[go: up one dir, main page]

HK1122991B - External preparation for skin - Google Patents

External preparation for skin Download PDF

Info

Publication number
HK1122991B
HK1122991B HK09100236.5A HK09100236A HK1122991B HK 1122991 B HK1122991 B HK 1122991B HK 09100236 A HK09100236 A HK 09100236A HK 1122991 B HK1122991 B HK 1122991B
Authority
HK
Hong Kong
Prior art keywords
hlb value
oil
ether
peg
skin
Prior art date
Application number
HK09100236.5A
Other languages
Chinese (zh)
Other versions
HK1122991A1 (en
Inventor
Takayuki Omura
Yoshihito Takakura
Original Assignee
Shiseido Company, Ltd.
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
Priority claimed from JP2005338363A external-priority patent/JP4679350B2/en
Priority claimed from JP2005338364A external-priority patent/JP2007145722A/en
Application filed by Shiseido Company, Ltd. filed Critical Shiseido Company, Ltd.
Priority claimed from PCT/JP2006/321925 external-priority patent/WO2007060823A1/en
Publication of HK1122991A1 publication Critical patent/HK1122991A1/en
Publication of HK1122991B publication Critical patent/HK1122991B/en

Links

Description

External preparation for skin
Technical Field
The present invention relates to a skin external preparation and an oil-in-water emulsion skin cosmetic containing a specific 2-ethylhexanoate. The present invention also relates to an oil-in-water or water-in-oil emulsion sunscreen cosmetic, and more particularly, to an oil-in-water or water-in-oil emulsion sunscreen cosmetic which is excellent in usability and formulation stability and can realize a high SPF value.
Background
Conventionally, oil-in-water emulsion skin cosmetics have been used for imparting moist, smooth, extensible, and soft feel to higher fatty acids such as stearic acid, palmitic acid, myristic acid, and behenic acid; waxes such as vaseline, carnauba wax, candelilla wax, ozokerite, and microcrystalline wax; solid oils of higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol are emulsified with an emulsifier. Further, in order to suppress the crystallization of the solid oil over time, it has been attempted to prevent the crystallization of the solid oil by blending a hydrocarbon oil which is liquid at room temperature such as liquid paraffin or squalane and which has good solubility in the solid oil, and an ester oil having a relatively long carbon chain and similar to the solid oil in terms of carbon chain, such as cetyl palmitate, isopropyl isostearate, isodecyl neopentanoate, or oleyl oleate (see, for example, the edited japanese technologist in "latest cosmetics science (revised supplement II)", published by the news bulletin, on 4 years, 7 months, 10 days, page 49).
However, the oil-in-water emulsion skin cosmetic prepared by the above method has satisfactory stability and a soft feeling when applied to the skin, but is not satisfactory in terms of usability because it is inferior in spreadability and skin absorption and has a sticky feeling. Further, when no solid oil is blended, the composition is excellent in stability over time, spreadability, and skin absorption properties, and is excellent in non-stickiness, but has a problem of lacking in a soft touch feeling.
Ultraviolet rays reaching the ground include UV-A (320-400 nm) and UV-B (290-320 nm), wherein the skin is subjected to erythema after the UV-A is excessively irradiated, so that an acute inflammatory reaction is generated, and then a skin blackening phenomenon is generated, and the skin cancer is caused. In addition, it is known that UV-B has a weak effect of causing erythema, but oxidizes reduced melanin of the skin to cause melanin pigmentation to blacken the skin, and it has been gradually known that long-term exposure is a cause of early aging of the skin. With the clear effect of ultraviolet rays on the skin, the demand for sunscreen cosmetics having a high ultraviolet-blocking effect has become higher. As an index for protecting the skin from ultraviolet rays, SPF (sun protection Factor) values are generally used, and the higher the SPF value is, the higher the artificial sunscreen effect is.
In general, a sunscreen cosmetic contains an ultraviolet absorber and an ultraviolet scattering agent in order to block ultraviolet irradiation to obtain a high SPF value. Ultraviolet absorbers block ultraviolet rays by absorbing light energy, and since general ultraviolet absorbers have a high polarity of absorption band, have skin irritation and are not good in terms of skin safety, silicone oil which is not irritating to skin and has good usability is used together. However, when an ultraviolet absorber as a highly polar oil is used together with a silicone oil as a nonpolar oil, the uniformity of the oil phase is poor, and there is a problem of emulsion stability or uneven application to the skin.
In addition, ultraviolet scattering agents block ultraviolet rays by scattering ultraviolet rays, and inorganic pigments such as zinc oxide, titanium dioxide, kaolin, and calcium carbonate have been used. These are highly safe to the skin and are useful as ultraviolet blocking agents because they block ultraviolet rays over a wide band and are inert.
However, these inorganic pigments, particularly titanium dioxide and zinc oxide, are, as described above, high in ultraviolet blocking effect and strong in hiding power (concealing power), and therefore cause whitening and whitening of the cosmetic film formed after application to the skin. For this reason, it has been proposed to use titanium dioxide and zinc oxide in fine particles (see, for example, Japanese patent laid-open publication No. Sho 47-42502, Japanese patent laid-open publication No. Sho 49-450 and Japanese patent laid-open publication No. Sho 64-7941). It is known that the finer these particles are, the higher the ultraviolet blocking effect is, and the higher the light transmittance in the visible light region is, the higher the transparency is.
However, these inorganic pigments generally have high aggregation properties of fine particles, and are difficult to stably disperse in a fine particle state in a formulation system of cosmetics and the like. Therefore, the desired ultraviolet-blocking effect and transparency are not achieved at present. Further, since these fine particle pigments have a high optical refractive index, the hiding property is improved after excessive use, but unnatural cosmetic phenomena such as whitening occur. Further, the aggregation of the particles hinders the spreadability of the cosmetic, and a feeling of astringency is generated when the cosmetic is applied to the skin, which causes a problem in usability.
Therefore, the amount of these ultraviolet scattering agents to be blended is limited, and it is not possible to provide a sunscreen cosmetic composition which can sufficiently exhibit the desired ultraviolet blocking effect. In order to solve this problem, as a technique for obtaining a sunscreen cosmetic excellent in usability, it has been proposed to use isononanoate as an oil phase dispersant (see, for example, Japanese patent laid-open No. 2000-169383). However, even by this method, it cannot be said that the homogeneity of the aqueous phase and/or the oil phase, the emulsion stability, and the dispersibility of zinc oxide and/or titanium dioxide are sufficient.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an oil-in-water type emulsion skin cosmetic excellent in stability with time and in usability (stretching of the skin, absorption into the skin, non-stickiness, smoothness, a soft feeling, and a firm feeling). In addition, the present invention has been made in view of the above-mentioned research and development on the application of the oil-in-water emulsion skin cosmetic, and has found an external preparation for skin which is extremely excellent in skin absorption, as described later.
The present invention aims to provide a sunscreen cosmetic which can sufficiently exert excellent ultraviolet blocking effects of an ultraviolet absorber and an ultraviolet scattering agent, and which is excellent in terms of usability such as good skin absorption and no stickiness.
More specifically, it is intended to provide an emulsion composition which is stable even in a system of a nonpolar oil such as a silicone oil using a combination of an ultraviolet absorber of a highly polar oil and a usability improver, and further to provide a cosmetic which can be stably and uniformly dispersed even when titanium dioxide or zinc oxide is blended as an ultraviolet scattering agent, and further can realize a high SPF value of natural makeup with a transparent feeling without whitening by improving redispersibility, and which is excellent in skin absorption and spreadability, is smooth and non-sticky, and has an excellent feeling in use.
As a result of intensive studies, the present inventors have found that a specific 2-ethylhexanoate ester is excellent in skin absorption, has excellent polar oil/nonpolar oil compatibility, and has an excellent effect of improving powder dispersibility, and have completed the present invention.
That is, the present invention provides an external preparation for skin containing isononyl 2-ethylhexanoate and/or 2-ethylhexyl 2-ethylhexanoate.
The present invention also provides the external preparation for skin, which contains 1.0 to 20.0 mass% of isononyl 2-ethylhexanoate and/or 2-ethylhexyl 2-ethylhexanoate.
The present invention also provides an oil-in-water emulsified skin cosmetic composition comprising (a) isononyl 2-ethylhexanoate and/or 2-ethylhexyl 2-ethylhexanoate, (b) one or more members selected from the group consisting of higher fatty acids and higher alcohols which are solid to semisolid at room temperature (25 ℃), (c) one or more members selected from the group consisting of homopolymers, copolymers, crosslinked polymers and mixtures thereof containing one or more members selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter referred to as "AMPS"), acrylic acid and derivatives thereof as a constituent unit, and (d) one or more members selected from the group consisting of nonionic surfactants having an HLB value of 9 or more.
The present invention also provides the oil-in-water emulsion skin cosmetic composition, which contains 1.0 to 20.0% by mass of the component (a), 0.5 to 8.0% by mass of the component (b), 0.1 to 5.0% by mass of the component (c), and 0.5 to 8.0% by mass of the component (d) in the total amount of the cosmetic composition.
The present invention also provides the above oil-in-water type emulsified skin cosmetic, wherein the component (c) is one or more selected from the group consisting of a vinylpyrrolidone/AMPS copolymer, a dimethylacrylamide/AMPS copolymer, an acrylamide/AMPS copolymer, a methylene bisacrylamide-crosslinked dimethylacrylamide/AMPS polymer, a mixture of polyacrylamide and sodium polyacrylate, a sodium acrylate/AMPS copolymer, a hydroxyethyl acrylate/AMPS copolymer, ammonium polyacrylate, a polyacrylamide/ammonium acrylate copolymer, and an acrylamide/sodium acrylate copolymer.
The present invention also provides the above oil-in-water emulsion skin cosmetic, wherein the component (d) is one or more selected from a polyoxyethylene adduct compound and a polyethylene glycol adduct compound.
The present invention also provides the above oil-in-water type emulsion skin cosmetic composition, wherein a nonionic surfactant having an HLB value of 9 or more and less than 15 and a nonionic surfactant having an HLB value of 15 or more are used in combination as the component (d).
The present inventors have made intensive studies to solve the above problems and found that an oil-in-water or water-in-oil sunscreen cosmetic composition prepared by using 2-ethylhexyl 2-ethylhexanoate and/or isononyl 2-ethylhexanoate has good compatibility between an ultraviolet absorber as a highly polar oil and a silicone oil as a nonpolar oil as a usability improver, is excellent in emulsion stability, and is excellent in dispersibility of titanium dioxide and zinc oxide. In particular, a composition is obtained which has excellent dispersibility even for fine particles having a high aggregation property in general, and which is excellent in stability, skin absorption and spreadability of a sunscreen cosmetic in the presence of a silicone surfactant, and which is excellent in both smooth and non-sticky feeling in use. The present invention has been developed based on this finding.
That is, the present invention provides an oil-in-water or water-in-oil emulsion sunscreen cosmetic composition comprising (a) 2-ethylhexyl 2-ethylhexanoate and/or isononyl 2-ethylhexanoate, (b) an ultraviolet absorber, (c) an ultraviolet scattering agent, and (d) a silicone oil.
The present invention also provides the sunscreen cosmetic composition, wherein the component (b) is one or more selected from the group consisting of p-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, β -diphenylacrylate derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranilic anhydride (anthrenil) derivatives, imidazoline derivatives, benzylidene malonate derivatives, and 4, 4-diarylbutadiene derivatives.
The invention also provides the sunscreen cosmetic, wherein the component (c) is zinc oxide and/or titanium dioxide.
The invention also provides the sunscreen cosmetic, wherein the average primary particle diameter of the zinc oxide is 5-40 nm.
In addition, the invention also provides the sunscreen cosmetic, wherein the average primary particle diameter of the titanium dioxide is 5-30 nm.
The present invention also provides the sunscreen cosmetic composition, wherein the total amount of the sunscreen cosmetic composition contains 1 to 60% by mass of the component (a), 3 to 20% by mass of the component (b), 0.5 to 50% by mass of the component (c), and 1 to 70% by mass of the component (d).
The present invention also provides the sunscreen cosmetic composition, further comprising (e) one or more selected from silicone surfactants, glycerin and fatty acid polyglycerin esters.
The silicone surfactant as component (e) is one or more selected from poly (oxyethylene-oxypropylene) methicone copolymers, polyoxyethylene methicone copolymers, silicone chain-branched methicone copolymers, alkyl chain-silicone chain-branched polyoxyethylene methicone copolymers, cross-linked polyoxyethylene methicones, alkylated cross-linked polyoxyethylene methicones, branched polyglycerol-modified silicones, cross-linked polyglycerol-modified silicones, alkylated cross-linked polyglycerol-modified silicones, and alkyl branched polyglycerol-modified silicones.
The present invention also provides the sunscreen cosmetic composition, wherein the component (e) is contained in an amount of 0.01 to 20% by mass based on the total amount of the cosmetic composition.
The present invention provides an external preparation for skin, which is particularly excellent in skin absorption. Further, the present invention provides an oil-in-water emulsion skin cosmetic excellent in stability over time and in usability (skin spreadability, skin absorption, non-stickiness, smoothness, soft feeling, and skin-tight feeling).
The present invention provides a sunscreen cosmetic which can sufficiently exhibit excellent ultraviolet blocking effects of an ultraviolet absorber and an ultraviolet scattering agent, has good skin absorption, is excellent in usability such as non-stickiness, and has excellent dispersibility and stability.
Detailed Description
The present invention is described in detail below.
External preparation for skin
In the skin external preparation of the present invention, either one or both of isononyl 2-ethylhexanoate and 2-ethylhexyl 2-ethylhexanoate are used.
Isononyl 2-ethylhexanoate is a compound represented by the following formula (I).
Further, 2-ethylhexyl 2-ethylhexanoate is a compound represented by the following formula (II).
Conventionally, low molecular weight esters such as isononanoate having a carbon chain length of 9 have been often blended in skin external preparations for improving usability such as skin absorption.
In the present invention, among the esters of 2-ethylhexanoic acid (having a carbon chain length of 8) having a shorter carbon chain than the isononanoate conventionally used, the esters shown in (I) and (II) above are particularly selected. These two esters have molecular weights of 270 and 256, respectively, and are the smallest ester oil among ester oils that can be used in cosmetics from the viewpoint of safety in the past. The isononanoate has a molecular weight lower than that of an isononanoate commonly used in a conventional skin external preparation, is smooth in use, is moist, is not sticky, and has excellent effects of improving skin absorption, polar oil/nonpolar oil compatibility, and powder dispersibility.
Particularly, isononyl 2-ethylhexanoate represented by the above formula (I) is not included in the official pharmacopoeia, and no external preparation for skin containing the compound has been known so far.
The amount of isononyl 2-ethylhexanoate and 2-ethylhexyl 2-ethylhexanoate to be blended is preferably 1.0 to 20.0% by mass, more preferably 3.0 to 15.0% by mass, in the skin external preparation. When the amount is less than 1.0% by mass, it is difficult to sufficiently exhibit the skin absorption effect, and when the amount is more than 20.0% by mass, the stability of the system may be deteriorated.
Oil-in-water emulsion skin cosmetic
The oil-in-water emulsified skin cosmetic composition of the present invention comprises (a) isononyl 2-ethylhexanoate and/or 2-ethylhexyl 2-ethylhexanoate, (b) one or more members selected from the group consisting of higher fatty acids and higher alcohols which are solid to semisolid at room temperature (25 ℃), (c) one or more members selected from the group consisting of homopolymers, copolymers, crosslinked polymers and mixtures comprising one or more members selected from the group consisting of 2-acrylamido-2-methylpropanesulfonic acid (═ AMPS) and acrylic acid and derivatives thereof as a constituent unit, and (d) one or more members selected from the group consisting of nonionic surfactants having an HLB value of 9 or more.
The components (a) are blended as the components for the skin external preparation in the same manner as described above. (a) The amount of the component (b) is preferably 1.0 to 20.0% by mass, more preferably 3.0 to 15.0% by mass, based on the total amount of the cosmetic. When the amount is less than 1.0% by mass, it is difficult to sufficiently exhibit the skin absorption effect, and when the amount is more than 20.0% by mass, the stability of the system may be deteriorated.
(b) The components are higher fatty acid and higher alcohol which are solid to semisolid at normal temperature (25 ℃).
Examples of the higher fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, margaric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, but are not limited thereto.
Examples of the higher alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, arachidyl alcohol, batyl alcohol, chimyl alcohol, carnauba alcohol, ceryl alcohol, coriander alcohol, myricyl alcohol, ceryl alcohol, elaidyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontanol, batyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecyl alcohol, and octyldecyl alcohol, but the higher alcohol is not limited to these examples. (b) The components may be mixed in one kind or two or more kinds.
(b) The amount of the component (b) is preferably 0.5 to 8.0% by mass, more preferably 1.0 to 5.0% by mass, based on the total amount of the cosmetic. When the amount is less than 0.5% by mass, the internal oil phase is poor in solidifying action, which causes a problem of stability, and it is difficult to impart a soft feeling to the skin in use, while when it exceeds 8.0% by mass, the effect (solidifying action of the internal oil phase, use property, etc.) accompanying the increase in the amount used is not observed, and the stability of the system is deteriorated such as crystal precipitation.
(c) The component (A) is a homopolymer, copolymer, crosslinked polymer or mixture containing one or more selected from 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), acrylic acid and derivatives thereof as a constituent unit. Specific examples of the component (c) include vinylpyrrolidone/AMPS copolymer, dimethylacrylamide/AMPS copolymer, acrylamide/AMPS copolymer, crosslinked polymer of methylenebisacrylamide-crosslinked dimethylacrylamide/AMPS, a mixture of polyacrylamide and sodium polyacrylate, sodium acrylate/AMPS copolymer, hydroxyethyl acrylate/AMPS copolymer, ammonium polyacrylate, polyacrylamide/ammonium acrylate copolymer, and acrylamide/sodium acrylate copolymer. Among them, preferred are homopolymers of AMPS, vinylpyrrolidone/AMPS copolymers, dimethylacrylamide/AMPS copolymers, sodium acrylate/AMPS copolymers, and crosslinked polymers of methylenebisacrylamide-crosslinked dimethylacrylamide/AMPS. (c) The components may be mixed in one kind or two or more kinds.
(c) The amount of the component (b) is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 3.0% by mass, based on the total amount of the cosmetic. If the amount is less than 0.1% by mass, separation, oil slick, emulsion breaking, aggregation and the like tend to occur, and this is not preferable from the viewpoint of stability. On the other hand, when the amount exceeds 5.0% by mass, the effect of the present invention is not enhanced, but the feeling of stickiness is felt.
The nonionic surfactant having an HLB value of 9 or more as the component (d) is not particularly limited as long as it can be used in combination with general cosmetics, and examples thereof include, but are not limited to, the following surfactants. And HLB is calculated by the above formula represented by the following formula l,
HLB＝7+11.7·log(MW/MO)
(wherein MW represents the molecular weight of the hydrophilic moiety and MO represents the molecular weight of the lipophilic moiety).
Polyglycerol fatty acid esters such as hexaglycerol monolaurate (HLB value 14.5), hexaglycerol monomyristate (HLB value 11), hexaglycerol monostearate (HLB value 9.0), hexaglycerol monooleate (HLB value 9.0), decaglycerol monolaurate (HLB value 15.5), decaglycerol monomyristate (HLB value 14), decaglycerol monostearate (HLB value 12.0), decaglycerol monoisostearate (HLB value 12.0), decaglycerol monooleate (HLB value 12.0), decaglycerol distearate (HLB value 9.5), decaglycerol diisostearate (HLB value 10.0), and the like.
Glycerol polyoxyethylene ether fatty acid esters such as glycerol polyoxyethylene 5-mole addition (described as [ POE (5) ], hereinafter the same) ether monostearate (HLB value 9.5), glycerol POE (15) ether monostearate (HLB value 13.5), glycerol POE (5) ether monooleate (HLB value 9.5), and glycerol POE (15) ether monooleate (HLB value 14.5).
Sorbitan polyoxyethylene ether fatty acid esters such as POE (20) ether coconut oil fatty acid ester (HLB value 16.9), POE (20) ether monopalmitate (HLB value 15.6), POE (20) ether monostearate (HLB value 14.9), POE (6) ether monostearate (HLB value 9.5), POE (20) ether tristearate (HLB value 10.5), POE (20) ether monoisostearate (HLB value 15.0), POE (20) ether monooleate (HLB value 15.0), POE (6) ether monooleate (HLB value 10.0), and POE (20) ether trioleate (HLB value 11.0).
Sorbitol polyoxyethylene ether fatty acid esters such as sorbitol POE (6) ether monolaurate (HLB value 15.5), sorbitol POE (60) ether tetrastearate (HLB value 13.0), sorbitol POE (30) ether tetraoleate (HLB value 11.5), sorbitol POE (40) ether tetraoleate (HLB value 12.5), and sorbitol POE (60) ether tetraoleate (HLB value 14.0).
Polyoxyethylene lanolin/lanolin alcohol/beeswax derivatives such as POE (10) lanolin (HLB value 12.0), POE (20) lanolin (HLB value 13.0), POE (30) lanolin (HLB value 15.0), POE (5) lanolin alcohol ether (HLB value 12.5), POE (10) lanolin alcohol ether (HLB value 15.5), POE (20) lanolin alcohol ether (HLB value 16.0), POE (40) lanolin alcohol ether (HLB value 17.0), and POE (20) sorbitol ether beeswax (HLB value 9.5).
Polyoxyethylene castor oil/hydrogenated castor oil such as POE (20) castor oil (HLB value 10.5), POE (40) castor oil (HLB value 12.5), POE (50) castor oil (HLB value 14.0), POE (60) castor oil (HLB value 14.0), POE (20) hydrogenated castor oil (HLB value 10.5), POE (30) hydrogenated castor oil (HLB value 11.0), POE (40) hydrogenated castor oil (HLB value 13.5), POE (60) hydrogenated castor oil (HLB value 14.0), POE (80) hydrogenated castor oil (HLB value 16.5), POE (40) hydrogenated castor oil (100) hydrogenated castor oil (HLB value 16.5), and the like.
Polyoxyethylene sterol/hydrogenated sterols such as POE (5) phytosterol ether (HLB value 9.5), POE (10) phytosterol ether (HLB value 12.5), POE (20) phytosterol ether (HLB value 15.5), POE (30) phytosterol ether (HLB value 18.0), POE (25) phytosterol ether (HLB value 14.5), and POE (30) cholestanol ether (HLB value 17.0).
Lauryl POE (2) ether (HLB value 9.5), lauryl POE (4.2) ether (HLB value 11.5), lauryl POE (9) ether (HLB value 14.5), cetyl POE (5.5) ether (HLB value 10.5), cetyl POE (7) ether (HLB value 11.5), cetyl POE (10) ether (HLB value 13.5), cetyl POE (15) ether (HLB value 15.5), cetyl POE (20) ether (HLB value 17.0), cetyl POE (23) ether (HLB value 18.0), stearyl POE (4) ether (HLB value 9.0), stearyl POE (20) ether (HLB value 18.0), stearyl POE (HLB value 21) ether (HLB value 18.0), oleyl POE (HLB) ether (HLB value 10.5), oleyl POE (10) ether (HLB value 14.5), POE (15) ether (oleyl value 16.0), oleyl (oleyl) ether (HLB value 17.0), oleyl POE (HLB) ether (HLB value 18.5), and oleyl POE (HLB value 16.5), oleyl ether (HLB value 16.10) ether (HLB value 16.0), oleyl (HLB value 20) ether (HLB value 18.0), oleyl ether (HLB value 20) ether (HLB value 20.0), oleyl ether (HLB value 10.5), and oleyl (HLB value) ether (HLB value 16.5), Behenyl POE (30) ether (HLB value 18.0), POE (2) (C)12-15) Alkyl ether (HLB value 9.0), POE (4) (C)12-15) Alkyl ether (HLB value 10.5), POE (10) (C)12-15) Polyoxyethylene alkyl ethers such as alkyl ether (HLB value 15.5), POE (5) secondary alkyl ether (HLB value 10.5), POE (7) secondary alkyl ether (HLB value 12.0), POE (9) alkyl ether (HLB value 13.5), and POE (12) alkyl ether (HLB value 14.5).
1 mol addition of polyoxypropylene (denoted as [ POP (1) ], the same applies hereinafter). And alkyl polyoxyethylene polyoxypropylene ethers such as hexadecyl POP (4) ether (HLB value 9.5), hexadecyl POE (10) POP (4) ether (HLB value 10.5), hexadecyl POE (20) POP (8) ether (HLB value 12.5), decyl tetradecyl POE (20) POP (6) ether (HLB value 11.0), and decyl tetradecyl POE (30) POP (6) ether (HLB value 12.0).
Polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate 10-mole addition ester (represented by [ PEG (10) ], which will be the same hereinafter) (HLB value 12.5), PEG (10) monostearate (HLB value 11.0), PEG (25) monostearate (HLB value 15.0), PEG (40) monostearate (HLB value 17.5), PEG (45) monostearate (HLB value 18.0), PEG (55) monostearate (HLB value 18.0), PEG100 monostearate (HLB value 18.8), PEG150 monostearate (HLB value 19), PEG (10) monooleate (HLB value 11.0), PEG distearate (HLB value 16.5), and PEG diisostearate (HLB value 9.5).
Polyoxyethylene glyceryl ether isostearates such as PEG (8) glyceryl ether isostearate (HLB value 10.0), PEG (10) glyceryl ether isostearate (HLB value 10.0), PEG (15) glyceryl ether isostearate (HLB value 12.0), PEG (20) glyceryl ether isostearate (HLB value 13.0), PEG (25) glyceryl ether isostearate (HLB value 14.0), PEG (30) glyceryl ether isostearate (HLB value 15.0), PEG (40) glyceryl ether isostearate (HLB value 15.0), PEG (50) glyceryl ether isostearate (HLB value 16.0), and PEG (60) glyceryl isostearate (HLB value 16.0).
Among them, polyoxyethylene adducts (═ POE adducts) and polyethylene glycol adducts (═ PEG adducts) are preferable, and PEG (10 to 150) monostearate is particularly preferable from the viewpoint of stability and usability (absorption into the skin and non-stickiness).
(d) Component (b) has an effect of emulsifying an oil phase containing component (a) and component (b). (d) One or more of the components may be used. (d) The amount of the component (b) is preferably 0.5 to 8.0% by mass, more preferably 1.0 to 5.0% by mass, based on the total amount of the cosmetic. When the amount is less than 0.5% by mass, the stability of the system is poor, while when the amount is more than 5.0% by mass, the expected effect corresponding to the increase in the amount to be blended is not observed, and the system tends to be sticky.
In the present invention, it is more preferable to use a component having an HLB value of 9 or more and less than 15 and a component having an HLB value of 15 or more in combination, from the viewpoint of stability. In this case, the component having an HLB value of 9 or more and less than 15 and the component having an HLB value of 15 or more are preferably used in combination in a total amount of 5 mass% or less, and in a ratio of 6/1 to 1/6 (mass ratio).
In the present invention, a surfactant having a low HLB value of less than 9 may be used within a range not affecting the effect and stability of the present invention. As the surfactant having an HLB value of less than 9, the following may be mentioned, but the surfactant is not limited to these examples.
Polyoxyethylene cetyl ethers such as POE (2) cetyl ether (HLB value 5), POE (3) cetyl ether (HLB value 6), and POE (5) cetyl ether (HLB value 8).
Polyoxyethylene oleyl ethers such as POE (3) oleyl ether (HLB value 6), POE (3) oleyl ether (HLB value 8), and POE (6) oleyl ether (HLB value 8).
POE (5) isohexadecyl ether (HLB value 8).
POE (5) isostearyl ethers (HLB value 8) and other polyoxyethylene isostearyl ethers.
POE (5) octyl dodecyl ether (HLB value 7) and other polyoxyethylene octyl dodecyl ethers.
POE (5) behenyl ether (HLB value 7) and other polyoxyethylene behenyl ethers.
POE (5) decyl-tetradecyl ether (HLB value 6) and other polyoxyethylene decyl-tetradecyl ethers.
POE (5) cholesteryl ether (HLB value 7) and other polyoxyethylene cholesteryl ethers.
Polyoxyethylene-polyoxypropylene decyl ethers such as POP (2) POE (3) decyl ether (HLB value of 7).
Sorbitan fatty acid esters such as sorbitan sesquioleate (HLB value 7) and sorbitan sesquiisostearate (HLB value 7).
Glyceryl monofatty acid glycerides such as glyceryl stearate (HLB value 5), self-emulsifying glyceryl stearate (HLB value 6), self-emulsifying glyceryl stearate (HLB value 7), glyceryl isostearate (HLB value 6), and glyceryl diisostearate (HLB value 3).
Propylene glycol esters of fatty acids such as propylene glycol stearate (HLB value 4), propylene glycol laurate (HLB value 5), propylene glycol distearate (HLB value 2), propylene glycol dioleate (HLB value 2), propylene glycol dilaurate (HLB value 2), and propylene glycol diisostearate (HLB value 2).
And fatty acid glycol esters such as ethylene glycol stearate (HLB value 4), ethylene glycol dilaurate (HLB value 2), ethylene glycol dioleate (HLB value 2), ethylene glycol distearate (HLB value 2), and fatty acid glycol esters of C14 to C18 (HLB value 2).
Polyethylene glycol monostearate such as PEG (2) stearate (HLB value 5), PEG (3) stearate (HLB value 7), and PEG (5) stearate (HLB value 8).
Monooleic acid polyethylene glycol esters such as oleic acid PEG (3) ester (HLB value 7).
Polyoxyethylene hydrogenated castor oils such as PEG (5) hydrogenated castor oil (HLB value 5), PEG (7) hydrogenated castor oil (HLB value 6), and PEG (10) hydrogenated castor oil (HLB value 7).
Polyethylene glycol isostearate esters such as PEG (3) isostearate (HLB value 7).
And cetyl polyoxyethylene ether stearates such as cetyl POE (3) ether stearate (HLB value 3), cetyl POE (4) ether stearate (HLB value 4), cetyl POE (6) ether stearate (HLB value 6), and cetyl POE (7) ether stearate (HLB value 7).
Polyoxyethylene stearyl ether stearates such as POE (4) stearyl ether stearate (HLB value 4), POE (6) stearyl ether stearate (HLB value 5), POE (9) stearyl ether stearate (HLB value 6), POE (7) stearyl ether stearate (HLB value 7), POE (10) stearyl ether stearate (HLB value 7), and POE (12) stearyl ether stearate (HLB value 8).
Polyoxyethylene lauryl ether stearates such as POE (3) lauryl ether stearate (HLB value 3), POE (5) lauryl ether stearate (HLB value 5), POE (8) lauryl ether stearate (HLB value 7), and POE (10) lauryl ether stearate (HLB value 8).
Polyoxyethylene lauryl ether isostearates such as POE (2) lauryl ether isostearate (HLB value 2), POE (5) lauryl ether isostearate (HLB value 5), POE (8) lauryl ether isostearate (HLB value 7), and POE (10) lauryl ether isostearate (HLB value 8).
Polyethylene glycol dilaurate esters such as PEG (2) dilaurate ester (HLB value 4), PEG (3) dilaurate ester (HLB value 5), PEG (4) dilaurate ester (HLB value 5), PEG (6) dilaurate ester (HLB value 5), PEG (8) dilaurate ester (HLB value 8).
Polyethylene glycol distearate esters such as PEG (2) distearate (HLB value 2), PEG (3) distearate (HLB value 3), PEG (4) distearate (HLB value 4), PEG (6) distearate (HLB value 5), PEG (8) distearate (HLB value 6), PEG (12) distearate (HLB value 8) and PEG distearate (HLB value 8).
Polyethylene glycol diisostearate esters such as PEG (2) diisostearate (HLB value 3), PEG (3) diisostearate (HLB value 3), PEG (4) diisostearate (HLB value 4), PEG (6) diisostearate (HLB value 5), PEG (8) diisostearate (HLB value 6), PEG (12) diisostearate (HLB value 8), and the like.
Polyethylene glycol dioleate esters such as PEG (2) dioleate ester (HLB value 3), PEG (3) dioleate ester (HLB value 3), PEG (4) dioleate ester (HLB value 4), PEG (6) dioleate ester (HLB value 5), PEG (8) dioleate ester (HLB value 6), and PEG (12) dioleate ester (HLB value 8).
Polyoxyethylene sorbitol ether/sorbitan ether fatty acid esters such as PEG (4) sorbitol ether tetraoleate (HLB value 3), PEG (3) sorbitol ether tristearate (HLB value 3), and PEG (4) sorbitan ether triisostearate (HLB value 3).
Polyoxyethylene glyceryl ether triisostearates such as PEG (3) glyceryl ether triisostearate (HLB value 2), PEG (5) glyceryl ether triisostearate (HLB value 3), PEG (10) glyceryl ether triisostearate (HLB value 3), and PEG (20) glyceryl ether triisostearate (HLB value 8).
Polyoxyethylene glyceryl ether diisostearate such as PEG (10) glyceryl ether diisostearate (HLB value 7).
Polyoxyethylene glyceryl ether isostearates such as PEG (3) glyceryl ether isostearate (HLB value 6), PEG (5) glyceryl ether isostearate (HLB value 8), and PEG (6) glyceryl ether isostearate (HLB value 8).
Polyoxyethylene glyceryl ether tristearates such as PEG (3) glyceryl ether tristearate (HLB value 2), PEG (4) glyceryl ether tristearate (HLB value 2), PEG (5) glyceryl ether tristearate (HLB value 3), PEG (6) glyceryl ether tristearate (HLB value 3), PEG (10) glyceryl ether tristearate (HLB value 5), and PEG (20) glyceryl ether tristearate (HLB value 8).
Polyoxyethylene glyceryl ether distearate such as PEG (4) glyceryl ether distearate (HLB value: 4).
Polyoxyethylene glyceryl ether trioleate such as PEG (3) glyceryl ether trioleate (HLB value 2), PEG (5) glyceryl ether trioleate (HLB value 3), PEG (10) glyceryl ether trioleate (HLB value 5), PEG (20) glyceryl ether trioleate (HLB value 8).
Isostearic acid polyoxyethylene hydrogenated castor oil such as isostearic acid PEG (5) hydrogenated castor oil (HLB value 4), isostearic acid PEG (10) hydrogenated castor oil (HLB value 5), isostearic acid PEG (15) hydrogenated castor oil (HLB value 7), isostearic acid PEG (20) hydrogenated castor oil (HLB value 8), etc.
Triisostearic polyoxyethylene hydrogenated castor oils such as triisostearic PEG (5) hydrogenated castor oil (HLB value 2), triisostearic PEG (10) hydrogenated castor oil (HLB value 4), triisostearic PEG (15) hydrogenated castor oil (HLB value 5), triisostearic PEG (20) hydrogenated castor oil (HLB value 6), triisostearic PEG (30) hydrogenated castor oil (HLB value 7), and triisostearic PEG (40) hydrogenated castor oil (HLB value 8).
Lauric acid PEG (20) hydrogenated castor oil (HLB value 8) and other lauric acid polyoxyethylene hydrogenated castor oils.
Polyoxyethylene trimethylolpropane tristearates such as PEG (3) trimethylolpropane tristearate (HLB value 2), PEG (5) trimethylolpropane tristearate (HLB value 3), PEG (10) trimethylolpropane tristearate (HLB value 5), and the like.
And polyoxyethylene trimethylolpropane trimyristate esters such as PEG (3) trimethylolpropane trimyristate (HLB value 2) and PEG (5) trimethylolpropane trimyristate (HLB value 3).
Polyoxyethylene trimethylolpropane distearate esters such as PEG (3) trimethylolpropane distearate (HLB value 3), PEG (4) trimethylolpropane distearate (HLB value 4), and PEG (3) trimethylolpropane distearate (HLB value 4).
Polyoxyethylene trimethylolpropane triisostearate such as PEG (3) trimethylolpropane triisostearate (HLB value 2) and PEG (20) trimethylolpropane triisostearate (HLB value 8).
N-acyl glutamic acid esters such as dihexyldecyl lauroyl glutamate (HLB value 3), dioctyldodecyl stearoyl glutamate (HLB value 3), dioctyldodecyl lauroyl glutamate (HLB value 3), dioctylPOE (2) dodecyl ether (HLB value 4), dioctylPOE (5) dodecyl ether lauroyl glutamate (HLB value 6), POE (2) distearyl ether lauroyl glutamate (HLB value 4), and POE (5) distearyl ether lauroyl glutamate (HLB value 7).
N-acyl neutral amino acid esters such as hexyldecyl myristoyl methyl aminopropionate (HLB value of 4).
Polyglyceryl fatty acid esters such as polyglyceryl (2) stearate (HLB value 6), polyglyceryl (2) stearate (HLB value 8), polyglyceryl (2) distearate (HLB value 4), polyglyceryl (3) distearate (HLB value 5), polyglyceryl (6) distearate (HLB value 8), polyglyceryl (10) tristearate (HLB value 8), polyglyceryl (2) diisostearate (HLB value 4), polyglyceryl (2) triisostearate (HLB value 3), polyglyceryl (3) diisostearate (HLB value 5), polyglyceryl (6) diisostearate (HLB value 8), triisopolyglyceryl (10) stearate (HLB value 8), polyglyceryl (2) oleate (HLB value 8), polyglyceryl (2) distearate (HLB value 4), and polyglyceryl (3) distearate (HLB value 5).
Silicone surfactants such as PEG (7) polydimethylsiloxane (HLB value 5) and PEG (10) polydimethylsiloxane (HLB value 6).
In the oil-in-water type emulsified skin cosmetic composition of the present invention, various oil components, oil-soluble components and the like may be blended in the oil phase (inner phase) in addition to the components (a) and (b). In addition, the aqueous phase (external phase) may contain various water-soluble components in addition to water, the components (c) and (d). In the present invention, the aqueous phase (external phase) is preferably 50.0 to 90.0 mass% based on the total amount of the cosmetic. When the water phase is less than 50.0% by mass, a heavy and sticky feeling may be caused. On the other hand, if it exceeds 90.0% by mass, the feeling of smoothness is not sufficient, and it is difficult to obtain the feeling of smoothness and wetness effect of the present invention.
In the oil-in-water type emulsion skin cosmetic composition of the present invention, other than the above-mentioned components, components which can be blended in a usual emulsion composition may be properly blended within a range not to impair the effects of the present invention. Examples of the components include, but are not limited to, ultraviolet absorbers, ultraviolet scattering agents, waxes, hydrocarbon oils, silicone oils, polyols, and water-soluble polymers.
Examples of the ultraviolet absorber include cinnamic acid-based ultraviolet absorbers such as p-aminobenzoic acid, octyl p-methoxycinnamate (2-ethylhexyl p-methoxycinnamate), mono-2-ethylhexanoyl di-p-methoxycinnamate, and methyl bis (trimethylsiloxane) silylisoamyl trimethoxycinnamate; 2, 2 '-hydroxy-5-methylphenylbenzotriazole, 2- (2' -hydroxy-5 '-tert-octylphenyl) benzotriazole, 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 4-methoxy-4' -tert-butyldibenzoylmethane, 5- (3, 3-dimethyl-2-norbornyl) -3-pentan-2-one, bis-ethylhexyloxyphenol-methoxyphenyltriazole, 2, 4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino ]1, 3, 5-triazine, dimorpholinopyridazinone and the like.
Examples of the ultraviolet scattering agent include powders of titanium dioxide fine particles, zinc oxide fine particles, iron oxide fine particles, cerium oxide fine particles, and the like, each having an average diameter of 10 to 100 nm.
Further, an ultraviolet scattering agent subjected to a hydrophobic treatment by a silane treatment such as methylhydrogenpolysiloxane or a silane coupling agent, a metal soap treatment, a fluorine treatment such as perfluoroalkylphosphoric acid diethanolamine salt or perfluoroalkylsilane, or a dextrin fatty acid ester treatment may be appropriately blended depending on the drug system.
Examples of the waxes include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, and jojoba wax.
Examples of the hydrocarbon oils include liquid paraffin, ceresin, squalane, pristane, paraffin, ceresin, squalene, vaseline, microcrystalline wax, polyethylene wax, and fischer-tropsch wax.
Examples of the silicone oil include chain polysiloxanes (e.g., polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, etc.), cyclic polysiloxanes (e.g., decamethylcyclopentapolysiloxane, dodecamethylcyclohexasiloxane, etc.), silicone resins having a three-dimensional network structure, silicone rubbers having an average molecular weight of 20 ten thousand or more, and various modified polysiloxanes (e.g., amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.).
Examples of the polyhydric alcohol include polyethylene glycol, glycerin, diglycerin, 1, 3-butanediol, erythritol, sorbitol, xylitol, maltitol, 1, 2-pentanediol, and hexanediol.
Examples of the water-soluble polymer include carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, glycogen, gum arabic, sodium hyaluronate, tragacanth, xanthan gum, mucopolysaccharide sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, keratin sulfate, locust bean gum, succinoglycan, chitin, chitosan, carboxymethyl chitin, and agar.
In addition, lower alcohols such as ethanol; antioxidants such as butylhydroxytoluene, delta-tocopherol, phytic acid, and the like; preservatives such as benzoic acid, salicylic acid, sorbic acid, alkyl parabens, phenoxyethanol, hexachlorophene, epsilon-polylysine and the like; organic or inorganic acids such as citric acid, lactic acid, and hexametaphosphoric acid, and salts thereof; vitamin E compounds such as vitamin a derivatives such as vitamin a, vitamin a palmitate and vitamin a acetate, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dicaprylate, vitamin B2 and its derivatives, vitamin B12, vitamin B15 and its derivatives, vitamin E compounds such as α -tocopherol, β -tocopherol and vitamin E acetate, vitamin D compounds, vitamin H, pantothenic acid and pantethine; gamma-terpineol ferulate, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid, stearyl glycyrrhetinate, hinokitiol, bisabolol, ginsenosides, luffa saponin, saponins such as soapberry saponin, panthenyl ethyl ether, arbutin, various drugs such as cepharanthine, rumex japonicus, sophora flavescens, nuphar pumila, tangerine, sage, milfoil, mallow, swertia japonica, thyme, angelica, spruce, birch, equisetum arvense, luffa, aesculus hippocastanum, saxifrage, scutellaria baicalensis, arnica, lily, mugwort, peony, aloe, gardenia, cherry leaves, and other plant extracts, beta-carotene, and the like.
The oil-in-water type emulsified skin cosmetic of the present invention includes emulsion-like or cream-like products such as lotions, skin creams, hair creams, liquid foundations, eyeliners, mascaras, and eye shadows. These products can be produced by a conventional method by blending the above-mentioned essential components and components usually blended in these cosmetics.
Sunscreen cosmetic
In the cosmetic of the present invention, as the component (a), either one or both of isononyl 2-ethylhexanoate represented by the above formula (I) and 2-ethylhexyl 2-ethylhexanoate represented by the above formula (II) are used.
In the present invention, among esters of 2-ethylhexanoic acid (carbon chain length: 8) having a shorter carbon chain than that of the esters of isononanoic acid conventionally used, the esters represented by the above (I) and (II) are selected and used. These two esters have molecular weights of 270 and 256, respectively, and from the viewpoint of conventional safety, the ester oil having the smallest molecular weight is included in the ester oils that can be used in cosmetics. Compared with isononanoate which is widely used in the prior skin external preparation, the isononanoate has smaller molecular weight, and has the advantages of smooth and moist use, no stickiness and good skin absorption. In addition, in a system using a highly polar oil ultraviolet absorber and a nonpolar oil silicone oil in combination, the homogenization of the oil phase is better than that of isononanoate. Further, the ultraviolet scattering agent such as zinc oxide or titanium dioxide is also superior to isononanoate in terms of dispersion and stabilization.
(a) The lower limit of the amount of the component (b) is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the amount is less than 1% by mass, it is difficult to sufficiently exhibit the effects in emulsion stability, dispersibility and usability, and even when it exceeds 60% by mass, the effect corresponding to the increase in the amount is not obtained.
The ultraviolet absorber as component (b) may be a wide range of ultraviolet absorbers generally used in cosmetics, and is not particularly limited, but preferably includes p-aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, β -diphenylacrylate derivatives, benzophenone derivatives, benzylidenecamphor derivatives, phenylbenzimidazole derivatives, triazine derivatives, phenylbenzotriazole derivatives, anthranilic anhydride (anthranil) derivatives, imidazoline derivatives, benzylidene malonate derivatives, 4-diarylbutadiene derivatives, and the like. But is not limited to these.
Examples of the para-aminobenzoic acid derivative include para-aminobenzoic acid (hereinafter, abbreviated as "PABA"), ethyl PABA, ethyldihydroxypropyl PABA, ethylhexyl dimethyl PABA (for example, Esacalol 507 from International specialty Chemicals (ISP)), glyceryl PABA, and PEG-25-PABA (for example, Uvinul P25 from BASF).
Examples of the salicylic acid derivative include homosalate (e.g., European HMS available from Rona/EM Industries), ethylhexyl salicylate (e.g., Neo Heliopan OS available from Hamamann and Reimer), dipropylene glycol salicylate (e.g., dispsal available from Scher), TEA salicylate (e.g., Neo Heliopan TS available from Hamamann and Reimer), and the like.
Examples of the cinnamic acid derivative include ethylhexyl methoxycinnamate (e.g., Parsol MCX available from rochon), isopropyl methoxycinnamate, isoamyl methoxycinnamate (e.g., Neo Heliopan E1000 available from hamen-rehma), cinoxate, DEA methoxycinnamate, diisopropyl methyl cinnamate, and ethyl-glycerol-hexanoate-dimethoxycinnamate.
Examples of the β, β -diphenylacrylate derivative include 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate (Octocrylene) (e.g., Uvinul N539 manufactured by basf corporation), and ethyl 2-cyano-3, 3-diphenylacrylate (Etocrylene) (e.g., Uvinul N35 manufactured by basf corporation).
Examples of the benzophenone derivative include benzophenone-1 (e.g., Uvinul 400 of BASF), benzophenone-2 (e.g., Uvinul D50 of BASF), benzophenone-3 or 2-hydroxy-4-methoxybenzophenone (e.g., Uvinul M40 of BASF), benzophenone-4 (e.g., Uvinul MS40 of BASF), benzophenone-5, benzophenone-6 (e.g., Helisorb11 of Norquay), benzophenone-8 (e.g., Spectra-Sorb UV-24 of American cyanamide), benzophenone-9 (e.g., Uvinul DS-49 of BASF), and benzophenone-12.
Examples of the benzylidenecamphor derivatives include 3-benzylidenecamphor (e.g., Mexoryl SD of Chimex), 4-methylbenzylidene camphor, benzylidenecamphor sulfonic acid (e.g., Mexoryl SL of Chimex), camphorbenzalkonium methosulfate (e.g., Mexoryl so of Chimex), terephthalylidene dicamphor sulfonic acid (e.g., Mexoryl SX of Chimex), and polyacrylamide methylbenzylidene camphor (e.g., Mexoryl SW of Chimex).
Examples of the phenylbenzimidazole derivative include phenylbenzimidazole sulfonic acid (e.g., Eusolex 232 from merck), disodium phenylbenzimidazole tetrasulfonate (e.g., Neo helopan AP from hammen-reimer), and the like.
Examples of the triazine derivative include methoxyphenyl triazine (e.g., Tinosorb S available from Ciba specialty Chemicals), ethylhexyl triazone (e.g., Uvinul T150 available from Pasteur), diethylhexyl butamido triazone (e.g., Uvasorb HEB available from Sigma 3V), and 2, 4, 6-tris (diisobutyl-4' -aminobenzylidenemalonate) -S-triazine.
Examples of the phenylbenzotriazole derivative include cresoltrazole trisiloxane (e.g., Silatrizole available from Rhodia Chimic corporation), methylenebis (benzotriazolyl tetramethylbutylphenol) (e.g., Tinosorb M available as a micronized water-soluble dispersant from Ciba specialty Chemicals, or Mixxim BB/100 available as a solid from Fairmount Chemical).
Examples of the anthranilic anhydride (anthranil) derivative include methyl anthranilate (for example, Neo Heliopan MA from haman-reimer).
Examples of the imidazoline derivative include ethylhexyl dimethoxybenzylidenedioxoimidazolidinylpropionate.
Examples of the benzylidene malonate derivative include an organopolysiloxane having a benzylidene malonate functional group (e.g., Parsol SLX from Roche).
Examples of the 4, 4-diarylbutadiene derivative include 1, 1-dicarboxy (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene and the like.
Among them, particularly preferred are ethylhexyl salicylate, ethylhexyl methoxycinnamate, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate, benzophenone-3, benzophenone-4, benzophenone-5, 4-methylbenzylidene camphor, p-xylylene dicamphor sulfonic acid, phenylbenzimidazole sulfonic acid, disodium phenylbisbenzimidazole tetrasulfonic acid, methoxyphenyl triazine, ethylhexyl triazone, diethylhexyl butamido triazone, 2, 4, 6-tris (diisobutyl-4 '-aminobenzylidene malonate) -s-triazine, cresolquzo trisiloxane, methylenebis (benzotriazolyl tetramethylbutylphenol), 1-dicarboxyl (2, 2' -dimethylpropyl) -4, 4-diphenylbutadiene, mixtures thereof, and the like. (b) One or more of the components may be used.
(b) The lower limit of the amount of the component (b) is preferably 3% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. When the amount is less than 3% by mass, it is difficult to obtain a sufficient SPF value, while when it exceeds 20% by mass, an effect corresponding to an increase in the amount is not obtained.
As the ultraviolet scattering agent of the component (c), zinc oxide and titanium dioxide are preferably used.
[ Zinc oxide ]
The zinc oxide used in the present invention is not particularly limited, and examples thereof include zinc oxides generally used in cosmetics. Zinc oxide having more excellent dispersibility is preferable, and for example, zinc oxide surface-treated by a known method may be used as needed.
Examples of the method of surface treatment include siloxane treatment such as methylhydrogenpolysiloxane and methylpolysiloxane; fluorine treatment with perfluoroalkyl phosphate, perfluoroalcohol, or the like; amino acid treatment with N-acylglutamic acid or the like; other examples include lecithin treatment; performing metal saponification treatment; treating fatty acid; alkyl phosphate treatment, and the like. Among them, zinc oxide subjected to a silicone surface treatment is preferable.
The silicone used for the surface treatment is not particularly limited, and examples thereof include various silicone oils such as methyl polysiloxane, methylphenyl polysiloxane, methylhydrogenpolysiloxane, methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentapolysiloxane, dodecamethylcyclohexasiloxane, octamethyltrimersiloxane, tetradecylhexapolysiloxane, dimethylsiloxane/methyl (polyoxyethylene) siloxane/methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane/methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane/methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane/methylhexadecyloxysiloxane copolymer, and dimethylsiloxane/methylstearyloxysiloxane copolymer. Methylhydrogenpolysiloxanes are preferred. The use of the silicone-treated zinc oxide is advantageous in increasing hydrophobicity, ultraviolet-blocking property, transparency, skin-friendly property, dispersibility, and providing excellent sunscreen cosmetics.
In particular, when the cosmetic of the present invention is a water-in-oil emulsion sunscreen cosmetic, zinc oxide subjected to the surface treatment is preferably used. On the other hand, in the case of an oil-in-water emulsion sunscreen cosmetic, it is preferable to use zinc oxide which has not been subjected to such a hydrophobic surface treatment.
The amount of the siloxane used for the surface treatment of zinc oxide is usually about 1 to 20 mass%, preferably 2 to 14 mass%, more preferably 2 to 10 mass%, particularly preferably 2 to 5 mass%, per 100 mass% of the siloxane-treated zinc oxide. The method of siloxane treatment of zinc oxide is not particularly limited, and conventionally known methods can be appropriately selected.
Specific examples of the zinc oxide usable in the present invention include MZ-300 (manufactured by テイカ, Inc., having a particle diameter of 30 to 40nm without a surface treatment agent), MZ-303S (manufactured by テイカ, Inc., having a particle diameter of 30 to 40nm, manufactured by テイカ, Inc., by polymethylsiloxane treatment), MZ-500 (manufactured by テイカ, having a particle diameter of 20 to 30nm without a surface treatment agent), MZ-505S (manufactured by テイカ, manufactured by polymethylsiloxane treatment, having a particle diameter of 20 to 30 nm), MZ-505M (manufactured by テイカ, Inc., having a particle diameter of 20 to 30nm without a surface treatment agent), MZ-700 (manufactured by テイカ, having a particle diameter of 10 to 20nm without a surface treatment agent), MZ-300 (manufactured by テイカ, manufactured by Mb., having a particle diameter of 20 to 30nm, manufactured by テイカ, Mb), MZ-707S (polymethylsiloxane treatment, particle diameter 10-20 nm, made by テイカ Corp.), FINEX-25 (no surface treatment agent, particle diameter 60nm, made by Sakai chemical Co., Ltd.), FINEX-25LP (polydimethyl siloxane treatment, particle diameter 60nm, made by Sakai chemical Co., Ltd.), FINEX-50 (no surface treatment agent, particle diameter 20nm, made by Sakai chemical Co., Ltd.), FINEX-50LP (polydimethyl siloxane treatment, particle diameter 20nm, made by Sakai chemical Co., Ltd.), FINEX-75 (no surface treatment agent, particle diameter 10nm, made by Sakai chemical Co., Ltd.), etc. But is not limited to these examples.
The zinc oxide used in the present invention is generally preferably zinc oxide having an average primary particle diameter of 40nm or less, more preferably 30nm or less. When the average primary particle diameter is larger than 40nm, whitening or leaving a white mark tends to occur. The lower limit of the average primary particle diameter is not particularly limited, but the smaller the particle diameter, the more expensive the particle diameter is, and from the viewpoint of economy, the particle diameter is preferably 5nm or more, and more preferably 10nm or more.
The average primary particle diameter in the present invention is not particularly limited, and is a primary particle diameter measured by a method generally used for zinc oxide and titanium dioxide. Specifically, the average value is determined as an average value of the sum of the major axis and the minor axis of the particle in a transmission electron micrograph.
The form of the particles is not particularly limited, and may be in the form of primary particles or may be an aggregate of secondary particles formed by aggregation. The shape may be spherical, elliptical, irregular, or the like, and is not particularly limited.
In a more preferred embodiment of the silicone-treated zinc oxide of the present invention, the zinc oxide is a dimethylhydrogenpolysiloxane-treated zinc oxide having an average primary particle diameter of 5 to 40nm (1 to 5% by mass of the surface treatment).
[ titanium dioxide ]
The titanium dioxide used in the present invention is not particularly limited, and examples thereof include titanium dioxide generally used in cosmetics. The crystal form of titanium dioxide is not particularly limited, and may be any of anatase type, rutile type, and brookite type.
Titanium dioxide having a higher ultraviolet blocking ability is preferable, and examples of the titanium dioxide include titanium dioxide surface-treated to enhance the ultraviolet scattering effect. The method of surface treatment is not particularly limited as long as it is a treatment usually employed for cosmetics, and examples of the treatment include a method of adsorbing oil and fat on the surface of titanium dioxide, a fatty acid treatment method of treating titanium dioxide esterified or etherified with a functional group such as a hydroxyl group with a fatty acid, a metal soap treatment method of using a fatty acid aluminum salt or zinc salt such as aluminum stearate or zinc stearate in place of a fatty acid, a silicone treatment method of using methylpolysiloxane or methylhydrogenpolysiloxane in place of a fatty acid, and a method of treating perfluoroalkyl fluoride in place of a fatty acid.
Preferably, the titanium dioxide is treated with aluminum stearate. The proportion of aluminum stearate contained in the aluminum stearate-treated titanium dioxide is not particularly limited, and may be 1 to 20% by mass. Further, the content of titanium dioxide is preferably 80 to 99% by mass.
In particular, when the cosmetic of the present invention is a water-in-oil type emulsion sunscreen cosmetic, the surface-treated titanium dioxide is preferably used. On the other hand, in the case of an oil-in-water type oxidation emulsion sunscreen cosmetic, it is preferable to use titanium dioxide which has not been subjected to such a hydrophobic surface treatment.
Specific examples of the titanium dioxide to be used in the present invention include titanium dioxide (タイペ - ク TIPAQUE) CR-50 (rutile type, alumina treatment, particle diameter 25nm, manufactured by Shigaku industries Co., Ltd.), Bayer titanium (バイエルチタン) R-KB-1 (rutile type, zinc oxide treatment, alumina treatment, silica treatment, particle diameter 30 to 40nm, manufactured by Bayer Co., Ltd.), titanium dioxide (タイペ - ク TIPAQUE) TTO-M-1 (rutile type, zirconium oxide, alumina treatment, particle diameter 10 to 25nm, manufactured by Shigaku industries Co., Ltd.), titanium dioxide (タイペ - ク TIPAQUE) TTO-D-1 (rutile type, zirconium oxide treatment, alumina treatment, particle diameter 20 to 3nm, manufactured by Shigaku industries Co., Ltd.), titanium dioxide (タイペ - ク TIPAQUE) A-100 (anatase type, no surface treatment, particle diameter 0.4 μm, manufactured by Shikushi industries, Inc.), クロノス (KRONOS) KA-10 (anatase type, untreated, particle diameter 0.3 to 0.5 μm, manufactured by Titania industries, Inc.), クロノス (KRONOS) KA-15 (anatase type, untreated, particle diameter 0.3 to 0.5 μm, manufactured by Titania industries, Inc.), クロノス (KRONOS) KA-20 (anatase type, alumina treatment, particle diameter 0.3 to 0.5 μm, manufactured by Titania industries, Inc.), クロノス (KRONOS) KA-30 (anatase type, untreated, particle diameter 0.2 to 0.4 μm, manufactured by Titania industries, Inc.), クロノス (KRONOS) KA-35 (anatase type, untreated, particle diameter 0.2 to 0.4 μm, manufactured by Titania industries, Inc.), クロノス (KRONOS) KA-80 (anatase type, alumina treatment, silica treatment, particle diameter of 0.3 to 0.5 μm, manufactured by titanium industries, Inc.), クロノス (KRONOS) KR-310 (rutile type, untreated, particle diameter of 0.3 to 0.5 μm, manufactured by titanium industries, Inc.), クロノス (KRONOS) KR-380 (rutile type, alumina treatment, silica treatment, particle diameter of 0.3 to 0.5 μm, manufactured by titanium industries, Inc.), クロノス (KRONOS) KR-460 (rutile type, alumina treatment, particle diameter of 0.2 to 0.4 μm, manufactured by titanium industries, Inc.), クロノス (KRONOS) KR-480 (rutile type, alumina treatment, silica treatment, particle diameter of 0.2 to 0.4 μm, manufactured by titanium industries, Inc.), クロノス (KRONOS) KR-270 (rutile type, zinc oxide treatment, alumina treatment, particle diameter of 0.2 to 0.4 μm, manufactured by titanium industries, and チタニツクス (TITAX) rutile type JR-301 (TINIX), alumina treatment with a particle diameter of 0.3 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-403 (rutile type, alumina treatment, silica treatment, particle diameter of 0.25 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-405 (rutile type, alumina treatment, particle diameter of 0.21 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-600A (rutile type, alumina treatment, particle diameter of 0.25 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-605 (rutile type, alumina treatment, particle diameter of 0.25 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-600E (rutile type, alumina treatment, particle diameter of 0.27 μm, manufactured by テイカ Co.), チタニツクス (TITANIX) JR-603 (rutile type, alumina treatment, zirconia treatment, particle diameter 0.28 μm, manufactured by テイカ Co., Ltd.), チタニツクス (TITANIX) JR-805 (rutile type, alumina treatment, silica treatment, particle diameter 0.29 μm, manufactured by テイカ Co., Ltd.), チタニツクス (TITANIX) JR-806 (rutile type, alumina treatment, silica treatment, particle diameter 0.25 μm, manufactured by テイカ Co., Ltd.), チタニツクス (TITANIX) JR-701 (rutile type, alumina treatment, silica treatment, zinc oxide treatment, particle diameter 0.27 μm, manufactured by テイカ Co., Ltd.), チタニツクス (TITANIX) JRNC (rutile type, alumina treatment, silica treatment, zirconia treatment, manufactured by テイカ Co., Ltd.), チタニツクス (TITANIX) JR-800 (rutile type, alumina treatment, silica treatment, テイカ Co., Ltd.), チタニツクス (TITANIX) JR (rutile type, untreated, particle diameter 0.27 μm, テイカ Co., Ltd.), チタニツクス (TITANIX) JA-1 (anatase type, untreated, particle diameter 0.18 μm, テイカ Co., Ltd.), チタニツクス (TITANIX) JA-C (anatase type, untreated, particle diameter 0.18 μm, テイカ Co., Ltd.), チタニツクス (TITANIX) JA-3 (anatase type, untreated, particle diameter 0.18 μm, テイカ Co., Ltd.), チタニツクス (TITANIX) JA-4 (anatase type, alumina treated, particle diameter 0.18 μm, テイカ Co., Ltd.), チタニツクス (TITANIX) JA-5 (anatase type, untreated, particle diameter 0.18 μm, テイカ Co., Ltd.), and the like. But is not limited to these examples.
In addition, the titanium dioxide may be prepared in fine particles to enhance the scattering effect. The fine particulate titanium dioxide is not particularly limited, and may be, for example, fine particulate titanium dioxide having an average primary particle diameter of 30nm or less, more preferably 20nm or less. When the average primary particle diameter is larger than 30nm, whitening or white residue tends to occur. The lower limit of the average primary particle diameter is not particularly limited, but the smaller the particle diameter, the more expensive the particle diameter is, and from the viewpoint of economy, the particle diameter is preferably 5nm or more, and more preferably 10nm or more.
(c) The lower limit of the total amount of the components in the sunscreen cosmetic composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 3% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. When the amount is less than 0.5% by mass, it is difficult to obtain a sufficient SPF value, while when it is more than 50% by mass, the desired effect of increasing the amount is not obtained and formulation is difficult. In particular, when zinc oxide or titanium dioxide is used as the component (c), if the amount is too large, problems occur in terms of usability and stability such as spreadability and whitening of the skin, and it is not preferable to use the composition.
When zinc oxide is blended as component (c), it is preferably blended in a range of 5 to 40 mass%. When titanium dioxide is blended, it is preferably blended in a range of 0.5 to 10 mass%.
The silicone oil as the component (d) includes silicone oils used in many general cosmetic compositions. Specific examples thereof include polymethylsiloxane, octamethylsiloxane, decamethyltetrapolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrapolysiloxane, decamethylcyclopentapolysiloxane, and the like. Preferred are octamethylcyclotetrapolysiloxane, decamethylcyclopentapolysiloxane, and the like. But is not limited to these examples. (d) The component (C) may be one or two or more components.
(d) The lower limit of the amount of the component (b) to be blended in the sunscreen cosmetic composition of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. When the amount is less than 1% by mass, the composition tends to become unstable, while when it is more than 70% by mass, the desired effect of the increase in the amount is not obtained, and the composition gives a sticky feeling and deteriorates the ultraviolet ray protection effect.
The cosmetic of the present invention comprises the above-mentioned components (a) to (d) as essential components, and from the viewpoint of usability and stability improvement, one or more kinds selected from silicone surfactants, glycerin and polyglycerin fatty acid esters may be blended as the component (e).
[ siloxane surfactant ]
The silicone surfactant is not particularly limited, and examples thereof include nonionic silicone surfactants obtained by modifying a silicone skeleton with a polyether group, an epoxy polyether group, a hydroxyl group, an amino group, an epoxy group, or the like; a cationic silicone surfactant obtained by modifying a siloxane skeleton with an ammonium salt group; amphoteric silicone surfactants obtained by modifying a siloxane skeleton with a sulfobetaine group, and the like, but the surfactant is not limited to these examples.
By using a silicone surfactant having a modified group introduced into a silicone chain, the dispersibility and stability of titanium dioxide and zinc oxide in the product can be significantly improved as compared with the use of 2-ethylhexanoate alone, and a cosmetic excellent in preparation can be produced.
From the viewpoint of adjusting the polarity in a wide range from hydrophilicity to lipophilicity, for example, a polyether-modified silicone surfactant is preferable. Among them, poly (oxyethylene-oxypropylene) methicone copolymers, polyoxyethylene methicone copolymers, silicone chain-branched methicone copolymers, alkyl chain-branched polyoxyethylene methicone copolymers, alkyl chain-silicone chain-branched polyoxyethylene methicone copolymers, cross-linked polyoxyethylene methicone, alkylated cross-linked polyoxyethylene methicone, branched polyglycerol-modified siloxane, cross-linked polyglycerol-modified siloxane, alkylated cross-linked polyglycerol-modified siloxane, and alkyl branched polyglycerol-modified siloxane are appropriately listed.
Examples of the poly (oxyethylene-oxypropylene) methicone copolymer include PEG/PPG-20/22 butyl ether dimethicone (KF-6012 available from shin-Etsu chemical Co., Ltd.), PEG/PPG-20/22 dimethicone (BY 22-008M available from Dow Corning Token Silicone Si Co., Ltd. (Bay レ. ダウコ - ニング. シリコ - ン strain), lauryl PEG/PPG-18 methicone (5200 Formulation Aid available from Dow Corning Token Li Co., Ltd. (Bay レ. ダウコ - ニング strain), PEG/PPG-19/19 polydimethylsiloxane (5330 Fluid manufactured by DONGKANGNING DONGLI, Inc. (DONGDONG レ, ダウコ - ニング), PEG/PPG-15/15 polydimethylsiloxane (5330 Fluid manufactured by DONGKANGNING DONGLI, Inc. (DONGDONG レ, ダウコ - ニング)), and so on.
Examples of the polyoxyethylene polymethylsiloxane copolymer include PEG-11 methyl ether polydimethylsiloxane (KF-6011 available from shin-Etsu chemical industries Co., Ltd.), PEG-9 polydimethylsiloxane (KF-6013 available from shin-Etsu chemical industries Co., Ltd.), PEG-3 (KF-6015 available from shin-Etsu chemical industries Co., Ltd.), PEG-9 methyl ether polydimethylsiloxane (KF-6016 available from shin-Etsu chemical industries Co., Ltd.), PEG-10 polydimethylsiloxane (KF-6017 available from shin-Etsu chemical industries Co., Ltd.), PEG-11 methyl ether polydimethylsiloxane (KF-6018 available from shin-Etsu chemical industries Co., Ltd.), PEG-9 polydimethylsiloxane (KF-6019 available from shin-Etsu chemical industries Co., Ltd.), and PEG-12 polydimethylsiloxane (SH 3735 3771M available from Dow Corning Dong Co., Ltd. (from Dow. レ, ダウコ - ニング strain), SH3772M, SH3773M, SH3775M, etc.).
Examples of the siloxane chain-branched polymethylsiloxane copolymer include PEG-9 polydimethylsiloxane ethylpolydimethylsiloxane (KF-6028 manufactured by shin-Etsu chemical Co., Ltd.).
Examples of the alkyl chain-branched polyoxyethylene polymethylsiloxane copolymer include PEG/PPG-10/3 oil ether polydimethylsiloxane (KF-6026 manufactured by shin-Etsu chemical Co., Ltd.).
Examples of the alkyl chain/siloxane chain-branched polyoxyethylene methicone copolymer include lauryl PEG-9 dimethicone ethyl dimethicone (KF-6038 manufactured by shin-Etsu chemical Co., Ltd.).
Examples of the crosslinked polyoxyethylene polymethylsiloxane include a polydimethylsiloxane/(PEG-10/15) crosslinked polymer (KSG-210 manufactured by shin-Etsu chemical industries, Ltd.), a cyclomethicone PEG-12 polydimethylsiloxane crosslinked polymer (9011 silicone elastomer mixture manufactured by Dow Corning Dongli silicone Co., Ltd. (Bay レ. ダウコ - ニング. シリコ - ン strain), and the like.
Examples of the alkylated cross-linked polyoxyethylene polymethylsiloxane include mineral oil PEG-15 lauryl polydimethylsiloxane cross-linked polymer (KSG-310 manufactured by shin-Etsu chemical industries, Ltd.), isododecane PEG-15 lauryl polydimethylsiloxane cross-linked polymer (KSG-320 manufactured by shin-Etsu chemical industries, Ltd.), tricaprylin PEG-15 lauryl polydimethylsiloxane cross-linked polymer (KSG-330 manufactured by shin-Etsu chemical industries, Ltd.), squalane PEG-15 lauryl polydimethylsiloxane cross-linked polymer PEG-10 lauryl polydimethylsiloxane cross-linked polymer (KSG-340 manufactured by shin-Etsu chemical industries, Ltd.), and the like.
Examples of the branched polyglycerin-grafted silicone include polyglycerin-3-disiloxane polydimethylsiloxane (KF-6100 manufactured by shin-Etsu chemical Co., Ltd.), and polyglycerin-3-polydimethylsiloxane ethyl polydimethylsiloxane (KF-6104 manufactured by shin-Etsu chemical Co., Ltd.).
Examples of the crosslinked polyglycerol-modified silicone include polydimethylsiloxane (polydimethylsiloxane/polyglycerol-3) crosslinked polymer (KSG-710 manufactured by shin-Etsu chemical industries, Ltd.).
Examples of the alkylated crosslinked polyglycerol-modified silicone include mineral oil- (lauryl dimethicone/polyglycerol 3) crosslinked polymer (KSG-810 manufactured by shin-Etsu chemical industries, Ltd.), isododecane- (lauryl dimethicone/polyglycerol 3) crosslinked polymer (KSG-820 manufactured by shin-Etsu chemical industries, Ltd.), glyceryl tricaprylate- (lauryl dimethicone/polyglycerol 3) crosslinked polymer (KSG-830 manufactured by shin-Etsu chemical industries, Ltd.), squalane- (lauryl dimethicone/polyglycerol 3) crosslinked polymer (KSG-840 manufactured by shin-Etsu chemical industries, Ltd.), and the like.
Examples of the alkyl branched polyglycerin-modified silicone include lauryl polyglycerin-3-dimethicone ethyl dimethicone (KF-6105, manufactured by shin-Etsu chemical Co., Ltd.).
Among them, a poly (oxyethylene/oxypropylene) polymethylsiloxane copolymer, an alkyl chain branched poly (oxyethylene/oxypropylene) polymethylsiloxane copolymer, a siloxane chain alkyl chain branched poly (oxyethylene/oxypropylene) polymethylsiloxane copolymer, and the like are preferably used.
[ Glycerol or polyglycerol fatty acid ester ]
Examples of the glycerin or polyglycerin fatty acid ester include glyceryl undecylenate, glyceryl myristate, glyceryl stearate, self-emulsifying glyceryl stearate, glyceryl isostearate, glyceryl oleate, glyceryl oleates, glyceryl dioleate, polyglyceryl stearate-2, polyglyceryl oleate-2, polyglyceryl dioleate-2, polyglyceryl isostearate-2, polyglyceryl diisostearate-2, polyglyceryl triisostearate-2, polyglyceryl stearate-4, polyglyceryl oleate-4, polyglyceryl tristearate-4, polyglyceryl pentaoleate-4, polyglyceryl laurate-6, polyglyceryl myristate-6, polyglyceryl stearate-6, polyglyceryl oleate-6, polyglyceryl tristearate-6, polyglyceryl myristate-6, polyglyceryl stearate-2, polyglyceryl isostearate-2, and the like, Polyglyceryl tetrabehenate-6, polyglyceryl pentastearate-6, polyglyceryl pentaoleate-6, polyglyceryl lactide ricinoleate-6, polyglyceryl laurate-10, polyglyceryl myristate-10, polyglyceryl stearate-10, polyglyceryl isostearate-10, polyglyceryl oleate-10, polyglyceryl linoleate-10, polyglyceryl distearate-10, polyglyceryl diisostearate-10, polyglyceryl tristearate-10, polyglyceryl trioleate-10, polyglyceryl pentastearate-10, polyglyceryl pentahydroxystearate-10, polyglyceryl pentaisostearate-10, polyglyceryl pentaoleate-10, polyglyceryl heptastearate-10, polyglyceryl heptaoleate-10, polyglyceryl pentaoleate, Polyglyceryl decastearate-10, polyglyceryl decaisostearate-10, polyglyceryl decaoleate-10, polyglyceryl decamacadamia nut fatty acid-10, polyglyceryl lactide ricinoleate-10, etc.
The cosmetic of the present invention may be in the form of any of oil-in-water emulsion and water-in-oil emulsion. In the oil-in-water emulsion sunscreen cosmetic composition, as the component (e), a polyoxyethylene polymethylsiloxane copolymer, glycerin or polyglycerin fatty acid ester, or the like is preferably used. In addition, in the water-in-oil type emulsion sunscreen cosmetic composition, as the component (e), an alkyl chain/silicone chain branched polyoxyethylene polymethylsiloxane copolymer, a polyoxyethylene polymethylsiloxane copolymer, or the like is preferably used.
(e) The amount of the component (c) to be blended is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more in the sunscreen cosmetic of the present invention. The upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. When the amount is less than 0.01% by mass, the stability of the cosmetic tends to be deteriorated, and when it is more than 20% by mass, the sticky feeling tends to be generated and the feeling in use tends to be deteriorated.
In the cosmetic of the present invention, other components usually used in cosmetics may be appropriately blended as necessary in addition to the above components. Examples of these components include water-soluble polymers, oil-soluble polymers, waxes, alcohols, hydrocarbon oils, fatty acids, higher alcohols, fatty acid esters, drugs, and the like. But is not limited to these examples.
Examples of the water-soluble polymer include homopolymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter, abbreviated as "AMPS"). The copolymer may be a copolymer with a comonomer such as vinylpyrrolidone, acrylamide, sodium acrylate, hydroxyethyl acrylate, or the like. That is, examples thereof include AMPS homopolymer, vinylpyrrolidone/AMPS copolymer, dimethylacrylamide/AMPS copolymer, acrylamide/AMPS copolymer, sodium acrylate/AMPS copolymer and the like.
Further, carboxyvinyl polymers, ammonium polyacrylate, sodium acrylate/alkyl acrylate/sodium methacrylate/alkyl methacrylate copolymers, carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextral alcohol, keratan sulfate, carob gum, succinoglucan, chitin, chitosan, carboxymethyl chitin, agar, and the like can be cited.
Examples of the oil-soluble polymer include trimethylsiloxane silicic acid, alkyl-modified siloxane, polyamide-modified siloxane, polydimethylsiloxane crosslinked polymer, (polydimethylsiloxane/vinyl polydimethylsiloxane) crosslinked polymer, and polymethylsilsesquioxane.
Examples of the wax include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, and jojoba wax.
Examples of the alcohols include lower alcohols such as ethanol and isopropanol, higher alcohols such as isostearyl alcohol, octyldodecanol and hexyldecanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, 1, 3-butanediol, dipropylene glycol and polybutylene glycol.
Examples of the alkane oils include liquid paraffin, ceresin, squalane, pristane, paraffin, ceresin, squalene, vaseline, microcrystalline wax, polyethylene wax, and Fischer-Tropsch wax.
Examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and arachidonic acid.
Examples of the higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, arachidyl alcohol, batyl alcohol, chimyl alcohol, carnauba alcohol, ceryl alcohol, coriander alcohol, myricyl alcohol, ceryl alcohol, elaidyl alcohol, isostearyl glyceryl ether, octyl alcohol, triacontanol, batyl alcohol, cetostearyl alcohol, oleyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecyl alcohol, and octyldecyl alcohol.
Examples of the fatty acid ester include myristyl myristate, cetyl palmitate, cholesterol stearate, and 2-octyldodecyl beeswax fatty acid.
Examples of the drug include salts of L-ascorbic acid and its derivatives, glycyrrhizic acid and its derivatives such as dipotassium glycyrrhizinate and monoammonium glycyrrhizinate, glycyrrhetinic acid and its derivatives such as stearyl glycyrrhetinate, allantoin, salts of tranexamic acid and its derivatives, salts of alkoxysalicylic acid and its derivatives, salts of glutathione and its derivatives, allantoin, azulene, and the like.
The oil-in-water or water-in-oil emulsion sunscreen cosmetic of the present invention includes emulsion-like preparations or cream-like preparations. These products can be produced by mixing the above essential components and the usual compounding ingredients for cosmetics by a conventional method.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The amount of the additive is% by mass.
Example I-1
The following oil components were each dropped to the skin on the inner side of the forearm in an amount of 10. mu.l, and the area (cm) after one minute was measured2). The results are shown in Table I-1.
TABLE I-1
Oil content Area (cm) after one minute of dropping2)
Pentaerythritol Tetraoctanoate 1.0
Tricaprylin 2.2
Squalane 2.4
Cetyl 2-ethylhexanoate 3.8
Diethylhexylsuccinate 3.9
Tripropylene glycol neopentanoate 4.0
Isononyl isononanoate 4.5
Isononyl 2-ethylhexanoate 6.5
2-Ethylhexanoic acid 2-ethylhexyl ester 7.2
The results in Table I-1 show that isononyl-2-ethylhexanoate and 2-ethylhexyl-2-ethylhexanoate have high spreading properties (spadingvalue) on human skin and good skin absorption properties as compared with other oil components conventionally used in cosmetics.
In addition, isononyl 2-ethylhexanoate is not collected in the specified standards, and has no precedent for using in combination with the existing cosmetics, but the compound is nontoxic and safe.
Example I-2
The usability (skin absorbability) of various ester oils blended in an oil-in-water emulsion cream system was evaluated as follows.
That is, the samples having the compositions shown in the following Table I-2 were evaluated for "skin absorption" according to the following evaluation criteria. The results are shown in Table I-2.
(evaluation criteria)
Very good: strong feeling of skin absorption
O: can be absorbed by skin
And (delta): slightly feeling skin absorption
X: can not feel absorbed by skin
TABLE I-2
Sample A Sample B Sample C Sample D Sample E
Ion exchange water Residual amount Residual amount Residual amount Residual amount Residual amount
dimethylacrylamide/AMPS/methylenebisacrylamide crosslinked polymer 0.5 0.5 0.5 0.5 0.5
Ethylenediaminetetraacetic acid trisodium salt 0.01 0.01 0.01 0.01 0.01
1, 3-butanediol 7.0 7.0 7.0 7.0 7.0
Hydroxyphenyl Ethyl ester 0.2 0.2 0.2 0.2 0.2
Hydroxy benzene butyl ester 0.1 0.1 0.1 0.1 0.1
Alpha-olefin oligomer 5.0 5.0 5.0 5.0 5.0
2-Ethylhexanoic acid 2-ethylhexyl ester 10.0
Isononyl 2-ethylhexanoate 10.0
Isononanoic acid 2-ethylhexyl ester 10.0
Isononyl isononanoate 10.0
Cetyl 2-ethylhexanoate 10.0
PEG (40) monostearate 0.5 0.5 0.5 0.5 0.5
Hexadecyl/octadecyl alcohol glucoside 0.1 0.1 0.1 0.1 0.1
Stearyl alcohol 0.7 0.7 0.7 0.7 0.7
Behenyl alcohol 2.5 2.5 2.5 2.5 2.5
Dimethyl silicone oil 5.0 5.0 5.0 5.0 5.0
Decamethyl cyclic pentasiloxane 3.0 3.0 3.0 3.0 3.0
Cosmetic grade glycerol (85%) 3.0 3.0 3.0 3.0 3.0
Absorbency of skin ◎ ○ ○ △ △～×
The results in Table I-2 show that samples A and B containing 2-ethylhexyl 2-ethylhexanoate and isononyl 2-ethylhexanoate exhibit better skin absorption than sample C, D, E containing ester oil which has been conventionally used. In particular, sample a had significantly better skin absorbency than the prior ester oil.
Examples I-3 to I-12 and comparative examples I-1 to I-4
Skin cream as an oil-in-water emulsion skin cosmetic was produced by the following method according to the formulation shown in tables I-3 to I-4 below.
(production method)
The components (1) to (11) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (12) to (24) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Then, the 70 ℃ oil phase was slowly added to the 70 ℃ water phase, and the mixture was emulsified with a homogenizer while adding the mixture. After emulsification, the mixture is quenched to be below 40 ℃ to obtain the target oil-in-water emulsified skin cream. The obtained cream (sample) was evaluated for stability and usability (extensibility on skin, absorption on skin, sticky feeling, smooth feeling, soft feeling, and tight feeling) by the following test methods. The results are shown in tables I-3 to I-4.
[ stability test ]
The appearance of the sample was observed visually and microscopically after it was left at 50 ℃ for one month, and judged according to the following evaluation criteria.
(evaluation criteria)
O: no separation or crystal precipitation was observed at all
And (delta): little separation or crystal precipitation was observed
X: separation or crystallization of the liquid phase (oil or water phase)
[ usability (extensibility on skin) ]
Practical tests were conducted by female professional volunteers (10 persons), and the extensibility on the skin was evaluated according to the following evaluation criteria.
(evaluation criteria)
Very good: all 10 were rated as soft, smooth and ductile
O: the 7-9 are evaluated as soft and smooth in extension
And (delta): 3-6 of the above-mentioned materials are rated as light, quick and smooth in extension
X: 0-2 rated as soft, smooth and ductile
[ usability (skin absorption) ]
Practical tests were conducted by female professional volunteers (10 individuals), and the skin absorption was evaluated according to the following evaluation criteria.
(evaluation criteria)
Very good: all 10 were rated as good skin absorption
O: the 7-9 evaluation shows that the skin absorbs well
And (delta): 3-6 rated as good skin absorption
X: 0-2 rated as good skin absorption
[ usability (sticky feeling) ]
Practical tests were conducted by female professional volunteers (10 individuals), and the sticky feeling was evaluated according to the evaluation criteria described below.
(evaluation criteria)
Very good: all 10 were rated as non-greasy, moist
O: 7-9 rated as non-greasy, moist
And (delta): 3-6 of the above-mentioned materials are rated as non-sticky and moist
X: 0-2 rated as non-greasy, moist
[ usability (smooth feeling) ]
Practical tests were conducted by female professional volunteers (10 individuals), and the smooth feeling was evaluated according to the evaluation criteria described below.
(evaluation criteria)
Very good: all 10 rated smooth
O: the 7-9 are rated as smooth
And (delta): 3-6 rated as smooth
X: 0-2 rated as smooth
[ usability (feeling of softness, feeling of use with skin softness) ]
Practical tests were conducted by female professional volunteers (10 individuals), and the soft feeling was evaluated according to the evaluation criteria described below.
(evaluation criteria)
Very good: all 10 were rated as soft and moist
O: 7-9 evaluated as soft and moist
And (delta): 3-6 of them rated as soft and moist
X: 0-2 rated as soft and moist
[ usability (skin-tightening feeling: feeling of use for feeling skin tightness) ]
Practical tests were conducted by female professional volunteers (10 individuals), and the skin firming sensation was evaluated according to the evaluation criteria described below.
(evaluation criteria)
Very good: all 10 were rated as having a firming sensation
O: 7-9 evaluated as having firming skin
And (delta): 3-6 rated as having firming sensation
X: 0-2 rated as firming
In tables I-3 to I-4, the following compounds were used.
Hexadecyl/stearyl glucoside(＊1)：[EMULGADE PL68/50](HLB value 8.0, manufactured by コグニス Co.)
Glyceryl monostearate (self-emulsifying type)(＊2)：[Nikkol MGS-ASEV](HLB value 6.0, manufactured by Sun chemical Co., Ltd.)
POE (5) glyceryl monooleate(＊3)：[Nikkol TMG0-5](HLB value 9.5, manufactured by Sun chemical Co., Ltd.)
PEG monostearate (10)(＊4)：[Emulex 810](HLB value 11, manufactured by Nippon emulsification Co., Ltd.)
POE (20) phytosterols(＊5)：[Nikkol BPS-20](HLB value 15.5, manufactured by Sun chemical Co., Ltd.)
POE (21) stearyl ether(＊6)：[Brij721](HLB value 15.5, manufactured by ユニケマ Co.)
AMPS homopolymers(＊7)：[Hostacerin AMPS](Clariant corporation)
acrylamide/AMPS copolymer(＊8)：[SEPIGEL 305](manufactured by SEPIC Co., Ltd.)
dimethylacrylamide/AMPS crosslinked polymer(＊9)：[SUpolymer G-1](manufactured by Toho chemical Co., Ltd.)
The results in tables I-3 to I-4 show that the skin creams of examples I-3 to I-10 of the present invention have excellent stability and usability (extensibility on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, tight feeling). Further, comparative examples I-1 to I-8 which did not satisfy the constituent requirements of the present invention could not have both the effects of stability and usability.
Other examples of the present invention are described below.
Examples I to 11: skin cream
(Components Complex) (mass%)
(1) Liquid paraffin 2.0
(2) Decamethyl cyclic pentasiloxane 6.0
(3) Isononyl 2-ethylhexanoate 6.0
(4) Glyceryl monostearate (self-emulsifying type) 2.0
([ EMALEX GMS-55FD ], HLB value 7.0, manufactured by Nippon emulsification Co., Ltd.)
(5) Polyethylene glycol monostearate (30EO) 4.0
([ EMALEX 830], HLB value 15, ester of Japan emulsification Co.)
(6) Isostearic acid PEG (8) ester 1.0
([ EMOLEX PEIS-8EX ], HLB value 10.0, ester of Japan emulsification Co.)
(7) Cetyl alcohol 2.5
(8) Batyl alcohol 2.5
(9) Jojoba oil 5.0
(10) Fragrance 0.1
(11) Residual amount of ion-exchanged water
(12)1, 3-butanediol 3.0
(13) Ascorbyl glucoside 2.0
(14) Para hydroxybenzoates 0.15
(15) Ethanol 3.0
(16) Sodium hydroxide 0.3
(17) vinylpyrrolidone/AMPS copolymer 0.5
([ ARISTOFLEX AVC ], Clariant (CLARIANT) Inc.)
(18) Citric acid 0.09
(19) Sodium citrate 0.01
(production method)
The components (1) to (10) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (11) to (19) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Emulsifying with a homogenizer while slowly adding the oil phase to the water phase kept at 70 ℃. After emulsification is finished, the mixture is quenched to be below 40 ℃ to obtain the target skin cream.
(evaluation)
The obtained skin cream was evaluated by the above test evaluation method, and as a result, it had good usability (usability evaluation: excellent in all of extensibility on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, and firm feeling), and good stability (stability evaluation:. smallcircle.).
Examples I to 12: oil-in-water emulsion foundation
(Components Complex) (mass%)
(1) Liquid lanolin 2.0
(2) Hydrogenated polyisobutene 4.0
([ PRIORINE 3758], manufactured by ユニケマ Co., Ltd.)
(3) 2-Ethylhexanoic acid 2-ethylhexyl ester 10.0
(4) Stearyl alcohol 0.5
(5) Glycerol monostearate 3.5
([ NIKKOL MGS-F20V ], HLB value 7.0, manufactured by Sun chemical Co., Ltd.)
(6) Polyethylene glycol monostearate (40EO) 0.5
([ NIKKOL MYS-40V ], HLB value 17.5, manufactured by sunlight chemical Co., Ltd.)
(7) Fragrance 0.1
(8) Residual amount of ion-exchanged water
(9) Dipropylene glycol 2.5
(10) Ethanol 1.0
(11) Parabens 0.1
(12) Talc powder 3.0
(13) Titanium dioxide 5.0
(14) Iron oxide Red 0.5
(15) Iron oxide yellow 1.4
(16) Iron oxide black 0.1
(17) Hydroxyethyl acrylate/AMPS copolymer (effective component 37.5%)
([ SIMULGEL NS ], manufactured by SEPIC corporation) 0.5(0.19)
(production method)
The components (1) to (7) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (8) to (17) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Emulsifying with a homogenizer while slowly adding the oil phase to the water phase kept at 70 ℃. After completion of the emulsification, the mixture was quenched to 40 ℃ or lower to obtain the desired oil-in-water emulsion foundation.
(evaluation)
The obtained oil-in-water emulsion foundation was evaluated by the test evaluation method described above, and as a result, it had good usability (usability evaluation: excellent in all of spreadability on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, and firm feeling), and good stability (stability evaluation:. good).
Examples I to 13: oil-in-water emulsion type sunscreen cream
(Components Complex) (mass%)
(1) Octyl p-methoxycinnamate 6.0
(2) Glycerol octyl di-p-methoxycinnamate 2.0
(3) 4-tert-butyl-4' -methoxydibenzoylmethane 2.0
(4) Tetrakis (octanoic acid/p-methoxycinnamic acid) pentaerythritol ester 3.0
(5) 2-Ethylhexanoic acid 2-ethylhexyl ester 7.5
(6) Isononyl 2-ethylhexanoate 7.5
(7) Polydimethylsiloxane (20 mPa. multidot.s) 3.0
(8) 0.5 parts of Vaseline
(9) Glycerol monooleate 1.2
([ NIKKOL NGO ], HLB value 2.5, manufactured by Sun chemical Co., Ltd.)
(10) Polyethylene glycol monostearate (45EO) 1.0
([ NIKKOL MYS-45MV ], HLB value 18.0, manufactured by Sun chemical Co., Ltd.)
(11) Residual amount of ion-exchanged water
(12) Dipropylene glycol 6.0
(13) Ethanol 3.0
(14) acrylamide/AMPS copolymer (40% active ingredient) 1.0(0.4)
([ セピゲル 305], SEPIC Co., Ltd.)
(15) Fragrance 0.1
(production method)
The components (1) to (10) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (11) to (15) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Emulsifying with a homogenizer while slowly adding the oil phase to the water phase kept at 70 ℃. After the emulsification is finished, the mixture is quenched to be below 40 ℃ to obtain the target oil-in-water emulsified sunscreen cream.
(evaluation)
The obtained oil-in-water emulsion-type sunscreen cream was evaluated by the above test evaluation method, and as a result, it had good usability (usability evaluation: excellent in extensibility on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, and firm feeling) and good stability (stability evaluation:. smallcircle.).
Examples I to 14: skin cream
(Components Complex) (mass%)
(1) Polydimethylsiloxane (6 mPa. multidot.s) 2.0
(2) Decamethyl cyclic pentasiloxane 6.0
(3) 2-Ethylhexanoic acid 2-ethylhexyl ester 12.0
(4) Glyceryl monostearate 0.5
([ EMALEX GMS-10SE ], HLB value 6.0, manufactured by Nippon emulsification Co., Ltd.)
(5) Stearic acid polyethylene glycol (10EO) ester 5.0
([ NIKKOL MYS-10V ], HLB value 11.0, manufactured by sunlight chemical Co., Ltd.)
(6) Hexadecanol/octadecanol 2.5
(7) Batyl alcohol 2.5
(8) Fragrance 0.1
(9) Residual amount of ion-exchanged water
(10)1, 3-butanediol 3.0
(11) Arbutin 5.0
(12) Ascorbic acid magnesium phosphate 1.0
(13) Para hydroxybenzoates 0.15
(14) Ethanol 3.0
(15) Sodium hydroxide 0.4
(16) dimethylacrylamide/AMPS copolymer 0.5
([ SINULGEL EPG ], manufactured by SEPIC corporation)
(17) Citric acid 0.09
(17) Sodium citrate 0.01
(production method)
The components (1) to (8) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (9) to (18) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Emulsifying with a homogenizer while slowly adding the oil phase to the water phase kept at 70 ℃. After emulsification is finished, the mixture is quenched to be below 40 ℃ to obtain the target skin cream.
(evaluation)
The obtained skin cream was evaluated by the above test evaluation method, and as a result, it had good usability (usability evaluation: excellent in extensibility on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, and firm feeling) and good stability (stability evaluation:. smallcircle.).
Examples I to 15: skin cream
(Components Complex) (mass%)
(1) Liquid Paraffin 1.0
(2) Decamethyl cyclic pentasiloxane 6.0
(3) Isononyl 2-ethylhexanoate 6.0
(4) Glyceryl monostearate 1.0
([ NIKKOL MGS-BSEV ], HLB value 8.0, manufactured by Sun chemical Co., Ltd.)
(5) Stearic acid polyethylene glycol (100EO) ester 2.0
([ Mirj59P ], HLB value 18.8, ユニケマ Co.)
(6) Triisostearic acid PEG (30) Glycerol ester 0.5
([ EMALEX GWIS-330], HLB value 10, manufactured by Nippon emulsification Co., Ltd.)
(7) Cetyl alcohol 2.5
(8) Batyl alcohol 2.5
(9) Fragrance 0.1
(10)1, 3-butanediol 3.0
(11) Residual amount of ion-exchanged water
(12) Trimethylglycine 1.0
(13) 4-Methoxysalicylic acid potassium 2.0
(14) 0.15 parts of phenoxyethanol
(15) Sodium hydroxide 0.4
(16) AMPS homopolymer 0.5
([ Hostacerin AMPS ], Klien (CLARIANT) Inc.)
(17) Citric acid 0.09
(17) Sodium citrate 0.01
(production method)
The components (1) to (9) were uniformly mixed and dissolved at 70 ℃ (oil phase). In addition, the components (10) to (18) were uniformly mixed and dissolved at 70 ℃ (aqueous phase). Emulsifying with a homogenizer while slowly adding the oil phase to the water phase kept at 70 ℃. After emulsification is finished, the mixture is quenched to be below 40 ℃ to obtain the target skin cream.
(evaluation)
The obtained skin cream was evaluated by the above test evaluation method, and as a result, it had good usability (usability evaluation: excellent in extensibility on the skin, absorption on the skin, sticky feeling, smooth feeling, soft feeling, and firm feeling) and good stability (stability evaluation:. smallcircle.).
Before the examples, the test method and the evaluation method used in the present invention will be explained.
Examples II-1 to II-18 and comparative examples II-1 to II-9
Sunscreen cosmetic compositions were prepared by using the formulations shown in the following tables II-1 to II-3. Examples II-1 to II-9 (Table II-1) were of the oil-in-water type, and examples II-10 to II-18 (Table II-2) were of the water-in-oil type. In Table II-3, comparative examples II-1 and II-7 were oil-in-water emulsion types, and comparative examples II-2 to II-6, II-8 and II-9 were water-in-oil emulsion types.
The sunscreen cosmetics (samples) obtained in examples II-1 to II-18 and comparative examples II-1 to II-9 were evaluated for sunscreen effect, dispersibility immediately after preparation, and stability under severe test conditions (temperature stability and transportation stability), respectively, according to the following evaluation criteria. Further, using each cosmetic, 5 items of spreadability, smoothness, white residue, stickiness and wetness were investigated for each of 20 volunteers, and the feeling of use was evaluated based on the results. The results are shown in tables II-1 to II-3, respectively.
[ sunscreen Effect ]
The SPF value of each sample was measured according to the "SPF measurement standard" established by the japan cosmetic industry association (established in 2006).
Evaluation criteria
Very good: SPF value above 50 and/or PA + + +
O: less than 50 and/or PA + +with SPF value more than 30
And (delta): the SPF value is more than 20 and less than 30 and/or PA +
X: SPF value less than 20
[ dispersibility immediately after production ]
After preparation of each sample, a portion was placed on a glass slide and the dispersion of the powder was observed visually and microscopically.
Evaluation criteria
Very good: good results are obtained. There was no agglomeration of the powder.
O: preferably. There are powder aggregates smaller than 1 mm.
And (delta): is poor. The powder aggregate has a particle size of 1-2 mm.
X: and (4) poor. There are powder aggregates with a size of more than 2 mm.
[ stability under harsh test conditions ]
(1) Temperature stability
Each sample was filled in a glass bottle or a plastic container, and stored at 0 ℃, 25 ℃, 40 ℃ and 50 ℃ for one month, and the change (presence or absence of discoloration, odor, precipitation/aggregation of powder, specific gravity, viscosity, emulsified state) and redispersibility (vibration frequency, dispersibility, specific gravity, viscosity required for dispersion) of the powder after vibration were observed for each sample.
(2) Rotational stability
Each sample was filled in a screw bottle, and a rotation test was performed on a rotator at a speed of 30 revolutions per minute for 5 hours, and the change (presence or absence of discoloration, odor, precipitation/aggregation of powder, specific gravity, viscosity, emulsified state) and the redispersibility (vibration frequency required for dispersion, dispersibility, specific gravity, viscosity) of the powder after the rotation test were observed for each sample.
Evaluation criteria
(i) The condition of the preparation change
Very good: good results are obtained. While maintaining almost the same state during manufacture.
O: preferably. Slight discoloration, odor, powder precipitation and aggregation, specific gravity change, viscosity change and sample separation.
And (delta): is poor. Obvious discoloration, odor change, powder precipitation and aggregation, specific gravity change, viscosity change and sample separation.
X: and (4) poor. Obvious discoloration, odor change, powder precipitation and aggregation, specific gravity change, viscosity change and sample separation.
(ii) Redispersibility of powders after vibration
Very good: good results are obtained. The same state is almost kept during the manufacture, and the recovery is rapid.
O: preferably. The vibration is needed several times, and the state can be recovered to the state close to the manufacturing state.
And (delta): is poor. Although recovery is achieved as the number of vibrations increases, it is inferior to the state at the time of manufacture.
X: and (4) poor. The powder was not recovered regardless of the frequency of vibration, and the redispersibility of the powder was poor.
[ feeling of use ]
The results of the above-mentioned 5 questionnaires (spreadability, smoothness, white residue, stickiness, and moist feeling) were evaluated according to the following criteria.
Very good: more than 15 of the 20 answered well.
O: 10-14 out of 20 had good answers.
And (delta): among 20, 5 to 9 of the above-mentioned animals responded well.
X: among 20, 4 or less answers well.
In tables II-1 to II-3, the following compounds were used.
Hydrophobically treated zinc oxide(＊1): methylhydrogenpolysiloxane-treated zinc oxide ([ SS-ActivoxC 80)]Manufactured by Showa Denko K.K.),
Hydrophobically treated titanium dioxide(＊2): aluminum stearate treated titanium dioxide ([ MT-014)]テイカ Co.) of,
Polyoxyethylene polymethylsiloxane copolymer(＊3): PEG-11 Methylether Dimethicone ([ KF-6011)]HLB value of 14.5, manufactured by shin-Etsu chemical Co Ltd.),
Glycerol monostearate(＊4)：([NIKKOL MGS-ASEV]HLB value of 6.0, manufactured by Sun-light chemical Co Ltd.),
Alkyl chain/siloxane chain branched polyoxyethylene polymethylsiloxane copolymer(＊5): lauryl PEG-9 Dimethicone Ethyl Dimethicone ([ KF-6038)]HLB value of 3.0, manufactured by shin-Etsu chemical Co Ltd.),
Polyglyceryl diisostearate-2 ester(＊6)：[Wogel 18DV](manufactured by Songbowax Ltd.),
Polydimethylsiloxane(＊7)：[SH200C-5cs](Dongli Si Dong-Kangning corporation (Chinese imperial seeds レ, ダウ, コ, ニング シリコ, ン strains)),
the results in tables II-1 to II-3 show that the oil-in-water or water-in-oil emulsion sunscreen cosmetic compositions of the present invention containing the components (a) to (d) are remarkably superior in dispersibility and stability to those of the cosmetic compositions of comparative examples, and accordingly, are superior in sunscreen effect and feeling of use.
The cosmetic disclosed by the invention has good extensibility to skin, does not have sticky or smooth feeling when used, and has a refreshing feeling, no stickiness and good touch feeling when used. Furthermore, no white marks are left on the skin, and makeup is facilitated.
These effects are seen from comparative examples, and specific effects can be obtained by using a specific 2-ethylhexanoate ester as the ester oil.
Other embodiments of the invention are listed below.
Examples II to 19: oil-in-water emulsion sunscreen cosmetic (cream type)
(Components Complex) (mass%)
(aqueous portion)
(1)1, 3-butanediol 7.0
(2) Zinc oxide 5.0
([ Nanofine-K-LP ] made by Sakai chemical company)
(3) EDTA disodium 0.05
(4) Triethanolamine 1.0
(5)2, 2-methylenebis (6- (2H-benzotriazol-2-yl) - (1, 1, 3, 3-tetramethylbutyl) phenol 1.0
([ Tinosorb M ], Ciba Speciality Chemicals Co., Ltd.)
(6) Residual amount of ion-exchanged water
(oil phase part)
(7) 4-Methylbenzylidene camphor 2.0
([ NEO HELIOPAN MBC ], manufactured by Symrise Inc.)
(8) Octyl salicylate 4.0
([ NEO HELIOPAN OS ], Symrise corporation)
(9) Isononyl 2-ethylhexanoate 10.0
(10) Decamethyl cyclic pentasiloxane 10.0
(11) Vaseline 5.0
(12) Stearyl alcohol 3.0
(13) Stearic acid 3.0
(14) Glyceryl monostearate 3.0
(15) Polyacrylic acid Ethyl ester 1.0
(16) Appropriate amount of glutathione
(17) Proper amount of p-hydroxybenzoate
(18) Proper amount of perfume
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The aqueous phase portion was fully dispersed with titanium dioxide, the oil phase portion was added, and emulsification was performed with a homogenizer. The emulsion is cooled by a heat exchanger.
The obtained oil-in-water emulsified sunscreen cosmetic has no sticky and non-smooth feeling, but has refreshing feeling, no stickiness, and good feeling. Furthermore, no white marks remain on the skin, and makeup is easy. Further, the SPF measurement described above showed an SPF value of 22 and a PA + value.
Examples II to 20: oil-in-water emulsion sunscreen cosmetic (emulsion type)
(Components Complex) (mass%)
(aqueous portion)
(1) Dipropylene glycol 6.0
(2) Ethanol 3.0
(3) Hydroxyethyl cellulose 0.3
(4) Phenylbenzimidazolesulfonic acids 1.5
([ NEO HELIOPAN HYDRO ], Symrise corporation)
(5) Benzylidene camphorsulfonic acid 1.5
([ Mexoryl SL ], manufactured by Chimex corporation)
(6) Zinc oxide 4.0
([ Zinc Oxide neutral ] particle diameter 40nm, manufactured by Symrise Inc.)
(7) Titanium dioxide ([ STR-100C ] made by Sakai chemical Co., Ltd.) 3.0
(8) Residual amount of ion-exchanged water
(oil phase part)
(9) Isononyl 2-ethylhexanoate 4.0
(10)2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1, 3, 5-triazine 0.5
([ Tinosorb S ], Ciba Speciality Chemicals Co., Ltd.)
(11) Ethylhexyl methoxycinnamate 5.0
([ Parsol MCX ], Roche)
(12) 4-tert-butyl-4' -methoxydibenzoylmethane 1.0
([ Parsol 1789], Roche)
(13) Benzophenone-31.0
([ Uvinul M40, BASF corporation.)
(14) Oleic acid oleyl ester 5.0
(15) Polydimethylsiloxane (6 mPa. multidot.s) 3.0
([ KF-96A-6], manufactured by shin-Etsu chemical Co., Ltd.)
(16) 0.5 parts of Vaseline
(17) Cetyl alcohol 1.0
(18) Sorbitan sesquioleate 0.8
(19) Vitamin E in proper amount
(20) Proper amount of perfume
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The aqueous phase was dispersed sufficiently with titanium dioxide, and the oil phase was added to emulsify with a homogenizer. The emulsion is cooled by a heat exchanger.
The obtained oil-in-water type emulsified sunscreen cosmetic has no sticky and non-smooth feeling, and has refreshing feeling, no stickiness, and good feeling in use. Furthermore, no white marks remain on the skin, and makeup is easy. Further, the SPF measurement described above showed an SPF value of 25 and a PA + +.
Examples II to 21: water-in-oil type emulsion sunscreen cosmetic (cream type)
(Components Complex) (mass%)
(aqueous portion)
(1)1, 3-butanediol 5.0
(2) Residual amount of ion-exchanged water
(oil phase part)
(3) Isononyl 2-ethylhexanoate 15.0
(4) 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate 5.0
([ NEO HELIOPAN 303], Symrise corporation)
(5) Butyl methoxydibenzoylmethane 3.0
([ NEO HELIOPAN ] manufactured by Symrise corporation)
(6)3- (4' -methylbenzylidene) -dl-camphor 3.0
([ Eusolex 6300, manufactured by Merck)
(7) Hydrophobic treatment (aluminum oxide/fatty acid aluminum saponification treatment) titanium dioxide 3.0
([ TTO-S-4], manufactured by Stone Productivity Co., Ltd.)
(8) Diisostearic acid glyceride 3.0
(9) Organically modified montmorillonite 1.5
(10) Decamethyl cyclic pentasiloxane 10.0
(11) Proper amount of p-hydroxybenzoate
(12) Proper amount of perfume
The oil and water phases were separately heated to 70 ℃ to dissolve them. The oil phase portion was sufficiently dispersed with titanium dioxide, and the water phase portion was added while homogenizing with a homogenizer.
The obtained water-in-oil type emulsified sunscreen cosmetic has no sticky or non-smooth feeling, and has refreshing feeling, no stickiness, and good feeling in use. Furthermore, no white marks remain on the skin, and makeup is easy. Further, the SPF measurement described above showed an SPF value of 40 and a PA + +.
Examples II to 22: water-in-oil type emulsion sunscreen cosmetic (cream type)
(Components Complex) (mass%)
(aqueous portion)
(1)1, 3-butanediol 2.0
(2) Glycerol 2.0
(2) Residual amount of ion-exchanged water
(oil phase part)
(3) 2-Ethylhexanoic acid 2-ethylhexyl ester 13.0
(4) Isononyl 2-ethylhexanoate 10.0
(5) Isoamyl p-methoxycinnamate 2.0
([ NEO HELIOPAN E1000], Symrise corporation)
(6)2, 4-bis { [4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1, 3, 5-triazine 3.0
([ Tinosorb S ], Ciba Speciality Chemicals Co., Ltd.)
(7)3- (4' -methylbenzylidene) -dl-camphor 3.0
([ Eusolex 6300, manufactured by Merck)
(8) Hydrophobic treatment (fatty acid saponification treatment) titanium dioxide 3.0
([ MT-014], manufactured by テイカ Co.)
(9) PEG-9 Dimethicone Ethyl Dimethicone 3.0
([ KF-6028] manufactured by shin-Etsu chemical industries, Ltd.)
(10) Polydimethylsiloxane (polydimethylsiloxane/polyglycerol-3) crosspolymer
1.5
([ KSG-710] manufactured by shin-Etsu chemical industries, Ltd.)
(11) Decamethyl cyclic pentasiloxane 5.0
(12) Polydimethylsiloxane 5.0
(13) Proper amount of p-hydroxybenzoate
(14) Proper amount of perfume
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The oil phase portion was sufficiently dispersed with titanium dioxide, and the water phase portion was added while homogenizing with a homogenizer.
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The aqueous phase was dispersed sufficiently with titanium dioxide, and the oil phase was added to emulsify with a homogenizer. The emulsion was cooled using a heat exchanger.
The obtained water-in-oil type emulsified sunscreen cosmetic has no sticky or non-smooth feeling, and has refreshing feeling, no stickiness, and good feeling in use. Furthermore, no white marks remain on the skin, and makeup is easy. Further, the SPF measurement described above showed an SPF value of 50 and a value of PA + + +.
Example II-23: water-in-oil type emulsion sunscreen cosmetic (emulsion type)
(Components Complex) (mass%)
(aqueous portion)
(1)1, 3-butanediol 5.0
(2) Dipropylene glycol 2.0
(3) Residual amount of ion-exchanged water
(oil phase part)
(4) 2-Ethylhexanoic acid 2-ethylhexyl ester 2.0
(5) 2.0 Isononyl 2-ethylhexanoate
(6) 2-cyano-3, 3-diphenylacrylic acid ethyl ester 5.0
([ Uvinul N35], BASF corporation)
(7) Ethylhexyl methoxycinnamate 5.0
([ NEO HELIOPAN AV ], Symrise corporation)
(8)1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione 5.0
([ Eusolex 9020] manufactured by Merck)
(9) Hydrophobically treated (polydimethylsiloxane treated) Zinc oxide 5.0
([ MT-FINEX-50LP ] made by Sakai chemical Co., Ltd.)
(10) Hydrophobic treated (alumina-polydimethylsiloxane treated) titanium dioxide 2.0
([ SAS-015], Sanhaocheng Co., Ltd.)
(11) PEG-3 polydimethylsiloxane 1.0
([ EF-6015], manufactured by shin-Etsu chemical Co., Ltd.)
(12) PEG-11 methyl Ether Dimethicone 2.5
([ EF-6018], manufactured by shin-Etsu chemical Co., Ltd.)
(13) Decamethyl cyclic pentasiloxane 2.0
(14) Dimethylpolysiloxane 2.0
(15) Proper amount of p-hydroxybenzoate
(16) Proper amount of perfume
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The oil phase was dispersed sufficiently with titanium dioxide, and the water phase was added while homogenizing with a homogenizer.
(production method)
The oil and water phases were separately heated to 70 ℃ to dissolve them. The aqueous phase was dispersed sufficiently with titanium dioxide, and the oil phase was added to emulsify with a homogenizer. The emulsion was cooled with a heat exchanger.
The obtained water-in-oil type emulsified sunscreen cosmetic has no sticky or non-smooth feeling, and has refreshing feeling, no stickiness, and good feeling in use. Furthermore, no white marks remain on the skin, and makeup is easy. Further, the SPF measurement described above showed an SPF value of 40 and a PA + +.

Claims (3)

1. An oil-in-water emulsified skin cosmetic composition comprising (a) isononyl 2-ethylhexanoate and/or 2-ethylhexyl 2-ethylhexanoate, (b) one or more members selected from the group consisting of higher fatty acids and higher alcohols which are solid to semisolid at ordinary temperature, (c) a crosslinked polymer selected from the group consisting of vinylpyrrolidone/2-acrylamide-2-methylpropanesulfonic acid copolymer, dimethylacrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer, acrylamide/2-acrylamide-2-methylpropanesulfonic acid copolymer, methylenebisacrylamide-crosslinked dimethylacrylamide/2-acrylamide-2-methylpropanesulfonic acid, a mixture of polyacrylamide and sodium polyacrylate, a surfactant, a, One or more selected from sodium acrylate/2-acrylamide-2-methylpropanesulfonic acid copolymer, hydroxyethyl acrylate/2-acrylamide-2-methylpropanesulfonic acid copolymer, ammonium polyacrylate, polyacrylamide/ammonium acrylate copolymer, and acrylamide/sodium acrylate copolymer, and (d) one or more selected from nonionic surfactants having an HLB value of 9 or more, wherein the total amount of the cosmetic composition contains 1.0 to 20.0% by mass of the component (a), 0.5 to 8.0% by mass of the component (b), 0.1 to 5.0% by mass of the component (c), and 0.5 to 8.0% by mass of the component (d).
2. The oil-in-water emulsion skin cosmetic composition according to claim 1, wherein the component (d) is one or more selected from the group consisting of a polyoxyethylene adduct compound and a polyethylene glycol adduct compound.
3. The oil-in-water type emulsified skin cosmetic composition according to claim 1, wherein a nonionic surfactant having an HLB value of 9 or more and less than 15 and a nonionic surfactant having an HLB value of 15 or more are used in combination as the component (d).
HK09100236.5A 2005-11-24 2006-10-26 External preparation for skin HK1122991B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2005338363A JP4679350B2 (en) 2005-11-24 2005-11-24 Oil-in-water emulsified skin cosmetic
JP338363/2005 2005-11-24
JP338364/2005 2005-11-24
JP2005338364A JP2007145722A (en) 2005-11-24 2005-11-24 Sun-screen cosmetic
PCT/JP2006/321925 WO2007060823A1 (en) 2005-11-24 2006-10-26 External preparation for skin

Publications (2)

Publication Number Publication Date
HK1122991A1 HK1122991A1 (en) 2009-06-05
HK1122991B true HK1122991B (en) 2011-12-09

Family

ID=

Similar Documents

Publication Publication Date Title
US20110250248A1 (en) External preparation for skin
AU2009216500B2 (en) Water-in-oil emulsion type sunscreen cosmetic
JP7583083B2 (en) Water-in-oil emulsion cosmetics
KR101354795B1 (en) Water-in-oil emulsion type sunscreen preparation
CN101312706A (en) External preparation for skin
WO2010098099A1 (en) Sunscreen cosmetic
JP5083801B2 (en) Water-in-oil emulsified sunscreen cosmetics
TWI394589B (en) Water-in-oil type emulsified sunscreen cosmetic
KR101371808B1 (en) Water-in-oil emulsified sunscreen cosmetic composition
KR101595215B1 (en) Oil-in-water emulsified sunscreen cosmetic
JP5366468B2 (en) Water-in-oil emulsion composition
JP2007145722A (en) Sun-screen cosmetic
JP2021519331A (en) Methods for enhancing UVA light protection with antioxidants
JP6006101B2 (en) UV absorber containing topical skin preparation
US20130121939A1 (en) Water-in-Oil Emulsified Cosmetic
JP2010195694A (en) Powder dispersion and cosmetic containing this powder dispersion
JP7347993B2 (en) sunscreen composition
HK1122991B (en) External preparation for skin
WO2022210145A1 (en) Cosmetic
HK1126686A (en) Water-in-oil emulsified sunscreen cosmetic composition
HK1148214B (en) Water-in-oil emulsion type sunscreen cosmetic
HK1126120A1 (en) Water-in-oil emulsion type sunscreen preparation
HK1126120B (en) Water-in-oil emulsion type sunscreen preparation