JP2009120664A - Surfactant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surfactant composition expressing good thickening effect even in the case of low inorganic salt concentrations. <P>SOLUTION: The surfactant composition contains a compound expressed by general formula (1) and a compound expressed by general formula (2), wherein formulas (1) and (2) are defined by R<SP>1</SP>O-(EO)<SB>m</SB>SO<SB>3</SB>M (1) and R<SP>2</SP>O-(AO)<SB>n</SB>SO<SB>3</SB>M (2), respectively, (in the formulas, R<SP>1</SP>and R<SP>2</SP>may be each independently an 8-24C alkyl group; EO is an ethyleneoxy group; AO is a 3-4C alkyleneoxy group; m is an average addition molar number of ethylene oxide and 0≤m≤3; n is an average addition molar number of an alkylene oxide and 0<n≤3; and M is a cation). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel surfactant composition, and specifically relates to a surfactant composition containing an alkyl ether sulfate ester salt having a specific structure.

  Examples of the anionic surfactants currently used for general purposes include alkyl sulfate ester salts (AS) and alkyl ether sulfate ester salts (AES). These are widely used not only for household purposes such as dishwashing detergents, shampoos, body washing agents, clothing detergents, and residential detergents, but also for chemical products such as emulsifiers for emulsion polymerization and dyeing aids. In general, these active agents are blended at a low concentration of about 20% by mass or less in the product blending system. However, in this concentration range, the AS and AES aqueous solutions are low-viscosity. It was necessary to adjust to an appropriate viscosity (Patent Documents 1 and 2). Therefore, many thickeners have been studied so far.

  Conventionally, as a thickener in various surfactants, fatty acid alkanolamides that are less irritating to skin and hair, such as fatty acid monoethanolamide (Patent Document 3), fatty acid diglycolamide, and fatty acid diethanolamide Was preferred. However, although fatty acid monoethanolamide and fatty acid diglycolamide are extremely excellent in thickening action, they have a high melting point, and therefore have the disadvantage of poor solubility when incorporated into detergents and cosmetics. Had. In particular, fatty acid monoethanolamide causes turbidity and blurring when stored in a large amount or stored at a low temperature, and therefore its use amount, product form, and application are limited.

Further, as a method for thickening an anionic surfactant aqueous solution, there is a method (thickening) in which an inorganic salt such as sodium chloride or sodium sulfate is added and the aqueous solution concentration is increased by aggregation of micelles. Inorganic salts are widely used because they are more soluble than the thickeners described above. However, the thickening effect with respect to the amount added is low, and a large amount of inorganic salt must be added when adjusting to the desired viscosity. A large amount of salt has problems such as viscosity change and irritation during washing.
JP 55-84399 A JP 56-72092 A JP 61-114727 A

  Accordingly, the present inventors have started searching for an anionic surfactant composition that has an excellent thickening effect, that is, an excellent thickening effect even when the inorganic salt concentration is low. If a surfactant composition having an excellent thickening effect is obtained, it is considered that the thickening behavior can be controlled with the cleaning component, and the use of the anionic surfactant as a raw material for various products can be expanded. .

  As a result of intensive studies, the present inventors have found that a surfactant composition containing a specific alkyl ether sulfate ester salt can provide an excellent thickening effect, and an aqueous solution can be prepared without changing the salt concentration. It has been found that the viscosity can be increased and the degree of viscosity increase can be controlled. Furthermore, it has been found that the advantageous effects are also exhibited in various products (for example, detergent compositions) derived from the surfactant composition.

The present invention relates to a surfactant composition obtained by mixing the compounds represented by the following general formula (1) and the following general formula (2).
R ¹ O— (EO) _m SO ₃ M (1)
_{^{R 2 O- (AO) n SO}} 3 M (2)
(In the formula, R ¹ and R ² represent the same or different alkyl group having 8 to 24 carbon atoms, EO is an ethyleneoxy group, and AO is an alkyleneoxy group having 3 or 4 carbon atoms. (The number of moles of ethylene oxide added is 0 ≦ m ≦ 3, n is the number of moles of alkylene oxide added and 0 <n ≦ 3. M is a cation.)

  The present invention also relates to a cleaning composition containing the surfactant composition of the present invention.

Moreover, this invention relates to the method of adding the compound represented by following General formula (2) to the aqueous solution containing an inorganic salt and an anionic surfactant, and making the said aqueous solution thick.
_{^{R 2 O- (AO) n SO}} 3 M (2)
(In the formula, R ² represents an alkyl group having 8 to 24 carbon atoms, AO represents an alkyleneoxy group having 3 or 4 carbon atoms, and n represents an average added mole number of alkylene oxide. 0 <n ≦ 3. (M is a cation.)

  The surfactant composition of the present invention exhibits good sensitivity to inorganic salts and has a high thickening effect. Further, the thickening behavior can be controlled by adding the compound of the general formula (2) without changing the inorganic salt concentration.

The surfactant composition of the present invention can be obtained by mixing a compound represented by the following general formula (1) and a compound represented by the following general formula (2) at an arbitrary ratio.
R ¹ O— (EO) _m SO ₃ M (1)
_{^{R 2 O- (AO) n SO}} 3 M (2)
(In the formula, R ¹ and R ² represent the same or different alkyl group having 8 to 24 carbon atoms, EO is an ethyleneoxy group, and AO is an alkyleneoxy group having 3 or 4 carbon atoms. (The number of moles of ethylene oxide added is 0 ≦ m ≦ 3, n is the number of moles of alkylene oxide added and 0 <n ≦ 3. M is a cation.)

  Here, the alkyl group of R in the general formulas (1) and (2) preferably has 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms. Furthermore, it is preferable that it is a linear alkyl group derived from fats and oils from the viewpoint of performance such as foaming power and emulsifying power and environmental aspects such as carbon neutral.

  Further, m in the general formula (1) is a number of 0 ≦ m ≦ 3 indicating the average number of moles of ethylene oxide added, and for the convenience of adjusting the thickening effect, preferably 0 ≦ m ≦ 2. 5, more preferably 0.1 ≦ m ≦ 2, particularly preferably 1 ≦ m ≦ 2.

  In the general formula (2), n is the average number of added moles of an alkylene oxide having 3 or 4 carbon atoms, and 0 <n ≦ 3. Therefore, preferably 0.1 ≦ n ≦ 2, more preferably 0.1 ≦ n ≦ 1.6, more preferably 0.2 ≦ n ≦ 1, and particularly preferably 0.5 ≦ n ≦ 1. .

  When considering comprehensively the reactivity, thickening performance, and convenience of adjusting the thickening effect at the time of production, the compound represented by the general formula (2) and the compound represented by the general formula (1) The average added mole number of AO and EO is preferably 0.1 to 2 for AO and 0 to 2.5 for EO, more preferably 0.2 to 1 for AO and 0 to 2 for EO. Particularly preferably, AO is 0.5 to 1 and EO is 1 to 2.

  The surfactant composition of the present invention is obtained by mixing the compound of the general formula (1) and the general formula (2). The compound represented by the general formula (1) [compound (1)] And a compound obtained by mixing the compound represented by the general formula (2) [compound (2)] under the condition satisfying the following formula (α) is preferable from the viewpoint of thickening performance.

  Here, the formula (α) means that the average added mole number of AO with respect to the total mole number of the compound (1) and the compound (2) is more than 0 and less than 2.

  Moreover, M in general formula (1) and general formula (2) is a cation group which forms a salt, and may be the same or different. Specific examples include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions such as triethanolammonium ions. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the alkaline earth metal include calcium. Among these, sodium and potassium are more preferable, and sodium is particularly preferable.

  The surfactant composition of the present invention is produced and used in the form of an aqueous solution or a hydrous paste from the viewpoint of handleability, and is represented by the compound represented by the general formula (1) and the following general formula (2). It may consist of compounds. Furthermore, it may be composed of a compound represented by the general formula (1), a compound represented by the following general formula (2), and water.

Although the compound represented by General formula (1) used for the surfactant composition of this invention is not specifically limited, For example, it manufactures from the process containing the following processes (I) and (II). be able to.
Step (I): A step of adding ethylene oxide in an average range of 0 <m ≦ 3 mol to 1 mol of an alcohol having an alkyl group having 8 to 24 carbon atoms.
Step (II): A step of sulfating and then neutralizing an alcohol having an alkyl group having 8 to 24 carbon atoms or the alkoxylate obtained in Step (I).

Although the compound represented by General formula (2) used for the surfactant composition of this invention is not specifically limited, For example, from the process containing the following processes (I ') and (II'). Can be manufactured.
Step (I ′): Step of adding propylene oxide or butylene oxide in an average range of 0 <n ≦ 3 mol to 1 mol of alcohol having an alkyl group having 8 to 24 carbon atoms: Step (II ′): Sulfating and then neutralizing the alkoxylate obtained in I ′).

  Step (I) is a step in which ethylene oxide is added to an alcohol having an alkyl group having 8 to 24 carbon atoms, preferably a linear alkyl group, in an average of more than 0 mol and 3 mol or less. Although the alkyl group of the alcohol used in the present invention is an alkyl group having 8 to 24 carbon atoms, it is preferably 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, because of the versatility and handling properties of the raw materials. Yes, and particularly preferably, it has 12 to 14 carbon atoms. Furthermore, a linear alkyl group is preferable for reasons such as foaming power and emulsifying power.

  Further, the amount of ethylene oxide used per 1 mol of the alcohol is more than 0 mol and a number of 3 mol or less, but for reasons of thickening performance, it is preferably 0.1 to 2.5 mol, more Preferably it is 0.5-2 mol.

  Step (I ′) is a step of adding propylene oxide or butylene oxide to an alcohol having an alkyl group having 8 to 24 carbon atoms, preferably a linear alkyl group, in an average range of more than 0 mol and 3 mol or less. . Although the alkyl group of the alcohol used in the present invention is an alkyl group having 8 to 24 carbon atoms, it is preferably 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, because of the versatility and handling properties of the raw materials. Yes, and particularly preferably, it has 12 to 14 carbon atoms. Furthermore, a linear alkyl group is preferable for reasons such as foaming power and emulsifying power.

  Moreover, although the usage-amount of propylene oxide with respect to 1 mol of said alcohol and a butylene oxide is more than 0 mol and a number of 3 mol or less, it is 0.1-2 mol preferably for the reason of thickening performance. More preferably, it is 0.2-1 mol.

  As a method for performing the steps (I) and (I ′), a conventionally known method can be used. That is, by adding 0.5 to 1 mol% KOH or the like as a catalyst in an autoclave as a catalyst, heating and dehydrating, and adding and reacting a predetermined amount of alkylene oxide at a temperature of 110 to 160 ° C. Can be manufactured. The autoclave to be used is preferably provided with a stirring device, a temperature control device, and an automatic introduction device.

  In steps (II) and (II ′), an alcohol having an alkyl group having 8 to 24 carbon atoms, preferably a linear alkyl group, or the alkoxylate obtained in steps (I) and (I ′) is sulfated. And then neutralizing. Examples of the sulfation method include methods using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid, and the like, and particularly prevent the generation of waste sulfuric acid and waste hydrochloric acid. From the viewpoint, a method in which sulfur trioxide is continuously supplied in a gaseous or liquid state simultaneously with the alkoxylate is preferable.

  As a method for neutralizing the sulfate, batch type, which performs neutralization while adding and stirring the sulfate to a predetermined amount of neutralizer, and continuously supplying the sulfate and neutralizer into the pipe, stirring and mixing Although the continuous type etc. which neutralize with a machine are mentioned, in this invention, there is no limitation in the neutralization method. Examples of the neutralizing agent used here include an aqueous alkali metal solution, aqueous ammonia, and triethanolamine, but an aqueous alkali metal solution is preferred, and sodium hydroxide is more preferred.

  The surfactant composition of the present invention comprises a compound [compound (1)] represented by the above general formula (1) and a compound [compound (2)] represented by the above general formula (2). In total, 5 to 80% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 25% by mass.

  In the surfactant composition of the present invention, the ratio of the compound (1) in the total amount of the compound (1) and the compound (2) is 20 to 95% by mass, more preferably 30 to 80% by mass, particularly 50 to 80% by mass. %, And the ratio of the compound (2) is preferably 5 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 20 to 50% by mass.

  In addition, the surfactant composition of the present invention can also contain an inorganic salt. Specifically, the total amount of the compound (1) and the compound (2) is 5 to 27% by mass, and one or more inorganic substances selected from alkali metal salts such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid. A surfactant composition containing 1 to 3% by mass, preferably 1 to 2% by mass of salt, and water and having a viscosity at 30 ° C. of 10 to 3000 mPa · s is provided. This viscosity is measured under the conditions of Examples described later.

  The surfactant composition of the present invention may consist essentially of the compound represented by the general formula (1), the compound represented by the general formula (2), an inorganic salt, and water. Here, “substantially” means a state containing 90 to 100% by mass of the four components of the compound.

As an example of the surfactant composition of the present invention, the mixture of the following (A) and (B) can obtain a good thickening effect even when the inorganic salt concentration is low, and the blending amount of (B) By adjusting, it is possible to control the thickening behavior.
(A) Alkyl sulfate ester salt obtained by sulfating / neutralizing an alkoxylate obtained by adding 0 to 2.5 mol of ethylene oxide on average with respect to 1 mol of a mixed alcohol having 12/14 carbon atoms.
(B) Alkyl sulfate ester salt obtained by sulfating / neutralizing an alkoxylate obtained by adding 0.1 to 2 moles of propylene oxide on average with respect to 1 mole of a mixed alcohol having 12/14 carbon atoms.

  This invention also includes the manufacturing method of surfactant composition which mixes a compound (1) and a compound (2) so that the following formula ((alpha)) may be satisfy | filled.

<Cleaning agent composition>
Since the surfactant composition of the present invention has a characteristic of being excellent in the thickening effect, it can be blended into various products such as a detergent composition and a cosmetic composition according to its use and purpose. . In particular, it is effective in a detergent composition for which a thickening effect is desired. Examples of the cleaning composition include a cleaning composition for body (including hair), a cleaning composition for clothing, a cleaning composition for hard surfaces, and the like.

  The content of the surfactant composition of the present invention in the cleaning composition is preferably 0.5 to 27 mass%, more preferably 1 to 25 mass% as the total content of the compounds (1) and (2). %, More preferably 5 to 25% by mass, particularly preferably 5 to 20% by mass.

  In addition to the surfactant composition of the present invention, the detergent composition includes a surfactant, a viscosity modifier, a foam-increasing agent, an alkali agent, a metal sequestering agent, an antiseptic, a fragrance, and a pigment that are usually used in this field Inorganic salts can be blended. The inorganic salt is preferably one or more inorganic salts selected from alkali metal salts such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carbonic acid and phosphoric acid, and more preferably an alkali metal salt of hydrochloric acid such as sodium chloride. . Further, the content of the inorganic salt is preferably 1 to 3% by mass, particularly preferably 1 to 2% by mass in the cleaning composition.

  Examples of the inorganic salt of the cleaning composition of the present invention and the surfactant composition of the present invention include sodium chloride, potassium chloride, sodium bromide, sodium sulfate, sodium nitrate, sodium carbonate, sodium monohydrogen phosphate, diphosphoric acid phosphate. Sodium hydrogen and the like are exemplified, but sodium chloride, potassium chloride, sodium sulfate and sodium carbonate are preferable, and sodium chloride and sodium sulfate are more preferable.

<Thickening method of aqueous anionic surfactant solution>
According to the present invention, there is provided a method of adding a compound represented by the above general formula (2) to an aqueous solution containing an inorganic salt and an anionic surfactant to thicken the aqueous solution. Examples of the anionic surfactant to be subjected to this method include alcohol-based anionic surfactants such as alkyl sulfate ester salt (AS) and alkyl ether sulfate ester salt (AES). Moreover, the aqueous solution used as the object of this method includes one having a viscosity (initial viscosity) before addition of the compound represented by the general formula (2) of 10 to 3000 mPa · s (30 ° C.). It is preferable to contain an anionic surfactant and an inorganic salt so that As the inorganic salt, those described above are used. By adding the compound represented by the general formula (2), the initial viscosity is preferably increased by 200 to 4000%, and the amount of the compound of the general formula (2) is preferably an amount that satisfies this.

Example 1 and Comparative Example 1
Average PO addition mole number is 1 mole alkyl (carbon number 12/14 = 72% by mass / 28% by mass) ether ether sulfate sodium [surfactant (2-1)], average EO addition mole number is 2 mol Alkyl (carbon number 12/14 = 75% by mass / 25% by mass) ether sulfate sodium ester [surfactant (1-1)] is mixed in the ratio shown in Table 1, and sodium chloride and ion-exchanged water are added. Then, an evaluation sample having a total surfactant concentration of 20% by mass and a sodium chloride concentration of 1.5% by mass was prepared. The viscosity of the obtained evaluation sample was measured with a B-type viscometer. The measurement conditions are shown below. Table 1 shows the evaluation sample composition and viscosity measurement results.
(Measurement condition)
・ Viscosity measuring equipment: B-type viscometer, TOKIMEC "DVL-B II"
・ Sample temperature: 30 ℃
・ Measurement time: 90 seconds ・ Rotor No. : 1-4
・ Rotation speed: 30rpm

Example 2
Alkyl (carbon number 12/14 = 72% by mass / 28% by mass) sodium sulfate ester [surfactant (2-2)] having an average PO addition mole number of 2 moles and an average EO addition mole number of 2 moles A certain alkyl (carbon number 12/14 = 75% by mass / 25% by mass) ether sulfate sodium ester [surfactant (1-1)] is mixed in the ratio shown in Table 1, and sodium chloride and ion-exchanged water are added. An evaluation sample having a total surfactant concentration of 20% by mass and a sodium chloride concentration of 1.5% by mass was prepared. The viscosity of the obtained evaluation sample was measured with a B-type viscometer under the same conditions as in Example 1. The measurement results are shown in Table 2.

Example 3 and Comparative Example 3
Alkyl (carbon number 12/14 = 72% by mass / 28% by mass) ether ether sulfate sodium [surfactant (2-1)] having an average PO addition mole number of 1 mol is added to alkyl (carbon number 12/14 = 72 mass% / 28 mass%) sodium sulfate ester [surfactant (1-2)] is mixed in the ratio of Table 1, sodium chloride and ion-exchanged water are added, and the total surfactant concentration is 20 mass%. An evaluation sample having a sodium chloride concentration of 1.5% by mass was prepared. The viscosity of the obtained evaluation sample was measured with a B-type viscometer under the same conditions as in Example 1. Table 3 shows the measurement results.

  As is apparent from Tables 1 to 3, the compound represented by the general formula (2) has a large thickening effect, can increase the viscosity of an aqueous solution of an anionic surfactant having a small thickening effect, and the above general formula. By changing the amount of the compound represented by formula (2), the thickening behavior of the aqueous solution can be controlled.

Claims (7)

A surfactant composition obtained by mixing the compounds represented by the following general formula (1) and the following general formula (2).
R ¹ O— (EO) _m SO ₃ M (1)
_{^{R 2 O- (AO) n SO}} 3 M (2)
(In the formula, R ¹ and R ² represent the same or different alkyl group having 8 to 24 carbon atoms, EO is an ethyleneoxy group, and AO is an alkyleneoxy group having 3 or 4 carbon atoms. (The number of moles of ethylene oxide added is 0 ≦ m ≦ 3, n is the number of moles of alkylene oxide added and 0 <n ≦ 3. M is a cation.) Obtained by mixing the compound represented by the general formula (1) [compound (1)] and the compound represented by the general formula (2) [compound (2)] under conditions satisfying the following formula (α). The surfactant composition according to claim 1, wherein

  In the total amount of the compound represented by the general formula (1) and the compound represented by the general formula (2), the ratio of the compound represented by the general formula (1) is 20 to 95% by mass. The surfactant composition of Claim 1 or 2 whose ratio of the compound represented by (2) is 5-80 mass%.   Furthermore, surfactant composition in any one of Claims 1-3 containing inorganic salt and water.   A cleaning composition containing the surfactant composition according to claim 1. A method in which a compound represented by the following general formula (2) is added to an aqueous solution containing an inorganic salt and an anionic surfactant to thicken the aqueous solution.
_{^{R 2 O- (AO) n SO}} 3 M (2)
(In the formula, R ² represents an alkyl group having 8 to 24 carbon atoms, AO represents an alkyleneoxy group having 3 or 4 carbon atoms, and n represents an average added mole number of alkylene oxide. 0 <n ≦ 3. (M is a cation.) The method of Claim 6 whose anionic surfactant is a compound represented by following General formula (1).
R ¹ O— (EO) _m SO ₃ M (1)
(In the formula, R ¹ represents an alkyl group having 8 to 24 carbon atoms, EO represents an ethyleneoxy group, m represents a number of 0 ≦ m ≦ 3 indicating an average added mole number of ethylene oxide, and M represents a positive number. Ion.)