CN110799173B

CN110799173B - Water-releasing type sun-proof cosmetic

Info

Publication number: CN110799173B
Application number: CN201880043041.5A
Authority: CN
Inventors: 小西将幸
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2017-06-29
Filing date: 2018-06-21
Publication date: 2023-05-12
Anticipated expiration: 2038-06-21
Also published as: CN110799173A; JP6930589B2; JPWO2019004048A1; WO2019004048A1

Abstract

Disclosed is a water-releasing sunscreen cosmetic which has excellent stability even when blended with an ultraviolet scattering agent, has high water resistance, is free from emulsion state failure during application, has good spreadability, and has excellent feel during use. A water-releasing sunscreen cosmetic composition comprising a water-in-oil emulsion comprising: (a) 1 or more than 2 selected from the group consisting of partially crosslinked polyether modified silicone and partially crosslinked polyglycerol modified silicone: 0.1 to 4 mass%, and (b) 1 or more than 2 non-crosslinked organic silicon active agents: 0.05 to 2 mass percent, (c) an aqueous component: 50 to 85% by mass, (d) a hydrophobicizing ultraviolet scattering agent having an average primary particle diameter of 200nm or less: 0.1 to 21 mass percent, (e) viscosity at 25 ℃ of 1 to 30mm ² Oil/s: 5 to 30% by mass, and the mass ratio of the component (b) to the component (d) represented by (b)/(d) is 0.05 to 0.4.

Description

Water-releasing type sun-proof cosmetic

Technical Field

The present invention relates to a water-releasing sunscreen cosmetic. In the present invention, the cosmetic composition may be referred to as a cosmetic.

Background

In the case of a sunscreen cosmetic, organic ultraviolet absorbers such as ethylhexyl methoxycinnamate are used to impart an ultraviolet protection effect, and since they have poor compatibility with silicones, stabilization of silicone-based cosmetics is difficult. Therefore, if the organic ultraviolet absorber is blended in a large amount, the feeling is also deteriorated, and there are problems such as occurrence of discoloration and odor.

In recent years, as a countermeasure against sunburn in daily life, in an oil-in-water type sunburn cosmetic which is easy to use continuously with a sense of use of water, a cosmetic which does not deteriorate the sense of occurrence of an organic ultraviolet absorber has been developed (patent document 1: japanese patent application laid-open No. 2013-91625). However, the oil-in-water type cosmetics have the following problems: low water resistance, and is easily dropped due to sweat, water, etc. exposure.

On the other hand, in order to obtain a water-in-oil type cosmetic having a moist feel, it is known to use a partially crosslinked polyether-modified silicone to prepare an emulsion having a high water content and a large particle diameter, and to obtain a cosmetic having a moist feel in use (patent document 2: japanese patent application laid-open No. 2001-2521). It is also known that by designing the emulsion particle size of such a large particle size, a water-releasing cosmetic can be produced.

Furthermore, a technique is known in which a water-in-oil type cosmetic having a high internal aqueous phase is obtained by combining an ultraviolet scattering agent and an absorber to obtain a water-moist sunscreen cosmetic (patent document 3: japanese patent application laid-open No. 2009-242294). However, since the ultraviolet scattering agent is excessively blended with the active agent, the water release feeling is not perceived, and no study has been made on the relationship between the ratio of these agents and the water wet feeling. In addition, a technique of obtaining a water-in-oil type water-releasing cosmetic containing an ultraviolet absorber is also known (patent document 4: japanese patent application laid-open No. 2011-219448). However, studies on the inclusion of ultraviolet scattering agents have not been conducted.

From the above, studies on a water-releasing sunscreen cosmetic containing an ultraviolet scattering agent, which is excellent in feel and water resistance and can impart a moist feel in use have been desired.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2013-91625

Patent document 2: japanese patent laid-open No. 2001-2521

Patent document 3: japanese patent laid-open No. 2009-242294

Patent document 4: japanese patent application laid-open No. 2011-219448

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a water-releasing sunscreen cosmetic which is excellent in stability even when an ultraviolet scattering agent is blended, has high water resistance, is free from the problem of smooth deterioration of an emulsified state at the time of application, has good spreadability, and has good feel in use. The term "water-release" refers to a phenomenon in which a water-in-oil emulsion is broken by a shearing force during application of a cosmetic, and an aqueous phase as an internal phase is ejected as water droplets.

Means for solving the problems

As a result of intensive studies to solve the problems, the present inventors have found that the above problems can be solved by using a water-releasing sunscreen cosmetic comprising a water-in-oil emulsion comprising:

(a) 1 or more than 2 selected from the group consisting of partially crosslinked polyether modified silicone and partially crosslinked polyglycerol modified silicone: 0.1 to 4 mass%,

(b) 1 or more than 2 non-crosslinking silicone active agents: 0.05 to 2 mass percent,

(c) Aqueous composition: 50 to 85 mass percent,

(d) A hydrophobicizing ultraviolet scattering agent having an average primary particle diameter of 200nm or less: 0.1 to 21 mass%,

(e) Viscosity at 25 ℃ of 1-30 mm ² Oil/s: 5 to 30 mass percent;

the mass ratio of the component (b) to the component (d) represented by (b)/(d) is 0.05 to 0.4.

Accordingly, the present invention provides the following water-releasing sunscreen cosmetics.

[1] A water-releasing sunscreen cosmetic comprises water-in-oil emulsion, which contains:

(c) Aqueous composition: 50 to 85 mass percent,

(e) Viscosity at 25 ℃ of 1-30 mm ² Oil/s: 5 to 30 mass percent;

[2] The water-releasing sunscreen cosmetic according to [1], further comprising (f) a partially crosslinked organopolysiloxane (however, excluding the above-mentioned component (a)).

[3] The water-releasing sunscreen cosmetic according to [1] or [2], wherein the component (b) is a non-crosslinked polyglycerin-modified silicone.

[4] The water-releasing sunscreen cosmetic according to any one of [1] to [3], wherein the component (d) comprises a dispersion dispersed in advance in an oil phase containing the component (b) and the component (e).

ADVANTAGEOUS EFFECTS OF INVENTION

The water-releasing sunscreen cosmetic of the present invention has excellent stability even when blended with an ultraviolet scattering agent, high water resistance, smooth break of the emulsified state at the time of application, good spreadability, and good feel in use.

Detailed Description

[ (a) component ]

The component (a) of the present invention is 1 or more selected from the group consisting of a partially crosslinked polyether-modified silicone and a partially crosslinked polyglycerol-modified silicone.

The partially crosslinked polyether-modified silicone is not particularly limited as long as it is a three-dimensional crosslinked product obtained by crosslinking an organopolysiloxane chain with polyether. As a specific example of the partially crosslinked polyether-modified silicone, for example, (dimethylpolysiloxane/(PEG-10/15)) crosslinked polymer and the like are known. These are commercially available as swellings containing silicone oil and other oils, and are commercially available under the trade names of KSG-210, 240 and the like (all manufactured by Xinyue chemical industries, ltd.). Examples of the crosslinked product having alkyl branches in the main chain (alkyl-modified partially crosslinked polyether-modified silicone) include (PEG-15/lauryl dimethylpolysiloxane) crosslinked polymer and (PEG-15/lauryl polydimethylsiloxyethyldimethylpolysiloxane) crosslinked polymer. Examples of the swelling materials containing silicone oil and other oils include KSG-310, 310Z, 330, 340, 320Z, 350Z, and 360Z (all manufactured by Xinyue chemical industries, ltd.).

The partially crosslinked polyglycerol-modified silicone is not particularly limited as long as it is a three-dimensional crosslinked product obtained by crosslinking an organopolysiloxane chain with polyglycerol. As a specific example of the partially crosslinked polyglycerol-modified silicone, a (dimethylpolysiloxane/polyglycerol-3) crosslinked polymer or the like is known. These are commercially available as swellings containing silicone oil and other oils, and are commercially available under the trade name of KSG-710 and the like (manufactured by Xinyue chemical industries, ltd.). Examples of the crosslinked product having alkyl branches in the main chain include (lauryl dimethyl polysiloxane/polyglycerin-3) crosslinked polymer and (polyglycerin-3/lauryl polydimethyl siloxyethyl dimethyl polysiloxane) crosslinked polymer. These are commercially available as swellings containing silicone oil and other oils, and are commercially available under the trade names of KSG-810, 820Z,830, 840, 850Z, etc. (all manufactured by Xinyue chemical industries, ltd.).

(a) The amount of the component (A) is 0.1 to 4% by mass, preferably 0.2 to 2% by mass, based on the whole cosmetic. If the content is less than 0.1% by mass, the emulsion stability of the cosmetic may be lowered, and if the content is more than 4% by mass, the feeling of wetness may be lost, and the feeling of use during application may be impaired.

(a) The components may be used alone or in combination of 2 or more kinds as appropriate, and for example, in the case where the relative blending ratio of the partially crosslinked polyether-modified silicone is high in the combination of the partially crosslinked polyether-modified silicone and the partially crosslinked polyglycerol-modified silicone, spreadability of the cosmetic tends to be improved, and in the case where the relative blending ratio of the partially crosslinked polyglycerol-modified silicone is high, the cosmetic tends to become a moist, soft feel in use. The blending ratio can be appropriately determined in control of the sense of use.

[ (b) component ]

The water-releasing sunscreen cosmetic of the present invention is blended with a non-crosslinked silicone active agent, particularly from the viewpoints of storage stability of the cosmetic and adjustment of feeling of use by adjustment of emulsified particle size. The silicone active agent is not particularly limited as long as it is a non-crosslinked silicone active agent that can be blended in cosmetics in general, and 1 kind may be used alone or 2 or more kinds may be used in combination as appropriate. Among these surfactants, preferred are linear or branched polyoxyethylene-modified organopolysiloxane, linear or branched polyoxyethylene-polyoxypropylene-modified organopolysiloxane, linear or branched polyglycerol-modified organopolysiloxane, linear or branched polyoxyethylene-alkyl co-modified organopolysiloxane, linear or branched polyoxyethylene-polyoxypropylene-alkyl co-modified organopolysiloxane, acrylic-silicone-based graft copolymer, and the like. Specific examples thereof include polyether-modified silicones such as KF-6011, 6013, 6043, 6017 and 6017P, silicone-branched polyether-modified silicones such as KF-6028 and 6028P, silicone-branched polyglycerin-modified silicones such as KF-6100, 6104 and 6106, acrylic-silicone-based graft copolymers such as KP-578, silicone-alkyl-branched polyether-modified silicones such as KF-6038, alkyl-branched polyether-modified silicones such as KF-6048, silicone-alkyl-branched polyglycerin-modified silicones such as KF-6105 (all manufactured by Xinyue chemical Co., ltd.).

In addition to the above-mentioned objects, these non-crosslinked silicone active agents are also used for the purpose of well dispersing the component (d). In particular, when a higher dispersing effect of the component (d) is desired, non-crosslinked polyglycerol-modified silicones are preferable, and specific examples thereof include KF-6100, 6104, 6106, KF-6105, and branched polyglycerol-modified silicones such as KF-6106, KF-6105 are particularly preferable.

(b) The amount of the component (A) is 0.05 to 2% by mass, preferably 0.2 to 1.6% by mass, more preferably 0.5 to 1.6% by mass, based on the whole cosmetic composition of the present invention. When the content is 0.05 mass% or more, the emulsion stability of the cosmetic is further improved, and when the content is 2 mass% or less, a moist feel and a good feel in use at the time of application are further obtained.

[ (c) component ]

The component (c) of the present invention is not particularly limited as long as it is an aqueous component that can be blended in a cosmetic in general. Specifically, water, moisturizers, water-soluble polymer compounds, skin-beautifying ingredients, water-soluble inorganic salts, pH adjusters, and the like can be cited. These can be used 1 kind alone or in combination of 2 or more kinds as appropriate.

The water includes, in addition to purified water, distilled water of fruits and plants, which are generally used in cosmetics, sea water, hot spring water, peat water, and the like, which are defined by the names of the expressions. When water is blended, the blending amount is preferably 5 to 85% by mass based on the component (c). If the content is less than 5% by mass, the feeling of water release is hardly felt, and if the content is more than 85% by mass, stabilization of the cosmetic may be difficult.

Examples of the humectant include lower alcohols such as ethanol and isopropanol; polyhydric alcohols such as sorbitol, maltose, xylitol and the like, and butanediol, dibutylene glycol, propylene glycol, dibutylene glycol, pentanediol, decanediol, octanediol, hexanediol, erythritol, glycerol, diglycerol, polyethylene glycol and the like; glucose, glyceryl glucoside, betaine, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, and the like. In the case of blending a humectant, the blending amount is preferably 5 to 70% by mass of the component (c). The stability of the cosmetic can be improved and the water release feeling can be regulated by the cooperation of the humectant.

Examples of the water-soluble polymer compound include natural water-soluble polymer compounds such as carrageenan, hyaluronate and xanthan gum; semisynthetic water-soluble polymer compounds such as hydroxyethyl cellulose, hydroxypropyl methylcellulose, and carboxymethyl cellulose; synthesizing water-soluble high molecular compounds from polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer and the like; and inorganic water-soluble polymer compounds such as bentonite and hectorite. When the water-soluble polymer compound is blended, the blending amount is preferably 0.01 to 1% by mass based on the component (c). The stability of the cosmetic can be improved and the water release feeling can be adjusted by compounding the water-soluble polymer compound.

Examples of the skin-beautifying ingredient include whitening agents such as arbutin, ascorbic acid and derivatives thereof; anti-inflammatory agents such as allantoin and glycyrrhetate; blood circulation promoters such as benzyl nicotinate, and the like.

Examples of the water-soluble inorganic salts include sodium chloride, magnesium sulfate, sodium hydroxide, potassium hydroxide, arginine, citric acid, sodium citrate, lactic acid, and glycolic acid, and pH adjusters.

(c) The amount of the component (A) is 50 to 85% by mass, preferably 55 to 85% by mass, more preferably 60 to 85% by mass, based on the whole cosmetic composition of the present invention.

[ (d) component ]

The ultraviolet scattering agent used as the raw material of the component (d) of the present invention is not particularly limited as long as it is a raw material that can be blended in cosmetics in general. Specifically, the metal oxide is 1 or 2 or more selected from titanium oxide, zinc oxide and cerium oxide. The metal oxide may be a composite powder of 2 or more kinds of titanium oxide, zinc oxide, and cerium oxide, or may be a composite powder with other powder. The average primary particle diameter is 200nm or less, preferably 150nm or less. If the particle diameter is larger than 200nm, the ultraviolet ray protection function is lowered and white remains. The lower limit is not particularly limited, and may be set to 10nm. The average primary particle diameter of the powder used as the ultraviolet scattering agent defined in the present invention is an average value of 20 particles obtained by using a transmission electron micrograph. When the powder is not spherical, the average value of the long diameters of the particles is taken as the average primary particle diameter.

The component (d) of the present invention is a hydrophobicized ultraviolet scattering agent. The hydrophobizing treatment is not particularly limited as long as it is a known surface treatment generally used in cosmetics. Examples of the inorganic treating agent include a silica coating, an alumina coating, and an aluminum hydroxide coating.

Examples of the organic treating agent include silicone oils such as silanes such as octylsilane (manufactured by Xinyue chemical industries, inc.: AES-3083), silylating agents, dimethyl silicones (manufactured by Xinyue chemical industries, inc.: KF-96A series), methyl hydrogen polysiloxanes (manufactured by Xinyue chemical industries, inc.: KF-99P, KF-9901, etc.), and silicone branched silicone treating agents (manufactured by Xinyue chemical industries, inc.: KF-9908, KF-9909, etc.); waxes; organofluorine compounds such as paraffin wax and perfluoroalkyl phosphate; a surfactant; amino acids such as N-acyl glutamic acid, metal soaps such as aluminum stearate and magnesium myristate, and the like. In particular, KF-9909 (manufactured by Xinyue chemical industries, ltd.) shows high dispersibility for oil agents such as silicone oil and ester oil, and is therefore used for sunscreens and foundations. These surface treatments may be used in combination of 1 kind or 2 or more kinds depending on the purpose, and all of inorganic and inorganic, organic and organic, inorganic and organic, and the like may be used.

The ultraviolet scattering agent subjected to such surface treatment may be commercially available. For example, for particulate titanium oxide, MT-01, 05, 100Z,100TV,100AQ,100WP,150EX,505SAS, 014Z, SMT-500SAS (manufactured by TAYCA), ST-455, 45 WS,457ECS,495M (manufactured by titanium industry), TTO-S1, S4, 51 (C), 55 (A), 55

(C) Trade names such as 80 (A) (manufactured by Shi Yuan Co., ltd.). As the particulate zinc oxide, trade names such as MZ-306X,500HP,505T,506X, MZY-203S,303S,210M3S, TMZ-HA1, MZX-3040TS,508OTS (manufactured by TAYCA), FINEX-50S-LP2, FINEX-30S-LP2, FINEX-50W, FINEX-33W-LP2, FINEX-25-LPT (manufactured by Shewanella chemical Co., ltd.) are commercially available.

(d) The amount of the component (A) to be blended is 0.1 to 21% by mass, preferably 1 to 18% by mass, more preferably 3 to 15% by mass, based on the total amount of the cosmetic composition, from the viewpoints of usability and shielding properties. If the amount is less than 0.1 mass%, a sufficient ultraviolet shielding effect cannot be obtained, and if the amount exceeds 21 mass%, the ductility in use may be deteriorated, and a water release feeling may not be obtained.

The mass ratio of the component (b) to the component (d) represented by (b)/(d) is 0.05 to 0.4, preferably 0.07 to 0.35, more preferably 0.08 to 0.3. If the content is less than 0.05, the stability and spreadability are deteriorated, and if the content exceeds 0.4, the feeling of water release is not obtained.

The component (d) may be blended as a dispersion dispersed in advance in an oil phase containing the component (b) and the component (e). Commercially available products may be used as the dispersion, and specifically SPD-T5, T6, T5L, Z5, Z6, Z5L, etc. (all manufactured by Xinyue chemical industries, ltd.) and the like are mentioned.

[ (e) component ]

Viscosity at 25 ℃ of 1-30 mm ² The oil of/s is generally one that can be convertedThe raw materials to be blended in the cosmetic are not particularly limited. Specifically, silicone oil, ester oil, and hydrocarbon oil can be used, and 1 can be used alone or 2 or more can be used in combination as appropriate.

The silicone oil is not particularly limited as long as it is a raw material that can be blended in a cosmetic in general, and specifically, dimethylpolysiloxane is exemplified; cyclopentasiloxane (decamethyl cyclopentasiloxane); a cyclohexasiloxane; disiloxane; trisiloxane; methyl trimethyl polysiloxane; octyl methyl polysiloxane; diphenyl dimethyl polysiloxane; methylphenyl polysiloxanes such as diphenylsiloxyphenyl trimethylpolysiloxane; methyl hexyl polysiloxane; methyl hydrogen polysiloxane; dimethylsiloxane-methylphenylsiloxane copolymers, and the like. Of these, volatile silicones that give a pleasant feel in use are preferred [ as a commercial product, manufactured by the shin-Equipped chemical industry Co., ltd.: TMF-1.5, KF-995, KF-96A-1cs, KF-96A-1.5cs, KF-96A-2cs, etc. ], low-viscosity silicone [ as a commercially available product, manufactured by Xinyue chemical industries, ltd.: KF-96A-6cs, etc.), a phenyl silicone used for the purpose of improving compatibility with other oils [ commercially available product, manufactured by the shiny chemical industry (ltd.): KF-56A ], and the like. These silicone oils can be used in an amount of 1 or 2 or more.

Examples of the other oils include cetyl ethylhexanoate, glyceryl triisooctanoate, glyceryl tri (caprylate/caprate), isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, dioctyl ether, isopropyl myristate, ethylhexyl palmitate, diethyl hexyl carbonate, dioctyl carbonate, alkyl (C12-15) benzoate, neopentyl glycol diethylhexanoate, propylene glycol dicaprate, diisopropyl sebacate, diethyl sebacate, diisopropyl adipate, mineral oil, squalane, light-weight isoparaffin, undecane, and the like.

(e) The viscosity of the components is 1-30 mm at 25 DEG C ² Preferably 1 to 25mm ² And/s, more preferably 1 to 20mm ² And/s. In the present invention, the kinematic viscosity is a measured value at 25℃obtained by using an Ostwald viscometer. Sometimes will be mm ² The/s is denoted cs.

(e) The amount of the component (A) is 5 to 30% by mass, preferably 8 to 27% by mass, more preferably 10 to 25% by mass of the total cosmetic.

[ (f) component ]

In the water-releasing sunscreen cosmetic of the present invention, it is preferable to blend a partially crosslinked organopolysiloxane (however, the component (a) is not included) in view of stability of the cosmetic and improvement of feel in use. The component (f) is not particularly limited as long as it is a partially crosslinked organopolysiloxane that can be usually blended in cosmetics, and 1 kind of the organopolysiloxane can be used alone or 2 kinds or more of the organopolysiloxanes can be used in combination as appropriate. (f) The component (a) is a compound having no polyether or polyglycerin structure in its molecular structure, unlike the component (a), and is an elastomer having structural tackiness by swelling an oil agent. Specific examples include (dimethylpolysiloxane/vinyldimethylpolysiloxane) crosslinked polymer, (vinyldimethylpolysiloxane/lauryldimethylpolysiloxane) crosslinked polymer, (laurylpolydimethylsiloxyethyldimethylpolysiloxane/divinyldimethylpolysiloxane) crosslinked polymer, and (dimethylpolysiloxane/phenylvinyldimethylpolysiloxane) crosslinked polymer. Examples of the swellings containing silicone oil and other oils include KSG-15, 1510, 16, 15AP, 19, 41A, 42A, 43, 44, 042Z, 045Z, 048Z, and 18A (all manufactured by Xinyue chemical industries, ltd.).

In the case of blending the component (f), the blending amount of the component (f) is preferably 0.1 to 4% by mass, more preferably 0.2 to 2% by mass of the whole cosmetic of the present invention. When the content is 0.1% by mass or more, the emulsion stability of the cosmetic is further improved, and when the content is 4% by mass or less, the feeling of water release is more easily perceived, and the feeling of use at the time of application is improved.

The cosmetic of the present invention may contain various components commonly used in cosmetics within a range that does not impair the effects of the present invention. The component (c) may include, for example, an oil agent other than the component (1) (e), a powder other than the component (2) (d), an oil-soluble gelling agent (3), a film-forming agent (4), a surfactant other than the components (5) (a) and (b), an ultraviolet absorber (6), and any other component (7). These can be used 1 kind alone or in combination of 2 or more kinds as appropriate. These components are appropriately selected and used according to the type of cosmetic, etc., and the blending amount is also appropriately selected from known blending amounts according to the type of cosmetic, etc.

(1) Oil agent other than component (e)

As the oil agent, solid, semisolid and liquid at room temperature can be used, for example, a viscosity ratio of 30mm at 25℃can be used ² Silicone oils with a large/s content, natural animal and vegetable oils and fats, semisynthetic oils and fats, hydrocarbon oils such as heavy mobile isoparaffins, fatty acids, ester oils with a medium viscosity or higher, fluorine-based oils, and the like can be blended appropriately for the purpose of adjusting the feel in use. In the case of blending the oil, the blending amount of the oil is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass of the whole cosmetic.

The silicone oil is not particularly limited as long as it is a raw material that can be blended in a cosmetic in general, and specifically includes linear or branched organopolysiloxanes having a viscosity ranging from high viscosity to high viscosity, such as dimethylpolysiloxane methyl hydrogen polysiloxane and dimethylsiloxane-methylphenylsiloxane copolymer, amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxane, pyrrolidone carboxylic acid-modified organopolysiloxane, gum (gum) like dimethylpolysiloxanes having a high degree of polymerization, gummy amino-modified organopolysiloxane, gummy dimethylsiloxane-methylphenylsiloxane copolymer and other silicone rubbers, and higher alkoxy-modified silicones such as silicone gums and rubber cyclic silicone solutions, stearoxy silicones, higher fatty acid-modified silicones, alkyl-modified silicones, long chain alkyl-modified silicones, amino acid-modified silicones, fluorine-modified silicones and the like. Of these, highly polymerized phenyl silicones [ commercially available from the company 54HV, etc. ] used for the purpose of polishing, and silicone waxes [ commercially available from the company of the more) which can be suitably used for the purpose of polishing and feel adjustment are more preferable: KP-561P, 562P, KF-7020S, etc ].

(2) Powder other than component (d)

Powder other than the component (d) can be blended as long as the effect of the present invention is not significantly impaired. The powder other than the component (d) used in the present invention is not particularly limited as long as it is a raw material that can be blended in a cosmetic in general. For example, silicone spherical powder, pigment, or the like can be used.

Examples of the silicone spherical powder include crosslinked silicone spherical powder (i.e., so-called silicone rubber powder composed of organopolysiloxane having a structure in which chains of diorganosiloxane repeating units are crosslinked), silicone resin particles (polyorganosiloxane resin particles having a three-dimensional network structure), and the like, and specific examples thereof include (dimethylpolysiloxane/vinyldimethylpolysiloxane) crosslinked polymer, polymethylsilsesquioxane, and the like. These are commercially available as spherical powders, for example, under the trade names of KMP-598, 590, 591, etc., and as swellings containing silicone oil, etc., under the trade names of KSG-016F, etc. (all manufactured by Xinyue chemical industries, ltd.).

In particular, silicone resin-coated silicone rubber powder can be suitably used for the purpose of imparting an effect of improving feel such as prevention of stickiness, and a morphological repair effect of wrinkles, pores, and the like. Specific examples of silicone resin-coated silicone rubber powder include (vinyl dimethylpolysiloxane/methylpolysiloxane silsesquioxane) crosslinked polymer, (diphenyldimethylpolysiloxane/vinyl diphenyldimethylpolysiloxane/silsesquioxane) crosslinked polymer, polyorganosiloxane-22, and polyorganosiloxane-1 crosslinked polymer, which are defined by the names of expression. These are commercially available under the trade names of KSP-100, 101, 102, 105, 300, 411, 441, etc. (all manufactured by Xinyue chemical industries, inc.).

The pigment is not particularly limited as long as it is a pigment generally used in make-up cosmetics. Examples thereof include inorganic pigments such as talc, mica, kaolin, silica, calcium carbonate, zinc oxide, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, cyanosis, carbon black, titanium suboxide, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, bismuth oxychloride, and titanium-mica-based pearl pigment; organic pigments such as zirconium, barium, or aluminum lakes, e.g., red No. 201, red No. 202, red No. 204, red No. 205, red No. 220, red No. 226, red No. 228, red No. 405, orange No. 203, yellow No. 205, yellow No. 4, yellow No. 5, cyan No. 1, cyan No. 404, and green No. 3; natural pigments such as chlorophyll and beta-carotene; dyes, and the like. It is possible to use products of which surface treatment is performed with silicone or the like. As a specific example of the colored pigment subjected to the silicone treatment, those sold under the trade names of KTP-09W, 09R, 09Y, 09B (all manufactured by Xinyue chemical industries, ltd.) and the like are available. In the cosmetic of the present invention, the pigment having an average primary particle diameter exceeding 200nm may be blended in an amount of preferably 0.5 to 15% by mass based on the whole cosmetic within a range not impairing the effect of the present invention.

(3) Oil-soluble gelling agent

The oil-soluble gelling agent is not particularly limited as long as it is a raw material that can be blended in cosmetics in general, and examples thereof include waxes, sugar fatty acid esters, and higher alcohols.

Examples of the waxes include synthetic hydrocarbon waxes such as ceresin, microcrystalline wax, and polyethylene wax; waxes derived from plants such as carnauba wax and candelilla wax; waxes derived from animals such as beeswax.

Examples of the sugar fatty acid ester include dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate.

Examples of the higher alcohol include alcohols having 14 to 22 carbon atoms. Examples of the clay mineral include disteardimonium hectorite, sela hectorite, and organomodified clay minerals of hectorite.

(4) Coating agent

The coating agent is not particularly limited as long as it is a raw material that can be blended in cosmetics in general, and specifically includes latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and polyalkyl acrylate, and cellulose derivatives such as dextrin, alkyl cellulose, and nitrocellulose; organosilicon polysaccharide compounds such as tris (trimethylsilyloxy) silylpropyl carbamate pullulan; organosilicon polyvinyl alcohol such as tris (trimethylsiloxy) silylpropyl carbamate (butylene glycol/vinyl alcohol) copolymer; acrylic-silicone graft copolymers such as (alkyl acrylate/dimethylpolysiloxane) copolymers; silicone resins such as trimethylsiloxysilicic acid; silicone-based resins such as silicone-modified polynorbornene and fluorine-modified silicone resins; a fluororesin; an aromatic hydrocarbon resin; a polymer emulsion resin; terpene-based resins; polybutene; a polyisoprene; alkyd resin; polyvinylpyrrolidone-modified polymers; rosin-modified resin; polyurethane, and the like.

Among these, silicone-based coating agents are preferable from the viewpoint of improving water resistance and makeup-holding properties, and among them, tris (trimethylsiloxy) silylpropyl pullulan [ as a commercial product, as a product dissolved in a solvent, manufactured by the believed chemical industry (ltd.): TSPL-30-D5, ID ], (alkyl acrylate/dimethylpolysiloxane) copolymer [ as a commercially available product, as a product dissolved in a solvent, manufactured by Xinyue chemical industries, ltd.: KP-543, 545, 549, 550, 545L, etc. ], trimethylsiloxysilicic acid [ commercially available as a solvent-soluble product, manufactured by the industrial singer chemical industry (ltd.): KF-7312, J, X-21-5250, etc. ], silicone-modified polynorbornene [ as a commercially available product, as a product dissolved in a solvent, manufactured by Xinyue chemical industries, inc.: NBN-30-ID, etc. ], etc., but not limited thereto.

(5) Surface active agent

Surfactants other than the above components (a) and (b) can be used. The surfactant is not particularly limited, and nonionic, anionic, cationic and amphoteric surfactants may be used. The present invention can be used in a usual cosmetic material without impairing the effect of the present invention.

(6) Ultraviolet absorber

The ultraviolet absorber is not particularly limited as long as it is a raw material that can be blended in cosmetics in general. In particular, the method comprises the steps of, examples thereof include trimethylcyclohexyl salicylate, octocrylene, 4-tert-butyl-4' -methoxydibenzoylmethane, 4- (2-. Beta. -glucopyranosylsiloxy) propoxy-2-hydroxybenzophenone, octyl salicylate, 2- [4- (diethylamino) -2-hydroxybenzoyl ] hexyl benzoate, dihydroxydimethoxybenzophenone, sodium dihydroxydimethoxybenzophenone disulfonate, dihydroxybenzophenone, dimethylpolysiloxane diethylbenzylidene malonate, 1- (3, 4-dimethoxyphenyl) -4, 4-dimethyl-1, 3-pentanedione, dimethoxybenzylidene dioxoimidazolidine propionate 2-ethylhexyl tetrahydroxybenzophenone, terephthal-xylylene-dicarbasylic acid, 2,4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino ] -1,3, 5-triazine, methyl bis (trimethylsiloxy) silylisopyranate trimethoxycinnamate, cresyl trisiloxane, 2-ethylhexyl p-dimethylaminobenzoate, isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, 2, 4-bis- [ {4- (2-ethylhexyloxy) -2-hydroxy } -phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate salts, sodium hydroxymoxybenzophenone sulfonate, phenylbenzimidazole sulfonic acid, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ], and the like. In addition, a UVA absorber (e.g., hexyl diethylaminohydroxybenzoate, etc.) and a UVB absorber (e.g., ethylhexyl methoxycinnamate, etc.) may be used in combination, or each may be optionally combined.

(7) Other optional ingredients

Examples of the other additives include oil-soluble preservatives, bactericides, anti-inflammatory agents, fragrances, and the like.

As the emulsified form of the water-in-oil emulsion, any form of the W/O emulsion and the O/W/O emulsion may be used. The water-releasing sunscreen cosmetic gives a sense of use that the internal aqueous phase pops up when applied to the skin.

The sunscreen cosmetic of the present invention is not particularly limited as long as it contains essential components, and can be applied to, for example, products to which a sunscreen effect is imparted, such as a cosmetic liquid, an emulsion, a cream, a massage cream, a skin care liquid, a hair care product, a foundation, a make-up base, a concealer, a fragrance, a blush, a lipstick, an eyeliner, and a body cosmetic. The cosmetic of the present invention may be in the form of a liquid, a cream, a solid, a gel, a thread, a stick, or the like.

[ method of production ]

The water-releasing sunscreen cosmetic of the present invention can be produced by a known method, and can be produced by a method comprising: the oil phase composition and the water phase composition containing the above components were mixed and emulsified by a blade, a Disper, and a homogenizer.

Examples

The present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, the amount of the compound represents mass, and the ratio represents mass ratio.

Examples 1 to 6 and comparative examples 1 to 8

The water-in-oil type cosmetics of the formulations shown in tables 2, 3, and 4 were prepared by the following methods, and the following characteristic evaluations were performed.

Preparation of cosmetics: examples 1 to 4 and comparative examples 1 to 8 >, respectively

A: component (1) was uniformly mixed.

B: component (3) was uniformly mixed.

C: for component (2), a paint shaker was used to prepare a (median diameter 1.5 mm) slurry.

D: and (3) adding the B into the A for emulsification, and adding the C to obtain the water-release type sun-screening cosmetic.

Preparation of cosmetics: example 5, 6 >

A: the component (2) was dispersed by a triple roll.

B: component (1) was uniformly mixed.

C: component (3) was uniformly mixed.

D: and C is added into B for emulsification, and A is added to obtain the water-release type sun-screening cosmetic.

(1) Stability of cosmetic materials

After the cosmetic was stored in a constant temperature bath at 50 ℃ for 1 month, the properties were visually observed and applied to the skin to examine the feel. As a result, the cosmetic that does not have problems such as separation and change in feel is referred to as "excellent", and the cosmetic that has problems is referred to as "x".

(2) Evaluation of Properties

For the cosmetics, 10 panelists were used to evaluate the items of water release feeling (collapse of water droplets), spreadability (extensibility), feel in use (no stickiness), water resistance (falling property due to sweat). The evaluation was performed according to the evaluation criteria shown in table 1, and the results were judged according to the following judgment criteria based on the average value of 10. The results are shown in tables 2 to 4.

TABLE 1

Decision criterion

And (3) the following materials: average division into more than 4.5 minutes

O: the average division is more than 3.5 minutes and less than 4.5 minutes

Delta: the average division is more than 2.5 and less than 3.5

X: the average division is more than 1.5 and less than 2.5

X×: average division into less than 1.5 minutes

Examples 1 to 4 and comparative examples 1 to 8

TABLE 2

(note 1) a partially crosslinked polyether modified silicone composition; KSG-210 < crosslinker: about 25%, dimethylpolysiloxane (6 cs): about 75% > (Xinyue chemical industry Co., ltd.)

(note 2) polyether modified silicone; KF-6017 (Xinyue chemical industry Co., ltd.)

(note 3) a partially crosslinked dimethylpolysiloxane composition; KSG-15 < crosslinker: about 7%, cyclopentasiloxane: about 93% > (Xinyue chemical industry Co., ltd.)

(note 4) organosilicon branched polyglycerol modified organosilicon; KF-6106 (Xinyue chemical industry Co., ltd.)

In the case of compounding a composition, the amount to be compounded is the compounding amount of the composition (the same applies hereinafter).

TABLE 3

Examples 5 and 6

TABLE 4

(note 1) alkyl-modified-partially crosslinked polyether-modified silicone composition; KSG-330 < crosslinker: about 20%, glyceryl triisooctanoate: about 80% > (Xinyue chemical industry Co., ltd.)

(note 2) organosilicon-alkyl branched polyether modified organosilicon; KF-6038 Xinyue chemical industry Co., ltd

(note 3) a partially crosslinked dimethylpolysiloxane composition; KSG-16 < crosslinker: about 25%, dimethylpolysiloxane (6 cs): about 75% > (Xinyue chemical industry Co., ltd.)

(note 4) organosilicon-alkyl branched polyglycerol modified organosilicon; KF-6105 (Xinyue chemical industry Co., ltd.)

(note 5) organosilicon treatment of titanium oxide; KTP-09W < average primary particle diameter: greater than 200nm (Xinyue chemical industry Co., ltd.)

(note 6) organosilicon treatment of ferric oxide; KTP-09R, 09Y, 09B < average primary particle diameter: greater than 200nm (Xinyue chemical industry Co., ltd.)

From the results of tables 2 and 4, it is clear that the water-releasing sunscreen cosmetics of examples 1 to 6 were excellent in stability (50 ℃ C. For 1 month), water-releasing feel (collapse of water droplets), spreadability (spreadability), feel in use (no tackiness), and water resistance (resistance to falling by sweat). From the results of table 4, it is found that example 5 in which the component (b) as the dispersant was a non-crosslinked polyglycerol-modified silicone further exhibited a water release feeling.

Comparative example 1, in which the component (a) of the present invention was not blended, was poor in stability because of poor emulsification state. In comparative examples 3 and 4 in which the amount of component (b) blended was large and comparative example 6 in which (b)/(d) exceeded 0.4, no feeling of water release was felt, and in comparative example 7 in which (b)/(d) was less than 0.05, stability and spreadability were poor. In comparative example 5 in which the amount of component (c) blended was small and comparative example 8 in which an ultraviolet scattering agent which had not been subjected to hydrophobization treatment was used instead of component (d), satisfactory characteristics were not obtained. Further, as is clear from the results of comparative example 2, a small amount of the component (b) contributes to an improvement in stability.

Example 7

Sun cream

< preparation of cosmetic >)

A: the components 1 to 7 were uniformly mixed.

B: the components 9 to 14 were uniformly mixed.

C: adding B into A for emulsification, and adding component 8 to obtain sunscreen cream.

(b)/(d)：0.11

(note 2) organosilicon-alkyl branched polyether modified organosilicon; KF-6038 (Xinyue chemical industry Co., ltd.)

(note 3) alkyl-modified-partially crosslinked dimethylpolysiloxane composition; KSG-43 < crosslinker: about 30%, glyceryl triisooctanoate: about 70% > (Xinyue chemical industry Co., ltd.)

(note 4) diphenylsiloxyphenyl trimethicone; KF-56A (manufactured by Xinyue chemical industry Co., ltd.)

(note 5) silicone treatment of the particulate zinc oxide dispersion; SPD-Z5 (organosilicon treated particulate Zinc oxide 60%) (manufactured by Xinyue chemical industry Co., ltd.)

The obtained sunscreen cream was confirmed to have good water release feel, feel in use, spreadability, storage stability and water resistance.

Example 8

Sun cream

< preparation of cosmetic >)

A: the components 1 to 7 were uniformly mixed.

B: the components 9 to 15 were uniformly mixed.

C: and (3) adding the B into the A for emulsification, and adding the 8 to obtain the sun cream.

(b)/(d)：0.3

(note 1) alkyl-modified-partially crosslinked polyglycerol-modified silicone composition; KSG-830 < crosslinker: about 20%, glyceryl triisooctanoate: about 80% > (Xinyue chemical industry Co., ltd.)

(note 2) organosilicon-alkyl branched polyglycerol modified organosilicon; KF-6105 (Xinyue chemical industry Co., ltd.)

(note 3) a silicone-alkyl modified partially crosslinked dimethylpolysiloxane composition; KSG-045Z < crosslinker: about 20%, cyclopentasiloxane: about 80% > (Xinyue chemical industry Co., ltd.)

(note 5) organosilicon composite powder; KSP-105 (Xinyue chemical industry Co., ltd.)

(note 6) treating the particulate titanium oxide dispersion with a metal soap; SPD-T5 (Metal soap treated particulate titanium oxide 40%) (manufactured by Xinyue chemical industry Co., ltd.)

Example 9

Foundation stick

< preparation of cosmetic >)

A: the components 9 to 12 were dispersed with a triple roll.

B: the components 1 to 8 were heated to 95℃and mixed homogeneously.

C: the components 13 to 16 and A were uniformly mixed and heated to 85 ℃.

D: c is added into B for emulsification, and after filling into a rod-shaped container, the mixture is slowly cooled to obtain a foundation rod.

(b)/(d)：0.27

(note 1) a partially crosslinked polyglycerol-modified silicone composition; KSG-710 < crosslinker: about 25%, dimethylpolysiloxane (6 cs): about 75% > (Xinyue chemical industry Co., ltd.)

(note 3) inulin stearate; one end ISK2 (manufactured by Qianye powder Co., ltd.)

(note 5) polymethylsilsesquioxane; KMP-590 (manufactured by Xinyue chemical industry Co., ltd.)

(note 6) organosilicon-alkyl branched polyglycerol modified organosilicon; KF-6105 (Xinyue chemical industry Co., ltd.)

(note 7) treating the titanium oxide with a silicone; KF-99P (manufactured by Xinyue chemical industries, ltd.) was compared with the average primary particle diameter: organosilicon-treated titanium with hydrophobized surface treatment for 200 nm-sized powder

(note 8) organosilicon treating of iron oxide; KTP-09R, 09Y, 09B < average primary particle diameter: 200nm great (Xinyue chemical industry Co., ltd.)

The obtained foundation bar was confirmed to have good water release feel, feel in use, spreadability, and excellent storage stability and water resistance.

Example 10

BB cream

< preparation of cosmetic >)

A: the components 9 to 14 were dispersed with a triple roll.

B: the components 1 to 8 and A were uniformly mixed.

C: the components 15 to 20 were uniformly mixed.

D: adding C into B for emulsification to obtain BB cream.

(b)/(d)：0.12

(note 3) a phenyl-modified-partially crosslinked dimethylpolysiloxane composition; KSG-18A < crosslinker: about 15%, diphenylsiloxyphenyl trimethicone: about 85% > (Xinyue chemical industry Co., ltd.)

(note 5) a trimethylsiloxysilicate solution; KF-7312J (Xinyue chemical industry Co., ltd.)

(note 6) an acrylic-silicone graft copolymer; KP-578 (Xinyue chemical industry Co., ltd.)

(note 7) organosilicon treating titanium oxide; KTP-09W < average primary particle diameter: greater than 200nm (Xinyue chemical industry Co., ltd.)

(note 8) organosilicon treating of iron oxide; KTP-09R, 09Y, 09B < average primary particle diameter: greater than 200nm (Xinyue chemical industry Co., ltd.)

The obtained BB cream was confirmed to have good water release feel, use feel, spreadability, storage stability and water resistance.

Example 11

Base cream

< preparation of cosmetic >)

A: the components 8 to 11 were dispersed with a triple roll.

B: the components 1 to 7 and A were uniformly mixed.

C: the components 12 to 17 were uniformly mixed.

D: and C is added into B for emulsification, and base cream is obtained.

(b)/(d)：0.08

(note 1) a partially crosslinked polyether modified silicone composition; KSG-210 < crosslinker: about 25%, dimethylpolysiloxane: about 75% > (Xinyue chemical industry Co., ltd.)

(note 2) silicone branched polyether modified silicone; KF-6028 (Xinyue chemical industry Co., ltd.)

(note 3) a partially crosslinked dimethylpolysiloxane composition; KSG-19 < crosslinker: about 15%, dimethylpolysiloxane: about 85% > (Xinyue chemical industry Co., ltd.)

(note 4) methyltrimethylpolysiloxane; TMF-1.5 (manufactured by Xinyue chemical industries, ltd.)

(injection 5) acrylic-silicone graft copolymer solution; KP-549 < polymer: 40% of methyltrimethylpolysiloxane: 60% > (Xinyue chemical industry Co., ltd.)

(note 6) phenyl modified organosilicon composite powder; KSP-300 (Xinyue chemical industry Co., ltd.)

(note 7) organosilicon branched polyglycerol modified organosilicon; KF-6106 (Xinyue chemical industry Co., ltd.)

The obtained base cream was confirmed to have good water release feel, feel in use, spreadability, storage stability and water resistance.

Example 12

Sun cream

< preparation of cosmetic >)

A: the components 6 to 8 were dispersed with a triple roll.

B: the components 1 to 5 are uniformly mixed at 85 ℃, 9 and A are added and uniformly mixed.

C: the components 10 to 15 were uniformly mixed.

D: and C is added into B for emulsification, and the sun cream is obtained.

(b)/(d)：0.1

(note 2) organosilicon branched polyglycerol modified organosilicon; KF-6106 (Xinyue chemical industry Co., ltd.)

(note 3) a palmitic acid dextrin; one end TL2 (manufactured by Qianye powder Co., ltd.)

(note 4) alkyl modified organosilicon composite powder; KSP-441 (Xinyue chemical industry Co., ltd.)

Example 13

Sun cream

< preparation of cosmetic >)

A: the components 8 to 10 are dispersed by a bead mill.

B: the components 1 to 7 were uniformly mixed, and the component A and the component 11 were added and uniformly mixed.

C: the components 12 to 17 were uniformly mixed.

D: and C is added into B for emulsification, and the sun cream is obtained.

/>

(b)/(d)：0.07

(note 3) polymethylsilsesquioxane; KMP-591 (manufactured by Xinyue chemical industry Co., ltd.)

Claims

1. A water-releasing sunscreen cosmetic comprising a water-in-oil emulsion comprising:

(b) A linear or branched non-crosslinked silicone active agent selected from 1 or more of polyoxyethylene modified organopolysiloxane, polyoxyethylene polyoxypropylene modified organopolysiloxane, polyglycerol modified organopolysiloxane, polyoxyethylene-alkyl co-modified organopolysiloxane, and polyoxyethylene polyoxypropylene-alkyl co-modified organopolysiloxane: 0.05 to 2 mass percent,

(c) Aqueous composition: 50 to 85 mass percent,

(d) A hydrophobicizing ultraviolet scattering agent having an average primary particle diameter of 200nm or less: 0.1 to 21 mass%, and

(e) Viscosity at 25 ℃ of 1-30 mm ² Oil/s: 5 to 30 mass percent,

(b) The mass ratio of the component (b) to the component (d) represented by/(d) is 0.05 to 0.4.

2. The water-releasing sunscreen cosmetic according to claim 1, further comprising (f) a partially crosslinked organopolysiloxane excluding the component (a).

3. The water-releasing sunscreen cosmetic according to claim 1 or 2, wherein the component (b) is a non-crosslinked polyglycerol-modified silicone.

4. The water-releasing sunscreen cosmetic according to claim 1 or 2, wherein the composition comprises a dispersion of component (d) dispersed in advance in an oil phase containing component (b) and component (e).