WO2022172645A1 - Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified - Google Patents

Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified Download PDF

Info

Publication number
WO2022172645A1
WO2022172645A1 PCT/JP2022/000034 JP2022000034W WO2022172645A1 WO 2022172645 A1 WO2022172645 A1 WO 2022172645A1 JP 2022000034 W JP2022000034 W JP 2022000034W WO 2022172645 A1 WO2022172645 A1 WO 2022172645A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
polyglycerin
fatty acids
compound
fatty acid
Prior art date
Application number
PCT/JP2022/000034
Other languages
French (fr)
Japanese (ja)
Inventor
善行 松本
智則 樋口
Original Assignee
太陽化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太陽化学株式会社 filed Critical 太陽化学株式会社
Priority to JP2022581242A priority Critical patent/JPWO2022172645A1/ja
Publication of WO2022172645A1 publication Critical patent/WO2022172645A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/45—Derivatives containing from 2 to 10 oxyalkylene groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/40—Succinic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44—Adipic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/50—Sebacic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/60—Maleic acid esters; Fumaric acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to compounds obtained by esterifying polyglycerin with fatty acids and dicarboxylic acids, solubilizers for poorly water-soluble substances containing the compounds, and cosmetics containing these.
  • surfactants are used to solubilize poorly water-soluble substances such as fragrances and essential oils in aqueous solutions.
  • poorly water-soluble substances such as fragrances and essential oils
  • the use of naturally derived raw materials, solubilization with a small amount of surfactant, solubilization that does not require heating energy (cold process), and surfactants that satisfy high biodegradability are eco-friendly solubilization. It can be said that it is a drug.
  • Polyglycerin fatty acid esters can be mentioned as materials for solubilizing poorly water-soluble substances.
  • Polyglycerin produced by the ring-opening polymerization method of petroleum-derived glycerin derivatives and polyglycerin from which the low-polymerization degree is removed (Patent Document 1) are used to esterify with fatty acids to solubilize poorly soluble substances. A method is reported. However, a large amount of surfactant is required for poorly soluble substances, and further reduction of surfactant is required.
  • An object of the present invention is to provide a novel compound that can solubilize fragrances and essential oils in small amounts.
  • the present invention relates to the following [1] to [4].
  • [1] A compound that is an ester of polyglycerol, fatty acid and dicarboxylic acid and satisfies the following (A) to (C).
  • (A) The total proportion of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids in the total fatty acids is 48% by mass or more
  • (B) The mass ratio of polyglycerin and fatty acids (polyglycerin:fatty acid) is 1:0.15 ⁇ 1:0.35
  • C) the dicarboxylic acid has 4 to 12 carbon atoms, and the molar ratio to polyglycerin (dicarboxylic acid/polyglycerin) is 0.1 to 0.8
  • a composition comprising the compound according to [1] and a polyglycerin fatty acid ester obtained by esterifying a fatty acid having 10 to 18 carbon atoms and polyglycerin.
  • the present inventors newly found that by using polyglycerin and esters of specific fatty acids and dicarboxylic acids, fragrances and essential oils can be solubilized even in small amounts.
  • the present inventors have newly found that the compound has a high solubilizing power even when a large amount of naturally-derived raw materials are used. Although the mechanism is unknown, it is presumed that cross-linking polyglycerin with dicarboxylic acid enhances the ability to form micelles and increases the solubilization region.
  • the compound of the present invention is an ester of polyglycerol, fatty acid and dicarboxylic acid, and satisfies (A) to (C) below.
  • A The total proportion of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids in the total fatty acids is 48% by mass or more
  • B The mass ratio of polyglycerin and fatty acids (polyglycerin:fatty acid) is 1:0.15 ⁇ 1:0.35
  • the dicarboxylic acid has 4 to 12 carbon atoms, and the molar ratio to polyglycerin (dicarboxylic acid/polyglycerin) is 0.1 to 0.8
  • Polyglycerin according to the compound of the present invention is preferably produced by a dehydration polymerization method of glycerin, from the viewpoint of using naturally-derived raw materials.
  • the average degree of polymerization of the polyglycerin according to the compound of the present invention is preferably 3 to 20, more preferably 4 to 10, from the viewpoint of solubilizing power, and may be within the range of any combination thereof.
  • the average degree of polymerization of polyglycerin in the present specification is the average degree of polymerization of polyglycerin calculated from the hydroxyl value by terminal group analysis, and is the average degree of polymerization calculated from (formula 1) and (formula 2). .
  • the fatty acid related to the compound of the present invention is preferably obtained by hydrolyzing and refining oils and fats extracted from natural animals and plants.
  • Fatty acids related to the compounds of the present invention include unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms (ie linear unsaturated fatty acids, branched saturated fatty acids, branched unsaturated fatty acids).
  • the fatty acid according to the compound of the present invention has a total ratio of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids of 48% by mass or more, preferably 55% by mass or more, of all fatty acids, It is more preferably 73% by mass or more, and from the viewpoint of solubilizing power, it is 100% by mass or less, preferably 89% by mass or less, more preferably 80% by mass or less, and the range may be any combination of these. .
  • Unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms include isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid and the like, and may contain one or more.
  • fatty acids related to the compounds of the present invention include unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms, as well as saturated fatty acids having 10 to 14 carbon atoms.
  • unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms, as well as saturated fatty acids having 10 to 14 carbon atoms.
  • saturated fatty acids having 10 to 14 carbon atoms.
  • capric acid, lauric acid, myristic acid and the like can be mentioned, and one or more of them can be contained.
  • the total amount of unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms and the mass ratio of saturated fatty acids having 10 to 14 carbon atoms is preferably 1:0 to 1:1, more preferably 1:0.03 to 1:0.95, still more preferably 1:0. 20-1:0.30.
  • fatty acids other than unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms and saturated fatty acids having 10 to 14 carbon atoms include caprylic acid, palmitic acid, stearic acid, and behenic acid. It can contain more than one species. From the viewpoint of solubilizing power, these fatty acids preferably account for 0 to 10 mass or less of all fatty acids.
  • the mass ratio of polyglycerin and fatty acid (polyglycerin:fatty acid) in the compound of the present invention is 1:0.15 to 1:0.35, preferably 1:0.15 to 1, from the viewpoint of solubilizing power. : 0.30.
  • the dicarboxylic acid related to the compound of the present invention is preferably obtained from plant raw materials.
  • Fatty acids related to the compounds of the present invention include linear or branched, saturated or unsaturated dicarboxylic acids having 4 to 12 carbon atoms. Specifically, succinic acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid and the like can be mentioned, and one or more of them can be contained.
  • the molar ratio (dicarboxylic acid/polyglycerin) to polyglycerin in the compound of the present invention is 0.1 to 0.8, preferably 0.3, from the viewpoint of solubilizing power and handleability of the compound during use. ⁇ 0.7, more preferably 0.4 to 0.6.
  • the nature-derived index in the compound of the present invention is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and still more preferably 0.9 or more, from the viewpoint of using naturally-derived raw materials. Yes, most preferably 1.0.
  • the natural origin index in this specification was calculated by the following formula based on ISO 16128. Note that 0.5 or less is set to 0.
  • Nature-derived index plant-derived carbon number / total carbon number
  • the compound of the present invention can be obtained by subjecting the above polyglycerin to fatty acid and dicarboxylic acid through an esterification reaction according to a general method for synthesizing polyglycerol fatty acid ester, and may be further purified according to a known method.
  • it can be produced by adding a catalyst such as an alkali to polyglycerin, fatty acid and dicarboxylic acid as raw materials and performing an esterification reaction at 200° C. or higher under normal pressure or reduced pressure.
  • the compound of the present invention can solubilize perfumes and essential oils in a small amount, it can be suitably used as a solubilizer for perfumes and essential oils.
  • the compounds of the present invention can solubilize various poorly water-soluble substances other than fragrances and essential oils, and can be widely used as solubilizers for poorly water-soluble substances.
  • the compound of the present invention and the solubilizer for poorly water-soluble substances of the present invention can be blended in cosmetics and the like, but it is preferable to use compounds with a high natural origin index.
  • Cosmetics include, for example, lotions, serums, perfumes, mouthwashes, hair mists, cleansing lotions, cleansing sheets, deodorant sheets, cleansing gels, facial cleansers, shampoos, body soaps, fragrances, and the like.
  • the term "sparingly water-soluble substance” refers to a substance that is hardly soluble in water, or is only slightly soluble in water, and preferably has a solubility in water of 0.1% by mass or less, more preferably It is 0.01% by mass or less.
  • poorly water-soluble substances used as raw materials for cosmetics include fragrances, essential oils, ester oils, hydrocarbon oils, animal and vegetable oils, fat-soluble vitamins, ultraviolet absorbers, preservatives, antibacterial agents, and compositions containing these ingredients. is mentioned.
  • Fragrances include hydrocarbon fragrances such as limonene, alcohol fragrances such as linalool, geraniol and menthol (L-menthol), aldehyde fragrances such as citral, ketone fragrances such as ⁇ -ionone, and phenol fragrances such as eugenol. etc.
  • Essential oils include lavender oil, eucalyptus oil, rose oil, jasmine oil, peppermint oil, anise oil, rosemary oil, bergamot oil, and other vegetable essential oils, as well as musk, leibyo, kairyu, and ryuzenkou.
  • Ester oils include isononyl isononanoate, isostearyl isostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, triethylhexanoin, and tri(caprylic/capric)glyceryl.
  • Hydrocarbon oils include hydrogenated polyisobutene, liquid paraffin, light liquid isoparaffin, squalane, phytosqualane, isododecane, and alkanes.
  • Animal and vegetable oils include avocado oil, almond oil, olive oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, jojoba oils, macadamia nut oil, coconut oil, lanolin, and the like.
  • Fat-soluble vitamins include vitamins such as tocopherol (tocopherol acetate), ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -trichoenol, ⁇ -trichoenol, ⁇ -trichoenol, etc. fat-soluble vitamins such as vitamin A such as E, retinol, and ⁇ -carotene;
  • ultraviolet absorbers examples include octyl methoxycinnamate, oxybenzone-3, and t-butylmethoxydibenzoylmethane.
  • Antiseptics and antibacterial agents include glyceryl monocaprylate, glyceryl monocaprate, glyceryl monolaurate, methylparaben, propylparaben, ethylhexylglycerin, and caprylyl glycol.
  • solubilization refers to adding water at room temperature (25° C.) so that the amount of the poorly water-soluble substance is 0.1% by mass, stirring for 10 minutes, and then measuring with a spectrophotometer (manufactured by Shimadzu Corporation: UV ⁇ 2600) refers to the case where the transmittance at a wavelength of 650 nm is 98% or more.
  • the compound of the present invention can also be used as a composition containing other ingredients. Accordingly, the present invention also provides compositions containing the compounds of the present invention.
  • the composition of the present invention can contain polyhydric alcohols such as polyglycerin fatty acid esters and glycerin, and from the viewpoint of utilizing naturally derived raw materials, glycerin is preferably contained. .
  • the content of glycerin relative to 100 parts by mass of the compound of the present invention is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, from the viewpoint of handling during use.
  • a preferred embodiment includes an embodiment containing the compound of the present invention and a polyglycerin fatty acid ester obtained by esterifying a fatty acid having 10 to 18 carbon atoms and polyglycerin.
  • Constituent fatty acids in this embodiment include saturated, unsaturated or branched fatty acids having 10 to 18 carbon atoms. Specific examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid, and one or more of them may be contained.
  • the content of the polyglycerol fatty acid ester relative to 100 parts by mass of the compound of the present invention is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, from the viewpoint of solubilizing power. .
  • composition of the present invention can not only be suitably used as a solubilizer for perfumes and essential oils, but also can be widely used as a solubilizer for poorly water-soluble substances. Moreover, these can be blended in cosmetics.
  • composition of the present invention is a cosmetic composition
  • surfactants oils, aqueous gelling agents, oily gelling agents, powders, antioxidants, colorants, and chelating agents , cooling agents, thickeners, plant extracts, vitamins, neutralizers, moisturizing agents, anti-inflammatory agents, pH adjusters, amino acids, and other ingredients that can be used in cosmetics.
  • Examples 1-24 and Comparative Examples 1-5 Alkaline catalysts were added to polyglycerin, fatty acids and dicarboxylic acids having the compositions shown in Tables 1 and 2, and an esterification reaction was carried out at 260° C. under normal pressure (760 Torr). After cooling, the reaction mixture was diluted with glycerin to 50% by mass to obtain compositions of Examples and Comparative Examples. Dilution with glycerin is for the purpose of improving handleability and does not affect the performance of the compound. The natural origin index of the compound before dilution with glycerin was calculated by the method described above. Tables 1 and 2 show the results.
  • the raw material polyglycerin in Examples 1 to 15, 17 to 24, and Comparative Examples 1 to 5 was produced by dehydration polymerization of glycerin, and was 100% naturally derived.
  • the raw material polyglycerin in Example 16 was produced by ring-opening polymerization of a glycerin derivative (derived from petroleum). The average degree of polymerization of polyglycerol was measured by the method described above. All of the raw material fatty acids were obtained by hydrolyzing and refining oils extracted from natural plants (coconut, palm, rapeseed, sunflower), and were 100% naturally derived.
  • the details of the raw material dicarboxylic acid are as follows.
  • Succinic acid, maleic acid, and adipic acid derived from petroleum have a natural origin index of 0, and sebacic acid and dodecanedioic acid are 100% naturally derived.
  • Succinic acid succinic anhydride (petroleum-derived, manufactured by Shin Nippon Rika Co., Ltd.)
  • Maleic acid maleic anhydride (petroleum-derived, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Sebacic acid (Natural origin, manufactured by Ito Seiso Co., Ltd.)
  • Dodecanedioic acid (Natural origin, manufactured by Okamura Oil Co., Ltd.)
  • the composition of each example that satisfies the above (A) to (C) is less than the comparative examples 1 to 4 that do not satisfy the above (A) to (C). It can be seen that the lavender oil could be solubilized. As for Comparative Example 5, gelation occurred during the reaction, and the solubilizing power could not be evaluated. In addition, usually, in order to solubilize, it is common to mix and cool after heating to about 70 ° C. In each example, it is possible to solubilize lavender oil even at room temperature without heating. there were. Also, from the comparison of Examples 15 and 16, it can be seen that the solubilizing power was high regardless of the natural origin index.
  • Reference example 1 Sodium hydroxide was added to polyglycerin and lauric acid, and an esterification reaction was carried out at 240° C. under normal pressure (760 Torr). After cooling, the reaction mixture was diluted with glycerin to a concentration of 50% by mass to obtain a composition of Reference Example 1.
  • the raw material polyglycerin was produced by dehydration polymerization of glycerin, and was 100% naturally derived. All of the fatty acids used as raw materials were obtained by hydrolyzing and refining oils and fats extracted from natural plants (derived from palm), and were 100% naturally derived.
  • Reference example 2 A polyglycerin was prepared in the same manner as in Reference Example 1, except that a polyglycerin produced by ring-opening polymerization of a glycerin derivative (derived from petroleum) was used as the raw material.
  • Reference example 3 PEG-40 hydrogenated castor oil (Emanone CH-40, manufactured by Kao Corporation) was diluted with glycerin to 50% by mass to obtain a composition of Reference Example 3.
  • compositions of Examples 1 and 15 were able to solubilize lavender oil in a smaller amount than the conventional products of Reference Examples 1 to 3.
  • Polyglyceryl-10 caprate Sodium hydroxide was added to polyglycerin and fatty acid (derived from coconut and palm), and an esterification reaction was carried out at 240° C. under normal pressure (760 Torr). After cooling, the reaction product was diluted with glycerin to 50% by mass to obtain a composition.
  • the raw material polyglycerin was produced by dehydration polymerization of glycerin, and was 100% naturally derived. Capric acid was used as the raw material fatty acid.
  • Polyglyceryl-10 myristate Prepared in the same manner as polyglyceryl-10 caprate, except that myristic acid (derived from coconut or palm) was used as the starting fatty acid.
  • Polyglyceryl-10 oleate Prepared in the same manner as polyglyceryl-10 caprate, except that oleic acid (derived from palm) was used as the starting fatty acid.
  • Example 15 As shown in Table 6, it can be seen that by using the composition of Example 15, even low-polar hydrocarbon oils and ester oils can be solubilized.
  • Example 29 by using a polyglycerin fatty acid ester obtained by esterifying an unsaturated fatty acid having 18 carbon atoms and polyglycerin, the ability to solubilize hydrocarbon oils and ester oils can be further enhanced. I understand.
  • the cosmetics of Formulation Examples 1 to 8 all had a transmittance of 98% or more, and the poorly water-soluble substances were solubilized.
  • the compound of the present invention can solubilize fragrances and essential oils in small amounts, more environmentally friendly product design can be expected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Fats And Perfumes (AREA)

Abstract

A compound that is an ester of a polyglycerol, a fatty acid, and a dicarboxylic acid, wherein the following conditions (A)-(C) are satisfied. (A) In the entire fatty acid, the total percentage of C18-22 unsaturated fatty acid and branched fatty acid is 48 mass% or greater. (B) The mass ratio (polyglycerol:fatty acid) of the polyglycerol and the fatty acid is 1:0.15-1:0.35. (C) The carbon number of the dicarboxylic acid is 4-12, and the molar ratio (dicarboxylic acid/polyglycerol) relative to the polyglycerol is 0.1-0.8.　Perfumes and essential oils can be made soluble with a small quantity of this compound, and thus more environmentally conscious product design can be expected.

Description

ポリグリセリンと脂肪酸及びジカルボン酸をエステル化した化合物Compound obtained by esterifying polyglycerin with fatty acid and dicarboxylic acid
　本発明は、ポリグリセリンと脂肪酸及びジカルボン酸をエステル化した化合物、該化合物を含有する難水溶性物質用可溶化剤、並びにこれらを含有する化粧料に関する。 The present invention relates to compounds obtained by esterifying polyglycerin with fatty acids and dicarboxylic acids, solubilizers for poorly water-soluble substances containing the compounds, and cosmetics containing these.
　化粧品分野において、香料や精油等の難水溶性物質を水溶液中に可溶化するため、界面活性剤が利用されている。近年、難水溶性物質を可溶化するだけでなく、環境にやさしい自然由来の界面活性剤が求められている。具体的には、自然由来原料の利用、少ない界面活性剤量での可溶化、加熱エネルギーを必要としない可溶化（コールドプロセス）、高い生分解性などを満たす界面活性剤が環境にやさしい可溶化剤といえる。 In the cosmetics field, surfactants are used to solubilize poorly water-soluble substances such as fragrances and essential oils in aqueous solutions. In recent years, there has been a demand for naturally derived surfactants that not only solubilize poorly water-soluble substances but are also environmentally friendly. Specifically, the use of naturally derived raw materials, solubilization with a small amount of surfactant, solubilization that does not require heating energy (cold process), and surfactants that satisfy high biodegradability are eco-friendly solubilization. It can be said that it is a drug.
　難水溶性物質の可溶化素材として、ポリグリセリン脂肪酸エステルが挙げられる。今までに石油由来のグリセリン誘導体の開環重合法で製造されたポリグリセリンや、低重合度部分を除去したポリグリセリン（特許文献１）を用いて脂肪酸とエステル化し、難溶性物質を可溶化する方法が報告されている。しかし、難溶性物質に対して必要な界面活性剤量が多く、さらなる界面活性剤の低減が求められている。 　Polyglycerin fatty acid esters can be mentioned as materials for solubilizing poorly water-soluble substances. Polyglycerin produced by the ring-opening polymerization method of petroleum-derived glycerin derivatives and polyglycerin from which the low-polymerization degree is removed (Patent Document 1) are used to esterify with fatty acids to solubilize poorly soluble substances. A method is reported. However, a large amount of surfactant is required for poorly soluble substances, and further reduction of surfactant is required.
特開２０１８－７０５２９号JP 2018-70529
　本発明の課題は、少ない量で香料や精油を可溶化できる新規の化合物を提供することである。 An object of the present invention is to provide a novel compound that can solubilize fragrances and essential oils in small amounts.
　本発明は下記［１］～［４］に関する。
［１］ポリグリセリンと脂肪酸及びジカルボン酸のエステルであって、下記（Ａ）～（Ｃ）を満たす、化合物。
（Ａ）全脂肪酸のうち、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計割合が４８質量％以上
（Ｂ）ポリグリセリンと脂肪酸の質量比（ポリグリセリン：脂肪酸）が１：０．１５～１：０．３５
（Ｃ）ジカルボン酸の炭素数が４～１２であり、ポリグリセリンに対するモル比（ジカルボン酸／ポリグリセリン）が０．１～０．８
［２］［１］記載の化合物と、炭素数１０～１８の脂肪酸とポリグリセリンをエステル化したポリグリセリン脂肪酸エステルを含有する、組成物。
［３］［１］記載の化合物又は［２］記載の組成物を含有する、難水溶性物質用可溶化剤。
［４］［１］記載の化合物又は［２］記載の組成物を含有する、化粧料。 The present invention relates to the following [1] to [4].
[1] A compound that is an ester of polyglycerol, fatty acid and dicarboxylic acid and satisfies the following (A) to (C).
(A) The total proportion of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids in the total fatty acids is 48% by mass or more (B) The mass ratio of polyglycerin and fatty acids (polyglycerin:fatty acid) is 1:0.15 ~1:0.35
(C) the dicarboxylic acid has 4 to 12 carbon atoms, and the molar ratio to polyglycerin (dicarboxylic acid/polyglycerin) is 0.1 to 0.8
[2] A composition comprising the compound according to [1] and a polyglycerin fatty acid ester obtained by esterifying a fatty acid having 10 to 18 carbon atoms and polyglycerin.
[3] A solubilizer for poorly water-soluble substances, containing the compound described in [1] or the composition described in [2].
[4] A cosmetic containing the compound described in [1] or the composition described in [2].
　本発明によれば、少ない量で香料や精油を可溶化できる新規の化合物を提供することができる。 According to the present invention, it is possible to provide a novel compound capable of solubilizing fragrances and essential oils in a small amount.
　本発明者らが上記課題について鋭意検討したところ、ポリグリセリンと特定の脂肪酸及びジカルボン酸のエステルを用いることで、少ない量でも香料や精油を可溶化できることを新たに見出した。また、当該化合物は、自然由来の原料を多く使用した場合でも、高い可溶化力を有することを新たに見出した。かかるメカニズムは不明であるが、ポリグリセリンをジカルボン酸で架橋することでミセルの形成能が高まり、可溶化領域が増大するためと推定される。 As a result of intensive studies on the above problems, the present inventors newly found that by using polyglycerin and esters of specific fatty acids and dicarboxylic acids, fragrances and essential oils can be solubilized even in small amounts. In addition, the present inventors have newly found that the compound has a high solubilizing power even when a large amount of naturally-derived raw materials are used. Although the mechanism is unknown, it is presumed that cross-linking polyglycerin with dicarboxylic acid enhances the ability to form micelles and increases the solubilization region.
　本発明の化合物は、ポリグリセリンと脂肪酸及びジカルボン酸のエステルであって、下記（Ａ）～（Ｃ）を満たす。
（Ａ）全脂肪酸のうち、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計割合が４８質量％以上
（Ｂ）ポリグリセリンと脂肪酸の質量比（ポリグリセリン：脂肪酸）が１：０．１５～１：０．３５
（Ｃ）ジカルボン酸の炭素数が４～１２であり、ポリグリセリンに対するモル比（ジカルボン酸／ポリグリセリン）が０．１～０．８ The compound of the present invention is an ester of polyglycerol, fatty acid and dicarboxylic acid, and satisfies (A) to (C) below.
(A) The total proportion of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids in the total fatty acids is 48% by mass or more (B) The mass ratio of polyglycerin and fatty acids (polyglycerin:fatty acid) is 1:0.15 ~1:0.35
(C) the dicarboxylic acid has 4 to 12 carbon atoms, and the molar ratio to polyglycerin (dicarboxylic acid/polyglycerin) is 0.1 to 0.8
　本発明の化合物に係るポリグリセリンは、自然由来原料を利用する観点から、グリセリンの脱水重合法で製造されたものなどが好ましい。本発明の化合物に係るポリグリセリンの平均重合度は、可溶化力の観点から、好ましくは３～２０、より好ましくは４～１０であり、これらいずれの組み合わせによる範囲としてもよい。本明細書におけるポリグリセリンの平均重合度とは、末端基分析法による水酸基価から算出されるポリグリセリンの平均重合度であり、（式１）及び（式２）から算出した平均重合度である。
（式１）平均重合度＝（１１２．２×１０３－１８×水酸基価）／（７４×水酸基価－５６．１×１０３）
（式２）水酸基価＝（ａ－ｂ）×２８．０５／試料の採取量（ｇ）
　ａ：空試験による０．５Ｎ水酸化カリウム溶液の消費量（ｍｌ）
　ｂ：本試験による０．５Ｎ水酸化カリウム溶液の消費量（ｍｌ）
上記（式１）中の水酸基価は社団法人日本油化学会編「日本油化学会制定　基準油脂分析試験法（Ｉ）１９９６年度版」に準じて（式２）で算出される。」 Polyglycerin according to the compound of the present invention is preferably produced by a dehydration polymerization method of glycerin, from the viewpoint of using naturally-derived raw materials. The average degree of polymerization of the polyglycerin according to the compound of the present invention is preferably 3 to 20, more preferably 4 to 10, from the viewpoint of solubilizing power, and may be within the range of any combination thereof. The average degree of polymerization of polyglycerin in the present specification is the average degree of polymerization of polyglycerin calculated from the hydroxyl value by terminal group analysis, and is the average degree of polymerization calculated from (formula 1) and (formula 2). .
(Formula 1) Average degree of polymerization = (112.2 × 10 3 -18 × hydroxyl value) / (74 × hydroxyl value - 56.1 × 10 3 )
(Formula 2) hydroxyl value = (ab) × 28.05 / amount of sample collected (g)
a: Consumption of 0.5N potassium hydroxide solution (ml) by blank test
b: Consumption of 0.5N potassium hydroxide solution (ml) in this test
The hydroxyl value in the above (Formula 1) is calculated by (Formula 2) in accordance with the Japan Oil Chemists' Society edition "Japan Oil Chemists' Society Standard Oil Analysis Test Method (I) 1996 Edition". ”
　本発明の化合物に係る脂肪酸は、自然由来原料を利用する観点から、天然の動植物より抽出した油脂を加水分解し、精製して得られたものなどが好ましい。本発明の化合物に係る脂肪酸として、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸（即ち、直鎖の不飽和脂肪酸、分岐鎖の飽和脂肪酸、分岐鎖の不飽和脂肪酸）が挙げられる。本発明の化合物に係る脂肪酸は、可溶化力の観点から、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計割合が、全脂肪酸のうち、４８質量％以上、好ましくは５５質量％以上、より好ましくは７３質量％以上であり、また、可溶化力の観点から、１００質量％以下、好ましくは８９質量％以下、より好ましくは８０質量％以下であり、これらいずれの組み合わせによる範囲としてもよい。炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸としては、イソステアリン酸、オレイン酸、リノール酸、リノレン酸、リシノレイン酸、エルカ酸などが挙げられ、１種又は２種以上を含有することができる。 From the viewpoint of using naturally-derived raw materials, the fatty acid related to the compound of the present invention is preferably obtained by hydrolyzing and refining oils and fats extracted from natural animals and plants. Fatty acids related to the compounds of the present invention include unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms (ie linear unsaturated fatty acids, branched saturated fatty acids, branched unsaturated fatty acids). From the viewpoint of solubilizing power, the fatty acid according to the compound of the present invention has a total ratio of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids of 48% by mass or more, preferably 55% by mass or more, of all fatty acids, It is more preferably 73% by mass or more, and from the viewpoint of solubilizing power, it is 100% by mass or less, preferably 89% by mass or less, more preferably 80% by mass or less, and the range may be any combination of these. . Unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms include isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid and the like, and may contain one or more.
　本発明の化合物に係る脂肪酸としては、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の他、炭素数１０～１４の飽和脂肪酸が挙げられる。具体的には、カプリン酸、ラウリン酸、ミリスチン酸などが挙げられ、１種又は２種以上を含有することができる。 Examples of fatty acids related to the compounds of the present invention include unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms, as well as saturated fatty acids having 10 to 14 carbon atoms. Specifically, capric acid, lauric acid, myristic acid and the like can be mentioned, and one or more of them can be contained.
　本発明の化合物に係る脂肪酸において、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計量と炭素数１０～１４の飽和脂肪酸の質量比（炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸：炭素数１０～１４の飽和脂肪酸）は、可溶化力の観点から、好ましくは１：０～１：１、より好ましくは１：０．０３～１：０．９５、さらに好ましくは１：０．２０～１：０．３０である。 In the fatty acid according to the compound of the present invention, the total amount of unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms and the mass ratio of saturated fatty acids having 10 to 14 carbon atoms (unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms: C10-C14 saturated fatty acid) is preferably 1:0 to 1:1, more preferably 1:0.03 to 1:0.95, still more preferably 1:0. 20-1:0.30.
　炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸や、炭素数１０～１４の飽和脂肪酸以外の脂肪酸としては、例えば、カプリル酸、パルミチン酸、ステアリン酸、ベヘン酸などが挙げられ、１種又は２種以上を含有することができる。これらの脂肪酸は、可溶化力の観点から、全脂肪酸のうち、好ましくは０～１０質量以下である。 Examples of fatty acids other than unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms and saturated fatty acids having 10 to 14 carbon atoms include caprylic acid, palmitic acid, stearic acid, and behenic acid. It can contain more than one species. From the viewpoint of solubilizing power, these fatty acids preferably account for 0 to 10 mass or less of all fatty acids.
　本発明の化合物におけるポリグリセリンと脂肪酸の質量比（ポリグリセリン：脂肪酸）は、可溶化力の観点から、１：０．１５～１：０．３５であり、好ましくは１：０．１５～１：０．３０である。 The mass ratio of polyglycerin and fatty acid (polyglycerin:fatty acid) in the compound of the present invention is 1:0.15 to 1:0.35, preferably 1:0.15 to 1, from the viewpoint of solubilizing power. : 0.30.
　本発明の化合物に係るジカルボン酸は、自然由来原料を利用する観点から、植物原料から得られたものなどが好ましい。本発明の化合物に係る脂肪酸として、炭素数４～１２で直鎖又は分岐鎖の飽和又は不飽和のジカルボン酸が挙げられる。具体的には、コハク酸、マレイン酸、アジピン酸、セバシン酸、ドデカン二酸などが挙げられ、１種又は２種以上を含有することができる。 From the viewpoint of using naturally-derived raw materials, the dicarboxylic acid related to the compound of the present invention is preferably obtained from plant raw materials. Fatty acids related to the compounds of the present invention include linear or branched, saturated or unsaturated dicarboxylic acids having 4 to 12 carbon atoms. Specifically, succinic acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid and the like can be mentioned, and one or more of them can be contained.
　本発明の化合物におけるポリグリセリンに対するモル比（ジカルボン酸／ポリグリセリン）は、可溶化力と、使用時の化合物のハンドリング性の観点から、０．１～０．８であり、好ましくは０．３～０．７、より好ましくは０．４～０．６である。 The molar ratio (dicarboxylic acid/polyglycerin) to polyglycerin in the compound of the present invention is 0.1 to 0.8, preferably 0.3, from the viewpoint of solubilizing power and handleability of the compound during use. ~0.7, more preferably 0.4 to 0.6.
　本発明の化合物における自然由来指数は、自然由来原料を利用する観点から、好ましくは０．５以上、より好ましくは０．７以上、さらに好ましくは０．８以上、さらに好ましくは０．９以上であり、最も好ましくは１．０である。本明細書における自然由来指数は、ＩＳＯ　１６１２８に基づき、下記式にて算出した。なお、０．５以下は０とする。
自然由来指数＝植物由来炭素数／総炭素数 The nature-derived index in the compound of the present invention is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and still more preferably 0.9 or more, from the viewpoint of using naturally-derived raw materials. Yes, most preferably 1.0. The natural origin index in this specification was calculated by the following formula based on ISO 16128. Note that 0.5 or less is set to 0.
Nature-derived index = plant-derived carbon number / total carbon number
　本発明の化合物は、ポリグリセリン脂肪酸エステルの一般的な合成法により、上記のポリグリセリンと脂肪酸及びジカルボン酸とをエステル化反応させることで得ることができ、公知の方法に従ってさらに精製してもよい。例えば、原料となるポリグリセリンと脂肪酸及びジカルボン酸にアルカリ等の触媒を加え、常圧もしくは減圧下、２００℃以上においてエステル化反応を行うことで製造することが可能である。 The compound of the present invention can be obtained by subjecting the above polyglycerin to fatty acid and dicarboxylic acid through an esterification reaction according to a general method for synthesizing polyglycerol fatty acid ester, and may be further purified according to a known method. . For example, it can be produced by adding a catalyst such as an alkali to polyglycerin, fatty acid and dicarboxylic acid as raw materials and performing an esterification reaction at 200° C. or higher under normal pressure or reduced pressure.
　本発明の化合物は、少ない量で香料や精油を可溶化することができるため、香料や精油の可溶化剤として好適に使用することができる。また、本発明の化合物は、香料や精油以外の種々の難水溶性物質についても可溶化することができ、難水溶性物質用可溶化剤として広く使用することができる。本発明の化合物や本発明の難水溶性物質用可溶化剤は、化粧料などに配合することができるが、自然由来指数の高い化合物等を用いるのが好ましい。化粧料としては、例えば、化粧水、美容液、香水、洗口液、ヘアミスト、クレンジング化粧水、クレンジングシート、デオドラントシート、クレンジングジェル、洗顔料、シャンプー、ボディソープ、芳香剤などが挙げられる。 Since the compound of the present invention can solubilize perfumes and essential oils in a small amount, it can be suitably used as a solubilizer for perfumes and essential oils. In addition, the compounds of the present invention can solubilize various poorly water-soluble substances other than fragrances and essential oils, and can be widely used as solubilizers for poorly water-soluble substances. The compound of the present invention and the solubilizer for poorly water-soluble substances of the present invention can be blended in cosmetics and the like, but it is preferable to use compounds with a high natural origin index. Cosmetics include, for example, lotions, serums, perfumes, mouthwashes, hair mists, cleansing lotions, cleansing sheets, deodorant sheets, cleansing gels, facial cleansers, shampoos, body soaps, fragrances, and the like.
　本明細書において、難水溶性物質とは、水にほとんど溶解しない、もしくは溶解してもわずかな量である物質を意味し、水への溶解度が好ましくは０．１質量％以下、より好ましくは０．０１質量％以下のものである。例えば、化粧品原料として用いられる難水溶性物質としては、香料、精油、エステル油、炭化水素油、動植物油、脂溶性ビタミン、紫外線吸収剤、防腐剤、抗菌剤、これらの成分を含む組成物などが挙げられる。 As used herein, the term "sparingly water-soluble substance" refers to a substance that is hardly soluble in water, or is only slightly soluble in water, and preferably has a solubility in water of 0.1% by mass or less, more preferably It is 0.01% by mass or less. For example, poorly water-soluble substances used as raw materials for cosmetics include fragrances, essential oils, ester oils, hydrocarbon oils, animal and vegetable oils, fat-soluble vitamins, ultraviolet absorbers, preservatives, antibacterial agents, and compositions containing these ingredients. is mentioned.
　香料としては、リモネン等の炭化水素系香料、リナロール、ゲラニオール、メントール（Ｌ－メントール）等のアルコール系香料、シトラール等のアルデヒド系香料、β－イオノン等のケトン系香料、オイゲノール等のフェノール系香料などが挙げられる。 Fragrances include hydrocarbon fragrances such as limonene, alcohol fragrances such as linalool, geraniol and menthol (L-menthol), aldehyde fragrances such as citral, ketone fragrances such as β-ionone, and phenol fragrances such as eugenol. etc.
　精油としては、ラベンダー油、ユーカリ油、ローズ油、ジャスミン油、ペパーミント油、アニス油、ローズマリー油、ベルガモット油等の植物性の精油、ジャコウ、レイビョウコウ、カイリュウ、リュウゼンコウなどが挙げられる。 Essential oils include lavender oil, eucalyptus oil, rose oil, jasmine oil, peppermint oil, anise oil, rosemary oil, bergamot oil, and other vegetable essential oils, as well as musk, leibyo, kairyu, and ryuzenkou.
　エステル油としては、イソノナン酸イソノニル、イソステアリン酸イソステアリル、２－エチルヘキサン酸セチル、パルミチン酸２－エチルヘキシル、トリエチルヘキサノイン、トリ(カプリル／カプリン酸)グリセリルなどが挙げられる。 Ester oils include isononyl isononanoate, isostearyl isostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, triethylhexanoin, and tri(caprylic/capric)glyceryl.
　炭化水素油としては、水添ポリイソブテン、流動パラフィン、軽質流動イソパラフィン、スクワラン、フィトスクワラン、イソドデカン、アルカンなどが挙げられる。 Hydrocarbon oils include hydrogenated polyisobutene, liquid paraffin, light liquid isoparaffin, squalane, phytosqualane, isododecane, and alkanes.
　動植物油としては、アボガド油、アーモンド油、オリーブ油、小麦胚芽油、米胚芽油、米糠油、サフラワー油、大豆油、トウモロコシ油、菜種油、パーム油、パーム核油、ヒマシ油、ヒマワリ油、ホホバ油、マカデミアナッツ油、ヤシ油、ラノリンなどが挙げられる。 Animal and vegetable oils include avocado oil, almond oil, olive oil, wheat germ oil, rice germ oil, rice bran oil, safflower oil, soybean oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, jojoba oils, macadamia nut oil, coconut oil, lanolin, and the like.
　脂溶性ビタミンとしては、トコフェロール（酢酸トコフェロール）、α－トコフェロール、β－トコフェロール、γ－トコフェロール、δ－トコフェロール、α－トリコエノール、β－トリコエノール、γ－トリコエノール、δ－トリコエノール等のビタミンＥ、レチノール、β－カロテン等のビタミンＡ等の脂溶性ビタミンなどが挙げられる。 Fat-soluble vitamins include vitamins such as tocopherol (tocopherol acetate), α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-trichoenol, β-trichoenol, γ-trichoenol, δ-trichoenol, etc. fat-soluble vitamins such as vitamin A such as E, retinol, and β-carotene;
　紫外線吸収剤としては、メトキシケイヒ酸オクチル、オキシベンゾン－３、ｔ－ブチルメトキシジベンゾイルメタンなどが挙げられる。 Examples of ultraviolet absorbers include octyl methoxycinnamate, oxybenzone-3, and t-butylmethoxydibenzoylmethane.
　防腐剤、抗菌剤としては、モノカプリル酸グリセリル、モノカプリン酸グリセリル、モノラウリン酸グリセリル、メチルパラベン、プロピルパラベン、エチルヘキシルグリセリン、カプリリルグリコールなどが挙げられる。 Antiseptics and antibacterial agents include glyceryl monocaprylate, glyceryl monocaprate, glyceryl monolaurate, methylparaben, propylparaben, ethylhexylglycerin, and caprylyl glycol.
　本明細書において、可溶化とは、難水溶性物質が０．１質量％になるように常温（２５℃）の水に添加し、１０分間攪拌した後、分光光度計（島津製作所製：ＵＶ－２６００）６５０ｎｍの波長での透過率が９８％以上となる場合を指す。 In the present specification, solubilization refers to adding water at room temperature (25° C.) so that the amount of the poorly water-soluble substance is 0.1% by mass, stirring for 10 minutes, and then measuring with a spectrophotometer (manufactured by Shimadzu Corporation: UV −2600) refers to the case where the transmittance at a wavelength of 650 nm is 98% or more.
　また、本発明の化合物は、他の成分を含む組成物として用いることもできる。従って、本発明においては、本発明の化合物を含有する組成物についても提供するものである。 The compound of the present invention can also be used as a composition containing other ingredients. Accordingly, the present invention also provides compositions containing the compounds of the present invention.
　本発明の組成物は、本発明の化合物の他、ポリグリセリン脂肪酸エステル、グリセリン、などの多価アルコールなどを含有することができ、自然由来原料を利用する観点から、グリセリンを含有することが好ましい。本発明の組成物において、本発明の化合物１００質量部に対するグリセリンの含有量としては、使用時のハンドリング性の観点から、好ましくは５０～１００質量部、より好ましくは７０～１００質量部である。 In addition to the compound of the present invention, the composition of the present invention can contain polyhydric alcohols such as polyglycerin fatty acid esters and glycerin, and from the viewpoint of utilizing naturally derived raw materials, glycerin is preferably contained. . In the composition of the present invention, the content of glycerin relative to 100 parts by mass of the compound of the present invention is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, from the viewpoint of handling during use.
　また、可溶化力の観点から好ましい態様として、本発明の化合物と、炭素数１０～１８の脂肪酸とポリグリセリンをエステル化したポリグリセリン脂肪酸エステルを含有する態様が挙げられる。本態様における構成脂肪酸としては、炭素数１０～１８の飽和、不飽和もしくは分岐脂肪酸が挙げられる。具体的には、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、リシノレイン酸などが挙げられ、１種又は２種以上を含有することができる。本態様の組成物において、本発明の化合物１００質量部に対する当該ポリグリセリン脂肪酸エステルの含有量は、可溶化力の観点から、好ましくは１０～４００質量部、より好ましくは２０～３００質量部である。 In addition, from the viewpoint of solubilizing power, a preferred embodiment includes an embodiment containing the compound of the present invention and a polyglycerin fatty acid ester obtained by esterifying a fatty acid having 10 to 18 carbon atoms and polyglycerin. Constituent fatty acids in this embodiment include saturated, unsaturated or branched fatty acids having 10 to 18 carbon atoms. Specific examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid, and one or more of them may be contained. In the composition of this aspect, the content of the polyglycerol fatty acid ester relative to 100 parts by mass of the compound of the present invention is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, from the viewpoint of solubilizing power. .
　本発明の組成物についても、本発明の化合物と同様に、香料や精油の可溶化剤として好適に使用することができるだけでなく、難水溶性物質用可溶化剤として広く使用することができる。また、これらを化粧料に配合することができる。 The composition of the present invention, like the compound of the present invention, can not only be suitably used as a solubilizer for perfumes and essential oils, but also can be widely used as a solubilizer for poorly water-soluble substances. Moreover, these can be blended in cosmetics.
　本発明の組成物が化粧料用組成物である場合において、上記各種成分の他、界面活性剤、油剤、水性ゲル化剤、油性ゲル化剤、粉体、抗酸化剤、着色剤、キレート剤、清涼剤、増粘剤、植物抽出液、ビタミン類、中和剤、保湿剤、抗炎症剤、pH調整剤、アミノ酸など、化粧料に用いることができる各種成分を更に含むことができる。 When the composition of the present invention is a cosmetic composition, in addition to the various components described above, surfactants, oils, aqueous gelling agents, oily gelling agents, powders, antioxidants, colorants, and chelating agents , cooling agents, thickeners, plant extracts, vitamins, neutralizers, moisturizing agents, anti-inflammatory agents, pH adjusters, amino acids, and other ingredients that can be used in cosmetics.
　以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these.
実施例１～２４及び比較例１～５
　表１、２に示す組成にて、ポリグリセリン、脂肪酸、ジカルボン酸にアルカリ触媒を加え、常圧（７６０Ｔｏｒｒ）下、２６０℃においてエステル化反応を行った。冷却後、反応物が５０質量％になるようグリセリンで希釈し、各実施例及び比較例の組成物を得た。なお、グリセリンでの希釈は、ハンドリング性をよくするためであり、化合物の性能に影響はない。グリセリン希釈前の化合物の自然由来指数は上記の方法により算出した。結果を表１、２に示す。 Examples 1-24 and Comparative Examples 1-5
Alkaline catalysts were added to polyglycerin, fatty acids and dicarboxylic acids having the compositions shown in Tables 1 and 2, and an esterification reaction was carried out at 260° C. under normal pressure (760 Torr). After cooling, the reaction mixture was diluted with glycerin to 50% by mass to obtain compositions of Examples and Comparative Examples. Dilution with glycerin is for the purpose of improving handleability and does not affect the performance of the compound. The natural origin index of the compound before dilution with glycerin was calculated by the method described above. Tables 1 and 2 show the results.
　なお、実施例１～１５、１７～２４、比較例１～５の原料のポリグリセリンは、グリセリンの脱水重合法で製造しており、１００％自然由来のものを使用した。実施例１６の原料のポリグリセリンはグリセリン誘導体（石油由来）の開環重合法で製造したものを使用した。ポリグリセリンの平均重合度については、上記の方法により測定した。原料の脂肪酸は、いずれも天然の植物（ヤシ、パーム、菜種、ヒマワリ）より抽出した油脂を加水分解し、精製して得られたものであり、１００％自然由来のものを使用した。原料のジカルボン酸の詳細は以下の通りである。石油由来であるコハク酸、マレイン酸、アジピン酸は、自然由来指数は０であり、セバシン酸、ドデカン二酸は１００％自然由来である。
コハク酸：無水コハク酸（石油由来　新日本理化社製）
マレイン酸：無水マレイン酸（石油由来　富士フイルム和光純薬社製）
アジピン酸：（石油由来　富士フイルム和光純薬社製）
セバシン酸：（自然由来　伊藤精油社製）
ドデカン二酸：（自然由来　岡村精油社製） The raw material polyglycerin in Examples 1 to 15, 17 to 24, and Comparative Examples 1 to 5 was produced by dehydration polymerization of glycerin, and was 100% naturally derived. The raw material polyglycerin in Example 16 was produced by ring-opening polymerization of a glycerin derivative (derived from petroleum). The average degree of polymerization of polyglycerol was measured by the method described above. All of the raw material fatty acids were obtained by hydrolyzing and refining oils extracted from natural plants (coconut, palm, rapeseed, sunflower), and were 100% naturally derived. The details of the raw material dicarboxylic acid are as follows. Succinic acid, maleic acid, and adipic acid derived from petroleum have a natural origin index of 0, and sebacic acid and dodecanedioic acid are 100% naturally derived.
Succinic acid: succinic anhydride (petroleum-derived, manufactured by Shin Nippon Rika Co., Ltd.)
Maleic acid: maleic anhydride (petroleum-derived, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Adipic acid: (derived from petroleum, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
Sebacic acid: (Natural origin, manufactured by Ito Seiso Co., Ltd.)
Dodecanedioic acid: (Natural origin, manufactured by Okamura Oil Co., Ltd.)
＜可溶化力の測定１＞
　各実施例・比較例の組成物と、ラベンダー油を５０℃で混合し、ラベンダー油（小川香料社製）が０．１質量％になるように常温（２５℃）の水に添加し、１０分間攪拌した後、分光光度計（島津製作所製：ＵＶ－２６００）６５０ｎｍの波長にて透過率を測定した。透過率が９８％以上となる場合の量（水中の各実施例・比較例の組成物の量）を、可溶化に必要な量とした。結果を表１、２に示す。 <Measurement of solubilizing power 1>
The composition of each example / comparative example and lavender oil are mixed at 50 ° C., added to water at room temperature (25 ° C.) so that lavender oil (manufactured by Ogawa Koryo Co., Ltd.) becomes 0.1% by mass, and 10 After stirring for 1 minute, transmittance was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-2600) at a wavelength of 650 nm. The amount (the amount of the composition of each example and comparative example in water) at which the transmittance becomes 98% or more was defined as the amount required for solubilization. Tables 1 and 2 show the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１、２に示すように、上記（Ａ）～（Ｃ）を満たす各実施例の組成物は、上記（Ａ）～（Ｃ）を満たさない比較例１～４に比べて、少ない量でラベンダー油を可溶化できたことが分かる。比較例５については、反応中にゲル化してしまい、可溶化力の評価ができなかった。また、通常は可溶化するため７０℃程度まで加温にしてから混合、冷却する方法が一般的であるが、各実施例では加熱することなく常温においてもラベンダー油を可溶化することが可能であった。また、実施例１５、１６の比較から、自然由来指数に関わらず、高い可溶化力であったことが分かる。 As shown in Tables 1 and 2, the composition of each example that satisfies the above (A) to (C) is less than the comparative examples 1 to 4 that do not satisfy the above (A) to (C). It can be seen that the lavender oil could be solubilized. As for Comparative Example 5, gelation occurred during the reaction, and the solubilizing power could not be evaluated. In addition, usually, in order to solubilize, it is common to mix and cool after heating to about 70 ° C. In each example, it is possible to solubilize lavender oil even at room temperature without heating. there were. Also, from the comparison of Examples 15 and 16, it can be seen that the solubilizing power was high regardless of the natural origin index.
＜可溶化力の測定２＞
　実施例１、１５、比較例４の組成物、難水溶性物質として表３に示す成分を５０℃で混合し、難水溶性物質が０．１質量％になるように常温（２５℃）の水に添加し、１０分間攪拌した後、分光光度計（島津製作所製：ＵＶ－２６００）６５０ｎｍの波長にて透過率を測定した。透過率が９８％以上となる場合の量（水中の各実施例・比較例の組成物の量）を、可溶化に必要な量とした。結果を表３に示す。 <Measurement of solubilizing power 2>
The compositions of Examples 1, 15, and Comparative Example 4 and the components shown in Table 3 as poorly water-soluble substances were mixed at 50°C, and heated at room temperature (25°C) so that the content of the poorly water-soluble substances was 0.1% by mass. After adding to water and stirring for 10 minutes, the transmittance was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-2600) at a wavelength of 650 nm. The amount (the amount of the composition of each example and comparative example in water) at which the transmittance becomes 98% or more was defined as the amount required for solubilization. Table 3 shows the results.
　表３で使用した難水溶性物質の詳細を以下に示す。
ローズマリー油（小川香料社製）
カモミール（小川香料社製）
シトロン（香栄興業社製）
ハーブブレンド（小川香料社製）
ローズ油（小川香料社製）
Ｌ－メントール（小川香料社製）
モノカプリル酸グリセリル（サンソフトNo.700P-2、太陽化学社製）
メトキシケイ皮酸エチルヘキシル（ユビナールMC80、BASFジャパン社製）
トコフェロール（トコフェロール100、日清オイリオ社製） Details of the sparingly water-soluble substances used in Table 3 are shown below.
Rosemary oil (manufactured by Ogawa Koryo Co., Ltd.)
Chamomile (manufactured by Ogawa Koryo Co., Ltd.)
Citron (manufactured by Koei Kogyo Co., Ltd.)
Herb blend (manufactured by Ogawa Koryo Co., Ltd.)
Rose oil (manufactured by Ogawa Koryo Co., Ltd.)
L-menthol (manufactured by Ogawa Koryo Co., Ltd.)
Glyceryl monocaprylate (Sunsoft No.700P-2, manufactured by Taiyo Kagaku Co., Ltd.)
Ethylhexyl methoxycinnamate (Ubinal MC80, manufactured by BASF Japan)
Tocopherol (Tocopherol 100, Nisshin OilliO Co., Ltd.)
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３に示すように、実施例１、１５の組成物を用いて、比較例４の組成物より少ない量で種々の難水溶性物質を可溶化することができたことが分かる。 As shown in Table 3, it can be seen that the compositions of Examples 1 and 15 were able to solubilize various poorly water-soluble substances in smaller amounts than the composition of Comparative Example 4.
参考例１
　ポリグリセリン及びラウリン酸に水酸化ナトリウムを加え、常圧（７６０Ｔｏｒｒ）下、２４０℃においてエステル化反応を行った。冷却後、反応物が５０質量％になるようグリセリンで希釈し、参考例１の組成物を得た。なお、原料のポリグリセリンは、グリセリンの脱水重合法で製造しており、１００％自然由来のものを使用した。原料の脂肪酸は、いずれも天然の植物（パーム由来）より抽出した油脂を加水分解し、精製して得られたものであり、１００％自然由来のものを使用した。 Reference example 1
Sodium hydroxide was added to polyglycerin and lauric acid, and an esterification reaction was carried out at 240° C. under normal pressure (760 Torr). After cooling, the reaction mixture was diluted with glycerin to a concentration of 50% by mass to obtain a composition of Reference Example 1. The raw material polyglycerin was produced by dehydration polymerization of glycerin, and was 100% naturally derived. All of the fatty acids used as raw materials were obtained by hydrolyzing and refining oils and fats extracted from natural plants (derived from palm), and were 100% naturally derived.
参考例２
　原料のポリグリセリンとして、グリセリン誘導体（石油由来）の開環重合法で製造したものを使用した以外は参考例１と同様にして調製した。 Reference example 2
A polyglycerin was prepared in the same manner as in Reference Example 1, except that a polyglycerin produced by ring-opening polymerization of a glycerin derivative (derived from petroleum) was used as the raw material.
参考例３
　ＰＥＧ－４０水添ヒマシ油（エマノーンＣＨ－４０、花王社製）が５０質量％になるようグリセリンで希釈し、参考例３の組成物を得た。 Reference example 3
PEG-40 hydrogenated castor oil (Emanone CH-40, manufactured by Kao Corporation) was diluted with glycerin to 50% by mass to obtain a composition of Reference Example 3.
＜可溶化力の測定３＞
　実施例１、１５の組成物と、従来から用いられている可溶化剤として参考例１～３とを比較した。可溶化力の測定方法及び自然由来指数の算出方法については実施例１と同様である。結果を表４に示す。 <Measurement of solubilizing power 3>
The compositions of Examples 1 and 15 were compared with Reference Examples 1 to 3 as conventionally used solubilizers. The method for measuring the solubilizing power and the method for calculating the index of natural origin are the same as in Example 1. Table 4 shows the results.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示すように、実施例１、１５の組成物は、従来品である参考例１～３に比べて少ない量でラベンダー油を可溶化できたことが分かる。 As shown in Table 4, it can be seen that the compositions of Examples 1 and 15 were able to solubilize lavender oil in a smaller amount than the conventional products of Reference Examples 1 to 3.
＜可溶化力の測定４＞
実施例２５～２９、比較例６
　表５、表６に示す組成物を調製し、実施例１と同様にして可溶化力を測定した。結果を表５、表６に示す。 <Measurement of solubilizing power 4>
Examples 25-29, Comparative Example 6
Compositions shown in Tables 5 and 6 were prepared, and the solubilizing power was measured in the same manner as in Example 1. Tables 5 and 6 show the results.
　表５、表６で使用した成分の詳細を以下に示す。
カプリン酸ポリグリセリル－１０：ポリグリセリン及び脂肪酸（ヤシ、パーム由来）に水酸化ナトリウムを加え、常圧（７６０Ｔｏｒｒ）下、２４０℃においてエステル化反応を行った。冷却後、反応物が５０質量％になるようグリセリンで希釈して組成物を得た。なお、原料のポリグリセリンは、グリセリンの脱水重合法で製造しており、１００％自然由来のものを使用した。原料の脂肪酸は、カプリン酸を使用した。
ミリスチン酸ポリグリセリル－１０：原料の脂肪酸をミリスチン酸（ヤシ、パーム由来）とした以外はカプリン酸ポリグリセリル－１０と同様にして調製した。
オレイン酸ポリグリセリル－１０：原料の脂肪酸をオレイン酸（パーム由来）とした以外はカプリン酸ポリグリセリル－１０と同様にして調製した。 Details of the components used in Tables 5 and 6 are shown below.
Polyglyceryl-10 caprate: Sodium hydroxide was added to polyglycerin and fatty acid (derived from coconut and palm), and an esterification reaction was carried out at 240° C. under normal pressure (760 Torr). After cooling, the reaction product was diluted with glycerin to 50% by mass to obtain a composition. The raw material polyglycerin was produced by dehydration polymerization of glycerin, and was 100% naturally derived. Capric acid was used as the raw material fatty acid.
Polyglyceryl-10 myristate: Prepared in the same manner as polyglyceryl-10 caprate, except that myristic acid (derived from coconut or palm) was used as the starting fatty acid.
Polyglyceryl-10 oleate: Prepared in the same manner as polyglyceryl-10 caprate, except that oleic acid (derived from palm) was used as the starting fatty acid.
　表６で使用した難水溶性物質の詳細を以下に示す。
フィトスクワラン（ＳＯＰＨＩＭ社製）
エチルヘキサン酸セチル（エキセパールＨＯ 花王社製） Details of the poorly water-soluble substances used in Table 6 are shown below.
Phytosqualane (manufactured by SOPHIM)
Cetyl ethylhexanoate (Exepar HO manufactured by Kao Corporation)
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５に示すように、実施例４、７の組成物と、炭素数１０～１４の飽和脂肪酸とポリグリセリンをエステル化したポリグリセリン脂肪酸エステルを併用することで、更に可溶化力を高めることができることが分かる。 As shown in Table 5, by using the compositions of Examples 4 and 7 together with a polyglycerin fatty acid ester obtained by esterifying a saturated fatty acid having 10 to 14 carbon atoms and polyglycerin, the solubilizing power can be further enhanced. I know you can.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表６に示すように、実施例１５の組成物を用いることで、極性の低い炭化水素油、エステル油についても可溶化できることが分かる。また、実施例２９に示すように、炭素数１８の不飽和脂肪酸とポリグリセリンをエステル化したポリグリセリン脂肪酸エステルを併用することで、炭化水素油、エステル油の可溶化力を更に高めることができることが分かる。 As shown in Table 6, it can be seen that by using the composition of Example 15, even low-polar hydrocarbon oils and ester oils can be solubilized. In addition, as shown in Example 29, by using a polyglycerin fatty acid ester obtained by esterifying an unsaturated fatty acid having 18 carbon atoms and polyglycerin, the ability to solubilize hydrocarbon oils and ester oils can be further enhanced. I understand.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　処方例１～８の化粧料は、いずれも透過率９８％以上であり難水溶性物質が可溶化されているものであった。 The cosmetics of Formulation Examples 1 to 8 all had a transmittance of 98% or more, and the poorly water-soluble substances were solubilized.
　本発明の化合物により、少ない量で香料や精油を可溶化できることから、より環境に配慮した製品設計が期待できる。 Because the compound of the present invention can solubilize fragrances and essential oils in small amounts, more environmentally friendly product design can be expected.

Claims (8)

  1. 　ポリグリセリンと脂肪酸及びジカルボン酸のエステルであって、下記（Ａ）～（Ｃ）を満たす、化合物。
    （Ａ）全脂肪酸のうち、炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計割合が４８質量％以上
    （Ｂ）ポリグリセリンと脂肪酸の質量比（ポリグリセリン：脂肪酸）が１：０．１５～１：０．３５
    （Ｃ）ジカルボン酸の炭素数が４～１２であり、ポリグリセリンに対するモル比（ジカルボン酸／ポリグリセリン）が０．１～０．８     A compound which is an ester of polyglycerin with fatty acid and dicarboxylic acid and satisfies the following (A) to (C).
    (A) The total proportion of unsaturated fatty acids with 18 to 22 carbon atoms and branched fatty acids in the total fatty acids is 48% by mass or more (B) The mass ratio of polyglycerin and fatty acids (polyglycerin:fatty acid) is 1:0.15 ~1:0.35
    (C) the dicarboxylic acid has 4 to 12 carbon atoms, and the molar ratio to polyglycerin (dicarboxylic acid/polyglycerin) is 0.1 to 0.8
  2. 　さらに下記（Ｄ）を満たす、請求項１記載の化合物。
    （Ｄ）炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸の合計量と炭素数１０～１４の飽和脂肪酸の質量比（炭素数１８～２２の不飽和脂肪酸及び分岐脂肪酸：炭素数１０～１４の飽和脂肪酸）が１：０～１：１     The compound according to claim 1, further satisfying the following (D).
    (D) the mass ratio of the total amount of unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms and the saturated fatty acids having 10 to 14 carbon atoms (unsaturated fatty acids and branched fatty acids having 18 to 22 carbon atoms: saturated fatty acid) is 1:0 to 1:1
  3. 　さらに下記（Ｅ）を満たす、請求項１又は２記載の化合物。
    （Ｅ）ポリグリセリンの平均重合度が３～２０     3. The compound according to claim 1 or 2, further satisfying the following (E).
    (E) The average degree of polymerization of polyglycerin is 3 to 20
  4. 　ジカルボン酸が、コハク酸、マレイン酸、アジピン酸、セバシン酸、及びドデカン二酸からなる群より選択される１種以上である、請求項１～３いずれか記載の化合物。 The compound according to any one of claims 1 to 3, wherein the dicarboxylic acid is one or more selected from the group consisting of succinic acid, maleic acid, adipic acid, sebacic acid, and dodecanedioic acid.
  5. 　自然由来指数が０．５～１．０である、請求項１～４いずれか記載の化合物。 The compound according to any one of claims 1 to 4, which has a nature origin index of 0.5 to 1.0.
  6. 　請求項１～５いずれか記載の化合物と、炭素数１０～１８の脂肪酸とポリグリセリンをエステル化したポリグリセリン脂肪酸エステルを含有する、組成物。 A composition comprising the compound according to any one of claims 1 to 5 and a polyglycerin fatty acid ester obtained by esterifying a fatty acid having 10 to 18 carbon atoms and polyglycerin.
  7. 　請求項１～５いずれか記載の化合物又は請求項６記載の組成物を含有する、難水溶性物質用可溶化剤。 A solubilizer for poorly water-soluble substances, containing the compound according to any one of claims 1 to 5 or the composition according to claim 6.
  8. 　請求項１～５いずれか記載の化合物又は請求項６記載の組成物を含有する、化粧料。 A cosmetic containing the compound according to any one of claims 1 to 5 or the composition according to claim 6.
PCT/JP2022/000034 2021-02-10 2022-01-04 Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified WO2022172645A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022581242A JPWO2022172645A1 (en) 2021-02-10 2022-01-04

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021020089 2021-02-10
JP2021-020089 2021-02-10

Publications (1)

Publication Number Publication Date
WO2022172645A1 true WO2022172645A1 (en) 2022-08-18

Family

ID=82837686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/000034 WO2022172645A1 (en) 2021-02-10 2022-01-04 Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified

Country Status (2)

Country Link
JP (1) JPWO2022172645A1 (en)
WO (1) WO2022172645A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7346772B1 (en) * 2022-03-25 2023-09-19 太陽化学株式会社 A compound obtained by esterifying polyglycerin with fatty acids and dicarboxylic acids.
WO2023181682A1 (en) * 2022-03-25 2023-09-28 太陽化学株式会社 Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104843A (en) * 2001-09-28 2003-04-09 Kanebo Ltd Oily make-up cosmetic
WO2004082645A1 (en) * 2003-03-19 2004-09-30 Kanebo Cosmetics Inc. Oily makeup cosmetics
JP2006273753A (en) * 2005-03-29 2006-10-12 Sakamoto Yakuhin Kogyo Co Ltd Transparent viscous oil and cosmetic compounded with the same
JP2006315975A (en) * 2005-05-11 2006-11-24 Sakamoto Yakuhin Kogyo Co Ltd Oil for cosmetic and cosmetic containing the same formulated therewith
WO2008013106A1 (en) * 2006-07-28 2008-01-31 The Nisshin Oillio Group, Ltd. Esterification reaction product, gelling agent containing the product, and cosmetic preparation containing them
JP2013519634A (en) * 2010-02-12 2013-05-30 エヴォニク ゴールドシュミット ゲーエムベーハー Cosmetic composition containing polyglycerol partial ester
JP2015044780A (en) * 2013-08-29 2015-03-12 株式会社コスモステクニカルセンター Solubilizer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104843A (en) * 2001-09-28 2003-04-09 Kanebo Ltd Oily make-up cosmetic
WO2004082645A1 (en) * 2003-03-19 2004-09-30 Kanebo Cosmetics Inc. Oily makeup cosmetics
JP2006273753A (en) * 2005-03-29 2006-10-12 Sakamoto Yakuhin Kogyo Co Ltd Transparent viscous oil and cosmetic compounded with the same
JP2006315975A (en) * 2005-05-11 2006-11-24 Sakamoto Yakuhin Kogyo Co Ltd Oil for cosmetic and cosmetic containing the same formulated therewith
WO2008013106A1 (en) * 2006-07-28 2008-01-31 The Nisshin Oillio Group, Ltd. Esterification reaction product, gelling agent containing the product, and cosmetic preparation containing them
JP2013519634A (en) * 2010-02-12 2013-05-30 エヴォニク ゴールドシュミット ゲーエムベーハー Cosmetic composition containing polyglycerol partial ester
JP2015044780A (en) * 2013-08-29 2015-03-12 株式会社コスモステクニカルセンター Solubilizer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIGUCHI TOMONORI: "Emulsification and solubilization characteristics of Polyglycerol Fatty Acid Esters", OREO-SAISENSU : JOURNAL OF JAPAN OIL CHEMISTS' SOCIETY, JAPAN OIL CHEMISTS' SOCIETY, JP, vol. 19, no. 10, 1 January 2019 (2019-01-01), JP , pages 405 - 410, XP055957544, ISSN: 1345-8949, DOI: 10.5650/oleoscience.19.405 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7346772B1 (en) * 2022-03-25 2023-09-19 太陽化学株式会社 A compound obtained by esterifying polyglycerin with fatty acids and dicarboxylic acids.
WO2023181682A1 (en) * 2022-03-25 2023-09-28 太陽化学株式会社 Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified

Also Published As

Publication number Publication date
JPWO2022172645A1 (en) 2022-08-18

Similar Documents

Publication Publication Date Title
WO2022172645A1 (en) Compound in which polyglycerol, fatty acid, and dicarboxylic acid have been esterified
KR20210079321A (en) High Potency Vitamin C Topical Formulation
KR20180031748A (en) A method for enriching the Pongga Mall of Karanja Oil
JP2014196282A (en) W/o/w type emulsion composition
CN107028774B (en) Heat stable suspension cosmetic composition
JP2014198704A (en) Emulsification composition
JP6930847B2 (en) Cosmetics or topical skin agents
JP6930846B2 (en) Cosmetics or topical skin agents
JP2019131524A (en) Cosmetic and skin external preparation
JP7301760B2 (en) Skin topical agent
JP7109860B2 (en) Cosmetics and external skin preparations
JP7125268B2 (en) Cosmetics and external skin preparations
JP7166063B2 (en) Cosmetics and external skin preparations
JP7051494B2 (en) Cosmetics and external skin preparations
JP7139034B2 (en) Cosmetics and external skin preparations
JP7140509B2 (en) How to control discoloration
WO2019171529A1 (en) Method for improving water solubility of sparingly-soluble component
WO2024090432A1 (en) Polyglycerol fatty acid ester
JP7112208B2 (en) Cosmetics and external skin preparations
JP7254447B2 (en) Cosmetics and external skin preparations
JP6930848B2 (en) Cosmetics or topical skin agents
JP2022060041A (en) Solubilization composition for poorly water-soluble substances
JP6898137B2 (en) Cosmetics or topical skin agents
JP7053151B2 (en) How to improve the solubility of poorly water-soluble components
JP2024096071A (en) Cosmetics or skin preparations

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22752478

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022581242

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22752478

Country of ref document: EP

Kind code of ref document: A1