JPH09104895A - Concentrated liquid cleansing agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a concentrated liquid cleansing agent composition having excellent fluidity, solubility in water and cleansing power and giving little stimulation to the skin. SOLUTION: This concentrated liquid cleansing agent composition contains (A) an anionic surfactant composed of a sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester expressed by the formula R<1> COO (AO)m CH3 (R<1> is a 13-21C alkyl containing unsaturated bond; AO is oxyethylene group or oxypropylene group; (m) is an integer of 3-30) or its salt and (B) one or more kinds of amphoteric surfactants selected from amine oxide-type surfactants and betaine-type surfactants at a weight ratio (A:B) of 80:20 to 30:70 and a total surfactant concentration of 55-100wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid concentrated detergent composition having good detergency, less irritation to the human body, and low water content.

[0002]

2. Description of the Related Art Anionic surfactants are widely used as cleaning agents because of their foaming power and cleaning performance. Further, household cleaning agents for tableware, housing, body, and hair need to be hypoallergenic to the human body because they come into direct contact with the human body at the time of use, and their shape is a liquid that is easy to use. Preferably. In order to satisfy these various conditions, an anionic surfactant such as a polyoxyethylene alkyl sulfate having good liquidity is used as a main agent, and an amphoteric surfactant is used in combination for the purpose of further improving mildness and cleaning performance. 25
An aqueous solution of about wt% is commercially available as a household cleaning agent.

As described above, the conventional liquid detergent is an aqueous solution having a surfactant concentration of about 5 to 25% by weight, but recently, it has been required to reduce the distribution cost and the environmental conservation by reducing the packaging material. Strong cleaning agents are strongly demanded.
However, it is extremely difficult to obtain a liquid concentrated detergent composition having a surfactant concentration of 30 to 40% by weight or more by conventional techniques. This is because when a conventional detergent surfactant is made into an aqueous solution of 30 to 40% by weight or more, a middle phase having no fluidity or a neat liquid crystal having low fluidity is formed. And
Since these liquid crystals have high viscosity, they have poor dispersibility in water and have a low dissolution rate in water when diluted, making it difficult to use as a household cleaning agent. Various methods for producing a liquid concentrated detergent have been studied, but there have been hardly any cases in which the concentration of the surfactant exceeds 50% by weight, which has been successful to the extent that it can be commercialized. This is because it is difficult to prevent the liquid crystal formation and the high-quality liquid concentrated detergent composition cannot be obtained only by concentrating the dilute liquid detergent aqueous solution. For example, when a hydrotrope such as ethanol is added to a detergent, liquid crystals are less likely to be formed and stability at low temperature is increased, but when a large amount is added, problems such as strong irritation to skin occur.

Further, Japanese Patent Publication No. 6-62991 discloses that
40-92 wt% surfactant mixture and 8-60 wt%
A liquid detergent composition comprising water is shown. This surfactant mixture is a mixture of at least 50% by weight of a polyether type nonionic surfactant having a specific structure, and the balance consisting of a sulfosuccinic acid ester salt having a specific structure, and mixing the specific surfactant in a specific ratio. Otherwise, a uniform liquid cannot be obtained and the liquid viscosity is high. Further, in JP-A-59-157199, a viscosity modifier is added to an anionic surfactant aqueous solution such as α-sulfofatty acid ester salt to obtain an aqueous solution having a low viscosity of 50% by weight. . A polyether alcohol composed of a higher alcohol and an alkylene oxide is used as the viscosity modifier, and the amount added is 10% by weight of the amount of the surfactant, which causes a decrease in foaming power and the like.
Further, in this publication, specifically, a high-concentration surfactant aqueous solution exceeding 50% by weight is not obtained.

Furthermore, Japanese Patent Laid-Open No. 64-16757 discloses that
A method for producing a sulfonated product of a polyalkylene glycol monoalkyl ether monounsaturated fatty acid ester or a salt thereof is further described in JP-A-4-502651, in which this compound is preferable as a low foaming textile product treatment preparation. There is. However, there is no description as a cleaning agent using this compound, and no specific description regarding the concentration at that time, and there is no description regarding use in a liquid cleaning composition having a particularly high concentration. In addition, when the present inventors conducted a confirmation test on the detergency, it was found that good detergency could not be obtained only with this compound.

As described above, a high-concentration liquid detergent having a surfactant concentration of more than 50% by weight, which is excellent in various problems such as detergency, fluidity, solubility and safety, has not yet been obtained.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above problems found in liquid concentrated detergents, has excellent detergency, is less irritating to the skin, and is 55% by weight or more. It is an object of the present invention to provide a liquid concentrated detergent composition having high fluidity even at a high concentration and having excellent solubility when diluted with water.

[0008]

According to the present invention, an anionic surfactant (A represented by the following general formula (1) consisting of a sulfonated product of a polyalkylene glycol monomethyl ether unsaturated fatty acid ester or a salt thereof: ) And one or more amphoteric surfactants (B) selected from amine oxide type surfactants and betaine type surfactants as essential components, and the weight ratio of (A) and (B) is ( A):
(B) = 80: 20 to 30:70, and the total concentration of the surfactant components is 55 to 100% by weight, and a liquid concentrated detergent composition is provided.

Embedded image R ₁ COO (AO) _m CH ₃ (1) (In the formula, R ₁ is an alkyl group containing an unsaturated bond having 13 to 21 carbon atoms, AO is an oxyethylene group or an oxypropylene group, and m is 3 Represents an integer of -30.)

The sulfonated product of the polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the above general formula (1) or a salt thereof according to the present invention is similar to a surfactant used in conventional household liquid detergents. Since it does not form liquid crystals in the presence of water, it does not solidify even when a concentrated aqueous solution is stored. Further, even if a stock solution or a concentrated aqueous solution is used for washing, there is no problem such as poor water solubility, and the present invention provides a polyalkylene glycol monomethyl ether unsaturated fatty acid represented by the general formula (1) having such a specific structure. A detergent composition containing a sulfonated ester or a salt thereof,
It is extremely fluid even at high concentrations, has good solubility when diluted in water, and is less irritating to the human body.
Based on the newly found findings, the polyalkylene glycol monomethyl ether unsaturated fatty acid ester sulfonates or salts thereof, by blending the specific amphoteric surfactant in a specific ratio, excellent detergency In addition to having less irritation to the skin, and having high fluidity even at a high concentration of 55% by weight or more and excellent solubility when diluted with water, the present invention has been completed. It was

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) used in the present invention.
The sulfonated compound of polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by or its salt will be specifically described. In the formula, R ₁ has ₁₃ to 2 carbon atoms
1 is an alkyl group containing an unsaturated bond, preferably 1
5 to 19 are alkyl groups containing one or two unsaturated bonds. Specifically, it is a residue such as palmitooleic acid, oleic acid, linoleic acid, and icosadienoic acid. AO is an oxyethylene or oxypropylene group. Furthermore, m is an integer of 3 to 30, preferably 5 to 20. When making salt, it is equivalent to monovalent,
Metal ions or organic ammonium cations are preferred as counterions. Specifically, it is formed from alkali metal ions such as sodium, potassium and lithium, alkaline earth metal ions such as magnesium, ammonium ions, lower amines such as trimethylamine and triethylamine, lysine, mono-, di- or tri-lower alkanolamines and the like. Substituted ammonium ions and the like.

Specific examples of the sulfonated product of the polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or its salt include hexaethylene glycol monomethyl ether oleate ester sulfate Na salt and pentadeca. Ethylene glycol monomethyl ether oleate Sulfate Na
Examples thereof include salts, sulfated Na salt of decaethylene glycol monomethyl ether linoleic acid ester, sulfated triethanolamine salt of icosaethylene glycol methoxypropyl ether oleic acid ester, and the like.

The sulfonated product of the polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) of the present invention or a salt thereof can be easily produced by a known method. For example, JP-A-64-167
As disclosed in Japanese Patent No. 57, the polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) is diluted by a known method, that is, gaseous sulfur trioxide, air, nitrogen or the like, Is a gas mixture containing about 1-10% by volume of sulfur trioxide, 5-100
The acid type compound is obtained by contacting at a temperature of ° C and sulfating. Further, by neutralizing the compound with a hydroxide or carbonate of an alkali metal or an alkaline earth metal, or ammonia water or amines, a salt type compound having a desired cation as a counter ion can be obtained.

The structure of the sulfonated product of the present invention is considered to be the following sulfonated alkene structure (5) or sulfonated hydroxyalkane structure (6), or a mixture thereof.

Embedded image

Embedded image

The liquid concentrated detergent composition of the present invention has a concentration of 5
It is a liquid detergent composition of 5% by weight or more, particularly 60 to 100% by weight, and if the concentration is less than 55% by weight, the effect of reducing distribution costs and packaging materials is small. The liquid detergent composition having a concentration of 55% by weight or more is a concentration range which is not targeted at all in the conventional literature relating to the liquid detergent composition.

The liquid concentrated detergent composition of the present invention is a sulfonated product of a polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or a salt thereof, which is less irritating to the skin and has an excellent cleaning effect. The main ingredient is the anionic surfactant (A), which is used together with a specific amphoteric surfactant (B) in order to improve the detergency. Even if the amphoteric surfactant is used in combination, the surfactant concentration can be adjusted to 55 to 100% by weight, and the detergency is remarkably improved. The compounding ratio (A) :( B) of the anionic surfactant (A) and the amphoteric surfactant (B) is in the range of 80:20 to 30:70 by weight, and (A) is too small. In that case, liquid crystal may be formed and the fluidity of the composition and the solubility in water may be reduced. On the contrary, if (B) is too small, the cleaning power may be low.

Next, an amphoteric surfactant used in combination with the anionic surfactant represented by the general formula (1) and a composition containing the amphoteric surfactant will be described. Composition containing an amine oxide type surfactant An amine oxide type surfactant such as an alkylamine oxide represented by the following general formula (2) or an alkylamide alkylamine oxide represented by the following general formula (3) ( B
-1) is a surfactant suitable for use in combination with the sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or a salt thereof (A). Incidentally, (B-1) is a known amphoteric surfactant.

[Image Omitted] R ₂ N (R ₃ ) ₂ → O (2)

Embedded image R ₄ CONHR ₅ N (R ₆ ) ₂ → O (3) In the general formula (2), R ₂ is an alkyl group or an alkenyl group having 8 to 18 carbon atoms, preferably 1 carbon atom.
It is an alkyl group of 0-14. Also, R ₃ has 1 to 1 carbon atoms.
4 is an alkyl group or a hydroxyalkyl group. On the other hand, in the general formula (3), R ₄ is an alkyl group or an alkenyl group having 7 to 17 carbon atoms, preferably 9 carbon atoms.
~ 13 alkyl groups. R ₅ has 2 to 6 carbon atoms.
R ₆ is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. That is, the (B-
The preferred amine oxide type surfactant as 1) is obtained from higher alcohols or fatty acids having 8 to 18 carbon atoms, and the amine oxide type surfactant may be a single product or a mixture. Further, as an example of an amine oxide-type surfactant suitable for more specific combination, examples of the alkyl amine oxide include lauryl dimethyl amine oxide, myristyl diethyl amine oxide,
Lauryl diethanolamine oxide and the like, examples of the alkylamide alkylamine oxide include coconut oil fatty acid amide propyldimethylamine oxide, lauric acid amide propyldimethylamine oxide, myristic acid amide hexyl diethanolamine oxide, and lauric acid amide ethyldiethylamine oxide. It is not limited to. When (A) and (B-1) are used in combination, the mixing ratio of (A) :( B-1) is preferably in the range of 8:20 to 30:70 by weight, and the more preferable mixing ratio is. It is 70:30 to 50:50. The concentration of the surfactant in the detergent composition is 55% by weight or more, especially 6%.
It is preferably from 0 to 90% by weight.

Composition containing Betaine-Type Surfactant A betaine-type amphoteric surfactant (B-2) such as carboxylbetaine, sulfobetaine, imidazolinium betaine, amidoalkylbetaine, etc. is represented by the general formula (1). An amphoteric surfactant suitable for use in combination with a sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester or a salt thereof (A). In addition, (B-
2) is also a known amphoteric surfactant. Examples of (B-2) include betaine-type surfactants having a hydrophobic carbon-hydrogen chain having 6 to 18 carbon atoms, and the preferred hydrophobic group has 8 to 14 carbon atoms. And as a specific example of (B-2), lauryl carboxyl betaine, myristyl carboxyl betaine, lauryl sulfobetaine, myristyl sulfobetaine, decyl imidazolinium betaine,
Examples thereof include lauryl imidazolinium betaine, lauroyl amidopropyl betaine, and coconut fatty acid amidopropyl betaine, but are not limited thereto.
When (A) and (B-2) are used together, (A) :( B-
The mixing ratio of 2) is preferably in the range of 8:20 to 30:70 by weight, and more preferably 70:30 to.
It is 50:50. The concentration of the mixture in the detergent composition is 5
It is preferably 5% by weight or more, and particularly preferably 60 to 90% by weight.

The liquid concentrated detergent composition detailed above is
Adjust the pH to 5.0-9.0 to reduce skin irritation.
It is preferable to set it in the range. Therefore, the above general formula (1)
The cation in the sulfonated product of the polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by or its salt is appropriately selected so that the pH falls within the above range, or a suitable pH adjuster is added to the composition. Can be prepared by.

If desired, various compounding agents may be added to the composition. That is, a compounding agent that is mixed with a household cleaning agent within a range that does not impair the object of the present invention; for example, moisturizing agents such as polyethylene glycol, propylene glycol, glycerin, sorbitol; methyl cellulose, polyoxyethylene glycol distearate, ethanol, etc. Viscosity modifiers; antiseptics such as p-oxybenzoic acid esters; germicides; antioxidants; fragrances; dyes; ultraviolet absorbers; Further, it is possible to add a surfactant other than the above to the composition, and an anionic surfactant such as polyoxyethylene alkyl ether sulfate or alkylbenzene sulfonate, polyoxyalkylene alkyl ether, polyoxy An alkylene monomethyl ether alkyl ester, a higher alkanolamide, a nonionic surfactant such as a sugar-based surfactant, and the like can be added.

The liquid concentrated detergent composition of the present invention is hypoallergenic to the human body and has excellent detergency. In addition, since the sulfonated product of polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or its salt has a low Kraft point, when it is made into a liquid detergent composition, the storage stability of the product is good and It has an advantage that separation of crystals and precipitation of crystals are unlikely to occur. Therefore, the composition is in the field of household detergents in which contact with the human body is inevitable, for example, liquid detergents for skin and hair such as body shampoos and shampoos, liquid detergents for tableware, and residential use such as walls and floors. It is suitable as a cleaning agent for liquid detergents, automobiles, furniture and appliances, liquid detergents for clothes and the like. The suitable fields of use are classified according to the surface to be washed; hard surfaces such as tableware, plastic surfaces, metal surfaces, glass surfaces, and ceramic surfaces;
It is classified into the surface of wood and bamboo such as furniture and pillars; the surface of human body such as skin and hair; however, the composition of the present invention is preferably used in each of the above fields.

[0021]

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

The cleaning composition was evaluated by the following methods. <State of cleaning agent aqueous solution> The state was examined visually and by observation with a polarizing microscope, and the case of a fluid transparent liquid was indicated by ◯, and the case of a non-fluid liquid crystal was indicated by x. <Diluting Solubility> A 1 wt% aqueous solution was used as the sample, and the former was indicated by ◯ and the latter by x, based on the results of visual observation of whether or not the solubility was good. <Protein denaturation rate> 50 mM phosphate buffer (pH 7.0)
To 100 ppm bovine serum albumin was added to the sample, and the surfactant concentration in the aqueous solution was adjusted to 1000 p in total.
pm. After leaving this aqueous solution at room temperature for 3 hours, 220
circular dichroism spectrum of nm is JAS manufactured by JASCO Corporation
It was measured by CO J-720. Then, the amount (%) decreased from the data (blank test) when the surfactant was not contained was defined as the denaturation rate. The smaller this value is, the less irritating the human body is. <Washing performance> A polypropylene aqueous solution containing artificial red oil stains containing oil red is added to a surfactant solution 18
0 ml (concentration of activator: 0.026 wt%) was added, and after stirring and washing with a rotary blade for 5 minutes, the cup in which the solution was discarded was air dried. The cleaning performance was evaluated as follows: the stains on the cup after washing were evenly removed: ○, some were removed: Δ, and none was removed at all: ×.

Examples 1 to 12 and Comparative Examples 1 to 10 Aqueous solutions having respective surfactant concentrations were prepared, and the state, dilution solubility, protein denaturation rate and washing performance were measured, and the results are shown in Tables 1 and 2. It was shown to. Table 1 shows Examples 1 to 6 in which the sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester or its salt (A) and an amine oxide amphoteric surfactant (B-1) were used in combination, and Comparative Examples thereof. 1 to 7 are described. In Table 2, Examples 7 to 12 in which the sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester or a salt thereof (A) and a betaine-type amphoteric surfactant (B-2) were used in combination, and Comparative Example 8 thereof were shown. 10 is described.

In Tables 1 and 2, the surfactants used in Examples and Comparative Examples are described by symbols, and the symbols represent the following compounds. (1) Sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or salt thereof (A) A-1: Sulfated Na salt of decaethylene glycol monomethyl ether oleic acid ester A-2 : Sulfated Na salt of pentadecaethylene glycol monomethyl ether oleic acid ester A-3: Sulfated Na salt of octaethylene glycol monomethyl ether linoleic acid ester A-4: Sulfated Na salt of decaethylene glycol monomethoxypropyl ether oleic acid ester salt

(2) Amine oxide type amphoteric surfactant (B-1) B-11: lauryl dimethylamine oxide B-12: lauroylamidopropyl dimethylamine oxide B-13: coconut fatty acid amide propyldiethanolamine oxide (3) betaine Type Amphoteric surfactant (B-2) B-21: Lauryl carboxylic betaine B-22: Lauryl sulfobetaine B-23: Laurylamidopropyl betaine B-24: Myristyl imidazolinium betaine

(4) Sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester having a structure other than the general formula (1) or a salt thereof (C) C-1: sulfated Na salt of monoethylene glycol monomethyl ether oleic acid ester C-2: Sulfated Na salt of polyethylene glycol linoleic acid ester (average addition amount of ethylene oxide: 50 mol) (5) Polyoxyalkylene alkyl ether sulfate (D) D-1: Dodecyl sulfate sodium salt D-2: Lauryl ethoxy sulphate sodium salt (average addition amount of ethylene oxide: 5 mol) The compound of the above (D) is an excellent surfactant which is often blended in a household liquid detergent.

[0027]

[Table 1]

[0028]

[Table 2]

From Tables 1 and 2, the detergent compositions of Examples are liquids having good flowability even when the surfactant concentration is 55% by weight or more, and have good dilution and solubility and extremely low protein denaturation rate. I understand. On the other hand, in the case of the detergent composition of the comparative example, when the concentration of the surfactant mixture is as high as 55% by weight or more, it becomes a non-fluid liquid crystal, and there is a composition which has a poor dilution solubility and a high protein denaturation rate. It was Further, a sulfonated compound of polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the general formula (1) or a salt thereof, and an amphoteric surfactant (B-
1 and a compound represented by B-2) are blended,
It is understood that it is not preferable if the mixing ratio is out of the range specified in the present invention (Comparative Examples 2 and 8). The general formula (1)
A sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester or a salt thereof (compounds of C-1 and C-2) similar to the compound represented by the formula (1) is represented by the general formula (1) which characterizes the present invention. Although it has a structure similar to that of the sulfonated polyalkylene glycol monomethyl ether unsaturated fatty acid ester or a salt thereof, it may have poor fluidity and dilution solubility and a high protein denaturation rate.

[0030]

The liquid concentrated detergent composition of the present invention has excellent fluidity even when it does not contain a solvent such as water or is a high-concentration solution, and forms a liquid crystal when diluted with water. Since it does not, the diluting solubility in water is very good. Further, the rate of protein denaturation is extremely small and the action on the skin is mild. Since the composition can be used for cleaning a wide range of surfaces such as skin and hair in addition to hard surfaces and wood surfaces, it is a preferable composition as various household liquid cleaners. That is, the composition of the present invention is suitable as a liquid cleaning agent for tableware, a liquid cleaning agent for homes, shampoo, body shampoo, etc. Since the volume is significantly reduced, it is extremely useful for reducing distribution costs, and since packaging materials can be reduced, environmental safety is also high.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C11D 1:75 1:90) (72) Inventor Masami Fujiwara, 1-3, Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Keiko Kuroiwa 1-3-7 Main Office, Sumida-ku, Tokyo Lion Corporation Inside (72) Inventor Tetsuo Tano 1-3-7 Main Office, Sumida-ku, Tokyo Within Lion Corporation

Claims (1)

[Claims] 1. An anionic surfactant (A) comprising a sulfonated product of a polyalkylene glycol monomethyl ether unsaturated fatty acid ester represented by the following general formula (1) or a salt thereof, an amine oxide type surfactant, and It contains at least one amphoteric surfactant (B) selected from betaine-type surfactants as an essential component, and the weight ratio of (A) and (B) is (A) :( B) = 80: 20. ~ 30: 70
And the total concentration of the surfactant components is 55 to 100
A liquid concentrated detergent composition, characterized in that it is in weight%. Embedded image R ₁ COO (AO) _m CH ₃ (1) (In the formula, R ₁ is an alkyl group containing an unsaturated bond having 13 to 21 carbon atoms, AO is an oxyethylene group or an oxypropylene group, and m is 3 Represents an integer of -30.)