JPH07116208B2 - Maltitol hydroxy aliphatic ether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to maltitol hydroxy aliphatic ether. More specifically, maltitol hydroxy, which has characteristics such as excellent chemical stability and mild properties to the skin, can be preferably used as a surfactant to be blended in pharmaceuticals and cosmetics. Regarding aliphatic ethers.

[Problems to be solved by conventional techniques and inventions]

Conventionally, a large amount of nonionic surfactants, especially nonionic surfactants containing no nitrogen atom as a constituent atom have been used as components of cosmetics and the like.

As a representative example of the nonionic surfactant containing no nitrogen atom, oxyethylene group, those containing a low molecular weight oxyalkylene group such as oxypropylene group as a polyoxyalkylene group, glycerin, pentaerythritol, sorbitan, Examples include higher fatty acid partial esters of polyhydric alcohol type compounds such as sorbit and sucrose.

Nonionic surfactants containing a low molecular weight oxyalkylene group have the advantage that the HLB range can be adjusted widely and arbitrarily, but on the other hand, they generally decompose relatively low-molecular-weight aldehydes that are irritating and relatively It is liable to occur, and cosmetics and the like using the same are liable to cause irritation and toxicity.

Further, for example, when a higher fatty acid partial ester type nonionic surfactant such as a polyhydric alcohol type compound such as a sorbitan partial ester, which is a sugar long-chain fatty acid partial ester currently widely used, is used as a component of cosmetics. Especially when used as a component of a cosmetic composition containing water and having a pH deviating from neutral, the ester bond is easily decomposed, and problems such as stability over time and skin irritation are likely to occur.
Furthermore, when a polyoxyalkylene ester type is used as an emulsifier, in addition to the decomposition of the ester bond, problems such as the above-mentioned aldehyde may occur, and the life of cosmetics, that is, the storable period and the storable period are also increased. Limits are likely to occur.

More recently, especially in the cosmetics industry, it is required that the quality of the surfactant be constant and that its function be clear.
There is a tendency to seek a substance that is as pure as possible. From this viewpoint, a nonionic surfactant produced from a mixture of various polyols is not preferable.

It is one of the objects of the present invention to solve the problem of the nonionic surfactants conventionally used as described above.

[Means for solving problems]

The present invention relates to maltitol hydroxyaliphatic ether having one or two hydroxyaliphatic groups having 10 to 22 carbon atoms.

〔Example〕

The maltitol hydroxy aliphatic ether of the present invention has the general formula (I): (Wherein A is a residue obtained by removing n hydroxyl groups from maltitol, R is an aliphatic group having 8 to 20 carbon atoms, preferably an alkyl group or an alkenyl group, and n is 1 or 2) or a general formula (II): (In the formula, A, R, and n are the same as the above).

Specific examples of R include, for example, an octyl group, a lauryl group, a palmityl group, a stearyl group, a 2-ethylhexyl group, an isostearyl group, a capryl group, an oleyl alcohol residue, a palmitolyl group, and an eicosenyl group. .

In the maltitol hydroxyaliphatic ether represented by the general formula (I) or (II), the residue A is a part that mainly exhibits hydrophilicity, and the part bonded to the residue A is mainly hydrophobic. Since it is a moiety, the number of carbon atoms in R must be 8 to 20, preferably 10 to 18, and n must be 1 or 2.

When R is out of the above range or when n is not 1 or 2, the balance between the hydrophilic group and the hydrophobic group in the maltitol hydroxy aliphatic ether represented by the general formula (I) or (II) is lost. Insufficient hydrophilicity or conversely lacking hydrophobicity narrows the range of use as an activator. Further, when the carbon number of R is larger than 20, it becomes difficult to obtain commercially and the maltitol hydroxy aliphatic ether represented by the general formula (I) and / or (II) is produced. The reactivity at that time is lowered, and its production becomes difficult.

Although the maltitol hydroxyaliphatic ether of the present invention as described above has different properties depending on the type of the aliphatic group, it is usually a highly viscous liquid or solid, and has, for example, detergency, dispersibility, emulsification, solubilization and feel. Since it has functions such as improving properties, it can be suitably used as various pharmaceuticals and cosmetic ingredients. Furthermore, since it does not contain an oxyalkylene group or a polyoxyalkylene group that easily decomposes to generate an aldehyde, and an ester bond that easily hydrolyzes, it has excellent chemical stability.

The maltitol hydroxyaliphatic ether of the present invention as described above is obtained, for example, by the present inventors in Japanese Patent Application No. 61-180989.
As described in Japanese Patent Application Laid-Open No. 63-35590, maltitol is dissolved in a non-aqueous solvent, and a general formula (III): (In the formula, R is the same as the above), and the reaction can be carried out in the presence of a catalyst.
The compound represented by the general formula (III) may be used alone or in combination of two or more kinds.

When the target sugar ether is a monoether, the molar ratio of maltitol used in this reaction and the compound represented by the general formula (III) is 1.5: 1 to 3.0: 1. It is preferable to use in excess, and further 2.
It is preferably around 0: 1. Further, when the target sugar ether is a diether, it is preferably 0.5: 1 to 1.4: 1, more preferably 0.8: 1 to 1.2: 1.

The non-aqueous solvent may be one that dissolves maltitol and does not substantially react with maltitol or the compound represented by the general formula (III), and the boiling point is preferably the reaction temperature or higher. . Specific examples of such a solvent include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-acetylmorpholine and N-methylsuccinimide.

The concentration of maltitol during the reaction is not particularly limited,
It is preferably dissolved at the reaction temperature. For example, when the solvent is dimethylformamide, even when the concentration of maltitol is 30% (% by weight, the same applies below), it is dissolved at the reaction temperature and the reaction proceeds smoothly.

As the catalyst, acids, alkalis, amines and the like generally known as epoxy group reaction catalysts can be used. For example, tertiary amines such as N-dimethylbenzylamine, sodium methylate, potassium hydroxide, and hydroxide. Sodium, lithium hydroxide and the like can be mentioned, and more preferable are tetra-lower alkyl or tri-lower alkyl such as tetraethylammonium hydroxide and trimethylbenzylammonium hydroxide, from the viewpoint of smooth reaction promotion and removability after completion of the reaction. Examples thereof include benzyl ammonium hydroxide.

The amount of the catalyst used is preferably 0.1 to 40% with respect to the compound represented by the general formula (III) used.

The reaction temperature is preferably 50 to 150 ° C, and further 80 to 130
C is preferred. When the reaction temperature is lower than 50 ° C, the reaction rate is slow, and when it exceeds 150 ° C, coloration likely due to thermal decomposition of maltitol is likely to occur.

Both maltitol and reaction solvent are generally hygroscopic,
Since the compound represented by the general formula (III) is consumed as an alkanediol when reacted in the presence of water,
After dissolving maltitol in a solvent, heat it to blow dry nitrogen gas, or heat dehydration under reduced pressure to remove water and then add the compound represented by general formula (III) to react. Is preferred.

When the used compound represented by the general formula (III) is consumed and the reaction is completed, an acid or alkali serving as a neutralizing agent for the catalyst, for example, acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid or the like is added to neutralize, The reaction solvent is distilled off. The reaction solvent is preferably distilled off under reduced pressure at a temperature of 100 ° C. or lower in order to avoid thermal decomposition of unreacted maltitol and reaction products.

The reaction product thus obtained contains, in addition to the desired maltitol hydroxyaliphatic ether, maltitol, maltitol hydroxyaliphatic ether having three or more hydroxyaliphatic ether groups bonded thereto, and the like. . Thus, for example, maltitol treats reaction products with MEK, MIBK, methyl alcohol, ethyl alcohol,
A maltitol hydroxyaliphatic ether having three or more hydroxyaliphatic ether groups bonded to it can be dissolved in a solvent in which maltitol such as isopropyl alcohol is dissolved / extracted in an extraction solvent that does not substantially dissolve it. For example, the reaction product is extracted with a solvent such as n-hexane or heptane, or the reaction product is dissolved in a mixed solvent of alcohol (such as methanol, ethanol, isopropyl alcohol) and water, and the solution is used as a high-porous polymer (such as Mitsubishi It is separated by a method such as passing through a high porous resin manufactured by Kasei Kogyo Co., Ltd. (It should be noted that by selecting a solvent, maltitol hydroxyaliphatic ether having two or more hydroxyaliphatic ether groups bonded thereto). Can also be removed).

In addition, when the residue after the reaction solvent is distilled off and it is difficult to extract it in the form of a solid lump, water or a salt in which salts such as salt are dissolved is combined with a solvent such as methyl ethyl ketone. When the reaction product is treated with a two-layer extraction solvent system, the unreacted maltitol is dissolved in the aqueous layer,
Most of the maltitol hydroxy aliphatic ether is dissolved in the organic layer, so that it can be easily separated.

The extract of maltitol hydroxyaliphatic ether obtained as described above may be used as a surfactant as it is, or may be used after evaporating and concentrating the extraction solvent.

Further, it may be used after being subjected to another post-treatment step such as decolorization with activated carbon or the like and precision purification with a column packed with an adsorbent.

The purified maltitol hydroxyaliphatic ether of the present invention has a structure represented by the general formula (I) and / or (II), but when it is used as a surfactant, It is not necessary to separate the compound represented by I) and the compound represented by the general formula (II), and it is difficult to separate them.

Further, when a mixture of a monoether having one hydroxyaliphatic ether group bonded and a diether having two hydroxyaliphatic ether groups is obtained, if it is necessary to separate the monoether and the diether, for example, this mixture is treated with an alcohol (for example, It can be separated by dissolving it in a mixed solvent of water (methanol, ethanol, isopropyl alcohol, etc.) and passing this solution through a high-porous polymer.

Next, the maltitol hydroxy aliphatic ether of the present invention will be described based on Examples.

Example 1 344 g of maltitol and 1700 g of dimethyl sulfoxide were placed in a flask, heated to 100 ° C. to dissolve them, and dry nitrogen gas was blown into the flask to dehydrate for about 15 minutes. After adding tetraethylammonium hydroxide 0.6g to this,
A mixture of linear 1,2-epoxyalkanes having 12 and 14 carbon atoms (mixing ratio of the two kinds is 1/1 by weight) 64 g (maltitol / epoxyalkane is 3/1 by mole ratio) is added, The reaction was performed at 8 ° C. for 8 hours with vigorous stirring.

After the reaction, the catalyst is neutralized, and dimethyl sulfoxide is reduced in pressure,
Almost completely distilled off at 80 ° C., the residue was extracted with 99% ethanol to remove unreacted maltitol, and ethanol was distilled off to obtain 174 g of a crude product of maltitol hydroxyalkyl ether.

When this crude product was separated by silica gel column chromatography using n-hexane as a developing solvent and then acetone, an extremely small amount of epoxy alkane was recognized as the first n-hexane fraction, and the main component was the acetone fraction. I was able to concentrate on. Acetone is distilled off, and syrup-like crude purified maltitol hydroxyalkyl ether
I got 170g.

About 0.2 g of the obtained crude product was dissolved in 10 ml of methanol,
This was used as a measurement sample, and an ear troscan (chloroform: methanol: acetic acid: water = 80: 10: 8: 2 (volume ratio) mixed solvent was used as a developing solvent.
-10, Chromatorod S-II was used for detection by the FID method, and the same applies below), and analysis was performed by the ascending method under the developing conditions of 25 ° C and 45 minutes.
The peaks (uncorrected) of the content rates of 2.9%, 10.6%, and 86.5% were observed in 27 (scan speed 30sec / sca).
n, chart speed 100mm / min). The peak at time 0.16 was due to diether and the peak at 0.27 was due to monoether. The results are shown in Fig. 1.

Next, the crude product was dissolved in a mixed solvent of ethanol and water and passed through a high-porous polymer to remove diether, and maltitol monoalkyl ether was isolated (yield 140 g).

The obtained alkitol monoalkyl ether was analyzed by the following methods (i) to (vii).

(I) IR spectrum analysis Using IRA-1 manufactured by JASCO Corporation, measured by the KBr tablet method at 28 ° C. was 3200 to 3500 cm ⁻¹ , 2800 to 3000
cm ^-1, respectively OH stretching vibration 1300～1450Cm ^-1 and 858cm ^-1, long chain stretching vibration of the alkyl CH, sugar ethers and maltitol and absorption and maltitol with ether bond with a hydroxy group α- Gurikokishido Absorption due to binding was observed. Results are shown in FIG.

For reference, IR spectrum of maltitol by KBr tablet method is shown in Fig. 3 (Starch Science, Vol. 19, No. 3, 14).
Reprinted from page 2 (1972)).

(Ii) ¹³ C NMR analysis Using a Mini Apec PC-120 manufactured by Nippon Bruker KK, DM
When SO-D ₆ was used as a solvent and the concentration was 10%, internal standard TMS, and the temperature was 30 ° C., various maltitol concentrations of 60 to 100 ppm (-), around 40 ppm (), and 10 to 30 ppm (-) were measured. Carbon-based peaks of carbon, impurities in the solvent DMSO-D ₆ and long-chain alkyl gases were observed. Results are shown in FIG.

(Iii) ¹ H NMR analysis Using JNX-PMX60 NMR SPECTROMETER manufactured by JASCO Corporation, using D ₂ O as a solvent and measuring 10% concentration, internal standard DSS, 30 ° C., 4.6 ppm
(), 3.3-4.1ppm and 5.1ppm (and), 1.3
ppm () and 0.6-1.0 ppm () to HOD (D
₂ O impurities), hydrogen of maltitol and hydrogen of OH, CH ₂ of long-chain alkyl groups and peaks based on terminal methyl groups of long-chain alkyl groups were observed. Results are shown in FIG.

(Iv) Compatibility with Solvents 20 g of maltitol monoalkyl ether was added to 20 ml of the solvent, and the mixture was stirred to examine the compatibility at 28 ° C. First result
Shown in the table.

In the case of MEK, when the temperature was raised to 70 ° C, it melted and became transparent, but when the temperature was lowered below 70 ° C, it began to crystallize.

(V) Softening point 5 g of a sample was placed in a beaker, placed in a constant temperature bath and kept at a predetermined temperature (60 ° C, 80 ° C, 100 ° C, 120 ° C), and the state of the sample after 24 hours was observed. When measured by this method, about 10
It was 0 ° C.

(Vi) When a methanol solution having a refractive index of 13% was prepared and measured,
It was 1.3658 (refractive index of methanol: 1.3826).

(Vii) Hydroxyl value (OHV) 0.1g of sample by the hydroxyl value measurement method of the cosmetic material standard general test method
It was 931.9 (theoretical value: 931.4) when measured using, and it was almost in agreement with the theoretical value.

Example 2 344 g of maltitol and 344 g of dimethyl sulfoxide were placed in a flask, heated to 100 ° C. to dissolve them, and dry nitrogen gas was blown into the flask to dehydrate for about 15 minutes. After adding 21.0 g of sodium hydroxide thereto, a mixture of linear 1,2-epoxyalkanes having 16 and 18 carbon atoms (the mixing ratio of the two kinds is 1/1 by weight) 64 g (maltitol / epoxyalkane) Was added at a molar ratio of 3/1) and reacted at 120 ° C. for 8 hours with vigorous stirring.

After the reaction, the catalyst is neutralized, and dimethyl sulfoxide is reduced in pressure,
Almost completely distilled off at 80 ° C., the residue was extracted with 99% ethanol to remove unreacted maltitol, and ethanol was distilled off to obtain 172 g of a crude product of maltitol hydroxyalkyl ether.

When this crude product was separated by silica gel column chromatography using n-hexane as a developing solvent and then with acetone, a very small amount of epoxy alkane was recognized as the first n-hexane fraction, and the main component was an acetone fraction. It was concentrated in minutes (yield 169g).

The physical properties of the obtained isolated and purified product (monoether) are shown in Example 1.
When examined in the same manner as above, the same results as in Example 1 were obtained.

EFFECT OF THE INVENTION Since the maltitol hydroxy aliphatic ether of the present invention has neither a low molecular weight oxyalkylene group nor an ester group, it is chemically stable and can be easily hydrolyzed or aldehyde. Will never be generated. Therefore, for example, a cosmetic using this maltitol hydroxyaliphatic ether is less irritating to the skin,
In addition, it has an excellent feel as a cosmetic product.

[Brief description of drawings]

FIG. 1 and FIG. 2 respectively show the chart and the IR spectrum obtained by the Eartroscan of the maltitol hydroxyalkyl ether obtained in Example 1 (analysis by TH-10, Chromatorod-SII, manufactured by Eartron). Fig. 3 is a chart showing the IR spectrum of maltitol, and Figs. 4 and 5 are obtained by ¹³ C NMR analysis of the maltitol hydroxyalkyl ether obtained in Example 1, respectively. It is a chart and a chart obtained by ¹ H NMR analysis.

Claims (1)

[Claims] 1. A maltitol hydroxyaliphatic ether having one or two hydroxyaliphatic groups having 10 to 22 carbon atoms.