JP2001316352A - Alkyl ether sulfate, method for producing the same and liquid detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkyl ether sulfate satisfying all of the characteristics of cleaning property, foaming performance, preservation stability and mildness on blending with a liquid detergent, and further having a low dioxane content. SOLUTION: This alkylether sulfate is obtained by using an alkoxylation catalyst consisting of a compounded metal oxide containing magnesium, aluminum and manganese for adding ethylene oxide to an alcohol and sulfonating the obtained adduct. The molar distribution of the EO addition is narrow and its dioxane content is <=30 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an alkyl ether sulfate, a method for producing the same, and a liquid detergent composition containing the same.

[0002]

2. Description of the Related Art Conventional alkyl ether sulfates have a wide range of molar distribution of ethylene oxide addition, and therefore have some problems when used in detergents.
In other words, the smaller the average number of moles added, the higher the detergency and foaming performance, but on the other hand, the higher the content of alkyl sulfate with no added moles, the lower the mildness (low skin irritation) and storage stability. I do. On the other hand, if the average number of added moles is increased, the mildness to the hand skin is increased, but the ratio of the high added mole adduct that hardly contributes to the detergency increases, and the detergency and the foam performance are reduced. The amount of 1,4-dioxane (hereinafter referred to as "dioxane") by-produced during sulfation increases.

As means for solving such a problem, use of an alkyl ether sulfate having a narrow addition molar distribution of ethylene oxide (EO) has been proposed (JP-A-4-72395). As a method for producing such an alkyl ether sulfate having a narrow EO addition molar distribution, there are, for example, the following three methods (1) to (3).

(1) In the presence of an acid catalyst such as a Lewis acid,
A method in which EO is added to a raw material alcohol to produce an alcohol ethoxylate having a narrow EO addition molar distribution, and sulfated. (2) In the presence of an alkali catalyst such as potassium hydroxide,
After obtaining an alcohol ethoxylate having a wide EO addition molar distribution, the desired EO addition molar distribution is adjusted by fractional distillation,
How to sulfate it. (3) Catalyst containing magnesium oxide as a main component
In the presence of (−16437), E was added to the starting alcohol.
A method in which O is added to produce an alcohol ethoxylate having a narrow EO addition molar distribution, and sulfated.

[0005] However, in the above method (1), since there are many by-products, there is a possibility that a problem may occur in the quality of the obtained product, and the dioxane content cannot be reduced sufficiently. In the method (2), a fractionation step is added,
The production process is complicated, the production cost is high, and the dioxane content is not sufficiently reduced. In the method (3), the step of obtaining the catalyst to be used is complicated, and the amount of polyethylene glycol by-produced by the addition of ethylene oxide is large, which adversely affects the filtration rate of the catalyst after the addition, resulting in an industrial scale. The production becomes difficult and the dioxane content is not sufficiently reduced.

[0006]

Therefore, the present invention provides a high detergency and a foaming property, storage stability and mild property (low skin irritation) when formulated in a liquid detergent. It is an object of the present invention to provide an alkyl ether sulfate having a satisfactory dioxane content and a method for producing the same.

[0007]

In order to achieve the above object, an alkyl ether sulfate of the present invention is an alkyl ether sulfate represented by the following general formula (I), wherein the alkyl ether sulfate is ethylene A mixture containing a plurality of molecular species having different numbers of moles of oxide addition, where nA is a positive integer, and nA is a positive integer, where nA is the number of moles of ethylene oxide added to the most abundant molecular species in the mixture. It has a configuration in which the proportion of molecular species having a mole number in the range of (nA-1) to (nA + 1) is 55 to 75% by mass, and the dioxane content in the mixture is 30 ppm or less.

R ¹ O (CH ₂ CH ₂ O) nSO ₃ M (I)

In the above formula (I), R ¹ is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, and n is an average ethylene oxide addition mole number and is a number of 1 to 6. And M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a mono-, di-, or trialkanol ammonium ion having an alkanol group having 2 to 3 carbon atoms.

The alkyl ether sulfate of the present invention has a high detergency when added to a liquid detergent, and has a foaming performance, storage stability and mildness (low skin irritation).
Can be satisfied. Moreover,
The alkyl ether sulfate of the present invention has a sufficiently low dioxane content of 30 ppm or less, and is of high quality.

In the alkyl ether sulfate of the present invention, the lower the content of dioxane, the better. Ideally, it is preferable that dioxane is not contained, that is, the content is 0 ppm, but this is not practical. Therefore, the lower limit of the dioxane content of the alkyl ether sulfate of the present invention is a value exceeding 0. Dioxane can be measured, for example, by gas chromatography (GC) according to the method described below.

The reason why the amount of dioxane produced as a by-product in the alkyl ether sulfate of the present invention is small is unknown, but the present inventors speculate as follows.
That is, it is considered that an EO chain having a certain length is required in order to obtain a six-membered ring structure of dioxane. Further, it is considered that the EO chain cleavage reaction proceeds from the point where SO ₃ attacks the oxygen atom of the EO chain. Therefore, it is considered that the longer the EO chain is and the more the oxygen atoms are, the higher the probability that dioxane is by-produced. However, the alkyl ether sulfates of the present invention have a narrow EO addition molar distribution and few long EO chains. For this reason, it is considered that the probability of producing dioxane as a by-product is small, and as a result, the amount of dioxane is reduced.

In the alkyl ether sulfate of the present invention, the molar ratio of ethylene oxide to nA molecular species is preferably 19 to 35% by mass.

Next, the process for producing an alkyl ether sulfate according to the present invention comprises the steps of: adding ethylene oxide to an alcohol in the presence of an alkoxylation catalyst containing a composite metal oxide containing magnesium and other metals; In this production method, the catalyst is removed from the obtained reaction product, and the reaction product is sulfated.

According to this production method, the alkyl ether sulfate of the present invention having the above properties can be produced,
Since this manufacturing method is an integrated process, the manufacturing efficiency is good. In this production method, it is preferable to remove the catalyst after bringing the reaction product into contact with the filter aid.

In the production method of the present invention, the composite metal oxide preferably contains at least one metal selected from Group 6A, Group 7A and Group 8, magnesium and aluminum. Further, the sulfation is preferably performed using gaseous sulfur trioxide.

Next, the liquid detergent composition of the present invention is characterized by containing the above-mentioned alkyl ether sulfate of the present invention. This liquid detergent has high detergency, foaming performance, storage stability, mildness (low skin irritation)
Excellent in all properties and safety.

In the liquid detergent composition of the present invention, the content of the alkyl ether sulfate is preferably in the range of 5 to 25% by mass, more preferably 10 to 25% by mass of the whole liquid detergent composition. .

The liquid detergent composition of the present invention further comprises, in addition to the alkyl ether sulfate (a), at least one of a sulfonic acid type anionic surfactant (b), an amine oxide type surfactant and a betaine type surfactant. It is preferable to contain one surfactant (c). In this case, it is preferable that the proportions (by mass) of the above (a), (b) and (c) satisfy the relationship represented by the following formula (II).

1 ≦ [(a) + (b)] / (c) ≦ 20 (II)

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The alkyl ether sulfate of the present invention is represented by the above general formula (I), and has a dioxane content of 30 ppm or less.

In the general formula (I), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms, preferably 8 to 24 carbon atoms.
20, more preferably 10 to 18 hydrocarbon groups.
R ¹ may be straight-chain or branched, and may be saturated or unsaturated. Further, R ¹ may optionally include a substituent such as a hydroxyl group.

R ¹ is a hexyl group, an octyl group,
Decyl group, lauryl group, myristyl group, palmityl group,
Stearyl, oleyl, aralkyl, behenyl and the like are preferred. Of these, decyl, lauryl, myristyl, palmityl, stearyl and oleyl are particularly preferred.

N is the average number of moles of ethylene oxide added. n is a number in the range 1-5, preferably 2-3.

M is a hydrogen atom, an alkali metal ion such as a lithium ion, a potassium ion or a sodium ion, an alkaline earth metal ion such as a calcium ion or a magnesium ion, an ammonium ion, or a monovalent compound having an alkanol group having 2 to 3 carbon atoms. An alkanol ammonium ion, a dialkanol ammonium ion or a trialkanol ammonium ion. Among them, alkali metal ions, ammonium ions,
Mono, di or trialkanol ammonium ions are preferred, potassium ions, sodium ions and trialkanol ammonium ions are particularly preferred.

As described above, the alkyl ether sulfate of the present invention is a mixture containing a plurality of molecular species having different EO addition mole numbers, and the distribution of the EO addition mole number satisfies the following conditions. (1) nA is an integer of 1 or more, that is, nA ≠ 0. (2) The proportion of the molecular species having an EO addition mole number in the range of (nA-1) to (nA + 1) is 55 to 75% by mass, preferably 60 to 70% by mass.

When these conditions are not satisfied, that is, nA = 0 or (nA-1) to (nA + 1)
If the proportion of the molecular species in the range is less than 55% by mass, problems such as coarse foam and high skin irritation occur.

The ratio of the molecular species having an EO addition mole number of nA is, for example, 19 to 35% by mass, preferably 20 to 35% by mass.
３０30% by mass.

Next, in the present invention, the measurement of dioxane can be performed by using, for example, GC by the following method.

(Method for Measuring Dioxane) A sample is diluted with water so that the dioxane content is equivalent to 10 ppm. On the other hand, using a 10 ppm ethanol solution of dioxane as a calibration curve, the dioxane content in the sample is determined by a one-point absolute calibration curve method.

(GC conditions) Apparatus Product name HP5890 Series II Plus (manufactured by Hewlett Packard) Column Product name DB-WAX (manufactured by J & W) Size 0.25 mm × 30 m Film thickness 0.25 μm Carrier gas He gas Linear velocity 30 cm / min Split ratio 20: 1 Detector FID Column temperature 40 ° C (Hold 6 min) → 200 ° C (Hold 10 min) Heating rate 30 ° C / min Inlet temperature 120 ° C Detector temperature 200 ° C Injection volume 1 microliter (μL) )

Next, in the method for producing an alkyl ether sulfate of the present invention, EO is added to an alcohol in the presence of the alkoxylation catalyst, and the catalyst is removed from a reaction product obtained by the addition. This is a production method in which the substance is sulfated.

The alkoxylation catalyst is preferably a composite metal oxide catalyst containing MgO as a main component and two or more metals other than magnesium added. As the catalyst,
6 described in JP-A-2000-61304
An alkoxylation catalyst comprising a metal oxide containing at least one metal selected from Group A, Group 7A and Group 8, magnesium and aluminum can be preferably used. This catalyst can be produced, for example, by the following method. First, by a coprecipitation method, a composite hydroxide containing magnesium, aluminum, and at least one metal selected from the group 6A, the group 7A, and the group 8 is produced, and a water-soluble salt is removed by washing with water, followed by drying. After that, the mixture is calcined to form a composite oxide, whereby the alkoxylation catalyst is obtained. The firing temperature is, for example, 300 to 1000.
° C, preferably 600 to 900 ° C, more preferably 70 ° C.
0-900 ° C.

The amount of the alkoxylation catalyst used is, for example, in the range of 0.001 to 3% by mass, and preferably in the range of 0.01 to 2% by mass, based on the starting alcohol used.

The alcohol to which ethylene oxide is added is preferably a linear or branched primary alkyl or alkenyl group having 6 to 24 carbon atoms to which an alcoholic hydroxyl group is bonded, and having 10 to 18 carbon atoms. Is more preferable. If the number of carbon atoms is less than 6, the hydrophobicity is insufficient, so that sufficient detergency cannot be obtained when the resulting alkyl ether sulfate is blended with a detergent. On the other hand, when the number of carbon atoms is larger than 24, the solubility of the alkyl ether sulfate is reduced, so that it is easy to precipitate during storage.

Preferred alkyl or alkenyl groups are the same as those exemplified in the explanation of R ^{1 in} formula (I). The alkyl group or alkenyl group may be derived from a natural product or a synthetic product.

Commercial products of such alcohols having an alkyl group or an alkenyl group include, for example, Dovanox (manufactured by Mitsubishi Chemical), Dovanol (manufactured by Mitsubishi Chemical), and Diadol (manufactured by Mitsubishi Chemical). And natural primary alcohols such as coco oil (manufactured by Kyowa Hakko Co., Ltd.) and Neodol (manufactured by Shell Chemical), and natural alcohols such as coconut oil higher alcohol.

In the present invention, when adding EO to alcohol, an inert gas may be used in combination with EO. The inert gas is not particularly limited as long as it does not hinder the addition reaction of EO, and examples thereof include a nitrogen gas and a helium gas.

The average number of moles of EO added is preferably in the range of 1 to 6, more preferably 1.5 to 4, and still more preferably 2 to 6.
~ 3.

The EO addition reaction temperature is, for example, 100 to 100.
The temperature is 200 ° C, preferably in the range of 120 to 190 ° C. The additional pressure of EO is, for example, 0.1 to 2M.
Pa, preferably in the range of 0.2 to 1.5 MPa.

The catalyst is removed from the reaction product (alcohol ethoxylate) obtained by the addition reaction. This can be performed, for example, by filtration.

Examples of the filter used for filtration include filter paper, polyester filter, two-layer filter of cellulose and polyester, sintered metal filter, metal mesh type filter and the like. Filtration is preferably performed under reduced pressure or pressure, and the temperature is, for example,
10 to 180 ° C., preferably 15 to 100 ° C.
It is in the range of ° C. Furthermore, you may filter by centrifugation, for example, using a decanter or a centrifugal clarifier.

Prior to such a filtration step, the reaction product is preferably brought into contact with a filter aid. The filter aids, for example, diatomaceous earth amorphous silicate containing SiO ₂ 80 to 95% aluminum silicate containing SiO ₂ about 70%, cellulose-based filter aid, activated carbon, activated alumina, synthetic Zeolites, clays or clay minerals are mentioned. Examples of the diatomaceous earth include Radiolite (trade names: # 100 to # 900, manufactured by Showa Chemical Industry Co., Ltd.), Celite 545 (trade name, manufactured by Celite), Hyfloss Parcel (trade name, manufactured by Celite), and trade name: Standard Spar cell (Celite), trade name filter cell (Ce
lite). Examples of the aluminum silicate include Topco # 31 (trade name, manufactured by Toko Perlite Industries, Ltd.). As the cellulose-based filter aid, trade names KC-Floc (manufactured by Nippon Paper Industries), trade name SW40
(Manufactured by Brown Corp.), trade name BW20 (Brown Corp.
BW40 (Brown Corp.), trade name BW100 (Brown Corp.), trade name BW200
(Made by Brown Corp.). Examples of the clay or clay mineral include activated clay and acid clay.
These filter aids may be used alone or in combination of two or more. The amount of the filter aid is preferably in the range of 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, and most preferably 0.1 to 5% by mass, based on the reaction composition.
-3% by mass. Preferred as a filter aid is a cellulosic filter aid.

Next, the alcohol ethoxylate is sulfated. Sulfation can be performed by a conventional method, and it is preferable to perform sulfation with gaseous sulfur trioxide. The concentration of the gaseous sulfur trioxide is, for example, in the range of more than 0 and 20 vol / vol% or less, preferably 4 to 10 vol / vol%.
Range. As the reactor used for sulfation, for example, a tank reactor or a thin-film falling reactor can be used, and a thin-film falling reactor is preferable. The reaction temperature is
For example, it is 20 to 100 ° C, preferably 20 to 50 ° C. When the reaction temperature is 100 ° C. or lower, the deterioration of the color tone can be prevented. On the other hand, when the temperature is 20 ° C. or higher, disturbance of the flow state can be prevented, and as a result, the deterioration of the color tone can be prevented, which is preferable.

Then, the obtained sulfate is neutralized using, for example, an aqueous solution of an alkali metal salt. The neutralization temperature at this time is preferably 100 ° C. or lower, more preferably 8 ° C.
0 ° C. or less. Neutralization at a temperature of 100 ° C. or lower is preferable because a reverse reaction in which the reactant returns to the raw material can be prevented.
The lower limit of the neutralization temperature is not particularly limited, but is, for example, 20 ° C. The neutralization method is, for example, batch neutralization,
There are a continuous neutralization system and the like, and a continuous circulation neutralization system equipped with an external cooling device is particularly preferable from the viewpoint of keeping the temperature constant. Further, at the time of neutralization, a polyhydric alcohol can be added as a viscosity reducing agent. As the polyhydric alcohol, for example, polyethylene glycol (for example, having a molecular weight of 200
５5000).

Thus, the alkyl ether sulfate of the present invention is obtained, and the alkyl ether sulfate of the present invention can be obtained by other production methods.

Next, the liquid detergent composition of the present invention contains the above-mentioned alkyl ether sulfate of the present invention.
As described above, the content ratio is 5% with respect to the whole composition.
The range of ２５25% by mass is preferred. When the content is 5% by mass or more, the detergency is further improved, and when the content is 25% by mass or less, an excessive increase in the viscosity of the liquid detergent composition can be sufficiently suppressed. Therefore, in order to prevent the liquid detergent composition from becoming gel-like or paste-like, it is not necessary to add a hydrotrope agent more than necessary to prevent an increase in viscosity. The content ratio is more preferably in the range of 10 to 25% by mass, and most preferably in the range of 15 to 25% by mass.

[0048] The detergent composition of the present invention preferably contains a sulfonic acid type anionic surfactant (b) because the detergency and foam performance are further improved.
The sulfonic acid type anionic surfactant is not particularly limited, for example, an α-olefin sulfonic acid having a carbon chain length of 10 to 18 or a salt thereof, an alkylbenzene sulfonic acid having a carbon chain length of 10 to 18 or a salt thereof, Carbon chain length 10
And α-sulfo fatty acids having a carbon chain length of 10 to 18 or salts thereof.
These may be used alone or in combination of two or more. The mixing ratio of these anionic surfactants is preferably in the range of 2 to 15% by mass based on the whole composition. Two
If it is at least 15% by mass, the detergency and the foam performance will be further improved, and if it is at most 15% by mass, the mildness and the storage stability will be more excellent. These sulfonic acid-type anionic surfactants are not particularly limited by the structure such as the alkyl chain length, the production method, and the like, and generally commercially available ones can be suitably used. Particularly preferred is 10 to 18.

In order to further improve the detergency, foam performance, mildness and storage stability, the detergent composition of the present invention comprises an amine oxide type surfactant or a betaine type surfactant, or the above two surfactants. It is preferred to contain both activators. Amine oxide type surfactants and betaine type surfactants are not particularly limited by the structure and production method such as the alkyl chain length, and generally commercially available ones can be suitably used. Ten~
Eighteen are particularly preferred. As the amine oxide type surfactant, for example, alkyldimethylamine oxide,
Alkanoylamidoalkyldimethylamine oxide,
Examples include alkyldiethylamine oxide. Of these, alkyldimethylamine oxide and alkanoylamidoalkyldimethylamine oxide are preferred, and alkyldimethylamine oxide is more preferred.
Examples of the betaine-type surfactant include betaine alkyldimethylacetate, betaine alkanoylamidoalkylacetate, and alkylhydroxysulfobetaine. Of these, alkyldimethyl acetate betaine and alkanoylamide alkyl acetate betaine are preferred, and alkanoylamide alkyl acetate betaine is more preferred.
The total mixing ratio of the amine oxide surfactant and the betaine surfactant to the entire liquid detergent composition is as follows:
The content is preferably 1 to 15% by mass, more preferably 2 to 10% by mass. When the content is 2% by mass or more, the above-mentioned properties are further improved. When the content is 10% by mass or less, the viscosity of the liquid detergent composition can be prevented from excessively increasing, and it is necessary to mix the hydrotrope agent more than necessary. Is also gone. When the amine oxide surfactant (x) and the betaine surfactant (y) are used in combination, the mass ratio of the two is, for example, preferably x: y = 1 to 10:10 to 1, and is preferably. Is x: y = 1 to 5: 5 to 1.

As described above, the alkyl ether sulfate (a), sulfonic acid type anionic surfactant (b), amine oxide type surfactant and betaine type surfactant represented by the general formula (I) are used. The mass ratio of at least one surfactant (c) preferably satisfies the relationship of the above formula (II). Here, [(a) + (b)] /
(C) shows the ratio of the total amount of the anionic surfactant to the total amount of the amine oxide type surfactant and the betaine type surfactant. If this value is 20 or less, the detergency and mildness will be further improved. When the value is 1 or more, the storage stability becomes more excellent, and the foam quality becomes more excellent in creamy feeling. Also, [(a) + (b)] / (c)
Is more preferably in the range of 2 to 15, most preferably 3 to 1
It is in the range of 0. Furthermore, when (a) / (b) is 2 or more, the creamy feeling of the foam quality is further improved.

The liquid detergent composition of the present invention is preferably further blended with an amide type nonionic surfactant since the creamy feeling of the foam can be further improved. Therefore, the amide type nonionic surfactant is
A substance capable of imparting a creamy feeling to the foam by a synergistic effect based on a hydrogen bond specific to an amide group. Fatty acid alkanolamides and fatty acid glucamides are preferred. However, such an amide type nonionic surfactant is not particularly limited by the structure such as the carbon chain length or the production method, and generally commercially available one can be suitably used. In particular, those having 10 to 18 carbon atoms are preferred. Preferred examples of the amide-type nonionic surfactant include fatty acid monoethanolamide, fatty acid diethanolamide, fatty acid propanolamide, fatty acid polyoxyethylene monoethanolamide, and fatty acid methylglucamide. The compounding ratio of the amide type nonionic surfactant is preferably in the range of 0 to 15% by mass, and particularly preferably in the range of 1 to 10% by mass, based on the whole liquid detergent composition. The addition of the amide type nonionic surfactant makes the foamy creamy feeling excellent. When the content is 1% by mass or more, the creamy feeling of the foam becomes more excellent, and when the content is 15% by mass or less, the viscosity increase of the liquid detergent composition can be prevented, and the hydrotrope agent is used more than necessary. There is no mixing.

Furthermore, various optional components can be added to the cleaning composition of the present invention in accordance with the purpose and use as long as the effect is not impaired. Such optional components include, for example, fatty acid soaps, phosphate ester surfactants, anionic surfactants such as amino acid surfactants such as acyl alaninate and acyl taurate, imidazoline type amphoteric surfactants, Examples include nonionic surfactants such as alcohol ethoxylates, alkyl polyglucosides, alkyl glyceryl ethers, and sucrose fatty acid esters, and cationic surfactants such as alkyl trimethyl ammonium salts. Hydrotropes such as aromatic carboxylic acids such as benzoates and aromatic sulfonic acids such as paratoluenesulfonic acid, xylenesulfonic acid, and cumenesulfonic acid can also be suitably blended. In addition, water-soluble solvents such as ethanol, various flavor-denatured ethanols, isopropanol, and butyl carbitol can also be suitably blended. Also, citric acid, malic acid,
Chelating agents such as ethylenediaminetetraacetic acid (EDTA) and glycolic acid, and high molecular compounds such as polyacrylic acid, polyacrylic acid / polymaleic acid copolymer, and polystyrenesulfonic acid can also be suitably blended. In addition, inorganic builders such as sodium sulfate and magnesium sulfate, viscosity modifiers, coloring agents, antioxidants, preservatives, bactericides, disinfectants,
Components normally used in liquid detergents such as anti-inflammatory agents, medicinal ingredients, fragrances, and natural extracts can also be suitably blended.

As the fragrance, for example, aliphatic hydrocarbons,
Hydrocarbons such as terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, ethers such as aliphatic ethers and aromatic ethers, aliphatic oxides, terpene oxides and the like Oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzene based Aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols,
Phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones,
Lactones such as terpene lactones, hydrogenated aromatic lactones, aromatic lactones, aliphatic esters, furan carboxylic esters, aliphatic cyclic carboxylic esters, cyclohexyl carboxylic esters, terpene carboxylic esters, aromatic carboxylic acids Esters such as acid esters, nitro musks, nitriles, amines, pyridines,
Synthetic flavors such as quinolines, pyrroles, nitrogen-containing compounds such as indole, and natural flavors from plants. These may be used alone or in combination of two or more.
The mixing ratio of the fragrance is, for example, more than 0 and 1% by mass or less, preferably 0.1 to 0.5% by mass, based on the whole liquid detergent composition.

[0054]

Next, examples will be described together with comparative examples.

Example 1 (1) Preparation of Catalyst 68.03 g of magnesium nitrate hexahydrate, 47.69 g of aluminum nitrate nonahydrate and 24.33 g of manganese nitrate hexahydrate were added to 450 g of deionized water. This was dissolved to obtain a solution A. On the other hand, 13.47 g of sodium carbonate was dissolved in 450 g of deionized water to obtain a solution B.
The solution A and the solution B were dropped into a catalyst preparation tank previously charged with 1800 g of deionized water in 1 hour while maintaining the pH at 9 and the temperature at 40 ° C. with a 2 mol / liter (L) aqueous NaOH solution, After completion of dropping, the mixture was aged for 1 hour.
The mother liquor was removed by filtration, and the precipitate was washed with 6000 g of deionized water and spray dried to obtain 30 g of a composite hydroxide. This composite hydroxide is heated at 800 ° C.
For 3 hours to obtain 19 g of a composite oxide catalyst (alkoxylation catalyst) of Mg, Al, and Mn.

(2) EO Addition 0.5 g of the above catalyst, 207.9 g of linear dodecanol (trade name "Conol 20P" manufactured by Shin Nippon Rika Co., Ltd.) and tridecanol mixed linear / branched (trade name "Diadol13" manufactured by Mitsubishi Chemical Corporation) 831.5 g was charged into an autoclave,
The inside of the autoclave was replaced with nitrogen gas. While stirring
After heating to 50 ° C and dehydrating under reduced pressure (reach 6.65 kPa),
Introduce nitrogen gas into the autoclave and return to normal pressure,
The temperature was raised to 160 ° C. Then, set the temperature to 180 ° C and the pressure to 0.5M
460.6g EO (equivalent to 2 additional moles) while maintaining at Pa
And stirring was continued until the equilibrium pressure was reached at the same temperature to complete the reaction. Thereafter, the reaction product was cooled to 80 ° C. to obtain a reaction product (reaction crude product).

(3) Separation of catalyst from reaction product (reaction crude) 400 g of the above reaction product was placed in a 1 L four-necked flask equipped with a stirrer and heated to 45 ° C. Then, 2 g of filter aid for body feed (trade name: KC Floc W-50S, manufactured by Nippon Paper Industries Co., Ltd.) (0.5% based on the reaction product) was added, and 45
The mixture was stirred at 30 ° C. for 30 minutes to obtain a mixture A. From the mixture A, 100 g of a precoat liquid was added to another four-necked flask (500
mL; with stirrer) and warmed to 45 ° C. 0.625 g (0.5%) of the above precoating liquid as a precoating filter aid
kg / cm ² ) KC Floc W-50S and 0.625g
(0.5 kg / cm ² ) of Hyflo Super Cell (Celite) was added, and the mixture was stirred at 45 ° C. for 30 minutes to obtain a precoating liquid B.

Using a pressure filter (inner diameter 4 cm) using a two-layer filter of cellulose and polyester as a filter medium, 45
The pre-coating liquid B was filtered at a temperature of 0.2 ° C. and a nitrogen pressure of 0.2 MPa to form a pre-coat layer. However, about the amount that comes out first
About 20 mL of the filtrate, a slight leakage of the filter aid was observed, so that the filtrate was passed through the filter again. After confirming that the filtrate of the precoating solution B had sufficient clarity, the mixture A was applied to the filter to obtain a filtrate having sufficient clarity. The filtrate obtained by the above operation (the combined filtrate of the precoating liquid B and the filtrate of the mixed liquid A) was used as purified alcohol ethoxylate.

(4) Sulfation of Alcohol Ethoxylate The purified alcohol ethoxylate was introduced into a thin film type falling type sulfonation reactor (inner diameter 10 mm × 2.5 m, equipped with an outer jacket) at a temperature of 45 ° C. and a supply rate of about 146. ~ 149
The reactor was supplied at a rate of g / min, and the inside of the reactor was allowed to flow down in a thin film form. Also, SO ₃ gas (concentration of about 7 to 8%, diluted with nitrogen gas) was introduced into the reactor at a supply rate of 40 g / min,
The purified alcohol ethoxylate was sulfated. The temperature of the SO ₃ gas was 50 ° C., and water at 30 to 40 ° C. was passed through the outer jacket of the reactor. A nitrogen gas was introduced between the alcohol ethoxylate and the SO ₃ gas. The obtained sulfate was neutralized with a 3.2% by mass aqueous sodium hydroxide solution at 70 ° C. or lower, and the surfactant concentration was 22%.
Thus, an alkyl ether sulfate having a mass ratio of 96.5% and a sodium sulfate of 0.07% by mass was obtained. In addition, the obtained sulfate is
Neutralization was performed at 70 ° C. or lower using a 20.7% by mass aqueous sodium hydroxide solution to obtain an alkyl ether sulfate (S-1) having a surfactant concentration of 65% by mass. It was a pumpable slurry. Then, to the obtained sulfate, polyethylene glycol (MW = 1000) was added at 25% by mass.
(To the amount of a pure surfactant) and further neutralized at 70 ° C. or lower with a 48% by mass aqueous sodium hydroxide solution to obtain an alkyl ether sulfate having a surfactant concentration of 60% by mass (S-2). The addition molar distribution of the alkyl ether sulfate (S-1, S-2) thus obtained is represented by
It was measured by high performance liquid chromatography (HPLC). Also, the amount of dioxane was measured by the method described above. The results are shown in Table 1 below. In addition, the measurement of the EO addition molar distribution and the amount of dioxane were similarly performed in the following Examples and Comparative Examples. Further, the dioxane amount is a ratio (ratio to the entire surfactant) in a mixture (surfactant) of alkyl ether sulfates of a plurality of molecular species, and the same applies to the following Examples and Comparative Examples. is there.

Example 2 EO addition, sulphation and neutralization were carried out in the same manner as in Example 1 except that the number of moles added was 5 in the EO addition.
By mass, alkyl ether sulfate (S-3) was obtained. The addition molar distribution and the amount of dioxane are shown in Table 1 below.

(Comparative Example 1) EO addition, sulfation and neutralization were carried out in the same manner as in Example 1 except that 0.05% by mass of potassium hydroxide (relative to the starting alcohol) was used as the alkoxylation catalyst, and the surface activity was increased. An alkyl ether sulfate (R-1) having an agent concentration of 60% by mass was obtained. The addition molar distribution and the amount of dioxane are shown in Table 1 below.

Comparative Example 2 EO addition, sulfation and neutralization were carried out in the same manner as in Comparative Example 1 except that the number of moles added was 5 in the EO addition.
By mass, alkyl ether sulfate (R-2) was obtained. The addition molar distribution and the amount of dioxane are shown in Table 1 below.

[Table 1] Sample No. S-1 S-2 S-3 R-1 R-2 Average addition mole number 2 25 25 (EO addition mole distribution (% by mass)) 0 13 13 1 23 5 5 17 17 17 1 16 5 225 25 25 15 7 3 24 24 8 12 8 4 14 14 1 8 9 9 5 5 5 5 5 7 9 6 6 2 2 2 2 2 6 9 7 0 0 0 1 3 4 9 9 0 0 6 3 8 9 0 0 2 2 7 10 0 1 1 0 0 1 1 5 1 2 0 0 0 0 1 4 1 3 0 0 0 0 0 3 1 4 0 0 0 0 3 3 15 or more 0 0 0 0 3 Maximum amount adduct (nA) 2 250 0 4 to 7 nA mol adduct ( Mass%) 25 25 25 239 nA ± 1 mol adduct (mass%) 66 66 65 39 27 dioxane content (ppm) 25 25 30 50 75

As shown in Table 1, the alkyl ether sulfates of Examples 1 and 2 had a narrow EO addition molar distribution and a low dioxane content of 30 ppm or less. In contrast, the alkyl ether sulfates of Comparative Examples 1 and 2 had a wide EO addition molar distribution and a dioxane content exceeding 30 ppm.

(Examples 3 to 7, Comparative Examples 3 and 4) The alkyl ether sulfates (S-1, S-2, S-3, R-1, R) of Examples 1 and 2 and Comparative Examples 1 and 2 were used. In addition to -2), each component shown in the following Table 2 was blended to prepare a liquid detergent composition, and various properties of foamy creamy feeling, detergency, mildness and storage stability were evaluated. . The results are also shown in the table. In addition, the said evaluation was performed by the method shown below. In the table, the composition is represented by "parts by mass". In addition, the composition of the fragrance in the table,
It is as shown in Table 3 below.

(Frosty creamy feeling)
A 40% by mass aqueous solution of a commercially available dishwashing foamer was evaluated for the feel of foam when rubbed by hand 10 times according to the following criteria. ：: The foam has a fine texture and is a viscous, creamy foam that does not easily drip from the foam. Δ: The texture of the foam is fine, but lacks a creamy feeling, and the foam is easily dripped off from the foam. ×: Foam quality is watery and heavy, and a large amount of water is spilled from the foam.

(Detergency) 1 g of beef tallow was uniformly applied to a 10 cm × 15 cm polyolefin tach container to obtain a severely soiled hydrophobic hard surface stain. 36 for commercial dishwashing shampoo
After taking g of water and 4 g of the detergent composition and rubbing it by hand several times,
The contaminated tapped containers were washed at 25 ° C. as usual in a home. After washing, the well was rinsed with water, and the cleaning ability was evaluated according to the following criteria based on the tactile sensation of touching the contaminated surface of the touch container at that time. ：: Touching any part of the Tach ゜ container gives a squeaky and frictional feeling and no nulling due to residual oil is felt. C: Touching the smooth surface of the Tach ゜ container gives a feeling of friction, and no oil remains, but nulls remain at the edges and corners. ×: Nulling is felt in the entire Tach ゜ container, and it is apparent that oil has clearly remained.

(Mildness) The mildness was evaluated by a hand immersion test by 20 panelists using a 1% by mass aqueous solution (35 ° C.) of the cleaning composition. That is, the immersion-drying operation was performed 15 times every minute, and the degree of hand roughness after 24 hours was visually judged according to the following criteria. ：: Hardly any rough hands. Δ: Signs of rough skin such as dry desquamation and red spot change are observed on a part of the keratinous surface of the skin. ×: Hand rough symptoms such as dry desquamation and red spot change are clearly observed.

(Storage stability) When 100 mL of the detergent composition was filled in a glass bottle and left in a -5 ° C constant temperature bath for one month,
Further, the appearance when left in a thermostat at 50 ° C. for one month was observed, and the storage stability was evaluated based on the following criteria. ：: No abnormalities in appearance such as generation of precipitates and discoloration were observed in storage under any conditions. Δ: Signs of change in appearance are observed during storage under any one of the conditions. ×: A clear change in appearance is observed during storage of one or both of them.

[Table 2] Example Comparative Example 3 4 5 6 7 3 4 (Component a) S- 115 S-215 20 14 S- 310 R-115 R- 220 (Component b) AOS 5 4 10 2 5 5 2 LAS 2 2 (component c) LAX 5 3 8 3 5 3 5 3 3 LPB 3 3 (component d) LDE 5 6 3 5 5 6 6 LMG 5 (other surfactant) LEO (15) 2 2 2 APG 3 2 3 (Common component) Ethanol 5 Polyethylene glycol 2 Na-toluenesulfonate 5 Na-benzoate 1 Na-citrate 0.2 Fragrance 0.2 Dye Small amount (Evaluation result) (a + b) / c 4 8 2.5 3 4 4 4 Creamy feeling of foam quality ○ ○ ○ ○ ○ ○ △ Detergency ○ ○ ○ ○ ○ ○ × Mildness ○ ○ ○ ○ ○ △ ○ Storage stability ○ ○ ○ ○ ○ △ ○ AOS: C14α olefin sulfonic acid Na LAX: lauryl dime Tylamine oxide LDE: Diethanolamide laurate LEO (15): Polyoxyethylene (15) lauryl ether LAS: C11-C13 Linear alkyl benzene sulfonate Na LPB: Amidopropyl laurate dimethyl dimethyl betaine LMG: Methyl glucamide laurate APG : Lauryl polyglucoside (1.2)

[Table 3] Perfume component content (% by mass) α-pinene 1 Orange oil sweet 40 Orange oil Valencia 12 Coriander oil 2 Citronella oil 2 Sweet fennel oil 1 Mandarin oil 5 Yuzu oil 1 Lime oil 12 Lemongrass oil 1 Lemon oil 20 Citral 2 cis-3-hexenol 10% by mass aqueous ethanol solution 1 Total 100

From Table 2 above, it can be seen that the detergent compositions of Examples 3 to 7 containing the alkyl ether sulfate of the present invention have all the characteristics of foamy creaminess, detergency, mildness and storage stability. It was excellent. On the other hand, the cleaning compositions of Comparative Examples 3 and 4 had a problem in one or more characteristics.

[0073]

As described above, the alkyl ether sulfate of the present invention has a high detergency when mixed with a liquid detergent, and satisfies all the properties of foaming performance, storage stability and mildness. Furthermore, the content of dioxane is low.
Therefore, the liquid detergent containing the alkyl ether sulfate of the present invention has high performance, for example, a liquid detergent for clothing, a detergent for kitchens (dishwashing detergent, etc.), a shampoo, a detergent for homes (floor, glass detergent). Etc.) can be widely used. Further, the alkyl ether sulfate of the present invention can be preferably used for various uses such as an emulsifier and a thickener, in addition to a detergent. And
According to the method for producing an alkyl ether sulfate of the present invention, the high-performance alkyl ether sulfate of the present invention can be produced easily and at low cost.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 1/90 C11D 1/90 17/08 17/08 // C07B 61/00 300 C07B 61/00 300 ( 72) Inventor Masahisa Yoshiya 1-3-7 Honjo, Sumida-ku, Tokyo Lion Corporation (72) Inventor Taku Nishio 1-3-7 Honjo, Sumida Ward, Tokyo Lion Corporation F-term (reference) 4C083 AA122 AC072 AC182 AC302 AC312 AC532 AC642 AC711 AC712 AC791 AC792 AD112 AD212 AD532 BB05 BB06 CC38 DD23 EE01 EE06 4H003 AB13 AB15 AB19 AB31 AC05 AC08 AC13 AC15 AD04 BA12 DA01 DA02 DA05 DA17 EB04 EB07 A03 FA03 A03 FA03 A02 FA02 AB02A AC60 BD70 BE43 4H039 CA61 CF90

Claims (9)

[Claims] 1. An alkyl ether sulfate represented by the following general formula (I), wherein the alkyl ether sulfate is a mixture containing a plurality of molecular species having different numbers of moles of ethylene oxide added. Assuming that nA is the number of moles of ethylene oxide added to the molecular species most present, nA is a positive integer, and the number of moles of ethylene oxide added is (nA-1) to (nA +
An alkyl ether sulfate wherein the proportion of the molecular species in the range of 1) is 55 to 75% by mass, and the 1,4-dioxane content in the mixture is 30 ppm or less. ^{_{R 1 O (CH 2 CH 2}} O) nSO 3 M (I) wherein formula (I), R ¹ is an alkyl or alkenyl group having 6 to 24 carbon atoms linear or branched, n represents the average ethylene The number of moles of added oxide is a number of 1 to 6, and M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, or a carbon atom of 2
Mono-, di- or trialkanol ammonium ions having up to 3 alkanol groups. 2. The alkyl ether sulfate according to claim 1, wherein the proportion of the molecular species having an ethylene oxide addition mole number of nA is 19 to 35% by mass. 3. An alcohol is added with ethylene oxide in the presence of an alkoxylation catalyst containing a composite metal oxide containing magnesium and other metals,
Removing the catalyst from the reaction product obtained thereby,
A method for producing an alkyl ether sulfate, wherein the reaction product is sulfated. 4. The production method according to claim 3, wherein the composite metal oxide contains at least one metal selected from Group 6A, Group 7A, and Group 8, magnesium, and aluminum. 5. The process according to claim 3, wherein the sulfation is carried out using gaseous sulfur trioxide. 6. A liquid detergent composition containing the alkyl ether sulfate according to claim 1 or 2. 7. The liquid detergent composition according to claim 6, wherein the content of the alkyl ether sulfate is 5 to 25% by mass of the whole liquid detergent composition. 8. In addition to the alkyl ether sulfate (a), at least one of a sulfonic acid type anionic surfactant (b), an amine oxide type surfactant and a betaine type surfactant (c) The liquid detergent composition according to claim 6, comprising: 9. An alkyl ether sulfate (a),
The ratio (by mass) of at least one of the sulfonic acid type anionic surfactant (b), the amine oxide type surfactant and the betaine type surfactant (c) is represented by the following formula (II). 9. The relationship as defined in claim 6, wherein
A liquid detergent composition according to any one of the above. 1 ≦ [(a) + (b)] / (c) ≦ 20 (II)