JP5823241B2 - Anionic surfactant composition - Google Patents

Description

  The present invention relates to an anionic surfactant composition containing a sulfate ester salt having a polyoxyalkylene chain.

  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.

  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.

  Various techniques for obtaining a composition containing a polyoxyalkylene alkyl ether sulfate ester salt at a high concentration have been proposed. Patent Document 1 discloses a surfactant composition containing a specific polyoxyalkylene alkyl ether sulfate having a propyleneoxy group and an ethyleneoxy group. Patent Document 2 discloses a higher secondary alkyl ether sulfate salt composition in which an alkyl group satisfies a predetermined branched structure condition. Patent Document 3 discloses a detergent composition containing a block-type polyoxyalkylene alkyl ether sulfate ester salt produced by adding propylene oxide and ethylene oxide.

JP 2010-168554 A JP-A-10-251215 JP 55-84399 A

  As mentioned above, polyoxyalkylene alkyl ether sulfates are applied to detergents such as dishwashing detergents, shampoos, and laundry detergents, but they are rich in foaming and have excellent foaming properties while being rinsed. In this case, it may be desirable that the foam disappears quickly so that the foam disappears quickly. However, foamability and foam extinction are contradictory effects and are difficult to achieve at the same time.

  An object of the present invention is to provide an anionic surfactant composition containing a high concentration of a sulfate ester salt excellent in both foaming properties and foam extinction properties and excellent in fluidity.

In the present invention, (a) a mixture of compounds represented by the following general formula (1) [hereinafter referred to as component (a)] is 60 to 80% by mass, and (b) water (hereinafter referred to as component (b)). An anionic surfactant composition comprising:
The average value of m in the mixture is 0.3 to 0.6, and the average value of n is 0.2 to 0.4.
The ratio of the compound in which m in the general formula (1) in the mixture is 0 and n is 0 is 40% by mass or more,
The total of the compound in which m in the general formula (1) is 2 or more, the compound in which n is 2 or more in the general formula (1), and the compound in which m + n is 2 or more in the general formula (1) in the mixture is 25 mass. % Or less,
The present invention relates to an anionic surfactant composition.
_{RO- (EO) m - (PO} ) n -SO 3 M (1)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and m and n are each an integer of 0 or more. And M represents an alkali metal or NH _4. )

  ADVANTAGE OF THE INVENTION According to this invention, the anionic surfactant composition excellent in fluidity | liquidity which contains the sulfate ester salt excellent in both foamability and foam extinction property in high concentration is provided. The anionic surfactant composition of the present invention is excellent in appearance such as transparency.

Schematic showing the evaluation method of foam extinction performed in the examples Schematic showing the perforated state of ion exchange water introduction means (water) used in the evaluation of foam extinction of the example

<(A) component>
The anionic surfactant composition of the present invention contains a mixture of compounds represented by the following general formula (1).
_{RO- (EO) m - (PO} ) n -SO 3 M (1)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and m and n are each an integer of 0 or more. And M represents an alkali metal or NH _4. )

  Here, R in the general formula (1) is foaming property, foam extinguishing property, foam persistence, low temperature stability and stability in hard water, the versatility of raw materials, and handling reasons, From the standpoint of coexistence of foamability and foam extinction at the time of dilution and fluidity at a high concentration, the carbon number is 8 to 12, preferably 12 carbons. R is preferably a straight chain, more preferably a straight chain alkyl group.

In the compound of the general formula (1), the addition form of EO, which is ethylene oxide, and PO, which is propylene oxide, is RO- ( EO) Blocks are added in the order of _m- (PO) _n- .

Further, the M in the general formula (1), a cation group forming a salt, an alkali metal or NH _4. Examples of the alkali metal include sodium, potassium, and lithium. Among these, sodium and potassium are more preferable, and sodium is particularly preferable.

  The average value of m ethylene oxide and the average value of n propylene oxide in the general formula (1) in the mixture of components (a) is from the performance aspect such as foaming property, foam disappearance, and fluidity at a high concentration. The average value of m is 0.3 to 0.6, preferably 0.3 to 0.4, and the average value of n is 0.2 to 0.4, preferably 0.2 to 0.3.

  Moreover, from the surface of coexistence of foamability and the foam extinction property at the time of dilution, the ratio of the compound whose m in the general formula (1) is 0 and n is 0 in the said mixture is 40 mass% or more. Preferably they are 40 mass% or more and 98 mass% or less, More preferably, they are 45 mass% or more and 98 mass% or less, More preferably, they are 50 mass% or more and 98 mass% or less, More preferably, the fluidity | liquidity in high concentration and low temperature stability Or from 50% by weight to 80% by weight or less from the viewpoint of stability in hard water, a compound in which m in the general formula (1) in the mixture is 2 or more, a compound in which n in the general formula (1) is 2 or more, and In the general formula (1), the sum of the compounds having m + n of 2 or more is 25% by mass or less, preferably 22% by mass or less, more preferably 20% by mass or less, and further preferably economic efficiency, foaming property and foam extinction property. From a viewpoint, it is 1 mass% or more and 20 mass% or less. M in the general formula (1) in the mixture is a compound having 2 or more, n in the general formula (1) is 2 or more, and m + n in the general formula (1) is 2 or more. It is preferable that the mass ratio of the compound in which n is 0 and n is 0 is 2.0 or more.

<(B) component>
The anionic surfactant composition of the present invention contains water as the component (b).

<Anionic surfactant composition>
The composition of the present invention is a polyoxyalkylene alkyl or alkenyl ether sulfate salt-containing composition. The present invention relates to a composition containing the component (a) at a high concentration, and the content of the component (a) in the composition is 60 to 80% by mass, preferably 60 to 75% by mass. The anionic surfactant composition of the present invention is excellent even at a relatively low temperature of 50 ° C. or lower while specifying a compound distribution of the component (a) and containing a high concentration of the component (a). The fluidity is high, the transparency is high, and a uniform and good appearance is obtained without separation. (B) Although a component is used in the quantity used as the remainder of a composition, it can be set as content of 20-40 mass% in a composition, and also 25-40 mass%.

Further, as a component other than the component (a) and the component (b), an inorganic salt, a polyoxyalkylene alkyl ether nonion that is not sulfated, or the like may be included.

The component (a) is not particularly limited, and can be produced from, for example, steps including the following steps (I) to (III).
Step (I): Step of adding ethylene oxide in an average range of 0.3 to 0.6 mole to 1 mole of alcohol having a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms (II) ): Step of adding propylene oxide in an average range of 0.2 to 0.4 mol to the ethylene oxide adduct obtained in the step (I) (III): Alkoxy obtained in the step (II) Sulfating the rate and then neutralizing

  Step (I) is a step of adding propylene oxide in an average range of 0.3 to 0.6 mole to 1 mole of alcohol having a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms. . The alkyl group of the alcohol used in the present invention is a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms.

  Moreover, it is preferable that the usage-amount of ethylene oxide with respect to 1 mol of said alcohol is an quantity which can manufacture the mixture applicable to (a) component. Specifically, ethylene oxide is 0.3 to 0.6 mol with respect to 1 mol of the alcohol, and preferably 0.3 to 0.4 mol in terms of foam extinction.

  Step (II) is a step of adding propylene oxide in an average range of 0.2 to 0.4 mol to the ethylene oxide adduct obtained in the above step (I). It is preferable that the usage-amount of propylene oxide with respect to 1 mol of said alcohol is an quantity which can manufacture the mixture applicable to (a) component. Specifically, the amount of ethylene oxide is 0.2 to 0.4 mol with respect to 1 mol of the alcohol, and preferably 0.2 to 0.3 mol from the viewpoint of fluidity at a high concentration.

  As a method for carrying out the steps (I) and (II), a conventionally known method can be used. That is, an autoclave is charged with alcohol and 0.5 to 1 mol% of KOH as a catalyst, heated and dehydrated, and added with a predetermined amount of ethylene oxide and propylene oxide at a temperature of 120 to 180 ° C, respectively. Can be manufactured. At this time, the addition form is block addition, and ethylene oxide addition [step (I)] and propylene oxide addition [step (II)] are performed in this order. The autoclave to be used is preferably provided with a stirring device, a temperature control device, and an automatic introduction device.

  In the present invention, the ratio of the compound in which m in the general formula (1) in the mixture of the component (a) is 0 and n is 0 is 40% by mass or more, and in the general formula (1) in the mixture of the component (a) The total of the compound in which m is 2 or more, the compound in which n in the general formula (1) is 2 or more, and the compound in which m + n in the general formula (1) is 2 or more is 25% by mass or less. In order to achieve such a compound distribution after setting the average value of m in the mixture of components (a) to 0.3 to 0.6 and the average value of n to 0.2 to 0.4, for example, KOH or Examples thereof include a method in which ethylene oxide and then propylene oxide are added to an alcohol by a conventional method using an alkali catalyst such as NaOH. In that case, if it adds so that ethylene oxide may be 0.3-0.6 mol and propylene oxide may be 0.2-0.4 mol with respect to 1 mol of alcohol, it corresponds to (a) component of this invention. To obtain a mixture.

  Step (III) is a step of sulfating and then neutralizing the alkoxylate obtained in the above step (II). 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.

  In addition, the mixture applicable to the (a) component of this invention can also be obtained using two or more single compounds from which m and n in General formula (1) differ.

  That is, the anionic surfactant composition of the present invention contains a plurality of compounds represented by the general formula (1), the average value of m in the composition is 0.3 to 0.6, and the average value of n is The ratio of the compound in which m in the general formula (1) in the composition is 0 and n is 0 in the composition is 40% by mass or more, and in the general formula (1) in the composition The total of the compound in which m is 2 or more, the compound in which n in the general formula (1) is 2 or more, and the compound in which m + n is 2 or more in the general formula (1) is 25% by mass or less, Also good.

  The anionic surfactant composition of the present invention preferably has a viscosity of 500 Pa · s or less, more preferably 100 to 500 Pa · s, from the viewpoint of handleability such as removal from a container. This viscosity was measured using a digital viscometer manufactured by Tokimec Co., Ltd. (DVL-B II type) at a temperature of the composition of 40 ° C. It was measured under the condition of 0.3 r / min with 4 rotors.

  In the present invention, “transparency” for an anionic surfactant composition means that it can be determined that light can be transmitted by visual observation in a state where bubbles are removed.

  The anionic surfactant composition of the present invention can be suitably used as a raw material for producing various cleaning agents, for example, textile product cleaning agents and hard surface cleaning agents.

Examples 1-3, Comparative Examples 1-7
(1) Preparation of anionic surfactant composition An alcohol having 12 carbon atoms (Kao Corporation, product name: Calcoal 2098) and KOH were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, and the pressure was reduced. Was dehydrated. After dehydration, nitrogen substitution was performed, the temperature was raised to a predetermined temperature, and then an alkylene oxide selected from ethylene oxide and propylene oxide was added individually in a predetermined order so that the average number of moles of addition shown in Table 1 was reached. . After the addition reaction / ripening, unreacted ethylene oxide or propylene oxide was removed. After removing unreacted ethylene oxide or propylene oxide, 90% lactic acid was added to the autoclave and stirred, followed by extraction to obtain an alkoxylate having the average alkylene oxide addition mole number in Table 1.

The obtained alkoxylate was sulfated in a thin-film sulfation reactor using SO ₃ gas. A sodium hydroxide aqueous solution was added to the obtained sulfate, and a high concentration anionic surfactant composition containing a polyoxyalkylene alkyl ether sulfate salt (component (a)) with the composition shown in Table 1 was obtained. In Table 1, components not corresponding to the component (a) are also shown in the column for the component (a) for convenience. All the compositions of the examples had transparency.

(2) Evaluation (2-1) Viscosity After removing bubbles from the anionic surfactant composition shown in Table 1 with a centrifuge, the viscosity was measured with a digital viscometer (DVL-B II type) manufactured by Tokimec Co., Ltd. Went. The measurement conditions were 40 ° C., No. The speed was 0.3 r / min with 4 rotors, and the unit was Pa · s. In this evaluation, when the viscosity is 500 Pa · s or less, it was judged that the fluidity is good and the physical properties are easy to handle.

(2-2) Initial foam amount The anionic surfactant composition was diluted with ion-exchanged water so that the concentration of the component (a) was 34 mM, and the pump former described in FIG. 1 of JP-A-2008-260852 The container was filled. Here, a single mesh having a mesh size of 200 / inch was attached to the foam discharge mechanism. Next, 3 g of foam was produced in a 500 ml graduated cylinder (material: glass, manufactured by IWAKI) by continuously pushing out the pump head part at the top of the container for 3 pushes. Note that the speed of pushing out was 1 second per push. The volume was recorded from the scale of the graduated cylinder and used as the initial amount of foam. In this evaluation, it was judged that foaming was sufficient if the amount of foam was 16 ml or more.

(2-3) Foam extinction Add 100 ml of ion-exchanged water to the foam through the means for introducing ion-exchanged water (manufactured by hand) installed at the top of the graduated cylinder against the foam generated by the above initial foam amount measurement. Then, the mixture was allowed to stand for 30 seconds after the addition, and further 100 ml of ion-exchanged water was added and the amount of bubbles after standing for 30 seconds was measured (100 ml of ion-exchanged water was added twice in total, total added amount Is 200 ml). From the initial amount of foam and the amount of foam after addition of 200 ml of ion-exchanged water (100 ml twice), the rate of change of the amount of foam represented by the following formula was determined to evaluate the foam extinction property. When the change rate of the amount of foam was 30% or more, it was judged that rapid foam disappearance by dilution (rinsing) could be achieved. In addition, what takes a negative value for the amount of foam changes means that the amount of foam increases (bubbles increase) by adding ion-exchanged water.
Foam change rate (%) = [1− (foam amount after addition of 200 ml of ion exchange water / initial foam amount)] × 100

  FIG. 1 shows the state when ion-exchanged water is added to the graduated cylinder. In FIG. 1, 1 is a graduated cylinder, 2 is a bubble, 3 is an ion exchange water introduction means (manufactured by hand), 4 is an opening of the introduction means, and FIG. 2 is an opening of the ion exchange water introduction means 3. FIG. 6 is a schematic view showing a state in which a portion 4 is perforated. A method for producing a hand-made water bottle, which is means for introducing ion-exchanged water, is as follows. First, from the bottom of a 250 ml polypropylene wide-mouthed bottle (manufactured by ASONE: I-boy wide-mouthed bottle) to the main body part having a height of about one third was excised. Next, as shown in FIG. 2, a polyethylene perforated plate having 13 holes with a diameter of 2 mm at 9 mm intervals was prepared for a thin circular polyethylene plate with a diameter of 4 cm. Finally, the above-mentioned polyethylene porous plate was fixed as the opening 4 to the lid opening (4 cm in diameter) at the top of the excised wide-mouth bottle, thereby producing ion exchange water introduction means 3 (handmade watering device). The ion exchanged water introducing means 3 (manufactured by hand) thus produced was fitted into the opening of the graduated cylinder 1 while being kept in an inverted state as shown in FIG. Ion exchange water was added from the excision side of the wide-mouth bottle.

In Table 1, “C ₁₂ ” means an alkyl group having 12 carbon atoms (lauryl group). Further, trace components such as unreacted components are omitted in Table 1. The “EO / PO addition order” is the addition order of EO and PO combined with RO-, EO / PO is the order of RO-EO-PO, and PO / EO is the order of RO-PO-EO. It means that. In addition, “compound of m = n = 0” means a compound in which m in general formula (a) is 0 and n is 0, and “compound of AOp ≧ 2” means “compound of general formula (a)” It means a compound in which m is 2 or more, a compound in which n in general formula (a) is 2 or more, and a compound in which m + n in general formula (a) is 2 or more.

Claims (7)

(A) An anionic surfactant composition containing 60 to 80% by mass of a mixture of compounds represented by the following general formula (1), and (b) 20 to 40% by mass of water,
The average value of m in the mixture is 0.3 to 0.6, and the average value of n is 0.2 to 0.4.
The ratio of the compound in which m in the general formula (1) in the mixture is 0 and n is 0 is 40% by mass or more,
The total of the compound in which m in the general formula (1) is 2 or more, the compound in which n is 2 or more in the general formula (1), and the compound in which m + n is 2 or more in the general formula (1) in the mixture is 25 mass. % Or less,
Anionic surfactant composition.
_{RO- (EO) m - (PO} ) n -SO 3 M (1)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and m and n are each an integer of 0 or more. And M represents an alkali metal or NH _4. ) (A) An anionic surfactant composition containing 60 to 80% by mass of a mixture of compounds represented by the following general formula (1) and (b) water as a remaining component,
The average value of m in the mixture is 0.3 to 0.6, and the average value of n is 0.2 to 0.4.
The ratio of the compound in which m in the general formula (1) in the mixture is 0 and n is 0 is 40% by mass or more,
The total of the compound in which m in the general formula (1) is 2 or more, the compound in which n is 2 or more in the general formula (1), and the compound in which m + n is 2 or more in the general formula (1) in the mixture is 25 mass. % Or less,
Anionic surfactant composition.
RO- (EO) _m -(PO) _n -SO _Three M (1)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 8 to 12 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and m and n are each an integer of 0 or more. Yes, M is alkali metal or NH _Four Indicates. ) M in the general formula (1) in the mixture is a compound having 2 or more, n in the general formula (1) is 2 or more, and m + n in the general formula (1) is 2 or more. There 0 and the weight ratio of n compounds of 0 is 2.0 or more, according to claim 1 or 2 anionic surfactant composition. The anionic surfactant composition according to any one of claims 1 to 3, wherein a ratio of the compound in which m in the general formula (1) in the mixture is 0 and n is 0 is 50% by mass or more and 98% by mass or less. . The total of the compound in which m in the general formula (1) in the mixture is 2 or more, the compound in which n in the general formula (1) is 2 or more, and the compound in which m + n is 2 or more in the general formula (1) is 1 mass. The anionic surfactant composition according to any one of claims 1 to 4 , wherein the anionic surfactant composition is not less than 20% and not more than 20% by mass. The anionic surfactant composition according to any one of claims 1 to 5 , wherein R of the general formula (1) in the mixture is a linear alkyl group having 12 carbon atoms. The anionic surfactant composition according to any one of claims 1 to 6 , wherein M in the general formula (1) in the mixture is sodium.

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