JPH06157388A - Branched alkyl ether of pentaerythritol and its production and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To obtain a new compound capable of forming a thermotropic liquid crystal in water disperse system, soluble in almost all solvents, having good dispersibility to water, exhibiting very excellent lubricating properties and useful as a emulsifier, a lubricating agent, a liquid forming agent, etc. CONSTITUTION:A compound of formula I (R<1> is 16-36C branched alkyl; R<2> to R<4> are H or 16-36C branched alkyl), e.g. 1mol isostearyl ether adduct of pentaerythritol of formula II. This compound is obtained by reacting pentaerythritol or its branched alkyl ether with a branched alkyl halide of the formula R<1>X (X is halogen) (preferably branched alkyl bromide such as isostearyl bromide or heptyldecyl bromide) in the presence of a basic substance (preferably NaOH, etc.), preferably at 80-150 deg.C. Furthermore, this reaction is preferably carried out by dissolving or dispersing the compound of formula II in an organic solvent such as methanol and then adding a branched alkyl halide thereto while removing water content.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel pentaerythritol branched alkyl ether useful as a base for cosmetics, an emulsifier, a lubricant, a liquid crystal forming agent, etc., a process for producing the same, and a cosmetic containing the same. .

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Polyol ethers such as polyoxyalkylene alkyl ethers and polyoxyalkylene ethers of sorbitan esters have been used as emulsifiers, solubilizers and lubricants for cosmetics and cosmetics. However, these polyol ethers are produced by the addition reaction of alkylene oxides such as ethylene oxide and propylene oxide, but the products obtained are mixtures having various polyoxyalkylene chain lengths, and high purity products are synthesized. It is difficult to obtain such a composition, and when used in cosmetics and cosmetics, sufficient performance may not be obtained.

In the natural world, there are many derivatives of polyhydric alcohols having an ether bond. Among them, monoalkyl ether of glycerin (referred to as glyceryl ether) is particularly well known. For example, fish lipids include palmityl glyceryl ether, stearyl glyceryl ether and oleyl glyceryl ether.

Such glyceryl ether has the W
Utilizing the / O type emulsifying property, it has been widely used as a cosmetic base and the like (JP-A-49-87612, JP-A-49-92239, JP-A-52-12109, etc.).
Further, paying attention to the fact that such glyceryl ether is a nonionic surfactant having many characteristics, attempts have been made to derive a polyol ether compound having a molecular structure similar to that of glyceryl ether from a polyhydric alcohol. (U.S. Pat. No. 2,258,892, Japanese Patent Publication No. 52-
18170, JP-A-53-137905, JP-A-5
4-145224). Further, among these glyceryl ether derivatives, a branched alkyl glyceryl ether having a branched alkyl group such as an isostearyl group in the alkyl group (Oil Chemistry, Vol. 36, No. 8, 588-598 (1987)) and diglycerin. Branched alkyl ether of diglycerin with a branched alkyl group introduced into
No. 24496, Japanese Examined Patent Publication No. 3-36815) and the like have been used in cosmetics and cosmetics as nonionic surfactants having excellent W / O type emulsifying properties.

However, while the branched alkyl glyceryl ether and the branched alkyl ether of diglycerin have excellent W / O type emulsifying properties, they are used for perfume cosmetics having a high water content such as shampoo, rinse or lotion. In this case, since the hydrophilicity is low, the dispersibility in water may be poor to cause poor emulsification, and there is a problem that a sufficient effect cannot be expected because the amount used is limited.

Therefore, it has been desired to develop a nonionic surfactant useful as a base for cosmetics, an emulsifier, a lubricant, a liquid crystal forming agent and the like.

[0007]

Under the circumstances, the inventors of the present invention have conducted diligent research, and as a result, the novel pentaerythritol branched alkyl ether represented by the following general formula (1) is thermotropic in an aqueous dispersion system. It forms a liquid crystal, exhibits extremely excellent lubricity, is compatible with almost all solvents, and has the properties of easily and almost uniformly dispersing when mixed with water. The present invention has been completed by finding that it exhibits extremely excellent performance as an agent, an emulsifier, a lubricant, and a liquid crystal forming agent, which has never been obtained.

That is, the present invention has the following general formula (1):

[0009]

[Chemical 5]

[In the formula, R ¹ represents a branched alkyl group having 16 to 36 carbon atoms, and R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a branched alkyl group having 16 to 36 carbon atoms] The present invention provides a pentaerythritol branched alkyl ether represented by, a method for producing the same, and a cosmetic containing the same.

In the general formula (1) representing the pentaerythritol branched alkyl ether of the present invention, among the groups represented by R ¹ , R ² , R ³ and R ⁴ , the branched alkyl group having 16 to 36 carbon atoms is In order to obtain the effects of the invention, the groups represented by the following general formula (2) or general formula (3) are preferable.

[0012]

[Chemical 6]

[In the formula, p and q each represent an integer of 0 to 33, and r and s each represent an integer of 0 to 31.
However, the sum of p and q is 13 to 33, and the sum of r and s is 1
1-31]

As the branched alkyl group, a branched alkyl group having 18 to 24 carbon atoms is particularly preferable, and the most preferable group is an isostearyl group represented by the following general formula (6) or a general formula (7). 2-heptylundecyl group and 2-octyldodecyl group represented by the general formula (8).

[0015]

[Chemical 7]

In the pentaerythritol branched alkyl ether (1) of the present invention, R ² , R ³ and R ⁴ are hydrogen atoms or branched alkyl groups having 16 to 36 carbon atoms,
All of these may be hydrogen atoms or branched alkyl groups, and hydrogen atoms and branched alkyl groups may be mixed. Further, the branched alkyl groups of R ¹ , R ² , R ³ and R ⁴ are all the same branched alkyl group,
Each may be a different branched alkyl group.

The pentaerythritol branched alkyl ether (1) of the present invention is a pentaerythritol or its branched alkyl ether (4) according to the following reaction formula.
Can be prepared by reacting a branched alkyl halide represented by the general formula (5) in the presence of a basic substance.

[0018]

[Chemical 8]

[In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and X represents a halogen atom]

In the production method of the present invention, pentaerythritol (in the general formula (4), R ² = R ³ = R ⁴ as a raw material is used.
= H), impurities other than the intended pentaerythritol may be contained therein, but if there is no practical problem, the impurities may be used as they are,
If there is a problem, it can be used after purification by a known purification method.

For example, pentaerythritol may contain dipentaerythritol or tripentaerythritol condensed with pentaerythritol as impurities, and a small amount of a glycidyl ether adduct of dipentaerythritol and tripentaerythritol is by-produced. However, if it does not affect the performance and quality of the product, it may be used as it is, and if it does not, it is preferable to use pentaerythritol purified as a raw material by crystallization.

Further, preferred specific examples of the branched alkyl halide used in the production method of the present invention include:
For example, methylpentadecyl, methylhexadecyl, methylheptadecyl (isostearyl), methyloctadecyl, methylbehenyl, ethylhexadecyl, ethyloctadecyl, ethylbehenyl, butyldodecyl, butylhexadecyl, butyloctadecyl, hexyldecyl, heptylundecyl, Examples thereof include branched alkyl halides such as octyldodecyl, decyldodecyl, decyltetradecyl, dodecylhexadecyl, and tetradecyloctadecyl. Here, examples of the halide include chloride, bromide, iodide and the like, and bromide is particularly preferable.

In the present invention, the halogenated branched alkyl (5) can be used alone or in combination of two or more kinds in the reaction, and is a straight-chain alkyl (5) as long as it is in practical use. Even those containing a halide as an impurity can be used in the reaction.

The reaction molar ratio of the raw materials in the production method of the present invention can be appropriately selected depending on the degree of etherification of the target compound pentaerythritol branched alkyl ether (1). For example, when pentaerythritol is used as a raw material and a product having a high content of 1 mol of a pentaerythritol branched alkyl ether is obtained, usually pentaerythritol: halogenated branched alkyl = 1.2:
It is only necessary to use pentaerythritol in excess at a ratio of 1.0 to 10.0: 1.0. In particular, considering the recovery of pentaerythritol and the increase in the amount of 1-mol adduct produced, pentaerythritol: halogenated branched Alkyl =
It is preferable to react at a ratio of 1.5: 1.0 to 5.0: 1.0. Further, in order to obtain a product having a high content of 2 mol adducts of pentaerythritol branched alkyl ether, it is usual to use pentaerythritol:
In the ratio of 0.3: 1.0 to 1.1: 1.0, it is sufficient to use the branched alkyl halide in excess as compared with the case of obtaining the 1-mol adduct, and particularly to increase the production amount of the 2-mol adduct. To do pentaerythritol: branched alkyl halide =
It is preferable to react at a ratio of 0.4: 1.0 to 0.8: 1.0.

In the production method of the present invention, pentaerythritol branched alkyl ether (1 to 3 mol adduct) obtained by reacting pentaerythritol with branched alkyl halide is further reacted with halogenated branched alkyl. Thus, a pentaerythritol branched alkyl ether (1) having two or more branched alkyl groups which are the same or different can be produced.

The reaction in the production method of the present invention is usually carried out without a solvent, but pentaerythritol or its branched alkyl ether (4) and halogenated branched alkyl (5) are used.
It is preferable to use an organic solvent for the purpose of assisting the mixing of the. Examples of such organic solvent include methanol, ethanol, t-butyl alcohol, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, N
-Methylpyrrolidone, tetrahydrofuran, ether,
Examples include dioxane, toluene, hexane, xylene and the like. The organic solvent is preferably used in an amount of 0.1 to 10.0 times the amount of pentaerythritol or its branched alkyl ether (4).

The basic substance used in the reaction is not particularly limited, but from the viewpoint of reactivity and economy, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium t-butoxide, It is preferable to use sodium hydride or the like. These basic substances are 1 to 4 times the molar amount of pentaerythritol or its branched alkyl ether (4), particularly 1 to 4 times.
It is preferably used in the range of 1.5 times the molar amount.

The reaction is carried out at 50 to 200 ° C., preferably 80
It is carried out at ˜150 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 200 ° C, the product is colored, which is not preferable.

In this reaction, when water is present in the reaction system, the halogen group of the halogenated branched alkyl (5) reacts with water to form an alcohol, and therefore pentaerythritol or its branched alkyl ether is used as an organic solvent. It is preferable to dissolve or disperse (4) and heat to blow dry nitrogen gas, or to heat and dehydrate under reduced pressure to remove water, and then add branched alkyl halide (5) to react. .

After completion of the reaction, the basic substance is removed by adding an organic acid such as acetic acid or citric acid or an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid to neutralize the basic substance or washing with water. Then, the organic solvent used in the reaction is removed. In order to avoid thermal decomposition of the reaction product, the organic solvent is preferably removed under reduced pressure, usually at a temperature of 120 ° C or lower.

The pentaerythritol branched alkyl ether (1) of the present invention thus obtained is usually 1 in which one molecule of alkyl halide is added to pentaerythritol.
It can be obtained as a mixture of a molar adduct, a 2-molar adduct in which two molecules of halogenated alkyl are added to pentaerythritol, or a polymolar adduct in which three or more molecules of branched alkyl halide are added to one molecule of pentaerythritol. The pentaerythritol-branched alkyl ether (1) thus obtained is generally used as a mixture of these 1-mole adduct, 2-mole adduct, or multi-mole adduct, if there is no problem in use. However, if there is a problem in terms of performance or blending with the product, it can be used after purification by a known purification method such as silica gel column chromatography or solvent extraction.

When the pentaerythritol branched alkyl ether (1) of the present invention is used in the cosmetic composition of the present invention, the compounding amount is not particularly limited, but is usually 0.1 to 90% by weight, and particularly 0.5 to 50%. Weight percent is preferred.

The cosmetics of the present invention are roughly classified into skin cosmetics and hair cosmetics, depending on the form of use.

When used as a skin cosmetic, other surfactants, oils, moisturizers, and UV absorbers which are generally used as a skin cosmetic ingredient are used, if necessary, within a range not impairing the effects of the present invention. , Alcohols, chelating agents, pH adjusters, preservatives, thickeners, pigments, fragrances and the like can be combined in any combination, and various forms such as oil / water, water / oil type emulsified cosmetics , Creams, lotions, lotions, oily cosmetics, lipsticks, foundations, skin cleansing agents and the like.

When used as a hair cosmetic,
If necessary, other surfactants, thickeners such as hydroxyethyl cellulose, perfumes, pearling agents, dyes, ultraviolet absorbers, antioxidants, preservatives and the like are added as long as the effects of the present invention are not impaired. You may. In addition, anionic polymers such as cationized cellulose and silicone derivatives such as dimethylpolysiloxane, amino-modified silicone and polyether-modified silicone may be blended in order to improve the feel of hair.

The hair cosmetic composition of the present invention can be prepared according to a conventional method. Further, its dosage form is not particularly limited, and various dosage forms such as emulsion, suspension, gel, transparent solution, aerosol, etc. can be used according to the application, and further, as a usage, general hair cosmetics, that is, pre-shampoo agent. , Shampoo, hair rinse, hair treatment, hair conditioner, conditioning blow agent, etc.

[0037]

INDUSTRIAL APPLICABILITY The pentaerythritol branched alkyl ether (1) of the present invention forms a thermotropic liquid crystal in a water dispersion system, exhibits extremely excellent lubricity and is compatible with almost all solvents. And because it has characteristics such as being almost uniformly dispersed easily when mixed with water,
It is extremely useful as a detergent for toiletries and cosmetics, an emulsifier, a dispersant, a wetting agent, a solubilizing agent, a liquid crystal forming agent and the like.

[0038]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, ¹ H-NMR spectrum is AC-200P NMR SP manufactured by BRUKER.
Using ECTROMETER, CDCl ₃ (in the presence of D ₂ O) was used as a solvent, and the measurement was carried out under the conditions of a concentration of 3%, internal standard TMS, and 25 ° C. Further, the IR spectrum was measured using a Hitachi 270-30 infrared spectrophotometer at 25 ° C in KBr.
It was measured by the liquid film method.

Example 1 Pentaerythritol 13.6 was added to a 5 l three-necked flask.
g and 2.3 l of t-butyl alcohol were added, and the mixture was heated and dissolved. 12.4 g of potassium t-butoxide was added to this solution.
Was added, and the mixture was heated with stirring at 60 ° C. for 30 minutes, and then 36.6 g of isostearyl bromide was added dropwise. After the dropping, the mixture was heated under reflux for 20 hours, and then the resulting precipitate was filtered. The solvent was distilled off under reduced pressure to obtain 35 g of pentaerythritol isostearyl ether crude product. It was confirmed by gas chromatography composition analysis that pentaerythritol isostearyl ether had 1 mol adduct, 2 mol adduct, and 3 mol.
It was confirmed to be a mixture of the molar adduct and the 4 molar adduct.

This crude product was separated and purified by silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1, and the desired 1-mol adduct of pentaerythritol isostearyl ether was eluted.
The elution fractions were collected and the solvent was distilled off to obtain a 1 mol adduct of pentaerythritol isostearyl ether 10 (yield 30%).

[0041]

[Table 1] Hydroxyl value 430 (calculated value 434) NMR (CDCl ₃ ): δ (ppm) 3.67 (6H, s, -C (C H ₂ OH) ₃ ), 3.44 (2H, s, -CH ₂ OC H ₂ C (CH ₂ OH)
₃ ), 3.41 (2H, t, -C H ₂ O-CH ₂ C (CH ₂ OH) ₃ ), 1.30 ~ 1.59 (29H,
b, -CH ₂ -,-CH-), 0.88 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretching) (-CH- , -CH ₂ -,-CH ₃ ) 2850, 2920; ν _CH (bending angle) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460; ν _CO (-CO-) 1110, 1035, 1010

Example 2 3.4 g of pentaerythritol and 50 ml of heptylundecyl bromide in 50 ml of N, N-dimethylformamide.
Add 3 g and, with stirring, 1.4 g of sodium hydroxide
Was added and reacted at 30 ° C. for 5 hours. After the reaction was completed, the insoluble substance in the reaction vessel was filtered off, and the solvent and unreacted raw materials were distilled off from the filtrate. The residual liquid was extracted with benzene-water, and the benzene layer was distilled off to obtain 6 g of a pentaerythritol heptylundecyl ether crude product. It was confirmed by gas chromatography composition analysis that it was a mixture of pentaerythritol heptylundecyl bromide 1 mol adduct, 2 mol adduct, 3 mol adduct and 4 mol adduct.

This crude product was separated and purified by silica gel column chromatography with an elution solvent of acetone: hexane = 2: 1, and the desired 1-mol adduct of pentaerythritol heptylundecyl ether was eluted, The eluate fractions were collected and the solvent was distilled off to obtain 2 g (yield 33%) of a 1 mol adduct of pentaerythritol heptylundecyl ether.

[0044]

[Table 2] Hydroxyl value 430 (calculated value 434) NMR (CDCl ₃ ): δ (ppm) 3.67 (6H, s, -C (C H ₂ OH) ₃ ), 3.44 (2H, s, -CH ₂ OC H ₂ C (CH ₂ OH)
₃ ), 3.40 (2H, t, -C H ₂ O-CH ₂ C (CH ₂ OH) ₃ ), 1.30 ~ 1.60 (29H,
b, -CH ₂ -,-CH-), 0.90 (6H, m, -CH ₃ ) IR (liquid film) cm ^-1 : ν _OH (-OH) 3200 to 3400; ν _CH (stretch) (-CH- , -CH ₂ -,-CH ₃ ) 2850, 2920; ν _CH (bending angle) (-CH-,-CH ₂ -,-CH ₃ ) 1375, 1460; ν _CO (-CO-) 1110, 1035, 1010

COMPARATIVE EXAMPLE 1 Pentaerythritol 13.6 was placed in a 5-liter three-necked flask.
g and 2.3 l of t-butyl alcohol were added, and the mixture was heated and dissolved. 12.4 g of potassium t-butoxide was added to this solution.
Was added, and the mixture was heated with stirring at 60 ° C. for 30 minutes, and then stearyl bromide (3.6 g) was added dropwise. After the dropping, the mixture was heated under reflux for 20 hours, and then the resulting precipitate was filtered. The solvent was distilled off under reduced pressure to obtain 34 g of a pentaerythritol stearyl ether crude product.

This crude product was separated and purified using silica gel column chromatography with an elution solvent of hexane: acetone = 2: 1 to elute the target pentaerythritol stearyl ether adduct of 1 mol. The elution fractions were collected and the solvent was distilled off to obtain the desired 1-mole adduct of pentaerythritol stearyl ether.
g (47% yield) was obtained. From the NMR and IR spectrum analysis, it was confirmed that the obtained compound was a 1 mol adduct of pentaerythritol stearyl ether.

Test Example 1 The pentaerythritol-branched alkyl ether of the present invention obtained in the Examples and the conventionally known compounds are described below.
The properties at room temperature and the dispersibility in water (concentration 5% by weight) were examined. The results are shown in Table 3. (Evaluation method) The properties at room temperature were examined by visual observation.
For dispersibility in water, 1 g of a sample was sampled in a 30 ml volume sample bottle, ion-exchanged water was added thereto so that the sample concentration was 5% by weight, and the sample bottle was shaken for 1 minute and allowed to stand for 5 minutes. After that, the dispersed state was visually observed.

[0048]

[Table 3]

Example 3 Using the compound of the present invention obtained in Example, a hair rinse agent having the composition shown in Table 4 was produced, and its rinse performance was examined. The results are shown in Table 4. (Manufacturing Method) To water heated to 70 ° C., components dissolved by being heated to the same temperature were added, stirred and mixed, and then cooled to room temperature with stirring to obtain a hair rinse agent. (Evaluation method) 20 g (15 cm in length) of hair of a Japanese woman who has never been subjected to cosmetic treatment such as cold perm or bleach has been bundled, and this hair bundle is commercial shampoo containing an anion activator as a main component. After the washing treatment, 2 g of the hair rinse agent shown in Table 4 was uniformly applied, followed by rinsing with running water for 30 seconds, and then towel drying. This wet hair bundle was sensory evaluated for softness, smoothness and oiliness. The evaluation criteria are shown as ⊚ for excellent, ◯ for good, Δ for normal, and x for inferior.

[0050]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 41/24 7419-4H

Claims (6)

[Claims] 1. The following general formula (1): [Wherein R ¹ represents a branched alkyl group having 16 to 36 carbon atoms, and R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or a branched alkyl group having 16 to 36 carbon atoms] Pentaerythritol branched alkyl ether. 2. A branched alkyl group having 16 to 36 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) is represented by the following general formula (2): [In formula, p and q show the integer of 0-33, respectively. However, the sum of p and q is 13 to 33], The pentaerythritol branched alkyl ether according to claim 1. 3. A branched alkyl group having 16 to 36 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) is represented by the following general formula (3): [In the formula, r and s each represent an integer of 0 to 31. However, the sum of r and s is 11 to 31], The pentaerythritol branched alkyl ether according to claim 1. 4. The following general formula (4): [Wherein R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a branched alkyl group having 16 to 36 carbon atoms] to pentaerythritol or a branched alkyl ether thereof represented by the following general formula (5 ) R ¹ -X (5) [wherein R ¹ represents a branched alkyl group having 16 to 36 carbon atoms and X represents a halogen atom] is reacted with a halogenated branched alkyl in the presence of a basic substance. The method for producing a pentaerythritol-branched alkyl ether according to claim 1, wherein the pentaerythritol-branched alkyl ether is produced. 5. A cosmetic containing the pentaerythritol branched alkyl ether according to claim 1. 6. The cosmetic according to claim 5, which is a skin cosmetic or a hair cosmetic.