JPH0470281B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to sugar ether-containing cosmetics. More specifically, the present invention relates to a sugar ether-containing cosmetic that has excellent chemical stability and is gentle on the skin. [Prior art/problems to be solved by the invention] Conventionally, nonionic surfactants, especially nonionic surfactants that do not contain nitrogen atoms as constituent atoms, have been used in large quantities as ingredients in cosmetics. has been done. Typical examples of the nonionic surfactants that do not contain nitrogen atoms include those containing low molecular weight oxyalkylene groups such as oxyethylene groups and oxypropylene groups as polyoxyalkylene groups;
Examples include higher fatty acid partial esters of polyhydric alcohol type compounds such as glycerin, pentaerythritol, sorbitan, sorbitol, and sucrose. Nonionic surfactants containing low-molecular-weight oxyalkylene groups have the advantage of being able to adjust the HLB range widely and arbitrarily; This is easy to cause, and cosmetics using it tend to be irritating and toxic. For example, if a nonionic surfactant of the higher fatty acid partial ester type of a polyhydric alcohol type compound such as sorbitan partial ester, which is a sugar long chain fatty acid partial ester currently widely used, is used as a component of cosmetics. , especially containing water
When used as an ingredient in cosmetics with a pH that deviates from neutrality, the ester bonds are likely to decompose, causing problems such as stability over time and skin irritation. Furthermore, when polyoxyalkylene ester-based emulsifiers are used as emulsifiers, in addition to decomposition of ester bonds, the above-mentioned problems due to aldehydes may occur, which limits the shelf life of cosmetics, that is, the shelf life and storage period. is likely to occur. Furthermore, in recent years, especially in the cosmetics industry, it is required that surfactants be of constant quality and have clear functions, so there is a tendency to seek something as close to pure as possible.From this perspective, various polyols Nonionic surfactants prepared from mixtures are not preferred. The present invention was made in order to solve the above-mentioned problems associated with conventionally used nonionic surfactants. [Means for Solving the Problems] The present invention is based on the general formula (): (In the formula, A is a disaccharide other than maltitol or
Residues obtained by removing n hydroxyl groups from sugars belonging to saccharides,
R ¹ and R ² are both hydrogen atoms, alkyl groups, or alkenyl groups, the total number of carbon atoms of R ¹ and R ² is 6 to 24, n is a number of 1 or more, and disaccharides other than maltitol or The present invention relates to a cosmetic containing a sugar ether whose number is 50% or less of the number of hydroxyl groups present in sugars belonging to trisaccharides. [Example] The sugar ether used in the present invention has the general formula (): (In the formula, A is a disaccharide other than maltitol or
Residues obtained by removing n hydroxyl groups from sugars belonging to saccharides,
R ¹ and R ² are both hydrogen atoms, alkyl groups, or alkenyl groups, the total number of carbon atoms of R ¹ and R ² is 6 to 24, n is a number of 1 or more, and disaccharides other than maltitol or 50% or less of the number of hydroxyl groups present in sugars belonging to trisaccharides). Specific examples of sugars belonging to disaccharides other than maltitol include sucrose, maltose, lactose, cellbiose, gentibiose, sucrose, etc. Specific examples of sugars belonging to trisaccharides include raffinose, gentianose, maltosaccharide, etc. Examples include maltotriitol, which is a partial reduction product of triose and maltotriose, panose, and isonurtotriose. The sugar ether used in the present invention does not contain sugar ethers from monosaccharides or sugars of quaternary or higher class, but
This is because the number of hydroxyl groups in monosaccharides is 6 or less, so when etherified into a surfactant, only relatively low hydrophilic products can be obtained. This is because it is difficult to obtain the raw material sugar in ether at a low cost with few impurities. Specific examples of C ₁ to _{C 24} alkyl groups and alkenyl groups other than hydrogen atoms for R ¹ and R ² include:
For example, methyl group, ethyl group, isopropyl group,
Examples include butyl group, octyl group, lauryl group, palmityl group, stearin group, 2-ethylhexyl group, isostearyl group, oleyl group, palmitoleyl group, eicosenyl group, and the like. In the compound represented by the general formula (), residue A is a moiety that primarily exhibits hydrophilicity, and the moiety bonded to residue A is a moiety that primarily exhibits hydrophobicity; therefore, R ¹ and R ² is a hydrogen atom, the total carbon atoms of R ¹ and R ² are at least C ₆ to C ₂₄ , and R ¹ and R ²
is preferably a C ₁₂ to C ₁₈ group, and n is a number of 1 or more, and the number is 50% or less of the number of hydroxyl groups present in sugars belonging to disaccharides or trisaccharides other than maltitol. , preferably a number of 1 to 2. If R ¹ , R ² , and n are out of the above range, the balance between hydrophilicity and hydrophobicity in the sugar ether represented by the general formula () will be disrupted, making it difficult to dissolve in water, and the range of use as an activator will be narrowed. . Furthermore, if the sum of the carbon atoms of R ¹ and R ² is larger than C ₂₄ , it will be difficult to obtain commercially, and
The reactivity in producing the compound represented by the general formula () decreases, making it difficult to produce sugar ether. The sugar ether represented by the general formula () can be obtained by combining sugar with the general formula () by the method described in Japanese Patent Application No. 180989/1989 by the present inventors. (wherein R ¹ and R ² are the same as above). From the viewpoint of reactivity, it is generally preferable for either R ¹ or R ² to be a small group, and preferably a hydrogen atom. The sugar ether obtained in this way has functions such as detergency, dispersibility, emulsification, solubilization, and texture-improving properties, so it can be used as an ingredient in various cosmetics and can be decomposed. Because it does not contain oxyalkylene groups or polyoxyalkylene groups that easily generate aldehydes, or ester bonds that are easily hydrolyzed, it has excellent chemical stability. When cosmetics are produced using surfactants instead of surfactants, cosmetics having the above-mentioned characteristics can be produced. Cosmetics as used in this specification include not only cosmetics under the Pharmaceutical Affairs Law, but also those belonging to quasi-drugs and medicines used for cosmetics, such as creams, lotions, shampoos, milky lotions, and rinses. The concept includes products such as treatments, foundations, hair preparations, perfumes, hair care products, and cleaning products. Next, the cosmetics of the present invention will be explained based on Examples. Synthesis Example 1 50 g of sucrose and 150 g of dimethyl sulfoxide were placed in a flask, heated and dissolved at 100° C., and dehydrated for about 15 minutes by blowing in dry nitrogen gas. Add to this 0.3g of tetraethylammonium hydroxide.
After that, 16 g of a linear 1,2-epoxyalkane having 6 carbon atoms (1/1 molar ratio of sucrose/epoxyalkane) was added, and the mixture was reacted at 120°C for 8 hours with vigorous stirring. After the reaction, the catalyst is neutralized, dimethyl sulfoxide is almost completely distilled off at 80°C under reduced pressure, the residue is extracted with 99% ethanol to remove unreacted sucrose, and the ethanol is further distilled to produce crude oil. 60g of hydroxyalkyl sucrose ether was obtained. When this crude product was divided using silica gel column chromatography using n-hexane and then acetone as developing solvents, a very small amount of epoxyalkane was observed as the initial n-hexane fraction, and the main component was the acetone fraction. (yield 55g) (hereinafter referred to as sucrose ether 1). This product was highly pure, showing 1 spot in thin metal chromatography using a mixed solvent of chloroform:methanol:acetic acid:water=80:10:8:2 (volume ratio) as the TLC developing solvent. .
Furthermore, analysis using the Griffin method revealed that approximately 10% (approximately 1) of the hydroxyl groups in sucrose were etherified. Synthesis Example 2 50 g of sucrose and 150 g of dimethyl sulfoxide were placed in a flask, heated and dissolved at 100° C., and dehydrated for about 15 minutes by blowing in dry nitrogen gas. After adding 0.5 g of sodium hydroxide to this, 35 g of a mixture of linear 1,2-epoxyalkanes having 16 and 18 carbon atoms in a weight ratio of 1/1 (sucrose/epoxyalkane in a molar ratio of 1/1) was added. was added and reacted at 120°C for 8 hours with vigorous stirring. After the reaction, the catalyst is neutralized, dimethyl sulfoxide is almost completely distilled off at 80°C under reduced pressure, the residue is extracted with 99% ethanol to remove unreacted sucrose, and the ethanol is further distilled to produce crude oil. 78g of hydroxy long chain alkyl sucrose ether was obtained. When this crude product was divided using silica gel column chromatography using first n-hexane and then acetone as developing solvents, a very small amount of epoxyalkane was recognized as the initial n-hexane fraction, and the main component was the acetone distillate. (yield 70g) (hereinafter referred to as sucrose ether 2). This product was highly pure, showing 1 spot in thin metal chromatography using a mixed solvent of chloroform:methanol:acetic acid:water=80:10:8:2 (volume ratio) as the TLC developing solvent. .
Furthermore, analysis using the Griffin method revealed that approximately 12% (approximately 1 hydroxyl group) of sucrose was etherified. Synthesis example 3 50g of maltose and 150g of N-methylpyrrolidone
After drying and dehydrating in the same manner as in Synthesis Example 1, 0.5 g of sodium hydroxide was added as a catalyst to prepare 27 g of a 1/1 weight ratio mixture of linear 1,2-epoxyalkanes having 12 and 14 carbon atoms ( Maltose/
After adding epoxyalkane (1/1 molar ratio), the mixture was reacted at 120°C for 5 hours. Thereafter, the solvent was almost completely distilled off at 80°C under reduced pressure, and the mixture was added to a two-phase solution of methyl ethyl ketone/saturated saline solution = 50/50 (volume ratio), stirred, and left to separate into layers. Ta. The separated methyl ethyl ketone layer was dehydrated and filtered through an anhydrous filter, and the methyl ethyl ketone was distilled off to obtain 69 g of crude hydroxyalkyl maltose ether (hereinafter referred to as maltose ether 1).
). The resulting maltose ether 1 was analyzed by the Cliffin method to account for approximately 12% of the hydroxyl groups of maltose (approximately 1
) were etherified. Synthesis example 4 50g of lactose and 150g of N-methylpyrrolidone
After drying and dehydrating in the same manner as in Synthesis Example 1, 0.8 g of sodium ethoxide was added as a catalyst.
After adding 35 g of a 1/1 mixture by weight of linear 1,2-epoxyalkanes having 16 and 18 carbon atoms (lactose/epoxyalkane in a molar ratio of 1/1), the mixture was allowed to react at 120°C for 5 hours. Ta. after that,
The solvent was almost completely distilled off at 80° C. under reduced pressure, and the mixture was added to a two-phase solution of methyl ethyl ketone/saturated saline solution = 50/50 (volume ratio), stirred, and allowed to stand still to separate the layers. The separated methyl ethyl ketone layer was dehydrated and filtered over an anhydrous filter, and the methyl ethyl ketone was distilled off to obtain 80 g of crude hydroxyalkyl lactose ether (hereinafter referred to as lactose ether 1). The obtained lactose ether 1 accounts for approximately 12% of the hydroxylation of lactose (approximately 1
) were etherified. Synthesis example 5 100g of raffinose and 150g of N-methylpyrrolidone
After drying and dehydrating in the same manner as in Synthesis Example 1, 1.0 g of sodium hydroxide was added as a catalyst, and the weight ratio of linear 1,2-epoxy alkanes having 20 and 22 carbon atoms was 1/1. 60g mixture of
(raffinose/epoxyalkane in a molar ratio of 1/1) was added, and the mixture was reacted at 120°C for 5 hours. Thereafter, the solvent was almost completely distilled off at 80°C under reduced pressure, and methyl ethyl ketone / saturated saline solution = 50 /
50 (volume ratio) and stirred, the mixture was allowed to stand still to separate the layers. The separated methyl ethyl ketone layer was dehydrated and filtered through an anhydrous filter, and the methyl ethyl ketone was distilled off to obtain 155 g of crude hydroxyalkyl lactose ether (hereinafter referred to as
(referred to as rough quinose ether 1). The obtained raffinose ether 1 was analyzed by the Griffin method and contained approximately 9% of the hydroxyl groups of raffinose.
(about 1 piece) was etherified. Synthesis example 6 100g of gentianose was added to dimethyl sulfoxide
After drying and dehydrating in the same manner as in Synthesis Example 1, 1.0 g of sodium hydroxide was added as a catalyst to form a mixture of linear 1,2-epoxyalkanes having 8 and 10 carbon atoms in a weight ratio of 1/1. 25g (Molar ratio of gentianose/epoxyalkane is 1/
After adding 1), the mixture was reacted at 120°C for 5 hours.
Thereafter, the solvent was almost completely distilled off at 80°C under reduced pressure, and methyl ethyl ketone/saturated saline solution = 50/50.
(volume ratio) was added to a two-phase system liquid, stirred, and then allowed to stand still to separate the layers. The separated methyl ethyl ketone layer was dehydrated and filtered through an anhydrous filter, and the methyl ethyl ketone was distilled off to obtain 120 g of crude hydroxyalkyl gentyanose ether (hereinafter referred to as
gentianose ether 1). The obtained gentianose ether 1 is Griffin
According to analysis by the method, about 9% (about 1 hydroxyl group) of gentianose was etherified. Synthesis Example 7 100g of maltotriose was dissolved in 150g of N-methylpyrrolidone, dried and dehydrated in the same manner as in Synthesis Example 1, and then 1.0g of sodium hydroxide was added as a catalyst to dissolve straight chains 1,2 having 12 and 14 carbon atoms. - 39 g of a 1/1 mixture by weight of epoxy alkanes
(maltotriose/epoxyalkane in a molar ratio of 1/1) was added, and the mixture was reacted at 120°C for 5 hours. Thereafter, the solvent was almost completely distilled off at 80°C under reduced pressure, and methyl ethyl ketone/saturated saline solution was
It was added to a 50/50 (volume ratio) two-phase liquid, stirred, and then left to separate into layers. The separated methyl ethyl ketone layer was dehydrated and filtered over an anhydrous filter, and the methyl ethyl ketone was distilled off to obtain 125 g of crude hydroxyalkyl maltotriose ether (hereinafter referred to as maltotriose ether 1). The obtained maltotriose ether 1 is
Analysis by the Griffin method revealed that approximately 9% (approximately 1) of the hydroxyl groups in ruffinose were etherified. Synthesis Example 8 100g of maltotriitol was dissolved in 150g of N-dimethyl sulfoxide, dried and dehydrated in the same manner as in Synthesis Example 1, and then 0.5g of sodium hydroxide was added as a catalyst to dissolve straight chain 1, having 16 and 18 carbon atoms.
1/1 mixture by weight of 2-epoxyalkane
After adding 50 g (maltotriitose/epoxyalkane in molar ratio of 1/1), the mixture was reacted at 120°C for 5 hours. Thereafter, the solvent was almost completely distilled off at 80°C under reduced pressure, and the mixture was added to a two-phase solution of methyl ethyl ketone/saturated saline solution = 50/50 (volume ratio), stirred, and left to separate into layers. Ta. The separated methyl ethyl ketone layer was dehydrated with anhydrous filtrate, filtered, and methyl ethyl ketone was distilled off to obtain 180 g of crude hydroxyalkyl maltotriitose ether.
(hereinafter referred to as maltotriitol ether 1). The obtained maltotriitol ether 1 is
Analysis by the Griffin method revealed that about 9% (about 1 hydroxyl group) of maltotriitol was etherified. Reference Example 1 (Hydrolyzability) A 1% aqueous solution of each of the sugar ethers obtained in Synthesis Examples 1 to 8 was heated at 90°C for 5 hours, but almost no hydrolysis was observed in any of the samples. On the other hand, with commercially available sucrose laurate (approximately 10% (approximately 1) of the hydroxyl groups of sucrose), as shown in Table 1, under the same conditions, approximately 20%
Decomposition of the ester group was observed. In addition, commercially available polyethylene glycol (PEG)
For lauric acid esters, as shown in Table 1,
Approximately 2% decomposition of ester groups was observed. In addition, to measure the degree of hydrolysis, take a certain amount of the aqueous solution after cooling, extract it with ethyl ether,
It was determined from the neutralization titer of the extract. When emulsifying during the extraction process, ethanol was added, phase separation was performed, and titration was performed. Reference Example 2 (Oxidizing properties) Each of the sugar ethers given in Synthesis Examples 1 to 8 was left in a container at 80° C. for 100 hours, and then 5 g of each sample was collected. Thereafter, 500 ml of water and 3 ml of diluted phosphoric acid were added and distilled. When the distilled volume reached 190 ml, the distillation was stopped and water was added to make 200 ml, which was used as a test solution. Take 10 ml of this test solution and add 5 ml of acetylacetone.
ml was added, shaken, and heated in a 60°C water bath for 10 minutes. After cooling, the absorbance at the maximum absorption wavelength around 420 μm was measured, but as shown in Table 1, no aldehyde was observed. On the other hand, when polyethylene glycol laurate was similarly treated and evaluated, the presence of aldehyde was observed as shown in Table 1. In addition, even when sucrose lauric acid ester was treated in the same manner instead of sucrose ether 1 and evaluated, the presence of aldehyde was not observed as shown in Table 1.

[Table] Example 1 and Comparative Example 1 Using sucrose ether 2 obtained in Synthesis Example 2 and manthotriitol ether 1 obtained in Synthesis Example 8, a cosmetic cream base with the following formulation was prepared. (Cream base formulation) (%) Liquid paraffin #70 20 Setanol 10 Maltotriitol ether 0.5 Sucrose ether 2 3.0 Hydroxyethyl cellulose 0.5 Propylene glycol 4.0 Purified water Remaining amount The cream base obtained is O/W type and is not oily. It exhibited very smooth properties and did not change at all even after being stored for 5 months. Further, even when stored at 30°C for 100 hours, there was almost no hydrolysis, and when evaluated in the same manner as in Reference Example 2, no aldehyde was observed. On the other hand, when the same test as in Reference Example 2 was conducted using polyethylene glycol laurate diester instead of sucrose ether 2 and polyethylene glycol oleate diester instead of maltotriitol ether, the presence of aldehyde was observed. Example 2 and Comparative Example 2 Using maltose ether 1 obtained in Synthesis Example 3, a shampoo having the following formulation was prepared. (Shampoo formulation) (%) Maltose ether 1 15.0 Triethanolamine lauryl sulfate
10.0 Imidazoline type amphoteric surfactant (Daiichi Kogyo Seiyaku Co., Ltd.)
Amogen M) 25.0 Lauric acid diethanolamide 5.0 Fragrances, preservatives, pigments Appropriate amount of purified water Remaining amount Even if the obtained shampoo is stored at 30℃, PH = 6.5, for 100 hours, there is almost no hydrolysis. Even when treated and evaluated in the same manner as in Reference Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol oleate diester was used instead of maltose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 3 and Comparative Example 3 Using Roughinose Ether 1 obtained in Synthesis Example 5, a lotion having the following formulation was prepared. (Lotion formulation) (%) Glycerin 4.0 Propylene glycol 4.0 Oleyl alcohol 0.1 Roughinose ether 1 1.5 Ethanol 8.0 Fragrance Trace amount of methyl parahydroxybenzoate 0.3 Purified water Remaining amount The obtained lotion was heated at 30℃, PH = 6.5, 100 hours. Even when stored under these conditions, there was almost no hydrolysis, and when evaluated in the same manner as in Reference Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol 400 oleic acid monoester was used instead of roughinose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 4 and Comparative Example 4 Gentianose ether 1 obtained in Synthesis Example 6
An emulsion with the following formulation was prepared using (Emulsion formulation) (%) Stearic acid 2.0 Cetol 1.5 Vaseline 2.0 Lanolin alcohol 2.0 Liquid paraffin 10.0 Gentianose ether 1 2.0 Glycerin 4.0 Triethanolamine 1.0 Fragrance, preservative Trace amount of purified water Remaining amount The obtained emulsion was heated to 30℃, pH = 6.5 and was stored for 100 hours, there was almost no hydrolysis, and when evaluated in the same manner as in Reference Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol laurate diester was used instead of gentianose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 5 and Comparative Example 5 Maltotriose ether 1 obtained in Synthesis Example 7 was used to prepare a rinse with the following formulation. (Rinse prescription) (%) Stearyltrimethylammonium chloride 2.0 Lanolin alcohol 3.0 Propylene glycol 5.0 Citric acid 0.1 Maltotriose ether 1 1.0 Fragrance, preservative Trace amount of purified water Remaining amount Rinse the resulting rinse at 30℃, PH = 6.5, 100 hours Even when stored under these conditions, almost no hydrolysis occurred, and even when treated and evaluated in the same manner as in Reference Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol 400 oleic acid monoester was used instead of maltotriose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 6 and Comparative Example 6 Using maltotriitol ether 1 obtained in Synthesis Example 8, a hair styling product having the following formulation was prepared. (Hair conditioner formulation) (%) Liquid paraffin 15.0 Lanolin alcohol 2.1 Maltotriitol ether 1 6.0 Lauric acid diethanolamide 3.0 Purified water Residue The obtained hair conditioner was stored at 30℃, PH = 6.5, for 100 hours. was hardly hydrolyzed, and even when evaluated in the same manner as in Reference Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol oleate diester was used instead of maltotriol ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 7 and Comparative Example 7 Raffinose Ester 1 obtained in Synthesis Example 5 was used to prepare a foundation having the following formulation. (Foundation formulation) (%) Stearic acid 2.8 Liquid paraffin 25.0 Triethanolamine 1.4 Propylene glycol 10.0 Roughinose ether 1 5.0 Titanium oxide 6.0 Bentonite 10.0 Pigment (iron oxide) Trace amount of fragrance, preservative Trace amount of purified water Remaining amount The foundation was heated to 30℃, PH=6.5,
Even when stored under conditions of 100 hours, there was almost no hydrolysis, and when evaluated in the same manner as in Reference Example 2, almost no aldehyde was produced. On the other hand, when polyethylene glycol lauryl acid diester was used instead of roughinose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. Example 8 and Comparative Example 8 Using maltose ether 1 obtained in Synthesis Example 3, a perfume with the following formulation was prepared. (Perfume formulation) (%) Ethyl alcohol 40.0 Fragrance 5.0 Maltose ether 1 1.5 Water 53.5 Total 100.0 Even if the obtained perfume was stored at 30℃, PH = 6.5, for 100 hours, there was almost no hydrolysis. Even when evaluated in the same manner as in Example 2, almost no aldehyde was observed. On the other hand, when polyethylene glycol 400 oleic acid monoester was used instead of maltose ether 1, aldehyde was found to be present when the same test as in Reference Example 2 was conducted. [Effects of the Invention] The sugar ether used in the cosmetics of the present invention does not have a low molecular weight oxyalkyl group or an ester group, so it is chemically stable, easily hydrolyzed, No aldehyde is generated. Therefore, cosmetics using this sugar ether have similar characteristics, are less irritating to the skin, and have an excellent feel as a cosmetic.

Claims (1)

[Claims] 1 General formula (): (In the formula, A is a disaccharide other than maltitol or
Residues obtained by removing n hydroxyl groups from sugars belonging to saccharides,
R ¹ and R ² are both hydrogen atoms, alkyl groups, or alkenyl groups, the total number of carbon atoms of R ¹ and R ² is 6 to 24, n is a number of 1 or more, and disaccharides other than maltitol or A cosmetic containing a sugar ether whose number is 50% or less of the number of hydroxyl groups present in sugars belonging to trisaccharides.