JP5422110B2 - Surfactant composition - Google Patents

Description

  The present invention relates to a surfactant composition. Specifically, it relates to a surfactant composition containing a polyoxyalkylene alkyl ether sulfate ester salt.

  A polyoxyalkylene alkyl ether sulfate salt is an anionic surfactant comprising a sulfate ester salt of a higher alcohol or its alkylene oxide adduct, has little irritation to the skin, and is a liquid cleanser such as dishwashing detergent, shampoo, clothing It is widely used as a main active agent for detergents.

  In the polyoxyalkylene alkyl ether sulfate ester salt, the influence of the alkyl group on detergency and stability in the composition is extremely large. When the alkyl group is linear, the detergency is excellent, but in terms of stability, precipitation at low temperature, gelation, etc. occur, and when the alkyl group is branched, the alkyl chain is linear compared to Although the cleaning power is slightly inferior, the stability is good.

  Further, polyoxyalkylene alkyl ether sulfates are not a single substance because of their general production method, and are mainly distributed as compositions containing water. The content of a general polyoxyalkylene alkyl ether sulfate salt in the composition is less than 30% by mass or around 70% by mass from the solution physical properties. When the content is less than 30% by mass, it cannot be said that it is preferable in terms of the capacity and production efficiency of the composition storage tank and reaction tank, transportation costs, and the like. Therefore, it is desirable that the concentration be as high as possible. On the other hand, if it exceeds 80% by mass, it is not preferable in terms of handling because of lack of fluidity.

  Thus, a composition containing a polyoxyalkylene alkyl ether sulfate ester salt at a high concentration is useful in the industrial stage, and various techniques for obtaining such a composition have been proposed. Patent Document 1 discloses that a solution containing ethanol, water, and higher secondary alcohol ethoxylate sulfate ester salt in a predetermined ratio can be obtained by a predetermined production method. Patent Document 2 discloses that among the polyoxyalkylene alkyl ether sulfate esters, compounds having a structure in which the alkyl group is secondary can be blended at a high concentration. Patent Document 3 discloses that a liquid surface active composition containing alcohol ethoxyl sulfate at a high concentration and substantially free of lower alcohols such as ethanol and methanol can be obtained by a predetermined production method. ing. Patent Document 4 discloses that a surfactant composition having a high concentration and a low viscosity can be obtained by combining a nonionic surfactant with an anionic surfactant such as a polyoxyalkylene alkyl ether sulfate ester salt. Is disclosed.

As compositions for various uses in which a polyoxyalkylene alkyl ether sulfate salt is blended, Patent Document 5 discloses an aqueous hair cleaner, and Patent Document 6 discloses a liquid detergent composition for dishwashing.
JP-A-49-15706 JP 57-149263 A JP-A-3-93900 International Publication No. 98/24865 Pamphlet JP 2004-203866 A JP-A-6-240292

  In the case of producing a secondary polyoxyalkylene alkyl ether sulfate salt described in Patent Document 2, in general sulfation, there is a problem in basic quality as a surfactant, such as deterioration of hue and unique odor. is there. On the other hand, in the case of the primary polyoxyalkylene alkyl ether sulfate, there is no such quality problem, so that stable quality can be obtained without using special production conditions and equipment.

  However, in the primary polyoxyalkylene alkyl ether sulfate ester salt, the structure of the alkyl group, the number of moles of alkylene oxide added, the counter ion, etc. greatly affect the physical properties and performance. In general, the polyoxyalkylene alkyl ether sulfate salt is distributed as a product blended at a concentration of about 20 to 30% by weight, but the stability from low temperature to room temperature may be impaired. An object of the present invention is to provide a liquid surfactant composition containing a polyoxyalkylene alkyl ether sulfate ester salt at a suitable concentration as a product and having excellent stability.

  The inventors of the present invention have reported that polyoxyalkylene alkyl ether sulfates, which have been conventionally obtained as a uniform and stable liquid, are stable liquids depending on the structure of the alkyl group, the number of added alkylene oxides, the counter ion, and the like. It has been found that the optimum composition for obtaining the difference is different. And it discovered that a stable liquid substance was obtained when the polyoxyalkylene alkyl ether sulfate ester salt which has a specific counter ion, ethanol, and water were combined with a specific composition.

The present invention includes (a) a compound represented by the following general formula (1) [hereinafter referred to as component (a)] 23 to 27% by mass, (b) ethanol (hereinafter referred to as component (b)) 3 to 7 mass. % And (c) water (hereinafter referred to as “component (c)”) 66 to 74% by mass.
_{RO (AO) n SO 3 M} (1)
(In the formula, R represents a hydrocarbon group having 8 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, M represents ammonium or alkanol ammonium, and n represents an average value of 0.85 to 0.85. The number of 1.35 is shown.)

  According to the present invention, there is provided a surfactant composition having a high concentration of the component (a) which is an active ingredient, excellent stability of the composition, and particularly capable of maintaining a uniform liquid state even from low temperature to room temperature (for example, 20 to 30 ° C.). can get.

[(A) component]
In the formula (1), R is preferably a linear or branched alkyl group or alkenyl group having 12 to 20 carbon atoms. When R has 9 to 24 carbon atoms, the polyoxyalkylene alkyl ether sulfate ester salt has a good balance of surface activity and solubility in water. Examples of the alkyl group and alkenyl group include various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, various icosyl groups, various docosyl groups, various octadecenyl groups, and the like.

  Examples of the alkylene group having 2 to 4 carbon atoms (linear or branched) represented by A include an ethylene group, a propylene group, a 1-methyltrimethylene group, a trimethylene group, and a tetramethylene group. Among these, an ethylene group and a propylene group are particularly preferable.

  Examples of M include ammonium and alkanol ammonium, and among these, ammonium is preferable. n is a number in the range of 0.85 to 1.35 on average, and indicates a suitable performance in cleaning agent applications (for example, cleaning performance).

  The polyoxyalkylene alkyl ether sulfate ester salt can be obtained by sulfating a higher alcohol or an alkylene oxide adduct thereof and then neutralizing it. Specific examples of higher alcohols include natural alcohols derived from coconut oil, palm oil, beef tallow and the like, and synthetic higher alcohols obtained by the oxo method, Ziegler method, paraffin direct oxidation method, and the like. The higher alcohol may be saturated or unsaturated, may be primary or secondary, and may be either linear or branched, but is preferably saturated or primary. The alkylene oxide adduct is preferably an ethylene oxide and / or propylene oxide adduct of the higher alcohol. Among these, an ethylene oxide adduct having an average addition mole number of 0.85 to 1.35 is particularly preferable.

  Examples of the sulfating agent used for sulfating a higher alcohol or an alkylene oxide adduct thereof include sulfur trioxide gas and chlorosulfonic acid. From the viewpoint of reducing the amount of chloride in the resulting anionic surfactant composition, it is preferable to use sulfur trioxide gas.

  There is no restriction | limiting in particular in the method of sulfation, It can carry out by a conventional method. For example, using a thin film type continuous reaction apparatus, diluted with an inert gas such as air or nitrogen, preferably with a sulfur trioxide gas having a concentration of 1 to 30% by volume, more preferably 1 to 20% by volume, higher alcohol or The alkylene oxide adduct can be sulfated. When the concentration of sulfur trioxide is in the range of 1 to 30% by volume, the gas volume is not too large and excessive reaction can be suppressed.

  The amount of sulfur trioxide used is usually in the range of stoichiometric amount × (0.95 to 1.05), preferably in the range of stoichiometric amount × (0.97 to 1.01). If the amount of sulfur trioxide used is within the above range, the amount of unreacted substances can be reduced, and the production of colored components and odorous components (for example, lower aldehydes, lower ketones, cyclic ethers, etc.) as by-products can be suppressed. be able to.

  The reaction apparatus is not particularly limited, and for example, a tank reaction apparatus, a thin film reaction apparatus, or the like can be used. As the thin film reactor, for example, a falling thin film reactor, a rising thin film reactor, a tubular gas-liquid mixed phase flow reactor, or the like can be used. The reaction time when using a thin film reactor is about 10 to 300 seconds.

  The sulfation temperature is preferably 15 to 70 ° C, more preferably 15 to 50 ° C. If it is 15 degreeC or more, the local excess reaction by fluid fall can be suppressed more, and if it is 70 degrees C or less, decomposition | disassembly of a product can be suppressed more.

  The polyoxyalkylene alkyl ether sulfate ester salt obtained as described above is neutralized so that the concentration of the compound becomes an aqueous solution of 23 to 27% by mass. Using this, the components (a) to (c) are finally adjusted so as to have the desired ratio of the present invention. In addition, it is preferable from the simplicity of a manufacturing method etc. to neutralize by mixing (b) component with neutralizer (ammonia etc.) or its aqueous solution.

  The surfactant composition of this invention contains 23-27 mass% of polyoxyalkylene alkyl ether sulfates which are (a) components. In the present invention, the “polyoxyalkylene alkyl ester sulfate ester salt” includes those having a structure other than an alkyl group such as an alkenyl group for the sake of convenience.

[Component (b)]
The component (b) is ethanol, and the surfactant composition of the present invention contains 3 to 7% by mass of the component (b).

[Component (c)]
The water of component (c) is (a), (b) component, the unreacted component, and the balance of inorganic salts in the surfactant composition of the present invention, and the content in the composition is 66 to 74% by mass. It is.

[Surfactant composition]
In the surfactant composition of the present invention, when the ratio of the components (a) to (c) is 100% by mass of the total of these three components, the point (V) [(a) component = 23% by mass, ( b) component = 6 mass%, (c) component = 71 mass%], point (W) [(a) component = 27 mass%, (b) component = 6 mass%, (c) component = 67 mass%] , Point (X) [(a) component = 26 mass%, (b) component = 4 mass%, (c) component = 70 mass%], point (Y) [(a) component = 24 mass%, (b ) Component = 3 mass%, (c) component = 73 mass%], and point (Z) [(a) component = 23 mass%, (b) component = 3 mass%, (c) component = 74 mass%] Are preferably within a range surrounded by a straight line connecting the five points, more preferably a point [(a) component = 23 mass%, (b) component = 6 mass%, (c) component = 71 mass%]. , Point [(a) = 25 mass%, (b) component = 6 mass%, (c) component = 69 mass%], point [(a) component = 25 mass%, (b) component = 4 mass%, (c) component = 71 Mass%], and points [(a) component = 23 mass%, (b) component = 4 mass%, (c) component = 73 mass%] contained in a ratio within a range surrounded by a straight line connecting the four points It is preferable from the viewpoint of maintaining the stability of the composition, particularly the stability against temperature change.

  The surfactant composition of the present invention may contain components other than the components (a) to (c) as long as the stability of the composition can be maintained. Preferably, the total of the components (a) to (c) is 90% by mass or more, and further 95% by mass or more in the composition.

  The surfactant composition of the present invention has good fluidity and can be obtained as a stable liquid. Here, good fluidity means a liquid state at room temperature (30 ° C.), and the viscosity is 10,000 mPa · s or less, more preferably 3000 mPa · s or less, more preferably 1000 mPa · s or less, particularly preferably 300 mPa · s. That is s or less.

  Other components that can be added include polyoxyalkylene alkyl ether remaining after the sulfation reaction, inorganic sulfate produced as a by-product during neutralization, excess neutralizing agent, and pH buffer such as phosphate and citrate. Agents, preservatives, antibacterial agents, metal chelating agents and the like. However, the content of the higher alcohol having more than 8 carbon atoms or its alkylene oxide adduct is preferably 1% by mass or less from the viewpoint of maintaining a stable liquid and adjusting the viscosity of the solution.

  The surfactant composition of the present invention comprises (1) an ammonium salt or alkanolamine salt of sulfuric acid, (2) an ammonium salt or alkanolamine salt of hydrochloric acid, and (3) an ammonium salt or alkanolamine salt of phosphoric acid. It is preferable that the content of each is 1% by mass or less from the viewpoint of suppressing the increase in the viscosity of the composition, particularly improving the fluidity at low temperatures.

  Thus, when adjusting the surfactant composition to the desired viscosity, the content of the remaining polyoxyalkylene alkyl ether, the inorganic sulfate salt formed as a by-product during neutralization, and the respective additives is appropriately adjusted. Can be achieved.

  The surfactant composition of the present invention preferably has a pH (20 ° C.) of 8 or less from the viewpoint of odor. Moreover, the surfactant composition of the present invention can be suitably used as a component of a liquid detergent composition. In this case, auxiliary agents such as pigments, fragrances, solubilizers, and builders can be appropriately added to the liquid detergent composition as necessary. Furthermore, other anionic surfactants, cationic surfactants, amphoteric surfactants, amide type nonionic surfactants and the like can be added for the purpose of adjusting detergency and foaming. Such a liquid detergent composition is used, for example, in shampoos, body shampoos, kitchen detergents, liquid soaps and the like.

  Further, the surfactant composition of the present invention has a viscosity of 10,000 mPa · s or less, preferably 2000 mPa · s or less, more preferably 500 mPa · s or less, and particularly preferably 200 mPa · s or less at normal temperature (30 ° C.). It is preferable.

Examples 1-6
Ethanolate of alcohol (average ethylene oxide) obtained by mixing 75/25 by weight ratio of higher alcohols mainly having 12 and 14 carbon atoms (trade name; Calcoal 2098 and 4098 manufactured by Kao Corporation) with a thin-film sulfation reactor The added mole number 1.0) is sulfated with sulfur trioxide gas diluted with dry air and is an aqueous ammonia solution containing ethanol, and the concentration of polyoxyethylene alkyl ether ammonium sulfate salt (component (a)) is 23 to 27 masses. %, Ethanol [(b) component] was neutralized so as to obtain an aqueous solution having a concentration of 3 to 6% by mass. The viscosity and appearance of the prepared sample were evaluated by the following methods. The results are shown in Table 1.

<Viscosity>
The prepared sample was allowed to stand for 1 hour in a thermostatic bath set to a measurement temperature, and then measured using a digital viscometer (DVL-B II type) manufactured by Tokimec Corporation. The viscosity was measured at 30 ° C.

<Appearance>
The prepared sample was allowed to stand at 20 ° C. for one day in a thermostatic bath where the temperature in the bath can be controlled to be constant, and the state was visually observed.

Comparative Examples 1-2
After concentrating the reaction product containing the polyoxyethylene alkyl ether sulfate ester salt obtained by the same method as in Examples 1 to 6 to remove volatile components, the polyoxyethylene alkyl ether sulfate ammonium salt (component (a)) It prepared so that it might become an aqueous solution whose density | concentration is 23-26 mass% and the density | concentration of ethanol [(b) component] is 0-2 mass%. Table 1 shows the results of evaluating the prepared samples in the same manner as in Example 1 and the like.

(note)
AES (1): R in general formula (1) is a linear alkyl group having 12 and 14 carbon atoms, A is an alkylene group having 2 carbon atoms, M is ammonium, and n is 1.0

It is a triangular chart which shows an example of the suitable composition of (a)-(c) component in the surfactant composition of this invention.

Claims (5)

(A) Compound represented by the following general formula (1) [hereinafter referred to as component (a)] 23 to 27 mass%, (b) ethanol (hereinafter referred to as component (b)) 3 to 7 mass%, and ( c) Water [hereinafter referred to as component (c)] 66-74% by mass A surfactant composition having good fluidity, wherein the total of components (a) to (c) is in the composition, Surfactant composition which is 95 mass% or more .
_{RO (AO) n SO 3 M} (1)
(In the formula, R represents a hydrocarbon group having 8 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, M represents ammonium or alkanol ammonium, and n represents an average value of 0.85 to 0.85. The number of 1.35 is shown.)   The component (a), component (b), and component (c) are the points (V) [(a) component = 23 mass%, component (b) in the triangle chart of FIG. = 6 mass%, (c) component = 71 mass%], point (W) [(a) component = 27 mass%, (b) component = 6 mass%, (c) component = 67 mass%], point ( X) [(a) component = 26 mass%, (b) component = 4 mass%, (c) component = 70 mass%], point (Y) [(a) component = 24 mass%, (b) component = 3 mass%, (c) component = 73 mass%], and point (Z) [(a) component = 23 mass%, (b) component = 3 mass%, (c) component = 74 mass%] The surfactant composition according to claim 1, which is contained in a ratio within a range surrounded by a straight line connecting the two.   The surfactant composition according to claim 1 or 2, wherein the content of a higher alcohol having 8 or more carbon atoms or an alkylene oxide adduct thereof is 1% by mass or less.   (1) Ammonium salt or alkanolamine salt of sulfuric acid, (2) Ammonium salt or alkanolamine salt of hydrochloric acid, and (3) Ammonium salt or alkanolamine salt of phosphoric acid are each 1% by mass or less. The surfactant composition according to any one of claims 1 to 3. The surfactant composition according to any one of claims 1 to 4, wherein the viscosity at 30 ° C is 1000 mPa · s or less.

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