JP7309373B2 - Water-in-oil emulsion composition - Google Patents

Description

The present invention relates to a water-in-oil emulsified composition containing a high concentration of nicotinic acid amide, more specifically, a polar oil having an IOB of 0.1 to 0.6, a volatile silicone oil having a viscosity at 25°C of Combined use of a non-volatile silicone oil with a viscosity of 6 to 100 mPa·s and a partially crosslinked emulsifying silicone elastomer results in an oil that is excellent in no precipitation of nicotinic acid amide, has good emulsification stability, and a non-sticky feeling when used. The present invention relates to medium-water emulsion compositions.

The skin develops spots, wrinkles, sagging, pigmentation, etc. due to internal factors such as aging and stress, and external factors such as ultraviolet rays and dry air. Above all, morphological changes such as wrinkles and sagging greatly affect the impression of appearance, and many people desire improvement. Many drugs have been proposed to prevent and improve such wrinkles and sagging. Among these, nicotinic acid amide is known to be highly safe and to have an anti-aging effect on the skin (see, for example, Patent Document 1). However, when nicotinic acid amide is blended at a high concentration, there is a problem that it leads to an unfavorable feeling of use such as stickiness. In order to solve this problem, various studies have been made so far to improve the feeling of use while blending nicotinamide at a high concentration.

A technique for reducing stickiness by combining nicotinic acid amide with a specific branched-chain hydrocarbon oil and ester oil to form an oil-in-water emulsion has been proposed (see, for example, Patent Document 2). In addition, nicotinic acid amide, a solid oil having a melting point of 40 ° C. or higher, methylphenylpolysiloxane and dimethylpolysiloxane having a specific viscosity are combined to create an oil-in-water cosmetic that has a good feel without stickiness or oiliness (for example, See Patent Document 3), and an oil-in-water cosmetic composition that combines nicotinic acid amide with a water-soluble film-forming polymer, polyoxyethylene methyl glucoside, and polyethylene glycol having a specific molecular weight. (See Patent Document 4, for example). Furthermore, as a water-in-oil emulsion composition, a non-sticky water-in-oil emulsion has been proposed in which nicotinamide is combined with specific amounts of a non-emulsifying crosslinked siloxane elastomer, an emulsifying crosslinked siloxane elastomer, and an emulsifier. (See Patent Document 5, for example).

JP-A-10-130135 Japanese Patent Publication No. 2003-502435 Japanese Patent Application Laid-Open No. 2004-300105 Japanese Patent Application Laid-Open No. 2004-300106 Japanese translation of PCT publication No. 2009-517478

However, although the techniques of Patent Documents 2 to 4 can suppress the stickiness caused by nicotinic acid amide, the emollient effect of the oil agent is poor and the moisturizing feeling is poor. On the other hand, the technique of Patent Document 5, in which nicotinic acid amide is blended in a water-in-oil emulsion composition, has an excellent emollient effect due to the high blending of an oil agent, and also has an excellent non-sticky feel.
Therefore, the present inventors investigated the inclusion of nicotinamide in a water-in-oil emulsified composition, and found that, although nicotinamide is highly soluble in water, the water content is sometimes low. In a water-in-oil emulsion composition that contains a large amount of water-in-oil emulsion composition, if it is blended at a high concentration of 1% by mass or more, it is likely to precipitate over time, especially under a high-temperature and low-temperature temperature cycle, and a new problem arises that the emulsion stability is significantly reduced. rice field.
That is, no water-in-oil type emulsified composition has been found that ensures no precipitation of nicotinic acid amide, ensures emulsion stability, and is excellent in no sticky feeling.

In view of such circumstances, the present inventors have made intensive studies to solve the above problems, and as a result, found that in a water-in-oil emulsified composition containing nicotinamide at a high concentration of 1 to 10% by mass, IOB is Unexpectedly, it was found that when a 0.1 to 0.6 polar oil agent was blended, the effect of suppressing crystal precipitation in the aqueous phase of nicotinic acid amide was high. was there.
Therefore, the present inventors further found that in a water-in-oil emulsified composition containing 1 to 10% by mass of nicotinic acid amide and a polar oil having an IOB of 0.1 to 0.6, the amount of all oily components is 20 to 60%. % by mass and containing a volatile silicone oil and a non-volatile silicone oil having a viscosity of 6 to 100 mPa·s at 25° C., and containing a partially crosslinked emulsifying silicone elastomer together, the emulsion stability is improved. While remarkably improving, it was discovered that it was excellent in the absence of sticky feeling, and the present invention was completed.

The water-in-oil emulsified composition of the present invention exhibits excellent effects such as no precipitation of nicotinic acid amide, excellent emulsion stability, and non-sticky feel in use, while containing nicotinic acid amide at a high concentration. It is.

The present invention provides the following components (a) to (e);
(a) Nicotinamide 1 to 10% by mass
(b) a polar oil having an IOB of 0.1 to 0.6; (c) a volatile silicone oil; (d) a nonvolatile silicone oil having a viscosity of 6 to 100 mPa·s at 25° C.; and (e) a partially crosslinked emulsifying silicone. A water-in-oil emulsion composition containing an elastomer,
A water-in-oil emulsion composition is provided in which the total amount of all oily components including the components (b), (c), (d) and (e) is 20 to 60% by mass.

The present invention provides a water-in-oil emulsion composition characterized in that the content ratio (a)/(e) of component (a) and component (e) is 0.8 to 8. is.

The present invention provides a water-in-oil emulsion composition, wherein the component (b) has a molecular weight of 400 or less.

The present invention provides a water-in-oil emulsion composition characterized in that the content ratio (b)/(e) of component (b) and component (e) is 0.4 to 20. is.

The present invention will be described in detail below. In this specification, "-" shall mean a range including numerical values before and after it. In addition, numerical values expressed in % are values based on mass unless otherwise specified.

Component (a): Nicotinamide Component (a) nicotinamide in the present invention is an amide of nicotinic acid (vitamin B3/niacin). Nicotinamide is a water-soluble vitamin, a known substance that is one of the vitamin B group, and can be extracted from natural products (such as rice bran) or synthesized by a known method. Specifically, those listed in the Japanese Pharmacopoeia 2008, 15th Edition can be used.

In the present invention, the amount of component (a) is 1 to 10% by mass (hereinafter simply "mass%" is abbreviated as "%"). If the amount of component (a) exceeds 10%, the lack of stickiness may not be excellent, and usability may be poor. If the amount of component (a) is less than 1%, the effect on the skin, such as the effect of improving rough skin, may be insufficient. The amount of component (a) is preferably from 3 to 10%, more preferably from 3 to 7%, from the viewpoints of no precipitation of nicotinic acid amide and no sticky feeling.

Component (b): Polar oil having an IOB of 0.1 to 0.6 The component (b) used in the present invention is a polar oil having an IOB of 0.1 to 0.6.
Here, the IOB (Inorganic-Organic balance) in the present invention is calculated by the following (Equation 1).
IOB = (Σ inorganic value/Σ organic) (Equation 1)
That is, IOB is based on the "inorganic value" and "organic value" set for each atom and functional group, and the "inorganic value" of the atoms and functional groups that make up organic compounds such as surfactants. , and "organicity value" (see Yoshio Koda, "Organic Conceptual Diagram-Basics and Applications-", pp. 11-17, Sankyo Publishing, 1984).

In the present invention, the component (b) is not particularly limited as long as it is a polar oil having an IOB of 0.1 to 0.6, and may be used in the fields of cosmetics, pharmaceuticals, quasi-drugs, etc. can be done.
Component (b) is not particularly limited, but specifically cetyl lactate (IOB = 0.42), myristyl lactate (IOB = 0.47), isopropyl myristate (IOB = 0.18), isotridecyl isononanoate (IOB = 0.19), octyldodecyl neopentanoate (IOB = 0.13), isostearyl neopentanoate (IOB = 0.14), isopropyl palmitate (IOB = 0.16), hexyl laurate (IOB = 0) .17),
Hexyldecyl ethylhexanoate (IOB = 0.13), isotridecyl isononanoate (IOB = 0.16), isopropyl isostearate (IOB = 0.15), ethyl isostearate (IOB = 0.15), ethylhexyl palmitate ( IOB = 0.13), octyldodecyl neodecanoate (IOB = 0.11), polyglyceryl-2 diisostearate (IOB = 0.41), polyglyceryl-2 triisostearate (IOB = 0.26), tetraisostearic acid Polyglyceryl-2 (IOB = 0.17), polyglyceryl-10 decaisostearate (IOB = 0.25) pentaerythrityl tetraisostearate (IOB = 0.15), isocetyl myristate (IOB = 0.10), tri Trimethylolpropane Isostearate (IOB=0.16), Octyldodecanol (IOB=0.26), Decyltetradecanol (IOB=0.21), Neopentyl Glycol Diethylhexanoate (IOB=0.32), Triethyl trimethylolpropane hexanoate (IOB=0.33), pentaerythritol tetraethylhexanoate (IOB=0.35), diisopropyl adipate (IOB=0.46), diisostearyl malate (IOB=0.28) , propylene glycol dicaprate (IOB=0.26), neopentyl glycol dicaprate (IOB=0.25), tripropylene glycol dineopentanoate (IOB=0.52), isodecyl benzoate (IOB=0.23), Propylene glycol dicaprylate (IOB = 0.32), isononyl isononanoate (IOB = 0.2), ethylhexyl isononanoate (IOB = 0.2), diethylhexyl sebacate (IOB = 0.24), isodecyl neopentanoate (IOB = 0.24). IOB = 0.22), ethylhexyl ethylhexanoate (IOB = 0.2), cetyl ethylhexanoate (IOB = 0.13), glyceryl triethylhexanoate (IOB = 0.36), diethylhexyl succinate (IOB = 0.32), octyl hydroxystearate (IOB=0.31), tri(caprylic-capric acid)glyceryl (IOB=0.33), etc., and one or more of these can be used.

Although the molecular weight of component (b) is not particularly limited, it is preferably 400 or less from the viewpoint of preventing precipitation of nicotinic acid amide and excellent emulsification stability.
Component (b) having a molecular weight of 400 or less is not particularly limited, but specific examples include cetyl lactate, myristyl lactate, isopropyl myristate, isotridecyl isononanoate, octyldodecyl neopentanoate, isostearyl neopentanoate, and isopropyl palmitate. , hexyl laurate, hexyldecyl ethylhexanoate, isotridecyl isononanoate, isopropyl isostearate, ethyl isostearate, ethylhexyl palmitate, octyldodecyl neodecanoate, isocetyl myristate, octyldodecanol, decyltetradecanol, neopentyl diethylhexanoate Glycol, diisopropyl adipate, tripropylene glycol dineopentanoate, isodecyl benzoate, propylene glycol dicaprate, isononyl isononanoate, ethylhexyl isononanoate, diethylhexyl sebacate, isodecyl neopentanoate, ethylhexyl ethylhexanoate, cetyl ethylhexanoate, succinic acid Diethylhexyl and the like can be mentioned, and one or more of these can be used.

Although the chemical structure of component (b) is not particularly limited, it preferably has a branched structure and a molecular weight of 400 or less, and more preferably has a molecular weight of 400 or less, because it is excellent in preventing precipitation of nicotinic acid amide. , isopropyl myristate, isotridecyl isononanoate, isostearyl neopentanoate, isopropyl palmitate, isotridecyl isononanoate, isopropyl isostearate, ethyl isostearate, octyldodecanol, cetyl 2-ethylhexanoate, glyceryl triethylhexanoate, diethylhexyl succinate more preferably one or more selected from isotridecyl isononanoate, octyldodecanol and cetyl 2-ethylhexanoate, still more preferably isotridecyl isononanoate and octyl They are dodecanol and cetyl 2-ethylhexanoate. This is because the smaller the molecular weight of component (b), the easier it is to be distributed from the oil phase to the aqueous phase, and if it has a branched structure, it can inhibit the precipitation of nicotinic acid amide crystals.

If the component (b) in the present invention is not contained, the precipitation of nicotinic acid amide may not occur and the emulsion stability may not be excellent. A polar oil having an IOB of less than 0.1 or a polar oil having an IOB exceeding 0.6 may be contained within a range that does not impair the effects of the present invention. However, when the contained polar oil only has an IOB of less than 0.1, the effect of suppressing nicotinic acid amide crystallization is inferior, and the precipitation of nicotinic acid amide is not excellent, and the emulsion stability is poor. It may not be good. If the polar oil contained is only one with an IOB exceeding 0.6, the emulsion stability may not be excellent.

The content of component (b) is not particularly limited, but is preferably 3 to 20%, more preferably 6 to 15%, from the viewpoints of no precipitation of nicotinic acid amide and emulsion stability. ~13% is even more preferred.

Component (c): Volatile Silicone Oil The component (c) volatile silicone oil used in the present invention is one or two selected from the group consisting of silicone oils having a boiling point of 100 to 260° C. under 1 atmosphere. That's it. Specifically, although not particularly limited, chain polysiloxanes such as methyltrimethicone, tetrakistrimethylsiloxysilane, dimethylpolysiloxane (viscosity at 25° C. of 1 to 5 mPa·s), methylphenylpolysiloxane, and methylhydrogenpolysiloxane cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, caprylyl methicone, etc., and one or two of these The above can be used. Among these, one or more selected from methyltrimethicone, tetrakistrimethylsiloxysilane, decamethylcyclopentasiloxane, and dimethylpolysiloxane (viscosity at 25°C of 1 to 5 mPa s) is preferred, and more preferably methyl It is one or more selected from trimethicone, tetrakistrimethylsiloxysilane, and decamethylcyclopentasiloxane. In addition, the viscosity in the present invention can be measured according to the second method of Viscosity Measurement Method, Standards for Cosmetic Ingredients, using a Brookfield viscometer.

When the component (c) in the present invention is not contained, the absence of precipitation of nicotinic acid amide and the absence of sticky feeling may not be excellent. The content of component (c) in the present invention is not particularly limited, but is preferably 10 to 30%, more preferably 15 to 25%, from the standpoint of excellent non-sticky feel.

Component (d): Non-volatile silicone fluid having a viscosity of 6 to 100 mPa·s at 25°C One or more selected from the group consisting of silicone oils having a boiling point exceeding 260°C at lower temperatures and having a viscosity at 25°C of 6 to 100 mPa·s.

Component (d) is not particularly limited, but specific examples thereof include dimethylpolysiloxane and methylphenylpolysiloxane having a viscosity at 25° C. of 6 to 100 mPa·s. can be used. Commercially available products include, but are not limited to, KF-96A-6CS, KF-96-10CS, KF-96-20CS, KF-96-50CS, KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. .

When the component (d) in the present invention is not contained, the absence of precipitation of nicotinic acid amide and the absence of stickiness may not be excellent. The content of component (d) in the present invention is not particularly limited, but from 3 to 20% is preferable in terms of excellent emulsification stability due to uniform mixing of oil-based components and excellent lack of sticky feeling. Preferably, 5 to 15% is more preferred.

Component (e): Partially Crosslinked Emulsifying Silicone Elastomer Component (e), the partially crosslinked emulsifying silicone elastomer used in the present invention, is obtained by crosslinking organopolysiloxane and partially has a three-dimensional crosslinked structure. However, it is a polymer that may contain a polyoxyalkylene group, a polyglycerin group or an alkyl group in the molecule. Partially crosslinked emulsifiable silicone elastomers in the present invention include, for example, those described in US Pat. Nos. 5,412,002, 5,837,793 and 5,811,487.

The polyoxyalkylene group is preferably a polyoxy C2-8 alkylene group, more preferably a polyoxy C2-4 alkylene group. Specific examples include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group and the like, and a polyoxyethylene group is particularly preferred. The degree of polymerization of polyoxyethylene is preferably 2-50, particularly preferably 5-30. Moreover, those having a residue (branched chain) in the organopolysiloxane chain are preferred.

The above alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 8-20, more preferably 10-16, even more preferably 10-14. Specific examples include a capryl group, a lauryl group, a myristyl group and the like.

Such component (e) partially crosslinked emulsifying silicone elastomer is not particularly limited as long as it is used in ordinary cosmetics, but examples include (dimethicone/(PEG-10/15)) crosspolymer. Partially crosslinked polyether-modified silicone, partially crosslinked alkyl-polyether co-modified silicone such as (PEG-15/lauryl dimethicone) crosspolymer, partially crosslinked polyglycerin-modified silicone such as (dimethicone/polyglycerin-3) crosspolymer , (lauryl dimethicone/polyglycerin-3) crosspolymer and other partially crosslinked alkyl-polyglycerin co-modified silicones, and one or more of these can be used.

Such component (e) partially crosslinked emulsifying silicone elastomer is commercially available in the form of a mixture, and KSG-210 (solid content 20-30% ), KSG-310 (solid content 25-35%), KSG-320 (solid content 20-30%), KSG-330 (solid content 15-30%) as a mixture of partially crosslinked alkyl-polyether co-modified silicone and oil agent 25%) and KSG-340 (solid content 25-35%), KSG-710 as a mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane (solid content 20-30%), partially crosslinked alkyl polyglycerin As a mixture of modified silicone and oil agent, KSG-810 (solid content 25-35%), KSG-820 (solid content 20-30%), KSG-830 (solid content 15-25%), and KSG-840 ( Solid content 25 to 35%) (both manufactured by Shin-Etsu Chemical Co., Ltd.).

The component (e) in the water-in-oil emulsion composition of the present invention is an oil-based component (b) a polar oil having an IOB of 0.1 to 0.6, (c) a volatile silicone oil, and (d) ) It has excellent compatibility with any non-volatile silicone oil with a viscosity of 6 to 100 mPa s at 25°C, and plays the role of a "binder" that uniformly mixes the entire oil phase component, improving emulsion stability. can be expected to contribute to Furthermore, component (e) unexpectedly brings about intermolecular interactions with water-soluble nicotinic acid amide that may be present in the aqueous phase, and plays a role in improving the dispersibility in the oil phase, The absence of nicotinic acid amide precipitation and the absence of sticky feeling can be improved. When the component (e) in the present invention is not contained, the absence of precipitation of nicotinic acid amide, emulsion stability, and absence of stickiness may not be excellent.

The content of component (e) in the present invention is not particularly limited, but is preferably 0.25 to 7%, more preferably 0.5 to 7%, in terms of no precipitation of nicotinic acid amide, emulsion stability, and no sticky feeling. 2.5% is more preferred.

In the present invention, in order to suppress nicotinic acid amide crystal formation and ensure emulsion stability, the total amount of all oily components including components (b), (c), (d), and (e) is 20 to 60%. is. If the total amount of all oily components including components (b), (c), (d), and (e) is less than 20%, the emulsion stability may not be excellent, and if it exceeds 60%, nicotinic acid In some cases, there is no precipitation of amide and the emulsion stability is not excellent. In addition, the total amount of all oily components including components (b), (c), (d), and (e) is preferably 25 to 55% in terms of no precipitation of nicotinic acid amide and excellent emulsion stability. , 30 to 50% is more preferred.

In the present invention, component (a) and component (e) can be contained as appropriate, and the content mass ratio (a)/(e) is from 0.8 to 0.8 in terms of excellent prevention of precipitation of nicotinic acid amide. 8 is preferred, 2.0 to 7.5 is more preferred, 3.6 to 7.2 is even more preferred, and 4 to 6 is even more particularly preferred. This is because the component (e) present at the emulsification interface unexpectedly brings about an intermolecular interaction with nicotinic acid amide, which can form crystals in the aqueous phase, resulting in poor dispersibility in the aqueous and oil phases. This is because it can play a role in improving the quality.

In the present invention, component (b) and component (e) can be contained as appropriate. 0.4 to 20 are preferred, 0.5 to 19 are more preferred, 1 to 15 are even more preferred, and 5 to 12 are even more particularly preferred. Partially crosslinked emulsifying silicone elastomer (e) serves as a "binder" that uniformly mixes component (b) with the entire oil phase including components (c) and (d), thereby improving emulsion stability. This is to allow

In addition to the components (a) to (e), the present invention provides optional components other than the components (a) to (e), that is, the components (a) to (e), as long as the effects of the present invention are not impaired. Other commonly known ingredients such as oily ingredients, surfactants, powders, aqueous ingredients, UV absorbers, moisturizing agents, antioxidants, cosmetic ingredients, preservatives, pigments, and perfumes may be contained.

Oily components other than components (b) to (e) are not particularly limited as long as they can be used in the fields of cosmetics, pharmaceuticals, quasi-drugs, etc., and include solid, semi-solid, liquid oils, and , animal oils, vegetable oils, mineral oils and synthetic oils can be used.

The surfactant is not particularly limited as long as it can be used in the fields of cosmetics, pharmaceuticals, quasi-drugs, etc., such as ionic surfactants and nonionic surfactants. Examples of nonionic surfactants include glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid esters and alkylene glycol adducts thereof, propylene glycol fatty acid esters and alkylene glycol adducts thereof, sorbitan fatty acid esters and alkylene glycol adducts thereof. sorbitol fatty acid esters and their alkylene glycol adducts, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, glycerin alkyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene hydrogenated castor oil, polyether-modified Examples include silicone and polyglycerin-modified silicone. etc. Examples of anionic surfactants include fatty acids such as stearic acid and lauric acid and inorganic and organic salts thereof, alkylbenzene sulfates, alkylsulfonates, α-olefinsulfonates, dialkylsulfosuccinates, α-sulfones, Acyl Methyl Taurate, N-Methyl-N-Alkyl Taurate, Polyoxyethylene Alkyl Ether Sulfate, Polyoxyethylene Alkyl Phenyl Ether Sulfate, Alkyl Phosphate, Polyoxyethylene Alkyl Ether Phosphate, Polyoxy ethylene alkylphenyl ether phosphate, N-acylamino acid salt, N-acyl-N-alkylamino acid salt, o-alkyl substituted malate, alkyl sulfosuccinate and the like. Amphoteric surfactants include amino acid-type and betaine-type carboxylic acid types, sulfate types, sulfonic acid types, and phosphate types, and those considered safe for the human body can be used. For example, N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N,N-dialkylaminoalkylenecarboxylic acid, N,N,N-trialkyl-N-sulfoalkyleneammonium betaine, N,N- Dialkyl-N,N-bis(polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine and the like can be mentioned. Examples of cationic surfactants include mono-long-chain alkyl-type quaternary ammonium salts, di-long-chain alkyl-type quaternary ammonium salts, and ethylene oxide (EO) addition-type quaternary ammonium salts. Specifically, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, dicetyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, dilauryldimethylammonium chloride, Dipolyoxyethylene chloride (15EO) coconut oil alkylmethylammonium, dipolyoxyethylene chloride (4EO) lauryl ether dimethylammonium and the like can be mentioned.

In the present invention, the surfactant is not particularly limited, but in terms of no precipitation of nicotinic acid amide and emulsion stability, polyether-modified silicone is preferable, and organopolysiloxane having a branched structure is more preferable. It is a polyoxyalkylene group-grafted polyoxyalkylene group (silicone-branched polyether-modified silicone). Specific examples of the silicone-branched polyether-modified silicone include PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG-9 polydimethylsiloxyethyl dimethicone, and the like. 1 type, or 2 or more types can be used. Lauryl PEG-9 polydimethylsiloxyethyl dimethicone is preferred because it is superior in that it does not precipitate nicotinic acid amide.

As for the powder, as long as it is a powder that is generally used in cosmetics, it has a shape such as spherical, plate-like, needle-like, etc.; There are no particular restrictions on the structure or the like, and examples include inorganic powders, glitter powders, pigment powders, metal powders, and composite powders. Specific examples include white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide and barium sulfate, iron oxide, titanium/titanium oxide sintered products, colored inorganic pigments such as chromium oxide, chromium hydroxide, Prussian blue and ultramarine blue. , muscovite, phlogopite, red mica, biotite, synthetic mica, sericite, synthetic sericite, kaolin, silicon carbide, bentonite, smectite, silicic anhydride, aluminum oxide, magnesium oxide, zirconium oxide, silicon Soil, aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, etc. White powder, titanium dioxide coated mica, titanium dioxide coated Bismuth oxychloride, titanium iron oxide mica, titanium blue-treated mica, titanium mica treated with carmine, bismuth oxychloride, bright powders such as fish scale foil, natural organic powders such as silk powder and cellulose powder, aluminum powder, gold powder, silver powder fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and the like. can be used alone or in combination of two or more.

Aqueous components include polyhydric alcohols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyethylene glycol, sorbitol, and maltitol, carboxyvinyl polymer, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, and the like. There is no particular limitation as long as it is commonly used in cosmetics.

Examples of moisturizing agents include proteins, mucopolysaccharides, collagen, elastin, keratin and the like.

The method for producing the water-in-oil emulsion composition of the present invention is not particularly limited, and is prepared by a conventional method. For example, after uniformly heating and dissolving an oil-based component containing components (b) to (e) as necessary, an aqueous component in which component (a) is uniformly dissolved is added and mixed to emulsify. can be prepared by

The water-in-oil emulsified composition of the present invention can be used in combination with other ingredients to form various dosage forms. Specifically, various dosage forms such as liquid, gel, paste, cream and solid can be used.

The water-in-oil emulsion composition of the present invention can be used as cosmetics for various purposes. For example, lotion, milky lotion, cream, beauty essence, massage agent, mask, hand cream, body lotion, body cream, skin care cosmetics such as sunscreen, foundation, eyeshadow, eyeliner, mascara, eyebrow, concealer, lipstick , finishing cosmetics such as lip balm, hair cosmetics such as hair mists, treatments, and hair creams. Examples of the method of use include a method of using hands, fingers, cotton, and a method of impregnating a non-woven fabric or the like.

The water-in-oil emulsion composition of the present invention can also be used as an external skin preparation. for example,
External liquids, external gels, creams, ointments, liniments, lotions, poultices,
plasters, sprays, aerosols and the like. In addition, the method of use thereof is the same as that of the cosmetics described above.

The present invention is further illustrated by the following examples. In addition, these do not limit this invention at all.

Examples 1 to 15 and Comparative Examples 1 to 8: Emulsions Emulsions of formulations shown in Tables 1 to 3 below were prepared, and the absence of precipitation of nicotinic acid amide, emulsion stability, and absence of stickiness were evaluated by the following methods. . The results are also shown in Tables 1-3.

*1: Salakos 913 (manufactured by Nisshin OilliO Group)
*2: Lysonol 20SP (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)
*3: Salakos 816T (manufactured by Nisshin OilliO Group)
*4: Cosmol 43V (manufactured by Nisshin OilliO Group)
*5: KLEAROL (manufactured by SONNEBORN)
* 6: KSG-710 (polymer content 25%, manufactured by Shin-Etsu Chemical Co., Ltd.)
* 7: KSG-16 (polymer content 25%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*8: KF-6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 9: KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 1 to 16 are uniformly mixed and dispersed at room temperature.
B: Components 17 to 21 are uniformly mixed and dissolved at room temperature.
C: B was added to A at room temperature, and the mixture was uniformly stirred and emulsified to obtain a milky lotion.

(Evaluation item)
stomach. No precipitation of nicotinic acid amide b. Emulsion stability c. Non-sticky feeling

[stomach. No precipitation of nicotinic acid amide]
For each sample, immediately after production and stored in a constant temperature bath at 20 to 40 ° C. (48 hour cycle) for 1 month, an upright microscope (manufactured by Olympus) was observed at a magnification of 100 times and an exposure time of 1/200 second. Observation was made under polarized light using a polarizer, and changes over time were evaluated according to the following 4-grade criteria.
Under polarized light, the crystals containing nicotinic acid amide appeared as a grayish image as unclear sparkles under a microscope as crystallization progressed. It is assumed that the number will increase.

4-step evaluation criteria
(Criteria) (Evaluation)
There is no change in the product stored for 1 month compared to the product immediately after production (no crystal glittering substance is observed): ◎
Indistinct sparkles are observed in the product stored for 1 month compared to the product immediately after production: ○
Slightly more small crystal glitters are observed in the product stored for 1 month compared to the product immediately after production: △
A large number of clear crystal glittering substances are observed in the product stored for 1 month compared to the product immediately after production: ×

[B. Emulsion stability]
The average particle size of emulsified droplets of each sample immediately after production and stored in a constant temperature bath at 50 ° C. for 1 month was measured with a submicron particle analyzer N5 (manufactured by Beckman Coulter), and the average particle size was measured immediately after production. The rate of change was evaluated according to the following 4-step criteria. In addition, when the following evaluation was Δ or ×, peeling occurred in appearance and the usability was not excellent.

4-step evaluation criteria
(Judgment criteria): (Evaluation)
Change rate of average particle size is less than 25%: ◎
Change rate of average particle size is 25% or more and less than 50%: ○
Change rate of average particle size is 50% or more and less than 70%: △
Change rate of average particle size is 70% or more: ×

[C. No stickiness]
A panel of 10 women in their 20s to 40s who had undergone sensory evaluation training and were able to perform evaluations according to a certain standard was selected. For each sample, the absence of stickiness felt when applied to the skin by a specialized panel was evaluated and scored in 5 stages according to the following absolute evaluation, and the average value was calculated from the total score of all the panel members for each sample, Judgment was made according to the 4-step judgment criteria.

Absolute Evaluation Criteria (Rating): (Rating)
5 points: no stickiness 4 points: almost no stickiness 3 points: slightly sticky feeling 2 points: sticky feeling 1 point: very sticky feeling

4-step judgment criteria (judgment): (average score)
◎: More than 4 points: Very good ○: More than 3 points and 4 points or less: Good △: More than 2 points and 3 points or less: Somewhat poor ×: 2 points or less: Poor

As is clear from Tables 1 to 3, the water-in-oil emulsion emulsions of Examples 1 to 15 of the present invention had all the properties of "no precipitation of nicotinic acid amide", "emulsion stability" and "no stickiness". It was a water-in-oil type emulsified milky lotion that was excellent in the item.
On the other hand, Comparative Example 1, in which the content of component (a) exceeded 10%, was inferior in no precipitation of nicotinic acid amide, emulsion stability, and no sticky feeling.
Comparative Example 2, in which the total amount of all oily components including components (b), (c), (d), and (e) was less than 20%, had no precipitation of nicotinic acid amide and was inferior in emulsion stability. .
Comparative Example 3, in which the total amount of all oily components including components (b), (c), (d), and (e) exceeded 60%, was inferior in the absence of nicotinic acid amide deposition and in the absence of sticky feeling. .
Comparative Example 4, which did not contain a polar oil having an IOB of 0.1 to 0.6 as component (b), was inferior in terms of nicotinic acid amide precipitation, emulsion stability, and non-stickiness.
Comparative Example 5, which did not contain component (c), was inferior in no precipitation of nicotinic acid amide and in emulsion stability.
Comparative Examples 6 and 7, which did not contain component (d) and contained a silicone oil having a viscosity of more than 100 mPa·s at 25° C., were inferior in terms of no precipitation of nicotinic acid amide and emulsification stability.
Comparative Example 8, which does not contain component (e) and contains a partially crosslinked non-emulsifying silicone elastomer, was inferior in terms of no precipitation of nicotinamide and emulsification stability.

Example 16: Water-in-oil emulsified foundation A water-in-oil emulsified foundation was prepared according to the composition and manufacturing method shown below.
(Composition) (%)
(1) Dimethylpolysiloxane 3% treatment Titanium oxide (average particle size 300 nm) 9
(2) 2% dimethylpolysiloxane treated black iron oxide 0.3
(3) Dimethylpolysiloxane 2% treated yellow iron oxide 1.8
(4) 2% dimethylpolysiloxane treated red iron oxide 0.6
(5) Sericite 1 treated with 3% dimethylpolysiloxane
(6) boron nitride 2
(7) Lauryl PEG-9
Polydimethylsiloxyethyl dimethicone *8 5
(8) Isododecane 5
(9) Decamethylcyclopentasiloxane 15
(10) Dimethylpolysiloxane (viscosity at 25 ° C. 10 mPa s)
5
(11) Propylene glycol dicaprate (IOB=0.26) *10 3
(12) Isopropyl myristate (IOB=0.18) *11 2
(13) Lauroyl glutamic acid di (octyldodecyl/phytosteryl/behenyl)
(IOB=0.30) *12 0.5
(14) 2-ethylhexyl para-methoxycinnamate (IOB = 0.28) *13 5
(15) 2-(4-diethylamino-2-hydroxybenzoyl)
Benzoic acid hexyl ester *14 0.7
(16) (Dimethicone/(PEG-10/15))
Crosspolymer mixture *15 5
(17) Nicotinamide 5.5
(18) Purified water remaining amount (19) Ethanol 5
(20) Phenoxyethanol 0.3
(21) Dipropylene glycol 5
* 10: Nikkor PDD (manufactured by Nikko Chemicals)
*11: IPM-EX (manufactured by Nippon Surfactant Industry Co., Ltd.)
*12: Eldew PS-306 (manufactured by Ajinomoto Co., Inc.)
*13: UVINUL MC80 (manufactured by BASF)
*14: UVINUL A PLUS (manufactured by BASF)
* 15: KSG-210 (polymer content 25%, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. Uniformly disperse components (1) to (8).
B. Components (9) to (16) are heated to 80° C. as necessary to disperse them uniformly, and added to A while stirring.
C. Ingredients (17)-(21) are uniformly mixed at room temperature.
D. While stirring B, C was gradually added and emulsified at room temperature to obtain a water-in-oil emulsified foundation.

The water-in-oil emulsion foundation of Example 16 obtained as described above was excellent in all of "no precipitation of nicotinic acid amide", "emulsion stability" and "no sticky feeling". rice field.

Example 17: Water-in-oil emulsified sunscreen A water-in-oil emulsified sunscreen was prepared according to the composition and manufacturing method shown below.
(Composition) (%)
(1) Fine zinc oxide (average particle size 25 nm, specific surface area 50 m2/g) 3
(2) Dimethylsilylated silica (average particle size 7 nm, specific surface area 300 m2/g) 0.5
(3) Decamethylcyclopentasiloxane 5
(4) Methyl trimethicone *16 10
(5) Lauryl PEG-9
Polydimethylsiloxyethyl dimethicone *8 1
(6) Neopentyl glycol diethylhexanoate (IOB=0.32) *17 2
(7) Decyltetradecanol (IOB=0.21) *18 5
(8) Cetyl lactate (IOB=0.42) *19 1
(9) isononyl isononanoate (IOB = 0.2) *20 1
(10) 2-ethylhexyl para-methoxycinnamate (IOB = 0.28) *13 3
(11) 4-tert-butyl-4′-methoxy-
Dibenzoylmethane *21 1
(12) Methylphenylpolysiloxane *22 3
(13) (PEG-15/lauryl dimethicone)
Crosspolymer *23 5
(14) Spherical PMMA *24 0.5
(15) Perfume 0.03
(16) Nicotinamide 4.5
(17) Purified water remaining amount (18) 1,3-butylene glycol 5
(19) sodium chloride 0.1
(20) Ethanol 2
(21) Phenoxyethanol 0.05
* 16: TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.)
*17: Cosmol 525 (manufactured by Nisshin OilliO Group)
* 18: Lysonol 24SP (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)
*19: CERAPHYL 28 (manufactured by ASHLAND SPECIALTY INGREDIENTS)
*20: Saracos 99 (manufactured by Nisshin OilliO Group)
*21: PARSOL 1789 (manufactured by L.C. UNITED)
* 22: KF-56 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 23: KSG-310 (polymer content 30%, manufactured by Shin-Etsu Chemical Co., Ltd.)
*24: Matsumoto Microsphere M311 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)

(Production method)
A. Uniformly disperse components (1) to (3).
B. Components (4) to (15) are heated to 80° C. as necessary, dispersed uniformly, and added to A with stirring.
C. Ingredients (16)-(21) are uniformly mixed at room temperature.
D. While B was stirred, C was gradually added and emulsified at room temperature to obtain a water-in-oil emulsified sunscreen.

The water-in-oil emulsion foundation of Example 17 obtained as described above was excellent in all of "no precipitation of nicotinic acid amide", "emulsion stability" and "no sticky feeling". rice field.

Example 18: Water-in-oil emulsified daytime beauty essence A water-in-oil emulsified daytime beauty essence was prepared according to the following composition and production method.
(Composition) (%)
(1) Dimethylpolysiloxane (viscosity at 25 ° C. 1.5 mPa s) 10
(2) Ethylhexyl palmitate (IOB=0.13) *25 2
(3) myristyl lactate (IOB=0.47) *26 2
(4) Diethylhexyl succinate (IOB=0.32) *27 5
(5) 2-ethylhexyl para-methoxycinnamate (IOB = 0.28) *13 1
(6) Mineral oil 1
(7) Squalane 3
(8) Cetyl PEG/PPG-10/1 Dimethicone *28 3
(9) Dimethylpolysiloxane (viscosity at 25 ° C. 20 mPa s)
3
(10) Dimethicone/octyl silylation treatment fine particle titanium oxide (average particle size 35 nm) 3
(11) Polymethylsilsesquioxane *29 0.5
(12) (lauryl dimethicone/polyglycerin-3)
Crosspolymer mixture *6 6
(13) Purified water remaining amount (14) Nicotinamide 4
(15) tripropylene glycol 5
(16) 1,3-butylene glycol 0.2
(17) sodium chloride 1
(18) Ethanol 2
(19) Chlorphenesin 0.03
*25: PALMESTER 1543 (manufactured by PALM OLEO)
*26: CERAPHYL 50 (manufactured by ASHLAND SPECIALTY INGREDIENTS)
*27: CRODAMOL OSU (manufactured by Croda Japan)
*28: ABIL EM-90 (manufactured by EVONIC)
*29: TOSPEARL 3000A (manufactured by Momentive Performance Materials)

A. Ingredients (1)-(12) are uniformly dispersed.
B. Ingredients (13)-(19) are uniformly mixed at room temperature.
C. While stirring A, B was gradually added and emulsified at room temperature to obtain a water-in-oil type emulsified daytime beauty essence.

The water-in-oil type emulsified daytime beauty essence of Example 18 obtained as described above was excellent in all of "no precipitation of nicotinic acid amide", "emulsion stability" and "no sticky feeling". It was something.

Example 19: Water-in-oil type emulsified concealer A water-in-oil type emulsified concealer was prepared according to the composition and manufacturing method shown below.
(Composition) (%)
(1) Dimethylpolysiloxane 3% treated titanium oxide (average particle size 250 nm) 15
(2) 2% dimethylpolysiloxane treated black iron oxide 0.3
(3) Dimethylpolysiloxane 2% treated yellow iron oxide 1.0
(4) 2% dimethylpolysiloxane treated red iron oxide 0.5
(5) Dimethylpolysiloxane 3% treated mica titanium 3
(6) (vinyl dimethicone/methicone silsesquioxane)
Crosspolymer *30 5
(7) PEG-9 polydimethylsiloxyethyl dimethicone *9 3
(8) isopropyl isostearate (IOB=0.15) *31 3
(9) isostearyl neopentanoate (IOB=0.14) *32 2
(10) 2-ethylhexyl para-methoxycinnamate (IOB = 0.28) *13 5
(11) Bisethylhexyloxyphenol methoxyphenyl triazine *33 0.5
(12) Decamethylcyclopentasiloxane 5
(13) Isododecane 5
(14) Methyl trimethicone *16 5
(15) Dimethylpolysiloxane (viscosity 20 mPa s at 25°C)
3
(16) Perfume 0.2
(17) (lauryl dimethicone/polyglycerin-3)
Crosspolymer mixture *6 5
(18) Methylparaben 0.1
(19) Ethanol 5
(20) Nicotinamide 6
(21) Purified water remaining amount (22) Butylene glycol 5
(23) glycerin 0.2
(24) Hyaluronic acid Na 0.1
(25) hydrolyzed silk 0.1
(26) glycine 0.1
(27) Hydrolyzed elastin 0.1
(28) Hyaluronic acid yeast fermentation liquid 0.1
(29) Vitamin E Nicotinate 0.01
* 30: KSP-101 (manufactured by Shin-Etsu Chemical Co., Ltd.)
*31: IPIS (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)
* 32: Neolite 180P (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)
*33: TINOSORB S (manufactured by BASF)

(Production method)
A. Uniformly disperse components (1) to (8).
B. Components (9) to (17) and component (29) are heated to 80° C. if necessary, dispersed uniformly, and added to A with stirring.
C. Ingredients (18)-(28) are mixed homogeneously at room temperature.
D. While B was stirred, C was gradually added and emulsified at room temperature to obtain a water-in-oil emulsified concealer.

The water-in-oil type emulsified concealer of Example 19 obtained as described above was excellent in all of "no precipitation of nicotinic acid amide", "emulsion stability" and "no sticky feeling". rice field.

Claims (4)

the following components (a) to (e);
(a) Nicotinamide 1 to 10% by mass
(b) 0.5 to 25% by mass of a polar oil having an IOB of 0.1 to 0.6
(c) 9 to 30% by mass of volatile silicone oil
(d) 1.8 to 20% by mass of a non-volatile silicone oil having a viscosity of 6 to 100 mPa·s at 25°C
(e) 0.25 to 7% by mass of a partially crosslinked emulsifying silicone elastomer
A water-in-oil emulsion composition containing
A water-in-oil containing a polyether-modified silicone surfactant, wherein the total amount of all oily components including the components (b), (c), (d), and (e) is 20 to 60% by mass. type emulsion composition. The water-in-oil emulsion composition according to claim 1, wherein the content ratio (a)/(e) of the component (a) and the component (e) is 0.8 to 8. 3. The water-in-oil emulsion composition according to claim 1, wherein the component (b) has a molecular weight of 400 or less. The water-in-oil type according to any one of claims 1 to 3, wherein the content ratio (b)/(e) of the component (b) and the component (e) is 0.4 to 20. emulsified composition.