JPS6028946A - Terpene alcohol diglycerin alkyl ether and cosmetic containing it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R is group shown by the formula II(m is 1-10; A and B are H or linked to form single bond; when m is >=2, A and B may be combination of the above-mentioned two cases; R' is H, or 1-24C aliphatic hydrocarbon group)]. EXAMPLE:2-Hydroxy-3-farnesyloxy-propylglyceryl ether. USE:Especially useful as a component for cosmetic. Having chemical stability, low irritation to the skin, having surface active properties, useful as an emulsifying agent, oil agent, wetting agent, viscosity builder, etc. PREPARATION:A terpene alcohol shown by the formula ROH is reacted with an epihalohydrin to give an alkylglycidyl ether shown by the formula III, which is reacted with a glycerin shown by the formula VI protected with groups at 2-, and 3-positions in the presence of a base, to form a 1,3-dioxolane compound shown by the formula IV. This compound is hydrolyzed by means of a proton acid catalyst in water under heating, the protecting groups are removed, to give a compound shown by the formula I wherein R' is H.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel terpene alcohol dicrycerin alkyl ether and cosmetics containing the same.

In nature, there are many derivatives of polyhydric alcohols having ether bonds, and among them, the monoalkyl ether of glycerin (referred to as 'glyceryl ether) is particularly prominent. For example, the lipids of fish contain palmityl glyceryl ether (called chimyl alcohol),
Contains stearyl glyceryl ether (batyl alcohol) and oleyl glyceryl ether (cerakyl alcohol).

This glyceryl ether is widely used in cosmetic base materials, etc., particularly by taking advantage of its W10 type emulsifying properties (Japanese Patent Application Laid-Open Nos. 49-87612 and 49-9223).
No. 9, Japanese Patent Publication No. 52-12109, Special Publication No. 57-362
60 etc.). In addition, the effect of promoting blood cells in the bone marrow,
It is also known to have pharmacological effects such as anti-inflammatory and anti-tumor activities (Japanese Patent Publication No. 10724-1972, Japanese Patent Publication No. 10724-1987,
No. 18171).

In addition, focusing on the fact that glyceryl ether is a unique surfactant with many properties, we also focused on the fact that glyceryl ether has a similar molecular structure to glyceryl ether (i.e.,
Attempts have been made to derive polyol ether compounds (comprised of ether bonds and hydrophilic OH groups in the molecule) from polyhydric alcohols (U.S. Pat. No. 2,258,8).
No. 92, JP 52-18170, JP 53-13
No. 7,905, JP-A-54-145.224, etc.).

The polyol ether compound thus obtained is used as a cosmetic base material by utilizing its W10 type emulsifying property (German Published Patent No. 2,455.287).
In addition to being a general emulsifier, it is also used as an antibacterial and antifungal agent.

The present inventors focused on the M requirements of polyol ether compounds, and derived mono- and dialkyl ethers of diglycerin, which are polyol ether compounds, from alkyl glycidyl ethers that can be easily produced from alcohol, and used them as cosmetic bases. We would like to first apply for application to JP-A-57-197235, JP-A-57-197236, JP-A-58-13530, JP-A-57-200587, and JP-A-58-49991).

On the other hand, in nature, there are multiple methyl branches (
Polyprenyl compounds (terpene compounds), which are so-called repeating isoprene units, exist in a wide variety of forms as compounds that command the following properties (while maintaining a regular positional relationship). It is well known that these polyprenyl compounds are widely used in fields such as fragrances, industrial chemicals, pharmaceuticals, cosmetics, and foods.Especially in recent years, knowledge has emerged that polyprenyl compounds have important pharmacological effects. Efforts are being made to apply this to pharmaceuticals such as antitumor agents (Japanese Patent Publication No. 45-13823, Japanese Unexamined Patent Application Publication No. 57-1982).
-192343, 57-192342, 57-
No. 192341, No. 57-192340, No. 57-1
No. 92339, No. 57-106618, No. 54-89
No. 035, No. 54-5043, No. 53-96330, etc.).

Under these circumstances, the present inventors have conducted intensive research on the surface chemistry of the polyprenyl compound described above, particularly its application to emulsifiers, and have found that diglycerin alkyl ether (hereinafter referred to as "diglycerin alkyl ether") derived from a specific terpene alcohol The present invention was completed based on the discovery that ether (referred to as "ether") has excellent properties and is useful as a cosmetic ingredient.

Therefore, the present invention provides the following general formula (1) [wherein R is an integer of 1 to 10, and A and B each represent a hydrogen atom or both together] and when m is 2 or more, A and B may be a combination of the above two cases), and R/ is a hydrogen atom or a group having 1 carbon number. to 24 saturated or unsaturated linear or branched aliphatic hydrocarbon groups] and cosmetics containing the diglycerin alkyl ether.

Conventionally, glyceryl ethers derived from terpene alcohols include glyceryl ethers of alicyclic monoterpene alcohols (West German Patent No. 711,916), mono- and sifitanyl glyceryl ethers (3-0-(3',
7', 11', 15'-tetramethylhexadecyl]glycerol and 2,3-di0-(3',
7', 11', 15'-tetramethylhexadecyl]glycerol) (Biochemistry.

Volume 4, pp. 1595-1599 (1965) +J
our own of Lipid Re5earch,
g vol. 9, pp. 782-788 (1968)]. Recently, a synthesis example of triglycosyl-sifitanylglycerol, a polysaccharide compound that is one of the lipid components of biological membranes, has been reported ('l'etrahedro
n Letters, Volume 22, 2819-2822
Page (1981)]. However, the diglycerol alkyl ether of the present invention is a new compound that has a different structure from the above-mentioned known compounds and has not been described in any literature.

The diglyceryl alkyl ether (I) of the present invention can be prepared, for example, from a terpene alcohol (II) according to the following reaction formula.
, a method known per se (Japanese Unexamined Patent Publication No. 197235/1983,
No. 58-13530).

(Ia) (Ib) (wherein, represents an aliphatic hydrocarbon group,
(2) (indicates the same as above) According to the present method, an alkyl glycidyl ether (a) is first produced by Williams-type ether synthesis of a terpene alcohol (n) and abihalohydrin. The starting terpene alcohol has the following formula (1), C)l.

(In the formula, A, B and m are the same as above).

This ether synthesis reaction is carried out by a method known per se using a phase transfer catalyst. That is, in a 30-60% aqueous solution of an alkaline substance such as an alkali metal hydroxide,
A quaternary onium salt (industrially preferred is a quaternary ammonium salt) is reacted with a phase transfer catalyst (t, -c, f) pen alcohol (10,!: epino-rohydrin (preferably epichlorohydrin). Alkaline The amount of the substance is (■) 1 to 10 mol, preferably 3 to 1 mol.
~6 mol, the quaternary onium salt is used in an amount of 0.01 to 0.20 mol, preferably 10.05 to 0.10 mol, and the evinohlochtrin is used in an amount of 1 to 10 mol, preferably 2 to 4 mol. The reaction temperature is preferably 30 to 80°C, particularly 45 to 60°C, and a solvent is not necessary, but hydrocarbons such as hexane, heptane, benzene, toluene, xylene, etc., ether, and tetrahydrofuran (THF) that are inert to the reaction are used. , diglyme, dioxane and the like can also be used. When doing so, the alkyl glycidyl ether (II) is obtained in a yield of 80 to 85% based on (■).

This alkyl glycidyl ether (I) has the 2nd position.

A 1°3-dioxolane compound is obtained by reacting glycerin (VD, for example, an acetal or ketal of glycerin (hereinafter referred to as "protected glycerin") with the 3-position protected with a suitable protecting group).

The aldehydes used to obtain the acetal include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde;
Alicyclic aldehydes such as cyclopentyl aldehyde and cyclohexyl aldehyde; aromatic aldehydes such as benzaldehyde and naphthyl aldehyde. Ketones that can be used to obtain ketals include aliphatic ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, and dipropyl ketone; alicyclic gutones such as cyclobutanone, cyclopentanone, and cyclohexanone; acetophenone, Examples include aromatic ketones such as benzophenone.

In order to obtain protected glycerin from these aldehydes or ketones and glycerin, both may be subjected to dehydration condensation in the presence of an acidic catalyst by a known method.

The reaction between the alkyl glycerin/dyl ether (II) and the protected glycerin (VD) is preferably carried out in the presence of a base catalyst. Examples of the base catalyst include alkali metal hydroxides (e.g. LiOH, NaOH, KOH, etc.), 7fiv-h metal alcolade (e.g. NaOMe, Na0Et
+t-BuOK, etc.), tertiary amines (e.g.,
Examples include triethylamine, tributylamine, tetramethylethylenediamine, tetramethyl-1,3-diaminopropane, and tetramethyl-1,6-:)aminohexane. This reaction generally involves the protection of an alkyl glycidyl ether (101 moles, 1 to 30 moles (preferably 1 to 15 moles)).
%lllf, 0.001-0.20% l (preferably 0.01-0.1 mol) in the presence of a base catalyst, 70-
It is carried out under conditions of 150°C (preferably 90 to 120°C).

The amount of protected glycerin used may theoretically be equimolar to that of the alkyl glycidyl ether (I[), but in reality, using a larger amount than equimolar provides a better yield and completes the reaction in a shorter time. Although the reaction proceeds even in the absence of a reaction solvent, it is most appropriate to use an excess amount of protected glycerin to serve as a solvent. Moreover, a solvent can also be used if necessary. As the reaction solvent, any solvent that does not adversely affect the reaction can be used, but hydrocarbons are suitable.

Hydrocarbons include pentane, hexane, heptane,
Preferred are fatty and harsh hydrocarbons such as octane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and mixtures thereof. By performing the reaction as shown in the paper, 1,3
-Dioxolane compound (1η is 80qI) or higher yield. If necessary, the 1,3-dioxolane compound side can be purified here by means such as distillation.

Diglycerin alkyl ether (Ia) can be obtained by hydrolyzing the thus obtained 1,3-dioxolane compound surface to remove the protecting group. Further, 1゜3-dioxolane compound (IV) was etherified to form dialkyl ether dioxolane compound (7), which was then converted into 7J
l] Diglycerol alkyl ether (Ib) is obtained by water decomposition and removal of the securing group.

The hydrolysis reaction on the 1,3-dioxolane compound side is carried out by a known method. i.e. sulfuric acid, u acid, 611
It is preferable to use a protonic acid catalyst such as IJ acid, p-toluenesulfonic acid, or acetic acid and heat in water. There is no particular limitation on the amount of acid catalyst used, but 0.01 to 0.2 N is sufficient. and preferably 0.05 to 0.10 normal.

Water includes water-soluble M solvents, such as lower alcohols such as methanol, ethanol, and isopropanol, THF,
Ethers such as diglyme and dioxane can be added.

The reaction temperature is preferably 50 to 100°C, particularly 50 to 60°C. If hydrolysis is carried out under these conditions, 1,3
- Almost quantitatively from the dioxolane compound side, α-monoalkyl ether of diglycerin (I
a) is obtained.

The latter method is as follows. First, the 1°3-dioxolane compound side is etherified. As the etherification agent, alkyl halides, alkyl esters of sulfonic acid, alkyl esters of sulfuric acid, etc. are used, and the number of carbon atoms is 1 to 1.
Preference is given to those having 24, preferably 1 to 18, especially 1 to 12, saturated or unsaturated straight-chain or branched aliphatic hydrocarbon groups.

Among these etherifying agents, alkyl bromides and alkyl iodites are particularly preferred. The alkyl group includes methyl, ethyl, propyl, butyl, octyl,
Straight chain aliphatic hydrocarbon groups such as decyl, dodecyl, hexadecyl, octadecyl, octadecenyl (oleyl);
Isopropyl, isobutyl, isoamyl, 2-ethelhexyl, 2-hebutylundecyl, 5,7.7-)'J
Methyl-2-(1,3,3-)rimetherpter)octyl, following formula % formula %) (wherein p is an integer of 4 to 10, q is an integer of 5 to 11, p and q are 11 to 17 branched aliphatic hydrocarbon groups such as methyl branched isostearyl groups; alicyclic carbon groups such as cyclohexyl, cyclopentyl, and cyclooctyl Hydrogen groups are mentioned. Although etherifying agents with aromatic hydrocarbon groups can also be used, those with aliphatic hydrocarbon groups are preferred in the present invention.

The amount of the etherification agent used is not particularly limited, but ([V)
It is preferable to use about 1 to 6 moles per mole. The etherification reaction is carried out in the presence of the same phase transfer catalyst used to obtain (I) from (n) above, that is, a quaternary onium salt. As the quaternary onium salt, quaternary ammonium salts are preferred because they are industrially easily available. Specific examples of quaternary ammonium salts include tetraalkylammonium salts (e.g., tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate,
trioctylmethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, etc.), or alkylammoniums having a polyoxyalkylene group, stearyldimethylammonium chloride, bisdetraoxyethylene stearylmethelammonium chloride, etc.), or Examples include vequin compounds, amine oxide compounds, and ion exchange resins. These quaternary onium salts may be used in a catalytic amount, but specifically, 0.005 to 1 mo# of dioxolane compound (IV).
0. ! 5 -T- le, preferably 0.05-0.1
A mole level is appropriate. Etherification is preferably carried out in an alkaline substance in the presence of a quaternary onium salt. Examples of alkaline substances include alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, etc.
Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are particularly suitable industrially.

The amount of alkaline substance used is the dioxolane compound GVI
1 to 10 moles per mole is suitable, and 10 to 80 moles per mole.
It is preferable to use it as an aqueous solution, more preferably 30 to 60 g. In addition, as a reaction solvent, any solvent that does not have an adverse effect on this reaction can be used. Among these, aliphatic hydrocarbons such as hegisane, octane, and hegetane; alicyclic hydrocarbons such as cyclopenkune and cyclohexane; Hydrocarbons: Aromatic hydrocarbons such as benzene, toluene, and quinlenato are preferred.Ethers such as diethyl ether, TiIF, diglyme, and dioxane can also be used.The reaction temperature is 40 to 80°C, preferably 40 to 60°C. When the diisolane compound (v) thus obtained is subjected to a hydrolysis reaction, the other target compound, diglycerin dial C ether (I
b) e can be obtained. The hydrolysis reaction of dioxolane compound (g) can also be carried out by a known method, for example, heating in water using a protonic acid catalyst such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, benzenesulfonic acid, or acetic acid. Good, there is no particular limitation on the amount of acid catalyst used, but 0.0
1 to 0.2 normal is sufficient, preferably 0.05 to 0
．． There are 10 regulations. A water-soluble organic solvent such as lower alcohols such as methanol, ethanol, and isopropanol, and ethers such as Ti(F, diglyme and dioxane) can be added to the water.The reaction temperature is 50 to 10 ml.
The temperature is 0°C, preferably 50-60°C. If hydrolysis is carried out under these conditions, 1゜3-dioxolane compound (
Another desired product, the α,β-dialkyl ether (Ib) of diglycerin, can be quantitatively obtained from the same product.

The diglycerin alkyl ether (1) of the present invention does not have easily decomposable bonds such as ester groups in its molecular structure, so it is chemically stable, causes little skin irritation, and has surfactant ability. Therefore, it is useful as an emulsifier, oil agent (emollient), humectant, thickener, etc., and especially as a component of cosmetics.

The properties of typical compounds of the present invention are as follows.

Table 1 * Concentration of diglycerin alkyl ether Diglycerin alkyl ether has polar groups such as hydroxyl groups, so it has hydrophilicity and hygroscopicity, and has good adsorption to the skin. Compared to conventional diglycerin alkyl ethers, the alkyl chain moiety has more methyl branches and no double bonds, which hinders the alignment of molecules in aqueous solutions and causes aggregates such as liquid crystals to form. The more it is formed, the more it becomes difficult to dissolve in water, and it appears to have strong pond-like properties. Therefore, when the compound of the present invention is blended into cosmetics and applied to the skin, it has high resistance to washing,
It exhibits a characteristic that it remains highly persistent on the skin, that is, it has an excellent long-lasting effect as a cosmetic. Therefore, the compounds of the present invention are particularly useful as emollients and humectants in cosmetics.

In addition, among the compounds of the present invention, those having a relatively large number of carbon atoms in the alkyl group, such as phyteil diglyceryl ether,
It is also useful as a curing agent used as a lipophilic surfactant.

The amount of the compound of the present invention incorporated into cosmetics may vary depending on various factors, but when used as an emulsifier, the amount is 0.2 to 1.
5% by weight, 2% when used as an oil or moisturizer
~50 heavy cracks are appropriate.

The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 Synthesis of 2-hydroxy-3-farnesyloxyprobyl glyceryl ether: (+) Into a 3β reaction vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, a 50% aqueous sodium hydroxide solution 36031 was added. '(180g as sodium hydroxide [4,
5 mol], farnesol 333.67 (1.5 mol)
, add 340 tons of hexane, and stir in the same manner. Then, 50% tetrabutyl ammo;, rum hydrogen sulfate 50.9
7 (25.5 mol of hydrogen sulfate)) was added. The temperature of the reaction mixture was maintained at room temperature, and 277.5% of epichlorohydrin was added from the dropping funnel.
ii' (3.0 mol) was added dropwise over about 30 minutes. During this time, the reaction mixture gradually heats up. After the dropwise addition is completed, the reaction mixture is kept at 4K at 50-55°C and stirring is continued for about 3 hours. It was confirmed by gas chromatography that farnesol had almost disappeared. Add 670 J of tap water to the reaction product and stir. Then, the hexane layer is collected by liquid separation. Hexane is distilled off under reduced pressure, and the residue is subjected to vacuum distillation. Farnesyl glycidiether 352 was obtained as a colorless and transparent solution. Yield 84%.

Boiling point 155-160℃ (0,6=L'-) Elemental analysis
As Cl8H3゜02 (calculated value) C77,6chi (77
, 65chi) i H10,6chi (10,86%) 011.
7th factor (11,49th) oxirane oxygen 5.62th factor (5,70th) iodine value
273 (273,6) I R (m-', liquid film) 3060,2975,29
30,2860°1670,1445.1375.12
50.1160~1040°1000~900.835'f(=NMRCδin ppm, ■tsu3, TM
S internal standard) 1.60.1.70 (both singlet, 1
2H, 4 methyl groups) 1.85-2.30 (multiplet, 8H, methylene group) 2
．． 40-2.90 (multiplet, 2H,-CH,0CH2
C) ICC20\1 2.95~3.30 (Multiple line, IH, -Cd20C
H, Czaf(t)\1 4.03 (double line) ztt, J -6,5Hz.

-Ctan20CH2Ck'1CK2) \1 4.90-5.50 (multiplet, 3H, olefin 7゛lotons) (11) In a 2J3 reaction vessel equipped with a reflux condenser, dropping funnel, thermometer, and stirrer. Acetone glycerin ketal 531.2 y-(4,02 mol), N, N
, N'.

N'-methyl 1.6-/aminohexane 13.
Add 8i (0.08 mol) and heat to 100℃ while stirring.
Heat to. Then, from the dropping funnel, farnesilg 1 nosidyl ether 224 obtained in (1) of Example 1 was added.
．． 7 # (0.8 mol) is added dropwise over a period of about 50 minutes. During this time, the temperature of the reaction mixture is maintained at 100°C. After the addition was completed, stirring was continued at 120° C. for another 6 hours. A gas chromatograph of the reaction mixture revealed that glycidyl ether had completely disappeared. The reaction product is cooled, then saturated saline solution is added and stirred. Further, dilute hydrochloric acid is added to neutralize the alkaline content and subsequent liquid treatment is performed.

The M layer is collected and excess acetone glycerol ketal is distilled off under reduced pressure. The residue is then subjected to vacuum distillation. 2,2-dimethyl-4-(2,2-dimethyl-4-(
2'-Hydroxy-3'-farnesiloxy)propoxymethyl-1°3-dioxolane 262.4P was obtained.

Yield: 80 cm.

Boiling point: 220-230°C (0.60Hy).

Elemental analysis As C24H4205 (calculated value) C70,
1% (70,21%); Hlo, 1aI) (10,31
%) 019.4chi (19,48chi) Hydroxyl value 137 (136,9) Iodine value 185 (185,7) IR (C1n-', liquid film) 3650-3150.31
00~2700°1645.1440,1370,12
45,1210.1170~900.835'H-NMR (δin ppm, CDCA, , T
MS internal standard) 1.33.1.38 (both singlet, 6
H21,60,1,67 (both singlet, 12H, 4 methylene groups) 1.85-2.40 (multiple helix, 8H, methylene group) 3
．． 05 (-double line, 1it, -OH) 3.30~
4.50 (multiplet, 12i(.

4.85-5.50 (multiplet, 3H, olefin proton) (curve) In a 1,80-liter reaction vessel equipped with a reflux condenser, a thermometer, and a stirrer, 10 of tap water, 1.24 P of concentrated sulfuric acid, and the above procedure were added. Dioxirane compound obtained in Example 1 (1i) 50%
(0,123 mol) and methanol 1001 were added and stirred. The temperature was then raised to 60°C and stirred for about 4 hours.

The reaction mixture was initially a heterogeneous suspension, but a homogeneous clear solution was obtained after about 4 hours.

Then, after adding dilute NaOH aqueous solution to neutralize the acid content,
Cooling is applied and ether extraction is carried out by adding ether (500d). The ether layer is collected by liquid separation, and the ether is distilled off under reduced pressure. Furthermore, 1+u+) and 150
A drying process was performed at ~60°C for 3 hours. 43.1 l of slightly yellow viscous liquid 2-hydroxy-3-farnesiloquine-probyl glyceryl ether was obtained. Yield 9
4.7chi.

Elemental analysis C2, lachiO6 (calculated value) C68,5
CH (68,07%); I (10,3% (10,34 CH) 021.2 CH (21,59 CH) Hydroxyl value 451 (455) Iodine value 205 (206) IR (cm-', liquid film ) 3650-3100.31
00-2700゜1670.1445,1375.11
70-960'H-NMR (δin ppm, CDC
Jh *TMS internal standard) 1.64, 1.70 (both singlet, 12H, 4 methyl groups) 1.85-2.30 (multiplet, 81-r, methylene group) 3.15-4. 70 (Multiple line, 15) I.

4.90-5.50 (Multiple line, 3H, olefin proton) Example 2 Synthesis of 2-methoxy-3-farnesyloxybrobyl glyceryl ether: (1) Reflux condenser, dropping funnel, temperature IW meter, 1 In a 1-type reaction vessel equipped with a stirrer, 97.6 ft of a 50% sodium hydroxide aqueous solution (48% as sodium hydroxide) was added.
87 [1,,22 mol]), hexane too much, dioxolane compound 50P obtained in (jl) of Example 1 above (
0,t23 mol) and stir. Then, 8.4 J of 50 titetraptylammonium hydrogen sulfate (4.2 P CO 0,0123 mol as hydrogen sulfate) was added to 71
0 and keep the temperature of the reaction mixture at 40°C.

Next, from the dropping funnel, 87.3 y-(
0,615 mol) was added dropwise little by little over about 30 minutes. After completion of the dropwise addition, the reaction mixture is stirred at 45 to 50° C. for about 9 hours to react. 200 ml of tap water was stirred into the reaction product from which the disappearance of the starting dioxolane compound was confirmed by gas chromatography of the reaction mixture. Then, the hexane layer is collected by liquid separation. After distilling off the hexane under reduced pressure, the residue was distilled under reduced pressure to obtain 2,2-dimethyl-4-(2'-methoxy-
3'-Farnesyloquine) propoxymethyl-1,3-
Dioxolane 45P was obtained. Yield 86.2%.

Boiling point: 195-200°G (0.35℃).

Elemental analysis As C25H4405 (calculated value) C70,
5% (70,72 units); H10,4% (10,44 units) 019.3% (18,84 units) Iodine value 188 (180) IR (Crn-', liquid film) 3150-2600.16
60.1440°1365.1290~1170.11
70-1000.835'H-NMR, (δin pp
m+ CDC, g5. TMS internal standard) 1.34.1
．． 40 (Both are singlet, 6H91,60,1,67 (Both are Itton, 12H, 4 methyl groups) 1.80-2.30 (Multiplet, 8H, methylene group) 3
．． 47 (-double line, 3H, -OC!14) 3.3
0-4.50 (multiplet, 12H.

4.80-5.50 (multiplet, 314, olefin proton) (11) Tap water 70% in a 1p reaction vessel equipped with a reflux condenser, thermometer, and stirrer. %, concentrated sulfuric acid 0.82P, dioxolane compound obtained in Example 2 (1) 34.47(0
, 081 mol) and methanol 701 were added in this order, and the mixture was heated to 60°C while stirring. After stirring at 60° C. for about 5 hours, the suspension-like reaction mixture becomes a slightly yellow homogeneous transparent solution. Add dilute aqueous sodium hydroxide solution to neutralize the acid content, and then cool. Then ether (
300rnl), the ether layer was collected by liquid separation, and the ether was distilled off under reduced pressure. Further, a drying process was performed at 1 mm H5'/60°C for about 3 hours. In this way, a slightly yellow viscous liquid 2=methoxy-3-farnesiloxyprobyl glyceryl ether 28.87- was obtained. Yield: 93 cm.

Elemental analysis C22H400! + as (calculated value) C68
,6% (68,7,1%); H10,4% (10,4
8%) 020.3% (20,80ti) Hydroxyl value 289.2 (292,2) Iodine value 19
8.3 (198) IR (cm-', liquid film) 3650-3100.31
00-2600゜1645.1440,1375,11
95.1170-1000.835'H-NMR (δi
n I) I) rill CDCl3. , TMS internal standard) 1.63.1.70 (both singlet, 12H,
4 methyl groups) 1.85-2.30 (multiplet, 8H, methylene group) 3
．． 49 (-double line, 3H, -0CHs) 3.15
~4.20 (multiplet, 14H.

4.85-5.55 (multiplet, 3H, olefin protons) Example 3 Synthesis of 2-octoxy-3-farnesiloquine-probyl glyceryl ether: (+) Methyl iodide in (1) of Example 2 Instead of octyl bromide 74.8? (0,387 mol), dioxolane compound 32.8J' (0.08 mol) obtained in (11) of Example 1, 50% aqueous sodium hydroxide solution 64z (32y as sodium hydroxide)
(o, s mol]), hexane 100g, tetrabutylammonium hydrogen sulfate 2.8 # (0,008 mol)
The reaction was carried out under the same conditions as in Example 2 (1) using each of the following. After the same treatment, 2,2-dimethyl-4-(2,2-dimethyl-4-(
2'-octoxy-3'-farnesiloxy)propoquinemethyl-1°3-dioxolane 37f was obtained. collection x
s s, s %.

Boiling point 240-250℃ (0.55℃) Elemental analysis C32H580! (calculated value) C73.2% (7
3,52%); H11, 2 Section (11,18 Chi) 015
．． 2chi (15,30chi) Iodine value 144 (145,6) IR (cm-', liquid film) 3100-2600,164
0,1440°1368, 1280~1170.117
0-1000.835'H-NMR (δin pp+n
, C1) CA3. TMS internal standard) 087 (triple line, 3 H, J=6.0Hz, 0 (CH2 beauty CH3
) 1.30 (Broad single line, 12H.

-0CR2(CH2)aCHl) 1.37.1.43 (both double line, 6H21.64.
1.70 (both singlet, 12i (, 4 methyl groups) 1.85-2.35 (multiplet, 8H, methylene group) 3
．． 30-4.50 (multiplet, 14f(.

4.85 to 5.55 (multiplet, 3H, olefin proton) (11) Dioxolane compound 3 obtained in (1) of Example 3 using the reaction apparatus used in (11) of Example 2
Example 2 (1
Hydrolysis was carried out under the same reaction conditions F as in 1). After the same treatment, a pale yellow viscous liquid 2-octoxy-3-farnesyloxyprobyl glyceryl ether 3hoy
I got it. Yield 98.7%.

Elemental analysis C2゜tI,, 0. As (calculated value) C7
2,0% (72,15 chi); I (11,3 chi (11,
28%) 01G, 2chi (16,57chi) Hydroxyl value 230 (232,4) Iodine value 162 (157,7) IR (crn-', liquid film) 3700-3050.30
50~2600°1660.1440,1375,11
80~ioo.

'H-NMR (δin ppm1 CDCl38.T
MS internal standard) 0.88 (triple line, 3H, J-6,
0Hz, -0(CH2)+Cps) 1.30 (Broad single line, 12H.

-0-Cut (Ci(JaCHs)1.63.1.
70 (both singlet, 12H, 4 methyl groups) 1.85-2.30 (multiplet, 8H, methylene group) 3
．． 30-4.40 (multiplet, 16H.

4.85 to 5.50 (multiplet, 3H, olefin proton) Example 4 Synthesis of 2-dobucyloxy-3-phalnesyloxyglobyl glyceryl ether: (1) In (il of Example 2), methyl iodide Dioxolane compound 32 obtained in Example 1 (11) was prepared by using dodecyl bromide 99.7 P (0.4 mol) in place of
．． 8P (0.08 mol), 50 thiosodium hydroxide aqueous solution 641 (32y-(o, s mol) as sodium hydroxide), hexane 100 ml. Tetrabutylammonium hydrogen sulfate 2.8 g-(0,008 mol) The reaction was carried out under the same conditions as in Example 2 (+) using each of the following.

After post-treatment in the same manner, low-boiling substances such as unreacted dodecyl bromide were distilled off under reduced pressure. The residue is a pale yellow, slightly viscous liquid of 2,2-dimethyl-4-(2'
-Dobsiloxy-3'-phalnesiloxy)furboxymethyl-1,3-dioxolane 40Pt was obtained. Yield 86
．． 4 chi.

Elemental analysis As CWH@05 (calculated value) C74,9chi (74,69chi); H11,3chi (11,49chi) O
'13.5chi (13,82chi) Iodine number 130 (131,5) IR (ctn-', liquid film) 3050-2700.1
660,1440°1365,1270~1170.1
170-1000.835'If-NMR (δ" pp
”+ CI) CAs * TMS internal standard) 0.86
(Triple line + 3 FI s J = 6.0) Iz.

-O-(CHz)ncH3) 1.30 (single line, 20H, -0-CL(t(%)
ccI(s) 1.33, 1.40 (both single line, 6H
91,60,1,67 (both single line, 12H, 4 methyl groups) 1.85-2.30 (multiple line, 8H, methylene group) 3
．． 30-4.50 (Multiplet, 141(.

4.85-5.50 (multiplet, 31 (, olefin proton) (11) Using the reaction apparatus used in (11) of Example 2,
Dioxolane compound obtained in Example 4 (1) 36.
0g-(0,0623mol), concentrated sulfuric acid 0.631F-1
A similar reaction was carried out using tap water 72z1 and methanol 729-. Post-treatment was carried out in the same manner (2-dobutyloxy-3-phalnesyloxyglobyl glyceryl ether 30? was obtained as a slightly yellow, slightly viscous liquid. Yield: 8
9.3 chi.

Elemental analysis Cs, as LzO5 (calculated value) C73,4
Chi (73,56 chi); H11,7% (11,60 chi)
014.5chi (14,85chi) Hydroxyl value 210 (208,2) Iodine value 140 (141,3) Engineering R (cm-', liquid film) 3650-3050.30
50~2700゜166υ, 1440.1380.1
180-1000+1(-NMR(δin pp+n,
CDC4, TMS internal standard) 0.88 (triple line,
3 H, J-6, 01 (Z.

-O-(CH2)IICH3) 1.30 (single line, 20H, -0-CHt (CH
J+. CH9) 1.6-2.1.70 (both single wire,
12H, 4 methyl groups) 1.84-2.29 (multiplet, 8H, methylene group) 3
．． 30-4.40 (multiplet, 16H.

4.85-5.50 (multiple wins, 3H, olefin proton) Example 5 Synthesis of 2-hydroxy-3-phyteirogin-probyl glyceryl ether: (1) Used in (1) of Example 1 A reaction apparatus was used, except that 1.5 mol of phytol was used instead of farnesyl.
Glycidyl etherification was performed under the same conditions as in Example 1 (1). After the same treatment, 474.9f of phytylglycidyl ether was obtained as a colorless transparent liquid by distillation under reduced pressure.
I got ~. Yield: 139.8 cm.

Boiling point 198-200°C (0,4) Iy) Elemental analysis C23I leakage 02 (calculated value) C77,7
8,35%); f (12,5 chi (12,58 chi) 09
．． 2chi (9,07chi) oxirane oxygen 420chi (4,54φ) iodine value
73.4 (72,0) IR (crn-', liquid film) 3030,2950,2
925,2860°1660.1450,1370,1
240.1160-1000°900.835'H-NMR (δin I) pmI CDC-e, ,
TMS internal standard) 0.85 (double line, 12H, J
-=5.0Hz, 4 methyl groups) 1.0 to 1.70 (broad single line, 19H, methylene-based methine group) 1.67, 1.73 (both single lines, 3H11,80 to
2.30 (broad multiplet, 2H.

3.40-3.90 (multiplet, 2 i(, -C1(
20CH2CHCH2)~\1 4.07(double line + 2 Hr J=6.0f(z'.

538 (triple line + I HIJ = 7.oHz + olefin proton) (11) Using the reaction apparatus used in (11) of Example 1,
Instead of farnesyl glycidyl ether, 0.9% of the farnesyl glycidyl ether obtained in (1) of Example 5 was used.
The reaction was carried out in the same manner as in Example 5 (11) except that 65 mol was used. After similar treatment and vacuum distillation, a pale yellow transparent solution of 2.2=dimethy#-4-('l'
1-pyroxy-3'-phyteyloxy)propoxymethyl-1,3-dioxolane 374y was obtained. Yield: 80 cm.

Boiling point 218-225℃ (0.6℃) Elemental analysis C2
As 9H5605 (calculated value) C71.6chi (71.8
5%); H11,7chi (11,64 section) 016.1%
(16,50ti) Hydroxyl value 117.7 (115,7) Iodine value 50
．． 4 (52,4) IR (Cm-', r&membrane) 3630-3150.
3050~2700°1660.1450.1365.
1280-1170.1170-940.835' 11-NMR (δin ppm, CDCB8.
TMS internal standard) o, 5s- (double line, 12H, J-
5.0Hz, 4 methyl groups 123 (broad single gland, 191 (methylene-based methine group) 1.33.1.40 (both singlet, 6H).

1.65.1.72 (both singlet, 3H1-CH,C
-cl[)120-) Cdan.

1.75-2.40 (broad multiplet, 2) I
.

kXs 2.95 (single line, 11(, -01() 3.35~
4.50 (multiplet, 12f(.

5.33 (double line, 1 i(, J=7.+) fiz
, olefin proton) G1)) Using the reaction vessel used in (iii) of Example 1, perform (1j) of the above-mentioned Example 5 as a dioxolanated @product.
Hydrolysis was carried out under the same reaction conditions as in Example 1 (11D) using 0.14 mol of diogisolan f-a' obtained in Example 1 (11D).

After similar post-treatment, 2-hydroxy-3-phyteiroquine-probyl glyceryl ether 61 was obtained in the form of a pale yellow viscous paste. il- was obtained. Yield 98, 1.

Elemental analysis C, H,, o, (calculated value) C70, (
i poly(70,22); H11.5 (11,79) 017.6% (17,99) Hydroxyl value 375 (378,5) Iodine value 55.9 (57,1) IR (cnr -', liquid film) 3650-3050.3
050-2700゜1660, 1455.1370.1
170-950') i-NMR (δin pprr+,
CDC4, TMS internal standard) 0.85 (duplex amount,
12f (, J-5,0Hz, 4 methyl groups) 1.22 (broad single line, 19f (, methylene group, methine group) 1.63.1.72 (both singlet, 3H2-cu, c
-=cHCH2o-) - c) I3 1.75-2.40 (broad multiplet, 2H2Hs 3.30-4.50 (multiplet, 15H.

(W Koshu 5.33 (Mitsukoshi Mr 11 (, J = 7.0iz, olefin proton) Example 6 Synthesis of 2-methoxy-3-phyteiroquine-7° lobil glyceryl ether; (:) Example 2 ( In 1), the dioxolane compound obtained in (11) of Example 5 (2,2-dimethyl-4-(2'-hydroxy3'-phytyloxy)propoxymethyl-1°3-, dioxolane) 0 Etherification was carried out under the same conditions as in Example 2 (1), using .14 mol of the product.

By distillation under reduced pressure, 2,2-dimethyl-4 is obtained as a colorless transparent liquid.
-(2'-methquine-3'-phyteyloxy)propoxymethyl-1,3-dioxolane 64? I got it. Yield 9
1.8 chi.

Boiling point 218-225℃ (0.7mmHf) Elemental analysis
As C30H and O3 (calculated value) C72.5% (72,
24chi); I (11,9chi (11,72chi) 016.
5chi (16,03chi) Iodine value 48.5 (50,9) IR (Crn', liquid film) 3150-2600.16
60,1450°1370,1285~1175.11
75~1000.840'f(-NMR(δin pp
m, CDC4, TMS internal standard) 0.85 (duplex?f
a, 12H, J=5.0Kz, 4 methyl groups) 1,. 23 (Broad singlet, 191-1. Metelelene-based methine group) 1.33, 1.40 (Both singlet, 6H.

1.64.1.72 (Both single line, -CmCi(C
)I20~■Ken3 1.75~2.40 (Broad multiplet, 2H2-C
H2C=C1(CH20- ~I C1(.

3.43 (single line, 3H, -0-CHs) 3.30
~4.50' (multiplet, 12f(.

5.35 (Mie 7m, IH, J-7.0Hz
, olefin proton) (11) In (11) of Example 2, 0.115 mol of the dioxolane compound obtained in (1) of Example 6 was used as the dioxolane compound, and the same procedure as in (11) of Example 2 was carried out. Hydrolysis was carried out under reaction conditions. Apply similar processing,
2-Methoxy-3-phytyloxyprobyl glyceryl ether 529-, which is a colorless, slightly viscous liquid, was obtained. Yield: 99 cm.

Elemental analysis As C27H,05 (calculated value) (near 1.
0chi (70,70%); H11.5% (11,87chi) Q18.0chi (17,44chi) Hydroxyl value 247 (244,6) Iodine value 57 (55,3) IR (Cm-' , liquid film) 3650-3100.30
50~2600°1660, 1440.1365.11
90.1170-1000.830'H-NMR(δ"
ppm1 CDcJ33. TMS internal standard) 0.8
7 (Double line, 12 H, J-5.0Hz, 4 methyl groups) 1.25 (Broad single line, 19i (, methylene base methine group) 1.65.1.73 (Both single line , 3H1-C=CH
C) I20-C and 3 1.75-2.50 (broad multiplet, 21-I
.

Cf (3 3,47 (single line, 3) I, -QC trouble,) 33
3-4.50 (Multiplet, 14) I.

5.36 (Triple line, IH, Iz+ olefin proton on J-7,0) Example 7 Synthesis of 2-butoxy-3-phytyloxyprobyl glyceryl ether: (+) 16 in (1) of Implementation FJ2 The dioxolane compound obtained in (11) of Example 5 (2,2-dimethyl-4-(2'-human-roxy-3'-phytyloxy)propoxymethyl-1-3-
0.124 mol of dioxolane was added at 744°C, and 0.124 mol of dioxolane was replaced with dioxolane.
Etherification was carried out using 496 mol under the same 4-IJ conditions as in Example 2 (1). Is it colorless and transparent due to vacuum distillation?
Night-3'-phyteyloxy) profoxmethyl-l.

3-dioxolane 64P was obtained. Yield 95.4%.

Boiling point 215-225℃ (0,35 degrees Hf!-) Elemental analysis As O5 for 0 companies (calculated value) C73.5 inches (73 degrees 28 degrees) i H12.3% (11,93 degrees) 015.0
(14,79%) Iodine value 50.0 (46,9) IR (an-', liquid film) 3100'-2700,1
660, 1450° 1365, 1280-1175.1
170-1000.840'H-NMR (δin pp
m, CDC4, TMS internal standard) 0.80 to 1.20
(Multiplet + 15 r4, 4 methyls of phytyl group + -(CH2)3CHs) 1.23 (Broad single line, 23 H, methylene base methine base of phytyl group -0CH2 (CHJXCHs 1.36, 1.41 (both single line, 6H11, 67,
1,73 (Both shore line, 3H9-C-CI (CHD-) 1 Cdan 3 1.75-2.50 (Broad multiple line, 2H1CH
8 3,30-4.55 (multiplet, 14H.

5.37 (Triple line, I H, J = 7.0 Hz, olefin proton) ((1) In (i+> of Example 2, the dioxirane compound 53 obtained in (1) of Example 7 as the dioxolane compound) Hydrolysis was carried out under the same reaction conditions as in Example 2 using 0.1 mol of 2-butoxy-3. -phytyroxyprobyl glyceryl ether 4
8? I got it. Yield 99.2%.

Elemental analysis as C30H110α (calculated value) C72,
3ch (71,95%); l (12,4ch (12,08%)
h) 016.3% (15,97 h) Hydroxyl value 230 (224,1) Iodine value 52. ．． 0 (50,7) IR (crn-', liquid film): 3630-3100.
3oso ~2700°1660.1450,1370
．． 1180-1000'H-NMR (δin ppm,
CDCJ133, TMS internal standard) 0.75~1
．． 10 (multiplet, 15i (, 4 methyl groups of the phyteil group + - 0 (CHJCL (3) 1, lO ~ 1.65
(Broad single line, 23H.

methylene group + methine group + -0-CH2(CH2)2CH31,65,1 of phiteil group
,70 (both singlets, 3H9-CH~Tsukuda cn2o-) ■ C mountain 1.80~2.30 (broad multiplets, 2H2-C
JJyC-cHCHtO-) C1(.

3.30-4.25 (multiplet, 16H.

5.33 (Triple line, IH, J=7.0Hz, olefin proton) Example 8 Synthesis of 2-octoxy-3-phytyloxyprobyl glyceryl ether; (1) In (1) of Example 2, As the dioxolane compound, the dioxolane compound obtained in (11) of Example 5 (2,2-dimethyl-4-(2'-hydroxy-3'-
Example 2 (1) Etherification was carried out under similar conditions. By distillation under reduced pressure, 2,2 is obtained as a colorless transparent liquid.
-dimethyl-4-(2'-octoxy-3'-phyteyloxy)propoxymethyl-1,3-dioxolane 65
I got 5'. Yield 90.8%.

Boiling point 252-265°C (0.6 Hg-) Elemental analysis C37H? 205 (calculated value) C74-64 (7
Section 4, 44): I (12゜4chi (12,16chi) 01
3.5% (13,40t) Iodine value 43.5 (42,5) I R (ryn-', liquid PM) 3075-2700
．． 1660.1450°1365.1280~1170
．． 1170-1000.850'1(-NMR(δin
ppm, CI) C4, TMS internal standard) 0.68~
1.10 (Multiplet, 151(, 4 methyl groups of phytyl group 10→CH2)7CH3) 1, 1O~1.70 (Broad multiplet, 31H.

methylene base methine group +-0=C1(t(CHJaCI(,)1.37
, 1.40 (both singlet, 6H21, 65, 1, 73
(Both singlets, 3 H1-C) (C=CHCH20-
) l-13 1,75~2.35 (Broad multiplex? 4 + 2
Hs3.30-4.50 (multiplet, 14H.

5.35 (triple line, 1, [(, J=7.0)Iz,
Olefin proton) (fil In (11) of Example Z, 60% (0.1 mol) of the dioxolane compound obtained in ++) of Example 8 was used as the dioxirane compound, and (1
Hydrolysis was carried out under the same reaction conditions as in 1). By performing the same post-treatment, 2-octoxy-3-phyteyloxyprobyl glyceryl edel 54P was obtained as a pale yellow liquid. Yield 96.4%.

Elemental analysis C841, 0. As (calculated value) C73,
5% (73,33chi); H12,0chi (12,31%
)oi4. s(14,36) Hydroxyl value 21)O(201,5) Iodine1147.0 (45,6)IR(z-'
, liquid film) 3640-3100.3050-2090
゜1660.1450, 1365.1185~1ooO
'l(-NMR(a in ppm, CDCA3,
TMS internal standard) 0.75 to 1.10 (multiplet, 1
5H, 4 methyl groups of phytyl group 0 (C1(2)? 0 legs,) 1.10-1.65 (broad single line, 31H.

methylene group + methine group + -0-CH, (Cl) a CHsl, 65.1
．． 70 (Both singlets, 3H1-CHtC-C[CH2
0-) 1.80-2.25 (broad multiplet, 2H1H3 3,30-4.30 (multiplet, 16H).

5.35 (Mie a, IH, J=7.0Hz,
Olefin Proton) Example 9 The washability (Note 1) of the diglycerin alkyl ether of the present invention and a comparative compound were compared by the following method. The results are shown in Table 2.

Table 2 (Note 1) Washability: 120±2 mg of the test compound was uniformly coated on a 2.5 crn x 3.5 cm glass plate using chloroform, and the mixture was heated at 30°C for 2! A propeller with a diameter of 5 mm was placed in this aqueous solution, and the mixture was stirred at 300 rpm for 2 minutes. Next, this glass plate was placed in 1 liter of water at 30° C. and stirred with the above-mentioned propeller at 30 rpm for 1 minute for rinsing. After drying, the weight of the glass plate was measured, the difference in weight was calculated, and the cleaning residue was calculated from the following formula.

The results of this test show that the diglycerin alkyl ether of the present invention has extremely high cleaning residue compared to conventional diglycerin alkyl ethers and commonly used moisturizers, and has a performance equivalent to or better than that of oil agents. However, it was found that these substances were not easily removed by washing.

Example 10 Hygroscopicity test of diglycerin alkyl ether of the present invention (
Note 2) was conducted to examine its performance as a moisturizer. The results are shown in Table 3.

Table 3 (Note 2) Hygroscopicity: Place 1.00 y of pre-dried test compound in a cylindrical glass container of φ2 cm x 2 r1n, and leave it at constant temperature and humidity of 93% at 25°C. The change in weight was measured, and the following formula also determined the hygroscopicity.

i 00 From the results of this test, it is clear that the diglycerin alkyl ether of the present invention not only has stronger oil properties than conventional diglycerin alkyl ether, but also has the same moisture absorption properties. Ta.

Example 11 An emulsification test (Note 3) was conducted on the diglycerin alkyl ether of the present invention and a comparative compound to compare their performance as emulsifiers. The results are shown in Table 4.

Hereinafter referred to as Sohaku (Note 3) Emulsification test: Test compound 51 was mixed with liquid paraffin 459- and heated to 75°C. Separately purified water 5
09- was heated to 75° C., added to the mixture of liquid paraffin and the test compound under stirring to emulsify it, and cooled to room temperature while stirring continued.

The emulsified state immediately after was observed, and the separated state after being stored at 25° C. for 7 days was further observed, and the emulsion stability was calculated using the following formula.

×100 From the results of this test, it was found that among the diglycerin alkyl ethers of the present invention, those having a relatively long alkyl group, the phiteyl group, were of the w10 type, comparable to conventional diglycerin alkyl ethers and known emulsifiers. It was revealed that it also has emulsifying power.

Example 12 (Cold cream) An emulsion having the following composition was prepared using 2-hydroxy-3-phytyloxyglobil glyceryl ether.

- Chill ■ Squalane 5.0 ■ Liquid paraffin 10.0 ■ Beeswax 3.0 ■ Lanolin 1.5 ■ Sorbitan monooleate 2.0 ■ Methylparaben 0.1 ■ Butylparaben 0.1 ■ Fragrance 0.2 0 Purified water Remaining Amounts ① to ③ and ② are heated and mixed at 70°C, and the mixture of ① and 0 heated to 70°C is added under stirring to emulsify. After that about 4
Miko's cream, which was obtained by cooling to 0°C and adding O, was suitable as a cold cream because it spread well and blended well into the skin.

Example 13 (Hand Cream) An emulsion having the following composition was prepared using 2-methoxy-3-phytyloxypropyl glyceryl ether.

Chill ■ Stearic acid 10.0 ■ Stearic monoglyceride 1.5 ■ Triethanolamine 0.3 ■ Methylparaben 0.1 ■ Butylparaben 0.1 ■ Fragrance 0.2 ■ F'11 water Remaining amount ■ ~ ■ 70 Mix and heat to ℃ and add ■～■ into this.

Add the mixture heated to 70°C in step (2) while stirring and emulsify. Thereafter, the mixture was cooled to 40°C and 2 was added to obtain a white emulsion. When used on the hands, this emulsion blends well into the skin and does not easily come off when washed, making it suitable as a hand cream.

Example 14 (Punk) Using 2-butyloxy-3-phytyloxyglobin glyceryl ether, a mixture having the following composition was prepared in 1i1
4 were made.

One chill ■ Polyvinyl alcohol 15.0 ■ Titanium oxide 5.0 ■ Ethylene glycol 4.0 ■ Methyl paraben 0.1 ■ Fragrance 0.2 0 Purified water Heat the remaining amount ■ to about 90℃ L/% While stirring ■ Add little by little until dissolved evenly. Next, ■, ■~■ were added, and (after stirring to homogeneity and cooling to 40°C, ■ was added. When the resulting mixture was applied to the skin, it dried into a single film and peeled off from the skin. It was suitable as a facial pack, as it provided just the right amount of stimulation when applied, and left a long-lasting moist feeling afterwards.

Practical Example 15 (Cleansing Cream) An emulsion having the following composition was prepared using 2-hydroxy-3-phytyloxyglopylglyceryl ether as an emulsifier.

■ Polyoxyethylene hydrogenated castor oil 2.2 ■ Geiro 2.5 ■ Setanol 2.0 ■ Liquid paraffin 18.5 ■ Preservative 0.2 ■ Fragrance 0.1 ■ Purified water Heat and mix the remaining amount ■～■ at 70℃ Then, (2) heated to 70°C is added to this mixture while stirring to emulsify. After cooling to about 40°C, (2) was added to obtain a white emulsion. This cream was suitable as a cleansing cream, as it was glossy, spread easily, and left a moist feeling even after washing the face.

Practical Example 16 (Cream Foundation) Using 2-methoxy-3-phyteiroquine-probil glyceryl ether as an emulsifier, an emulsion having the following composition was prepared.

Al ■ Polyoxyethylene stearate 2.5 ■ Isopropyl myristate 6.0 ■ Stearic acid 5.0 ■ Merck 12.0 ■ Titanium oxide 5゜0 ■ Red iron 0.5 ■ Methylparaben 0.1 ■ Propylparaben 0.1 [Inc.] Fragrance 0.2 0 Purified water Heat and mix the remaining amounts ■～■, ■ to 70℃, and add 70% of ■0 to this mixture.
Add the heated mixture to the mixture while stirring and emulsify. 70℃
Add (1) to (2) to this emulsion kept at a temperature of 0.5°C, stir and mix again, and when cooled to 40°C, add (2). When the emulsion thus obtained was used as a foundation, it was resistant to perspiration and had properties that made it difficult for makeup to come off.

Example 17 (Lotion) A mixture having the following composition was prepared using 2-hydroxy-3-farnesyloquine-probyl glyceryl ether.

■Glycine 1.0■Sodium pyrrolidonecarboxylate 1.0■Glycerin 1000■Pholyoxyethylene cetyl ether-1,5 thyl■Ethanol 10.0 ■Fragrance 0.2■Purified water Mix and stir the remaining amounts ■～■. A homogeneous solution was obtained. This lotion blended well into the skin (and had a moist feel).

Example 18 (Lip balm) A mixture having the following composition was prepared using 2-methoxy-3-farnesyloxyprobyl glyceryl ether.

■ Liquid paraffin 37.0 ■ Jojoba oil 16.0 ■ Carnauba wax 13.0 ■ Microcrystalline wax 14.0 ■ Vaseline 10.0 After heating and mixing the six ingredients to 85°C and stirring thoroughly to make them uniform, Immediately pour into a mold and cool.

The resulting mixture was a slightly soft solid with a milky white luster, and when molded into a stick, it blended well and spread well as a lip balm, and was difficult to remove from the lips.

Example 19 (Eyeshadow) A mixture having the following composition was prepared using 2-octoxy-3-farnesyloxyprobyl glyceryl ether.

■ Squalane 30.0 ■ Castor oil 36.0 ■ Carnauba wax 3.0 ■ Ceresin wax 10.0 ■ Microcrystalline wax 5.0 ■ Titanium oxide 8.0 ■ Titanium mica 2.0 ■ Group blue 3.0 ■ ~ Heat and melt ■ to make it uniform. Add ① to ①, which were mixed well in advance, to this, and knead the whole mixture with a roll mill. This is melted again and poured into a container to be molded. The resulting mixture was a soft, bluish-white solid, and when used as an eye shadow, it blended well into the skin and had excellent properties that made it difficult to remove makeup.

Margin below

Claims (1)

[Claims] 1. General formula (I) [wherein R is the following formula cu. B (m represents an integer from 1 to 10, A and B each represent a hydrogen atom or exist (.) indicates that they form a single bond together, and when mi2 or more, A and B
may be a combination of the above two cases), and R' represents a hydrogen atom or a saturated or 4-saturated linear or branched aliphatic hydrocarbon group having 1 to 24 carbon atoms. Diglycerin alkyl ether of terpene alcohol represented by ]. 2, +1) The diglycerin alkyl ether of a terpene alcohol according to claim 1, wherein R is a farnesyl group. 3. The diglycerol alkyl ether of a terpene alcohol according to claim 1, wherein R in the formula (1) is a phytyl group. 4. The cyclycerin alkyl ether of a terpene alcohol according to claim 2, wherein (Formula 11 is a farnesyl group, and R' is a hydrogen atom or a saturated straight-chain alkyl group having 1 to 12 carbon atoms.) The diglycerol alkyl ether of a terpene alcohol according to claim 3, wherein (I1 is a phyteyl group, and R' is a hydrogen atom or a saturated straight-chain alkyl group having 1 to 12 carbon atoms). :6. General formula (1) [wherein R is the following formula cf(. and when m is 2 or more, A and B may be a combination of the above two cases), and R' is a hydrogen atom or a group having 1 to 24 carbon atoms. A cosmetic containing a diglycerin alkyl ether of a terpene alcohol represented by the following: saturated or unsaturated linear or branched aliphatic hydrocarbon group.