JP2932377B2 - Liquid detergent thickening method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to an amphoteric surfactant,
Contains nonionic and anionic surfactants
The present invention relates to a method for thickening a liquid detergent. In the method of the present invention
More thickened liquid surfactants are formulated, stored and used
Excellent stability at the time of cleaning, and the body to be cleaned (eg, skin,
It adheres moderately to tableware, etc. and shows a good feeling of use.
is there. [0002] BACKGROUND OF THE INVENTION In recent years, bases in kitchen detergents and shampoos
Low toxicity and low sting to surfactants used as
Intensity is being demanded. With such drugs
And amidoamine-type amphoteric surfactant and amidobetaine
Amphoteric surfactants are widely used. [0003] Amidoamine type amphoteric surfactants and amidoben
Tine-type amphoteric surfactants have traditionally been used as amphoteric reactants.
Manufactured using monochloroacetic acid. But things
Performing an amphoteric reaction with chloroacetic acid inevitably results in chloride
Sodium is by-produced and removed during normal processing
Product, sodium chloride remains in the product.
There is a problem. Also obtained from monochloroacetic acid
Amidoamine-type amphoteric surfactants and amidobetaine-type surfactants
Detergents such as shampoos and kitchen detergents
Low compatibility with other surfactants when formulated in a composition
Is difficult to formulate because of poor cold resistance.
Was. [0004] As a method of improving such disadvantages, there are various methods.
Some salt-free amidoamine-type amphoteric surfactants and
A method for producing a dobetaine-type amphoteric surfactant has been proposed.
You. For example, in the amphoteric reaction, ethyl acrylate
There is a method using such an acrylic acid ester. Acri
When amphoteric reaction is performed using
Does not form a by-product,
Alcohol is by-produced. Other salt-free types
Acrylic acid is directly added as a method for producing a surfactant.
There has been proposed a method for performing amphoteric treatment, but unreacted
The problem of having to remove the acrylic acid
is there. [0005] SUMMARY OF THE INVENTION Fatty acid diethanol alcohol
Including amide type nonionic surfactant and anionic surfactant
Conventional amidoamine and amidobetaine
Problem when compounding an amphoteric surfactant,
It is liquid and cannot maintain stability, resulting in cloudiness and
Under stable conditions, it can solidify and become a liquid cleaner
In addition to the lack of
と し て Even if compounded, sufficient viscosity is not obtained,
Do not easily run off when picked up or picked up
However, there is a problem in terms of usability, and this problem is strongly resolved.
Had been requested. The present invention relates to a fatty acid diethanolamide type
Contains ionic surfactant and anionic surfactant
For liquid detergents, amphoteric produced by a specific method
The above problems can be solved by using a surfactant as a thickener.
It is intended to provide a thickening method capable of solving the problem. [0007] A liquid detergent according to the present invention.
Thickening method is based on fatty acid diethanolamide type nonionic
Liquid detergent composition containing surfactant and anionic surfactant
In order to increase the viscosity of the product, the following general formula
(I) or (II): [0008] Embedded image (However, in the above formula, R₁ And R_Four Is
Each independently of one another an alkyl group having 9 to 19 carbon atoms
Or an alkenyl group;_Two And R_Three Each
Independently of each other, a hydroxyethyl group or a hydrogen atom
Represents, R_Five And R₆ Are independent of each other
Represents an ethyl group, an ethyl group or a hydroxyethyl group. )
The amidoamine compound represented by the following general formula (III
 ): ClCH_Two COOM (III) (Where M is a hydrogen atom, an alkali metal atom,
Ammonium group or alkanolamine or lower
Represents the cation residue of an aliphatic amine. ) Indicated by
Monochloroacetic acid or its salt reacts
The mixture is subjected to reverse osmosis membrane treatment,
Amphoteric surfactant concentrated by removing
Is added to the liquid detergent composition as a thickener.
It is characterized by the following. [0010] BEST MODE FOR CARRYING OUT THE INVENTION Fatty acid diacid used in the method of the present invention
Examples of ethanolamide type nonionic surfactants include
Diethanolamide thearate, Diethanolamine laurate
And coconut oil fatty acid diethanolamide.
I can do it. Anionic surfactant used in the method of the present invention
Examples of higher alcohol sulfates, sulfo
Higher fatty acid salt, sulfonated higher fatty acid higher alcohol
Ester salt, higher alcohol sulfosuccinate
Salts, and α-sulfo higher alcohol acetates and the like.
You. The amphoteric surfactant for thickening used in the method of the present invention.
The activating agent is an amidamine compound of the general formula (I) or (II).
To the compound, monochloroacetic acid of the formula (III) or a salt thereof.
Reaction, and the resulting reaction product mixture is subjected to reverse osmosis membrane treatment.
And the salt (chlorinated)
Sodium) and the reaction products in the membrane impervious liquid
Was obtained by concentrating. Used for the production of amphoteric surfactant for thickening
The compound of the general formula (I) may be a fatty acid or a fatty acid ester.
And diamine compounds such as aminoethylethanolamine
With 2-alkyl-1- (2-hydrido)
Imidazolines such as (roxyethyl) -2-imidazoline
Can be easily obtained by hydrolyzing the compound
You. An amidoamine compound represented by the general formula (I)
For example, N-cocoyl-N '-(2-hydrogen
Roxyethyl) ethylenediamine, N-lauroyl-N
-(2-hydroxyethyl) ethylenediamine, N-ca
Proyl-N '-(2-hydroxyethyl) ethylenedi
Amine, N-stearoyl-N '-(2-hydroxy
Tyl) ethylenediamine, N-oleoyl-N '-(2
-Hydroxyethyl) ethylenediamine, N-cocoyl
-N- (2-hydroxyethyl) ethylenediamine, N
-Lauroyl-N- (2-hydroxyethyl) ethylene
Diamine, N-caproyl-N- (2-hydroxyethyl
L) ethylenediamine, N-stearoyl-N- (2-
Hydroxyethyl) ethylenediamine, N-oleoyl
-N '-(2-hydroxyethyl) ethylenediamine and the like
Can be mentioned. [0014] Further, other than the reverse osmosis membrane-treated product of the composition of the present invention,
The compound of the general formula (II) as a starting material of
Is a fatty acid ester and N, N-dimethylpropanediamine
Easy by condensing with diamine compounds such as
Can be obtained. As the compound of the general formula (II),
For example, N-lauroyl-N ', N'-dimethylprop
Diamine, N-cocoyl-N ', N'-dimethylpro
Pandiamine, N-caproyl-N ', N'-dimethyl
Propanediamine, N-stearoyl-N ', N'-di
Methylpropanediamine, N-oleoyl-N ', N'
-Dimethylpropanediamine, N-lauroyl-N ',
N'-diethylpropanediamine, N-lauroyl-
N ', N'-dihydroxyethylpropanediamine and the like
No. The amide of the general formula (I) or (II)
Mine compound and 1 to 25 mol of monochloroacetic acid and hydroxylic acid
Sodium chloride in an aqueous solution at a temperature of 70 to 95 ° C.
A mixture containing the reaction product is obtained.
You. In this mixture, a main product represented by the following formula (I ′)
Or (II ') amphoteric surfactant and chloride as a by-product
Sodium and unreacted raw materials are mixed. [0016] Embedded image [In the above formulas (I ') and (II'),
M is the same as defined above;_Two', R_Three'Is -CH_TwoCO
OM, a hydroxyethyl group or a hydrogen atom,
R_Four, R_Five, R₆, M are the same as defined above] Used for the reaction product mixture
As a reverse osmosis membrane, for example, a cellulose acetate membrane,
Sulfonated polysulfone membrane, polyamide sulfone membrane, etc.
Is raised. Using these reverse osmosis membranes,
Min-type amphoteric surfactants and amidobetaine-type amphoteric surfactants
To process the reaction product mixture containing the
The amidoamine type amphoteric surfactant in the product mixture or
The concentration of the amidobetaine-type amphoteric surfactant is 5 to 45%,
Preferably adjusted to 20-40%, pressure 5-40kg / cm
^TwoThe temperature varies depending on the type of reverse osmosis membrane, but in general,
Process at room temperature. The amount of liquid to be treated decreases with the processing time
Therefore, reverse osmosis membrane treatment is performed while replenishing water to the liquid to be treated.
Do. Amphoteric surfactant produced by the above method
Is salt-free and the reaction product is concentrated
This is used as a thickening agent for fatty acid diethanolamine.
Mixed with de-type nonionic surfactant and anionic surfactant
Then, unexpectedly, the viscosity of the obtained liquid detergent increases,
Can be The liquid obtained by the method of the present invention
Detergent has excellent cleaning performance and foam stability, and can be stored
It has stability, especially cold resistance. The liquid detergent obtained by the method of the present invention
And the reason for expressing the above performance is still not enough
Although it is not clear, the special production method of the amphoteric surfactant mentioned above
In the method, by-products of the synthesis reaction by reverse osmosis membrane treatment
Some sodium chloride is removed and unreacted raw materials and
One factor is that low-molecular by-products have also been removed.
Seem. [0021] The present invention will be described in more detail with reference to the following examples.
You.Production Example 1 2-coconut fatty acid alkyl-N- (2-hydroxyethyl
1) 1 mol of imidazoline (272 g) and sodium hydroxide
20 g of water and 842 g of water at a temperature of 80 to 90 ° C. for 1 hour.
After heating and stirring for 2 hours, 189 g of 2 mol of monochloroacetic acid was added.
140 g of sodium hydroxide and charged at a temperature of 80 to 90
C. for 3 hours to give N-lauroyl-N'-hydroxy
Siethyl-N'-carboxymethylethylenediamine
Contains amidoamine type amphoteric surfactant as main component
1460 g of a reaction product mixture was obtained. Including salt
The prevalence is 8%, the dry residue is 38%, at 25 ° C.
The viscosity was 800 cp (this is referred to as sample 1).
Next, the reaction product containing the amidoamine type amphoteric surfactant
The pH of the mixture was adjusted to 7 with hydrochloric acid, and purified water 1 was added thereto.
90 g was added to adjust the solid concentration to 35%. This solution
0.4 m of liquid area ^TwoPolyamide sulfone membrane
Reverse osmosis membrane treatment equipment (trade name “20 RO / UF
Strike module: Techno Universe Co., Ltd.)
20kg / cm^TwoAnd treated by removing the membrane permeate
Water was added so that the liquid volume did not decrease. 27 in total
After taking 50 g of permeate, stop adding water,
Then, 550 g of the permeate was taken, and the solid concentration of the treatment liquid was adjusted to 3
0%. Amphoteric interface obtained by this reverse osmosis membrane treatment
The salt concentration in the aqueous solution containing the activator is 0.5%,
The balance was 30%. Also, its viscosity at 25 ° C
Was 110 cp (this is referred to as sample 1). [0022]Production Example 2 1 mol (208 g) of coconut oil fatty acid and N, N-dimethyl
1 mol (102 g) of lopandiamine was added under reduced pressure for 160-
Reaction at 200 ° C. for 4 hours to remove 1 mol of water produced
Was. 800 g of water and 2 mol of sodium hydroxide (80
g), and add 1 mol (117 g) of monochloroacetic acid to about
The reaction was carried out for 5 hours to obtain a dry residue of 36.2.
%, Salt 5.3%, viscosity of 10.5cp at 25 ° C, pale yellow transparent
1260 g of a bright solution was obtained (this is referred to as sample 2).
Next, add 200 g of water to this to adjust the solid content to 30%.
After the film area 0.4m^TwoPolyamide sulfone membrane
Reverse osmosis membrane treatment equipment (trade name "20 RO / U"
F Test Module ": Techno Universe Co., Ltd.)
Pressure 20kg / cm^TwoTo remove the membrane permeate.
Add water so that the amount of processing solution does not decrease due to
Was. After taking a total of 2500 g of permeate, add water
And take another 300 g of permeate, and
The partial concentration was 30%. Obtained by this reverse osmosis membrane treatment
Aqueous solution containing amidobetaine-type amphoteric surfactant
30.5% residue, 0.8% salt concentration at 25 ° C
The viscosity was 8.3 cp (this is referred to as Sample 2). [0023]Examples 1-3, Comparative Examples 1-3 Amidoamine-type amphoteric surfactants obtained in Production Examples 1 and 2
Osmosis treatment of amphoteric and amidobetaine-type amphoteric surfactants
(1-, 2-) and untreated (1-, 2-)
To determine the difference between
Uryl sulfate triethanolamine salt and 1 or polio
Ani selected from sodium xylene ethylene lauryl sulfate
On surfactant and coconut oil fatty acid diethanolamide
Three-component system with ionic surfactant (active ingredient 20%, pH 7.
0) A composition was prepared with the composition shown in Table 1 and
Were measured for compatibility, low temperature stability and viscosity. Each test method
The method was as follows. [Compatibility] The test solution was released at 20 ° C. for 24 hours.
After placing it, observe its appearance with the naked eye according to the following criteria.
Was determined. ○… Whole uniform and transparent solution Δ: Slight cloudiness or separation was observed. ×: cloudy or separated [Low-temperature stability] The test solution was kept at -5 ° C for 3 days.
After standing, the appearance was visually observed and the following criteria were used.
Judgment was made. ○… Whole uniform and transparent solution Δ: Slight cloudiness or separation was observed. ×: cloudy or separated [Viscosity] Test solution using a B-type rotational viscometer
Was measured at 25 ° C. Table 1 shows the test results. [0028] [0029] [Table 1] [0030] According to the method of the present invention, the viscosity is increased.
As a result, stability during formulation, storage and use is good,
A liquid detergent that adheres moderately to the washing body and has a good usability
Is obtained.

Continuation of the front page (56) References JP-A-60-168795 (JP, A) JP-A-60-193954 (JP, A) JP-A-59-156402 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) C11D 1/94 C07C 233/36 C07C 233/38

Claims (1)

(57) [Claims] In order to increase the viscosity of a liquid detergent composition containing a fatty acid diethanolamide type nonionic surfactant and an anionic surfactant, the following general formula (I) or (II): (Wherein, R ₁ and R ₄ each independently represent an alkyl group or an alkenyl group having 9 to 19 carbon atoms, and R ₂ and R ₃ each independently represent a hydroxyethyl group or a hydrogen And R ₅ and R ₆ each independently represent a methyl group, an ethyl group or a hydroxyethyl group.) In the amidoamine compound represented by the following general formula (III): ClCH ₂ COOM (III) ( However, in the above formula, M is a hydrogen atom, an alkali metal atom,
It represents an ammonium group or a cation residue of an alkanolamine or a lower aliphatic amine. ), And subjecting the reaction product mixture to reverse osmosis membrane treatment to remove the salt content together with the membrane permeate and use the amphoteric surfactant concentrated as a thickener. A method for thickening a liquid detergent, which is added to the liquid detergent composition.