JP3078738B2 - Oily solid cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention provides moisture to the skin,
The present invention relates to an oil-based solid cosmetic which can prevent and improve rough skin and inflammation and has a long lasting makeup.

[0002]

2. Description of the Related Art To moisturize and soften skin,
It is known that the moisture of the stratum corneum is important. And the retention of the water, water-soluble components contained in the stratum corneum,
That is, it is attributed to free amino acids, organic acids, urea or inorganic ions. From such a viewpoint, improvement or prevention of rough skin has been achieved by blending these substances alone or in combination with a medicated skin external preparation or cosmetic. In addition to the above substances, many moisturizing substances having a high affinity for water have been developed and are used for the purpose of improving rough skin and giving moist feeling.

[0003]

However, even when these moisturizing substances are applied to the skin, the effect is temporary, fundamentally improving the hydration ability of the entire stratum corneum and essentially reducing skin roughness. Could not be prevented or improved. Various studies have been made on oil-based cosmetics so far in terms of long-lasting makeup, but sufficient performance has not yet been realized. Therefore, an object of the present invention is to contain ceramide and the like as a substance having an effect of fundamentally improving the water retention ability of the stratum corneum, to provide sufficient moisture to the skin, and to prevent and improve rough skin and inflammation. It is an object of the present invention to provide an oil-based solid cosmetic that can be made and has good makeup.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have made intensive studies to solve the above problems, and as a result,
As described below, (A) ceramide or its similar structural substance
(B) a specific silicone derivative, (C) (semi) solid fat,
(D) Liquid oil and (E) a pigment are combined to provide an oily solid cosmetic that provides sufficient moisture to the skin, enhances the ability to retain moisture, prevents / improves rough skin, bulkiness, etc., and cosmetics The inventors have found that the present invention has good durability, and completed the present invention.

That is, the present invention provides the following component (A):
It is intended to provide an oily solid cosmetic containing (B), (C), (D) and (E). (A) The following general formula (1)

[0006]

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[Wherein, R ¹ and R ² represent a linear or branched saturated or unsaturated hydrocarbon group having 8 to 26 carbon atoms]
And the following general formulas (2) and (3)

[0008]

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[Wherein, R ³ represents a linear or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ⁴ represents a linear or branched saturated or unsaturated hydrocarbon group having 9 to 25 carbon atoms. Represents an unsaturated hydrocarbon group, X and Y represent a hydrogen atom or a hydroxyl group, k represents a number of 0 or 1, m represents an integer of 0 to 4, l and n represent an integer of 0 to 3 Show)

[0010]

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[Wherein, R ⁵ and R ⁶ are the same or different and each represent a linear or branched, saturated or unsaturated, optionally hydroxylated hydrocarbon group having 1 to 40 carbon atoms;
R ⁷ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond; R ⁸ represents a hydrogen atom, 1 to 12 carbon atoms;
Represents a linear or branched alkoxy group or a 2,3-dihydroxypropyloxy group. However, when R ⁷ is a single bond, R ⁸ is a hydrogen atom. One or more compounds selected from the group consisting of ceramide-like structural substances represented by the following general formula (4):

[0012]

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[Wherein R ⁹ , R ¹⁵ and R ¹⁸ are the same or different and are each a hydrogen atom, an alkyl group having 1 to 32 carbon atoms or a phenyl group, or — (CH ₂ ) _x O (C ₂ H ₄ O) _y (C ₃ H ₆ O) _z R (where at least one of R ⁹ , R ¹⁵ and R ¹⁸ is-(C
H ₂₎ is _{x O (C 2 H 4 O} ) y (C 3 H 6 O) z R. ), R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are the same or different,
A hydrogen atom, an alkyl group having 1 to 32 carbon atoms or a phenyl group;
Represents an alkyl group of ~ 32, x represents a number of 1-18,
r, s, y, and z each represent an average number of polyoxyalkylene groups in the molecule of 1 to 50% by weight.] (C) semi-solid fat or solid Fat, (D) liquid oil, (E) pigment

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Among the components (A) used in the present invention, ceramide is represented by the above general formula (1) and is a known compound. (1) In the formula, the hydrocarbon groups represented by R ¹ and R ² are linear or branched having 8 to 26 carbon atoms, and may be saturated or unsaturated. Specific examples include octyl, Nonyl, decyl, dodecyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicodecyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, nonenyl,
Decenyl, dodecenyl, undecenyl, tridecenyl,
Tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, nonadienyl, decadienyl, dodecadienyl, pentadienyl, didecadienyl, pentadienyl, didecadienyl, pentadienyl, tridecadienyl , Heptadecadienyl, octadecadienyl, nonadecadiethyl, eicosadienyl, heneicosadenyl, docosadienyl, tricosadienyl, tetracosadenyl, pentacosadenyl, hexacosadenyl, 2-hexyldecyl, 2-octylun Decyl, 2-decyltetradecyl, isostearyl group and the like. These hydrocarbon groups may be substituted by one or more hydroxyl groups. R
¹ is preferably a straight-chain alkyl group having 15 to 23 carbon atoms, particularly preferably pentadecyl, heptadecyl and tricosyl groups, and R ² is preferably a straight-chain saturated or unsaturated alkyl or alkenyl group having 15 to 23 carbon atoms, Pentadecyl, heptadecyl and pentadecenyl groups are preferred. Among the ceramides represented by the general formula (1), particularly preferred compounds are compounds obtained by combining the case where each of R ¹ and R ² in the general formula (1) is a group in the above particularly preferred range.

In the component (A), the ceramide-like structural material represented by the general formula (2) can be prepared by a known method [for example, Polish Journal of Chemistry (Po. J. Chem.)]. 52 , 1059 (197
8); 52 , 1283 (1978);
Nos. 17421, 54-144308 and 5
Nos. 4-147937, 62-228048, and 63-216852]. (2) In the formula, examples of the linear or saturated or unsaturated hydrocarbon group branched carbon atoms 10 to 26 represented by R ^3, those of the R ¹ and carbon atoms 10 to 26 in R ² and examples of the linear or branched, saturated or unsaturated hydrocarbon group of 9-25 represented by R ^4, include those of the R ¹ and carbon atoms in R ² 10 to 26. R ³ is preferably a straight-chain saturated alkyl group having 12 to 18 carbon atoms, particularly preferably tetradecyl, hexadecyl and octadecyl group, and R ⁴ is preferably a straight-chain saturated alkyl group having 9 to 18 carbon atoms, particularly nonyl and pentadecyl. And a heptadecyl group. Among the ceramide-like structural substances represented by the general formula (2), a particularly preferred compound is a compound obtained by combining the case where each of R ³ and R ^{4 in the} general formula (2) is a group in the above particularly preferred range. It is.

In the component (A), the ceramide-like structural material represented by the general formula (3)
(3) In the formula, as a linear or branched, saturated or unsaturated, optionally hydroxylated hydrocarbon group having 1 to 40 carbon atoms represented by R ⁵ and R ⁶ , methyl, ethyl, propyl, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, henycosyl, docosyl, nonacosyl, triacontyl, isostearyl, isoheptadecyl, 2-ethylhexyl, 1 −
Ethylheptyl, 8-heptadecyl, 8-heptadecenyl, 8,11-heptadecadienyl, 2-heptylundecyl, 9-octadecenyl, 1-hydroxynonyl,
Examples thereof include 1-hydroxypentadecyl, 2-hydroxypentadecyl, 15-hydroxypentadecyl, 11-hydroxyheptadecyl, and 11-hydroxy-8-heptadecenyl group.

R ⁵ is preferably a linear or branched alkyl or alkenyl group having 8 to 26 carbon atoms, such as octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl, tricosyl, isostearyl, 2-ethylhexyl, 2-heptylundecyl and 9-octadecenyl and the like. Particularly preferred hydrocarbon groups as R ⁵ is a linear or branched alkyl group having 12 to 22 carbon atoms, for example dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl and methyl-branched isostearyl group.

R⁶Is a straight or branched chain having 9 to 25 carbon atoms
Optionally branched hydroxylated alkyl or
Lucenyl groups are preferred, e.g. nonyl, undecyl, tri
Lidecyl, pentadecyl, heptadecyl, hencosium
, Nonacosyl, isoheptadecyl, 1-ethylhepti
8-heptadecyl, 8-heptadecenyl, 8,11
-Heptadecadienyl, 1-hydroxynonyl, 1-
Droxypentadecyl, 2-hydroxypentadecyl,
15-hydroxypentadecyl, 11-hydroxyhept
Tadecyl and 11-hydroxy-8-heptadecenyl and the like
Is mentioned. R ⁶A particularly preferred hydrocarbon group as
A linear or branched alkyl group having a prime number of 11 to 21,
For example, undecyl, tridecyl, pentadecyl, hepta
Decyl, henycosyl and methyl-branched isoheptadecyl
And the like.

R ⁷ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond. Examples of the alkylene group include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and 1-methylethylene. , 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-ethylethylene, 1-methyltetramethylene, 2-ethyltrimethylene, and the like. R ⁷ is preferably a linear alkylene group having 1 to 6 carbon atoms, among which methylene, ethylene and trimethylene are particularly preferred.

R ⁸ represents a hydrogen atom, a linear or branched alkoxy group having 1 to 12 carbon atoms or a 2,3-dihydroxypropyloxy group. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, hexyloxy. Octyloxy, decyloxy, 1-methylethoxy, 2-ethylhexyloxy group and the like.
R ⁸ is preferably a hydrogen atom, an alkoxy group having 1 to 8 carbon atoms and a 2,3-dihydroxypropyloxy group,
Of these, hydrogen atom, methoxy, ethoxy, propoxy,
Butoxy, 1-methylethoxy, 2-ethylhexyloxy and 2,3-dihydroxypropyloxy groups are particularly preferred.

Among the ceramide-like structural substances represented by the general formula (3), particularly preferred compounds are those represented by the general formula (3):
^The compound is a combination of the case where ⁵ , R ⁶ , R ⁷ and R ⁸ are each a group in the above particularly preferred range.

The ceramide-like structure substance (3) used in the present invention can be obtained, for example, by the following production method 1 or production method 2.

[0023]

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[0024]

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(Wherein, R ⁵ , R ⁶ and R ⁷ have the same meanings as described above, and R ^8f represents a hydrogen atom or a linear or branched alkoxy group having 1 to 12 carbon atoms. ⁷
Is a single bond, R ^8f is a hydrogen atom. R ¹⁹ , R ²¹ ,
R ²³ and R ^{24 each} represent a straight-chain or branched-chain saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, particularly preferably Is a methyl group. R ²² represents a hydrogen atom, an alkali metal atom or a COR ²¹ group, and R ²⁰ and R ²⁵ each represent a leaving group such as a halogen atom, a mesylate group or a tosylate group. As R ²⁰ , chlorine and bromine atoms,
Particularly, a chlorine atom is preferable, and as R ²⁵ , a mesylate group and a tosylate group are preferable in terms of availability. )

[0026]

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[0027]

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(In the formula, R ⁵ , R ⁶ , R ^{19 to} R ²⁵ have the same meaning as described above, and R ^7g represents a linear or branched alkylene group having 1 to 6 carbon atoms.)

The reaction conditions in each step of Production Method 1 and Production Method 2 are as follows.

Step 1) Glycidyl ether (5) and amine (6F) or (6
G) without solvent, or water or a lower alcohol such as methanol, ethanol or isopropanol; an ether solvent such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether; a hydrocarbon solvent such as hexane, benzene, toluene or xylene; or The amino alcohol derivative (7F) or (7G) can be produced by reacting at room temperature to 150 ° C. in an arbitrary mixed solvent of the above.

Step 2) A fatty acid ester (8), preferably a fatty acid lower alkyl ester such as a fatty acid methyl ester or a fatty acid ethyl ester, is added to the amino alcohol derivative (7F) or (7G) by an alkali such as potassium hydroxide or sodium hydroxide. Metal hydroxides, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as potassium carbonate, alkaline earth metal carbonates such as calcium carbonate, sodium methoxide, sodium ethoxide, potassium-tert-
In the presence of a basic catalyst such as an alkali metal alcoholate such as butoxide, a room temperature to 15 mm under a reduced pressure of normal pressure to 0.01 mmHg.
The amide derivative (9F) or (9G) can be produced by reacting at 0 ° C. At this time, the amount of the basic catalyst used is amino alcohol derivative (7F) or (7F).
It is preferably 0.01 to 0.2 equivalent to G), and it is preferable to carry out the reaction while removing the alcohol generated by the reaction outside the system, since the reaction proceeds rapidly.

Step 3) The amide derivative (9F) or (9G) is also prepared by adding the fatty acid chloride (10) to the amino alcohol derivative (7F) or (7G) without using a solvent or chloroform, methylene chloride, 1,2-dichloroethane. Such as pyridine, triethylamine, etc. in a halogenated hydrocarbon solvent such as, for example, tetrahydrofuran, dioxane, an ether solvent such as ethylene glycol dimethyl ether, a hydrocarbon solvent such as hexane, benzene, toluene and xylene, or a mixed solvent thereof. After the reaction at room temperature to 100 ° C. in the presence or absence of a base such as a tertiary amine to convert the compound into an amide-ester derivative (11F) or (11G),

Step 4) The ester group is converted to an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate, or calcium carbonate. Alkaline earth metal carbonates such as
It can also be produced by selective hydrolysis under basic conditions such as alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.

Step 5) Amide derivative (9F) or (9G) is added with 1 to 20 equivalents of epoxide (12), preferably epichlorohydrin,
1 to 10 equivalents of hydroxylated solvent without solvent or in water or an ether solvent such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, a hydrocarbon solvent such as hexane, benzene, toluene, xylene, or any mixed solvent thereof Room temperature in the presence of alkali metal hydroxides such as potassium and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as potassium carbonate, and alkaline earth metal carbonates such as calcium carbonate The amide derivative (13F) or (13G) can be produced by reacting at ~ 150 ° C. At this time, quaternary ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, stearyltrimethylammonium chloride, bistetraoxyethylenestearylmethylammonium chloride, and lauryldimethylcarboxyammonium It is preferable to carry out the reaction in the presence of a phase transfer catalyst such as betaine such as betaine from the viewpoint of yield and the like.

Step 6) The ceramide-like structural substance (13F) or (13G) is converted to an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, potassium carbonate or the like. Basic conditions such as alkaline earth metal carbonates such as alkali metal carbonates and calcium carbonate, or mineral acids such as sulfuric acid and hydrochloric acid, Lewis acids such as boron trifluoride and tin tetrachloride, acetic acid, tetradecanoic acid, and hexadecane Under acidic conditions such as carboxylic acids such as acids and sulfonic acids such as p-toluenesulfonic acid, or under base-acid mixed conditions, room temperature to
By hydrating at 300 ° C., a ceramide-like structural material (3F) or (3G) can be produced.

Step 7) The ceramide-like structural substance (3F) or (3G) is also obtained by adding the ceramide-like structural substance (13F) or (13G) to a carboxylic acid derivative (14), preferably a lower fatty acid such as acetic acid,
Lower fatty acid alkali metal salts such as sodium acetate, lower fatty acid anhydrides such as acetic anhydride alone or in combination, in the presence or absence of a basic catalyst such as a tertiary amine such as triethylamine, and reacted, After conversion to the ester-amide derivative (15F) or (15G),

Step 8) The ester group is converted to an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate, or calcium carbonate. Alkaline earth metal carbonates such as
It can also be produced by selective hydrolysis under basic conditions such as alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.

Step 9) The ceramide-like structural substance (3F) or (3G) is also obtained by adding a carbonyl compound (16), preferably a lower aliphatic ketone such as acetone or methyl ethyl ketone, to the ceramide-like structural substance (3F) or (3G). , Sulfuric acid, hydrochloric acid, a mineral acid such as phosphoric acid, carboxylic acid such as acetic acid, boron trifluoride, reaction in the presence of an acid catalyst such as Lewis acid such as tin tetrachloride, 1,
3-dioxolan-amide derivative (18F) or (18
After converting to G),

Step 10) Mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, carboxylic acids such as acetic acid, p
-It can also be produced by deketalization under acidic conditions such as sulfonic acid such as toluenesulfonic acid.

Step 11) The 1,3-dioxolan-amide derivative (18F) or (18G) is also used as the amide derivative (9F) or (9G)
A glycerol derivative (17), an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as potassium carbonate, and an alkali such as calcium carbonate. In the presence of a base such as an earth metal carbonate or an alkali metal hydride such as sodium hydride, in the absence of a solvent or an aprotic polar solvent such as N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, ethylene glycol It can also be produced by reacting in an ether-based solvent such as dimethyl ether, a hydrocarbon-based solvent such as hexane, benzene, toluene and xylene, or an arbitrary mixed solvent thereof.

Examples of the ceramide-like structural substance obtained by the production method 1 include the following.

[0042]

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[0043]

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Examples of the ceramide-like structural substance obtained by the production method 2 include the following.

[0045]

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The ceramide and the ceramide-like structural material of the component (A) can be purified by a known method. When ceramide and a ceramide-like structural substance are incorporated into the oil-based solid cosmetic of the present invention, even a purified product purified to 100% purity, including an intermediate or a reaction by-product without any purification, has a purity of 70 to 100. % Mixture, excellent effect and performance,
And there is no problem in safety. The component (A) also includes solvates represented by these hydrates.

The amount of the component (A) to be added to the oily solid cosmetic of the present invention is not particularly limited, and varies depending on the kind of the cosmetic, but 0.001 to 50% by weight based on the total amount of the oily cosmetic of the present invention.
(Hereinafter, simply referred to as “%”), and when it is particularly 0.1 to 20%, a sufficient effect can be obtained and the feel is further improved.

The polyoxyalkylene-modified organopolysiloxane of the component (B) is represented by the above formula (4). These are, for example, Nippon Unicar, Shin-Etsu Chemical, Toray Dow Corning Silicone, Toshiba Those marketed by Silicone can be used.

These polyoxyalkylene-modified organopolysiloxanes need to have a polyoxyalkylene group in a molecule of 1 to 50% in order to obtain a good finished feeling and a long lasting cosmetic. It is particularly preferable that the group is contained in the molecule in an amount of 1 to 25%.

The component (B) may be used singly or as a mixture of two or more types, and the amount thereof is not particularly limited.
It is preferable to mix 0.1 to 50% in the whole composition, and particularly to mix 1 to 20%, more preferably 2 to 15%, because it is more excellent in cosmetic durability and good in feeling and preferable.

The semi-solid fat or solid fat of the component (C) used in the present invention includes, for example, mokuro, hardened tallow, carnauba wax, candelilla wax, rice wax, beeswax, ceresin wax, microcrystalline wax, paraffin Wax, polyethylene wax, ethylene propylene copolymer, hardened jojoba oil, lanolin, petrolatum and the like. Among these, it is particularly preferable to mix polyethylene wax, ceresin wax and microcrystalline wax.

The component (C) may be used alone or as a mixture of two or more. The amount of the component (C) may be appropriately determined depending on the kind of the cosmetic. 1-5
0% is preferable, especially 5 to 30%, more preferably 5 to 30%.
It is preferable to mix 20% in terms of shape retention and feel.

The liquid oil of the component (D) used in the present invention is preferably a liquid oil having fluidity at room temperature, and specific examples thereof include dimethylpolysiloxane, dimethylcyclopolysiloxane, and methylphenylpolysiloxane. Squalane, light liquid paraffin, α-olefin oligomer, liquid polyisobutylene, 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, jojoba alcohol, ethyl glycol octanoate, ethylene glycol palmitate, propylene glycol isostearate , Propylene glycol ricinoleate, propylene glycol di (caprylate / caprate), propylene glycol dicaprylate, propylene glycol dimyristate,
Propylene glycol dicaprate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, glyceride triisostearate, glyceride diisostearate, glyceride trioctanoate, glyceride tri (caprylic / capric acid), glyceride ricinoleate, diglyceride isostearate, diglyceride diisostearate Diglyceride triisostearate, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, pentaerythrit tetraoctanoate, diisostearyl adipate, dioctyl adipate, diisopropyl isostearate, cholesteryl isostearate, isononyl isononanoate, elca Octyl dodecyl acid, octyl oxystearate, Cetyl titanate, octyl dodecyl oleate, oleyl oleate, dioctyl succinate, isocetyl stearate, isopropyl palmitate, octyl dodecyl myristate, myristyl myristate, diisostearyl malate, decyl oleate, octyl dodecyl ricinoleate, jojoba Examples include oil, liquid lanolin, liquid diglyceride, olive oil, avocado oil, castor oil and the like.

Of these, straight-chain or branched-chain ester oils having 18 to 36 carbon atoms are particularly preferred.

The component (D) can be used alone or in admixture of two or more. The amount of the component (D) is not particularly limited, but is preferably 1 to 80% of the total composition, more preferably 5 to 7%.
0%, more preferably 10 to 65%, is preferable in terms of coating feeling and gloss.

As the pigment of the component (E) used in the present invention, known pigments usually used in cosmetics such as talc, sericite, mica, kaolin, silica, nylon powder, polyethylene powder, cellulose powder and the like can be used. Extenders; coloring agents such as carbon black, titanium oxide, iron oxide, zinc oxide, ultramarine, navy blue, chromium oxide, organic tar dyes and lakes; and composite pigments such as titanium mica and iron oxide coated mica. In addition, these cosmetic pigments can be used as silicones, higher fatty acids, higher alcohols,
Those treated with a fatty acid ester, metal soap, amino acid or alkyl phosphate can also be used.

The amount of the component (E) is not particularly limited, but is preferably 0.1 to 80% of the total composition, particularly 1.0 to 60%, and more preferably 5 to 40%. preferable.

The oily solid cosmetic of the present invention substantially does not contain water, that is, excludes water-in-oil (W / O) or oil-in-water (O / W) cosmetics.

The oil-based solid cosmetic of the present invention contains, in addition to the above-mentioned components, other oil-based raw materials and surfactants substantially free of water other than those described above, as long as the effects of the present invention are not impaired. , A medicinal component, a preservative, an antioxidant, a humectant, an ultraviolet absorber, a fragrance, and the like.

The oil-based solid cosmetic of the present invention can be produced by heating, mixing, stirring, etc. the above-mentioned components according to a conventional method, such as makeup cosmetics such as lipstick, foundation, eyeshadow, eyeliner and the like. It can be.

[0061]

Industrial Applicability The oil-based solid cosmetic of the present invention gives sufficient moisture to the skin, enhances the ability to retain moisture, can prevent and improve rough skin and inflammation, and is excellent in long-lasting makeup.

[0062]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In Production Examples 1 to 10, ceramide-like structural substances represented by the general formula (3) were produced according to Production Method 1, and in Production Examples 11 and 12, they were produced according to Production Method 2.

Production Example 1 In a 2-liter 5-neck flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube and a distillation apparatus, 743.2 g (8.34 mol) of 3-methoxypropylamine and ethanol 15 were added.
Of hexadecyl glycidyl ether 165.9 while heating and stirring at 80 ° C. under a nitrogen atmosphere.
g (0.56 mol) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 12 hours, and then ethanol and excess 3-methoxypropylamine were distilled off by heating under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the amino alcohol derivative (7a). 19
6.5 g (91% yield versus hexadecyl glycidyl ether) were obtained (step 1).

[0064]

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The obtained amino alcohol derivative (7a)
Its physical properties are as follows.

Melting point: 53 ° C. IR (ν _neat , cm ⁻¹ ); 3340, 2930, 285
5,1470,1310,1120,1065,95
5,900,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.3 Hz, 3H), 1.25 to 1.45 (m, 26
H), 1.45 to 1.85 (m, 6H), 2.57 to
2.76 (m, 4H), 3.32 (s, 3H), 3.3
8 to 3.48 (m, 6H), 3.77 to 3.89 (m,
1H).

In a 1-liter 5-necked flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube and a distillation apparatus, 61.3 g of the molten compound (7a) obtained in the above (Step 1) (151.3 g) was added.
8.13 mmol) and 1.53 g (7.91 mmol) of a 28% methanol solution of sodium methoxide were stirred and stirred at 60 ° C. for 30 minutes under a nitrogen atmosphere. Next, 38.3 g (158.1 mmol) of methyl tetradecanoate was added thereto under the same conditions.
Was added dropwise over 1 hour. After completion of the dropwise addition, the mixture is further reduced in pressure (8
The mixture was stirred at 60 ° C. for 5 hours to complete the reaction. After cooling, the reaction mixture was purified by silica gel column chromatography to obtain 88.7 g (yield 94%) of a ceramide-like structural material (9a) (step 2).

[0068]

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The physical properties of the obtained ceramide-like structural material (9a) are as follows.

White solid Melting point: 48 ° C. IR (ν _neat , cm ⁻¹ ); 3440, 2930, 286
0, 1650, 1625, 1470, 1225, 121
0, 1110, 950, 720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.3 Hz, 6H), 1.15 to 1.95 (m, 5
3H), 2.36 (t, J = 7.5 Hz, 2H), 3.
29 to 3.55 (m, 10H), 3.33 (s, 3
H), 3.85 to 3.95 (m, 1H).

In a 1-liter 5-neck flask equipped with a stirrer, a nitrogen inlet tube and a distillation apparatus, 94.5 g (158.0 mmol) of the compound (9a) obtained in the above (Step 2) and 1.53 g of tetrabutylammonium bromide were placed. (4.74mmo
l), 32.2 g (347.6 mmol) of epichlorohydrin
l), 12.6 g (315.0 mmol) of sodium hydroxide
And 66 ml of toluene.
Stirred for 0 hours. The obtained reaction mixture was washed three times with water at 70 ° C., and toluene and excess epichlorohydrin were distilled off by heating under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a ceramide-like structural material (13a). 94.9 g (92% yield) were obtained (Step 5).

[0072]

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Ceramide-like structural substance obtained (13a)
Its physical properties are as follows.

White solid Melting point: 38-39 ° C. IR (ν _neat , cm ⁻¹ ); 2930, 2855, 165
0, 1470, 1425, 1380, 1210, 112
0,905,840,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.0 Hz, 6H), 1.10 to 1.45 (m, 4
6H), 1.45 to 1.90 (m, 6H), 2.25 to
2.48 (m, 2H), 2.50 to 2.68 (m, 1
H), 2.70 to 2.85 (m, 1H), 3.02 to
3.20 (m, 1H), 3.20 to 4.00 (m, 13
H), 3.32 (s, 3H).

The compound (13a) obtained in the above (Step 5) was placed in a 100 ml autoclave equipped with a stirrer.
71.3 g (109.0 mmol), water 11.78 g (65
4.1 mmol), sodium hydroxide 0.087 g (2.1
8 mmol) and 0.87 g (4.36 mmol) of tetradecanoic acid
l) and stirred in a closed system at 160 ° C. for 6 hours.
The reaction mixture was cooled, washed twice with 2% saline at 80 ° C., and then purified by silica gel column chromatography to obtain the target ceramide-like structural material (3
a) 68.3 g (93% yield) were obtained (step 6).

[0076]

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The physical properties of the obtained ceramide-like structural material (3a) are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 3445, 2930, 286
0, 1630, 1470, 1420, 1380, 130
5,1210,1120,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.15 to 1.44 (m, 4
6H), 1.44-1.95 (m, 8H), 2.25-
2.45 (m, 2H), 3.20 to 3.90 (m, 16
H), 3.33 (s, 3H).

In a 500 ml four-necked flask equipped with a stirring device, a nitrogen introducing tube and a distillation device, the above (Step 5)
31.0 g (47.4 mmol) of the compound (13a) obtained in
11.9 g (663.7 mmol) of water, sodium acetate 1
3.6 g (165.9 mmol) and acetic acid 104.9 g (1
746.8 mmol) at 70 ° C. under a nitrogen atmosphere.
Stirred for hours. Excess acetic acid was distilled off by heating under reduced pressure to obtain a mixture containing the ester-amide derivatives (15a-1), (15a-2) and (15a-3) (step 7).

[0080]

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Next, without removing the mixture containing these ester-amide derivatives from the flask,
59.3 g of 8% aqueous sodium hydroxide solution (711.2 mm
ol), 18 g of water and 200 ml of butanol.
For 3 hours. Butanol is distilled off by heating under reduced pressure.
The residue was diluted with 250 ml of toluene and washed twice with water at 70 ° C. The toluene was distilled off by heating under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired ceramide-like structural material (3a) 22.3.
g (yield 70%) was obtained (step 8).

Production Example 2 4680 g (52.5 mol) of 3-methoxypropylamine and ethanol 90 were placed in a 10-liter 5-neck flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube and a distillation apparatus.
0 g, and while heating and stirring at 80 ° C. under a nitrogen atmosphere, 1045 g of hexadecyl glycidyl ether was added thereto.
(3.50 mol) was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 1 hour, and then ethanol and excess 3-methoxypropylamine were distilled off by heating under reduced pressure to obtain a product mainly composed of an amino alcohol derivative (7a) (step). 1).

The product containing compound (7a) as a main component in a 10-liter 5-neck flask obtained in the above (Step 1) was
9.82 g (0.175 mol) of potassium hydroxide was added,
The mixture was stirred for 3 hours under a reduced pressure (60 to 10 Torr) at 80 ° C. while distilling off water generated by blowing in nitrogen. Next, while stirring under the same conditions, methyl tetradecanoate 8 was added thereto.
82.3 g (3.64 mol) were added dropwise over 3 hours.
At this time, generated methanol was distilled off. After the completion of the dropwise addition, the mixture is further blown with nitrogen and under reduced pressure (60 to 10 Torr).
While distilling off the methanol produced at 0-45 ° C, 1
The reaction was completed by stirring for 0 hour to obtain a product mainly composed of a ceramide-like structural material (9a) (Step 2).

The product containing compound (9a) as a main component in a 10-liter 5-neck flask obtained in the above (Step 2) was added to
33.9 g of tetrabutylammonium bromide (0.
105 mol), 712.5 g of epichlorohydrin (7.
70 mol) and 2100 g of toluene, and 1750.0 g of a 48% aqueous sodium hydroxide solution (20.0 g) in a 48% aqueous solution of sodium hydroxide while stirring at 45 ° C. under a reduced pressure (150 to 50 Torr) while blowing in nitrogen.
1.0 mol) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further stirred for 10 hours under the same conditions to complete the reaction. After the reaction mixture was washed four times with water at 70 ° C., toluene and excess epichlorohydrin were distilled off by heating under reduced pressure to obtain a product mainly composed of a ceramide-like structural material (13a) (Step 5). .

To a product containing compound (13a) as a main component in a 10-liter 5-neck flask obtained in (Step 5) above, 378.2 g (21.0 mol) of water and 48% aqueous solution of sodium hydroxide were added. 83 g (0.070 mol) and 32.0 g (0.14 mol) of tetradecanoic acid were added, and the mixture was stirred at 100 ° C. for 2.5 days under a nitrogen atmosphere. Add 8 reaction mixture
After washing three times with 2% saline at 0 ° C., the resultant was dehydrated by heating under reduced pressure to obtain 2261.5 g of a product mainly containing the target compound (3a) (Step 6). This product contained 70% of the compound (3a), and also contained an intermediate represented by the following formula, a reaction by-product, and the like.

[0086]

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[0087]

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Production Example 3 Production Example 1 was repeated except that methyl hexadecanoate was used in place of methyl tetradecanoate in Step 2 of Production Example 1.
The reaction was carried out in the same manner as in Steps 1 and 2 to obtain a ceramide-like structural material (9b) (Steps 1 and 2).

[0089]

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The physical properties of the obtained ceramide-like structural material (9b) are as follows.

Melting point: 55 ° C. IR (ν _neat , cm ⁻¹ ); 3430, 2930, 285
5,1620,1470,1205,1110,95
0,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.26 to 1.89 (m, 5
7H), 2.36 (t, J = 7.6 Hz, 2H), 3.
29-3.52 (m, 10H), 3.33 (s, 3
H), 3.88-3.95 (m, 1H).

In Step 5 of Production Example 1, compound (9
The reaction was carried out in the same manner as in Step 5 of Production Example 1, except that the compound (9b) obtained in the above (Step 2) was used instead of a).
A ceramide-like structural material (13b) was obtained (Step 5).

[0093]

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Ceramide-like structural material obtained (13b)
Its physical properties are as follows.

White solid Melting point: 44 to 45 ° C. IR (ν _neat , cm ⁻¹ ); 2930, 2860, 165
0, 1470, 1425, 1380, 1210, 112
0,910,845,755,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.15 to 1.45 (m, 5
0H), 1.45 to 1.73 (m, 4H), 1.73 to
1.90 (m, 2H), 2.25 to 2.48 (m, 2
H), 2.50 to 2.68 (m, 1H), 2.70 to
2.85 (m, 1H), 3.00 to 3.18 (m, 1
H), 3.18-4.00 (m, 13H), 3.32.
(S, 3H).

In Step 6 of Production Example 1, compound (13)
Compound (13b) obtained in the above (Step 5) instead of a)
Was reacted in the same manner as in Step 6 of Production Example 1 except that hexadecanoic acid was used instead of tetradecanoic acid, to obtain a target ceramide-like structural material (3b) (Step 6).

[0097]

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The physical properties of the obtained ceramide-like structural material (3b) are as follows.

Melting point: 33 ° C. IR (ν _neat , cm ⁻¹ ); 3445, 2930, 286
0, 1650, 1630, 1470, 1420, 138
0, 1305, 1210, 1120, 1080. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.45 (m, 5
0H), 1.45 to 1.95 (m, 7H), 2.25 to
2.55 (m, 3H), 3.20 to 3.92 (m, 16
H), 3.33 (s, 3H).

In a 500 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 34.1 g (50.0 mmol) of the compound (13b) obtained in the above (Step 5) and acetic anhydride 2
5.5 g (250.0 mmol) and triethylamine 2
5.3 g (250.0 mmol) were charged and 1
The mixture was stirred at 00 ° C for 10 hours. The reaction mixture was concentrated under reduced pressure while heating, and the obtained residue was purified by silica gel column chromatography to obtain 34.9 g (89% yield) of an ester-amide derivative (15b) (step 7).

[0101]

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The obtained ester-amide derivative (15
The physical properties of b) are as follows.

Brown transparent liquid ¹ H-NMR (CDCl ₃ , δ); 0.88 (brt,
J = 6.4 Hz, 6H), 1.26 to 1.83 (m, 5
6H), 2.03 to 2.20 (m, 6H), 2.33.
(T, J = 7.1 Hz, 2H), 3.12 to 4.35
(M, 15H), 3.32 (s, 3H), 5.04-
5.43 (m, 1H).

In a 200 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 33.9 g (43.2 mmol) of the compound (15b) obtained in the above (Step 7), 0.42 g of a 28% methanol solution of sodium methoxide. (2.16
mmol) and 200 ml of methanol, and stirred at room temperature for 3.5 hours under a nitrogen atmosphere. While heating the reaction mixture,
The mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 16.0 g (yield 53%) of the target ceramide-like structural material (3b) (step 8).

The compound (9) obtained in the above (Step 2) was placed in a 3-liter 4-neck flask equipped with a stirrer and a nitrogen inlet tube.
b) 45.2 g (72.0 mmol), 2.86 g (119.2 mmol) of sodium hydride and 800 ml of toluene were charged, and the mixture was stirred at 55 ° C. for 30 minutes under a nitrogen atmosphere. Next, 34.8 g (121.5 mmol) of 1,2-isopropylidenedioxy-3-tosyloxypropane was added thereto, and the mixture was stirred at 100 ° C. for 18 hours. The reaction mixture was added with 20 ml of 2-propanol under ice cooling to inactivate unreacted sodium hydride, and then concentrated under reduced pressure under heating. The resulting residue was purified by silica gel column chromatography to obtain 51.0 g (96% yield) of a 1,3-dioxolane-amide derivative (18b) (Step 1).
1).

[0106]

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The physical properties of the obtained 1,3-dioxolan-amide derivative (18b) are as follows.

Colorless transparent liquid ¹ H-NMR (CDCl ₃ , δ); 0.88 (brt,
J = 6.4 Hz, 6H), 1.20 to 1.90 (m, 6
2H), 2.36 (t, J = 7.0 Hz, 2H), 3.
30-4.25 (m, 19H).

The compound (1) obtained in the above (Step 11) was placed in a 2-liter 4-neck flask equipped with a stirrer and a nitrogen inlet tube.
8b) 51.0 g (68.9 mmol), 0.50 g (2.63 mmol) of tosylic acid monohydrate and 500 ml of methanol
And stirred at room temperature under a nitrogen atmosphere for 12 hours. The reaction mixture was concentrated under reduced pressure while heating, and the obtained residue was purified by silica gel column chromatography to obtain 41.0 g (yield: 85%) of the target ceramide-like structural material (3b) (step 10). ).

Production Example 4 A reaction was carried out in the same manner as in Production Example 1 except that methyl dodecanoate was used in place of methyl tetradecanoate in Step 2 of Production Example 1, and a ceramide-like structural material ( 9c) was obtained (steps 1 and 2).

[0111]

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The physical properties of the obtained ceramide-like structural material (9c) are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 3435, 2930, 285
5,1620,1470,1220,1110,72
0. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.20 to 1.90 (m, 4
9H), 2.36 (t, J = 7.6 Hz, 2H), 3.
25-3.52 (m, 10H), 3.33 (s, 3
H), 3.88-3.95 (m, 1H).

In Step 5 of Production Example 1, compound (9
Instead of a), the compound (9c) obtained in the above (Step 2)
The reaction was carried out in the same manner as in Step 5 of Production Example 1 except for using, to obtain a ceramide-like structure substance (13c) (Step 5).

[0115]

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Ceramide-like structural substance obtained (13c)
Its physical properties are as follows.

Pale yellow liquid IR (ν _neat , cm ^-1 ); 2940, 2875, 175
0, 1650, 1470, 1380, 1210, 112
0,910,845. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.45 (m, 4
2H), 1.45 to 1.75 (m, 4H), 1.75 to
1.90 (m, 2H), 2.25 to 2.50 (m, 2
H), 2.50 to 2.68 (m, 1H), 2.70 to
2.85 (m, 1H), 3.00 to 3.18 (m, 1
H), 3.18-4.00 (m, 13H), 3.32.
(S, 3H).

In Step 7 of Production Example 1, compound (13)
Compound (13c) obtained in the above (Step 5) instead of a)
The reaction was carried out in the same manner as in Steps 7 and 8 of Production Example 1 except that was used, to obtain a target ceramide-like structural material (3c) (Steps 7 and 8).

[0119]

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The physical properties of the obtained ceramide-like structural material (3c) are as follows.

Colorless transparent liquid IR (ν _neat , cm ^-1 ); 3430, 2930, 286
0, 1650, 1630, 1470, 1380, 126
0,1210,1115,1080,795,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.15 to 1.45 (m, 4
2H), 1.45 to 1.97 (m, 8H), 2.25 to
2.45 (m, 2H), 3.15 to 3.92 (m, 16
H), 3.33 (s, 3H).

Production Example 5 In Step 2 of Production Example 1, instead of methyl tetradecanoate, Lunac P-70 (manufactured by Kao Corporation) (weight ratio of tetradecanoic acid, hexadecanoic acid, octadecanoic acid: 3: 7)
0:27) under heating and refluxing with methanol in the presence of a sulfuric acid catalyst.
The reaction was carried out in the same manner as in Production Example 1, Step 1 and Step 2 except that the methyl ester of -70 was used, to obtain a ceramide-like structural material (9d) (Steps 1 and 2).

[0123]

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The physical properties of the obtained ceramide-like structural material (9d) are as follows.

Melting point; 50 ° C. IR (ν _neat , cm ⁻¹ ); 3430, 2930, 286
0,1620,1470,1205,1110,95
0,720.

In Step 11 of Production Example 3, compound (9
The reaction is carried out using the compound (9d) obtained in the above (Step 2) instead of b), and the resulting 1,3-dioxolan-amide derivative (18d) is purified in the next step 10 without purification.
The reaction was carried out in the same manner as in Steps 11 and 10 of Production Example 3 except that the above reaction was carried out to obtain a target ceramide-like structural material (3d) (Steps 11 and 10).

[0127]

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The physical properties of the obtained ceramide-like structural material (3d) are as follows.

Melting point: 32 ° C. IR (ν _neat , cm ⁻¹ ): 3445, 2930, 286
0, 1650, 1630, 1470, 1380, 121
0, 1120, 1080, 720.

Production Example 6 The reaction was carried out in the same manner as in Production Example 1, except that octadecyl glycidyl ether was used in place of hexadecyl glycidyl ether. (Step 1).

[0131]

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The obtained amino alcohol derivative (7e)
Its physical properties are as follows.

Melting point: 57-58 ° C IR (ν _neat , cm ^-1 ); 3340, 2930, 285
5,1470,1120,960,900,840,7
20. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.3 Hz, 3H), 1.25 to 1.45 (m, 30
H), 1.45 to 1.85 (m, 6H), 2.55 to
2.75 (m, 4H), 3.32 (s, 3H), 3.3
5 to 3.50 (m, 6H), 3.77 to 3.89 (m,
1H).

In Step 2 of Production Example 1, compound (7
The reaction was carried out in the same manner as in Step 2 of Production Example 1, except that the compound (7e) obtained in the above (Step 1) was used instead of a).
A ceramide-like structural material (9e) was obtained (Step 2).

[0135]

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The physical properties of the obtained ceramide-like structural material (9e) are as follows.

White solid Melting point: 49 ° C. IR (ν _neat , cm ⁻¹ ); 3440, 2930, 286
0, 1650, 1625, 1470, 1225, 121
0, 1110, 950, 720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.3 Hz, 6H), 1.15 to 1.95 (m, 5
7H), 2.36 (t, J = 7.5 Hz, 2H), 3.
30 to 3.55 (m, 10H), 3.33 (s, 3
H), 3.85 to 3.95 (m, 1H).

In Step 5 of Production Example 1, compound (9
The reaction was carried out in the same manner as in Step 5 of Production Example 1, except that the compound (9e) obtained in the above (Step 2) was used instead of a).
A ceramide-like structural material (13e) was obtained (Step 5).

[0139]

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Ceramide-like structural material obtained (13e)
Its physical properties are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 2930, 2860, 165
0,1425,1380,1260,1210,112
0,910,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.0 Hz, 6H), 1.10 to 1.45 (m, 5
0H), 1.45 to 1.90 (m, 6H), 2.25 to
2.50 (m, 2H), 2.50 to 2.68 (m, 1
H), 2.70 to 2.85 (m, 1H), 3.01 to
3.20 (m, 1H), 3.20 to 4.00 (m, 13
H), 3.32 (s, 3H).

In Step 7 of Production Example 1, compound (13)
Compound (13e) obtained in the above (Step 5) instead of a)
The reaction was carried out in the same manner as in Steps 7 and 8 of Production Example 1 except that was used, to obtain a target ceramide-like structural material (3e) (Steps 7 and 8).

[0143]

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The physical properties of the obtained ceramide-like structural material (3e) are as follows.

Melting point: 23 ° C. IR (ν _neat , cm ⁻¹ ): 3425, 2930, 286
0, 1650, 1630, 1470, 1380, 122
0,1210,1120,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.17 to 1.45 (m, 4
9H), 1.45 to 1.92 (m, 8H), 2.22 to
2.45 (m, 2H), 3.20 to 3.90 (m, 17
H), 3.33 (s, 3H).

Production Example 7 The procedure was repeated except that the compound (7e) obtained in Step 1 of Production Example 6 was replaced with the compound (7e) obtained in Step 2 of Production Example 1 and methyl hexadecanoate was used instead of methyl tetradecanoate. Performed a reaction in the same manner as in Step 2 of Production Example 1 to obtain a ceramide-like structural material (9f) (Steps 1 and 2).

[0147]

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The physical properties of the obtained ceramide-like structural material (9f) are as follows.

White solid Melting point: 54 to 55 ° C. IR (ν _neat , cm ⁻¹ ); 3430, 2930, 285
5,1620,1470,1220,1205,111
0,950,885,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.25 to 1.95 (m, 6
1H), 2.36 (t, J = 7.6 Hz, 2H), 3.
29-3.52 (m, 10H), 3.33 (s, 3
H), 3.88-3.95 (m, 1H).

In Step 5 of Production Example 1, compound (9
The reaction was carried out in the same manner as in Step 5 of Production Example 1 except that the compound (9f) was used instead of a) to obtain a ceramide-like structural material (13f) (Step 5).

[0151]

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Ceramide-like structural substance obtained (13f)
Its physical properties are as follows.

White solid Melting point: 45 to 47 ° C. IR (ν _neat , cm ⁻¹ ); 2930, 2860, 165
0, 1470, 1425, 1380, 1210, 112
0,910,845,755,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.15 to 1.45 (m, 5
4H), 1.45 to 1.73 (m, 4H), 1.73-
1.90 (m, 2H), 2.25 to 2.48 (m, 2
H), 2.50 to 2.68 (m, 1H), 2.70 to
2.85 (m, 1H), 3.00 to 3.18 (m, 1
H), 3.18-4.00 (m, 13H), 3.32.
(S, 3H).

In Step 7 of Production Example 1, compound (13)
Compound (13f) obtained in the above (Step 5) instead of a)
The reaction was carried out in the same manner as in Steps 7 and 8 of Production Example 1 except that was used, to obtain a target ceramide-like structural material (3f) (Steps 7 and 8).

[0155]

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The physical properties of the obtained ceramide-like structural material (3f) are as follows.

White solid Melting point: 35 ° C. IR (ν _neat , cm ⁻¹ ); 3445, 2930, 286
0, 1650, 1630, 1470, 1420, 138
0, 1305, 1210, 1120, 1080. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.45 (m, 5
4H), 1.45 to 1.95 (m, 7H), 2.25 to
2.55 (m, 3H), 3.20 to 3.95 (m, 16
H), 3.33 (s, 3H).

Production Example 8 The reaction was carried out in the same manner as in Production Example 1, except that tetradecyl glycidyl ether was used in place of hexadecyl glycidyl ether. Was obtained (step 1).

[0159]

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The obtained amino alcohol derivative (7 g)
Its physical properties are as follows.

White solid Melting point: 47 ° C. IR (ν _neat , cm ⁻¹ ); 3340, 2930, 285
5,1470,1310,1120,1065,99
5,900,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.3 Hz, 3H), 1.25 to 1.45 (m, 26
H), 1.45 to 1.85 (m, 6H), 2.57 to
2.75 (m, 4H), 3.32 (s, 3H), 3.3
8 to 3.48 (m, 6H), 3.75 to 3.88 (m,
1H).

In Step 2 of Production Example 1, compound (7
Compound (7 g) obtained in the above (Step 1) instead of a)
Was reacted in the same manner as in Step 2 of Production Example 1 except that methyl hexadecanoate was used instead of methyl tetradecanoate to obtain a ceramide-like structural material (9 g) (Step 2).

[0163]

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The physical properties of the obtained ceramide-like structural material (9 g) are as follows.

White solid Melting point: 47 ° C. IR (ν _neat , cm ⁻¹ ): 3440, 2930, 285
5,1620,1470,1205,1110,95
0,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.26 to 1.89 (m, 5
2H), 2.36 (t, J = 7.6 Hz, 2H), 3.
29-3.52 (m, 11H), 3.33 (s, 3
H), 3.88-3.95 (m, 1H).

In Step 5 of Production Example 1, compound (9
Instead of a), the compound obtained in the above (Step 2) (9 g)
The reaction was carried out in the same manner as in Step 5 of Production Example 1 except that was used, to obtain a ceramide-like structural material (13 g) (Step 5).

[0167]

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Ceramide-like structural material obtained (13 g)
Its physical properties are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 2930, 2860, 165
0, 1470, 1425, 1380, 1210, 112
0,910,845,755,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.7 Hz, 6H), 1.15 to 1.45 (m, 4
6H), 1.45 to 1.73 (m, 4H), 1.73-
1.90 (m, 2H), 2.25 to 2.50 (m, 2
H), 2.50 to 2.68 (m, 1H), 2.70 to
2.85 (m, 1H), 3.00 to 3.18 (m, 1
H), 3.18-4.00 (m, 13H), 3.32.
(S, 3H).

In Step 7 of Production Example 1, compound (13)
Instead of a), the compound (13) obtained in the above (Step 5)
Except for using g), the reaction was carried out in the same manner as in Steps 7 and 8 of Production Example 1, and the target ceramide-like structural material (3 g)
(Steps 7 and 8).

[0171]

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The physical properties of the obtained ceramide-like structural material (3 g) are as follows.

White solid Melting point: 27 ° C. IR (ν _neat , cm ⁻¹ ); 3445, 2930, 286
0, 1650, 1630, 1470, 1420, 138
0, 1305, 1210, 1120, 1080, 72
0. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.45 (m, 4
5H), 1.45 to 1.93 (m, 7H), 2.20 to
2.60 (m, 3H), 3.20 to 3.90 (m, 17
H), 3.33 (s, 3H).

Production Example 9 A reaction was carried out in the same manner as in Production Example 1, except that 2-methoxyethylamine was used in place of 3-methoxypropylamine in the same manner as in Production example 1. ) Was obtained (Step 1).

[0175]

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The obtained amino alcohol derivative (7h)
Its physical properties are as follows.

Melting point: 54 to 55 ° C. IR (ν _neat , cm ⁻¹ ); 3430, 2920, 285
5,1470,1120,1065,900,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.3 Hz, 3H), 1.25 to 1.70 (m, 30
H), 2.57-2.76 (m, 4H), 3.32.
(S, 3H), 3.38-3.48 (m, 6H), 3.
77-3.89 (m, 1H).

In Step 2 of Production Example 1, compound (7
Compound (7h) obtained in the above (Step 1) instead of a)
Was reacted in the same manner as in Step 2 of Production Example 1 except that methyl hexadecanoate was used instead of methyl tetradecanoate to obtain a ceramide-like structural material (9h) (Step 2).

[0179]

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The physical properties of the obtained ceramide-like structural material (9h) are as follows.

White solid Melting point: 51 to 52 ° C. IR (ν _neat , cm ⁻¹ ); 3420, 2920, 285
5,1620,1470,1110,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.87 (t, J =
6.4 Hz, 6H), 1.15 to 1.70 (m, 55
H), 2.25 to 2.50 (m, 2H), 3.20 to
4.00 (m, 11H), 3.34 (s, 3H).

In Step 5 of Production Example 1, compound (9
The reaction was carried out in the same manner as in Step 5 of Production Example 1, except that the compound (9h) obtained in the above (Step 2) was used instead of a).
A ceramide-like structural material (13h) was obtained (Step 5).

[0183]

Embedded image

The obtained ceramide-like structural material (13h)
Its physical properties are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 2930, 2855, 165
0, 1470, 1420, 1380, 1310, 125
0, 1190, 1120, 910, 850, 720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.13 to 1.45 (m, 5
0H), 1.45 to 1.70 (m, 4H), 2.30 to
2.50 (m, 2H), 2.50 to 2.70 (m, 1
H), 2.70 to 2.85 (m, 1H), 3.00 to
3.20 (m, 1H), 3.20 to 4.00 (m, 13
H), 3.32 (s, 3H).

In Step 6 of Production Example 1, compound (13)
Compound (13h) obtained in the above (Step 5) instead of a)
The reaction was carried out in the same manner as in Step 6 of Production Example 1 except that was used, to obtain a target ceramide-like structural material (3h) (Step 6).

[0187]

Embedded image

The physical properties of the obtained ceramide-like structural material (3h) are as follows.

Melting point: 31 to 32 ° C. IR (ν _neat , cm ⁻¹ ); 3450, 2930, 286
0, 1630, 1470, 1380, 1300, 119
0, 1160, 720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.4 Hz, 6H), 1.15 to 1.75 (m, 54
H), 2.20 to 2.45 (m, 3H), 3.20 to
3.90 (m, 17H), 3.33 (s, 3H).

In Step 11 of Production Example 3, compound (9
The reaction was carried out in the same manner as in Step 11 of Production Example 3 except that the compound (9h) obtained in the above (Step 2) was used instead of b) to obtain a 1,3-dioxolane-amide derivative (18h). (Step 11).

[0191]

Embedded image

The physical properties of the obtained 1,3-dioxolan-amide derivative (18h) are as follows.

Colorless transparent liquid ¹ H-NMR (CDCl ₃ , δ); 0.88 (t, J =
6.4 Hz, 6H), 1.15 to 1.70 (m, 54
H), 1.34 (s, 3H), 1.40 (s, 3H),
2.36 (t, J = 7.0 Hz, 2H), 3.25-
4.30 (m, 19H).

In Step 10 of Production Example 3, compound (1
The compound (18) obtained in the above (Step 11) in place of 8b)
The reaction was carried out in the same manner as in Step 11 of Production Example 3 except that h) was used, to obtain a target ceramide-like structural material (3h) (Step 10).

Production Example 10 The reaction was carried out in the same manner as in Production Example 1, except that ethylamine was used in place of 3-methoxypropylamine in Production step 1, and the amino alcohol derivative (7i) was obtained. (Step 1).

[0196]

Embedded image

The obtained amino alcohol derivative (7i)
Its physical properties are as follows.

White solid Melting point: 60-61 ° C. IR (ν _neat , cm ⁻¹ ); 3400, 2930, 285
5,1470,1310,1110,955,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.4 Hz, 3H), 1.11 (t, J = 7.2 Hz,
3H), 1.15 to 1.70 (m, 30H), 2.55
~ 2.80 (m, 4H), 3.35 to 3.53 (m, 4
H), 3.79-3.93 (m, 1H).

In Step 2 of Production Example 1, compound (7
Compound (7i) obtained in the above (Step 1) instead of a)
Was performed in the same manner as in Step 2 of Production Example 1 except that methyl hexadecanoate was used instead of methyl tetradecanoate to obtain a ceramide-like structural material (9i) (Step 2).

[0200]

Embedded image

The physical properties of the obtained ceramide-like structural material (9i) are as follows.

White solid Melting point: 56 ° C. IR (ν _neat , cm ⁻¹ ); 3410, 2930, 286
0, 1625, 1470, 1380, 1305, 124
5,1210,1110,950,855,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (t, J =
6.4 Hz, 6H), 1.15 to 1.75 (m, 57
H), 2.34 (t, J = 7.6 Hz, 2H), 3.3
0 to 3.55 (m, 9H), 3.85 to 4.00 (m,
1H).

In Step 5 of Production Example 1, compound (9
The reaction was carried out in the same manner as in Step 5 of Production Example 1, except that the compound (9i) obtained in the above (Step 2) was used instead of a).
A ceramide-like structural material (13i) was obtained (Step 5).

[0204]

Embedded image

Ceramide-like structural substance obtained (13i)
Its physical properties are as follows.

Colorless transparent liquid IR (ν _neat , cm ⁻¹ ); 2930, 2855, 165
0, 1470, 1425, 1380, 1210, 112
0,905,840,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.10 to 1.75 (m, 5
7H), 2.25 to 2.50 (m, 2H), 2.50
2.70 (m, 1H), 2.70 to 2.85 (m, 1
H), 3.0-4.00 (m, 12H).

In Step 6 of Production Example 1, compound (13)
Compound (13i) obtained in the above (Step 5) instead of a)
The reaction was carried out in the same manner as in Step 6 of Production Example 1 except that was used, to obtain a target ceramide-like structural material (3i) (Step 6).

[0208]

Embedded image

The physical properties of the obtained ceramide-like structural material (3i) are as follows.

White solid Melting point: 35 to 36 ° C. IR (ν _neat , cm ⁻¹ ); 3445, 2930, 286
0, 1630, 1470, 1420, 1380, 130
5,1210,1120,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.13 to 1.75 (m, 5
7H), 2.31 (t, J = 7.5 Hz, 2H);
20-3.90 (m, 16H).

Production Example 11 The reaction was carried out in the same manner as in Production Example 1, except that ethanolamine was used in place of 3-methoxypropylamine. (Step 1).

[0212]

Embedded image

The obtained amino alcohol derivative (7j)
Its physical properties are as follows.

White solid Melting point: 70-73 ° C. ¹ H-NMR (CDCl ₃ , δ); 0.85 (t, J =
6.4 Hz, 3H), 1.23 (brs, 28H),
2.60 to 2.80 (m, 4H), 3.10 to 3.90
(M, 10H).

In Step 2 of Production Example 1, compound (7)
Compound (7j) obtained in the above (Step 1) instead of a)
Was performed in the same manner as in Step 2 of Production Example 1 except that methyl hexadecanoate was used instead of methyl tetradecanoate to obtain a ceramide-like structural material (9j) (Step 2).

[0216]

Embedded image

The physical properties of the obtained ceramide-like structural material (9j) are as follows.

Melting point; 75 ° C. IR (ν _neat , cm ⁻¹ ); 3320, 2925, 285
0, 1615, 1470, 1440, 1380, 111
0,1060,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.86 (t, J =
6.4 Hz, 6H), 1.00 to 1.60 (m, 54
H), 2.20 to 2.50 (m, 2H), 3.10
4.10 (m, 13H).

In a 500 ml four-necked flask equipped with a stirrer, a dropping funnel and a nitrogen inlet tube, 15.2 g (0.042 mol) of the compound (7j) obtained in the above (Step 1).
l), pyridine (10.0 g, 0.126 mol) and chloroform (200 ml) were charged, and stirred under ice-cooling under a nitrogen atmosphere while adding 34.6 g of hexadecanoyl chloride (0.
126 mol) was added dropwise over 30 minutes. After dropping,
The mixture was further stirred at room temperature for 2 hours. The reaction mixture was washed with water and concentrated under reduced pressure to obtain the ester-amide derivative (11
45.1 g of the crude product of j) was obtained (step 3).

[0220]

Embedded image

The obtained ester-amide derivative (11)
Physical properties of j) are as follows.

¹ H-NMR (CDCl ₃ , δ); 0.86
(Br t, J = 6.4 Hz, 12H), 1.25 (b
rs, 106H), 2.20 to 2.40 (m, 6
H), 3.30-3.60 (m, 8H), 4.00-
4.30 (m, 2H), 5.10 to 5.20 (m, 1
H).

In a 1-liter 4-neck flask equipped with a stirrer, 45.1 of the compound (11j) obtained in the above (Step 3) was added.
g, potassium carbonate 5.8 g (0.084 mol) and water-
450 g of a mixed solvent of methanol (1: 1) was charged, and the mixture was heated under reflux with stirring for 3 hours. A ceramide-like structural material (9j) was extracted from the reaction mixture by extracting chloroform-soluble matter and purifying it by silica gel column chromatography.
15.0 g (yield 60%, but from compound (7j)) was obtained (step 4).

In a 200-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 10.0 g (16.7 mmol) of the compound (9j) obtained in the above (Step 2) and 0.162 g (0.16 g) of tetrabutylammonium bromide. 50mmo
l), epichlorohydrin 6.49 g (70.1 mmo
l), 2.77 g (69.3 mmol) of sodium hydroxide and 20 g of a mixed solvent of toluene-dioxane (1: 1) were charged, and the mixture was stirred at 40 ° C. for 15 hours under a nitrogen atmosphere. The obtained reaction mixture was diluted with toluene, washed with water and saturated saline, and concentrated under reduced pressure while heating. The obtained residue was purified by silica gel column chromatography to give 6.9 g of a ceramide-like structural material (13j) (yield: 5).
8%) (step 5).

[0225]

Embedded image

The obtained ceramide-like structural material (13j)
Its physical properties are as follows.

White solid Melting point: 42 to 43 ° C. IR (ν _neat , cm ⁻¹ ): 2930, 2855, 165
0, 1470, 1420, 1380, 1250, 121
0,1115,910,845,755,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.3 Hz, 6H), 1.10 to 1.42 (m, 5
0H), 1.45 to 1.70 (m, 4H), 2.30 to
2.50 (m, 2H), 2.50 to 2.68 (m, 2
H), 2.70 to 2.85 (m, 2H), 3.00 to
3.20 (m, 2H), 3.20 to 4.00 (m, 15
H).

In Step 6 of Production Example 1, compound (13)
Compound (13j) obtained in the above (Step 5) in place of a)
Was reacted in the same manner as in Step 6 of Production Example 1 except that hexadecanoic acid was used instead of tetradecanoic acid, to obtain a target ceramide-like structural material (3j) (Step 6).

[0229]

Embedded image

The physical properties of the obtained ceramide-like structural material (3j) are as follows.

Melting point; 60 ° C. IR (ν _neat , cm ⁻¹ ); 3385, 2920, 285
5,1655,1470,1420,1380,130
0, 1205, 1120, 1045, 985, 930,
850,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.45 (m, 5
0H), 1.45 to 1.70 (m, 4H), 2.25 to
2.50 (m, 2H), 3.20 to 4.10 (m, 25
H).

The compound (9) obtained in the above (Step 2) was placed in a 3-liter 4-neck flask equipped with a stirrer and a nitrogen inlet tube.
j) 50.3 g (84.1 mmol), 8.7 g (362.5 mmol) of sodium hydride and 500 ml of N, N-dimethylformamide were charged, and charged at room temperature under a nitrogen atmosphere at room temperature.
Stirred for minutes. Next, while heating and stirring at 60 ° C. under a nitrogen atmosphere, 1,2-isopropylidenedioxy-3 was added thereto.
73.5 g (256.7 mmol) of tosyloxypropane
Of N, N-dimethylformamide was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 8 hours, water was added under ice cooling to inactivate unreacted sodium hydride, and the mixture was extracted three times with diethyl ether.
The obtained organic layer was washed twice with a saturated saline solution and then concentrated under reduced pressure while heating. The obtained residue was purified by silica gel column chromatography to give 40.1 g of 1,3-dioxolane-amide derivative (18j) (yield 5).
8%) (step 11).

[0233]

Embedded image

The physical properties of the obtained 1,3-dioxolan-amide derivative (18j) are as follows.

Colorless transparent liquid IR (ν _neat , cm ^-1 ); 3000, 2950, 287
5,1660,1480,1425,1380,126
0,1210,1120,1090,1060,85
0,720. _{^{1 H-NMR (CDCl 3,}} δ); 0.88 (br t,
J = 6.4 Hz, 6H), 1.15 to 1.48 (m, 6
2H), 1.34 (s, 3H), 1.36 (s, 3
H), 1.40 (s, 3H), 1.41 (s, 3H),
1.48 to 1.70 (m, 4H), 2.25 to 2.50
(M, 2H), 3.20-4.40 (m, 21H).

The compound (1) obtained in the above (Step 11) was placed in a 1-liter 4-neck flask equipped with a stirrer and a nitrogen inlet tube.
8j) 40.1 g (53.2 mmol), 1.01 g (5.30 mmol) of tosylic acid-monohydrate and 400 ml of a mixed solvent of methanol-ethanol (1: 1) were charged and stirred at 40 ° C. for 20 hours under a nitrogen atmosphere. did. After adding 450 mg of sodium bicarbonate to the reaction mixture, the mixture was concentrated under reduced pressure while heating, and the obtained residue was purified by silica gel column chromatography to obtain 30.0 g of the target ceramide-like structural material (3j) ( (Yield 84%) (Step 1)
0).

Preparation Example 12 In Step 2 of Preparation Example 1, the compound (7j) obtained in Step 1 of Preparation Example 11 was replaced with compound (7j) obtained in Step 1 of Preparation Example 11, and instead of methyl tetradecanoate, Lunac P- 70
(Mixture of tetradecanoic acid, hexadecanoic acid, octadecanoic acid in a weight ratio of 3:70:27) under heating and refluxing, except that a methyl ester of Lunac P-70 produced by reacting with methanol in the presence of a sulfuric acid catalyst was used. Is
The reaction was carried out in the same manner as in Step 2 of Production Example 1 to obtain a ceramide-like structural material (9k) (Steps 1 and 2).

[0238]

Embedded image

The physical properties of the obtained ceramide-like structural material (9k) are as follows.

White solid Melting point: 72 to 75 ° C. IR (ν _neat , cm ⁻¹ ); 3320, 2925, 285
0, 1615, 1470, 1440, 1380, 111
0,1060,720.

In Step 11 of Production Example 11, compound (9) obtained in the above (Step 2) was substituted for compound (9j).
k), and the same reaction as in steps 11 and 10 of Production Example 11 except that the obtained 1,3-dioxolan-amide derivative (16k) was reacted in the next step 10 without purification. To obtain the desired ceramide-like structural material (3k) (Steps 11 and 10).

[0242]

Embedded image

The physical properties of the obtained ceramide-like structural material (3k) are as follows.

White solid Melting point: 42 to 43 ° C. IR (ν _neat , cm ⁻¹ ); 3390, 2920, 285
5,1655,1470,1420,1380,130
0, 1205, 1120, 1045, 985, 930,
850,720.

Example 1 (Lipstick) Each component having the composition shown in the following Table 1 was heated to 80 ° C., mixed uniformly, poured into a molding die, and cooled and solidified to produce a lipstick. About the obtained lipstick, 10 panelists
When this was used, it was evaluated for stretchability, stickiness, moist feeling, difficulty in bulking, and difficulty in discoloration, and was evaluated according to the following criteria. Table 2 shows the results.

Judgment Criteria: A: Eight or more out of ten evaluated as good. ；: 6 to 7 or more out of 10 evaluated as good. Δ: 4 to 5 or more out of 10 evaluated as good. ×: Three or less out of ten evaluated as good.

[0247]

[Table 1]

[0248]

[Table 2]

As is clear from Table 2, all of the products of the present invention had good cosmetic durability, were hard to be bulky, and were excellent in moist feeling.

Example 2 (Oil-based foundation) An oil-based foundation having the following composition was produced by the following production method.

(Production Method) The oil phase component was heated and melted at 90 ° C., and the powder component was added thereto, mixed and degassed. This was filled in a gold plate and then cooled to obtain an oily foundation.

[0252]

(%) Dimethyl polysiloxane (6 cs) 10.0 Polyoxyalkylene-modified organopolysiloxane (1) (SH3772C manufactured by Dow Corning Toray) 15.0 Candelilla wax 3.0 Micro candelilla wax 7. 0 Ceramide-like structural substance (3c) obtained in Production Example 4 5.0 Fragrance 0.1 Squalane Remaining sericite (hydrophobic treatment ^* ) 25.0 Bengala (hydrophobic treatment ^* ) 1.0 Iron oxide yellow (hydrophobic) ^* ) 2.0 Black iron oxide (hydrophobic treatment ^* ) 0.2 Titanium oxide (hydrophobic treatment ^* ) 15.0 *: Hydrophobized pigment and methyl hydrogen polysiloxane by heat treatment.

Example 3 (solid powder eyeshadow) A solid powder eyeshadow having the following composition was produced.

(Production method) The powdery components were mixed by stirring in a blender, and the oil phase component dissolved by heating was sprayed on the components, followed by further stirring. Then, it was pulverized and compression-molded by a molding machine to obtain a solid powder eyeshadow.

[0255]

TABLE 4 (%) Mica (hydrophobic treatment ^*) 20 Talc (hydrophobic treatment ^*) 23 nylon powder 5 ultramarine (hydrophobic treatment ^*) 5 Iron oxide (hydrophobic treatment ^*) 2 Mica titanium (hydrophobic treatment ^* ) 10 paraffin wax 5 squalane 3 aluminum stearate 5 isostearate cholesteryl ester 2 polyoxyalkylene-modified organopolysiloxanes (1) (Nippon Unicar Co., FZ2171) 8 ceramide-like structure material (3c obtained in production example 4) 2 dimethyl Polysiloxane (6cs) 10 *: A pigment and methylhydrogenpolysiloxane that have been hydrophobized by heat treatment.

The oil-based solid cosmetics of the present invention obtained in Examples 2 and 3 are all excellent in the effect of enhancing the ability of the skin to retain moisture, preventing / improving the roughness of the skin, and have excellent long-lasting makeup. there were.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 7/032 A61K 7/032 // C07C 233/18 C07C 233/18 233/20 233/20 (72) Inventor Koichi Murayama Tochigi 2606 Kao Co., Ltd., Kaga Co., Ltd., Kaigacho, Haga-gun, Japan Pref. (56) References JP-A-5-246836 (JP, A) JP-A-4-193816 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/00 A61K 7/02 A61K 7/032 C07C 233/18 C07C 233/20

Claims (2)

(57) [Claims] 1. The following components (A), (B), (C),
An oily solid cosmetic containing (D) and (E). (A) The following general formula (1) Wherein R ¹ and R ^{2 each} represent a straight-chain or branched-chain saturated or unsaturated hydrocarbon group having 8 to 26 carbon atoms, and ceramides represented by the following general formulas (2) and (3) ) [Wherein, R ³ represents a linear or branched saturated or unsaturated hydrocarbon group having 10 to 26 carbon atoms, and R ⁴ represents 9 to 2 carbon atoms.
5 represents a linear or branched saturated or unsaturated hydrocarbon group, X and Y represent a hydrogen atom or a hydroxyl group, k represents a number of 0 or 1, m represents an integer of 0 to 4, l and n are 0
And represents an integer of from 3 to 3] [Wherein, R ⁵ and R ⁶ are the same or different and each have 1 to 4 carbon atoms.
0 represents a linear or branched, saturated or unsaturated, optionally hydroxylated hydrocarbon, and R ⁷ has 1 to 6 carbon atoms.
R ⁸ represents a hydrogen atom, a linear or branched alkoxy group having 1 to 12 carbon atoms or a 2,3-dihydroxypropyloxy group. However, when R ⁷ is a single bond, R ⁸ is a hydrogen atom. One or more compounds selected from the group consisting of ceramide-like structural substances represented by the following formulas: (B) the following general formula (4): [Wherein, R ⁹ , R ¹⁵ and R ¹⁸ are the same or different and are each a hydrogen atom, an alkyl group having 1 to 32 carbon atoms or a phenyl group, or-(CH ₂ ) _x O (C ₂ H ₄ O) _y (C ₃ H ₆ O) _z R (provided that R ⁹ , R
^At least one of ¹⁵ and R ¹⁸ is-(CH ₂ ) _x O (C ₂ H ₄ O) _y (C
A ₃ H ₆ O) _z R. ), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁶ and R ¹⁷ are the same or different and each represent a hydrogen atom,
Represents an alkyl group or a phenyl group of ~ 32, R is the same or different and represents a hydrogen atom or an alkyl group of 1 to 32 carbon atoms, x represents a number of 1 to 18, r, s, y and z represent A polyoxyalkylene-modified organopolysiloxane represented by the following formula: (C) a semisolid fat or solid fat, (D) a liquid oil, (E) Pigment 2. Component (A) is present in an amount of 0.001 to 50% by weight,
0.1 to 50% by weight of the component (B), 0.1% of the component (C)
The oil-based solid cosmetic according to claim 1, which comprises about 50% by weight, 1 to 80% by weight of the component (D), and 0.1 to 80% by weight of the component (E).