JP6305157B2 - Composition, cosmetics - Google Patents

Description

  The present invention relates to a composition and a cosmetic.

  The stratum corneum on the skin surface is mainly composed of keratinocytes and keratin intercellular lipids. The stratum corneum lipids connect corneocytes to each other, build a lipid barrier, prevent foreign substances from entering from the outside, and maintain moisture in the skin. The stratum corneum lipid is composed mainly of a compound group (ceramide) formed by amide bond of sphingosine and fatty acid.

  If ceramide can be supplied to the skin surface from outside the body, the barrier function and the like can be improved. Therefore, ceramide has attracted attention as a component of cosmetics or skin external preparations applied to the skin surface.

  However, since ceramide has high crystallinity, there is a problem that stability in compositions such as cosmetics is low.

  As a composition attempted to solve this problem, a ceramide-containing composition in which at least one of a specific polyglycerol fatty acid ester and glycerol mono-fatty acid ester is contained in ceramides is known (Patent Document 1). 2). According to this composition, crystallization / precipitation of ceramides can be suppressed to a predetermined extent.

JP 2011-073992 A JP2013-053146A

However, the above conventional composition still has room to suppress crystallization and precipitation of ceramides.
Therefore, the present invention provides a composition that can suppress crystallization and precipitation of ceramides in the composition and can increase the stability of the ceramides in the composition, and in a cosmetic. An object of the present invention is to provide a cosmetic that can suppress the ceramides from crystallizing and precipitating and can enhance the stability of the ceramides in the cosmetic.

The gist of the present invention is as follows.
The composition of the present invention comprises ceramides and labdenic acids. Here, in the composition of the present invention, the ratio of the labdenic acids to the ceramides is preferably 0.01 to 100, and more preferably 0.1 to 50.
The cosmetic of the present invention is characterized by containing the composition of the present invention.
In addition, the "ratio" about the component contained in the composition of this invention and the cosmetics of this invention points out a mass ratio.

The gist of the present invention is as follows.
The compositions of the present invention, viewed contains a ceramide analog and Rabuden acids, Rabuden acids represented by the following formula (S4)
[Wherein the bond by three dotted lines represents two single bonds and one double bond]
The ratio of labdenic acids to ceramides is 0.01 to 50 .
The cosmetic of the present invention is characterized by containing the composition of the present invention.
The method for inhibiting crystallization / precipitation of ceramides of the present invention is characterized by using labdenic acids.
In addition, the "ratio" about the component contained in the composition of this invention and the cosmetics of this invention points out a mass ratio.

About the composition according to this invention and the composition used as the comparative example of this invention, the result of having made the microscope observation under polarization | polarized-light under the conditions of 20 times of magnification and exposure time 1/300 second using an upright microscope is shown. It is a photograph. (A) is a photograph in the case of a composition (Example A7) according to the present invention comprising ceramides and labdenic acids, and (b) is a comparative example of the present invention comprising ceramides and jojoba oil. It is a photograph in the case of a composition (comparative example A3).

  Hereinafter, embodiments of the composition of the present invention and the cosmetic of the present invention will be described in detail.

(Composition)
An example composition of the present invention (hereinafter, also referred to as “example composition”) needs to contain ceramides and labdenic acids.

  The present invention has been found that, in a composition containing ceramides and labdenic acids, labdenic acids have the effect of reducing the crystallinity of the ceramides. According to the composition of this invention, it can suppress that ceramides crystallize and precipitate in a composition, and can improve stability in the composition of ceramides. Although labdenic acids are known to have a moisturizing effect, a whitening effect, etc., there is no description or suggestion that they have an effect of suppressing crystallization and precipitation of ceramides.

  Moreover, according to the composition of the present invention, as described above, the stability of the ceramides in the composition is increased, so that the ceramides can be uniformly applied onto the skin. Therefore, the barrier function of the stratum corneum on the skin surface, and thus the foreign substance intrusion preventing effect and the moisture retaining effect can be enhanced.

-Ceramides-
The ceramides in the present invention are a compound having a structure in which a sphingoid and a fatty acid are amide-bonded as a basic structure (hereinafter also referred to as “basic ceramide”), a derivative of the above basic ceramide (hereinafter also referred to as “ceramide derivative”). An analog synthesized by mimicking the above basic ceramide and its derivatives (hereinafter also referred to as “ceramide analog”), a sphingoid.
The ceramides in the present invention may be derived from a synthetic product, a natural product (for example, a plant extract) or the like.

--Basic ceramide--
As the basic structure of the basic ceramide, a structure represented by the following formula (S1) can be given.
Of the basic ceramides represented by the above formula (S1), ceramide 1 to ceramide 10 are ceramides (skin ceramides) contained in the human stratum corneum.
In fact, there are various modified examples of ceramides derived from humans and other animals with respect to the sphingoid and fatty acid alkyl chain lengths shown in the above formula (S1). The basic ceramide includes compounds having the same skeleton as the compound shown in the formula (S1) except for the alkyl chain length.
Further, as the above basic ceramide, either a natural type (D (−) form) optically active substance or a non-natural type (L (+) form) optically active form may be used. A mixture with a non-natural type may be used. The relative configuration of a plurality of asymmetric carbons in the basic ceramide structure may be a natural configuration, a non-natural configuration other than that, or a mixture thereof. Good.

Examples of the sphingoid moiety contained in ceramides include natural sphingosine and its analogs. Specific examples of the natural sphingosine include sphingosine, swfdihydrosphingosine, phytosphingosine, 6-hydroxysphingosine (shown in the above formula (S1)), sphingadienin, dehydrosphingosine, dehydrophytosphingosine, and these And derivatives such as N-alkylated products (for example, N-methylated products) and acetylated products.
Examples of the fatty acid moiety contained in the ceramides include saturated fatty acids, α-hydroxy fatty acids, ω-hydroxy fatty acids, and derivatives thereof.
The sphingoid part and the fatty acid part contained in the ceramides may be derived from a synthetic product, a natural product (for example, a plant extract) or the like.

--Ceramide derivative--
Examples of the ceramide derivative include a ceramide compound modified in the molecule with a saccharide (hereinafter also referred to as “sugar ceramide”). Examples of the saccharide used in the sugar ceramide include monosaccharides such as glucose and galactose; disaccharides such as lactose and maltose; oligosaccharides and polysaccharides in which these monosaccharides and disaccharides are polymerized by glucoside bonds Is mentioned. As another ceramide derivative, a ceramide compound (hereinafter referred to as “sugar ceramide”) modified in the molecule with a saccharide analog in which the hydroxyl group contained in the saccharide unit of the saccharide is substituted with another functional group in the saccharide ceramide. Also referred to as “analogue”. Examples of the saccharide analog used for the sugar ceramide analog include glucosamine, glucuronic acid, N-acetylglucosamine and the like.
The number of sugar units in sugar ceramide and sugar ceramide analogs is preferably 1 to 5 from the viewpoint of dispersion stability in the composition, and 1 or 2 (in the case of sugar ceramide, the sugar is glucose or lactose, respectively. ) Is more preferable, and 1 is particularly preferable.
Sugar ceramide and sugar ceramide analogs may be obtained by chemical synthesis or by purchase of commercially available products.
Examples of commercially available sugar ceramides include (trade name) “plant sphingo liquor FR1” manufactured by Okayasu Shoten.

--Ceramide analogs--
Examples of the ceramide analog include a ceramide compound represented by the following formula (S2).

--Sphingoid--
Furthermore, the ceramides in the present invention include sphingoids. Examples of the sphingoid include those used for the sphingoid part contained in the aforementioned ceramides.
Specific examples of the phytosphingosine preferably used in the present invention include “Phytosphingosine” (trade name) manufactured by Evonik Goldschmidt GmbH.

  What was illustrated as said ceramides may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ceramides in the present invention are preferably basic ceramides, more preferably skin ceramides, and particularly preferably ceramides 2 from the viewpoint of sufficiently obtaining the effects of the present invention described above.

-Labdenic acids-
Labdenic acids in the present invention are represented by the following formula (S3)
[Wherein R ¹ represents —CH ₂ OH or COOR ⁶ , wherein R ⁶ represents hydrogen, a lower alkyl group having 1 to 3 carbon atoms, or a cation capable of forming a salt with COO—, R ^{2 to} R ⁵ each independently represents a hydrogen atom or a methyl group,... A is a ═C (CH ₃ ) —, —C (CH ₃ ) ═, —C (═CH ₂ ) —, -CH (CH ₃₎ - or _{-C (OH) (CH 3)} - represents a. ]
The compound represented by these is pointed out.
The labdenic acids in the present invention may be derived from a synthetic product, a natural product (for example, a plant extract) or the like.

The compound represented by the above formula (S3) is represented by the following formula (S4).
[Wherein the bond by three dotted lines represents two single bonds and one double bond]
The compounds represented by the following formulas (S5) to (S7)
Rubbed-8-ene-15-oic acid ((S5)), Rubbed-7-en-15-oic acid ((S6)), Rubbed-8 (17) -en-15-oic Acid ((S7)) is included. In addition, the compounds of the above formulas (S5) to (S7) can be isomerized by heating or heating in the presence of an acid catalyst, respectively, and the ratio of (S5), (S6), and (S7) is, for example, About 1: 1: 1, 8: 2: 0, or 7: 3: 0.

  What was illustrated as said labdenic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

The carboxyl group that the labdenic acid used in the present invention has in the molecule may be a free carboxylic acid, such as a carboxylate, for example, an alkali metal salt such as a sodium salt or a potassium salt; a calcium salt, a magnesium salt, or the like Alkaline earth metal salt; ammonium salt; primary amine salt such as monomethylammonium salt, secondary amine salt such as dimethylammonium salt and dicyclohexylammonium salt, and amine salt such as tertiary amine salt such as trimethylammonium salt There may be.
If the carboxyl group is a free carboxylic acid, the oil solubility of labdenic acids can be increased, and if the carboxyl group is a carboxylic acid salt, the water solubility of labdenic acids can be increased. Therefore, in the present invention, water-soluble labdenic acids and oil-soluble labdenic acids can be properly used as necessary.
Conversion from free carboxylic acid to carboxylate, for example, conversion from carboxylate to free carboxylic acid by reaction with alkali metal hydroxide, alkaline earth metal hydroxide, amine, etc. Can be easily carried out, for example, by reaction with hydrochloric acid, sulfuric acid or the like.

  When the labdenic acid is obtained by chemical synthesis, for example, a method (J. Chem. Soc., 1956, 4262-4271) using labdenoic acid by dehydration reaction of labdanolic acid can be used. As another synthesis method, first, manur or sclareol is used, alcohol is used as a solvent, vanadic acid or molybdic acid is used as a catalyst, and allyl alcohol is obtained by an allyl rearrangement reaction performed in the presence of boric acid. Allyl alcohol is converted into an aldehyde by an oxidation reaction using a ruthenium-phosphine complex as a catalyst, and this aldehyde is converted into a carboxylic acid by an oxidation reaction performed in the presence of an oxidizing agent such as sodium chlorite and amidosulfuric acid. In addition, a method of converting carboxylic acid into labdenic acids by a dehydration reaction using an acid catalyst can also be used.

When labdenic acid is obtained by extraction from a plant, the plant used is not particularly limited as long as it is a plant containing labdenic acid or a salt thereof, but is preferably a plant belonging to the family Hannibalidae, and in particular, Cistus ladaniferus L. Cistus criticus L. , Cistus monoperiensis L .; Cistus salvifolius is more preferred. These plants may be used alone or in combination of two or more.
The plant part used for extraction is not particularly limited, and examples thereof include leaves, branches, trunks, and bark. The extraction may be performed immediately after collection of the plant, may be performed after drying the collected plant, or may be performed after treatment (for example, cutting or pulverization) of the dried plant. As a solvent used for extraction, water, lower alcohol, petroleum ether, hydrocarbon, or a combination thereof is desirable. Here, the lower alcohol refers to an alcohol having 1 to 4 carbon atoms, and methanol and ethanol are particularly preferable.

  Here, the ratio of labdenic acids to ceramides is preferably 0.01 or more. If the said ratio is 0.01 or more, the said effect of improving the stability in the composition of ceramides can fully be ensured. Moreover, it is preferable that the said ratio is 100 or less. If the said ratio is 100 or less, the said effect of improving the stability in the composition of ceramides can be acquired, ensuring the effect of ceramides holding a water | moisture content in a stratum corneum.

  The ratio of labdenic acid to ceramides is preferably the same as the above lower limit, preferably 0.1 or more, more preferably 0.25 or more, and the same meaning as the above upper limit. Preferably it is 50 or less, more preferably 20 or less.

  The composition of an example may be a composition composed only of ceramides and labdenic acids. In this case, ceramides and labdenic acids may be mixed without a solvent.

  An example composition may include components other than ceramides and labdenic acids. Components other than ceramides and labdenic acids include oils, alcohols, water, surfactants, humectants, gelling agents (aqueous gelling agents and oily gelling agents) and thickeners, powders, UV absorbers , Preservatives and antibacterial agents, antioxidants, beauty ingredients (whitening agents, cell activators, anti-inflammatory agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, etc. Is mentioned. These may be used alone or in combination of two or more.

(Cosmetics)
An example cosmetic of the present invention (hereinafter, also referred to as “example cosmetic”) needs to contain the composition of the example of the present invention.

  According to the cosmetic of the present invention, the effect of the composition of the present invention described above can be obtained, that is, the effect of increasing the stability of ceramides in the cosmetic, the barrier function of the stratum corneum on the skin surface, and thus It is possible to obtain the effect of enhancing the foreign matter intrusion preventing effect and the moisture retention effect.

The ratio of ceramides to an example cosmetic can be 0.0001% by mass or more, preferably 0.001% by mass or more, and more preferably 0.005% by mass or more. Moreover, the said ratio can be 10 mass% or less, Preferably it is 5 mass% or less, More preferably, it is 1 mass% or less.
Moreover, the ratio of the labdenic acid with respect to cosmetics of an example can be 0.0005 mass% or more, Preferably it is 0.001 mass% or more, More preferably, it is 0.01 mass% or more. Moreover, the said ratio can be 20 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 1 mass% or less.

  In an example cosmetic, from the viewpoint of enhancing the effect of the cosmetic of the present invention, it is preferable to use an appropriately selected surfactant as a component other than ceramides and labdenic acids, and anionic and / or nonionic It is more preferable to use a surfactant, and it is particularly preferable to use a water-soluble nonionic surfactant.

  As described above, the ceramides in the cosmetic of the present invention are preferably natural optically active substances from the viewpoint of enhancing the barrier function and the like, and include ceramide 1, ceramide 2, ceramide 3, ceramide 4, ceramide 5, ceramide 6, Sphingosine, phytosphingosine, and sugar ceramide are more preferable, and ceramide 2, ceramide 3, and ceramide 6 are particularly preferable in view of versatility.

  As the labdenic acid in the cosmetic of the present invention, from the viewpoint of suppressing crystallization / precipitation of ceramides and enhancing the barrier function and the like, the above-mentioned labd-8-ene-15-oic acid (formula (S5)) ), Rubbed-7-ene-15-oic acid (formula (S6)), rubbed-8 (17) -en-15-oic acid (formula (S7)).

  An example cosmetic can be prepared in various forms such as, for example, liquid, emulsion, cream, solid, gel, and paste. Moreover, cosmetics of an example can be prepared with various dosage forms, such as an oil-based type, a water-in-oil type emulsion system, and an oil-in-water type emulsion system. Examples of cosmetics include skin care cosmetics such as lotions, milky lotions, creams, beauty essences, cosmetic oils, lip balms, hand creams, facial cleansers, cleansings; foundations, makeup bases, cheeks, Makeup cosmetics such as eye shadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick, lip gloss; hair tonic, hair cream, shampoo, rinse, conditioner, hair conditioner, etc. It can be set as various cosmetics, such as cosmetics.

  The cosmetic of the present invention includes quasi drugs. Moreover, the composition of this invention can also be included in things other than the above-mentioned cosmetics, for example, skin external preparations.

  In the composition of the present invention, for example, ceramides and labdenic acids are mixed, the mixture is heated at a temperature higher than the melting point of ceramides (for example, 70 to 140 ° C.), and then gradually (for example, 2 It can be produced by cooling (at ~ 30 ° C / min).

  As shown in the description of the present specification, the present invention provides a crystallization / precipitation inhibitor for ceramides containing labdenic acids as an active ingredient, and a method for suppressing crystallization / precipitation of ceramides using labdenic acids. Can do.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Example at all.

<Test P> Production of labdenic acid Hereinafter, Production Example 1 of labdenic acid will be described.
A labdenic acid represented by the following formula (S4) used in the following test is passed through the compounds represented by the following formulas (S9) and (S10) using the compound represented by the following formula (S8) as a starting material. Manufactured. In addition, the wavy line in following formula (S8) represents that it is an E body, a Z body, or these mixtures about a double bond.

  To a 2 L reaction vessel equipped with a drain pipe and a thermometer, 690.68 g of a 1,2,4-trimethylbenzene solution of primary allyl alcohol of the above formula (S8) was added. Under a nitrogen atmosphere, at 31 ° C., 21.733 g of dichloro (p-cymene) ruthenium (II) and 23.93 g of tris (4-methoxyphenyl) phosphine were added to the reaction vessel. The reaction solution was heated at 170 to 180 ° C. for 2 hours to oxidize the aldehyde. Thereafter, the reaction was stopped by cooling to 46 ° C. A part of the reaction solution after stopping the reaction was analyzed by HPLC to determine the conversion rate and yield of this reaction (conversion rate: 100%, yield: 61.95%). 710 g of a 1,2,4-trimethylbenzene solution containing the aldehyde of the above formula (S9) was used in the next reaction without purification.

In a 2 L reaction vessel equipped with a thermometer, 710 g of a 1,2,4-trimethylbenzene solution of the aldehyde of the above formula (S9), 300 g of 1,2,4-trimethylbenzene, 0.2 g of acetic acid, sulfamic acid (H ₂ NSO ₂ OH) _54.57g, the water 27.28g were added. The mixture was cooled to −5 ° C. in a dry ice-acetone bath. Next, an aqueous solution prepared by dissolving 63.54 g of 80% sodium chlorite (NaClO ₂ ) in 190.6 g of water was added dropwise over a period of 100 minutes between −8 to −4 ° C. After reacting at the same temperature for 2 hours, 425 g of 20% Na ₂ SO ₃ aqueous solution was added dropwise at −5 to −3 ° C. over 30 minutes, and then stirred at 40 to 50 ° C. for 30 minutes to completely decompose the peroxide. . After the separation, it was washed twice with 250 g of 5% saline to obtain 1000 g of a 1,2,4-trimethylbenzene solution of the hydroxycarboxylic acid of the above formula (S10). This was used in the next reaction without purification.

  To a 2 L reaction vessel equipped with a drain pipe and a thermometer, 1000 g of a 1,2,4-trimethylbenzene solution of hydroxycarboxylic acid of the above formula (S10) and 2.68 g of 20% sulfuric acid aqueous solution were added, and heated under reflux. The dehydration reaction was performed for 3 hours while draining water at 170 to 176 ° C. After completion of the reaction, the reaction solution was cooled, 74.9 g of 28% sodium methylate methanol solution was added, and the product carboxylic acid was converted to a sodium salt. When 154 g of water was added thereto, it was separated into an upper neutral fraction and a lower carboxylic acid sodium salt fraction. After removing the upper layer, the lower layer was washed twice with 200 mL of heptane. To the lower layer, 200 mL of heptane and 95.2 g of a 20% aqueous sulfuric acid solution were added, and the carboxylic acid was extracted with heptane while converting the sodium salt of the carboxylic acid into the carboxylic acid. The product was recovered by heating the solvent under reduced pressure, and then the product was distilled under reduced pressure to obtain 100 g of a double bond position isomer mixture of carboxylic acids represented by the above formula (S4). The yield was 35.8%.

Hereinafter, Production Example 2 of labdenic acid will be described.
10 g of commercially available Labdanum absolute was subjected to molecular distillation, and 4.3 g of a fraction having a boiling point of 180 ° C. to 220 ° C./13.3 Pa (hereinafter referred to as Ext-1) was collected. When this Ext-1 was analyzed, the Ext-1 includes a rubbed-8-en-15-oiic acid (formula (S5)) and a rubbed-7-en-15-euic acid (formula (S6)). , Rubbed-8 (17) -ene-15-oiic acid (formula (S7)).

<Test A> Confirmation of effect of suppressing crystallization and precipitation of ceramides of labdenic acids (Example A7)
In a 50 mL beaker, 1.0 g of ceramide 2 and 9.0 g of labdenic acid of Production Example 1 were mixed without solvent. With respect to the composition thus prepared, the following experiments (1) and (2) were conducted. Details of the composition are shown in Table 1 (in Table 1, the composition is shown by weight).

(1) Measurement of ceramide crystal precipitation temperature The prepared composition was heated to 120 ° C to obtain a transparent solution (uniform solution), and then cooled to 40 ° C while stirring. During this time, the crystallization of ceramides was visually observed, and when white crystals began to be observed, the temperature at that time was measured as the ceramide crystal precipitation temperature, and the white crystals were confirmed by 40 ° C. If not, it was assumed that there was no crystal precipitation of ceramides (indicated by “◯” in Table 1 below). The results are shown in Table 1. After cooling, almost no crystallization of labdenic acids was observed.

(2) Microscopic observation The above composition at 40 ° C. was observed with a microscope under polarized light using an upright microscope (manufactured by Olympus) at a magnification of 20 times and an exposure time of 1/300 seconds. It was. Under polarized light, when ceramides existed as crystals in the composition, they were observed as white glitters. Part of the results are shown in FIGS. 1 (a) and 1 (b).

(Examples A1 to A6, A8 to A14, Comparative Examples A1 to A4)
A composition was prepared in the same manner as in Example A7 except that the composition shown in Table 1 was used, and experiments (1) and (2) were conducted. The results are shown in Table 1.

  From the results of <Test A>, it has been clarified that labdenic acids have a high ability to dissolve ceramides and show an effect of suppressing crystallization and precipitation of ceramides.

<Test B> Confirmation of the effect of suppressing crystallization and precipitation of ceramides of labdenic acids in cosmetics (Example B1)
Ceramide II, labdenic acid of Production Example 1 and PEG 60 hydrogenated castor oil were mixed, and the mixture was heated to 100 ° C. to obtain a uniform solution (Solution A). 1,3-Butylene glycol and ethanol were added to this solution and mixed uniformly while maintaining the temperature at 50 ° C. (Solution B). Solution B was added to purified water and the solution was gradually cooled to 40 ° C. Thus, a cosmetic (skin lotion) further containing a cosmetic ingredient in addition to ceramides and labdenic acids was prepared. The details of the cosmetic (skin lotion) are shown in Table 2 (in Table 2, the composition is expressed in% by weight).

(Light transmittance measurement)
The prepared composition was subjected to a light transmittance measurement experiment. The prepared composition was heated to 40 ° C. to make a transparent solution (uniform solution), and then allowed to stand at room temperature. The light transmittance at 550 nm immediately after standing and after 3 days from the start of standing was measured using a spectrophotometer (UV-2500PC UV-VIS REDCORDING SPECTROPHOMETER, manufactured by Shimadzu Corporation). For the measurement, a glass cell having an optical path length of 10 mm (optical path width of 10 mm) was used, and purified water was used as a reference sample. The light transmittance was determined according to the following criteria. The results are shown in Table 2.
[Criteria] (judgment result: judgment content)
×: Less than 10% Δ: 30% to less than 50% ○: 50% to less than 70% ◎: 70% or more

(Examples B2 to B9)
A cosmetic was prepared in the same manner as in Example B1 except that the composition shown in Table 2 was used, and an experiment for measuring light transmittance was performed. The results are shown in Table 2.

  From the results of <Test B>, even in cosmetics further containing cosmetic ingredients in addition to ceramides and labdenic acids, labdenic acids have a high ability to dissolve ceramides and have the effect of suppressing crystallization and precipitation of ceramides. It became clear to show.

<Test C> Confirmation of skin barrier function improving effect of cosmetic (Example C1)
In the same manner as in <Test B>, cosmetics further containing cosmetic ingredients in addition to ceramides and labdenic acids were prepared using the components shown in Table 3. Details of the cosmetics are shown in Table 3 (in Table 3, the composition is shown by weight ratio).

An experiment was conducted to confirm the effect of improving the barrier function of the prepared cosmetic. The upper arms of 10 healthy men in their 20s and 30s were treated with acetone ether to cause rough skin. For this rough skin, the prepared cosmetics were used continuously for one week twice a day for each arm. The amount of moisture transpiration (TEWL) of the skin was measured using a moisture transpiration meter (Vapometer, manufactured by Delphine). The amount of water transpiration was calculated as a relative value when the amount of water evaporation was 100 when no treatment was performed on rough skin. Based on the average of the relative values, the moisturizing effect of the cosmetic was determined according to the following criteria. The results are shown in Table 3.
[Criteria] (judgment result: judgment content)
◎: Average relative value is less than 80 ○: Average relative value is 80 or more and less than 90 △: Average relative value is 90 or more and less than 100 ×: Average relative value is 100 or more

(Comparative Examples C1, C2)
A cosmetic was prepared in the same manner as in Example C1 except that the composition shown in Table 3 was used, and an experiment was conducted to confirm the effect of improving the barrier function. The results are shown in Table 3.

  From the results of <Test C>, it has been clarified that the cosmetics further including cosmetic ingredients other than the ceramides and labdenic acids retain the skin barrier function improving effect that ceramides originally have.

<Test D>
Below, the formulation according to this invention and the formulation example of the cosmetics and skin external preparation containing the composition according to this invention are shown. In addition,% in the following Examples D1-D4 is the value which made the whole quantity 100 mass%.

(Example D1)
A cosmetic solution was prepared using the components shown below.
(Ingredient of serum) (%)
1. Isostearyl alcohol 0.5
2. Phospholipid 1.0
3. Glyceryl monostearate 0.3
4). Cetyl isooctanoate 3.0
5. Mineral oil 1.0
6). Triethylhexanoin 2.0
7). Behenyl alcohol 0.2
8. Cetostearyl alcohol 0.3
9. Ceramide 3 0.2
10. Labdenic acid of Production Example 2 0.5
11. Glycerin 12.0
12.1,3-butylene glycol 8.0
13. Purified water residue 14. Xanthan gum 0.1
15. Hydroxypropyl methylcellulose 0.1
16. Phenoxyethanol 0.3
17. Fragrance 0.2

  The said components 1-10 were mixed and this mixture was heated to 90 degreeC, and it was set as the uniform solution (solution A). Subsequently, the said components 11-16 were mixed, and this mixture was heated to 70 degreeC, and it was set as the uniform solution (solution B). Solution B was added to solution A and emulsified at 70 ° C. (solution C). Solution C was cooled to 40 ° C., 17 was added thereto, and mixed well to obtain a cosmetic liquid.

  For the prepared serum, an experiment similar to the experiment for measuring light transmittance in <Test B> and an experiment similar to the experiment for confirming the barrier function improving effect in <Test C> were performed. It was found that the cosmetic liquid of Example D1 was excellent in the effect of suppressing crystallization and precipitation of ceramides and the effect of improving the barrier function.

(Example D2)
An emulsion was prepared using the components shown below.
(Emulsion component) (%)
1. Polyoxyethylene monostearate (20 mol) sorbitan 1.5
2. Polyoxyethylene trioleate (20 mol) sorbitan 1.5
3. Glyceryl monostearate 1.0
4). Stearic acid 0.8
5. Behenyl alcohol 0.8
6). Squalane 5.0
7). Pentaerythrityl tetraoctanoate 3.0
8). Hexa (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl
1.0
9. Ceramide 6 1.0
10. Labdenic acid of Production Example 1 0.3
11. Carboxyvinyl polymer 0.1
12 Methyl paraoxybenzoate 0.1
13. Sodium hydroxide 0.05
14 Purified water residue 15. Ethanol 5.0
16. Fragrance 0.05

  The said components 1-10 were mixed and this mixture was heated to 90 degreeC, and it was set as the uniform solution (solution A). Subsequently, the said components 11-14 were mixed and this mixture was heated to 70 degreeC, and it was set as the uniform solution (solution B). The solution A was added to the solution B, and it cooled to room temperature, the said 15 and 16 were added here, and it mixed well, and obtained the emulsion.

  For the prepared emulsion, an experiment similar to the experiment for observing the crystallization / precipitation state of ceramides and the experiment for confirming the effect of improving the barrier function in <Test C> were performed. It turned out that the emulsion of Example D2 is excellent in the effect which suppresses crystallization and precipitation of ceramides, and the barrier function improvement effect.

(Example D3)
A solid lip balm was prepared using the components shown below.
(Ingredients of solid lip balm) (%)
1. Carnauba wax 5.0
2. Ceramide 1 10.0
3. Microcrystalline wax 4.0
4). Polybutene 30.0
5. 5. Glyceryl tri-2-ethylhexanoate Residual amount Liquid paraffin 5.0
7). Labdenic acid of Production Example 2 1.0
8). Vitamin E 0.5
9. Preservative appropriate amount10. Perfume appropriate amount

  The said components 1-7 were mixed and this mixture was heated to 100 degreeC, and it was set as the uniform solution (solution A). Next, the above components 8 to 10 were added to the solution A and mixed well (solution B). Solution B was poured into a metal pan and cooled and solidified to obtain a solid lip balm.

  The prepared solid lip balm was subjected to an experiment for observing the crystallization and precipitation of ceramides and an experiment for confirming the improvement of the skin barrier function. It turned out that the solid lip cream of Example D3 is excellent in the effect which suppresses crystallization and precipitation of ceramides, and the barrier function improvement effect.

(Example D4)
A sunscreen cream was prepared using the ingredients shown below.
(Ingredients of sunscreen cream) (%)
1. Purified water residue 2. Iota carrageenan 0.01
3. 1,3-butylene glycol 3.5
4). Sodium hydroxide 0.3
5. Sucrose stearate 0.3
6). Purified water 1.0
7). Calcium chloride 0.1
8). Silicone-treated fine particle zinc oxide 11.0
9. 2-methoxyhexyl paramethoxycinnamate 8.0
10. Phytosphingosine 0.5
11. Labdenic acid 0.2
12 Dimethicodiethylbenzalmalonate 2.5
13. Methyl paraoxybenzoate 0.2
14 Ethanol 5.0
15. Perfume appropriate amount

  The said components 1-7 were mixed and this mixture was heated to 70 degreeC, and was heated and swollen (solution A). Subsequently, the said components 8-12 were mixed and this mixture was heated to 70 degreeC, and it was set as the uniform solution (solution B). Solution B was added to solution A, emulsified, and then cooled to room temperature (solution C). The above components 13 and 14 were added to solution C and mixed well (solution D). The above component 15 was added to Solution D and mixed well to obtain a sunscreen cream.

  About the prepared sunscreen, the experiment which observes the mode of crystallization and precipitation of ceramides, and the experiment which confirms the mode of improvement of the barrier function of skin were conducted. It turned out that the sunscreen cream of Example D4 is excellent in the effect which suppresses crystallization and precipitation of ceramides, and the barrier function improvement effect.

  According to the composition of this invention, it can suppress that ceramides crystallize and precipitate in a composition, and can improve stability in the composition of ceramides. According to the cosmetic of the present invention, ceramides can be prevented from crystallizing and precipitating in the cosmetic, and the stability of the ceramide in the cosmetic can be enhanced.

Claims (8)

Viewing including the ceramides and Rabuden acids,
The labdenic acids are represented by the following formula (S4)
[Wherein the bond by three dotted lines represents two single bonds and one double bond]
A compound represented by
The ratio of the labdenic acid to the ceramide is 0.01 to 50 . The composition according to claim 1 , wherein a ratio of the labdenic acids to the ceramides is 3 to 50. The composition according to claim 1 or 2, further comprising at least one selected from the group consisting of water, 1,3-butylene glycol, and glycerin. The composition according to claim 3, further comprising water, wherein the water content is 67.4 to 81.7% by mass. Cosmetics containing the composition of any one of Claims 1-4 . A method for inhibiting crystallization and precipitation of ceramides, characterized by using labdenic acids. The method for inhibiting crystallization and precipitation according to claim 6, wherein the ceramides and the labdenic acids are mixed, the mixture is heated at a temperature higher than the melting point of the ceramides, and then gradually cooled. The labdenic acids are represented by the following formula (S4)
[Wherein the bond by three dotted lines represents two single bonds and one double bond]
The method for inhibiting crystallization / precipitation according to claim 6 or 7, which is a compound represented by the formula: