JP2020117500A - External composition for skin - Google Patents

Abstract

To provide an external composition for skin with suppressed coloration.SOLUTION: An external composition for skin is prepared that contains (A) nicotinamide 3 mass% or more, (B) two or more selected from the group consisting of hyaluronic acid, a derivative thereof, a salt thereof, and a heparin analog; and (C) an amphiphilic compound.SELECTED DRAWING: None

Description

The present invention relates to an external composition for skin. More particularly, the present invention relates to a topical skin composition containing nicotinamide.

Nicotinic acid amide is one of the vitamins and has been used as a component for promoting blood circulation, anti-inflammatory, ceramide synthesis, etc. in the skin care field, and also as a whitening, anti-wrinkle and anti-aging agent. It is also known to have an effect.

For example, Patent Document 1 proposes a whitening agent containing at least one selected from the group consisting of riboflavin, pyridoxine hydrochloride, nicotinic acid amide, and calcium pantothenate as an active ingredient.

Further, Patent Document 2 is characterized by containing (a) nicotinic acid amide and (b) one or more kinds selected from the group consisting of urea and an α-hydroxycarboxylic acid compound having 2 to 28 carbon atoms. Skin anti-aging cosmetics have been proposed.

JP 2004-217629 A JP, 10-130135, A

In order to effectively exert the various effects of nicotinamide, a formulation containing nicotinamide at a high concentration has been developed. However, the inventors of the present invention selected from the group consisting of nicotinic acid amide of 3% by mass or more of component (A), hyaluronic acid of component (B), a derivative thereof, a salt thereof, and a heparin-like substance. A new problem was found that coloring occurs when the above and the above coexist.

Therefore, an object of the present invention is to provide an external composition for skin in which coloration is suppressed even when a high concentration of component (A), nicotinic acid amide, of 3% by mass or more is blended.

The present inventors, as a result of repeated intensive studies to solve the above problems,
(A) 3 mass% or more of nicotinic acid amide; and (B) hyaluronic acid, a derivative thereof, a salt thereof, and two or more kinds selected from the group consisting of heparin-like substances, and (C) an amphipathic property. It has been found that inclusion of a compound can suppress coloring, and has completed the present invention.

That is, the present invention provides the following external composition for skin.
Item 1.
(A) Nicotinic acid amide 3% by mass or more;
(B) Hyaluronic acid, a derivative thereof, a salt thereof, and two or more kinds selected from the group consisting of heparin-like substances; and (C) an external composition for skin containing an amphipathic compound.
Item 2.
Item 2. The composition according to Item 1, wherein the content of the component (A) is 3 to 20% by mass.
Item 3.
The component (C) is a compound represented by the following general formula (I), 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxy. Item 3. The composition according to Item 1 or 2, which is one or more selected from diglycol, diethylhexyl succinate, diethoxyethyl succinate, and alkanediol having 5 to 10 carbon atoms.

（式中、
Ｚは、水素原子、又は、炭素数１〜３０のヒドロキシ化合物からｎ個のヒドロキシ基を除去することによって得られる残基を意味し；
ＡＯは、３〜４個の炭素原子を有するオキシアルキレン基を意味し；
ＥＯは、オキシエチレン基を意味し；
ＢＯは、４個の炭素原子を有するオキシアルキレン基を意味し；
ｎは、１〜９を意味し；
ａ，ｂ及びｃは、それぞれＡＯ、ＥＯ、ＢＯの平均付加モル数を意味し、独立して０〜２００である。但し、ａ、ｂ及びｃが全て０になることはない。また、ｎが２以上の時、複数のａ、ｂ及びｃはそれぞれ同一でも異なってもよい。Ｚが水素原子の時はｎは１である。
なお、ＡＯ及びＥＯは、ランダムに又はブロックの形態で付加されていてよい。）
項４．
前記（Ｃ）成分が、下記一般式（ＩＩ）で表される化合物、２−メタクリロイルオキシエチルホスホリルコリン・メタクリル酸ブチル共重合体、（エイコサン二酸／テトラデカン二酸）デカグリセリル、シクロヘキサンジカルボン酸ビスエトキシジグリコール、コハク酸ジエチルヘキシル、コハク酸ジエトキシエチル、及び、炭素数５〜１０のアルカンジオールから選ばれる１種又は２種以上である、請求項１又は２に記載の組成物。

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
BO means an oxyalkylene group having 4 carbon atoms;
n means 1 to 9;
a, b and c mean the average number of moles of addition of AO, EO and BO, respectively, and are independently 0 to 200. However, a, b, and c are not all 0. When n is 2 or more, a, b and c may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. )
Item 4.
The component (C) is a compound represented by the following general formula (II), 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxy. The composition according to claim 1 or 2, which is one or more selected from diglycol, diethylhexyl succinate, diethoxyethyl succinate, and alkanediol having 5 to 10 carbon atoms.

（式中、
Ｚは、水素原子、又は、炭素数１〜３０のヒドロキシ化合物からｎ個のヒドロキシ基を除去することによって得られる残基を意味し；
ＡＯは、３〜４個の炭素原子を有するオキシアルキレン基を意味し；
ＥＯは、オキシエチレン基を意味し；
ｎは、１〜９を意味し；
ａ及びｂは、それぞれＡＯ、ＥＯの平均付加モル数を意味し、独立して０〜２００である。但し、ａ及びｂが全て０になることはない。また、ｎが２以上の時、複数のａ、ｂはそれぞれ同一でも異なってもよい。Ｚが水素原子の時はｎは１である。
なお、ＡＯ及びＥＯは、ランダムに又はブロックの形態で付加されていてよい。）
項５．
前記一般式（Ｉ）及び（ＩＩ）において、Ｚが、水素原子であるか、若しくは、炭素数４〜２４のアルキルモノアルコール、グリセリン、トリメチロールプロパン、エリスリトール、ペンタエリスリトール、アルキルグルコシド、ジグリセリン、キシリトール、ジペンタエリスリトール、ソルビトール、イノシトール、スクロース、トレハロース、又は、マルチトールからｎ個のヒドロキシ基を除去することによって得られる残基である、項３又は４に記載の組成物。
項６．
前記一般式（Ｉ）及び（ＩＩ）において、Ｚが、水素原子であるか、若しくは、炭素数４〜２４のアルキルモノアルコール、グリセリン、又は、ジグリセリンからｎ個のヒドロキシ基を除去することによって得られる残基である、項３又は４に記載の組成物。

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
n means 1 to 9;
a and b mean the average addition mole number of AO and EO, respectively, and are 0-200 independently. However, a and b do not all become 0. When n is 2 or more, a and b may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. )
Item 5.
In the general formulas (I) and (II), Z is a hydrogen atom, or an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, trimethylolpropane, erythritol, pentaerythritol, alkyl glucoside, diglycerin, Item 5. The composition according to Item 3 or 4, which is a residue obtained by removing n hydroxy groups from xylitol, dipentaerythritol, sorbitol, inositol, sucrose, trehalose, or maltitol.
Item 6.
In the general formulas (I) and (II), Z is a hydrogen atom, or by removing an n hydroxy group from an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, or diglycerin. Item 5. The composition according to Item 3 or 4, which is the obtained residue.

According to the present invention, 2 or more kinds selected from the group consisting of nicotinic acid amide having a high concentration of 3% by mass or more of component (A), hyaluronic acid of component (B), a derivative thereof, a salt thereof, and a heparin-like substance. Even when and coexist, it is possible to provide an external composition for skin in which coloring is suppressed.

In the present specification, the unit "mass%" of the content is synonymous with "g/100g".

The external composition for skin of the present invention is
(A) Nicotinic acid amide 3% by mass or more;
(B) Hyaluronic acid, a derivative thereof, a salt thereof, and two or more kinds selected from the group consisting of heparin-like substances; and (C) an amphipathic compound for external application to the skin.

[(A) Nicotinic acid amide]
The nicotinic acid amide contained in the external composition for skin of the present invention is an amide compound of nicotinic acid (vitamin B ₃ /niacin) and is a water-soluble vitamin. Nicotinic acid may be an extract from a natural product or a product synthesized by a known method. Specifically, those listed in the 17th revised Japanese Pharmacopoeia can be used. In addition to the blood circulation promoting action and the rough skin improving action, a melanin production inhibiting action and a whitening effect are known.

In the external composition for skin of the present invention, the content of the component (A) with respect to the total amount of the composition is appropriately set depending on the balance with other components. The content of the component (A) is 3% by mass or more, preferably 4% by mass or more, and more preferably, with respect to the total amount of the composition, from the viewpoint of sufficiently imparting the effects of whitening, anti-aging and the like. It can also be 5% by mass or more. Further, the content of the component (A) is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 8% by mass based on the total amount of the composition. % Or less. The content of the component (A) is preferably 3% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and further preferably 3% by mass to 10% by mass with respect to the total amount of the composition. And even more preferably 3% by mass to 8% by mass.

[(B) Two or more kinds selected from the group consisting of hyaluronic acid, derivatives thereof, salts thereof, and heparin-like substances]
Hyaluronic acid is a kind of acidic mucopolysaccharide, and is a polysaccharide containing a disaccharide of glucuronic acid and N-acetylglucosamine as a constituent unit. Hyaluronic acid can be extracted and recovered from chicken crowns, animal tissues such as shark skin, umbilical cord, eyeball, skin, and cartilage, hyaluronic acid-producing microorganisms such as Streptococcus microorganisms, cultures of animal cells or plant cells. .. Alternatively, a commercially available product can be purchased.

As described above, hyaluronic acid obtained by extraction from animal tissues, microorganisms, etc. is generally said to have an average molecular weight of about 1,000,000 or more, and is known to be an extremely high polymer. In the present invention, such a high molecular weight hyaluronic acid may be used, or a low molecular weight hyaluronic acid obtained by decomposing the high molecular weight hyaluronic acid may be used. Low molecular weight hyaluronic acid is a method of hydrolyzing a high molecular weight hyaluronic acid in the presence of an acid or an alkali such as hydrochloric acid, a method of treating with an enzyme such as hyaluronidase, or a method of physically cutting by ultrasonic waves or shearing, It can be obtained by a method of fermenting with a microorganism. Moreover, a low molecular weight hyaluronic acid can also be used by purchasing a commercially available product. In the external composition for skin of the present invention, although not limited, preferably, low molecular weight hyaluronic acid oligosaccharides such as tetrasaccharides, hexasaccharides and octasaccharides, and double bonds at the 4- and 5-positions of D-glucuronic acid. The unsaturated hyaluronic acid which it has is used.

The average molecular weight of hyaluronic acid is not particularly limited as long as the effects of the present invention are exhibited, and may be, for example, about 1 to 5,000,000. From the viewpoint that the effect of the present invention can be more effectively exerted, the average molecular weight of the hyaluronic acid of the present invention is preferably about 100 to 700,000, more preferably about 200 to 600,000, and It is preferably about 4000 to 500,000, even more preferably about 5000 to 400,000, and particularly preferably about 8000 to 2 million.

The average molecular weight when low-molecular-weight hyaluronic acid is used is preferably about 100 to 350,000, more preferably about 100 to 100,000, and even more preferably about 10 to 350,000 from the viewpoint of remarkably exerting the effect of the present invention. It is 200 to 50,000, even more preferably about 200 to 30,000, and particularly preferably about 500 to 20,000.

In the present specification, the average molecular weight means the weight average molecular weight. The weight average molecular weight can be determined by a known measurement method. Specifically, it can be measured by size exclusion chromatography. The conditions are (column: TSKgel GMPWXL 7.8 mm×30 cm (manufactured by Tosoh Corporation), column temperature: constant temperature around 40° C., detector: differential refractometer, mobile phase: 0.2 mol/L NaCl, Flow rate: 0.3 mL/min, injection amount: 100 μL, standard substance: pullulan standard product (STANDARD P-82, Showa Denko KK).

The derivative of hyaluronic acid is not particularly limited as long as it is pharmacologically or physiologically acceptable, and examples thereof include acetylated hyaluronic acid in which a hydroxyl group is acetylated, sulfated hyaluronic acid in which a hydroxyl group is sulfated, and cationized. Cationized hyaluronic acid, hydrophobized hydrolyzed hyaluronic acid (hydrolyzed alkyl (C12-13) glyceryl etc.), crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, alkylene glycol hyaluronate, silanol hyaluronate and or These salts etc. can be mentioned. The derivative of hyaluronic acid is preferably acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, hydrolyzed alkyl hyaluronate (C12-13) glyceryl, carboxymethyl hyaluronic acid, crosslinked hyaluronic acid, dimethylsilanol hyaluronate, hyaluronic acid. Propylene glycol acid and/or salts thereof are used. More preferably, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, crosslinked hyaluronic acid, dimethylsilanol hyaluronate, propylene glycol hyaluronate and/or salts thereof are used.

The salt of hyaluronic acid or a derivative thereof is not particularly limited as long as it is pharmacologically or physiologically acceptable, and examples thereof include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, zinc and aluminum. Examples thereof include salts with metals, ammonium salts, basic amino acid salts, amine salts such as triethanolamine, and the like. Preferably, sodium salt, potassium salt, or zinc salt is used as the salt of hyaluronic acid or its derivative. Specific salts of hyaluronic acid or its derivatives include, for example, sodium hyaluronate, potassium hyaluronate, calcium hyaluronate, magnesium hyaluronate, zinc hyaluronate, ammonium hyaluronate, monoethanolamine hyaluronate, acetylated sodium hyaluronate. , Acetylated potassium hyaluronate, acetylated calcium hyaluronate, acetylated magnesium hyaluronate, zinc acetylated hyaluronate, ammonium acetylated hyaluronate, sodium hyaluronate crosspolymer, and hydroxypropyltrimonium hyaluronate.

In the external composition for skin of the present invention, two or more kinds selected from the group consisting of hyaluronic acid, derivatives thereof, salts thereof, and heparin-like substances are used in combination. In the case where the component (A) nicotinic acid amide of 3% by mass or more and the component (B) hyaluronic acid, a derivative thereof, a salt thereof, or two or more kinds selected from the group consisting of heparin-like substances are mixed together. Although coloring occurs, coloring is suppressed by further containing (C) the amphipathic compound. The external composition for skin of the present invention contains at least two or more selected from the group consisting of hyaluronic acid, acetylated hyaluronic acid, hydrolyzed hyaluronic acid, cationized hyaluronic acid, crosslinked hyaluronic acid, and heparin-like substances. Preferably.

As hyaluronic acid, its derivatives, and salts thereof used in the present invention, commercially available products can be used. For example, as hyaluronic acid, trade name "sodium hyaluronate HA12N" (Shiseido Co., Ltd.) average molecular weight 110 to 1.6 million, trade name "hyaluronic acid FCH-150" (Kikkoman Biochemifa Corporation) average molecular weight 140 to 1.8 million, Product name "sodium hyaluronate SZE" (Shiseido Co., Ltd.) average molecular weight 110 to 1.6 million, product name "Hyaluronic acid FCH-120" (Kikkoman Biochemifa Co., Ltd.) average molecular weight 100 to 1.4 million, product name "Hyaluron Sun HA-" LQ" (Kewpie Corporation) average molecular weight 85-1,600,000, trade name "hyaluronic acid FCH-80" (Kikkoman Biochemifa Corporation) average molecular weight 60-1,000,000, trade name "hyaluronic acid FCH-60" (Kikkoman Biochemifa) Ltd.) Average molecular weight 500,000-700,000, trade name "Hyaluronic acid FCH-SU" (Kikkoman Biochemifa Co., Ltd.) average molecular weight 5-110000, trade name "Hyaluronic acid (L)" (FAP Japan Co., Ltd.) average molecular weight 50,000 or less, trade name "Hialooligo" (Kewpie Corporation) average molecular weight 10,000 or less, trade name "Hyaluronic acid (SL)" (FAP Japan Co., Ltd.) average molecular weight 10,000 or less, trade name "Micro hyaluronic acid FCH" ( Kikkoman Biochemifa Co., Ltd.) Average molecular weight 5000 or less) and the like. As a derivative of hyaluronic acid, a trade name “Acetylated sodium hyaluronate” (Shiseido Co., Ltd.) average molecular weight of 1 to 100,000, a trade name “Hyalover” (Kewpie Co., Ltd.) average molecular weight of 500 to 800,000, a trade name “Hyaro repair” (Kewpie Co., Ltd.) Average molecular weight of 10,000 or less, trade name "Hyarujeon" (Kikkoman Biochemifa Co., Ltd.), trade name "Hialocatch" (Kewpie Co., Ltd.) average molecular weight 800,000 to 1.2 million, trade name "Hial cage system" Commercially available products such as (IR Asrl) and trade name "DSHCN6" (EXSYMOL SAM) can be exemplified.

The heparin-like substance means a general term for polysulfated mucopolysaccharides such as chondroitin polysulfate, and an average of 0.5 to 5 molecules, preferably an average of 0.6 to 3 molecules of sulfuric acid per one molecule of the monosaccharide constituting the mucopolysaccharide. It is preferable to have a group. More specifically, the heparin-like substance contains heparin, chondroitin sulfate D called chondroitin polysulfate, chondroitin sulfate E, and the like.

The heparin-like substance can be obtained by sulfating a mucopolysaccharide, or can be extracted and purified from an internal organ including bronchi of an animal such as bovine or pig using an aqueous carrier, and then sulfated if necessary. It can also be obtained. Since such a heparin-like substance has been developed as a raw material for pharmaceuticals and cosmetics, such commercially available products can also be used.

In the external composition for skin of the present invention, as the heparin-like substance, those contained in the Japanese Pharmacopoeia Standards are preferably used.

In the external composition for skin of the present invention, as the combination of the component (B), acetylated hyaluronic acid, cationized hyaluronic acid, cross-linked hyaluronic acid, or hyaluronic acid among two or more kinds of hyaluronic acid, derivatives thereof and salts thereof is used. It is preferable that any one of these salts is contained, and at least sodium hyaluronate, acetylated sodium hyaluronate, sodium hyaluronate crosspolymer, or hydroxypropyltrimonium hyaluronate is contained, or at least acetylated hyaluronic acid. It is more preferable that sodium is contained and combined with a heparin analogue, and at least sodium hyaluronate, acetylated sodium hyaluronate, sodium hyaluronate crosspolymer, or hydroxypropyltrimonium hyaluronate is contained, and a heparin analogue is contained. It is particularly preferable to combine with.
Among them, as the combination of the component (B), acetylated hyaluronic acid and sodium hyaluronate, acetylated hyaluronic acid and zinc hyaluronate, acetylated hyaluronic acid and low molecular weight hyaluronic acid, acetylated hyaluronic acid and low molecular weight zinc hyaluronate, Acetylated hyaluronic acid and hydroxypropyltrimonium hyaluronate, acetylated hyaluronic acid and hydrolyzed alkyl (C12-13) glyceryl hyaluronate, acetylated hyaluronic acid and carboxymethyl hyaluronic acid, acetylated hyaluronic acid and cross-linked hyaluronic acid, acetyl Hyaluronic acid and dimethylsilanol hyaluronate, acetylated hyaluronic acid and propylene glycol hyaluronate, and combinations of acetylated hyaluronic acid and heparin analogues are preferred,
Acetylated hyaluronic acid and sodium hyaluronate, acetylated hyaluronic acid and zinc hyaluronate, acetylated hyaluronic acid and low molecular weight hyaluronic acid, acetylated hyaluronic acid and low molecular weight zinc hyaluronate, acetylated hyaluronic acid and hydroxypropyltrimonium hyaluronate More preferred is a combination of acetylated hyaluronic acid and dimethylsilanol hyaluronate, acetylated hyaluronic acid and propylene glycol hyaluronate, and acetylated hyaluronic acid and heparin-like substances,
It is more preferred to include a combination of acetylated hyaluronic acid and sodium hyaluronate, acetylated hyaluronic acid and low molecular weight hyaluronic acid, acetylated hyaluronic acid and hydroxypropyltrimonium hyaluronate, and acetylated hyaluronic acid and heparin-like substances.
In addition, as the combination of the component (B) in another embodiment, hyaluronic acid crosspolymer sodium and sodium hyaluronate, hyaluronic acid crosspolymer sodium and zinc hyaluronate, hyaluronic acid crosspolymer sodium and low molecular weight hyaluronic acid, hyaluronic acid crosspolymer Polymer sodium and low molecular weight zinc hyaluronate, hyaluronic acid crosspolymer sodium and hydroxypropyltrimonium hyaluronate, hyaluronic acid crosspolymer sodium and hydrolyzed alkyl hyaluronate (C12-13) glyceryl, hyaluronic acid crosspolymer sodium and carboxymethyl hyaluronic acid Preferred are combinations of sodium hyaluronate crosspolymer with dimethylsilanol hyaluronate, sodium hyaluronate crosspolymer with propylene glycol hyaluronate, and sodium hyaluronate crosspolymer with heparin-like substances.
Further, as the combination of the component (B) in another embodiment, hydroxypropyltrimonium hyaluronate and sodium hyaluronate, hydroxypropyltrimonium hyaluronate and zinc hyaluronate, hydroxypropyltrimonium hyaluronate and low molecular weight hyaluronan, Hydroxypropyltrimonium hyaluronate and low molecular weight zinc hyaluronate, hydroxypropyltrimonium hyaluronate and cross-linked hyaluronic acid, hydroxypropyltrimonium hyaluronate and hydrolyzed alkyl (C12-13) glyceryl hyaluronate, hydroxypropyltrimonium hyaluronate And carboxymethyl hyaluronic acid, hydroxypropyltrimonium hyaluronate and dimethylsilanol hyaluronate, hydroxypropyltrimonium hyaluronate and propylene glycol hyaluronate, and combinations of hydroxypropyltrimonium hyaluronate and heparin-like substances are preferred.
Further, as a combination of three or more kinds, at least two kinds of acetylated hyaluronic acid and sodium hyaluronate, or at least two kinds of acetylated hyaluronic acid and low molecular weight hyaluronic acid, or at least acetylated hyaluronic acid and hydroxypropyl hyaluronate. Trimonium, or at least acetylated hyaluronic acid and hyaluronic acid crosspolymer sodium, or at least acetylated hyaluronic acid and heparin-like substance, or at least hydroxypropyltrimonium hyaluronate and hyaluronic acid Two types of sodium, or at least hydroxypropyltrimonium hyaluronate and low molecular weight, two types of hyaluronic acid, or at least two types of hyaluronan crosspolymer sodium and sodium hyaluronate, or at least sodium hyaluronate crosspolymer and low molecule A combination of three or more kinds including two kinds of hyaluronic acid is preferable,
Acetylated hyaluronic acid and sodium hyaluronate and low molecular weight hyaluronic acid, acetylated hyaluronic acid and sodium hyaluronate and hydroxypropyltrimonium hyaluronate, hydroxypropyltrimonium hyaluronate and sodium hyaluronate and low molecular weight hyaluronic acid, hyaluronic acid crosspolymer Sodium and sodium hyaluronate and low molecular weight hyaluronic acid, acetylated hyaluronic acid and sodium hyaluronate and heparin analogues, hydroxypropyltrimonium hyaluronate and sodium hyaluronate and heparin analogues, hyaluronic acid crosspolymer sodium and sodium hyaluronate and heparin Similar substances, acetylated hyaluronic acid and low molecular weight hyaluronic acid and hydroxypropyltrimonium hyaluronate, acetylated hyaluronic acid and low molecular weight hyaluronic acid and heparin analogs, hydroxypropyltrimonium hyaluronate and low molecular weight hyaluronic acid and heparin analogs, Alternatively, it is more preferable to include a combination of sodium hyaluronate crosspolymer, a low molecular weight hyaluronic acid, and a heparin-like substance.

In the external composition for skin of the present invention, the total content of the component (B) is not particularly limited and may be appropriately set according to the types of other compounding ingredients, etc., but from the viewpoint of significantly exerting the effect of the present invention. With respect to the total amount of the composition, preferably 0.0001 mass% or more, more preferably 0.0005 mass% or more, further preferably 0.001 mass% or more, still more preferably 0.001 mass%. As described above, particularly preferably 0.001 mass% or more.
The total content of the component (B) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1% by mass based on the total amount of the composition. % Or less, particularly preferably 0.5% by mass or less.
The total content of the component (B) is preferably 0.0001 to 5% by mass, more preferably 0.0005 to 3% by mass, still more preferably 0.001 to 2% by mass, relative to the total amount of the composition. Even more preferably, it is 0.001 to 1% by mass, and particularly preferably 0.001 to 0.5% by mass.

In the external composition for skin of the present invention, the ratio of the total content of the component (B) to the component (A) is not particularly limited, but the component (B) is preferably 0 with respect to 1 part by mass of the component (A). 0.0001 to 2 parts by mass, more preferably 0.0005 to 1 part by mass, and further preferably 0.001 to 0.1 part by mass.

In the external composition for skin of the present invention, the total content of hyaluronic acid, its derivative, and salts thereof alone relative to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
Hyaluronic acid, its derivative, and the total content of the salts alone is preferably 0.00001 mass% or more, more preferably 0.0001 mass% or more, and further preferably, relative to the total amount of the composition. It is 0.001 mass% or more.
The total content of hyaluronic acid, its derivatives, and salts thereof alone is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass, based on the total amount of the composition. % Or less.
The total content of hyaluronic acid, its derivatives, and salts thereof alone is preferably 0.00001 to 2% by mass, more preferably 0.0001 to 1% by mass, and still more preferably the total amount of the composition. Is 0.001 to 0.5 mass %.

In the external composition for skin of the present invention, the content of the heparin-like substance alone with respect to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of the heparin-like substance is preferably 0.005 mass% or more, more preferably 0.001 mass% or more, still more preferably 0.01 mass% or more, particularly preferably, with respect to the total amount of the composition. , 0.1 mass% or more.
The content of the heparin-like substance is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass, based on the total amount of the composition. It is as follows.
The content of the heparin-like substance is preferably 0.005 to 10% by mass, more preferably 0.001 to 5% by mass, still more preferably 0.01 to 1% by mass, relative to the total amount of the composition. Particularly preferably, it is 0.1 to 1% by mass.

[(C) Amphiphilic component]
An amphipathic component is a compound that has both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and as a result, has an affinity for both the aqueous phase and the oil phase (organic phase). Refers to.

Such an amphipathic component is not particularly limited, but examples thereof include an alkylene oxide derivative, a phosphorylcholine-containing polymer, a divalent carboxylic acid ester, an alkanediol having 5 to 10 carbon atoms, and hydroxyethylurea. As the component (C) of the present invention, any of these compounds may be used alone or in combination of two or more. By blending the component (C) with the components (A) and (B), it is possible to provide a composition for external use for skin in which coloring is suppressed even when a high concentration of nicotinic acid amide is blended. It will be possible.

The component (C) is preferably an alkylene oxide derivative represented by the following general formula (I), 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexane. One or more selected from bisethoxydiglycol dicarboxylate, diethylhexyl succinate, diethoxyethyl succinate, and alkanediol having 5 to 10 carbon atoms.

（式中、
Ｚは、水素原子、又は、炭素数１〜３０のヒドロキシ化合物からｎ個のヒドロキシ基を除去することによって得られる残基を意味し；
ＡＯは、３〜４個の炭素原子を有するオキシアルキレン基を意味し；
ＥＯは、オキシエチレン基を意味し；
ＢＯは、４個の炭素原子を有するオキシアルキレン基を意味し；
ｎは、１〜９を意味し；
ａ，ｂ及びｃは、それぞれＡＯ、ＥＯ、ＢＯの平均付加モル数を意味し、独立して０〜２００である。但し、ａ、ｂ及びｃが全て０になることはない。また、ｎが２以上の時、複数のａ、ｂ及びｃはそれぞれ同一でも異なってもよい。Ｚが水素原子の時はｎは１である。
なお、ＡＯ及びＥＯは、ランダムに又はブロックの形態で付加されていてよい。）

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
BO means an oxyalkylene group having 4 carbon atoms;
n means 1 to 9;
a, b and c mean the average number of moles of addition of AO, EO and BO, respectively, and are independently 0 to 200. However, a, b, and c are not all 0. When n is 2 or more, a, b and c may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. )

From the viewpoint of providing a composition for external use for skin in which coloring is suppressed, the alkylene oxide derivative is preferably a compound represented by the following general formula (II).

（式中、
Ｚは、水素原子、又は、炭素数１〜３０のヒドロキシ化合物からｎ個のヒドロキシ基を除去することによって得られる残基を意味し；
ＡＯは、３〜４個の炭素原子を有するオキシアルキレン基を意味し；
ＥＯは、オキシエチレン基を意味し；
ｎは、１〜９を意味し；
ａ及びｂは、それぞれＡＯ、ＥＯの平均付加モル数を意味し、独立して０〜２００である。但し、ａ及びｂが全て０になることはない。また、ｎが２以上の時、複数のａ、ｂはそれぞれ同一でも異なってもよい。Ｚが水素原子の時はｎは１である。
なお、ＡＯ及びＥＯは、ランダムに又はブロックの形態で付加されていてよい。）

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
n means 1 to 9;
a and b mean the average addition mole number of AO and EO, respectively, and are 0-200 independently. However, a and b do not all become 0. When n is 2 or more, a and b may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. )

The alkylene oxide derivative used in the present invention is a polymer of a specific alkylene glycol (when Z is a hydrogen atom) or a specific alkylene oxide group (general formula (I)) in a specific hydroxy compound (corresponding to Z). And a compound (corresponding to a portion except Z in (II)) (when Z is a group obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms).

In the alkylene oxide derivative used in the present invention, AO is an oxyalkylene group having 3 to 4 carbon atoms, from the viewpoint of providing a skin external composition in which coloring is suppressed, and examples thereof include an oxypropylene group and an oxybutylene group. (Oxy n-butylene group, oxyisobutylene group, oxy t-butylene group), oxytrimethylene group, oxytetramethylene group and the like. AO is preferably an oxypropylene group or an oxybutylene group, more preferably an oxypropylene group.

In the alkylene oxide derivative used in the present invention, BO is an oxyalkylene group having 4 carbon atoms, and examples thereof include an oxybutylene group (oxy n-butylene group, oxyisobutylene group, oxy t-butylene group), oxytetramethylene. Groups and the like. It is preferably an oxybutylene group.

In the alkylene oxide derivative used in the present invention, a, b and c are each independently 0 to 200. a and b are each independently preferably 1 to 100, more preferably 2 to 70, still more preferably 2 to 50, and particularly preferably 2 to 20. c is preferably 2 to 150. Moreover, in another embodiment, c is preferably 0.5 to 100, more preferably 0.8 to 50, and still more preferably 1 to 30.

In the chemical formula (I), a+b+c, which is the total number of AO, EO, and BO monomer units, is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more, from the viewpoint of markedly exhibiting the effect of the present invention. Is. Further, a+b+c is preferably 400 or less, more preferably 300 or less, further preferably 250 or less, and particularly preferably 200 or less, from the viewpoint of remarkably exerting the effect of the present invention.

In the chemical formula (II), a+b, which is the total number of AO and EO monomer units, is preferably 3 or more, more preferably 5 or more, and still more preferably 10 or more, from the viewpoint of significantly exhibiting the effect of the present invention. .. Further, a+b is preferably 300 or less, more preferably 250 or less, still more preferably 200 or less, and particularly preferably 150 or less, from the viewpoint of remarkably exerting the effect of the present invention.

In the formulas (I) and (II), Z is a hydrogen atom, or an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, or tri, from the viewpoint of providing a composition for external use for skin in which coloring is suppressed. Methylolpropane, erythritol, pentaerythritol, alkylglucosides, diglycerin, xylitol, dipentaerythritol, sorbitol, inositol, sucrose, trehalose, or a residue obtained by removing n hydroxy groups from maltitol, That is, it is preferably a residue derived from these alcohol compounds, which is a hydrogen atom, or an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin (three hydroxy groups to which an alkylene oxide group can be added), Alkyl glucosides having 1 to 24 carbon atoms (4 hydroxy groups to which an alkylene oxide group can be added), diglycerin (4 hydroxy groups to which an alkylene oxide group can be added) or sorbitol (hydroxy to which an alkylene oxide group can be added) More preferably, it is a residue obtained by removing n hydroxy groups from 6), and is a hydrogen atom, or is an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, or diglycerin. A residue obtained by removing n hydroxy groups is more preferable, and a residue obtained by removing n hydroxy groups from an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, or diglycerin. Is more preferable.

In the chemical formula (I) or (II), when Z is an alkyl monoalcohol having 4 to 24 carbon atoms, butyl alcohol, tetradecyl tetraalcohol, cetanol and stearyl alcohol are among the following from the viewpoint of remarkably exerting the effect of the present invention. Butyl alcohol and tetradecyl tetra alcohol are particularly preferable.

In the chemical formula (I) or (II), when Z is an alkyl glucoside, an alkyl glucoside having 1 to 24 carbon atoms is preferable, and an alkyl glucoside having 1 to 16 carbon atoms is preferable from the viewpoint of remarkably exerting the effect of the present invention. More preferably, an alkyl glucoside having 1 to 10 carbon atoms is even more preferable, and an alkyl glucoside having 1 to 5 carbon atoms is particularly preferable.

Such an alkylene oxide derivative can be synthesized by a known method. For example, it can be obtained by addition-polymerizing ethylene oxide and alkylene oxide having 3 to 4 carbon atoms to a hydroxy compound having 1 to 30 carbon atoms and then reacting with alkylene oxide having 4 carbon atoms. In addition, in the step of adding-polymerizing ethylene oxide and a C3-C4 alkylene oxide to a C1-C30 hydroxy compound, ethylene oxide and alkylene oxide may be random-polymerized or block-polymerized. Good. For the addition reaction, an alkali catalyst, a phase transfer catalyst, a Lewis acid catalyst or the like can be used. Generally, it is preferable to use an alkali catalyst such as potassium hydroxide.

The molecular weight of such an alkylene oxide derivative is not limited as long as the effects of the present invention are exhibited, but from the viewpoint of significantly exhibiting the effects of the present invention, it is preferably 120 or more, more preferably 200 or more, It is more preferably 300 or more, and particularly preferably 400 or more.

The property of the alkylene oxide derivative is not limited as long as the effects of the present invention are exhibited, but in the above formulas (I) and (II), from the viewpoint of significantly exhibiting the effects of the present invention, it is preferably a semi-solid state at 25°C. It is preferable that the component is (including paste) to liquid.

Further, such alkylene oxide derivatives include, for example, polyoxyalkylene glyceryl ether, polyoxyalkylene alkyl glucoside, polyoxypropylene alkyl ether, polyoxyalkylene sorbit, polyoxyalkylene erythritol ether, polyoxyalkylene pentaerythritol ether, and polyoxyalkylene. Alkylene diglyceryl ether, polyoxyalkylene trimethylolpropane, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene xylitol, polyoxyalkylene dipentaerythritol, polyoxyalkylene inositol, polyoxyalkylene sucrose ether, polyoxy Examples thereof include alkylene trehalose ether and polyoxyalkylene maltitol ether.
Among them, alkylene oxide derivatives are polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene alkyl. Glucoside, polyoxyethylene alkyl glucoside, polyoxypropylene alkyl glucoside, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene sorbit, polyoxyethylene sorbit, polyoxypropylene erythritol ether, polyoxyethylene erythritol ether , Polyoxyethylene pentaerythritol ether, polyoxyethylene polyoxypropylene erythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxy Ethylene polyoxypropylene diglyceryl ether, polyoxyethylene trimethylolpropane, polyoxypropylene trimethylolpropane, polyoxyethylene polyoxypropylene trimethylolpropane, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxybutylene polyoxy Ethylene polyoxypropylene glycol, polyoxyethylene xylitol, polyoxypropylene alkylene xylitol, polyoxyethylene polyoxypropylene xylitol, polyoxyethylene polyoxypropylene dipentaerythritol, polyoxyethylene dipentaerythritol, polyoxypropylenedipentaerythritol, poly Oxyethylene inositol, polyoxypropylene inositol, polyoxyethylene polyoxypropylene inositol, polyoxyethylene sucrose ether, polyoxypropylene sucrose ether, polyoxyethylene polyoxypropylene sucrose ether, polyoxyethylene trehalose ether, polyoxypropylene trehalose ether, Polyoxyethylene Polyoxypropylene Trehalose ether, Polyoxyethylene One or more selected from maltitol ether, polyoxypropylene maltitol ether, and polyoxyethylene polyoxypropylene ether are preferable,
Polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene alkyl glucoside, polyoxyethylene alkyl glucoside , Polyoxypropylene alkyl glucoside, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxypropylene sorbit, polyoxyethylene sorbit, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene diglyceryl ether, poly One or more selected from oxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene trimethylolpropane, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxybutylene polyoxyethylene polyoxypropylene glycol. Is more preferable,
Polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether, polyoxybutylene polyoxyethylene polyoxypropylene alkyl glucoside, polyoxypropylene alkyl glucoside , Polyoxyethylene alkyl glucoside, polyoxypropylene alkyl glucoside, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxypropylene glycol, polyoxyethylene One or more selected from polyoxypropylene glycol and polyoxybutylene polyoxyethylene polyoxypropylene glycol is more preferable,
Polyoxyethylene methyl glucoside, polyoxypropylene methyl glucoside, polyoxyethylene polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxybutylene polyoxyethylene polyoxypropylene methyl glucoside, polyoxypropylene diglyceryl ether, Polyoxyethylene polyoxypropylene glycol and polyoxyethylene polyoxypropylene glyceryl ether are particularly preferable.

These alkylene oxide derivatives include Unilube 50MB-26 (polyoxyethylene polyoxypropylene butyl ether (17EO) (17PO)) and Unilube 50MB-168 (polyoxyethylene polyoxypropylene butyl ether (37EO). )( 38P.O.)), Solvure GS-01 (polyoxyethylene polyoxypropylene decyl tetradecyl ether (24E.O.) (30P.O.)), Uniol HS-1600D (PPG-25 sorbitol), pronone. #208 (PEG/PPG-150/35 copolymer), pronone #124P (polyoxyethylene (20) polyoxypropylene (20) glycol), pronone #184R (polyoxyethylene (26) polyoxypropylene (30) glycol) , Uniol D-2000 (PPG-34), Macbioobride MG10E (polyoxyethylene methyl glucoside (10EO)), Macbiobroide MG-20E (polyoxyethylene methylglucoside (20EO)), Mac Biobride MG-10P (polyoxypropylene methyl glucoside (10P.O.), McBiobride MG-20P (polyoxypropylene methyl glucoside (20P.O.)), Wilburide MG2070 (polyoxybutylene polyoxyethylene polyoxy) Propylene methyl glucosit), Unilube 5TP-300KB (PEG-5//PPG-65 pentaerythrityl); Unilube 50TG-32 (polyoxyethylene polyoxypropylene glyceryl ether (24EO) (24PO)). , Wilbride S-753 (polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO)), UNIOX G-1200 (glyceres-26) (above) , Manufactured by NOF CORPORATION; SY-DP14 (PPG-14 polyglyceryl-2 ether), SY-DP9 (PPG-9 diglyceryl) (above, manufactured by Sakamoto Yakuhin Co., Ltd.); Newpol GP-1000 (PPG- 16 glyceryl ether), Newpol SP-750 (PPG-10 sorbitol), Newpol PE-68 (PEG/PPG-160/30 copolymer), Newpol PE-78 (PEG/PPG-150/35 copolymer) (above) , Sanyo Kasei Co., Ltd.); Emulgen PP-290 (PEG/PPG-160/30 copolymer, manufactured by Kao Corporation); Glucam E-10 (polyoxyethylene methyl glucoside (10E. O. )), GlucamP-10 (polyoxypropylene methyl glucoside (10 EO)), Glucam P-20 (polyoxypropylene methyl glucoside (20 EO)) (above, manufactured by Lubrizol); SG-DTD630 (polyoxyethylene). Polyoxypropylene decyl tetradecyl ether (30EO) (6PO)), SG-DTD620 (polyoxyethylene polyoxypropylene decyl tetradecyl ether (20EO) (6PO)), PEN4612. (Polyoxyethylene polyoxypropylene decyl tetradecyl ether (12EO) (6PO)), PBC-34 (polyoxyethylene polyoxypropylene cetyl ether (20EO) (4PO)) , SG-G2424 (polyoxyethylene polyoxypropylene glyceryl ether (24EO) (24PO)) (above, Nikko Chemicals Co., Ltd.), dipropylene glycol (DPG) (above, ADEKA Co., Ltd.), etc. Is marketed under the name of.
As commercial products of the alkylene oxide derivative, from the viewpoint of remarkably exerting the effect of the present invention, Unilube 50MB-26, Unilube 50MB-168, Solvure GS-01, Pronone #208, Pronone #124P, Pronone #184R, Uniol D-. 2000, McBio Bride MG-10E, McBio Bride MG-20E, MacBio Bride MG-10P, MacBio Bride MG-20P, Willbride MG2070, Unilube 5TP-300KB, Unilube 50TG-32, Willbride S-753, UNIOX G-1200, SY-DP14, SY-DP9, Newpol GP-1000, Newpol PE-68, Newpol PE-78, Emulgen PP-290, SG-DTD630, SG-DTD620, and dipropylene glycol. It is preferably at least one selected from the group consisting of
Unilube 50MB-26, Unilube 50MB-168, Solvure GS-01, Pronon #208, Pronon #124P, Pronon #184R, McBiobride MG-10P, Macbiobride MG-20P, Willbride MG2070, Willbride S-753. , Unilube 50TG-32, SY-DP14, SY-DP9, Newpol PE-68, Newpol PE-78, Emulgen PP-290, SG-DTD630, and SG-DTD620. More preferably.

In the present invention, the alkylene oxide derivative may be used alone or in any combination of two or more.

The phosphorylcholine-containing polymer refers to all polymers including an organic compound containing phosphorylcholine as a monomer. Although not particularly limited, a 2-methacryloyloxyphosphorylcholine-containing polymer, which is a polymer obtained by polymerizing a monomer containing 2-methacryloyloxyethylphosphorylcholine, is preferable from the viewpoint of remarkably exerting the effect of the present invention. Of these, one or more selected from the group consisting of 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer (polyquaternium-51) and polymethacryloyloxyethylphosphorylcholine are preferable, and 2-methacryloyloxyethylphosphorylcholine/methacryl is preferable. Butyl acid copolymers are more preferred. Examples of commercially available phosphorylcholine-containing polymers include Lipidure-PMB (2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer solution, polyquaternium-51), and Lipidure-HM (polymethacryloyloxyethylphosphorylcholine) (both NOF ( 1 type or 2 or more types selected from the group consisting of)), and Lipidure-PMB (2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer liquid) is more preferable.

The divalent carboxylic acid ester is an ester obtained by condensing a divalent carboxylic acid with a hydroxy group such as glycol or glycol ether, and is not particularly limited, and examples thereof include Neosolue-Aqua and Neosolue-AquaS((eicosanedioic acid/tetradecanedioic acid. Acid) polyglyceryl-10), Neosolue-Aqulio (cyclohexanedicarboxylic acid bisethoxydiglycol) (all manufactured by Nippon Seika Co., Ltd.), 1,4-cyclohexanedicarboxylic acid bis(triethylene glycol monoethyl ether), adipic acid Bis(diethylene glycol monoethyl ether), bis(triethylene glycol monoethyl ether) adipate, diethoxyethyl succinate (CRODAMOL DES), diethylhexyl succinate (CRODAMOL OSU) (all manufactured by Croda Japan Co., Ltd.) Among them, among them, Neosolue-Aqua/Neosolue-AquaS ((eicosanedioic acid/tetradecanedioic acid) polyglyceryl-10), Neosolue-Aqulio (cyclohexanedicarboxylic acid bisethoxydiglycol), diethoxyethyl succinate (CRODAMOL DES), cos. Diethylhexyl acid (CRODAMOL OSU) is preferred, and Neosolue-Aqua.Neosolue-AquaS ((eicosanedioic acid/tetradecanedioic acid)polyglyceryl-10) and Neosolue-Aqulio (cyclohexanedicarboxylic acid bisethoxydiglycol) are more preferred, and Neo is. Even more preferred is Aquilio (bisethoxydiglycol cyclohexanedicarboxylate).

The alkanediol preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and still more preferably 5 to 6 carbon atoms, from the viewpoint of remarkably exerting the effect of the present invention. For example, 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol are preferable, 1,2-pentanediol and 1,2-hexanediol are more preferable, and 1,2-pentanediol is further preferable. preferable. In addition, commercial products are not particularly limited, but HYDROLITE (manufactured by Simrise Co., Ltd.) and KMO-6 (manufactured by Osaka Organic Chemical Industry) can be used.

In the present invention, as the component (C), in addition to the above-mentioned alkylene oxide derivative, 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxy Diglycol, diethylhexyl succinate, diethoxyethyl succinate and alkanediol having 5 to 10 carbon atoms are preferable. In addition to the above alkylene oxide derivative, 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosan Acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxydiglycol, 1,2-pentanediol, 1,2-hexanediol, or 1,2-octanediol is more preferable, and in addition to the above alkylene oxide derivative, 2- Methacryloyloxyethyl phosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, bisethoxydiglycol cyclohexanedicarboxylate, 1,2-pentanediol, 1,2-hexanediol are even more preferable. As the component (C), one type may be used alone, or two or more types may be used in any combination.

In the external composition for skin of the present invention, the total content of the component (C) is not particularly limited and is appropriately set according to the type of the component (B), the types of other compounding components, etc. From the viewpoint of remarkably producing the effect, the composition is preferably contained in an amount of 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably. Is 0.05% by mass or more, and most preferably 0.1% by mass or more.
The total content of the component (C) is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 12% by mass or less, and still more preferably 10% by mass based on the total amount of the composition. % Or less, and most preferably 8% by mass or less.
The total content of the component (C) is preferably 0.001 to 20% by mass, more preferably 0.005 to 15% by mass, further preferably 0.01 to 12% by mass, relative to the total amount of the composition. Even more preferably, it is 0.05 to 10% by mass, and most preferably 0.1 to 8% by mass.

In the external composition for skin of the present invention, the ratio of the total content of the component (C) to the component (B) is not particularly limited, but the component (C) is preferably 0 with respect to 1 part by mass of the component (B). 0.01 to 50000 parts by mass, more preferably 0.05 to 10000 parts by mass, still more preferably 0.1 to 5000 parts by mass.

In the external composition for skin of the present invention, the content of the alkylene oxide derivative alone with respect to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of the alkylene oxide derivative alone is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1% by mass or more based on the total amount of the composition.
The content of the alkylene oxide derivative alone is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less, based on the total amount of the composition.
The content of the alkylene oxide derivative alone is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 10% by mass relative to the total amount of the composition. It is 8% by mass.

In the external composition for skin of the present invention, the content of (eicosandioic acid/tetradecanedioic acid) decaglyceryl alone relative to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of (eicosandioic acid/tetradecanedioic acid) decaglyceryl alone is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably, based on the total amount of the composition. It is 0.01% by mass or more, and even more preferably 0.05% by mass or more.
The content of (eicosandioic acid/tetradecanedioic acid) decaglyceryl alone is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less, based on the total amount of the composition. , And even more preferably 5% by mass.
The content of (eicosanedioic acid/tetradecanedioic acid) decaglyceryl alone is preferably 0.001 to 15% by mass, more preferably 0.005 to 10% by mass, and further preferably based on the total amount of the composition. Is 0.01 to 8% by mass, and even more preferably 0.05 to 5% by mass.

In the external composition for skin of the present invention, the content of cyclohexanedicarboxylic acid bisethoxydiglycol alone with respect to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of cyclohexanedicarboxylic acid bisethoxydiglycol alone is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.01% by mass with respect to the total amount of the composition. % Or more, and even more preferably 0.05% by mass or more.
The content of cyclohexanedicarboxylic acid bisethoxydiglycol alone is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and further more preferably, based on the total amount of the composition. Is 5% by mass.
The content of cyclohexanedicarboxylic acid bisethoxydiglycol alone is preferably 0.001 to 15% by mass, more preferably 0.005 to 10% by mass, and still more preferably 0.1% to the total amount of the composition. 01 to 8% by mass, and even more preferably 0.05 to 5% by mass.

In the external composition for skin of the present invention, the content of the 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer alone relative to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of the 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer alone is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further preferably, based on the total amount of the composition. Is 0.005 mass% or more, and even more preferably 0.01 mass% or more.
The content of the 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer alone is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass relative to the total amount of the composition. It is 5 mass% or less, and even more preferably 0.2 mass% or less.
The content of the 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer alone is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, relative to the total amount of the composition. It is more preferably 0.005 to 0.5% by mass, and even more preferably 0.01% to 0.2% by mass.

In the external composition for skin of the present invention, the content of the alkanediol having 5 to 10 carbon atoms alone with respect to the total amount of the composition is not particularly limited as long as the effects of the present invention are exhibited.
The content of the alkanediol having 5 to 10 carbon atoms is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.01% with respect to the total amount of the composition. It is at least mass%, and even more preferably at least 0.1 mass%.
The content of the alkanediol having 5 to 10 carbon atoms is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, and further more preferably 5% by mass or less, based on the total amount of the composition. It is preferably 3% by mass or less.
The content of the alkane diol having 5 to 10 carbon atoms is preferably 0.0001 to 10% by mass, more preferably 0.001 to 7% by mass, and further preferably 0 based on the total amount of the composition. 0.01 to 5 mass %, and even more preferably 0.1 to 3 mass %.

The external composition for skin of the present invention preferably further contains chondroitin sulfate and/or its salt from the viewpoint of remarkably exerting the effect of the present invention.
Chondroitin sulfate is one type of glycosaminoglycan having a structure in which sulfuric acid is bound to a sugar chain in which two sugars, D-glucuronic acid and N-acetyl-D-galactosamine, are repeated.

The chondroitin sulfate used in the present invention is not particularly limited as to its origin as long as it is pharmacologically or physiologically acceptable, and is derived from, for example, cartilage (salmon cartilage etc.) of mammals or fish. Those that do can be used.

The salt of chondroitin sulfate is not particularly limited as long as it is pharmacologically or physiologically acceptable. Specific examples of the salt of chondroitin sulfate include salts with organic acids [for example, monocarboxylic acid salts (acetic acid salts, trifluoroacetic acid salts, butyric acid salts, palmitic acid salts, stearic acid salts, etc.), polycarboxylic acid salts (Fumarate, maleate, etc.), Oxycarboxylate (Lactate, Tartrate, Citrate, Succinate, Malonate, etc.), Organic sulfonate (Methanesulfonate, Toluenesulfonate) , Tosylate, etc.)], salts with inorganic acids (eg, hydrochloride, sulfate, nitrate, hydrobromide, phosphate, etc.), salts with organic bases (eg, methylamine, triethylamine, etc. Salts with organic amines such as triethanolamine, morpholine, piperazine, pyrrolidine, tripyridine and picoline), salts with inorganic bases [eg ammonium salts; alkali metals (sodium, potassium etc.), alkaline earth metals (calcium, Magnesium, etc.), salts with metals such as aluminum, etc.] and the like.

These chondroitin sulfates and/or salts thereof may be used alone or in any combination of two or more. From the viewpoint of remarkably exerting the effect of the present invention, as chondroitin sulfate and/or a salt thereof, a salt with an inorganic base of chondroitin sulfate is preferable, an alkali metal salt of chondroitin sulfate is more preferable, sodium chondroitin sulfate, potassium chondroitin sulfate, At least one selected from the group consisting of sodium dermatan sulfate and potassium dermatan sulfate is more preferable, and sodium chondroitin sulfate and/or potassium chondroitin sulfate is particularly preferable. In addition, chondroitin sulfate is also referred to as chondroitin sulfate, and sodium chondroitin sulfate is also referred to as sodium chondroitin sulfate.

In the external composition for skin of the present invention, the total content of chondroitin sulfate and/or its salt relative to the total amount of the composition is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 7% by mass, and further preferably Is 0.001 to 5% by mass, even more preferably 0.005 to 3% by mass, and most preferably 0.01 to 1% by mass.

[Other ingredients]
In addition to the above-mentioned essential components, the external composition for skin of the present invention, in order to add other useful actions, a UV scattering agent, a UV absorber, a component having a DNA damage preventing and/or repairing action, Whitening ingredient, anti-inflammatory ingredient, refreshing agent, organic acid, anti-glycation ingredient, antibacterial ingredient, cell activating ingredient, astringent ingredient, antioxidant ingredient, anti-aging ingredient, moisturizing ingredient, polyhydric alcohol, keratin softening ingredient, vitamins Various components such as a blood circulation promoting component, a sebum adsorbing component, a peptide or its derivative, an amino acid or its derivative and the like may be blended alone or in combination of two or more. Each of these components is not particularly limited as long as it can be used in the fields of pharmaceuticals, quasi drugs, cosmetics, etc., and any component can be appropriately selected and used. In addition, those corresponding to the following plural components can be added as components having any efficacy among them.

As the ultraviolet scattering agent, for example, inorganic compounds such as zinc oxide, titanium oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate, anhydrous silicic acid, cerium silicate, hydrous silicic acid, and the like. Inorganic compounds such as hydrous silicic acid, aluminum hydroxide, inorganic powders such as mica and talc, or composites with resin powders such as polyamide, polyethylene, polyester, polystyrene and nylon, and silicone oil and fatty acids. Those treated with aluminum salts, alkyl titanates and the like can be mentioned. Among them, inorganic compounds such as zinc oxide, titanium oxide and iron oxide, and inorganic compounds such as aluminum hydroxide, hydrous silicic acid, inorganic powder such as mica and talc, and silicone oil are preferable. When blending the ultraviolet scattering component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.001 to 35% by mass with respect to the total amount of the external composition for skin of the present invention. , Preferably about 0.1 to 25% by mass.

The UV absorber is not limited, but preferably salicylic acid UV absorber, cinnamic acid UV absorber, benzoylmethane UV absorber, benzoate ester UV absorber, triazine derivative UV absorber, It may be a benzalmalonate derivative UV absorber, an octocrylene-based UV absorber, an imidazolesulfonic acid derivative UV absorber, a benzophenone derivative UV absorber, or the like.

Specifically, as the ultraviolet absorber, salicylic acid-based ultraviolet absorbers such as 2-ethylhexyl salicylate, homomenthyl salicylate, or ethylene glycol salicylate; diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl; paradihydroxypropylbenzoic acid Cinnamic acid UV absorbers such as ethyl or 2-ethylhexyl p-methoxycinnamate; Benzoylmethane UV absorbers such as 4-tert-butyl-4'-methoxydibenzoylmethane; 2-[4-(diethylamino )-2-Hydroxybenzoyl]benzoic acid hexyl ester and other benzoic acid ester derivative UV absorbers; 2-methoxyhexyl dimethoxybenzylidenedioxoimidazolidinepropionate; 2,2′-methylenebis[6-(2H-benzotriazol-2) Iyl)-4-(1,1,3,3-tetramethylbutyl)phenol]; 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4 -Methoxyphenyl)-1,3,5-triazine, diethylhexylbutamidotriazone, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine and other triazines Derivatives; benzalmalonate derivative such as dimethicodiethylbenzalmalonate UV absorber; Octocrylene UV absorber such as 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester; 2-phenylbenzo Imidazol-5-sulfonic acid, phenyldibenzimidazole disodium tetrasulfonate, etc., imidazolesulfonic acid derivative UV absorbers; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5- Examples thereof include sulfonic acid and salts thereof, benzophenone derivative ultraviolet absorbers such as dihydroxydimethoxybenzophenone, dihydroxybenzophenone, and tetrahydroxybenzophenone.

In the present invention, although not limited, examples of such an ultraviolet absorber include 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4′-methoxydibenzoylmethane, and 2-[4-(diethylamino)-. 2-Hydroxybenzoyl]benzoic acid hexyl ester, 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidine propionate, 2,2′-methylenebis[6-(2H-benzotriazol-2yl)-4-(1,1,3) ,3-Tetramethylbutyl)phenol], 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5- Triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dimethicodiethylbenzalmalonate, 2-cyano-3,3-diphenylpropa-2. -Enoic acid 2-ethylhexyl ester and 2-phenylbenzimidazole-5-sulfonic acid are preferable, and para-methoxycinnamic acid 2-ethylhexyl, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-[4 -(Diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1 ,3,5-triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, and 2-phenylbenzimidazole-5-sulfonic acid are more preferable. , 2-Methylhexyl paramethoxycinnamate, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy} -Phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine are further More preferable.

As the ultraviolet absorber, a commercially available product can be used, or a synthetic product can be used.

Examples of commercially available products include, but are not limited to, Parsol EHS (manufactured by DSM Nutrition Japan), ESCALOL 587 (manufactured by Ashland Japan), EusolexOS (manufactured by Merk), Parsol HMS (manufactured by DSM Nutrition Japan), Uvinul MC80 (manufactured by BASF), Parsol MCX (manufactured by DSM Nutrition Japan), Parsol 1789 (manufactured by DSM Nutrition Japan), Ubinal A Plus Granular, soft shade DH, Tinosorb M (manufactured by BASF), MilesBix 3 MilesBix. /100, Tinosorb S (manufactured by BASF), Uvasorb HEB, Ubinar T150 (manufactured by BASF), Heliosun OTZ (manufactured by O'Laughlin Industries), Parsol SLX (manufactured by DSM Nutrition Japan), and Pars MUS New Tris 40 (Parsol). Made), Escalol 597 (manufactured by Ashland Japan), Parsol HS (manufactured by DSM Nutrition Japan), Eusolex232 (manufactured by Merk), NeoHeliopanAP (manufactured by Harman & Reimer), Ubinard M40, Escalol 567 Ashland Japan. Manufactured), Ubinard MS40 (manufactured by BASF), EESORB107 (manufactured by Cipro Kasei), SEESORB100 (manufactured by Cipro Kasei), and SEESORB106 (manufactured by Cipro Kasei).

In the external composition for skin of the present invention, the total content of the ultraviolet absorber is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 6% by mass with respect to the total amount of the composition. As described above, particularly preferably 7% by mass or more. Further, the total content of the ultraviolet absorber is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less with respect to the total amount of the composition. Moreover, the total content of the ultraviolet absorber is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, further preferably 5 to 10% by mass, and particularly preferably, the total amount of the composition. , 7 to 10% by mass.

In the external composition for skin of the present invention, the ratio of the total content of the ultraviolet absorber to the component (A) is not particularly limited, but the ultraviolet absorber is preferably 0. 6 to 2 parts by mass, more preferably 1 to 2 parts by mass, still more preferably 1.4 to 2 parts by mass.

Further, these ultraviolet scattering agents and ultraviolet absorbers may be compounded, supported or encapsulated in another component, and the combination thereof is not particularly limited.

Examples of components having a DNA damage preventing and/or repairing action include components derived from animals (eg Artemia); components derived from plants (eg Cat's claw); DNA, DNA salts, RNA, RNA salts Nucleic acid components such as The content of the component having a DNA damage preventing and/or repairing action can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 10% to the total amount of the external composition for skin of the present invention. It is 0.001 to 3% by mass, preferably about 0.01 to 1% by mass. The content in the case of using an animal component or a plant component is, in terms of an extract such as an extract, preferably about 0.00001 to 0.1% by mass, more preferably, relative to the total amount of the external composition for skin of the present invention. Is about 0.0001 to 0.01 mass %.

Examples of the whitening component include placenta; arbutin; kojic acid; ellagic acid; phytic acid; tranexamic acid; rucinol; chamomile ET; hydroquinone, 4-methoxysalicylic acid potassium salt; linoleic acid and its derivatives; ascorbic acid and its salts, ascorbine. Vitamin Cs such as acid derivatives (sodium ascorbyl phosphate, magnesium ascorbyl phosphate, ascorbyl tetra-2-hexyldecanoate, 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, ascorbic acid glucoside, iso Stearyl ascorbyl phosphate disodium, dipalmitate L-ascorbyl, palmitate ascorbyl phosphate 3 sodium, glyceryl ascorbic acid, bisglyceryl ascorbic acid, alkylglyceryl ascorbic acid, etc.), vitamin A or its derivative, pantothenic acid or its derivative, etc. Vitamins and the like. Furthermore, a plant component having a whitening effect may be used as a whitening component, and as such a plant component, iris (iris), almond, aloe, acerola, oolong tea, agets, sorghum, lauren, hypericum, lorricula, seaweed, cuckoo, Gardenia, Kujin, Chlorella, Rice, Rice Haiga, Oryzanol, Komenuka, Saishin, Peppermint, Perilla, Peony, Senkyu, Sohakuhi, Soybeans, Natto, Tea, Touki, Tousensis, Hamamelis, Safflower, Peacock, Yokuinin, Asenyak, Oyster Diospyros kaki), kiwi, black bean, gentian, ginseng, sage, radish, azalea, parsley, holly, hop, thyme, clove, chimp, licorice, chamomile, prunes, spirea, murasakisiki, sow, grapefruit, spinach, lemon, kiwi , Pine, neem, artichoke, horsetail, psyllium, evening primrose, bilberry, himefuuro, sakusou, shiroiyanagi, yukinoshita, centella asiatica, rosemary, lavender, sanshuyu and the like. When these plant components are used in the external composition for skin of the present invention, the form of the plant component is not particularly limited, but it can be usually used in the form of a plant extract (plant extract) or an essential oil. The name in parentheses in the plant component is the scientific name, alias or crude drug name of the plant.
In the present invention, although not particularly limited, such whitening ingredients include placenta; arbutin; kojic acid; ellagic acid; phytic acid; tranexamic acid; rucinol; chamomile ET; hydroquinone; 4-methoxysalicylic acid potassium salt; linoleic acid. And derivatives thereof; ascorbic acid, sodium ascorbate, sodium ascorbate phosphate, magnesium ascorbate phosphate, ascorbyl tetra-2-hexyldecanoate, 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, ascorbic acid Glucosides, Vitamin A oils; Iris, almonds, aloe, acerola, ages, sardines, aurens, gents, sardines, seaweeds, cuckons, chlorella, rice, rice hyga, oryzanols, rice bran, perilla, peony, sowakuhi, soybeans, tea, duckweed. , Hamamelis, Buttonpi, Yokuinin, Kiwi, Sage, Parsley, Holly, Hop, Thyme, Clove, Chinpi, Kanzo, Chamomile, Prunes, Astragalus, Purple Sakibuki, Souzuki, Grapefruit, Spinach, Lemon, Kiwi, Pine, Neem, Artichoke, One or more selected from extracts extracted from horse mackerel, psyllium, evening primrose, bilberry, himeberry, hemlock, holly, willow ash, Centella asiatica, rosemary, lavender, and sanshyu are preferable,
Placenta; Arbutin; Kojic acid; Phytic acid; Tranexamic acid; Hydroquinone; Ascorbic acid, Sodium ascorbate, Sodium ascorbyl phosphate, Ascorbyl phosphate magnesium, Ascorbyl tetra-2-hexyldecanoate, 2-O-ethylascorbic acid , 3-O-ethylascorbic acid, ascorbic acid glucoside, vitamin A oil; iris root extract, almond oil, aloe vera extract, acerola extract, ages extract, sardine extract, hypericum extract, sardine extract, seaweed extract, cuckoo extract, chamomile extract. , Peony extract, Sophoraceae extract, Soybean extract, Tea extract, White bean extract, Calendula officinalis, Hamamelis, Yokuinin, Coix extract, Hop extract, Prune extract, Licorice extract, Oil-soluble licorice extract, Shimotsukisou extract, Murasakikib extract, Alpinia matsushimai seed extract , Grapefruit extract, Isabella rose extract, Lemon extract, Kiwi extract, Pine extract, Neem leaf extract, Artichoke extract, Horse mackerel extract, Mackerel extract, Evening primrose extract, Evening primrose oil, Bilberry leaf extract, Scutellaria extract, Salix officinalis extract, Centella asiatica extract. More preferably, one or two or more selected from Sanshuyu fruit extract.

When the whitening component described above is added to the external composition for skin of the present invention, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but with respect to the total amount of the external composition for skin, for example, , About 0.0003 to 10% by mass, preferably about 0.01 to 5% by mass. The content in the case of using a plant extract is, for example, about 0.00001 to 20 mass%, preferably about 0.0001 to 15 mass% with respect to the total amount of the external composition for skin, in terms of extract and the like. , And more preferably 0.001 to 10% by weight.

As the anti-inflammatory component, for example, allantoin, calamine, tranexamic acid, glycyrrhizinic acid or a derivative thereof or a salt thereof (for example, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, etc.), glycyrrhetinic acid or a derivative thereof or a salt thereof (for example, Glycyrrhetinic acid, stearyl glycyrrhetinate, etc.), zinc oxide, aminocaproic acid, azulene and its derivatives (eg, guaiazulene, azulene, etc.), tocopherol acetate, pyridoxine hydrochloride, menthol, camphor, turpentine oil, indomethacin, salicylic acid or its derivatives, steroids Alternatively, a derivative thereof or a salt thereof (for example, hydrocortisone, prednisolone), ufenamate, bufexamac, ibuprofen piconol, glycol salicylate, a component derived from a plant (for example, comfrey, laurel, dokudami) and the like can be mentioned. Preferably, allantoin, tranexamic acid, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, glycyrrhetinic acid, stearyl glycyrrhetinate, aminocaproic acid, azulene and one or more kinds selected from derivatives thereof or Dokudami extract, more preferably, One or more selected from allantoin, tranexamic acid, dipotassium glycyrrhizinate, glycyrrhetinic acid, and aminocaproic acid. When the anti-inflammatory component is blended, its content can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.0003 to 10 relative to the total amount of the external composition for skin of the present invention. % By weight, preferably about 0.01 to 5% by weight.

Examples of the antibacterial component include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, ethanol, benzethonium chloride, cresol, gluconic acid and its derivatives, popidone iodine, potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, and photosensitizer. No. 101, Photosensitizer 201, Paraben, Phenoxyethanol, Alkyldiaminoglycine hydrochloride, Cetylpyridinium chloride, Pyroctoolamine, Miconazole or its salt, Chlorobutanol, Ethylhexylglycerin, Butylcarbamic acid propynyl iodide, Capryl hydroxamic acid, Phenethyl alcohol, Methylisothiate Examples thereof include azolinone, sorbic acid, β-glycyrrhetinic acid, and components derived from plants (eg, Clara, rosemary, mulberry, eucalyptus, etc.). Preferably, salicylic acid, benzalkonium chloride, ethanol, benzethonium chloride, gluconic acid, isopropyl methylphenol, paraben, phenoxyethanol, cetylpyridinium chloride, chlorobutanol, ethylhexylglycerin, propynyl butylcarbamate iodide, capryl hydroxamic acid, sorbic acid, One or more selected from β-glycyrrhetinic acid is preferable. When blending the antibacterial component, the content thereof can be appropriately selected in consideration of the feeling of use and effect on the skin, but is, for example, about 0.0003 to 10 mass with respect to the total amount of the external composition for skin of the present invention. %, preferably about 0.01-5% by weight.

Examples of the cooling agents include menthol and its derivatives, terpenes such as camphor, borneol, geraniol, cineol, anethole, limonene, and eugenol (these may be d-, l-, or dl-forms); eucalyptus oil. , Essential oils such as bergamot oil, peppermint oil, cool mint oil, spearmint oil, fennel oil, peppermint oil, cinnamon oil, rose oil and turpentine oil. Among them, a combination with 1-menthol, menthyl glyceryl ether, menthyl lactate, menthyl 3-hydroxybutyrate, menthoxypropanediol, camphor, eucalyptus oil, peppermint oil, and peppermint oil is preferable.

Examples of organic acids include gluconic acid, aspartic acid, aminoethylsulfonic acid, citric acid, glutamic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, maleic acid, propionic acid, malic acid, salicylic acid, glycolic acid, phytin. Examples thereof include acids, tartaric acid, acetic acid, lactic acid, pantothenic acid, glycyrrhetinic acid, alginic acid, ascorbic acid, benzoic acid, adipic acid, glutamic acid, azelaic acid and salts thereof. As the salt, for example, a salt of a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid, a salt of an organic acid such as maleic acid or methanesulfonic acid, an alkali metal salt such as sodium or potassium, an alkaline earth metal salt, an ammonium salt, Examples thereof include basic amino acid salts and amine salts such as triethanolamine. Among them, gluconic acid, citric acid, glutamic acid, succinic acid, malic acid, salicylic acid, glycolic acid, phytic acid, tartaric acid, lactic acid, glycyrrhetinic acid and combinations thereof with one or more kinds selected from salts thereof are more preferable.

Examples of the anti-saccharification component include plant extracts such as Budreja axillaris leaf extract, plum fruit extract, and edelweiss extract, evening primrose oil, Amla fruit, fruit juice or extracts thereof, L-arginine, L-lysine, and hydrolysis. Casein, hydrolyzable tannin, carnosine and the like can be mentioned.

Examples of the cell activating component include amino acids such as γ-aminobutyric acid and ε-aminocaproic acid: vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, pyrroloquinoline quinone pantothenate; gluconic acid, phytic acid, glycol Α-hydroxy acids such as acid and lactic acid; tannin, flavonoid, saponin, allantoin, Photosensitizer No. 301, components derived from plants (eg, soybean bud, bilberry leaf, etc.) and the like. When blending the cell activating component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but with respect to the total amount of the external composition for skin of the present invention, for example, about 0.0003 to It is 10% by mass, preferably about 0.001 to 5% by mass.

Examples of astringent components include alum, chlorohydroxyaluminum, aluminum chloride, allantoin aluminum salt, metal salts of zinc paraphenolsulfonate, basic aluminum zinc lactate, zinc sulfate, potassium aluminum sulfate; tannic acid, citric acid, lactic acid. , And organic acids such as succinic acid. When blending the astringent component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but with respect to the total amount of the external composition for skin of the present invention, for example, about 0.0003 to 20 mass. %, preferably about 0.01 to 10% by weight.

Examples of the antioxidant component include butylhydroxyanisole, dibutylhydroxytoluene, sodium bisulfite, sodium pyrosulfite, erythorbic acid and its salt, ascorbic acid and its salt, flavonoid, glutathione, glutathione peroxidase, glutathione-S-transferase, catalase. , Superoxide dismutase, thioredoxin, taurine, thiotaurine, hypotaurine, plant extracts (honeysuckle flower extract, etc.) and the like. When blending the antioxidant component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but for example, about 0.00001 to 10% by mass relative to the total amount of the external composition for skin of the present invention. , Preferably about 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass.

Examples of the antiaging component include hydrolyzed soybean protein, retinoid (retinol, retinoic acid, retinal, etc.), pangamic acid, ursolic acid, turmeric extract, sphingosine derivative, silicon, silicic acid, N-methyl-L-serine, mevalonolactone. , Peptides (caproyl tetrapeptide-3, oligopeptide-24, etc.) and the like. Of these, hydrolyzed soybean protein, retinol, retinol acetate, retinol palmitate, caproyl tetrapeptide-3, and oligopeptide-24 are preferable. When blending the antiaging component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.0003 to 10 relative to the total amount of the external composition for skin of the present invention. % By weight, preferably about 0.01 to 5% by weight.

Examples of moisturizing ingredients include amino acids such as alanine, serine, aspartic acid, glycine, proline, hydroxyproline, glucosamine, theanine, and arginine and their derivatives; polyhydric alcohols such as glycerin and 1,3-butanediol; sorbitol, xylitol. , Sugar alcohols such as erythritol, maltose/sucrose condensate (glucooligosaccharide), glyceryl glucoside; glycosyl trehalose, trehalose; ceramide, glucosyl ceramide, cholesterol, phytosterols, cholesterol derivatives, phytosterol derivatives; lecithin, hydrogenated lecithin and other phosphorus Lipids; NMF-derived components such as lactic acid, sodium lactate, sodium pyrrolidonecarboxylate, and urea; collagen, elastin, keratin, chitin, chitosan, and their hydrolysates; hydroxyethylurea; plants (eg, chamomile, hamamelis, tea, Ingredients derived from perilla, grapefruit, armchair, etc.), and the like. Among them, glycine, arginine, glycerin, 1,3-butanediol, glycosyltrehalose, ceramide, glucosylceramide, cholesterol, cholesterol derivative, phytosterol derivative, hydrogenated lecithin, lactic acid, sodium lactate, sodium pyrrolidonecarboxylate, urea, collagen, A combination with one or more selected from elastin, keratin and hydroxyethylurea is preferable. When blending a moisturizing component, the content thereof can be appropriately selected in consideration of the feeling of use and effect on the skin, but is, for example, about 0.001 to 20 mass with respect to the total amount of the external composition for skin of the present invention. %, preferably about 0.01 to 10% by weight.

Examples of the polyhydric alcohol include diols having 2 to 4 or 11 or more carbon atoms, polyhydric alcohols having 3 or more hydroxy groups, and the like, for example, glycerin, diglycerin, triglycerin, propylene glycol, 1,3-butane. Examples include diol, ethylene glycol, diethylene glycol, isoprene glycol, and 1,3-butylene glycol. Of these, a combination with one or more selected from glycerin, diglycerin, propylene glycol, and 1,3-butylene glycol is preferable. When blending a polyhydric alcohol, the content can be appropriately selected in consideration of the feeling of use on the skin and the moisturizing effect, but with respect to the total amount of the external composition for skin of the present invention, for example, about 0.1 to 20% by weight, preferably about 0.5 to 15% by weight.

Examples of the keratin softening component include lanolin, urea, phytic acid, lactic acid, lactate, glycolic acid, salicylic acid, malic acid, citric acid, fruit acid, phytic acid, urea and sulfur. Among these, a combination with lactic acid, sodium lactate, glycolic acid, salicylic acid, phytic acid, and citric acid is preferable. When blending the keratin softening component, its content can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, 0.0001 to 50 mass with respect to the total amount of the external composition for skin of the present invention. %, preferably about 0.001 to 50% by weight, more preferably about 0.01 to 25% by weight.

Examples of vitamins include retinol, retinol acetate, retinol palmitate, retinol propionate, retinol linoleate, and other retinol derivatives, retinal, retinoic acid, methyl retinoate, ethyl retinoate, retinol retinoate, and d-δ-tocotone. Vitamin A's such as ferryl retinoate, α-tocopheryl retinoate and β-tocopheryl retinoate; professionals such as β-carotene, α-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthin and echinenone Vitamin A; dl-α-tocopherol, dl-α-tocopherol succinate, dl-α-tocopherol calcium succinate, δ-tocopherol, tocopherol nicotinate, dl-α-tocopheryl acetate, tocopherol linoleate, (linoleic acid/ Vitamin Es such as (oleic acid) tocopherol and (ascorbyl/tocopheryl) potassium phosphate; riboflavin, flavin mononucleotide, flavin adenine dinucleotide, riboflavin butyrate ester, riboflavin tetrabutyrate ester, riboflavin 5'-phosphate sodium salt, riboflavin tetra Vitamin B2s such as nicotinic acid ester; nicotinic acids other than the above-mentioned component (A) such as methyl nicotinate, nicotinic acid and benzyl nicotinate; ascorbyl stearate, disodium isostearyl ascorbyl phosphate, L-ascorbyl dipalmitate. , Ascorbyl tetraisopalmitate (ascorbyl tetra-2-hexyldecanoate), ascorbyl palmitate trisodium phosphate, ascorbic acid, sodium ascorbate, dehydroascorbic acid, sodium ascorbate phosphate, magnesium ascorbate phosphate, ascorbate Vitamin Cs such as glucoside, 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, glycerylascorbic acid, bisglycerylascorbic acid, alkylglycerylascorbic acid; methylhesperidin, ergocalciferol, cholecalciferol and the like. Vitamin Ds; Vitamin Ks such as phylloquinone and farnoquinone; Vitamin B1s such as thiamine and salts thereof (eg, dibenzoylthiamine hydrochloride, thiamine hydrochloride, thiamine diphosphate); pyridoxine hydrochloride, pyridoxine acetate, Pyridoxal hydrochloride, 5'-phosphate Vitamin B6s such as lidoxal and pyridoxamine hydrochloride, vitamin B12s such as cyanocobalamin, hydroxocobalamin and deoxyadenosylcobalamin; folic acid such as folic acid and pteroylglutamic acid; pantothenic acid, calcium pantothenate, pantothenyl alcohol (panthenol), Pantothenic acids such as D-pantetheine, D-pantethine, coenzyme A, pantothenyethyl ether, calcium pantetheine sulfonate; biotins such as biotin and biocytin; other than those, carnitine, ferulic acid, α-lipoic acid, orotic acid, Vitamin-like acting factors such as γ-oryzanol, pyrroloquinoline quinone, hesperidin and glucosylherperidine, ubiquinone, and salts thereof can be mentioned. Of these, combinations with vitamins B, vitamins C, vitamins E, vitamins A, and vitamin-like factors are preferable, and pyridoxine hydrochloride, pantothenyl alcohol (panthenol), riboflavin, cyanocobalamin, ascorbic acid, glucoside ascorbic acid, 3-O-ethylascorbic acid, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, acetic acid dl-α-tocopherol, ascorbyl palmitate, ascorbyl tetra-2-hexyldecanoate, retinol, retinol palmitate, propionic acid A combination with one or more selected from retinol, retinol acetate, pyrroloquinoline quinone or a salt thereof, ubiquinone and γ-oryzanol is more preferable. When blending vitamins, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.001 to 30 mass with respect to the total amount of the external composition for skin of the present invention. %, preferably about 0.01 to 25% by weight, more preferably about 0.01 to 20% by weight.

Examples of the blood circulation promoting component include plants (e.g., Panax ginseng, ashitaba, arnica, ginkgo, fennel, ginkgo, Dutch oak, chamomile, roman chamomile, carrot, gentian, burdock, rice, hawthorn, shiitake mushroom, hawthorn, hazelnut, sycamore. , Senburi, thyme, clove, cock, touki, tounin, spruce, carrot, garlic, butcher bloom, grape, button, horse chestnut, melissa, yuzu, yokinin, rosemary, rosehip, cock, touki, spruce, peach, apricot, Walnut, corn)-derived components; dl-α-tocopherol acetate, tocopherol nicotinate, glucosyl hesperidin, hesperidin. When blending the blood circulation promoting component, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.00001 to 10 relative to the total amount of the external composition for skin of the present invention. % By mass, preferably 0.0001 to 5% by mass, more preferably about 0.001 to 5% by mass. When using a plant-derived component, the content is, in terms of an extract such as an extract, for example, about 0.00001 to 20 mass%, preferably about 0.0001 to 15 mass% with respect to the total amount of the external composition for skin. %, and more preferably 0.001 to 10% by mass.

Examples of the sebum adsorbing component include talc, mica, hydroxyapatite, zinc oxide, aluminum silicate and the like. Among them, mica, hydroxyapatite and zinc oxide are preferable, and mica is particularly preferable. When the sebum adsorbing component is blended, its content can be appropriately selected in consideration of the feeling of use on the skin and the effect, but is, for example, about 0.001 to 35 relative to the total amount of the external composition for skin of the present invention. % By weight, preferably about 0.1 to 25% by weight.

Examples of the peptide or its derivative include keratin-degrading peptide, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, succinylated atelocollagen, gelatin, elastin, elastin-degrading peptide, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride. Degraded collagen, elastin degrading peptide, conchiolin degrading peptide, hydrolyzed conchiolin, silk protein degrading peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean protein degrading peptide, hydrolyzed soybean protein, wheat protein, wheat protein degrading peptide, hydrolysis Examples include wheat proteins, casein-degrading peptides, acylated peptides (palmitoyl oligopeptides, palmitoyl pentapeptides, palmitoyl tetrapeptides, etc.) and the like. Among them, selected from keratin degrading peptide, hydrolyzed keratin, fish-derived collagen elastin, elastin degrading peptide, collagen degrading peptide, hydrolyzing collagen, succinylated atelocollagen, elastin degrading peptide, hydrolyzed silk, soybean protein degrading peptide, hydrolyzed soybean protein, It is more preferable to use one kind or a combination of two or more kinds. When the peptide or its derivative is blended, the content thereof can be appropriately selected in consideration of the feeling of use on the skin and the effect, but for example, about 0.0001 to the total amount of the external composition for skin of the present invention. 35% by weight, preferably about 0.001 to 10% by weight.

Examples of amino acids or derivatives thereof include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine. , Methionine, leucine, isoleucine, valine, histidine, threonine, tyrosine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, creatine, epsilon aminocaproic acid, tryptophan, ornithine, N-stearoyl-L. -Sodium glutamate, lysine dilauroylglutamate and salts thereof, dilauroylglutamate (phytosteryl/octyldodecyl), dilauroylglutamate (octyldodecyl/phytosteryl/behenyl) and the like. Further, these amino acids or their derivatives may be solvates such as hydrates, and may be in any of d-form, l-form and dl-form. Among them, one or more kinds selected from l-amino acids or their derivatives are preferable.

In addition to the above-mentioned components, the composition for external use of the present invention may be appropriately blended with components generally used in the fields of pharmaceuticals, quasi drugs, cosmetics, etc., depending on the use or dosage form thereof. Good. The components that can be blended are not particularly limited, and examples include bases or carriers, surfactants, thickeners, antioxidants, preservatives, preservatives, pH adjusters, chelating agents, stabilizers, and irritation reducing agents. Additives such as colorants, dispersants, and fragrances can be added. In addition, these components can be blended individually by 1 type or in arbitrary combination of 2 or more types. In addition, the content thereof can be appropriately determined within a range that is conventionally known and does not impair the effects of the present invention. Furthermore, those corresponding to the following plurality of components can be added as components having arbitrary functions among them.

As a base or carrier, an aqueous base such as water; liquid paraffin, liquid isoparaffin, squalane, vaseline, paraffin, microcrystalline wax, polybutene, polyethylene powder, gelled hydrocarbon (plastibase, etc.), ozokerite, α-olefin oligomer Hydrocarbons such as light liquid paraffin and light iso liquid paraffin; phenyl-modified silicones such as methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, and cyclic silicones such as decamethylcyclopentasiloxane. , Methylhydrogenpolysiloxane, methyltrimethicone, dimethiconol, dimethiconol crosspolymer, caprylylmethicone and other alkyl modified silicones, crosslinked alkyl modified silicones, amino modified silicones, polyether modified silicones, polyglycerin modified silicones, crosslinked polyethers Modified silicone, crosslinked alkyl polyether modified silicone, silicone/alkyl chain co-modified polyether modified silicone, silicone/alkyl chain co-modified polyglycerin modified silicone, polyether modified branched silicone, polyglycerin modified branched silicone, acrylic silicone, phenyl modified Silicone, silicone oils such as silicone resins; higher alcohols such as cetanol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, isostearyl alcohol, phytosterols, cholesterol; isostearic acid, lauric acid, myristic acid, palmitin. Higher fatty acids such as acids, stearic acid, and behenic acid; cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose; polyvinylpyrrolidone;; polyvinyl butyrate; polyethylene glycol; dioxane; butylene glycol adipic acid polyester; myristic acid Isopropyl, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, isononyl isononanoate, diisopropyl adipate, decyl oleate, isodecyl oleate, hexyldecyl dimethyloctanoate, diisopropyl sebacate, di-2-ethylhexyl sebacate, myristin Acid 2-hexyldecyl, 2-hexyldecyl palmitate, diisopropyl adipate, isotonate isononanoate Lydecyl, cetyl lactate, isostearyl isostearate, cholesteryl 12-hydroxystearyl acid, cholesteryl stearate, cholesteryl oleate, macadamia nut fatty acid phytosteryl oleate, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, di-2- Ethyl glycol ethylhexylate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri-2-ethylhexyl trimellitate, tritridecyl trimellitate, tri-2-ethylhexyl trimethylolpropane, triisostearate trimethylolpropane, tetra-2- Pentaerythritol ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, tri(caprylic acid/capric acid) glyceryl, tri(caprylic acid/capric acid/myristic acid/stearic acid) glyceryl, oleic acid Oleyl, dilauroylglutamate (phytosteryl/octyldodecyl), dilauroylglutamate (octyldodecyl/phytosteryl/behenyl), triethyl citrate, dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl), dimer dilinoleic acid Esters such as merlinoleyl, dipentaerythrityl tripolyhydroxystearate, tri(behenic acid/isostearic acid/eicosandioic acid) glyceryl; jojoba oil, miuro, candelilla wax, rice bran wax, cotton wax, carnauba wax, lanolin and other waxes Avocado oil, linseed oil, camellia oil, macadamia nut oil, kukui nut oil, hazelnut oil, corn oil, olive oil, safflower oil, kyounin oil, cinnamon oil, jojoba oil, grape seed oil, sunflower oil, almond oil, shea butter, Southern oil, rapeseed oil, sesame oil, cocoa butter, coconut oil, hardened coconut oil, palm oil, palm kernel oil, okra kernel oil, mokurou, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil , Oils such as tea seed oil, evening primrose oil, and shea butter; polysaccharides such as dextrin and maltodextrin; vinyl-based polymers such as carboxyvinyl polymer and alkyl-modified carboxyvinyl polymer; lower alcohols such as ethanol and isopropanol; Sugar alcohols such as sorbitol, xylitol, erythritol, mannitol; water, etc. Are listed. As the base or carrier selected from these components, one kind may be used alone, or two or more kinds may be used in combination. Further, the amount used thereof is appropriately selected from the range known to those skilled in the art. When the external composition for skin of the present invention contains water, the content thereof is not particularly limited, since the amount of water varies depending on the form of the cosmetic. For example, the amount of water is preferably 5 to 99% by mass, more preferably 8 to 95% by mass, and further preferably 10 to 90% by mass with respect to the total amount of the external composition for skin of the present invention.

Examples of the surfactant include sorbitan monoisostearate, sorbitan monostearate, tetra-2-ethylhexyl diglycerol sorbitan, sorbitan monooleate, sorbitan monoisostearate and sorbitan monolaurate, and olive oil fatty acid sorbitan. Sorbitan fatty acid ester: polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (80) sorbitan monolaurate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, isostearic acid Polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene (20) sorbitan; glycerin fatty acid ester such as glycerin monooleate, glycerin monostearate, and glycerin monomyristate; glycerin such as monoisostearyl glyceryl ether and monomyristyl glyceryl ether Alkyl ethers; polyglycerin fatty acid esters such as diglyceryl monostearate, decaglyceryl decasterate, decaglyceryl decaisostearate, and diglyceryl diisostearate; propylene glycol fatty acid esters such as propylene glycol monostearate; poly Hydrogenated castor oil derivatives such as oxyethylene hydrogenated castor oil 40, polyoxyethylene hydrogenated castor oil 50, polyoxyethylene hydrogenated castor oil 60, polyoxyethylene hydrogenated castor oil 80; polyoxyethylene such as polyoxyethylene monococonut fatty acid glyceryl Glycerin fatty acid ester; polyoxyethylene (20) phytosterols, polyoxyethylene (30) phytosterols, polyoxyethylene (25) phytostanols, polyoxyethylene (30) cholestanol and other polyoxyethylene sterols, hydrogenated sterols; sucrose Fatty acid ester; polyoxyalkylene alkyl (or alkenyl) ether sulfate, ether carboxylate, alkyl phosphate ester salt, N-acyl amino acid salt, acylated taurate; amines such as stearylamine and oleylamine; polyoxyethylene methyl Silicone-based surfactants such as polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lecithin, hydrogenated lecithin, saponin, surfactin Examples include naturally occurring surfactants such as sodium, cholesterol and bile acids.

Examples of the thickener include polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, vinyl thickeners such as carboxyvinyl polymer, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, Cellulosic thickeners such as carboxyethyl cellulose, guar gum, sclerotium gum, tamarind gum, xanthan gum, gellan gum, dextran, pectin, pullulan, gelatin, locust bean gum, carrageenan, agar, acrylic acid alkyl methacrylate copolymer, poly Sodium acrylate, bentonite, dextrin fatty acid ester, dimethyl distearyl ammonium hectorite, sodium alginate, propylene glycol alginate ester, polyethylene glycol, macrogol, (hydroxyethyl acrylate/acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurine ammonium/ Vinylpyrrolidone) copolymer and the like. Among them, xanthan gum, alkyl acrylate copolymer, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxyvinyl polymer, dimethyl distearyl ammonium hectorite, (hydroxyethyl acrylate/acryloyl dimethyl taurine Na) copolymer, (acryloyl) A dimethyltaurine ammonium/vinylpyrrolidone) copolymer is preferred.

Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, ascorbic acid derivative, tocopherol, tocopherol derivative, erythorbic acid, sodium erysorbate, L-cysteine hydrochloride, coenzyme Q10 and the like. Ubiquinones, lignans such as sesamin, curcumin, capsaicin, gingerol, resveratrol, anthocyanin, cyanidin, bilberry extract, and analogs or derivatives thereof.

Examples of the preservative or preservative include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and paraoxybenzoate. Benzyl benzoate, methyl paraoxybenzoate, phenoxyethanol, benzyl alcohol, chlorobutanol, sorbic acid and its salts, chlorhexidine gluconate, methylisothiazolinone, propynyl butylcarbamate, capryl hydroxamic acid, phenethyl alcohol, ethylhexylglycerin, caprin. Examples thereof include glyceryl acid and isopropylmethylphenol. When a preservative/preservative is added, its content can be appropriately selected in consideration of the feeling of use on the skin and the effect, but it is, for example, about 0.001 based on the total amount of the external composition for skin of the present invention. % To 5% by weight, preferably about 0.01 to 1% by weight.

Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, etc.), organic acids (lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, sodium succinate, etc.), inorganic bases (potassium hydroxide, hydroxide). Sodium, etc.), organic bases (triethanolamine, diisopropanolamine, triisopropanolamine, etc.) and the like.

Examples of the chelating agent include ethylenediamine tetraacetic acid (edetic acid), ethylenediamine tetraacetic acid salt (sodium salt (sodium edetate: Japanese Pharmacopoeia, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphoric acid. , Metaphosphoric acid, and the like. Of these, sodium edetate is preferable.

Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, butylhydroxyanisole and the like.

Examples of the irritation reducing agent include licorice extract, gum arabic, polyvinylpyrrolidone and the like.

[PH]
The external composition for skin of the present invention may generally have physical properties of pH 2.0 to 9.0, but from the viewpoint of low irritation to the skin and mucous membranes and good feeling on use on skin, it is preferably pH 3. The pH is 0 to 8.5, more preferably pH 4.0 to 8.0, still more preferably pH 4.5 to 7.5, and still more preferably pH 5.0 to 7.5.

[Method for producing external composition for skin]
The method for producing the external composition for skin of the present invention is not particularly limited, and in addition to the above-mentioned components (A) to (C), the above-mentioned other components and the like are appropriately selected and blended, and emulsification is carried out by a conventional method as necessary. It can be done and manufactured.

[Property/Formulation]
The properties of the external composition for skin of the present invention are not particularly limited, and may be liquid, fluid, or semi-solid. In addition, the dosage form includes, for example, a liquid agent, a suspension agent, an emulsion, a cream agent, an emulsion, an ointment agent, a gel agent, a liniment agent, a lotion agent, an aerosol agent, a sheet agent in which a non-woven fabric is impregnated with a drug solution, a mist agent, etc. It can be a formulation. Among them, emulsions, creams, emulsions, ointments, gels, lotions and sheets are preferable, and creams, emulsions, gels, lotions and sheets are particularly preferable. When it contains an oily base and an aqueous base such as an emulsion, a cream or an ointment, it may be a W/O type or an O/W type. The O/W type is more preferable from the viewpoint of ensuring viscosity and the feeling of use (stickiness, spreadability, moistness, etc.).

[Use applications]
Specific examples of the use as an external composition for quasi-drugs or cosmetics include, for example, lotion, emulsion, gel, cream, beauty essence, sunscreen cosmetic, pack, mask, all-in-one gel, Basic cosmetics such as hand creams, body lotions, and body creams; as well as cleansing cosmetics such as face washes, hand soaps, makeup removers, body shampoos, shampoos, rinses, and treatments, foundations, makeup bases, etc. Makeup cosmetics, lip cosmetics such as lip balms, lip liners, lip gels; hair rinses for hair, hair treatments, hair conditioners, hair gels, hair mousses, hair mist, hair lotions, hair styling agents such as styling agents, etc. Are listed. Of these, an external composition for skin is particularly preferable. That is, the external composition of the present invention can be a skin external composition for pharmaceuticals, quasi drugs, or cosmetics. The formulation form of the external composition for skin is the same as that of the external composition of the present invention. Further, usable bases or carriers, additives, active ingredients, and preferable ones thereof are the same as those in the case of the external composition of the present invention.

[container]
The external composition for skin of the present invention can be used by being housed in a container having an appropriately selected shape and material according to the purpose of use and application. Specific examples of the container include spray type, bottle type, tube type, jar type, drop type, dispenser type, stick type, pouch bags, and cheer packs. Due to the effect of the present invention in which coloring is suppressed, the external composition for skin of the present invention can increase the degree of freedom in design with respect to the color of the container, the transparency, shape, and design of the container from the viewpoint of appearance. For example, for a composition that is colored over time, it is necessary to select an opaque container, or to select a container color corresponding to the degree and tint of coloring. In the external composition for skin of the present invention, for example, It is possible to select a container color that can be avoided in a transparent container or a composition in which coloring such as white is seen. Here, the transparent container includes both a colorless transparent container and a colored transparent container. In addition, the external composition for skin of the present invention can be preferably used for a container dosage form such as a jar type in which the composition is easily visible in a wide range due to the effect of the present invention in which coloring is suppressed.

Examples of the material of the container include polyethylene terephthalate, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, metal (aluminum, etc.), and the like. In addition, these materials may be subjected to various coating treatments in consideration of strength, flexibility, weather resistance, stability of components, etc., or may be combined or laminated by mixing these materials, for example. It can be used as a container material. Examples of the coating material include epoxy resin and polyamide-imide. Of these, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ethylene vinyl alcohol resin, and metal (aluminum, etc.) are preferably used.

[How to use]
The external composition for skin of the present invention can be suitably used for the purpose of promoting blood circulation, anti-inflammation, and promoting ceramide synthesis in expectation of physiological activity of nicotinic acid amide. In addition, whitening, anti-wrinkle and anti-aging effects can be expected, and it is useful as a multi-functional preparation including a whitening agent and a sunscreen. The external composition for skin of the present invention can be used once or several times a day in accordance with the intended use and the like in a well-known or commonly used usage and dose.

[Color suppression method]
In another embodiment, the present invention can also provide a method for suppressing coloration of an external composition for skin containing (A) nicotinamide. (A) Nicotinic acid amide; (B) Hyaluronic acid, derivatives thereof, salts thereof, and two or more kinds selected from the group consisting of heparin-like substances; and (C) External composition for skin containing amphipathic compound As a result, it is possible to suppress the coloring of the external composition for skin. In the above method, the components (A) to (C) and other optional components, properties, dosage forms, applications, etc. are in accordance with the description of the above composition.

In the present specification, “coloring” refers to coloring that can be detected by a device such as a color difference meter or an absorptiometer regardless of the form of the external composition for skin of the present invention. The coloring may be visible, but coloring that is difficult to detect visually is also called coloring here. For example, when the external composition for skin of the present invention is prepared as an aqueous composition, it is preferably colorless and transparent, but due to an accelerated test for thermal stability, it turns yellow with time. Staining suppression refers to preventing, delaying and reducing such coloring. In the present specification, the suppression of coloration is derived from the change with time of the composition containing the components (A) to (C), with the composition containing the components (A) and (B) at the same concentration as a control. Coloring is detected with a color difference meter (manufactured by Konica Minolta Co., Ltd.), and a change in b ^* value, that is, a Δb ^* value is compared to improve the degree of coloring at a level at which it can be detected.

In another embodiment, without limitation, one or more selected from the group consisting of (A) nicotinamide 5% by mass or more; (B) hyaluronic acid, its derivatives, salts thereof, and heparin-like substances. And (C) an amphipathic compound-containing external composition for skin. In the examples described below, when nicotinic acid amide of 5% by mass or more of the component (A) is blended, coloring occurs even if only one component (B) is allowed to coexist, which is different from the above. Challenges have been found. In this case, the component (B) preferably contains at least acetylated hyaluronic acid and/or its salt. With respect to this problem as well, it is possible to exert the effect of suppressing coloration by adding the amphipathic compound (C). The components (B) and (C) that can be contained in addition to the above, other optional components, the content, properties, dosage form, use, etc. are in accordance with the description of the above composition.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

The components used in the examples are as follows. The numerical value in each table is the content of the component itself described in the component name.

Polyoxyethylene methyl glucoside: McBioobride MG-10E (manufactured by NOF CORPORATION)
Polyoxypropylene methyl glucoside (10P.O.): McBiobride MG-10P (manufactured by NOF CORPORATION)
Polyoxyethylene polyoxypropylene butyl ether (17EO) (17PO): Unilube 50MB-26 (manufactured by NOF CORPORATION)
Polyoxyethylene polyoxypropylene glyceryl ether (24EO) (24PO): Unilube 50TG-32 (manufactured by NOF CORPORATION)
Polyoxybutylene polyoxyethylene polyoxypropylene methyl glucoside: Willbride MG2070 (manufactured by NOF CORPORATION)
Polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether (3BO) (8EO) (5PO): Willbride S-753 (manufactured by NOF CORPORATION)
Polyoxypropylene diglyceryl ether: SY-DP14 (Sakamoto Yakuhin Kogyo Co., Ltd.)
Polyoxyethylene polyoxypropylene glycol (19E.O.) (21P.O.): Pronone #124P (manufactured by NOF CORPORATION)
Polyoxyethylene polyoxypropylene glycol (26EO) (30PO): Pronone #184R (manufactured by NOF CORPORATION)
Cyclohexanedicarboxylic acid bisethoxydiglycol: Neosolue aquilio (manufactured by Nippon Seika Co., Ltd.)
(Eicosanodioic acid/tetradecanedioic acid) decaglyceryl: Neosolue-AquaS (manufactured by Nippon Seika Co., Ltd.)
2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer: Lipidure-PMB (BG) (manufactured by NOF CORPORATION)
Polyoxyethylene polyoxypropylene decyl tetradecyl ether (24EO) (13PO): Solvure GS-01 (NOF CORPORATION)
Polyoxypropylene sorbit (25 PO): Uniol HS-1600D (manufactured by NOF CORPORATION)

[Test Example 1 Thermal stability test]
A sample was prepared by mixing various components with the compositions shown in Tables 1 to 3 below by a conventional method, and then the sample was placed in a 20 mL glass vial and heated in a constant temperature bath set at 60° C. for 1 week. After one week, changes in color (changes in appearance and changes in color difference) were evaluated visually and by a spectrocolorimeter.

(Evaluation method)
The evaluation criteria for the change in colored appearance are as follows.
For each sample filled in a transparent glass vial, the one stored for 1 week in a constant temperature bath at 4°C was used as a reference, and the one stored for 1 week in a constant temperature bath at 60°C (accelerated test) showed a difference in color visually. Was judged.

(Visual coloring criteria)
◎ No change ○ Almost no coloring × Coloring

Further, a more detailed evaluation method of the color difference by the spectrocolorimeter is as follows.
Each sample filled in a transparent glass vial was stored in a constant temperature bath at 4°C for 1 week, and then stored in a constant temperature bath at 60°C for 1 week (accelerated test). A color difference meter (CM3500d: Konica Minolta).

(Evaluation method)
Using a spectrophotometer (CM3500d: manufactured by Konica Minolta), the coloration of the preparation after the heat test was evaluated by the b ^* value. Specifically, the b ^* value after the accelerated test of each example and the b ^* value of the reference sample corresponding to each example stored in a constant temperature bath at 4° C. for 1 week were measured, and each test was performed. in the example, the sample after the accelerated test, the difference between b ^* values of the corresponding reference sample - was assessed by calculating the ([Delta] b ^* value = sample b ^* value after the accelerated test of the reference sample b ^* values).
The b ^* value is used as an index of transparency. Therefore, the larger the Δb ^* value is, the more the effect of suppressing the coloring of the preparation is exhibited. The results of b ^* value and Δb ^* value are also shown in Tables 1 to 3.

(Color difference judgment standard)
◎ Δb ^* less than 0.4 ○ Δb ^* 0.4 or more and less than 0.5 × Δb ^* 0.5 or more

As shown in Table 1, coloring was not caused only by blending the component (B) (Comparative Example 1), however, 3% by mass or more of the component (A) nicotinic acid amide, and the component (B) hyaluronic acid and a salt thereof. , And a new problem that coloring occurs when two or more kinds selected from the derivatives are mixed together (Comparative Example 2). On the other hand, as shown in Tables 2 and 3, in each of the Examples, it was confirmed that the coloring with time was suppressed when the amphipathic compound (C) was further contained.

[Test Example 2 Thermal stability test]
A sample was prepared by mixing various components with the compositions shown in Tables 4 to 6 below by a conventional method, and then the sample was placed in a 20 mL glass vial and heated in a thermostat set at 60° C. for 1 week. After one week, changes in color (changes in appearance and changes in color difference) were evaluated visually and by a spectrocolorimeter. The evaluation method is the same as in the case of Test Example 1.

[Color suppression]
In addition to the evaluation method of Test Example 1, based on the [Delta] b ^* values in Comparative example problem occurs, it was evaluated by calculating the coloration degree of inhibition by the following equation the effect of the [Delta] b ^* values due to the addition of the component C ..

Suppressing coloration degree = ([Delta] b ^* value of Comparative Example in which problems occurred - [Delta] b ^* values for each Example) / [Delta] b ^* value × 100 of each example

In Example 2-1 to Example 2-10, the Δb ^* value in Comparative Example 2-1 was used as a reference for calculating the degree of coloring suppression.

(Criteria for determining the degree of color suppression)
◎ Color suppression degree 30% or more ○ Color suppression degree 10% or more and less than 30% △ Color suppression degree 4% or more and less than 10%

As shown in Table 4, coloring was not caused only by blending the component (B) (Comparative Example 1), but 5% by mass or more of the component (A) nicotinic acid amide and the component (B) hyaluronic acid or a derivative thereof , And a new problem that coloring occurs when two or more kinds selected from the salts thereof are blended together (Comparative Example 2-1). On the other hand, as shown in Tables 5 and 6, in each of the Examples, it was confirmed that the coloring with time was suppressed when the amphipathic compound (C) was further contained. Further, when nicotinic acid amide of 5% by mass or more of the component (A) is blended, even if the coexisting component (B) is only one kind of sodium acetylated hyaluronate, coloring occurs, which is the above. Different novel problems were found (Comparative Example 2-4). For the problem in the case of blending 5% by mass or more of the component (A) nicotinic acid amide, when the (C) amphipathic compound used in Example 2-1 to Example 2-10 is contained. It was confirmed that the coloring with time was suppressed.

[Test Example 3 Thermal stability test]
A sample was prepared by mixing various components with the compositions shown in Tables 7 to 8 below by a conventional method, and then the sample was placed in a 20 mL glass vial and heated in a thermostat set at 60° C. for 1 week. After one week, changes in color (changes in appearance and changes in color difference) were evaluated visually and by a spectrocolorimeter. The evaluation method is the same as in the case of Test Example 2. In Example 3-1 to Example 3-5, the Δb ^* value in Comparative Example 3-2 was used as the reference for calculating the degree of coloring suppression.

As shown in Table 7, coloring was not caused only by blending the component (B) (Comparative Example 3-1), but 5% by mass or more of the component (A) nicotinic acid amide, and the component (B) hyaluronic acid, A new problem was found that coloring occurs when the derivative and two or more kinds selected from the salt thereof are mixed together (Comparative Example 3-2). On the other hand, as shown in Table 8, in each of the Examples, it was confirmed that the coloring with time was suppressed when the amphipathic compound (C) was further contained.

[Test Example 4 Thermal stability test]
A sample was prepared by mixing various components with the compositions shown in Tables 9 to 10 below by a conventional method, and then the sample was placed in a 20 mL glass vial and heated in a constant temperature bath set at 60°C for 1 week. After one week, changes in color (changes in appearance and changes in color difference) were evaluated visually and by a spectrocolorimeter. The evaluation method is the same as in the case of Test Example 2. In Example 4-1 to Example 4-3, the Δb ^* value in Comparative Example 4-2 was used as the reference for calculating the degree of coloring suppression.

As shown in Table 9, coloring was not caused only by blending the component (B) (Comparative Example 4-1), but 5% by mass or more of the component (A) nicotinic acid amide, and the component (B) hyaluronic acid, A novel problem has been found that coloring occurs when the derivative and two or more kinds selected from the salt thereof are mixed together (Comparative Example 4-2). On the other hand, as shown in Table 10, in each of the examples, it was confirmed that the coloring with time was suppressed when the amphipathic compound (C) was further contained.

[Test Example 5 Thermal stability test]
A sample was prepared by mixing various components with the compositions shown in Tables 11 to 13 below by a conventional method, and then the sample was placed in a 20 mL glass vial and heated in a constant temperature bath set at 60° C. for 1 week. After one week, changes in color (changes in appearance and changes in color difference) were evaluated visually and by a spectrocolorimeter. The evaluation method is the same as in the case of Test Example 2. In Examples 5-1 to 5-12, the Δb ^* value in Comparative Example 5-2 was used as a reference for calculating the degree of coloring suppression.

As shown in Table 11, coloring was not caused only by blending the component (B) (Comparative Example 5-1), but nicotinic acid amide of 3% by mass or more of the component (A), hyaluronic acid of the component (B), A novel problem has been found in that coloring occurs when the derivative, the salt thereof, and two or more kinds selected from the group consisting of heparin-like substances are mixed together (Comparative Example 5- 2). On the other hand, as shown in Tables 12 to 13, in each of the examples, it was confirmed that the coloring with time was suppressed when the amphipathic compound (C) was further contained.

[Example of formulation]
The external composition for skin (Formulation Examples 1 to 26) of the present invention was prepared based on the formulations shown in Tables 14 to 39 below.

In each of the formulation examples, an external composition for skin in which coloring was suppressed was obtained. Further, it was a good composition for external use on the skin with excellent feeling in use.

Claims (6)

(A) Nicotinic acid amide 3% by mass or more;
(B) Hyaluronic acid, derivatives thereof, salts thereof, and two or more kinds selected from the group consisting of heparin-like substances; and (C) an external composition for skin. The composition according to claim 1, wherein the content of the component (A) is 3 to 20% by mass. The component (C) is a compound represented by the following general formula (I), 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxy. The composition according to claim 1 or 2, which is one or more selected from diglycol, diethylhexyl succinate, diethoxyethyl succinate, and alkanediol having 5 to 10 carbon atoms.

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
BO means an oxyalkylene group having 4 carbon atoms;
n means 1 to 9;
a, b and c mean the average number of moles of addition of AO, EO and BO, respectively, and are independently 0 to 200. However, a, b, and c are not all 0. When n is 2 or more, a, b and c may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. ) The component (C) is a compound represented by the following general formula (II), 2-methacryloyloxyethylphosphorylcholine/butyl methacrylate copolymer, (eicosanedioic acid/tetradecanedioic acid) decaglyceryl, cyclohexanedicarboxylic acid bisethoxy. The composition according to claim 1 or 2, which is one or more selected from diglycol, diethylhexyl succinate, diethoxyethyl succinate, and alkanediol having 5 to 10 carbon atoms.

(In the formula,
Z means a hydrogen atom or a residue obtained by removing n hydroxy groups from a hydroxy compound having 1 to 30 carbon atoms;
AO means an oxyalkylene group having 3-4 carbon atoms;
EO means an oxyethylene group;
n means 1 to 9;
a and b mean the average addition mole number of AO and EO, respectively, and are 0-200 independently. However, a and b do not all become 0. When n is 2 or more, a and b may be the same or different. When Z is a hydrogen atom, n is 1.
The AO and EO may be added randomly or in the form of blocks. ) In the general formulas (I) and (II), Z is a hydrogen atom, or an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, trimethylolpropane, erythritol, pentaerythritol, alkyl glucoside, diglycerin, The composition according to claim 3 or 4, which is a residue obtained by removing n hydroxy groups from xylitol, dipentaerythritol, sorbitol, inositol, sucrose, trehalose, or maltitol. In the general formulas (I) and (II), Z is a hydrogen atom, or by removing an n hydroxy group from an alkyl monoalcohol having 4 to 24 carbon atoms, glycerin, or diglycerin. The composition according to claim 3 or 4, which is the obtained residue.