JP2007015939A - Secondary alcohol ethoxylate sulfate salt-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary alcohol ethoxylate sulfate salt-containing composition having such high functions as higher detergency and emulsifying power as anionic surfactant. <P>SOLUTION: The secondary alcohol ethoxylate sulfate salt-containing composition comprises 30-75 mass% of water or a ≤3C alcohol and the balance 25-65 mass% of surfactants, wherein a secondary alcohol ethoxylate sulfate salt of general formula(1)( wherein, (x+y)=5-17; n is an integer of ≥0; p is the valence of M, wherein M is an alkali metal ion, alkaline earth metal ion, ammonium ion or a substituted ammonium ion ) accounts for 80-90 mass% of the surfactants and a secondary alcohol ethoxylate of general formula(2)( wherein, (x+y)=5-17; and n is an integer of ≥0 ) accounts for 10-20 mass% of the surfactants. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a sulfate-containing composition of a secondary alcohol ethoxylate.

Alcohol ethoxylate sulfate is an anionic surfactant with excellent detergency, bubbling power, solubility, emulsifying power, hard water resistance, low temperature stability, foam resistance, biodegradability, and skin irritation. Since it is extremely small, it is used in industrial and household cleaning compositions, cosmetics, and shampoo compositions.

  As anionic surfactants, alkyl allyl sulfonates, primary alcohol sulfates, primary alkyl ether sulfates, secondary alkyl ether sulfates, and the like are known. In particular, linear alkyl benzene sulfonates have a tendency to be regulated because they are poorly biodegradable and have an adverse effect on the environment.

  Alkyl allyl sulfonates and primary alcohol sulfates are easily affected by the hardness of water and have poor water solubility.

  The first alkyl ether sulfate ester salt is not only high in viscosity and easily gelled, but also has insufficient surface activity such as surface tension and osmotic force, and is also insufficient in detergency and emulsification power.

  On the other hand, the known second alkyl ether sulfate salt is easy to handle and has a surface tension because it is less viscous and less gelled than the existing first alcohol sulfate sulfate salt and the first alkyl ether sulfate ester salt. The penetrating power is good, the foam is good, the cleaning power and the emulsifying power are excellent and useful.

Various studies have been made on the production of a sulfate salt of alcohol ethoxylate, and sulfuric acid, chlorosulfonic acid (see Patent Document 1), sulfur trioxide, sulfamic acid (see Patent Document 2), and the like as sulfating agents. Is being considered. Of these, sulfur trioxide is widely used because it is the cheapest. For example, an alcohol ethoxylate of a sulfurized oxide is flowed in a thin film through a vertical cylindrical tube, and diluted with an inert gas in parallel with the thin film flow. Many continuous production methods in which contact is made by flowing sulfur oxide to perform sulfation have been proposed (see Patent Documents 3 and 4).
When a sulfated alcohol ethoxylate produced by a conventionally known one is used as an anionic surfactant, the detergency and emulsification ability are insufficient with respect to contaminants having a large amount of oil and fat components.

Japanese Patent Publication No. 4-25943 Japanese Patent No. 1643141 Specification U.S. Pat. No. 3,839,391 US Pat. No. 4,097,242

An object of the present invention is to provide a secondary alcohol ethoxylate sulfate-containing composition having a higher function with higher detergency and emulsifying power as an anionic surfactant.

In order to solve the above-mentioned problem, 80 to 90% by mass of the second alcohol ethoxylate sulfate salt is contained as a ratio in the surfactant in the composition, and 10 to 20% by mass of the second alcohol ethoxylate is contained. Thus, a sulfate salt-containing composition having high detergency and emulsification ability can be provided.

According to the method of the present invention, a sulfate salt-containing composition having high detergency and emulsification ability can be provided.

The inventors of the present invention have repeatedly investigated a composition containing a second alcohol ethoxylate sulfate salt as a sulfate salt-containing composition having high detergency and emulsifying ability. By coexisting with alcohol ethoxylate, it was surprisingly found that it shows higher detergency against contaminants rich in fats and oils, leading to the present invention.

That is, the present invention relates to the composition of an anionic surfactant.
That is, in the composition containing the second alcohol ethoxylate sulfate salt, the composition is 30 to 75% by mass of water or an alcohol having 3 or less carbon atoms, and the surfactant concentration is 25 to 65% by mass.
The following general formula (1)

(Wherein, x + y = 5 to 17, n is an integer of 0 or more, p represents the valence of M, and M represents an alkali metal ion, alkaline earth metal ion, ammonium ion, or substituted ammonium ion). The present invention relates to a composition containing a second alcohol ethoxylate sulfate salt, in which the second alcohol ethoxylate sulfate salt represented is contained in an amount of 80 to 90% by mass in the surfactant in the composition.
Another invention of the present invention is a composition containing a second alcohol ethoxylate sulfate salt, the composition of which is 30-75% by mass of water or an alcohol having 3 or less carbon atoms, and the surfactant concentration is 25-65. Mass%,
The following general formula (1)

(Wherein, x + y = 5 to 17, n is an integer of 0 or more, p represents the valence of M, and M represents an alkali metal ion, alkaline earth metal ion, ammonium ion, or substituted ammonium ion). The second alcohol ethoxylate sulfate salt represented is contained in an amount of 80 to 90% by mass in the surfactant in the composition, and the following general formula (2)

(In the formula, x + y = 5 to 17, n represents an integer of 0 or more.) The second alcohol ethoxylate represented by 10 to 20% by mass is contained as a proportion in the surfactant in the composition. And a secondary alcohol ethoxylate sulfate salt-containing composition.

The present invention is described in further detail below.
The secondary alcohol ethoxylate used in the present invention can be produced by various methods.

  For example, a method of ethoxylating a secondary alcohol obtained by oxidation of a straight-chain paraffin having 8 to 20 carbon atoms with ethylene oxide or ethylene carbonate. Specifically, Japanese Patent No. 809426 discloses saturated aliphatic carbonization. A method of synthesizing a secondary alcohol by liquid-phase oxidation of hydrogen with a molecular oxygen-containing gas in the presence of a boron compound is described. Japanese Patent No. 764490 discloses alcohols mainly containing a carbonyl compound as an impurity. Is used as a raw material, and a method for producing an alkylene oxide adduct of alcohols is described.

  Further, a method of adding ethylene glycol to an olefin having 8 to 20 carbon atoms, specifically, a long-chain olefin and (poly) alkylene glycol are reacted in the presence of a catalyst in JP-A-10-168018, A process for producing (poly) alkylene glycol monoalkyl ethers is described.

  Various methods can be used for producing the secondary alcohol ethoxylate sulfate salt used in the present invention.

  The second alcohol ethoxylate is used as the raw material alcohol ethoxylate, and sulfuric acid, chlorosulfonic acid, sulfur trioxide, sulfamic acid, or the like is used as the sulfating agent.

  The sulfation reaction of the present invention is an exothermic reaction, and it is preferable to remove heat because more heat than necessary promotes the formation of by-products. The shape of the reactor in the present invention is not particularly limited, and may be a tank type or a tube type. Moreover, a batch type or a continuous type may be sufficient.

  A method of diluting the reaction raw material with a solvent during the reaction is also effective for heat removal.

  When sulfuric acid, chlorosulfonic acid, or sulfamic acid is used as the sulfating agent, a tank reactor equipped with a stirrer or a tube reactor can be used for the reaction. Although the reaction can be carried out either batchwise or continuously, the continuous method is preferred because continuous neutralization is possible.

  The material of the reactor is not particularly limited, but acid-resistant materials such as SUS and glass are preferable from the viewpoint of corrosion of equipment and suppression of decomposition of raw materials and products.

  When sulfur trioxide is used as the sulfating agent, the sulfur trioxide is diluted with an inert gas such as air, nitrogen, carbon dioxide gas or sulfurous acid gas.

  As an example of the shape of the reactor, as the tank reactor, for example, a method in which a reactor equipped with a stirrer is divided into two stages and continuously sulfated (Palesterra method, USP3198849) can be used.

  As a tubular reactor, many thin-film reactors have been proposed in which a reaction raw material is caused to flow in a thin film shape on a tube wall and sulfur trioxide is supplied as a gas in a cocurrent or countercurrent reaction (for example, Verol method: USP 3438742). Allied system: USP3328460, Richard system: JP-B-42-252, Stepan system: JP-B-43-13043, Masony system: USP393272, Chemisson system: USP3839391, Kao system: USP4097242) Any device can be used.

  A particularly preferred reaction system using sulfur trioxide is a tube-type cocurrent thin film reactor.

  The material of the reactor is not particularly limited, but acid-resistant materials such as SUS and glass are preferable from the viewpoint of corrosion of equipment and suppression of decomposition of raw materials and products.

  The sulfur trioxide concentration in the total gas supplied to the reaction zone is 0.1 to 5.0% by volume, and a sulphate with good hue is obtained. More preferably, it is 0.3-3.0 volume%, Most preferably, it is 0.4-2.5 volume%. If it is at least the lower limit, the yield and productivity tend to be improved, and if it is not more than the upper limit, the hue tends to be low.

  The average flow rate of all gases supplied to the reaction zone in the cocurrent thin film reactor is 4 to 100 m / s, more preferably 20 to 80 m / s, and particularly preferably 30 to 60 m / s in terms of linear velocity. . When the amount is not less than the lower limit, diffusion of the second alcohol ethoxylate liquid film by the gas flow is good and the liquid film becomes thin and a uniform reaction occurs, so that the hue of the product is lowered and the yield is improved. When the amount is not more than the upper limit value, the liquid film is retained, so that the yield is improved and the pressure loss in the reactor is reduced, so that the energy consumed for the operation is reduced.

  The feed rate of the raw material second alcohol ethoxylate to the cocurrent thin film reactor is determined by the sulfur trioxide feed rate and the molar ratio of the second alcohol ethoxylate and sulfur trioxide. The raw material molar ratio is 0.8 to 1.2, preferably 0.95 to 1.05 sulfur trioxide with respect to the second alcohol ethoxylate. When the amount is not less than the lower limit, the reaction is completed and the conversion rate of the secondary alcohol ethoxylate is improved, so that the product quantity tends to be improved. When the amount is not more than the upper limit, the raw material is not decomposed, which is preferable.

  The reaction temperature is in the range of -20 ° C to 80 ° C, more preferably 20 ° C to 60 ° C. Since this reaction is an exothermic reaction, in order to control the reaction temperature, it is preferable to have a structure capable of removing heat from the reactor wall surface such as a reactor with a jacket.

  After completion of the reaction, the reaction product is separated from an inert gas containing unreacted sulfur trioxide. Separation may be performed by an ordinary method, and generally a cyclone or the like can be used. In the case of a tank reactor, the separation can be carried out by adding sulfur trioxide up to a set molar ratio, completing the sulfation reaction, and then introducing it into a separation device for gas-liquid separation. In the case of a tubular reactor, it can be carried out by continuously introducing the liquid flowing out from the outlet of the reactor to the separator for gas-liquid separation.

  The reaction product obtained in the present invention is neutralized with an alkaline substance such as caustic soda, ammonia or ethanolamine, and used as a detergent. The neutralization step is preferably performed after gas-liquid separation with a cyclone or the like, preferably within 30 minutes after separation of sulfur trioxide by gas-liquid separation, and more preferably within 15 minutes. In the case of the upper limit or less, the hue is low because it prevents the decomposition reaction of the product, which is a side reaction, by sulfur trioxide that cannot be removed by gas-liquid separation, the product sulfur oxide, other acidic substances, etc. This is preferable because the yield is improved.

  Further, during the neutralization, heat of neutralization is generated due to the reaction between the acid and the base, and the decomposition reaction proceeds when the temperature rises. In order to suppress this decomposition reaction, it is preferable to remove heat, preferably remove to 50 ° C. or less, more preferably 40 ° C. or less. A general method can be applied as the heat removal method. For example, after using a tubular reactor with a jacket, a multi-tubular reactor with a heat exchanger, a tank reactor with a cooling coil, or after diluting with a solvent to cool the sulfate Can be neutralized. Here, the solvent may be any substance that is stable to sulfur trioxide or a basic substance, and examples thereof include water and sulfate salts.

  Surfactants in the present invention include fatty acid salts, α-sulfo fatty acid esters, alkylbenzene sulfonates, alkyl sulfates, alkyl ether sulfate esters, alkyl sulfate triethanolamine and other anionic surfactants, fatty acid diethanolamide, Nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether, cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium chloride and alkylpyridinium chloride, amphoteric interfaces such as alkylcarboxybetaine Includes all active agents.

  As the composition of the second alcohol ethoxylate sulfate salt liquid composition of the present invention, the lower limit of the concentration of the second alcohol ethoxylate sulfate salt in the liquid composition is 20% by mass, preferably 25% by mass. is there. Since a high detergency is obtained above the lower limit, it is preferable. The upper limit is 70% by mass, preferably 65% by mass, and by setting it to the upper limit or less, the second alcohol ethoxylate sulfate salt can be produced with good hue, which is preferable.

  The lower limit of the concentration of the secondary alcohol ethoxylate in the liquid composition is 5% by mass, preferably 10% by mass. The presence of the lower limit value or more is preferable because the detergency and emulsification power are further improved with respect to contaminants with a large amount of oil and fat components as compared with the prior art second alcohol ethoxylate sulfate salt composition. The upper limit is 25% by mass, preferably 20% by mass. By being below the upper limit, the solubilizing ability of the fat and oil component is improved without impairing the emulsifying power and detergency of the second alcohol ethoxylate sulfate salt.

  In the liquid composition, water or alcohol having 3 or less carbon atoms is contained, and the lower limit thereof is 25% by mass, preferably 30% by mass. Since fluidity | liquidity comes out by existing more than a lower limit, it is preferable. The upper limit is 80% by mass, preferably 75% by mass. It is preferable that the concentration is not more than the upper limit value because the surfactant concentration becomes sufficient and the detergency comes out.

  In addition to the above components, the liquid composition can also contain components such as sulfuric acid, sodium sulfate, secondary alcohol, and secondary alcohol sulfate.

  The yield measurement of the sulfate salt is obtained by the Epton method. In the Epton method, methylene blue hydrochloride as an indicator and chloroform as a solvent are added to a target solution, and sodium lauryl sulfate or cetylpyridinium bromide is titrated as a standard solution for a cationic activator. The point that has shifted to is the end point.

There are no particular restrictions on the method for producing the composition containing the second alcohol ethoxylate sulfate salt and the second alcohol ethoxylate. For example, a predetermined amount of the second alcohol ethoxylate sulfate salt and the second alcohol ethoxylate are stirred. It can be produced by mixing in a tank or by suppressing the conversion rate low by the sulfation reaction of the secondary alcohol ethoxylate. At that time, another surfactant, for example, an oxygen-containing compound such as alcohol can be mixed in an amount of about 5% by mass.
Moreover, additives other than surfactant can also be added.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
Detergency is evaluated by the following method.

1. Detergency for kitchen (Evaluation method) Pour oil stain liquid into a dish and dry it to adjust many oil stain dishes. The synthesized surfactant was added to the sponge as an aqueous solution of a predetermined concentration, and the oil stain dish was continuously washed and rinsed until it was visually judged that the oil stain remained without being removed. Count the number of dishes.

(Tableware) Ceramic, diameter 20cm
(Oil stain liquid composition (%)) Beef tallow 10.0, soybean oil 10.0, monoolein 0.25, oil red 0.1, n-hexane 80.0.

(Drying) Temperature 25 ° C. × Time 30 minutes (Synthetic product aqueous solution) Concentration 0.02%, dripping amount onto sponge 20 g
(Sponge) Commercial product for general kitchen cleaning W7.5cm × L11.0cm
(Rinsing water) Tap water.

2. Rinsability (Evaluation Method) A tableware coated with an activator is immersed in still water for a predetermined time, and after being pulled up, the surface is evaluated by touch and the immersion time required until it is determined that no sticky feeling remains is measured.

(Tableware) Ceramic, diameter 20cm
(Temperature) Room temperature (Activator aqueous solution concentration) 0.5%
(Addition amount) 3.0g
(Use water) Pure water.

Example 1 (sulfation reaction)
Using a cylindrical SUS304 reaction tube having an inner diameter of 8 mm and a length of 1.5 m, the reaction was carried out under the condition that the gas-liquid flow was an upward co-current flow. Sulfur trioxide gas diluted to 0.67% by volume with an inert gas (nitrogen) was allowed to flow into the reaction tube from a nozzle provided at the bottom of the reaction tube. The temperature of this mixed gas was 39 ° C. A raw material in which 1 mol of ethylene glycol was added to an olefin having a carbon chain length of 12 was synthesized based on JP-A-10-168018, Example 1. This raw material contained 98.0% by mass of ethylene glycol monododecyl ether, 0.4% by mass of dodecanol, and 1.6% by mass of diethylene glycol monododecyl ether. This raw material was injected into the reaction tube from an injection port provided at the bottom of the reaction tube at a rate of 7.5 g / min, and was raised in a thin film along the inner wall of the reaction tube. The linear velocity of all gases was 40 m / s, and the molar ratio of sulfur trioxide to secondary alcohol ethoxylate was 0.90. Part of the generated heat of reaction was removed by 50 ° C. water flowing outside the reaction tube. The fluid exiting the reaction tube was separated into gas and product by a cyclone. The reaction product was immediately neutralized with an aqueous caustic soda solution to give a 25% by mass aqueous solution of secondary alcohol ethoxylate sulfate.
The yield of the secondary alcohol ethoxylate sulfate salt was 83.3% by the Epton method. Since the yield of the second alcohol ethoxylate sulfate salt is 83.3% by the Epton method, the second alcohol ethoxylate sulfate salt is 83.3 mass% as a proportion in the surfactant, The alcohol ethoxylate was 16.6% by mass. The surfactant content in the composition was 30.0% by mass, water was 69.5% by mass, and the others were obtained as 0.5% by mass.

Example 2
(Sulphation reaction)
The sulfation reaction was carried out by the method of Example 1 except that the secondary alcohol ethoxylate was adjusted to a rate of 8.0 g / min, that is, the molar ratio of sulfur trioxide to the secondary alcohol ethoxylate was 0.96.
The yield of the secondary alcohol ethoxylate sulfate was 89.0% by the Epton method.
Since the yield of the second alcohol ethoxylate sulfate salt is 89.0% by the Epton method, the second alcohol ethoxylate sulfate salt is 89.0% by mass as a proportion in the surfactant, The alcohol ethoxylate was 11.0% by mass. The surfactant content in the composition was 28.1% by mass, water was 71.3% by mass, and the others were 0.6% by mass.

Comparative Example 1
(Sulphation reaction)
The sulfation reaction was carried out by the method of Example 1 except that the secondary alcohol ethoxylate was set at a rate of 8.4 g / min, that is, the molar ratio of sulfur trioxide to the secondary alcohol ethoxylate was 1.01.
The yield of the secondary alcohol ethoxylate sulfate was 93.3% by the Epton method.
Since the yield of the secondary alcohol ethoxylate sulfate is 93.3% by the Epton method, the secondary alcohol ethoxylate sulfate is 93.3% by mass as a proportion in the surfactant, The alcohol ethoxylate was 6.6% by mass. The surfactant content in the composition was 26.8% by mass, water was 72.6% by mass, and the others were obtained as 0.6% by mass.
An evaluation test was performed on the surfactants obtained in Examples 1 and 2 and Comparative Example 1, and the results are shown in Table 1.

Compared with the comparative example, the number of washed sheets is improved by increasing the proportion of the secondary alcohol ethoxylate in the surfactant.

Since the composition of the present invention is excellent in detergency and emulsifying power, it is useful as industrial and household detergent compositions, cosmetics, and shampoo compositions.

Claims (2)

In the second alcohol ethoxylate sulfate salt-containing composition, the composition is water, or the content of the alcohol having 3 or less carbon atoms is 30 to 75 mass%, the surfactant is 25 to 65 mass%,
The following general formula (1)

(Wherein, x + y = 5 to 17, n is an integer of 0 or more, p represents the valence of M, and M represents an alkali metal ion, alkaline earth metal ion, ammonium ion, or substituted ammonium ion). The 2nd alcohol ethoxylate sulfate salt containing composition by which 80-90 mass% of the 2nd alcohol ethoxylate sulfate salt represented is contained as a ratio in surfactant in this composition. The following general formula (2)

(In the formula, x + y = 5 to 17, n represents an integer of 0 or more.) The second alcohol ethoxylate represented by 10 to 20% by mass is contained as a proportion in the surfactant in the composition. The composition containing a secondary alcohol ethoxylate sulfate salt according to claim 1.