JP2023084322A - oily solid cosmetics - Google Patents

Abstract

To provide oily solid cosmetics with excellent high-temperature stability and usability, and a smooth surface.SOLUTION: The above problems are solved by an oily solid cosmetic with: (A) a solid and/or semi-solid oil; (B) an oily component that is liquid at 25°C; (C) a polyglycerol fatty acid ester having an average degree of polymerization of 2 to 20 and a constituent fatty acid being one or more selected from the group consisting of unsaturated fatty acids having 8 to 22 carbon atoms and branched fatty acids; and (D) a polyglycerol fatty acid ester having an average degree of polymerization of 2 to 20 and a constituent fatty acid being at least one or more selected from the group consisting of monocarboxylic acids and derivatives thereof as well as at least one or more selected from the group consisting of polyglycerol acids and derivatives thereof.SELECTED DRAWING: None

Description

There is an application for the application of Article 30, Paragraph 2 of the Patent Act. Panel display 1-1. Meeting name: CITE JAPAN 2021 1-2. Title: Oil thickening and gelling agent 1-3. Date of issue: May 19-21, 2021 2. Oral presentation 2-1. Meeting name: CITE JAPAN 2021 2-2. Presentation title: Introduction of a thickening and gelling agent for oils with plant-derived polyglycerin as the main skeleton 2-3. Announcement date: May 19, 2021 3. Publication in abstracts 3-1. Publication: Summary of the 60th Annual Meeting of the Japan Oil Chemists' Society 3-2. Title: Development of an oil-thickening and gelling agent with polyglycerin as the main skeleton and excellent feel when applied 3-3. Date of announcement: August 31, 2021 4. Oral presentation 4-1. Meeting name: The 60th Annual Meeting of the Japan Oil Chemists' Society 4-2. Title of presentation: Development of an oil-thickening and gelling agent with polyglycerin as the main skeleton and excellent feel when applied 4-3. Announcement date: September 6, 2021

TECHNICAL FIELD The present invention relates to an oily solid cosmetic.

Oil-based solid cosmetics are applied to a wide range of formulations such as skin care, cleansing, and makeup that are applied to the skin and lips (Patent Documents 1 and 2). Oil-based solid cosmetics contain solid oils such as waxes in addition to liquid oils, and are oil gels in which the fluidity of the liquid oils is suppressed by incorporating the liquid oils into the card house structure formed by the solid oils. forming a structure. In addition, oil-based solid cosmetics are easier to handle than liquid formulations, and have the property that when stress is applied during use, part of the structure collapses and the liquid oil spreads.

Conventional oil-based solid cosmetics have a hard oil-gel structure at low temperatures such as in winter, making it difficult to take out from a container or to spread the cosmetic. In order to solve these problems, there is a technique of adjusting the melting point and crystallinity by using petroleum-based raw materials such as polyethylene, polypropylene, synthetic wax, and microcrystalline wax as the solidified wax. However, in recent years, there has been an increasing demand for formulations that do not use petroleum-based waxes due to the demand for sustainable raw materials. When a solid oil with a high melting point is blended in order to impart stability at high temperatures, it becomes difficult to spread and spread poorly during application, making it difficult to achieve both usability and storage stability in oil-based solid cosmetics. .

There is also a method of stabilizing the oil gel structure even at high temperatures by using an oil gelling agent in combination. However, the surface of the molded cosmetic is rough and tends to cause problems such as impairing the appearance, and it cannot be said that the problem is sufficiently solved.

Japanese Patent Application Laid-Open No. 2021-017401 JP 2017-095375 A

An object of the present invention is to provide an oily solid cosmetic which is excellent in high-temperature stability and usability and has a smooth surface.

As a result of extensive studies, the present inventors have found that (A) a solid oil and/or semi-solid oil, (B) an oily component that is liquid at 25°C, and (C) polyglycerol have an average degree of polymerization of 2 to 20, Polyglycerin fatty acid ester whose constituent fatty acid is one or more selected from the group consisting of unsaturated fatty acids having 8 to 22 carbon atoms and branched fatty acids, (D) polyglycerol having an average degree of polymerization of 2 to 20, and the constituent fatty acids An oily solid cosmetic using a polyglycerin fatty acid ester which is at least one selected from the group consisting of monocarboxylic acids and derivatives thereof and at least one selected from the group consisting of polycarboxylic acids and derivatives thereof. found to solve the above problems.

The oily solid cosmetic of the present invention has excellent high-temperature stability, spreads well when applied, and has an excellent appearance when molded. The oil-based solid cosmetic composition of the present invention is easy to spread even without using petroleum wax, and satisfies the demand for a formulation consisting only of sustainable raw materials.

The present invention will be described in detail below. The scope of the present invention is not limited to this embodiment, and forms in which modifications are made within the scope of the present invention also belong to the present invention. In addition, "-" in the notation representing the range includes the upper limit and the lower limit. All units indicating contents are % by weight unless otherwise specified.

The solid oil or semi-solid oil of component (A) is not particularly limited, but petroleum waxes include polyethylene wax (melting point: 90 to 120°C), paraffin wax (melting point: 50 to 70°C), Hydrocarbon waxes such as microcrystalline wax (melting point: 54-102°C), Fischer-Tropsch wax (melting point: 108-120°C), ceresin (melting point: 61-95°C), okezolite (melting point: 61-90°C) mentioned. Natural waxes include carnauba wax (melting point: 80-86°C), beeswax (melting point: 64°C), candelilla wax (melting point: 68-72°C), and rice bran wax (melting point: 70-83°C). , jojoba wax (melting point: 55°C). In addition, hydrogenated jojoba oil (melting point: 68°C), hydrogenated castor oil (melting point: 84°C), hydrogenated palm oil (melting point: 65°C), hydrogenated coconut oil (melting point: 70°C), which are composed of naturally derived raw materials ° C), tristearin, tribehenin, shea butter (melting point: 36-45 ° C), macadamia nut oil polyglyceryl-6 esters behenate, (isostearic acid/behenic acid) (glyceryl/polyglyceryl-6) esters (melting point: 28-40 °C) and the like. These can be used either singly or in combination of two or more. From the viewpoint of shape retention and storage stability, the melting point of component (A) as a whole is preferably 40 to 110°C, more preferably 60 to 110°C. Further, in the present invention, it is more preferable not to contain petroleum wax.

Component (A) is preferably blended in an amount of 1 to 30%, more preferably 3 to 20%, relative to the oily solid cosmetic.

The liquid oily component used for component (B) is not particularly limited as long as it is an oily agent that is liquid at 25°C. For example, isocetyl isostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, tetra Pentaerythryl octanoate, tri-2-heptylundecanoic acid glyceride, diisobutyl adipate, 2-hexyldecyl sebacate, diisostearyl malate, isopropyl myristate, 2-octyldodecyl oleate, hexyldecyl dimethyloctanoate, myristine 2-hexyldecyl acid, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, ethyl stearate, isocetyl stearate, decyl oleate, oleic acid Dodecyl, oleyl oleate, lauryl lactate, cholesteryl 12-hydroxystearate, castor oil fatty acid methyl ester, 2-ethylhexyl succinate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, diisopropyl sebacate, sebatine Di-2-ethylhexyl acid, neopentyl glycol dicaprate, neopentyl glycol dioctoate, hexyl laurate, hexyldecyl dimethyloctanoate, diethyl phthalate, dibutyl phthalate, dioctyl succinate, triethylhexanoin, tripropylene dipivalate Glycol tri-2-ethylhexanoate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, trimethylolpropane triisostearate, glyceryl triisopalmitate, tri(caprylic/capric)glyceryl, tri(caprylic/capric) caprin, myristine, stearate), glyceryl tri-2-ethylhexanoate, glyceryl tricaprylate, glyceryl trioleate, glyceryl trilinoleate, glyceryl tripalmitoleate, ester oils such as fluorine-modified ester oils, and linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, mustard oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, almond oil, rapeseed oil, Animal and plant-derived ester oils such as sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, egg yolk oil, beef leg fat, liver oil, etc. may be used; Hydrocarbon oils such as α-olefin oligomer, light isoparaffin, light liquid isoparaffin, liquid isoparaffin, liquid paraffin, squalane, polybutene, and hydrogenated polyisobutene; Chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane , octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and other cyclic silicones, amino-modified silicone oils, polyether-modified silicone oils, carboxy-modified silicone oils, alkyl-modified silicone oils, ammonium salt-modified silicone oils, silicone oils such as fluorine-modified silicone oils; higher fatty acids such as oleic acid, tall oil fatty acids, isostearic acid; higher alcohols such as lauryl alcohol, oleyl alcohol, isostearyl alcohol, octyldodecanol, and jojoba alcohol; It is preferable to use

(B) The liquid oily component is preferably blended in an amount of 1 to 50%, more preferably 10 to 40%, of the solid oily cosmetic.

The polyglycerin fatty acid ester of component (C) has an average degree of polymerization of polyglycerin of 2 to 20, and the constituent fatty acids are unsaturated fatty acids and/or branched fatty acids having 8 to 22 carbon atoms.

(C) The polyglycerin constituting the polyglycerol fatty acid ester has an average degree of polymerization of 2-20, preferably 2-15. Here, the average degree of polymerization is the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value obtained by terminal group analysis. Specifically, it is calculated from the following formulas (1) and (2).
Molecular weight = 74n + 18 (1)
Hydroxyl value = 56110 (n + 2) / molecular weight (2)

The hydroxyl value in the above formula (2) is a numerical value that is an index of the number of hydroxyl groups contained in polyglycerin, and the amount of acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerin is The number of milligrams of potassium hydroxide required to combine. The number of milligrams of potassium hydroxide is calculated in accordance with the Japan Oil Chemistry Society compilation "Establishment of the Japan Oil Chemistry Society, Standard Oil Analysis Test Method, 2003 Edition".

(C) The fatty acid constituting the polyglycerol fatty acid ester is one or more selected from the group consisting of unsaturated fatty acids having 8 to 22 carbon atoms and branched fatty acids, and isostearic acid and oleic acid having 18 carbon atoms. is preferred.

(C) The esterification rate of polyglycerin fatty acid ester is preferably 30 to 100%, more preferably 40 to 100%, and most preferably 70 to 100%. Here, the esterification rate is the average degree of polymerization of polyglycerin calculated from the hydroxyl value (n), the number of hydroxyl groups possessed by this polyglycerin (n+2), and the number of moles of fatty acid added to polyglycerin (M). , is a value calculated by the following formula (3). A hydroxyl value is a value calculated by the above formula (2).
Esterification rate (%) = (M/(n+2)) x 100 (3)

(C) Specific examples of polyglycerol fatty acid esters include diglyceryl 2-ethylhexanoate, diglyceryl isostearate, diglyceryl diisostearate, diglyceryl tetraisostearate, triglyceryl isostearate, tetraglyceryl diisostearate, and pentaisostearate. Decaglyceryl, decaglyceryl nonisostearate, decaglyceryl decaisostearate, diglyceryl oleate, triglyceryl oleate, tetraglyceryl oleate, hexaglyceryl oleate, decaglyceryl oleate, decaglyceryl 2-ethylhexanoate, etc. and one or more of these are used. Trade names include IS-204P, IS-1009P, IS-1005P, KEH-1010, and O-201P (all manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.).

(C) Polyglycerol fatty acid ester is preferably blended in an amount of 5 to 70%, more preferably 10 to 60%, of the oily solid cosmetic. By setting the amount in the range of 5 to 70% based on the oily solid cosmetic, it is possible to obtain an oily solid cosmetic with excellent high-temperature stability and a smooth surface.

The polyglycerin fatty acid ester of component (D) has an average degree of polymerization of polyglycerin of 2 to 20, and the constituent fatty acids are at least one selected from the group consisting of monocarboxylic acids and derivatives thereof, and polycarboxylic acids. and at least one selected from the group consisting of derivatives thereof.

(D) The polyglycerin constituting the polyglycerin fatty acid ester has an average degree of polymerization of 2 to 20, preferably 4 to 20, calculated from the hydroxyl value.

(D) The monocarboxylic acid constituting the polyglycerin fatty acid ester is not particularly limited, but examples include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, ricinoleic acid, palmitic acid, Tooleic acid, isooctyl acid (2-ethylhexanoic acid, etc.), isononanoic acid (3,5,5-trimethylhexanoic acid, etc.), isopalmitic acid, isostearic acid (2-heptylundecanoic acid, polymethyl component manufactured by Emery) branched type, etc.), cerotic acid, montanic acid, melissic acid, etc., and linear and saturated monocarboxylic acids are preferred.

(D) The polycarboxylic acid constituting the polyglycerin fatty acid ester is not particularly limited. 1,12-dodecamethylenedioic acid, 1,15-pentadecamethylenedioic acid, 1,28-octacosamethylenedioic acid, 1,7-ethyloctadecanedioic acid and the like, which are saturated dicarboxylic acids. preferable.

The above monocarboxylic acid and polycarboxylic acid may be derivatives. Derivatives include these acid anhydrides and acid halides.

(D) The polyglycerin fatty acid ester is preferable in that it exhibits a function of excellent feeling in use by being a mixture of monocarboxylic acid and polycarboxylic acid.

(D) The esterification rate of the total fatty acid constituting the polyglycerin fatty acid ester is preferably 30 to 70%, more preferably 40 to 60%. If the esterification rate in all the constituent fatty acids is 30 to 70%, it can provide an excellent feel when blended in an oily solid cosmetic.

(D) When a dicarboxylic acid such as eicosanedioic acid is used as the polycarboxylic acid constituting the polyglycerol fatty acid ester, the esterification rate of the dicarboxylic acid is not particularly limited, but the esterification rate is 2 to 2. It is preferably 8%, more preferably 3-7%. If the dicarboxylic acid esterification rate is in the range of 2 to 8%, the cross-linking reaction of the polyglycerin fatty acid ester can be appropriately controlled, and the desired polyglycerin fatty acid ester can be obtained. Also, the dispersibility when added to an oil agent is improved.

(D) Polyglycerol fatty acid ester is preferably blended in an amount of 1 to 30%, more preferably 2 to 20%, relative to the oily solid cosmetic. By setting the amount in the range of 1 to 30% with respect to the oily solid cosmetic, both high-temperature stability and good spreadability can be achieved.

In the oily solid cosmetic composition of the present invention, the total amount of component (A) and component (D) in all components is preferably 5 to 40%. If the combined amount of component (A) and component (D) is 5 to 40%, a cosmetic composition with even better high-temperature stability can be obtained.

The oil-based solid cosmetic composition of the present invention contains components that are usually contained in cosmetics, as long as the effects are not impaired, such as oil-based components, alcohols, water-soluble polymers, moisturizing agents, aqueous components such as water, powders, and interface components. Active agents, cosmetic ingredients, UV absorbers, antioxidants, preservatives, fragrances, and the like can be contained.

The aqueous component is not particularly limited as long as it is soluble in water and commonly used in cosmetics, and includes alcohols such as ethyl alcohol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, Examples include glycols such as polyethylene glycol, glycerols such as glycerin, diglycerin and polyglycerin, and saccharides such as dextrin, glucose, sorbitol, xylitol, trehalose, oligosaccharides and cellulose. Examples of water-soluble polymers include natural ones such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate and carrageenan; semisynthetic ones such as methylcellulose, hydroxyethylcellulose and carboxymethylcellulose; carboxyvinyl polymers; Synthetic ones such as alkyl-added carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, and sodium polyacrylate, as well as proteins, mucopolysaccharides, collagen, elastin, keratin, etc., and one or more of these are used. be able to.

The powder is not particularly limited as long as it is commonly used in cosmetics. Silicic acid, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic phlogopite, sericite, talc, kaolin , silicon carbide, barium sulfate, boron nitride, bismuth oxychloride and other inorganic powders, nylon, polymethyl methacrylate, polyalkyl acrylate, organopolysiloxane elastomer, polymethylsesquioxane, crosslinked silicone and network silicone block Organic powders such as copolymers, polystyrene, acrylonitrile-methacrylic acid copolymers, vinylidene chloride-methacrylic acid copolymers, polyethylene, urethane, wool, silk, crystalline cellulose, N-acyl lysine, organic tar pigments, Pigment powders such as lake pigments such as organic pigments, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing anhydrous silicic acid, zinc oxide containing anhydrous silicic acid, titanium oxide Composite powders such as coated glass powder, titanium oxide-coated synthetic phlogopite, mica titanium, iron oxide-coated mica titanium, Prussian blue-coated mica titanium, carmine-coated mica titanium, polyethylene terephthalate/aluminum/epoxy laminated powder, polyethylene terephthalate/poly Examples include laminated film powders such as methyl methacrylate laminated powders. In addition, these powders may be combined with one of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, amino acids, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, and the like. Alternatively, two or more of them may be used for surface treatment.

The surfactant is not particularly limited as long as it is commonly used in cosmetics, and includes nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like. Examples include glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid esters and alkylene glycol adducts thereof, sucrose fatty acid esters, polyoxyethylene hydrogenated castor oil, lecithin and the like, and one or two of these can be used. The above can be used.

Examples of antioxidants include α-tocopherol, ascorbic acid, and dibutylhydroxytoluene; examples of cosmetic ingredients include vitamins, antiphlogistic agents, herbal medicines, and the like; examples of antiseptics include paraoxybenzoic acid esters, phenoxyethanol, and pentanediol. , Examples of UV absorbers include benzophenone, PABA, cinnamic acid, salicylic acid, 4-tert-butyl-4'-methoxybenzoylmethane, triazine, oxybenzone, etc. Alternatively, two or more kinds can be used.

The oil-based solid cosmetic composition of the present invention can be used in various pasty or solid forms, such as lipsticks, lipsticks, lipliners, eyeliners, eyeshadows, cheeks, foundations, concealers, and pressed powders. , balms, skin care products such as cleansing balms, and hair care products such as hair treatments.

The method for preparing the oily solid cosmetic of the present invention is not particularly limited.
EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited by these examples.

<(D) Synthesis example 1 of polyglycerol fatty acid ester>
131.9 g of polyglycerol having an average degree of polymerization of 10, 355.0 g of behenic acid, and 35.7 g of eicosanedioic acid were placed in a reaction vessel, 0.25 g of sodium hydroxide was added, and the mixture was heated at 250° C. for 3 hours under a nitrogen stream. A reaction was carried out to obtain 500 g of a reaction product having an esterification rate of 55% (monocarboxylic acid esterification rate 50%, polycarboxylic acid esterification rate 5%) in all constituent fatty acids.

<(D) Synthesis example 2 of polyglycerin fatty acid ester>
138.6 g of polyglycerol having an average degree of polymerization of 20, 346.6 g of behenic acid, and 34.9 g of eicosanedioic acid were placed in a reaction vessel, 0.25 g of sodium hydroxide was added, and the mixture was heated at 250° C. for 3 hours under a nitrogen stream. A reaction was carried out to obtain 500 g of a reaction product having an esterification rate of 55% (monocarboxylic acid esterification rate 50%, polycarboxylic acid esterification rate 5%) in all constituent fatty acids.

<Examples 1 to 8, Comparative Examples 1 to 4>
Oil-based solid cosmetics having compositions shown in Tables 1 and 2 were prepared by the following manufacturing method.

(Production method)
After heating the raw materials to 80° C. and dissolving and mixing them, 10 g of the mixture was placed in a 20 mL capacity plastic jar and cooled to room temperature to produce an oily solid cosmetic composition.

(High temperature stability)
The obtained oily solid cosmetic was stored in a constant temperature bath at 50° C. for 1 week, and then visually evaluated according to the following criteria.
(standard)
○: Solid, no change on the surface △: Solid, but slight oil floating on the surface ×: Solid, but liquid oil oozes out over half of the surface , or not solid

(exterior)
The obtained oily solid cosmetic was stored in a constant temperature bath at 5° C. for 1 week, and then visually evaluated for “appearance at the time of molding” according to the following criteria.
(standard)
○: The surface is smooth and glossy △: The surface is slightly rough
×: The surface is rough and lacks gloss

(Good spreadability)
The obtained oily solid cosmetic was stored in a constant temperature bath at 25° C. for 12 weeks, and sensory evaluation was performed by 20 panelists. 1 g of the above composition was applied to the forearm, and spreadability was calculated on a scale of 5 out of 5 and the spreadability was calculated and evaluated according to the following criteria.
(standard)
◎: 4.0 points or more (very good)
○: 3.0 points or more and less than 4.0 points (good)
△: 2.0 points or more and less than 3.0 points (slightly bad)
×: 2.0 points or less (bad)

※１：Ｓフェイス ＶＬ－２１１（阪本薬品工業製）
※２：Ｓフェイス ＩＳ－２０４Ｐ（阪本薬品工業製）
※３：Ｓフェイス ＩＳ－１００９Ｐ（阪本薬品工業製）

*1: S face VL-211 (manufactured by Sakamoto Yakuhin Kogyo)
*2: S face IS-204P (manufactured by Sakamoto Yakuhin Kogyo)
*3: S face IS-1009P (manufactured by Sakamoto Yakuhin Kogyo)

Examples 1 to 8, which are oily solid cosmetics of the present invention containing components (A) to (D), are comparative example 1 which does not contain component (C) and component (D), and component (D). Compared to Comparative Example 2 without component (D), Comparative Example 3 using an oil thickener other than component (D), and Comparative Example 4 using an ester other than component (C), in terms of high temperature stability, good spreadability and appearance was excellent.

Claims (1)

An oily solid cosmetic containing the following components (A) to (D).
(A) Solid oil and/or semi-solid oil (B) Liquid oily component at 25°C (C) Polyglycerin having an average degree of polymerization of 2 to 20 and unsaturated fatty acids having 8 to 22 carbon atoms and Polyglycerin fatty acid ester which is at least one selected from the group consisting of branched fatty acids (D) The average degree of polymerization of polyglycerin is 2 to 20, and the constituent fatty acid is selected from the group consisting of monocarboxylic acids and derivatives thereof and at least one or more polyglycerol fatty acid esters selected from the group consisting of polycarboxylic acids and derivatives thereof