JP3008612B2 - Lime soap dispersant and soap-based detergent composition containing these - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lime soap dispersant excellent in dispersing ability of lime soap (soap scum) generated during washing or rinsing and a detergent composition containing the same.

[0002]

2. Description of the Related Art Soaps (fatty acid alkali metal salts) have been used for a long time as detergents for clothes, baths, and facial cleansing because of their excellent detergency and safety. However, soap reacts with calcium ions and the like in water to produce lime soap which is insoluble in water, causing various adverse effects. Particularly when used in hard water, this adverse effect is remarkable. For example, when soap is used for washing, the resulting lime soap deposits on clothing, causing the fabric to yellow and unpleasant odors. Furthermore, the deposition of lime soap in the washing machine is called "black garbage" and may cause clogging of water pipes.

[0003] In the case of toilet soaps, unpleasant odors and stains on wash basins and bathrooms are easily caused.
Conventionally, as a dispersant for such a lime soap, an ethylene oxide adduct of an aliphatic higher alcohol, a polyoxyethylene polyoxypropylene block copolymer, α-sulfofatty acid methyl, sulfated fatty acid alkanolamide, betaine, sulfobetaine, amino Carboxylic amphoteric surfactants and the like have been proposed, but these have been improved to some extent but are not satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lime soap dispersant having excellent lime soap dispersing ability without impairing the excellent characteristics of the soap, and a cleaning composition containing the same. is there.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a surfactant composed of a specific polyoxyethylene alkyl ether ethyl dialkylamine derivative was dispersed in lime soap. Have the ability
In addition, it has been found that when added to a soap-based detergent, the cleaning power is enhanced, and the present invention has been completed.

That is, a polyoxyethylene alkyl ether ethyl dialkylamine oxide type surfactant represented by the general formula (1) and / or a polyoxyethylene alkyl ether ethyl dialkylamino betaine type surfactant represented by the general formula (2) A lime soap dispersant comprising an amphoteric surfactant as an active ingredient and a soap-based detergent composition comprising one or both of them.

Wherein R ₁ is an alkyl group having 12 to 22 carbon atoms, an alkenyl group, an alkylphenyl group, R ₂ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, and n is a positive number having 0 to 15 carbon atoms. Is shown.)

Wherein R ₄ is an alkyl group having 12 to 22 carbon atoms, an alkenyl group, an alkylphenyl group, R ₅ and R ₆ are alkyl groups having 1 to 3 carbon atoms, and n is a positive number having 0 to 15 carbon atoms. Shown.)

Particularly preferred compounds in the present invention include polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 2 or more} and polyoxyethylene dodecyl ether ethyl diethylamine oxide {n in the general formula (1). Is 2 or more, polyoxyethylene tetradecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 5 or more}, and polyoxyethylene hexadecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 7 or more}. ,

Polyoxyethylene octadecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 9 or more}; polyoxyethylene octadecenyl ether ethyl dimethylamine oxide {n in the general formula (1) is 9 or more}; Oxyethylene icosyl ether ethyl dimethylamine oxide {n in general formula (1) is 11 or more}, polyoxyethylene nonylphenyl ether ethyl dimethylamine oxide {general formula (1)
N is 7 or more｝,

Polyoxyethylene dodecyl ether ethyl dimethylaminoacetic acid betaine {n in general formula (2) is 2 or more}; polyoxyethylene tetradecyl ether ethyl dimethylaminoacetic acid betaine {n in general formula (2) is 5 or more}; Polyoxyethylene hexadecyl ether ethyl dimethylaminoacetic acid betaine {n in the general formula (2) is 7 or more}, polyoxyethylene octadecyl ether ethyl dimethylaminoacetic acid betaine {n in the general formula (2) is 9 or more}, polyoxyethylene Octadecenyl ether ethyldimethylaminoacetate betaine {n in the general formula (2) is 9 or more};

Polyoxyethylene icosyl ether ethyl dimethylaminoacetic acid betaine {n in general formula (2) is 11 or more}, polyoxyethylene nonylphenyl ether ethyl dimethylaminoacetic acid betaine {n in general formula (2) is 7 or more} ,

The polyoxyethylene alkyl ether ethyl dialkylamine oxide type surfactant and / or the polyoxyethylene alkyl ether ethyl dialkylaminoacetic acid betaine type amphoteric surfactant of the present invention is used in an amount of 3 to 20% by weight, preferably 3 to 20% by weight, based on the detergent. What is necessary is just to mix | blend 5-15 weight%. If the amount is less than 3% by weight, a sufficient lime soap dispersing effect cannot be obtained, and if the amount exceeds 20% by weight, the dispersion of the lime soap is not improved. When both are used in combination, a blending amount of 3 to 20% by weight per detergent is sufficient.

The lime soap dispersant of the present invention is generally blended with ordinary soap. As the soap, powdery soap for washing such as sodium salt or potassium salt of tallow fatty acid or coconut oil fatty acid, solid soap for washing or cosmetic soap is used. It is used for soaps and medicated soaps. Formulation of the lime soap dispersant of the present invention is added at the stage of neat soap of soap base in the case of powdered soap.
Alternatively, a method such as dry blending with the finished powdered soap can be performed. Further, in the case of solid soap, it may be added during the kneading process with soap chips. As the compounding temperature, a room temperature or a temperature necessary for compounding can be appropriately selected.

[0013] Other additives to the soap include sodium sulfate, zeolite, soda ash, sodium silicate, sodium citrate,
Carboxymethylcellulose, titanium oxide, a fragrance, a chelating agent, a coloring agent, a preservative, an ultraviolet absorber, and the like can be appropriately compounded within a range that does not impair the effects of the present invention.

A method for producing a polyoxyethylene alkyl ether ethyl dialkylamine oxide represented by the general formula (1) uses a polyoxyethylene aletherethyl dialkylamine represented by the general formula (3) as a raw material, An aqueous solution of hydrogen peroxide was added dropwise to the amine and water system at 50 to 80 ° C. over several hours, and after the completion of the addition, the mixture was subjected to an aging reaction at the same temperature for several hours to obtain a reaction rate of 98 to 1
A 00% aqueous solution of polyoxyethylene alkyl ether ethyl dialkylamine oxide can be obtained.

Embedded image (Wherein, R ₇ is an alkyl group having 12 to 22 carbon atoms, an alkenyl group, an alkylphenyl group, and R ₈ and R ₉ have 1 to 3 carbon atoms.
And n represents a positive number of 0 to 15. )

The method for producing the polyoxyethylene alkyl ether ethyldialkylaminoacetic acid betaine represented by the general formula (2) uses the polyoxyethylene alkyl ether ethyl dialkylamine represented by the general formula (3) as a raw material. Monochloroacetic acid or sodium monochloroacetate, or both, in a tertiary amine and water system of
At a temperature of about 0 to 90 ° C., the mixture is charged over several hours, and after the completion of the charging, an aging reaction is performed for several hours at the same temperature to obtain a polyoxyethylene alkyl ether ethyldialkylaminoacetic acid having a conversion of 95 to 99%. A betaine aqueous solution can be obtained.

Now, the present invention will be described in further detail with reference to Examples. However, the present invention is not limited by this.

[0017]

【Example】

Example 1 1.5 ml of a 5% solution of sodium oleate was
Place about 35 ml of a female stoppered stoppered test tube, then put a small amount of polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 2} into the test tube and add 10 ml of hard water (hardness 1000 ppm). In addition, distilled water was further added to make the total volume 30 ml. After stoppering and repeating the handstand 20 times, the test tube was allowed to stand in a thermostat at 25 ° C. for 30 seconds to observe the state of the lime soap particles. If the lump precipitate is visible with a clear liquid, the polyoxyethylene dodecyl ether ethyl dimethylamine oxide required to disperse the lime soap is in short supply, and the amine oxide was gradually added.
The point at which the lumps were evenly distributed over the entire test tube, the contents became translucent, and no precipitation occurred was defined as the end point.

The lime soap dispersing ability is applied to the following equation:
Calculated. Lime soap dispersibility (%) = (Aml × 0.25) /0.025 Aml: ml of detergent added up to the time when precipitation did not occur. The results are shown in Table 1.

Embodiment 2 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is replaced with 2}, and polyoxyethylene tetradecyl ether ethyl dimethylamine oxide {n in general formula (1) is 4}. , And in the same manner as in Example 1. Table 1 shows the results.

Embodiment 3 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is replaced with 2}, but polyoxyethylene hexadecyl ether ethyl methyl propylamine oxide {n in general formula (1) is 7} Was performed in the same manner as in Example 1. Table 1 shows the results.

Embodiment 4 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) is replaced with 2}, and polyoxyethylene octadecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 9}, except that Performed in the same manner as in Example 1. Table 1 shows the results.

Embodiment 5 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is replaced with 2}, but polyoxyethylene octadecenyl ether ethyl dimethylamine oxide {n in general formula (1) is 9} Was performed in the same manner as in Example 1. Table 1 shows the results.

Embodiment 6 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is replaced with 2}, and polyoxyethylene docosyl ether ethyl dimethylamine oxide {n in general formula (1) is 15}. Performed in the same manner as in Example 1. Table 1 shows the results.

Embodiment 7 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) is replaced with 2}, but polyoxyethylene nonylphenyl ether ethyl dimethylamine oxide {n in the general formula (1) is 7}. , And in the same manner as in Example 1. Table 1 shows the results.

Embodiment 8 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is 2} instead of dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is 0}
The procedure was performed in the same manner as in Example 1, except that was used. Table 1 shows the results.

Embodiment 9 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is replaced with 2}, but polyoxyethylene dodecyl ether ethyl dimethylamino acetate betaine {n in general formula (2) is 2} , And in the same manner as in Example 1. Table 1 shows the results.

Embodiment 10 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 1 except that polyoxyethylene tetradecyl ether ethyldimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 1 shows the results.

Embodiment 11 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 1 except that polyoxyethylene octadecyl ether ethyl dimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 1 shows the results.

Embodiment 12 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was performed in the same manner as in Example 1 except that polyoxyethylene octadecenyl ether ethyl dimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 1 shows the results.

Embodiment 13 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 1 except that n in Formula (2) was replaced by polyoxyethylene docosyl ether ethyldimethylaminoacetate betaine (n in Formula (2) was 15).
The same was done. Table 1 shows the results.

Embodiment 14 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was performed in the same manner as in Example 1 except that polyoxyethylene nonylphenyl ether ethyl dimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 1 shows the results.

Embodiment 15 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
N is 2 in place of dodecyl ether ethyl dimethylaminoacetic acid betaine {n in the general formula (2)
Was performed in the same manner as in Example 1 except that 0 ° was used. Table 1 shows the results.

Example 16 60 parts by weight of a mixed fatty acid (tallow: coconut oil = 8: 2) sodium, 20 parts by weight of sodium carbonate (first grade reagent), 9 parts by weight of zeolite (Silton B manufactured by Mizusawa Chemical Co., Ltd.), carboxy Methyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd.)
1 part, polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the formula (1) is 2}
10 parts by weight were blended to prepare a powdered laundry soap. Next, a test was conducted under the following condition A, and the amount of lime soap was examined. In the evaluation, the amount of the generated lime soap was classified into three stages: good (○), slightly good (△), and poor (x).

<Condition A> Water: 75 ppm (CaCO ₃ ) Detergent concentration: 0.1% Contaminated cloth: Artificial contaminated cloth (cotton, Hitachi-Lion method) Bath ratio: 40 Washing ... Terg-O-Tometer
100 rpm x 10 minutes ・ Rinse…… Terg-O-Tometer 1
00 rpm x 3 minutes

The detergency in the composition was calculated by the following formula after washing for 10 minutes, dehydration and rinsing for 3 minutes under the condition B shown below, and measuring the reflectance of the contaminated cloth. Detergency (%) = (A / B) × 100 A: Reflectance of contaminated cloth after cleaning−Reflectance of contaminated cloth before cleaning B: Reflectance of uncontaminated cloth−Reflectance of contaminated cloth It was measured with a UV integrating sphere 550 nm using a double beam spectrophotometer UV-200S (manufactured by Shimadzu Corporation).

<Condition B> Water (hardness): 100 ppm (CaCO ₃ ) Detergent concentration: 0.1% Contaminated cloth: Artificial contaminated cloth (cotton, Hitachi-Lion method) Bath ratio: 30 Washing Terg-O-Tometer Temperature 10C The results are shown in Table 2.

Embodiment 17 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16 except that n was 2 in place of polyoxyethylene tetradecyl ether ethyl dimethylamine oxide {n in general formula (1) was 4}.
The same was done. Table 2 shows the results.

Embodiment 18 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 16 except that n was 2 in place of polyoxyethylene hexadecyl ether ethylmethylpropylamine oxide {n in the general formula (1) was 7}. Table 2 shows the results.

Embodiment 19 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16 except that n was 2 in place of polyoxyethylene octadecyl ether ethyl dimethylamine oxide {n in the general formula (1) was 9}.
The same was done. Table 2 shows the results.

Embodiment 20 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 1, except that n was 2 in place of polyoxyethylene octadecenyl ether ethyl dimethylamine oxide {n in general formula (1) was 9}.
Performed similarly to 6. Table 2 shows the results.

Embodiment 21 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16 except that n was 2 in place of polyoxyethylene docosyl ether ethyl dimethylamine oxide {in formula (1), n was 2}.
The same was done. Table 2 shows the results.

Embodiment 22 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 1, except that n in Formula (2) was replaced by polyoxyethylene nonylphenyl ether ethyl dimethylamine oxide {n in Formula (1) was 7}.
Performed similarly to 6. Table 2 shows the results.

Embodiment 23 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was performed in the same manner as in Example 16 except that dodecyl ether ethyl dimethylamine oxide {n in general formula (1) was 0} instead of 2 in formula (1). Table 2 shows the results.

Embodiment 24 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16 except that n was 2 in place of polyoxyethylene dodecyl ether ethyldimethylaminoacetate betaine in Formula (2).
The same was done. Table 2 shows the results.

Embodiment 25 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 16 except that beta in polyoxyethylene tetradecyl ether ethyldimethylaminoacetate {n in the general formula (2) was 4} instead of 2 in formula (2). Table 2 shows the results.

Embodiment 26 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 16 except that polyoxyethylene octadecyl ether ethyl dimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 2 shows the results.

Embodiment 27 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16, polyoxyethylene octadecenyl ether ethyl dimethylaminoacetate betaine was used instead of 2 in the formula (2). Table 2 shows the results.

Embodiment 28 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 1 except that n in Formula (1) was replaced by polyoxyethylene docosyl ether ethyldimethylaminoacetate betaine (n in Formula (2) was 15).
Performed similarly to 6. Table 2 shows the results.

Embodiment 29 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 16 except that n was 2 in place of polyoxyethylene nonylphenyl ether ethyldimethylaminoacetate betaine {n in the general formula (2) was 7}. Table 2 shows the results.

Embodiment 30 FIG. Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
N is 2 in place of dodecyl ether ethyl dimethylaminoacetic acid betaine {n in the general formula (2)
Was performed in the same manner as in Example 16 except that 0 ° was used. Table 2 shows the results.

Comparative Example 1 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) was replaced with dodecyldimethylamine oxide in place of 2} in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 2 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) was replaced with tetradecyldimethylamine oxide in place of 2} in the same manner as in Example 1.
Table 3 shows the results.

Comparative Example 3 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {in the general formula (1), n was 2}, and the same operation as in Example 1 was performed except that α-sulfostearic acid methyl ester sodium salt was used. Table 3 shows the results.

Comparative Example 4 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) was replaced with α-sulfo tallow fatty acid methyl ester sodium salt instead of 2} in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 5 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n was 2 in the general formula (1)), and the procedure was the same as in Example 1, except that betaine tetradecyldimethylaminoacetate was used. Table 3 shows the results.

Comparative Example 6 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {similar to Example 1 except that polyoxyethylene dodecyl ether (the number of moles of ethylene oxide added was 10 mol) was used instead of n in the general formula (1). I went to. Table 3 shows the results.

Comparative Example 7 Except that polyoxyethylene polyoxypropylene block copolymer (Pluronic L-61 manufactured by Asahi Denka Kogyo Co., Ltd.) was used instead of polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in general formula (1) is 2} Was performed in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 8 Instead of polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in the general formula (1) is 2}, 10 parts by weight of a mixed fatty acid (tallow: coconut oil = 8: 2) was used, and a total of 70 parts by weight was used. Other than that, it carried out similarly to Example 16. Table 4 shows the results.

Comparative Example 9 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide {n in formula (1) was replaced with tetradecyldimethylamine oxide in place of 2} in the same manner as in Example 16. Table 4 shows the results.

Comparative Example 10 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was performed in the same manner as in Example 16 except that betaine of coconut oil fatty acid amidopropyldimethylaminoacetate was used in place of 2%. Table 4 shows the results.

Comparative Example 11 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
In Example 16 except that n was 2 °, carboxymethylated polyoxyethylene dodecyl ether sodium salt (ethylene oxide 3 mol adduct) was used.
The same was done. Table 4 shows the results.

Comparative Example 12 Polyoxyethylene dodecyl ether ethyl dimethylamine oxide ｛General formula (1)
Was carried out in the same manner as in Example 16 except that in place of 2 °, polyoxyethylene dodecyl ether sulfate sodium sulfate (addition product of 3 mol of ethylene oxide) was used. Table 4 shows the results.

[0063]

According to the present invention, a lime soap dispersant having excellent hue stability, water solubility, solubilizing power, lime soap dispersing ability and low pH dependency can be obtained. Further, even when it is blended in a detergent composition mainly composed of fatty acid soap, it has excellent lime soap dispersibility and can enhance the detergency.

[Table 1]

[Table 2]

[Table 3]

[Table 4] Patent applicant Shin Nippon Rika Co., Ltd.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-54159 (JP, A) JP-A-3-153797 (JP, A) JP-A-60-89458 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C11D 10/04 C11D 9/02 C11D 1/75 C11D 1/90 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A polyoxyethylene alkyl ether ethyl dialkyl amine oxide type surfactant represented by the general formula (1) and / or a polyoxy ethylene alkyl ether ethyl dialkyl amino acetate betaine type represented by the general formula (2). A lime soap dispersant comprising an amphoteric surfactant as an active ingredient. Embedded image (Wherein, R ₁ is an alkyl group having 12 to 22 carbon atoms, an alkenyl group, an alkylphenyl group, and R ₂ and R ₃ are each a group having 1 to ₃ carbon atoms.
And n represents a positive number of 0 to 15. ) (Wherein, R ₄ represents an alkyl group having 12 to 22 carbon atoms, an alkenyl group, an alkylphenyl group, and R ₅ and R ₆ represent 1 to 3 carbon atoms.
And n represents a positive number of 0 to 15. ) 2. A polyoxyethylene alkyl ether ethyl dialkylamine oxide type surfactant represented by the general formula (1) of claim 1 and / or a polyoxyethylene alkyl represented by the general formula (2) of the same. A soap-based detergent composition comprising a betaine-type etherethyldialkylaminoacetate amphoteric surfactant.