JP2003055691A - Surface active agent composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface active agent composition which excels in flowability at a high concentration and, simultaneously, at a low viscosity, and contains a phosphoric acid ester salt of an organic hydroxy compound, and its manufacturing method. SOLUTION: The surface active agent composition comprises (a) 50-90 wt.% phosphoric acid ester salt of an organic hydroxy compound to be represented by formula (I): RO(AO)n H (wherein R is an 8-24C alkyl group or an alkenyl group; A is a 2-4C alkylene group; and n is a number of 0-20), (b) 1-8 wt.% 1-3C monohydric alcohol, and (c) 1-30 wt.% at least one compound to be selected from the group consisting of 1-3C polyhydric alcohols and polyalkylene glycols having a molecular weight of <=5,000, and has a viscosity at 30 deg.C and at a shear rate of 50 s<-1> of <=3,000 mPa.s, and its manufacturing method is disclosed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant composition which can be suitably used as a personal cleansing agent, an emulsifier, etc. and has a high concentration, low viscosity and excellent fluidity, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Phosphate ester salts of organic hydroxy compounds, which are one type of surfactants, are used in the fields of detergents, emulsifiers, fiber treatment agents, rust preventives, and medical products. It is used. Particularly, alkali metal salts such as sodium and potassium of phosphoric acid monoesters having a long-chain alkyl group, and alkanolamine salts such as triethanolamine are water-soluble and have excellent foaming power and detergency, and also have toxicity and skin irritation. Since it has low activity, it is useful for products such as shampoo and facial cleanser that are used directly on the human body.

At present, phosphoric acid ester salts of organic hydroxy compounds, which are widely used industrially, react higher alcohols or polyoxyethylene alkyl ethers with phosphorylating agents such as phosphorus pentoxide, polyphosphoric acid and phosphorus oxychloride. It is obtained by neutralizing the obtained acidic phosphoric acid ester with an alkaline substance by performing operations such as deodorization as necessary.

Generally, the viscosity of an aqueous solution of a phosphate ester salt increases as the phosphate ester salt concentration, that is, the surfactant concentration, is increased. If the concentration of the surfactant exceeds about 30% by weight, the viscosity sharply increases, and the handling becomes very difficult, and the workability and handleability are impaired.
Therefore, the phosphoric acid ester salt aqueous solution of the organic hydroxy compound has been used in an amount of about 30% by weight or less to form a uniform liquid state. However, handling at such a low concentration, for example, when manufacturing a high-concentration liquid detergent, etc., is restricted by the composition of the product due to the concentration of the surfactant, which reduces the degree of freedom in mixing and further It is not desirable from the viewpoint of the property (storage, transportation, etc.).

An object of the present invention is to provide a surfactant composition containing a phosphoric acid ester salt of an organic hydroxy compound, which has a high concentration, low viscosity and excellent fluidity, and a method for producing the same.

[0006]

The present invention contains the following components (a), (b) and (c), wherein the content of the component (a) is 50 to 90% by weight, and the content of the component (b) is Content is 1
8% by weight, the content of the component (c) is 1 to 30% by weight, the viscosity at a temperature of 30 ° C. and a shear rate of 50 s ⁻¹ is 3,000 mPa · s or less, and a method for producing the same. I will provide a. (A) Phosphoric ester salt of organic hydroxy compound represented by the general formula (I) (hereinafter referred to as organic hydroxy compound (I)) RO (AO) _n H (I) (In the formula, R has 8 to 24 carbon atoms. Is a linear or branched alkyl group or alkenyl group, A is an alkylene group having 2 to 4 carbon atoms, n is a number of 0 to 20 representing the average number of moles of alkylene oxide added, and n A are the same. (B) Monovalent alcohol having 1 to 3 carbon atoms (c) Polyhydric alcohol having 1 to 3 carbon atoms and molecular weight 5,
At least one compound selected from the group consisting of 000 or less polyalkylene glycols

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the organic hydroxy compound (I) constituting the phosphoric acid ester salt of the organic hydroxy compound which is the component (a) of the present invention, R is a linear or branched alkyl group having 8 to 24 carbon atoms. It is a group or an alkenyl group, and an alkyl group or an alkenyl group having 8 to 18 carbon atoms is preferable. A is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. n is a number from 0 to 20, and a number from 0 to 10 is preferable.

The phosphoric acid ester salt of an organic hydroxy compound is obtained by phosphorylating this organic hydroxy compound (I) with a phosphorylating agent and performing deodorizing or the like as necessary, and then using the resulting acidic phosphoric acid ester as an alkaline substance. Neutralized by
Obtained by removing water if necessary. The neutralization with an alkaline substance is preferably carried out during the production of the surfactant composition, as described later.

Examples of the phosphorylating agent used for phosphorylating the organic hydroxy compound (I) include phosphorus pentoxide, polyphosphoric acid, phosphorus oxychloride, etc., which may be used alone or in admixture of two or more. Can be used. The amount of the phosphorylating agent may be adjusted according to the composition of the target acidic phosphoric acid ester. Among these, phosphorus pentoxide and polyphosphoric acid are preferable because they are free from by-products such as hydrochloric acid gas and are less likely to be loaded on the equipment.

When phosphorus pentoxide and polyphosphoric acid are used as the phosphorylating agent, the viewpoint of reducing the by-product of orthophosphoric acid, which adversely affects the stability of products such as detergents, and the detergency are adversely affected. From the viewpoint of reducing the by-product of phosphoric acid diester, the value of phosphorus pentoxide (138% by weight in terms of orthophosphoric acid, in the case of polyphosphoric acid, the value obtained by dividing polyphosphoric acid concentration by 138 is the phosphorus pentoxide equivalent weight ratio It is preferable that the amount of water is 0.5 to 1.5 mol and the amount of the organic hydroxy compound (I) is 1 to 3 mol per 1 mol.

The acidic phosphoric acid ester may contain unreacted organic hydroxy compound (I) remaining after completion of phosphorylation, orthophosphoric acid and the like.

According to the method of the present invention, the phosphoric acid ester salt of the organic hydroxy compound is obtained as a mixture of phosphoric acid monoester salt and phosphoric acid diester salt. The ratio of the phosphoric acid monoester salt and the phosphoric acid diester salt is 60% by weight, based on the total amount of the phosphoric acid monoester salt and the phosphoric acid diester salt, from the viewpoint of water solubility, foamability, and the like. The above is preferable, and 70 wt% or more is more preferable.

The content of the component (a) in the surfactant composition of the present invention is 50 to 90% by weight, preferably 60 to 80%.
% By weight. By setting the content of the component (a) to 50% by weight or more, there are no restrictions on the composition of the composition in the product, and the degree of freedom in composition increases. Further, when the content is 90% by weight or less, a surfactant composition having sufficient fluidity is obtained, handling becomes easy, and workability and handleability are improved. Here, the content of the component (a) is the total amount of the phosphoric acid monoester salt and the phosphoric acid diester salt, and the content is not the content of the phosphoric acid ester salt but the content of the phosphoric acid ester equivalent.

Examples of the component (b) of the present invention include methanol, ethanol and propanol, preferably ethanol.

The content of the component (b) in the surfactant composition of the present invention depends on the content of the component (a) and / or water, but is 1 to 8% by weight, preferably 1 to 5% by weight. %.
By setting the content of the component (b) to 8% by weight or less, it becomes easy to obtain a surfactant composition having a flash point of 40 ° C. or higher. Handling is easy because it does not fall under the category of dangerous goods. Further, when the content is 1% by weight or more, a surfactant composition having sufficient fluidity is obtained, handling becomes easy, and workability and handleability are improved.

Examples of the component (c) of the present invention include polyhydric alcohols having 1 to 3 carbon atoms such as ethylene glycol and propylene glycol, polyethylene glycol and polypropylene glycol having a molecular weight of 5,000 or less, preferably 3,000 or less. Examples include polyalkylene glycol. Polypropylene glycol is preferable, and dipropylene glycol is particularly preferable. These may be used alone or in combination of two or more kinds.

The content of the component (c) in the surfactant composition of the present invention is 1 to 30% by weight, preferably 1 to 20% by weight.
Is. The viscosity of the surfactant composition decreases as the content of the component (c) increases under the same temperature condition. However, by setting the content of the component (c) to 30% by weight or less, the concentration of the component (a) Can be increased, there is no restriction on the composition of the product,
Greater flexibility in formulation. Further, when the content of the component (c) is 1% by weight or more, a surfactant composition having sufficient fluidity can be obtained, handling becomes easy, and workability and handleability are improved.

The surfactant composition of the present invention comprises (a),
In addition to the components (b) and (c), water, phosphoric acid, the organic hydroxy compound (I) and the like may be contained. The water is derived from water produced during neutralization of the acidic phosphate ester, added water, and the like.
From the viewpoint of decreasing the viscosity of the surfactant composition and increasing the flash point, it is preferable to contain water.

From the viewpoint of improving workability and handleability, the surfactant composition of the present invention has a viscosity at a temperature of 30 ° C. and a shear rate of 50 s ⁻¹ of 3,000 mPa · s or less, preferably 1,800 mPa · s or less. Is. Viscosity 3
When it is 000 mPa · s or less, it has sufficient fluidity, bubbles easily disappear even when mixed, and handling becomes easy.
As the viscosity, the value obtained by the measuring method shown in the examples is used.

The surfactant composition of the present invention contains the organic hydroxy compound (I) in the presence of the components (b) and (c).
The method of mixing the acidic phosphoric acid ester and the alkaline substance, the component (b), the component (c), the acidic phosphoric acid ester of the organic hydroxy compound (I) and the alkaline substance are continuously mixed. You can

As the alkaline substance used here,
Examples thereof include hydroxides such as sodium hydroxide, potassium hydroxide and ammonium hydroxide, carbonates such as sodium carbonate and potassium carbonate, amines such as monoethanolamine, diethanolamine and triethanolamine. One of these or Two or more kinds can be used.

The amount of the alkaline substance is not particularly limited and can be arbitrarily set according to the concentration of the active ingredient of the desired phosphoric acid ester salt of the organic hydroxy compound (I).
Although a solid alkaline substance can be used, a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution are preferable from the viewpoint of easy handling and the like.

Amount of alkaline substance (hereinafter referred to as neutralization degree)
Is preferably 1.0 to 2.0 times equivalent, and more preferably 1.0 to 1.5 times equivalent to acid phosphate. 1.0
When the amount is more than double equivalent, the low temperature stability of the phosphate ester salt is improved, and when it is less than 2.0 equivalent, it does not show strong basicity, it is easy to handle, and corrosion of equipment is also avoided. it can.

The neutralization reaction with an alkaline substance can be carried out in either a continuous type or a batch type apparatus, but the continuous type apparatus can make the equipment compact as compared with the batch type apparatus. The continuous type is preferable. In particular, since the reaction is an exothermic reaction, it is necessary to perform it while removing the amount of heat generated, and a continuous heat removal type reaction apparatus is preferable. At that time, the neutralization temperature is controlled to 20 to 80 ° C, preferably 30 to 60 ° C. By setting the neutralization temperature to 80 ° C. or lower, hydrolysis and coloring of the phosphoric acid ester salt of the organic hydroxy compound (I) can be suppressed. Further, when the temperature is 20 ° C. or higher, the viscosity increase of the phosphoric acid ester salt of the organic hydroxy compound (I) can be suppressed, and the handling becomes easy.

When a solid alkaline substance is used, it is preferable to use a device such as a kneader or a kneader that gives a strong shearing force to the neutralization reaction. For example, as a continuous type, a KRC kneader or an ultimate kneader ( ) Kurimoto Steel Works), Continuous Earth Kneader (Fuji Paudal)
Co., Ltd., continuous kneader (Satake Chemical Machinery Co., Ltd.) and the like. At that time, it is preferable to add water at the same time. The amount of water added can be arbitrarily set according to the required concentration of the phosphate ester salt.

The method of adding the components (b) and (c) is as follows.
In the case of the continuous method, in order to suppress an increase in viscosity during neutralization, a method of simultaneously adding the acidic phosphoric acid ester and the alkaline substance is preferable. Further, in the case of the batch method, a method of preliminarily dissolving it in an alkaline substance such as an aqueous solution of sodium hydroxide or an acidic phosphate ester can be mentioned. Further, the component (b) and the component (c) may be added after the production of a highly viscous neutralized product. Either method can be selected depending on the situation.

If desired, other components can be added to the surfactant composition of the present invention. As other components, for example, dibutyl hydroxytoluene,
Antioxidants such as butylhydroxyanisole, preservatives such as methylparaben, hypochlorite (sodium, potassium salts, etc.), decolorizing agents such as hydrogen peroxide, metal chelating agents such as ethylenediaminetetraacetic acid, and other pH buffering agents, etc. Is mentioned. Such other components can be used within a range that does not impair the object of the present invention.

[0028]

EXAMPLES Synthesis Example 1: Preparation of Acidic Phosphate Ester Ethoxylate of a higher alcohol having 11 carbon atoms (branching rate of 20%) and an average ethylene oxide (EO) addition mole number of 3 (trade name Neodol 1-3, Shell Co.) Made, molecular weight 30
4) 6082 g (20.0 mol) of 85% phosphoric acid 469
g (corresponding to 2.0 mol of phosphorus pentoxide and 10.0 mol of water). Then, phosphorus pentoxide 114 at a temperature of 40 to 50 ° C.
After gradually adding 9 g (8.1 mol), the temperature was raised to 80 ° C. and the reaction was performed for 12 hours. Then, 77 g of ion-exchanged water was added, and hydrolysis was carried out at 90 ° C. for 1 hour. When the amount of phosphoric acid monoester, phosphoric acid diester, orthophosphoric acid in the obtained acidic phosphoric acid ester was quantified by the following method,
The phosphoric acid monoester was 71.3% by weight, the phosphoric acid diester was 20.7% by weight, and the orthophosphoric acid was 4.7% by weight.

<Quantitative Method for Phosphoric Acid Monoester, Phosphoric Acid Diester and Orthophosphoric Acid> About 1 g of a sample was accurately weighed, and 100 mL of ethanol and 50 mL of water were added and dissolved. Perform a potentiometric titration with 1 / 2N KOH
The equivalence point (AV ₁ ) and the second equivalence point (AV ₂ ) were measured.
Next, weigh accurately about 1g of the sample, and use 100m of ethanol.
L and 50 mL of water were added and dissolved, then 2N CaCl
About 20 mL of ₂ was added, and potentiometric titration was performed using 1/2 N KOH to measure the third equivalent point (AV ₃ ). The amounts of phosphoric acid monoester, phosphoric acid diester, and orthophosphoric acid were calculated by the following formulas (1) to (3).

Phosphoric acid monoester (% by weight) = (2AV ₂ −AV ₁ −AV ₃ ) × phosphoric acid monoester molecular weight / 56108 (1) Phosphoric acid diester (% by weight) = (2AV ₁ −AV ₂ ) × Phosphoric acid diester molecular weight / 56108 (2) Orthophosphoric acid (wt%) = (AV ₃ −AV ₂ ) × 98/56108 (3) Examples 1-2 Pipeline homomixer PL manufactured by Tokushu Kika Kogyo Co., Ltd. −
A loop type continuous neutralization reactor (internal volume: 1,160 cm ³ ) incorporating the SL type was continuously charged with the acidic phosphate ester obtained in Synthesis Example 1 and a 48% sodium hydroxide aqueous solution under the conditions shown in Table 1. And was neutralized under the conditions of a temperature of 40 ° C. and a circulation ratio of 10 times. At the same time, ethanol was used as the component (b) and dipropylene glycol was used as the component (c).
Continuously added under the conditions shown in (1) to obtain a surfactant composition. The obtained surfactant composition did not require defoaming because bubbles easily disappeared.

Examples 3 to 4 A 48% aqueous sodium hydroxide solution and ion-exchanged water are shown in Table 1.
An alkaline substance was prepared by mixing under the conditions shown in. 258.8 g of the acid phosphate obtained in Synthesis Example 1 was charged into a 1 L stainless steel container, and ethanol was added as a component (b) and dipropylene glycol was added as a component (c) under the conditions shown in Table 1. Mixed. Then, the mixture was neutralized by gradually dropping an alkaline substance under stirring at a temperature of 30 to 40 ° C. to obtain a surfactant composition.
The obtained surfactant composition did not require defoaming because bubbles easily disappeared.

Comparative Example 1 A 48% aqueous sodium hydroxide solution and ion-exchanged water were prepared as shown in Table 1.
An alkaline substance was prepared by mixing under the conditions shown in. 257.3 g of the acidic phosphoric acid ester obtained in Synthesis Example 1 was charged into a 1 L stainless steel container, and an alkaline substance was gradually added dropwise under stirring at a temperature of 30 to 40 ° C. to neutralize. afterwards,
Ebara Seisakusho Co., Ltd. continuous vacuum deaerator UCD 0-CM
Was used to defoam to obtain a surfactant composition.

Comparative Example 2 A 48% aqueous sodium hydroxide solution and ion-exchanged water were prepared as shown in Table 1.
An alkaline substance was prepared by mixing under the conditions shown in. 251.2 g of the acidic phosphoric acid ester obtained in Synthesis Example 1 was charged into a 1 L stainless steel container, and dipropylene glycol as a component (c) was added and mixed under the conditions shown in Table 1. Then, an alkaline substance was gradually added dropwise to the mixture under stirring at a temperature of 30 to 40 ° C. for neutralization. After that, defoaming was performed using a continuous vacuum deaerator UCD 0-CM manufactured by EBARA CORPORATION to obtain a surfactant composition.

With respect to the surfactant compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the viscosity, fluidity and flash point were measured under the following conditions. The results are shown in Table 1.

<Viscosity> Using a viscometer VT550 manufactured by HAAKE, using PK11- (plate / cone) in the high viscosity region and SV-DIN (cylinder) in the low viscosity region as a sensor, the temperature is 30 ° C and the shear rate is 50 s ^It was measured under the condition of ^-1 .

<Flowability> 50 g of the surfactant composition was sampled in a 100 ml glass sample bottle and the temperature was 30
℃. The sample bottle was tilted, the fluidity was visually observed, and the sample was ranked in 5 stages from 1 [easy] to 5 [difficult].

<Flash point> A simple flash point tester 230-CM manufactured by Sogo Co., Ltd. was used and measured according to the method of ASTM D3278.

[0038]

[Table 1]

[0039]

According to the present invention, it is possible to obtain a surfactant composition having a high concentration and a low viscosity, which is excellent in workability and handleability.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/37 C11D 3/37 17/08 17/08 // C07F 9/09 C07F 9/09 K F term (reference) 4D077 AA05 AB10 AB12 AC01 AC10 BA01 BA02 BA03 BA07 DC02Y DC08Z DC12Y DD32Y DD33Y DE07Y DE08Y DE32Y 4H003 AB39 BA12 CA16 DA02 EA21 EB04 EB06 EB34 ED02 FA30 FA37 FA45 4H050 AA02 AA03 AB68 BC04 WA19 WA23

Claims (4)

[Claims] 1. A composition comprising the following components (a), (b) and (c), wherein the content of the component (a) is 50 to 90% by weight:
The content of the component (b) is 1 to 8% by weight, the content of the component (c) is 1 to 30% by weight, the temperature is 30 ° C., and the shear rate is 5
A surfactant composition having a viscosity at 0 s ^-1 of 3,000 mPa · s or less. (A) Phosphoric acid ester salt of organic hydroxy compound represented by the general formula (I) RO (AO) _n H (I) (In the formula, R is a linear or branched alkyl group having 8 to 24 carbon atoms or Alkenyl group, A is an alkylene group having 2 to 4 carbon atoms, n is a number of 0 to 20 which represents the average number of moles of alkylene oxide added, and n A's may be the same or different.) (B) Monohydric alcohol having 1 to 3 carbon atoms (c) Polyhydric alcohol having 1 to 3 carbon atoms and molecular weight 5,
At least one compound selected from the group consisting of 000 or less polyalkylene glycols 2. The surfactant composition according to claim 1, which has a flash point of 40 ° C. or higher. 3. The method for producing a surfactant composition according to claim 1, wherein the acidic phosphoric acid ester of the organic hydroxy compound and the alkaline substance are mixed in the coexistence of the components (b) and (c). 4. The method for producing a surfactant composition according to claim 1, wherein the component (b), the component (c), the acidic phosphoric acid ester of the organic hydroxy compound and the alkaline substance are continuously mixed.