JPH07126692A - Cleaning agent composition - Google Patents

Abstract

PURPOSE:To obtain a cleaning agent composition for body containing a maleilated fatty acid (salt) and a nonionic surfactant in a specific weight ratio, excellent in low irritation, foaming property, hard water resistance and feeling of use after washing up and having proper detergency. CONSTITUTION:This cleaning agent composition contains (A) a maleilated fatty acid or its salt and (B) a nonionic surfactant in an amount of 5-60wt.% as a total amount of the components A and B. The weight ratio of the component A to the component B is (20/1) to (1/20). The cleaning agent composition has good stability with the lapse of time and it is useful as a body shampoo composition, a hand soap composition, a facial cleansing agent composition, a hair shampoo composition, a cleansing agent for clothes, cleaning agent for dishes, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a detergent composition having low irritation, foamability, hard water resistance, excellent feeling after washing, moderate detergency and good stability over time. Regarding

[0002]

2. Description of the Related Art Detergent compositions vary depending on the type of object to be cleaned.
It is divided into body, clothing, hard surface, etc., and each has different characteristics in terms of prescription. However, there are common functions required for all detergent compositions, and these have been diversified in recent years. That is, in terms of performance, it has good hard water resistance, excellent foaming properties, has an appropriate detergency, has an excellent feeling when actually used, and the composition is stable over time. There is also that it is safe to use, so-called hypoallergenic,
A detergent composition that totally satisfies these requirements is desired.

Currently, as a personal cleansing composition, higher fatty acid salts are useful because of the refreshing feeling after washing and the ease of foam breakage. The higher fatty acid salts are blended with various surfactants to obtain higher fatty acid salts alone. A composition has been developed which compensates for defects such as poor stability over time. Examples of such higher fatty acid salt-based compositions include compositions obtained by combining a higher fatty acid salt, a synthetic surfactant, a humectant such as glycerin and vegetable oil, and a cationic polymer compound (JP-A-62-25199).
Japanese Patent Publication No. JP-A-54-13512, a composition in which a sodium salt of a higher fatty acid is combined with a nonionic surfactant or an alkyl ether sulfate type anionic surfactant (JP-A-54-13512).
(Japanese Patent Laid-Open No. 61-287992), and a composition in which a triethanolammonium salt of a higher fatty acid and an acyl glutamate type anionic surfactant are combined.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention In a personal cleansing composition based on a salt of a higher fatty acid, the number of carbon atoms is generally 12 to
A fatty acid salt of 18 was often used, and a salt of a fatty acid having 12 carbon atoms gave good foaming property, but it had a strong irritation to the skin. 16 carbons in consideration of skin irritation
When a salt of fatty acid No. 18 or 18 is used, the foamability during use is significantly reduced, and the stability over time is also reduced. Further, in the detergent composition based on the higher fatty acid salt, since the detergency is excessive,
I feel the tightness of the skin. Further, the higher fatty acid salt has a problem in terms of hard water resistance, and has a drawback that foaming property and detergency are significantly lowered depending on the hardness of water used. If the ratio of other synthetic surfactants is increased to solve these drawbacks, the feeling of refreshing after washing is impaired, and a feeling of sliminess may be felt, or foam breakage may become worse. Was there.

The present invention has low irritation, excellent foamability, hard water resistance, excellent feeling after washing, and proper detergency.
Moreover, it is an object of the present invention to provide a detergent composition having good stability over time.

[0006]

[Means for Solving the Problems] As a result of repeated studies for solving the above problems, a combination of a maleated fatty acid or a salt thereof and a nonionic surfactant at a specific ratio results in unprecedented characteristics. It came to obtain a cleaning composition with That is, the present invention contains the following a and b, a + b is 5 to 60% by weight, and the weight ratio of a and b is 20/1 to
The detergent composition is 1/20. a. Maleated fatty acid or salt thereof. b. Nonionic Surfactant As a method for obtaining the maleated fatty acid of the component a or a salt thereof, the method described in JP-B-53-7412, JP-B-61-41502, etc., for example, a catalyst such as silica or alumina There is a method of adding maleic anhydride at 150 to 300 ° C. in the presence of or without a catalyst. Maleic unsaturated fatty acid is obtained by hydrolyzing the maleic anhydride adduct,
Further, hydrogenation of this gives maleated saturated fatty acid. The salt is obtained by neutralizing these maleated fatty acids with a basic substance.

The unsaturated fatty acid used as the raw material of the component a is preferably one having 10 to 26 carbon atoms, for example, obtsylic acid, caproleic acid, undecylenic acid, linderic acid, tudzuic acid, fizeteric acid, myristoleic acid, palmitoleic acid. Acid, petroselinic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, linoleic acid, α-
Eleostearic acid, β-eleostearic acid, linolenic acid, γ-linolenic acid, ricinoleic acid, gadoleic acid,
Gondoinic acid, eicosapentaenoic acid, cetoleic acid,
Examples thereof include erucic acid, brassic acid, docosahexaenoic acid, ceracoleic acid, and ximenoic acid. When the carbon number is less than 10, irritation becomes strong, and when it exceeds 26, foaming property and stability with time deteriorate.

The maleated fatty acid salt does not need to have all the carboxyl groups neutralized, and free carboxyl groups may be present. The maleated fatty acid salt obtained by the basic substance is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic ammonium salt or the like, and examples thereof include lithium salt, sodium salt, potassium salt, 1/2 magnesium salt, 1/2 magnesium salt, Calcium salt, ammonium salt, triethanol ammonium salt, monoethanol ammonium salt,
Examples thereof include diethanol ammonium salt. The component b may be any nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoethanolamide, fatty acid. Examples include diethanolamide, alkylamine oxide, fatty acid amideamine oxide, polyoxyethylene polyoxypropylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyalkyl glycoside, and specific examples include polyoxyethylene ( 4 mol)
Lauryl ether, polyoxyethylene (6 mol) oleyl ether, polyoxyethylene (10 mol) nonylphenyl ether, polyoxyethylene (2 mol) lauric acid ester, polyoxyethylene (4 mol) stearic acid ester, sorbitan lauric acid ester , Polyoxyethylene (21 mol) sorbitan stearate, coconut oil fatty acid monoethanolamide, oleic acid diethanolamide, lauryl dimethylamine oxide,
Coconut oil fatty acid amide dimethylamine oxide, polyoxyethylene (25 mol) polyoxypropylene (30 mol)
Examples thereof include glycol, polyoxyethylene (20 mol) polyoxypropylene (4 mol) cetyl ether, and lauryl glycoside.

A + b is 5 to 60% by weight, but 5% by weight
If it is less than 60% by weight, the foaming property, detergency and feel of use required for the detergent composition cannot be obtained. The weight ratio of a and b is 20
The ratio is / 1 to 1/20, but if a is larger than this, foaming property, hard water resistance and stability over time are deteriorated, and if b is larger, irritation becomes stronger and usability deteriorates. The cleaning composition of the present invention is a component that is generally blended as desired, for example, higher alcohols such as cetanol and stearyl alcohol, polyhydric alcohols such as glycerin, ethylene glycol, polyethylene glycol, squalane, jojoba oil, olive oil, castor oil. , Lanolin, lecithin, α-
Oils such as olefin oligomers, cellulose ether type cationic polymer compounds, cationic polyvinylpyrrolidone derivatives, cationic polyacrylic acid derivatives, cationic polyamide derivatives, polydimethyldiallylammonium chloride, dimethyldiallylammonium chloride and acrylic acid Copolymers of amides, cationic polymer compounds such as alkyl polyethylene imines, highly polymerized methyl polysiloxanes, silicon derivatives such as dimethyl siloxane / methyl (polyoxyethylene) siloxane copolymers, sodium silicate, sodium carbonate, alumino silicate Builders such as sodium acidate and sodium tripolyphosphate, pearlizing agents such as ethylene glycol distearate and styrene polymer, sterilizing agents such as paraoxybenzoic acid ester and phenoxyethanol, 5 Tonic agents such as methyl-2-isopropylcyclohexanol and capsicum tincture, ethylenediaminetetraacetic acid derivatives, citric acid, chelating agents such as trisodium nitrilotriacetic acid, UV absorbers such as benzophenone derivatives and benzotriazole derivatives, and other dyes, fragrances, etc. Can be included to the extent that the effects of the present invention are not impaired.

[0010]

EXAMPLES The present invention will be specifically described with reference to examples. The maleated fatty acid salts used in the examples are shown in Table 1. The maleic anhydride was added to the raw material fatty acid as follows. Maleated fatty acid salts A, B, D, E and F 4 mol of maleic anhydride was added to 1 mol of raw material fatty acid, reacted for 5 hours at 180 ° C. under a nitrogen stream, and then unreacted maleic anhydride was removed by washing Thus, a maleic anhydride-added fatty acid was obtained. After hydrolyzing the maleic anhydride-added fatty acid, the neutralization value was measured and neutralized with a predetermined amount of basic substance to obtain a maleated fatty acid salt. The average number of moles of maleic anhydride added was calculated from the acid value of water collected during washing with water.

Maleated fatty acid salt C 6 mol of maleic anhydride was charged to 1 mol of raw material fatty acid, and the following operations were performed in the same manner as described above.

[0012]

[Table 1]

(Note 1) "EXTRA OLEIC 9" manufactured by NOF CORPORATION
0 "(average molecular weight 281.1) is used. (Note 2) "EXTRA OLEIC 80R" (average molecular weight 280.5) manufactured by NOF CORPORATION is used. (Note 3) "EXTRA LINOLEIC 90" (average molecular weight 279.3) manufactured by NOF CORPORATION is used. (Note 4) "NAA-34" manufactured by NOF CORPORATION (average molecular weight 274.2)
use. (Note 5) "EXTRA OLEIC 99" (average molecular weight 282.0) manufactured by NOF CORPORATION is used.

The test methods and evaluation methods used in the examples will be described below. (1) Skin irritation It was evaluated by the closed patch test. That is, for each of 10 men and women with healthy skin, a closed patch test was performed for 24 hours on the inner side of the upper arm using an aqueous solution having a concentration of 0.5% by weight of the detergent composition, and evaluated by visual judgment.
The average value of 20 people was calculated with 0 point when no change was observed on the skin, 1 point when slight erythema was observed on the skin, and 2 points when erythema or edema was clearly observed on the skin. The following three grades were used for the evaluation. Skin irritation is weak (average value less than 0.5 points) Medium skin irritation (average value is 0.5 points or more and less than 1.0 points) Skin irritation is strong (average value is 1.0 points or more)

(2) Foamability Using an aqueous solution having a concentration of 1% by weight of the detergent composition, the foam height was measured at 25 ° C. immediately after the sample was charged and 5 minutes after the sample was charged, by the Ross Miles method. A cleaning agent having a foam height of 150 mm or more immediately after the sample was introduced and a foam retention rate of 90% or more obtained by the following formula was evaluated as a cleaning agent having a good foaming property. Persistence of foam = [(foam height after 5 minutes) / (foam height immediately after sample introduction)] x 100

(3) Hard water resistance 50 g of a 1% strength by weight aqueous solution of a detergent composition is placed in a 100 ml beaker having a black cross on the bottom and stirred. Artificial hard water (1.1% by weight CaCl ₂ solution, 1% by weight CaCO ₃ )
Read the amount of artificial hard water dropped when the black cross on the bottom of the beaker disappears from above. The CaCO ₃ concentration in the aqueous solution was calculated from the following formula, and the hard water resistance was evaluated in the following three stages.

CaCO ₃ concentration (ppm) = [(drop amount) / (drop amount + 50)] ×
10 ⁴ Good hard water resistance (CaCO ₃ concentration 300ppm or more) Medium hard water resistance (CaCO ₃ concentration 100ppm or more but less than 300ppm) Poor hard water resistance (CaCO ₃ concentration less than 100ppm)

(4) Detergency Using an aqueous solution having a concentration of 1% by weight of the detergent composition, Terg-ot
Wool muslin artificially contaminated cloth is washed with a meter (Kamishima Seisakusho) under the conditions of 40 ° C., 70 rpm, and 10 minutes. After drying the contaminated cloth, color computer (Suga Test Machine Co., Ltd.)
Surface reflectivity was measured by the following formula, and the detergency was calculated from the following formula, and the following three levels were evaluated.

[0019]

[Equation 1]

Excessive cleaning power (60% or more cleaning power) Good cleaning power (25% or more and less than 60% cleaning power) Weak cleaning power (less than 25% cleaning power)

(5) Feeling slimy during washing 20 women were used as panelists to evaluate the feeling of sliminess when washed with 5 g of the composition. 0 if you do not feel slimy
The average value of 20 persons was calculated by scoring 1 point when the feeling of a rather slimy feeling was strong and 2 points when the feeling of a slimy feeling was persistent and taking a long time to rinse, and evaluated in the following 3 grades. No slimy feeling (average value less than 0.5 points) Slight slimy feeling (average value 0.5 points or more but less than 1.0 points) Persistent slimy feeling (average value 1.0 points or more)

(6) Tightening sensation on the skin after washing Twenty women were panelists and the sensation on the tightness of the skin after washing with 5 g of the composition was evaluated. The average of 20 persons was calculated by setting 2 points when the skin was not completely stiff, 1 point when the skin was slightly stiff, and 0 points when it was felt that the skin was very stiff. . No feeling of tightness (average value of 1.5 points or more) Some feeling of tightness (average value of 1.0 to less than 1.5 points) Very taut (average value of less than 1.0 points)

(7) Refreshing sensation after washing With 20 women as panelists, the refreshing sensation after washing with 5 g of the composition was evaluated. 2 points if you feel it is very refreshing, 1 if you feel it is not very refreshing
The average value of 20 persons was calculated by setting the point, when it was felt that it was not slimy at all, as 0 point, and evaluated in the following 3 grades. Sufficient refreshing feeling is obtained (average value of 1.5 points or more).
(Less than point) No refreshing feeling (average value less than 1.0 point)

(8) Stability over time The composition was stored at -5 ° C for 1 month, and its appearance was observed and evaluated according to the following three grades. ◯: Good stability (transparent dissolution or slight turbidity, no change in appearance) Δ: Slightly poor stability (slightly cloudy) ×: Poor stability (separation, precipitation observed, or solidification)

Examples 1 to 5 and Comparative Examples 1 to 10 Samples having the compounding compositions shown in Tables 2 to 4 were prepared and their performances were evaluated. The results are shown in Tables 5-7. The unit in the table indicates% by weight.

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

From Tables 5 to 7, the compositions of Examples 1 to 5 of the present invention have low irritation, foamability, hard water resistance, excellent feeling after washing, and proper detergency. It is clear that the composition has good stability over time. Since the composition of Comparative Example 1 uses a alone, its foaming property is low and its hard water resistance is not good. The composition of Comparative Example 2 has a low foaming property because b is used alone, has a strong slimy feel at the time of washing, does not have a refreshing feel after washing, and is not stable with time. Since the composition of Comparative Example 3 uses b alone, it has a strong irritancy and a strong slimy feeling at the time of washing, and a refreshing feeling after washing cannot be obtained. Since the composition of Comparative Example 4 uses sodium lauric acid salt instead of a and b, it is irritating,
After washing, the skin feels tight and the water resistance and stability over time are poor. Since the composition of Comparative Example 5 uses sodium laurate and potassium stearate instead of a and b, it has strong irritancy, detergency, and a tight feeling on the skin after washing, hard water resistance, and stability over time. The sex is bad. Since the composition of Comparative Example 6 uses sodium lauric acid salt and potassium stearate salt instead of a, it has poor hard water resistance and stability with time. Since the composition of Comparative Example 7 had a + b of less than 5% by weight, its foaming property and detergency were low, and its hard water resistance was not good. In the composition of Comparative Example 8, since a + b exceeds 60% by weight, irritation, detergency and tightness of skin after washing are strong, and stability with time is not good. The composition of Comparative Example 9 was a
Since / b exceeds 20/1, the foaming property is low, the hard water resistance and the stability over time are not good. The composition of Comparative Example 10 was a
Since / b is less than 1/20, it has a strong slimy feel during cleaning,
I can't get a refreshing feeling after washing.

Example 6 A transparent body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt F 30 Polyoxyethylene (20 mol) lauryl ether 10 Polyoxyethylene (2 mol) oleyl ether 2 Propylene glycol 0.5 Butyl paraoxybenzoate 0.1 Methyl paraoxybenzoate 0.1 Fragrance 0.5 Purified water balance

When this transparent body shampoo composition was evaluated according to the above evaluation method, the following good results were obtained. Skin irritation 0.2 Foam height immediately after sample application 208mm Foam height after 5 minutes 206mm Foam persistence rate 99.0% Hard water resistance 445ppm Detergency 37.5% Slimy feeling 0.2 Tight feeling 1.7 Light feeling 1.8 Temporal stability 〇

Example 7 A pearly body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt F 15 Maleated fatty acid salt B 10 Polyoxyethylene (4 mol) Oleic acid ester 8 Polyoxyethylene (4 mol) Stearic acid ester 1 Ethylene glycol distearate 2 Phenoxyethanol 0.3 Methyl paraoxybenzoate 0.1 Fragrance 0.3 Purified water balance The pearl-like body shampoo composition was evaluated according to the above-mentioned evaluation method, and the following good results were obtained. The stability with time was based on the following method.

The composition was placed at -5 ° C, 25 ° C and 45 ° C under 1
It was stored for a month, the appearance was observed, and the evaluation was made according to the following two grades. ◯: Good stability (no change in appearance from before storage at any temperature) ×: Poor stability (separation is recognized at any temperature,
Skin irritation 0.3 Foam height immediately after sample injection 203mm Foam height after 5 minutes 200mm Foam persistence 98.5% Hard water resistance 445ppm Detergency 37.2% Slimy feeling 0.2 Tight feeling 1.7 Light feeling 1.8 Stability over time

Example 8 An unscented body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt B 30 Polyoxyethylene (6 mol) sorbitan coconut oil fatty acid ester 5 Isobutylene tetramer 0.5 Sodium salicylate 0.2 Methyl paraoxybenzoate 0.2 Purified water balance

When this unscented body shampoo composition was evaluated according to the above evaluation method, the following good results were obtained. Skin irritation 0.3 Foam height immediately after sample injection 205mm Foam height after 5 minutes 201mm Foam retention rate 98.0% Hard water resistance 398ppm Detergency 35.7% Slimy feeling 0.2 Tight feeling 1.8 Light feeling 1.8 Temporal stability 〇

Example 9 A hand soap composition having a refreshing feeling was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt C 15 Polyoxyethylene (20 mol) Polyoxypropylene 10 (4 mol) Cetyl ether Glycerin 0.5 Olive oil 0.3 5-Methyl-2-isopropylcyclohexanol 0.1 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Fragrance 0.1 Purified water balance

When this hand soap composition having a refreshing feeling was evaluated according to the above evaluation method, the following good results were obtained. Skin irritation 0.2 Foam height immediately after sample application 212mm Foam height after 5 minutes 210mm Foam retention rate 99.1% Hard water resistance 705ppm Detergency 35.4% Slimy feeling 0.3 Tight feeling 1.7 Light feeling 1.7 Temporal stability 〇

Example 10 A facial cleansing composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt D 17 Palmityl glycoside 8 Propylene glycol 1 Squalane 0.3 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Perfume 0.1 Purified water balance

When this face-washing composition was evaluated according to the above-mentioned evaluation method, the following good results were obtained. Skin irritation 0.2 Foam height immediately after sample application 210mm Foam height after 5 minutes 205mm Foam retention rate 97.6% Hard water resistance 567ppm Detergency 32.8% Slimy feeling 0.2 Tight feeling 1.8 Light feeling 1.7 Temporal stability 〇

Example 11 A hair shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt A 8 Oleic acid diethanolamide 5 Lauryl dimethylamine oxide 5 Cellulose ether type cationic polymer compound (Note 1) 0.5 Cetanol 0.1 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Perfume 0.1 Purified water Remainder (Note 1) "Gelner QH3" manufactured by Daicel Chemical Industries, Ltd.
00 ”was used.

When this hair shampoo composition was evaluated, the following good results were obtained. The evaluation method was in accordance with (1) to (4) and (8) of the evaluation methods performed in Examples 1 to 5, and the rinsing property during washing was as follows. Twenty women were panelists, and their hair was washed with 5 g of the composition and the feeling when rinsed was evaluated. The average value of 20 people was calculated by setting 2 points when the hair did not squeak and smooth rinse, 1 point when feeling a slight squeaky feeling during rinsing, 0 point when strong squeaking and discomfort felt, and the following. Three
The grade was evaluated.

Rinseability is good (average value is 1.5 points or more) Rinseability is not sufficient (average value is 1.0 point or more and less than 1.5 points) Rinseability is poor (average value is less than 1.0 point) Skin irritation 0.3 Foam height immediately after introduction of sample 237 mm Height of foam after 5 minutes 235mm Sustained rate of foam 99.2% Hard water resistance 872ppm Detergency 37.8% Rinseability 1.8 Stability over time 〇

Example 12 A liquid detergent composition for clothing was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid salt A 20 Polyoxyethylene (6 mol) oleyl ether 5 Coconut oil fatty acid monoethanolamide 5 Sodium aluminosilicate 7 Propylene glycol 3 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Perfume 0.1 Purified water balance

When this liquid detergent composition for clothes was evaluated according to the above evaluation methods (1) to (4) and (8), the following good results were obtained. Skin irritation 0.2 Foam height immediately after sample injection 202mm Foam height 5 minutes after 200mm Foam persistence 99.0% Hard water resistance 483ppm Detergency 41.6%

[0048]

The cleaning composition of the present invention is hypoallergenic,
It has excellent foamability, hard water resistance, and feeling after washing, has suitable detergency, and has good stability over time. Therefore, body shampoo compositions, hand soap compositions, facial cleansing compositions, and hair. It can be used in shampoo compositions, clothes detergent compositions, dishwashing detergent compositions and the like.

Claims (1)

[Claims] 1. The following a and b are contained, and a + b is 5 to
A cleaning composition comprising 60% by weight and a weight ratio of a to b of 20/1 to 1/20. a. Maleated fatty acid or salt thereof. b. Nonionic surfactant.