereto to obtain sunscreen cream (O/W type). The uniformly mixed to obtain mixture (B). Then, mixture (B) results of sensory evaluation are shown in Table 78. was added to mixture (A) for emulsification. The resulting 55 emulsion was put into a resin bottle in which a stainless steel TABLE 77 ball was placed to obtain multi-phase emulsion Sunscreen (W/O type). The results of sensory evaluation are shown in Comparative Table 76. Raw material Example 38 Example 39 1. Esterification reaction product 1O.O TABLE 75 60 (Production Example 2) 2. Polyglyceryl-2 trilisostearate 1O.O Comparative 3. Titanium oxide 1O.O 1O.O Raw material Example 37 Example 38 4. Cetyl 2-ethylhexanoate 7.0 7.0 5. Liquid paraffin 3.0 3.0 1. Esterification reaction product 12.0 6. POE-sorbitan monooleate (20 E.O.) 0.7 0.7 (Production Example 1) 65 7. Sorbitan sesquioleate O.3 O.3 2. Lanolin 12.O 8. Stearic acid 1.O 1.O US 7,632,957 B2 49 50

TABLE 77-continued TABLE 79-continued Comparative Example Comparative Raw material Example 38 Example 39 Raw material 39 Example 40 9. Cetostearyl alcohol 1.O 1.O 14. Decaglycerin fatty acid ester eicosadioate O.S O.S 10. Glyceryl monostearate 1.O 1.O condensate 11. Hydrogenated Soybean phospholipid O.S O.S 15. Preservative O.1 O.1 12. Perfume O.1 O.1 16. Perfume O.1 O.1 13. Sodium hydroxide O.15 O.15 17. 1,3-Butylene glycol S.O S.O 14. 1,3-Butylene glycol 1O.O 1O.O 10 18. Purified water balance balance 15. Preservative O.3 O.3 Total 1OO.O 1OO.O 16. Xanthan gum O.2 O.2 17. Purified water balance balance Total 1OO.O 1OOO TABLE 8O 15 Sensory test Example 39 Comparative Example 40 TABLE 78 Effective length A Sensory test Example 38 Comparative Example 39 Adhesion A Film-forming feeling O Effective length A Adhesion A Film-forming feeling A The followings were confirmed by the results shown in Table 80. It was recognized that the sunscreen milky lotion (W/O The followings were confirmed by the results shown in type) of Example 39 was excellent in adhesion to skin and Table 78. 25 film-forming feeling (uniformity of cosmetic film), and the It was recognized that the sunscreen cream (O/W type) of makeup was maintained for a long time. These effects of the Example 38 was excellent in adhesion to skin and film-form sunscreen milky lotion (W/O type) of Example 39 were ing feeling (uniformity of cosmetic film), and the makeup was higher than those of the sunscreen milky lotion (W/O type) of maintained for a long time. The sunscreen cream (O/W type) Comparative Example 40, and the makeup was maintained of Example 38 was excellent in both adhesion and film 30 for a longer time. In addition, it was confirmed that the solu forming feeling compared to those of the Sunscreen cream bility of 4-tert-butyl-4'-methoxydibenzoylmethane, which (O/W type) of Comparative Example 39, and the makeup was has low solubility, was improved by being mixed with an maintained for a longer time. esterification reaction product (Production Example 1). Example 39 and Comparative Example 40 35 Examples 40 to 42 and Comparative Example 41 Production of Sunscreen Milky Lotion (W/O Type) Production of Sunscreen Cream (W/O Type) Sunscreen milky lotion (W/O type) having the formula Sunscreen cream (W/O type) having the formula shown in shown in Table 79 was produced by the following process. 40 Table 81 was produced by the following process. Raw materials 1 to 7 were uniformly mixed to obtain Raw materials 1 and 5 were mixed and heated for dissolv mixture (A). At the same time, raw materials 8 to 11 were ing raw material 5, and raw materials 2 to 4 and 6 to 16 were uniformly mixed to obtain mixture (B). Then, mixture (B) added thereto. The resulting mixture was uniformly mixed to was added to mixture (A), and the resulting mixture was obtain mixture (A). At the same time, raw materials 17 and 18 45 emulsified to obtain sunscreen cream (W/O type). The results were uniformly mixed to obtain mixture (B). Then, mixture of sensory evaluation are shown in Table 82. In this embodi (B) was added to mixture (A), and the resulting mixture was ment, the SPF value was measured with UV-1000F manufac emulsified to obtain sunscreen milky lotion (W/O type). The tured by LabSphere Inc. in order to evaluate ultraviolet-pro results of sensory evaluation are shown in Table 80. tection effect as sunscreen. The obtained SPF values were 50 assessed according to the following evaluation criteria, and TABLE 79 samples satisfying the criteria represented by O were defined Example Comparative to be acceptable. Raw material 39 Example 40 O: SPF not less than 20 A: SPF not less than 10 and less than 20 1. Esterification reaction product 12.O 55 (Production Example 1) X: SPF less than 10 2. Lanolin 12.O In addition, the long-term stability was evaluated by leav 3. Octyl paramethoxycinnamate S.O S.O ing Sunscreen cream at a constant temperature of 50° C. for 4. Oxybenzone 3.0 3.0 5. 4-tert-Butyl-4'-methoxydibenzoylmethane 2.0 2.0 one month and visually inspecting a change in the appear 6. Hydrophobicized titanium dioxide S.O S.O ance. The long-term stability was evaluated according to the 7. Hydrophobicized zinc oxide S.O S.O 60 criteria shown below. Samples satisfying the criteria repre 8. Squalane 2O.O 2O.O 9. Isononyl isononanoate S.O S.O sented by or O were defined to be acceptable. 10. Silicone oil S.O S.O (9: No appearance change 11. Silicone resin 2.0 2.0 12. Glycerin diisostearate 2.0 2.0 O: Slight appearance change without a tendency of sepa 13. Poly(oxyethylene?oxypropylene) O.S O.S 65 ration methylpolysiloxane copolymer A: A little of separation X: Complete separation US 7,632,957 B2 51 52

TABLE 81 Comparative Raw material Example 40 Example 41 Example 42 Example 41 1. Esterification reaction product S.O S.O S.O (Production Example 1) 2. Organic modified hectorite 1.5 1.5 1.5 1.5 3. Liquid paraffin 2S.O 3O.O 4. Squalane 2SO 1O.O 5. Dimethyl polysiloxane 1O.O 6. Trioctanoin S.O 7. Titanium dioxide S.O S.O S.O S.O 8. 1,3-Butylene glycol 1S.O 1S.O 1S.O 1S.O 9. Preservative O.S O.S O.S O.S 10. Perfume O.1 O.1 O.1 O.1 11. Purified water balance balance balance balance Total 1OO.O 1OOO 1OOO 1OO.O

TABLE 82 2O TABLE 83-continued Example Example Example Comparative Sensory test 40 41 42 Example 41 Comparative Raw material Example 43 Example 42 Effective length A Adhesion A 25 Film-forming feeling O 9. Microcrystalline wax 2.0 2.O SPF value O O O X 10. Polyethylene wax 4.0 4.0 Long-term stability X 11. Dipentaerythrite fatty acid ester S.O S.O 12. Oxobenzone 1.O 1.O The followings were confirmed by the results shown in 13. Dimethyl polysiloxane 3.0 3.0 Table 82. 30 14. Cetyl 2-ethylhexanoate 41.6 41.6 It was recognized that the sunscreen cream (W/O type) of 15. Preservative O.2 O.2 each of Examples 40 to 42 was excellent in effective length, 16. Perfume O.1 O.1 adhesion to skin, and film-forming feeling (uniformity of cosmetic film), and the SPF values were high. These effects of Total 1OO.O 1OO.O the sunscreen cream (W/O type) of each of Examples 40 to 42 35 were higher than those of the sunscreen cream (W/O type) of Comparative Example 41. TABLE 84

Example 43 and Comparative Example 42 40 Sensory test Example 43 Comparative Example 42 Production of Stick-Type Oil Concealer Effective length A Adhesion A Color development O Stick-type oil concealer having the formula shown in Table Film-forming feeling A 83 was produced by the following process. 45 Raw materials 8 to 15 were heated to 70° C. and uniformly mixed to obtain mixture (A). Then, raw materials 1 to 7 and 16 The followings were confirmed by the results shown in were added to mixture (A), and the resulting mixture was Table 84. uniformly mixed to obtain mixture (B). Mixture (B) was It was recognized that the stick-type oil concealer of heated again for defoaming. The defoamed mixture was put 50 Examples 43 was excellent in color development, adhesion to into a stick-type container and then cooled to room tempera skin, and film-forming feeling (uniformity of cosmetic film), ture to obtain stick-type oil concealer. The results of sensory and the makeup was maintained for a longtime. These effects evaluation are shown in Table 84. of the stick-type oil concealer of Examples 43 were higher TABLE 83 than those of the stick-type oil concealer of Comparative 55 Example 42, and the makeup was maintained for a longer Comparative time. Raw material Example 43 Example 42 1. Esterification reaction product 2O.O Example 44 and Comparative Example 43 (Production Example 1) 2. Esterification reaction product 2O.O 60 (Production Example 3) Production of Body Soap 3. Bengara S.O S.O 4. Yellow iron oxide 3.0 3.0 5. Black iron oxide O.1 O.1 Body soap having the formula shown in Table 85 was 6. Stearic acid-treated titanium oxide 1O.O 1O.O produced by the following process. 7. Mica 3.0 3.0 65 8. Candelilla wax 2.0 2.0 Raw materials 1 to 11 were uniformly mixed to obtain body soup. The results of sensory evaluation are shown in Table 86. US 7,632,957 B2 53 54 The followings were confirmed by the results shown in TABLE 85 Table 88. It was recognized that the body powder of Example 45 well Comparative adhered and spread on skin, and the makeup was maintained Raw material Example 44 Example 43 for a long time. These effects of the body powder of Example 1. Esterification reaction product 3.0 45 were higher than those of the body powder of Comparative (Production Example 1) Example 44, and the makeup was maintained for a longer 2. Cholesteryl hydroxystearate 3.0 time. 3. Lauric acid 8.0 8.O 4. Myristic aid 1.5 1.5 5. Palmitic acid 1.5 1.5 10 Example 46 and Comparative Example 45 6. Potassium hydroxide 3.0 3.0 7. Coconut oil fatty acid diethanolamide 1.O 1.O Production of Water-in-Oil Type Hand Cream 8. Ethylene glycol distearate 1.O 1.O 9. Preservative O.S O.S 10. Perfume O.1 O.1 Water-in-oil-type hand cream having the formula shown in 11. Purified water balance balance 15 Table 89 was produced by the following process. Total 1OOO 1OO.O Raw material 1 or 2 and raw materials 3 to 7 were mixed. Then, raw material 8 was added thereto, and the resulting mixture was dispersed with a dispersion mixer to obtain mix ture (A). The remaining raw materials were uniformly mixed TABLE 86 and dispersed in mixture (A) to obtain water-in-oil-type hand Sensory test Example 44 Comparative Example 43 cream. The results of sensory evaluation are shown in Table 90. Softness A Moisturizing feeling O Gloss O A TABLE 89 Cleansing properties O A 25 Example Comparative Raw material 46 Example 45 The followings were confirmed by the results shown in 1. Esterification reaction product 3O.O Table 86. (Production Example 1) It was recognized that the body Soap of Example 44 was 2. Esterification reaction product 3O.O excellent in cleansing properties and imparted softness, mois 30 (Production Example 3) turizing feeling, and gloss to skin by using it. These effects of 3. Squalane S.O S.O 4. Vaseline 1.O 1.O the body soap of Example 44 were higher than those of the 5. Octamethylcyclopentasiloxane 1O.O 1O.O body soap of Comparative Example 43. 6. Cetyl isooctanoate 1O.O 1O.O 7. Alkyl-containing polyoxyalkylene-modified 3.0 3.0 Example 45 and Comparative Example 44 35 organopolysiloxane 8. Silica 3.0 3.0 9. Ethyl alcohol S.O S.O Production of Body Powder 10. 1,3-Butylene glycol S.O S.O 11. Purified water 27.9 27.9 Body powder having the formula shown in Table 87 was 12. Moisturizing ingredient (hyaluronic acid) O.1 O.1 produced by the following process. 40 Raw materials 3 to 6 were uniformly mixed and dispersed Total 1OOO 1OOO to obtain mixture (A). Raw material 1 or 2 was added to mixture (A), and the resulting mixture was pulverized to obtain body powder. The results of sensory evaluation are TABLE 90 shown in Table 88. 45 Sensory test Example 46 Comparative Example 45 TABLE 87 Moisturizing feeling O Adhesion A Comparative Softness O O Raw material Example 45 Example 44 Film-forming feeling A 50 1. Esterification reaction product S.O (Production Example 1) 2. Polyglyceryl-2 triisostearate S.O The followings were confirmed by the results shown in 3. Talc 70.O 7O.O Table 90. 4. Mica 19.9 19.9 It was recognized that the water-in-oil-type hand cream of 5. Nylon powder S.O S.O 55 Example 46 well adhered, moisturized, and softened skin, 6. Preservative O.1 O.1 and film-forming feeling was maintained for a long time. Total 1OO.O 1OOO These effects of the water-in-oil-type hand cream of Example were higher than those of the water-in-oil-type hand cream of Comparative Example 45. 60 TABLE 88 The invention claimed is: Sensory test Example 45 Comparative Example 44 1. An esterification reaction product prepared by esterify ing dipentaerythritol and a 12-hydroxy Stearic acid polymer Effective length O A Adhesion A and having a hydroxyl value of 20 to 70 mg KOH/g and an Spread O 65 acid value of 3 mg KOH/g or less. 2. The esterification reaction product according to claim 1, wherein the hydroxyl value is 20 to 60 mg KOH/g. US 7,632,957 B2 55 56 3. The esterification reaction product according to claim 1, 9. The cosmetic product according to claim 8, wherein the wherein the hydroxyl value is 25 to 50 mg KOH/g. content of the esterification reaction product is 0.1 to 80% by 4. The esterification reaction product according to claim 1, a SS. wherein the hydroxyl value is 30 to 40 mg KOH/g. 10. The cosmetic product according to claim 8, wherein the 5. The esterification reaction product according to claim 1, wherein the 12-hydroxy Stearic acid polymer has a polymer content of the esterification reaction product is 1 to 40% by ization degree of 2 to 12. a SS. 6. The esterification reaction product according to claim 1, 11. The cosmetic product according to claim 8, wherein the wherein the 12-hydroxy Stearic acid polymer has a polymer cosmetic product is selected from the group consisting of lip ization degree of 4 to 12. 10 cosmetics, foundation, emollient cream, milky lotion, 7. The esterification reaction product according to claim 1, makeup bases, hair cream, shampoo, hair rinse, hair condi wherein the 12-hydroxy Stearic acid polymer has a polymer tioners, hand cream, serum, eyebrow and eye cosmetics, nail ization degree of 6 to 12. cosmetics, and Sunscreen cosmetics. 8. A cosmetic product containing an esterification reaction product according to claim 1.