JP2000178245A - Sugar alcohol alkyl ether sulfate compound, anionic surfactant and detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having a high foaming power and good in foam stability even in hard water having a high hardness and even in the coexistence of oily dirt, scarcely causing irritation to skin and hair and useful as a detergent component. SOLUTION: This sugar alcohol alkyl ether sulfate compound is represented by the formula [R is a 6-26C higher alkyl, a 6-26C higher alkenyl or the like; A is a 2-3C alkylene oxide or the like; B is a 6-8C sugar alcohol residue; (m) is 0-10; (n) is 1-5; M is H, an alkali(ne earth) metal or an organic ammonium such as ammonium], e.g. sodium sorbitol lauryl ether sulfate. The compound represented by the formula can be obtained by a combination of well-known methods such as condensation of an alkyl halide or a polyoxyalkylene alkyl ether sulfate with a sugar alcohol in the presence of a basic or an acidic catalyst. The compound represented by the formula is contained as an anionic surfactant in a detergent composition to manifest effects thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention is excellent in biodegradability,
In addition, an anionic surfactant which has high foaming power and good foam stability even in the presence of high hardness hard water and oily dirt, is low irritating to skin and hair and is useful as a detergent component. And a cleaning composition using the same.

[0002]

2. Description of the Related Art Conventionally, petroleum anionic surfactants and nonionic surfactants have been widely used as components of detergents commonly used in households such as tableware, hair, and the body. I have. Recently, surfactants used in the above applications have excellent detergency, foaming power, foam removal during rinsing, good feeling of use such as a refreshing feeling after rinsing, and irritation to the skin. There is a demand for multifunctional and high-performance ones such as less biodegradability. Therefore, in order to satisfy such demands, development has been advanced from both sides of a detergent composition and a surfactant.
In the case of a detergent composition, the pH is changed from weakly acidic to neutral to suppress irritation to the skin, while a surfactant can be used under the same conditions, and the cleaning performance, feeling of use, and various It has been selected from the viewpoint of safety and has a lower burden when discharged to the environment, and has been proposed as a next-generation surfactant. For example, a sugar alcohol alkyl ether which is a sugar surfactant is disclosed in JP-A-8-26.
No. 9493 and JP-A-8-60189 introduce the application of a new surfactant to a detergent composition.

[0003]

However, in the case of a sugar alcohol alkyl ether, when an optimal chain length is selected, it is characterized by less irritation to the skin, hard water resistance and excellent detergency, but shampoo. When applied as a surfactant such as a personal cleansing agent, not only the foaming power is remarkably reduced in the presence of oily dirt, but also the foam stability is inferior to existing petroleum surfactants. It has serious practical problems. Therefore, it is not satisfactory for practical use, and a surfactant having further improved foaming power and foam stability in the presence of oily soil has been required. Therefore, as a result of examining in detail the relationship between the chemical structure of the sugar alcohol alkyl ether surfactant, the surfactant activity, the irritancy to the skin, and the like, the foaming power, And found that the foam stability was improved, and completed the present invention. That is, the present invention has a high foaming power and good foam stability even in the presence of high-hardness hard water and oily soil, and has an anionic interface which is less irritating to skin and hair and is useful as a detergent component. It is intended to provide an activator. Another object of the present invention is to provide a detergent composition containing such an anionic surfactant.

[0004]

According to the present invention, there is provided a sugar alcohol alkyl ether sulfate compound represented by the following general formula (1).

[0005]

Embedded image R—O— (A) m (B) nOSO ₃ M (1) (wherein, R is a linear or branched higher alkyl group or higher alkenyl group or hydroxyalkyl group having an average of 6 to 26 carbon atoms) A: alkylene oxide group having 2 to 3 carbon atoms, used alone or in combination. B: sugar alcohol residue having 6 to 8 carbon atoms m: average number of added moles 0 to 10 n: average condensation number 1 to 5 M: A hydrogen atom, an alkali metal, an alkaline earth metal, an organic ammonium such as ammonium or alkanolammonium, or a basic amino acid group is represented.) According to the present invention, an anionic surfactant comprising the compound and at least one A species-containing cleaning composition is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R
Is a 6-26 linear or branched alkyl, alkenyl or hydroxyalkyl group. The optimal carbon chain length is greatly affected by the type of sugar alcohol, foaming power,
From the viewpoint of foam stability and preferably, the carbon number is 10 to 24.
Which is a linear or branched alkyl group, alkenyl group or hydroxyalkyl group, which can be used alone or in combination. Specific examples include decyl, undecyl, dodecyl, myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, 2-hexyldecyl, 2-octylundecyl, 2-decyltetradecyl, decenyl Groups, dodecenyl group, myristenyl group, palmitenyl group, oleyl group, 2-ethylhexenyl group, 2-hydroxydodecyl group, 2-hydroxymyristyl group, and 2-hydroxypalmityl group. A is an alkylene oxide group having 2 to 3 carbon atoms, specifically, an ethylene oxide and a propylene oxide group. They are used alone or as a mixture. m is the average number of moles of the alkylene oxide added and is 0 to 1
0, preferably 0 to 3 in terms of foaming power and foam stability.
It is. B is a sugar alcohol residue, specifically having 6 to 6 carbon atoms
This is a sugar alcohol residue obtained by removing two hydroxyl groups from the sugar alcohol of No. 8. Examples of such sugar alcohols include allitol, glucitol, mannitol, iditol, galactitol, talitol, bolemitol, perseitol, octitol and the like. n is the average number of condensed moles of the sugar alcohol residue, and is preferably 1 to 3 from the viewpoint of foaming power and foam stability. Examples of the counter ion of the sulfate group include a hydrogen atom, examples of the alkali metal include sodium, potassium, and lithium, and examples of the alkaline earth metal include calcium and magnesium. Also,
Examples of the organic ammonium include ammonium, and examples of the alkanol ammonium include mono, di, and triethanol ammonium, normal, and isopropanol ammonium. As a basic amino acid group,
Examples thereof include a hydroxylysine group, an arginine group, a histidine group, and a lysine group. Two or more of these can be used in combination.

The compound represented by the general formula (1) according to the present invention can be produced by combining known methods. For example, a method of condensing an alkyl halide or a polyoxyalkylene alkyl ether sulfate with a sugar alcohol in the presence of a basic or acidic catalyst, an alcohol or a polyoxyalkylene alkyl ether and a sugar alcohol in the presence of an acidic catalyst Can be produced by reacting a sulfating reagent with a sugar alcohol alkyl ether or a polyoxyalkylene sugar alcohol alkyl ether which is a known substance produced by a method of condensing to a material, followed by neutralization with an aqueous alkali solution. . As the sulfating reagent, a commonly used sulfating reagent such as sulfuric anhydride, chlorosulfonic acid, sulfamic acid, alkyl sulfate, acyl sulfate, or an adduct thereof with a Lewis base can be used. Examples of the Lewis base include pyridine, trialkylamine, ammonia, morpholine, cyclohexylamine, dimethylformamide, dimethylacetamide, diethyl ether, dioxane, dimethylsulfoxide and the like.

[0008] Under the high temperature of the produced sulfate,
Using a mild sulfating reagent that is mild in terms of hydrolysis resistance during long-term storage, the primary hydroxyl groups of sugar alcohol alkyl ethers or polyoxyalkylene sugar alcohol alkyl ethers are selectively sulfated to provide hydrolysis resistance. It is preferable to prepare a primary sulfate having a good quality. As such a sulfating reagent, for example, an alkyl sulfate having a lower alkyl group is used. Alkyl sulfates include methyl sulfate, ethyl sulfate,
Propyl sulfate, butyl sulfate and the like can be mentioned. The counter ions of these alkyl sulfates are an alkali metal ion and an alkaline earth metal ion, and include sodium, potassium, magnesium, calcium and the like.

The reaction of a sugar alcohol alkyl ether or a polyoxyalkylene sugar alcohol alkyl ether with an alkyl sulfate proceeds even in the absence of a catalyst. However, from the viewpoint of the reaction rate and the quality of the product such as color tone and odor, acidic catalysts are used. The use of is preferred. Examples of such an acidic catalyst include sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, acidic ion exchange resin, and solid acid. The amount of the acid catalyst to be used is 0.0001 to 10% by weight, preferably 0.001 to 2% by weight, based on the sugar alcohol alkyl ether or the polyoxyalkylene sugar alcohol alkyl ether and the alkyl sulfate.

[0010] The reaction molar ratio of the sulfating reagent to the sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether is selected from the viewpoint of the remaining amount of the sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether remaining unreacted. You. In order to improve the detergency against oily dirt and to further reduce the irritation to the skin, the smaller the molar ratio of the sulfating reagent is, the more the sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether remains. In order to obtain a satisfactory reaction rate, the molar ratio of the sulfating reagent is preferably large, and the preferred molar ratio of the reaction is 0.1 to 1.5, more preferably
0.2 to 1.1. The reaction temperature is 0 to 50 ° C, preferably room temperature. The reaction time is 1 to 10 hours.

Although this reaction can be carried out without a solvent, it is preferable to use a solvent in order to lower the viscosity of the reaction solution and to allow the reaction to proceed smoothly. As the solvent, 1,4-
Dioxane, tetrahydrofuran, hexane, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, pyridine, dimethylsulfoxide, etc., and the amount of sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether used 1 to 5 times the total weight of the sulfating reagent and the total weight of the sulfating reagent are appropriate. In the reaction, a lower alcohol is by-produced as the reaction proceeds. The completion of the reaction can be expedited by removing the lower alcohol out of the system. Examples of such a method include a method in which the reaction is performed under a reduced pressure of 0.1 to 100 Torr, a method in which the reaction is performed under a nitrogen stream, and the like. After the completion of the sulfation reaction, the solvent is distilled off under reduced pressure to obtain the anionic surfactant of the present invention. The sugar alcohol alkyl ether sulfate or polyoxyalkylene sugar alcohol alkyl ether sulfate obtained as described above is a product in which primary hydroxyl groups are selectively sulfated by a sulfate reagent, at a high temperature, and for a long time. It has excellent stability under storage.

[0012] The anionic surfactant of the present invention obtained by the above-mentioned production method includes disulfate of primary alcohol and secondary alcohol of sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether, As impurities, a small amount of unreacted sugar alcohol alkyl ether or polyoxyalkylene sugar alcohol alkyl ether, sugar alcohol, and inorganic salts such as sodium sulfate are contained. Both components are water-soluble and the reaction product is pH
It can be used as an anionic surfactant with excellent foaming power and foam stability as it is just by adjusting it.However, when using a high-purity product such as a surfactant for liquid detergent, re-use it. Purification can also be performed using a known purification method such as crystallization, solvent extraction, column chromatography, ion exchange resin, electrodialysis and the like.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The anionic surfactant of the present invention comprises:
Although it shows excellent surface activity even when used alone, it is possible to achieve further improvement of detergency and further reduction of irritation to skin and hair by using in combination with a specific nonionic surfactant. . As such nonionic surfactants, sugar alcohol alkyl ethers or polyoxyalkylene sugar alcohol alkyl ethers, which are precursors of the anionic surfactant of the present invention, particularly sorbitol alkyl ether, polyoxyalkylene sorbitol alkyl ether are used for skin, Although preferred from the viewpoint of irritation to hair and feeling of use, polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene higher alcohol ether, polyoxyethylene secondary alcohol ether and the like can also be used. When the anionic surfactant (A) represented by the general formula (1) is used in combination with the nonionic surfactant (B),
In order that the characteristics of the anionic surfactant of the present invention can be fully exhibited, the mixing ratio (A) / (B) must be 98% by weight.
/ 2 to 5/95, preferably 80/20 to 20/80. The amount of the anionic surfactant of the present invention in the detergent composition varies depending on the dosage form of the detergent, but is 0.5 to 50% by weight of the composition in a liquid state, and 1 to 50% by weight in a paste form.
It is preferably 70% by weight and 1 to 80% by weight in the case of solid type.

The anionic surfactant of the present invention can be used in combination with existing anionic surfactants and amphoteric surfactants. Anionic surfactant is used for the purpose of further improving the foaming power, alkyl sulfate salt, polyoxyethylene alkyl sulfate salt,
α-sulfo fatty acid ester salt, α-olefin sulfonate, alkyl or hydroxyalkyl ether carboxylate, polyoxyethylene alkyl ether carboxylate, N-acylated taurine salt, N-acylated methyl taurine salt, N-acyl Glycine salt, N-acylated aspartate, N-acylated sarcosine, N-acylated glutamate, higher fatty acid salt, alkyl benzene sulfonate, alkyl sulfonate, monoalkyl phosphate ester salt, alkyl amide ether sulfate Examples thereof include an ester salt, a fatty acid monoglyceride sulfate ester salt, an alkyl iminodicarboxylic acid salt, a secondary amide type N-acyl amino acid salt, a tartaric acid alkyl amide salt, a malic acid alkyl amide salt, and a citric acid alkyl amide salt.

The amphoteric surfactant is used for the purpose of further improving the foaming power, foam stability and mildness to the skin, and includes an amido-amino acid type amphoteric surfactant, a glycine type and an alanine type amino acid type amphoteric surfactant. , Sulfobetaine, carboxybetaine, phosphobetaine, imidazolinium betaine surfactant and the like.

The pH when the detergent is dissolved in water varies depending on the type and use of the active agent to be mixed. However, in the case of shampoos, body shampoos and kitchen detergents, irritation to the skin and damage to the object to be washed are considered. , PH 5-8, for laundry detergent,
pH 6-11 is preferred.

The cleaning composition of the present invention may contain, if necessary, known auxiliary components to be added to the cleaning composition. Such auxiliary ingredients include builders, humectants,
Viscosity modifiers, preservatives, anti-inflammatory agents, antioxidants, ultraviolet absorbers, sequestering agents, anti-migration agents, bactericides, water-soluble polymer compounds, water-soluble inorganic salts, organics used for pH control and Inorganic compounds, pearlescent agents, pigments, fragrances, enzymes,
Bleaching agents and the like.

[0018]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 In a 500 ml four-necked flask equipped with a vacuum stirrer, a Liebig condenser, and a thermometer, 35.1 g (0.1 mol) of sorbitol lauryl ether and 14.8 g (0.1 mol) of sodium ethyl sulfate were placed. , Dioxane 20
0 ml and concentrated sulfuric acid 0.1 ml as a catalyst were charged. After stirring at room temperature for 1 hour, the pressure in the flask was gradually reduced from normal pressure to 35 mm while removing by-produced ethyl alcohol.
The mixture was stirred for 5 hours under reduced pressure of Hg to complete the reaction. Subsequently, after dioxane was distilled off, the generated solid was washed with methylene chloride to remove sulfuric acid, and 41.6 g of sodium sorbitol lauryl ether sulfate (yellow solid) (yield 95).
%, Purity by high performance liquid chromatography is 96%)
I got The analysis results of the obtained sodium sorbitol lauryl ether sulfate are shown below.

[0020] IR analysis _{^{3380cm -1 (-OH) 1250cm -1 (}} OSO 3 Na) 1240cm -1 (OSO 3 Na) 113-cm -1 (C-O-C) 1080cm -1 (C-O-C ) NMR analysis value (deuterated water solvent) 0.85 ppm (t, j = 6.6 Hz, 3H) 1.26 ppm (s, 18H) 1.56 ppm (m, 2H) 3.41 to 3.75 ppm (m, 10H)

Example 2 In Example 1, sorbitol palm alkyl ether was used in place of sorbitol lauryl ether.
Sorbitol coconut alkyl ether sodium sulfate (light yellow solid) (yield 94%, purity 95) according to Example 1.
%, The quantification method was based on Example 1). Example 3 In Example 1, sorbitol myristyl ether sodium was used instead of sorbitol lauryl ether, and sodium sorbitol myristyl ether sulfate (light yellow solid) (94% yield, 96% purity) was used according to Example 1.
The quantification method was based on Example 1).

Examples 4 to 6 and Comparative Examples 1 and 2 The performances of the compounds shown in Table 1 were evaluated as follows.

(1) Foaming power Using artificial hard water adjusted to a hardness of 10 ° DH using CaCl ₂ , a surfactant concentration of 0.9 adjusted to pH 5.5.
A mixed soil (lanolin / paraffin / triolein / tristearin = 90 /
4/4/2) 20 ml of a solution containing 0.2% by weight was prepared, placed in a 100 ml stoppered Epton tube, and shaken at room temperature for 20 times for 10 seconds. It was measured. The evaluation was made based on the following criteria by comparing with the amount of bubbles of sodium lauryl ether sulfate. Evaluation criteria; ：: Many bubbles ○: Equal bubbles ×: Little bubbles

(2) Feeling of use Using a hair bundle (30 g), washing with a 10% solution of each sample having a pH of 5.5, washing, rinsing with tap water, feeling of sliminess, refreshing, and after drying The moist feeling and the refreshing feeling of the hair bundle were evaluated by sensory evaluation according to the following evaluation criteria. The test was performed by five men and women. Evaluation criteria; 3: refreshing 2: normal 1: slimy The average value of the evaluation results was calculated, and when the average value was 2.5 or more (以上), when it was 2.4 to 1.5. Was determined as (△), and the case of 1.4 or less was determined as (x).

(3) Skin irritation 1% by weight of the liquid detergent composition and 0.1% ovalbumin.
A buffer solution having a pH of 7 containing 5% by weight was prepared, and evaluated 24 hours after the denaturation rate of ovalbumin (protein denaturation, measured by high performance liquid chromatography). Denaturation rate 30%
Less than (◎), modification rate 30-80% (（), modification rate 8
0% or more was regarded as (x).

[0026]

[Table 1]

Next, examples of specific formulations using the anionic surfactant of the present invention as a detergent component will be shown.

Example 7 Shampoo composition Anionic surfactant obtained in Example 2 8% by weight Sodium acylglutamate (coconut fatty acid) 5 Coconut fatty acid diethanolamide 5 Sorbitol coconut alcohol ether 3 Polypropylene glycol 5 Dye, perfume Appropriate amount Purified water balance This shampoo was hypoallergenic to the skin and foamed well on hair to which a hairdressing agent had adhered.

Example 8 Shampoo Composition Anionic Surfactant Obtained in Example 3 8 (wt%) Lauroyl-N-methyltaurine Sodium 5 Sorbitol Lauryl Ether 5 Lauryl Amidopropyl Acetate Betaine 5 Glycerin 3 Citric Acid Appropriate Perfume , Pigment suitable amount purified water balance This shampoo was hypoallergenic to the skin, had fine and stable foaming, and was well washed.

Example 9-Body soap composition Anionic surfactant obtained in Example 2 8 (% by weight) Sodium lauroylglutamate 7 Coconut fatty acid diethanolamide 5 Coconut fatty acid sodium 2 Ethanol 3 Polypropylene glycol 5 Pigment, perfume Appropriate amount Purification Water Balance This body soap was less irritating to the skin, had fine foaming, was less slimy upon rinsing, had less residual feeling on the skin, and had a good feel upon use.

Example 10-Hand soap composition Anionic surfactant obtained in Example 3 12 (wt%) sorbitol coconut alcohol ether 5 coconut fatty acid diethanolamide 3 coconut fatty acid potassium 2 2-decyltetradecyltrimethylammonium chloride 0 3.3 Propylene glycol 5 Dye, perfume Appropriate amount Purified water balance This hand soap was less irritating to the skin, stably foamed, and had a good use feeling.

Example 11 Toothpaste Composition Calcium hydrogen phosphate 50 (% by weight) Glycerin 15 Propylene glycol 3 Saccharin sodium 0.1 Sodium lauryl sulfate 1.0 Anionic surfactant obtained in Example 1 0.7 Carboxymethylcellulose 0.7 Carrageenan 0.2 Sodium benzoate 0.5 Methyl paraben 0.02 Butyl paraben 0.02 Anethole 0.1 Mensofuran 0.01 Perfume Appropriate amount Purified water balance This dentifrice has good low temperature stability and strong bitterness It was excellent in usability.

Example 12-Mouthwash composition Ethanol 10 (% by weight) Sorbitol 6 Sodium bicarbonate 1 Sodium carbonate 0.6 Lauryl sorbitol ether 1.8 Anionic surfactant obtained in Example 1 0.2 Mono Sodium fluorophosphate 0.6 Methyl paraben 0.03 Ethyl paraoxybenzoate 0.02 Fragrance Appropriate amount Purified water balance This mouthwash had good storage stability, and was excellent in detergency and usability.

Example 13 Composition of Detergent for Tableware Vegetables Anionic surfactant obtained in Example 2 10 (wt%) polyoxyethylene dodecyl ether (p = 10) 7 dodecyldimethylamine oxide 3 polypropylene glycol 2 ethanol 3 Pigment, flavor appropriate amount Purified water balance This dishwashing vegetable detergent had little irritation to the skin, and had good detergency and foaming power against oily dirt.

Example 14 Detergent Composition for Liquid Yarn Anionic Surfactant Obtained in Example 2 5 (wt%) Polyoxyethylene dodecyl ether (p = 10) 10 C ₁₁ -C ₁₃ Secondary Alcohol Ethoxylate (P = 8) 5 Diethanolamine 1 Ethanol 2 Dye, perfume Appropriate amount Purified water balance This yarn detergent had good detergency and foaming power.

Example 15 Detergent Composition for Bathtub Anionic surfactant obtained in Example 3 6 (wt%) C ₁₁ -C ₁₃ secondary alcohol ethoxylate (p = 8) 3 polyoxyethylene polyoxypropylene Butyl ether 2.5 Propylene glycol 3 Sodium citrate 5 Dye, Fragrance Appropriate amount Purified water Balance This bathtub detergent has rich and creamy foam,
Moreover, the detergency was good.

[0037]

The compound of the present invention is easily biodegradable and foams even in the presence of hard water having high hardness and oily soil,
It is a novel anionic surfactant which has good foam stability, is less irritating to skin and hair, and is useful as a cleansing component. Therefore, the detergent composition containing the surfactant of the present invention can be used for shampoos, body shampoos, hand soaps, detergents for tableware and vegetables, detergents for homes, detergents for clothes, and oral cavity such as toothpastes and mouthwashes. Can be widely used as supplies.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C083 AB292 AB312 AB472 AC102 AC122 AC132 AC172 AC242 AC302 AC472 AC482 AC642 AC662 AC692 AC712 AC781 AC782 AC792 AC862 AD272 AD352 AD532 BB05 CC23 CC38 CC41 EE09 EE10 FF01 4H003 AB09 AB30 AC03 AC08 AC08 DA01 DA02 DA17 EB34 ED02 ED28 FA02 FA03 FA15 FA17 FA18 FA28 4H006 AA01 AA03 AB68 AB70

Claims (3)

[Claims] (A) a sugar alcohol alkyl ether sulfate compound represented by the following general formula (1): R—O— (A) m (B) nOSO ₃ M (1) : A linear or branched higher alkyl group or higher alkenyl group or hydroxyalkyl group having an average of 6 to 26 carbon atoms A: an alkylene oxide group having 2 to 3 carbon atoms, used alone or as a mixture B: 6 to 8 carbon atoms M: average number of moles added: 0 to 10 n: average number of condensations: 1 to 5 M: hydrogen atom, alkali metal, alkaline earth metal, organic ammonium such as ammonium or alkanol ammonium, or a basic amino acid group .) 2. An anionic surfactant comprising the sugar alcohol alkyl ether sulfate compound according to claim 1. 3. A cleaning composition comprising at least one anionic surfactant according to claim 2.