JPH07207298A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain a detergent composition being lowly irritating and improved in foaming properties, use of feeling of the washing, detergency, and long-term stability by mixing a maleinized fatty acid ester or its salt with an amphoteric surfactant. CONSTITUTION:The composition is obtained by mixing a maleinized fatty acid ester (A) prepared by reacting 1mol of a starting fatty acid ester made from a 10-26 C unsaturated fatty acid and a 1-4 C alcohol or being an unsaturated oil of fat itself such as corn oil with 4mol of maleic acid for about 5 hr at 180 deg.C in a nitrogen stream, and washing off unreacted maleic anhydride out of the product or a salt (A) prepared by hydrolyzing this and neutralizing the hydrolyzate with a basic substance with an amphoteric surfactant (B) such as alkylbetaine in amounts to give a total of components A and B of 5-60wt.% and an A/B weight ratio of 20/1-1/20, and mixing the resulting mixture with opitonally a higher alcohol, an oil, a cationic polymer component, a bactericide, a tonic, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition which is hypoallergenic, has excellent foaming properties, has an excellent feeling after washing, has an appropriate detergency, and has good stability over time.

[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 excellent foamability, has an appropriate detergency, has an excellent feeling when actually used, and that the composition is stable over time. In addition, it is safe and so-called hypoallergenic, and a cleaning composition that totally satisfies them 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
The fatty acid salt of 18 is often used, but the use of the fatty acid salt of 12 carbon atoms gives good foaming property, but it has strong irritation to the skin. In consideration of skin irritation, when a salt of a fatty acid having 16 or 18 carbon atoms is used, the foamability during use is significantly reduced and the stability over time is also reduced. In addition, a detergent composition based on a higher fatty acid salt has an excessive detergency, so that the skin feels tight. 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.

It is an object of the present invention to provide a detergent composition which is hypoallergenic, has excellent foaming properties, has a feeling of use after washing, has an appropriate detergency and has good stability over time. To do.

[0006]

[Means for Solving the Problems] As a result of repeated studies for solving the above-mentioned problems, a maleic acid compound of a fatty acid ester or a salt thereof and an amphoteric surfactant were combined at a specific ratio, and thus unprecedented. It came to obtain a characteristic detergent composition. That is, the present invention provides the following a, b
Containing 5 to 60% by weight of a + b, the weight ratio of a to b is 20
It is / 1-1 / 20, It is a detergent composition characterized by the above-mentioned. a. Maleic acid ester of fatty acid or salts thereof. b. Amphoteric surfactant.

As a method for obtaining the maleated compound of the fatty acid ester of the component a or a salt thereof, the method described in JP-B-53-7412, JP-B-61-41502 and the like, for example, catalysts such as silica and alumina can be used. In the presence or in the absence of catalyst, 15
There is a method of adding maleic anhydride at 0 to 300 ° C. By hydrolyzing the maleic anhydride adduct, a maleated unsaturated fatty acid ester is obtained, and when this is hydrogenated, a maleated saturated fatty acid ester is obtained. By neutralizing these maleated fatty acid esters with a basic substance, their salts can be obtained.

The unsaturated fatty acid ester used as the raw material of the component a is synthesized from unsaturated fatty acid and alcohol, and the unsaturated fatty acid preferably has 10 to 26 carbon atoms, for example, obtsylic acid, caproic acid, Undecylenic acid, linderic acid, tzunic acid, fizeteric acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, linoleic acid, α-eleostearic acid, β-eleostearic acid Acids, linolenic acid, γ-linolenic acid, ricinoleic acid, gadoleic acid, gondoinic acid, eicosapentaenoic acid, cetoleic acid, erucic acid, brassic acid, docosahexaenoic acid, ceracoleic acid, xymenoic acid and the like, and the carbon number is less than 10. , The irritation becomes strong, and when it exceeds 26, foaming property and stability over time To below. The alcohol preferably has 1 to 4 carbon atoms, and is methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycerin, ethylene. Glycol, propylene glycol, diethylene glycol and the like can be mentioned, and when the carbon number exceeds 4, the foamability and the stability with time decrease.

As a raw material for the component a, an oil or fat having an unsaturated bond may be used as it is, for example, corn oil,
Cottonseed oil, olive oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, coconut oil, palm oil,
Palm kernel oil, castor oil, linseed oil, tung oil, lard, beef tallow,
Herring oil, deer oil, crumb oil, menhaden oil, tall oil and the like can be mentioned.

The maleated fatty acid ester salt does not have to have all the carboxyl groups neutralized, and free carboxyl groups may be present. The maleated fatty acid ester salt obtained by the basic substance is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic ammonium salt, etc., for example, a lithium salt, a sodium salt, a potassium salt, a 1/2 magnesium salt, 1 / Dicalcium salt, ammonium salt, triethanol ammonium salt, monoethanol ammonium salt, diethanol ammonium salt and the like can be mentioned.

The component b may be any amphoteric surfactant, for example, alkyl betaine, amidobetaine, imidazolinium betaine, amidoamino acid type amphoteric surfactant, alkylglycine, alkyliminodiacetic acid, β-alkyl. Propionic acid, alkyliminodipropionic acid, alkyldiaminoethylglycine, alkylsulfobetaine, amidosulfobetaine, alkylphosphobetaine, and the like, specific examples include lauryldimethylaminoacetic acid betaine, stearyldihydroxyethylaminoacetic acid betaine, coconut oil fatty acid. Amidopropyl dimethylamino acetic acid betaine, coconut oil fatty acid amide ethylhydroxyethylglycine sodium salt, coconut oil fatty acid amide hydroxyethylethyliminodiacetic acid sodium salt, laurylglycine β- lauryl aminopropionic acid sodium salt, Rauriruiminoji acid sodium salt,
Lauryl imino dipropionic acid sodium salt, lauryl diaminoethyl glycine, lauryl dimethyl-2-hydroxypropyl sulfobetaine, oleic acid amidopropyl dimethyl-2-hydroxypropyl sulfobetaine, N- (2-lauryl-2-hydroxyethyl) -N
-Methylaminoethanol phosphate sodium salt and the like can be mentioned.

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, and if a is larger than this, foaming property and temporal stability are deteriorated, and if b is larger, irritation becomes stronger and usability is deteriorated.

The detergent composition of the present invention contains, if desired, components generally added, for example, higher alcohols such as cetanol and stearyl alcohol, polyhydric alcohols such as glycerin, ethylene glycol and polyethylene glycol, squalane, and α-olefin oligomer. Oil content, etc.
Cellulose ether type cationic polymer compound, cationic polyvinylpyrrolidone derivative, cationic polyacrylic acid derivative, cationic polyamide derivative, polydimethyldiallylammonium chloride, copolymer of dimethyldiallylammonium chloride and acrylic acid amide, Cationic polymer compounds such as alkyl polyethylene imine, highly polymerized methyl polysiloxane, silicone derivatives such as dimethyl siloxane / methyl (polyoxyethylene) siloxane copolymer, sodium silicate, sodium carbonate, sodium aluminosilicate, sodium tripolyphosphate Such as builder, ethylene glycol distearate, pearlizing agent such as styrene polymer, paraoxybenzoic acid ester, bactericide such as phenoxyethanol, 5-methyl-2
-Tonic agents such as isopropylcyclohexanol and capsicum tincture, ethylenediaminetetraacetic acid derivatives, chelating agents such as citric acid and trisodium nitrilotriacetic acid,
An ultraviolet absorber such as a benzophenone derivative and a benzotriazole derivative, and a dye, a fragrance and the like can be contained to the extent that the effects of the present invention are not impaired.

[0014]

EXAMPLES The present invention will be specifically described with reference to examples. The maleated fatty acid ester salts used in the examples are shown in Table 1. The addition of maleic anhydride to the raw material fatty acid ester and the preparation of the maleated fatty acid ester salt were carried out as follows.

Maleated fatty acid ester salts A and B:
4 mol of maleic anhydride was charged to 1 mol of the raw material fatty acid ester, and the mixture was stirred at 180 ° C. for 5 hours in a nitrogen stream. Unreacted maleic anhydride was removed by washing with water to obtain a maleic anhydride-added fatty acid ester. After hydrolysis of this maleic anhydride-added fatty acid ester, the neutralization value is measured,
A maleated fatty acid ester salt was obtained by neutralizing with a predetermined amount of basic substance. The average number of moles of maleic anhydride added is
The water at the time of washing with water was collected and calculated from the acid value.

Maleated fatty acid ester salt C: 6 mol of maleic anhydride was charged to 1 mol of the starting fatty acid ester, and the following operations were carried out in the same manner as described above. Maleated fatty acid ester salts D, E and F: 5 mol of maleic anhydride was charged to 1 mol of the raw material oil and fat, and the following operations were performed in the same manner as described above.

[0017]

[Table 1]

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) Foaming property 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 put in and after 5 minutes by the loss-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) Detergency Using an aqueous solution having a concentration of 1% by weight of the detergent composition, Terg-ot
Using an ometer (Kamishima Seisakusho), wash the wool muslin artificially contaminated cloth 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.

[0021]

[Equation 1]

Excessive cleaning power (cleaning power 60% or more) Good cleaning power (cleaning power 25% or more and less than 60%) Weak cleaning power (cleaning power less than 25%) (4) Sliminess during cleaning A female was used as a panelist to evaluate 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 feeling a little slimy feeling, 1 point when feeling a slimy feeling persistent, and 2 points when feeling slickness was persistent and taking a long time for rinsing, 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)

(5) Tightening sensation on the skin after washing Twenty women were panelists, and the sensation on the skin tightness 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)

(6) Refreshing Feeling After Washing Twenty women were panelists and the refreshing feeling after washing with 5 g of the composition was evaluated. 2 points if you feel very refreshed, 1 point if you feel that it is not very refreshed,
The average value of 20 persons was calculated with 0 point when it was felt that it was not slimy at all, 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)

(7) Stability with 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 10 and Comparative Examples 1 to 10 Samples having the formulations shown in Tables 2 to 5 were prepared and their performances were evaluated. The results are shown in Tables 6-9. The numbers in the table indicate% by weight.

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

[0034]

[Table 9]

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

Example 11 A transparent body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt A 30 Palm oil Alkyl dimethylamino acetic acid betaine 10 Propylene glycol 0.5 Butyl paraoxybenzoate 0.1 Methyl paraoxybenzoate 0.1 Perfume 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 212mm Foam height after 5 minutes 209mm Foam retention rate 98.6% Detergency 31.5% Slimy feeling 0.3 Tight feeling 1.7 Light feeling 1.7 Temporal stability 〇

Example 12 A pearly body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt B 15 Maleated fatty acid ester salt D 10 Lauric acid amidopropyl dimethylamino acetic acid betaine 8 Ethylene glycol distearate 2 Phenoxyethanol 0.3 Methyl paraoxybenzoate 0.1 Fragrance 0.3 Purified water Residual pearly body shampoo When the composition was evaluated according to the above evaluation method, 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 222mm Foam height after 5 minutes 219mm Foam retention rate 98.6% Detergency 32.2% Slimy feeling 0.3 Hot feeling 1.7 Light feeling 1.7 Temporal stability 〇

Example 13 An unscented body shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt C 30 Coconut oil fatty acid amide Ethyl hydroxyethyl glycine sodium salt 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 200mm Foam retention rate 97.6% Detergency 32.7% Slimy feeling 0.3 Tight feeling 1.8 Light feeling 1.8 Temporal stability 〇

Example 14 A hand soap composition having a refreshing feeling was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt E 20 β-laurylaminopropionic acid sodium salt 8 Glycerin 0.5 5-Methyl-2-isopropylcyclohexanol 0.1 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Perfume 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 0.3 Foam height immediately after sample application 207mm Foam height after 5 minutes 203mm Foam retention rate 98.1% Detergency 37.6% Slimy feeling 0.3 Tight feeling 1.7 Light feeling 1.7 Temporal stability 〇

Example 15 A facial cleansing composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt F 17 Lauryl iminodiacetic acid sodium salt 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 0.3 Foam height immediately after sample application 207 mm Foam height after 5 minutes 202 mm Foam persistence rate 97.6% Detergency 33.8% Slimy feeling 0.2 Tight feeling 1.8 Light feeling 1.7 Temporal stability 〇

Example 16 A hair shampoo composition was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt A 8 Coconut oil fatty acid amide propyldimethylaminoacetic acid betaine 10 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 balance (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 (3) and (7) of the evaluation methods performed in Examples 1 to 10, and the rinsability 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 of 20 people was calculated by setting 2 points when the hair was not squeaky and the rinsing was smooth, 1 point when feeling a slight squeaky feeling during rinsing, and 0 points when the squeaking was strong and discomfort. 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 0.2 Foam height immediately after sample introduction 231 mm Foam height after 5 minutes 225mm Foam persistence 97.4% Detergency 31.8% Rinseability 1.8 Stability over time 〇

Example 17 A liquid detergent composition for clothing was prepared according to the following formulation. Chemical name Weight% Maleated fatty acid ester salt E 10 Maleated fatty acid ester salt F 12 Lauryl glycine sodium salt 5 Sodium aluminosilicate 8 Propylene glycol 3 Butyl paraoxybenzoate 0.2 Methyl paraoxybenzoate 0.2 Lauryldiaminoethylglycine 0.1 Perfume 0.1 Purified water Residue

When this liquid detergent composition for clothes was evaluated according to the above evaluation methods (1) to (3) and (7), the following good results were obtained. Skin irritation 0.3 Foam height immediately after sample injection 192 mm Foam height after 5 minutes 188 mm Foam persistence 97.9% Detergency 42.6% Stability over time 〇

[0051]

The cleaning composition of the present invention is hypoallergenic,
Foaming property, excellent feeling of use after washing, having appropriate detergency, and good stability over time, so body shampoo composition, hand soap composition, face wash composition, hair shampoo composition, It can be used as a detergent composition for clothes, a detergent composition for tableware and the like.

Claims (1)

[Claims] 1. A detergent composition comprising the following a and b, wherein a + b is 5 to 60% by weight, and the weight ratio of a and b is 20/1 to 1/20. a. Maleic acid ester of fatty acid or salts thereof. b. Amphoteric surfactant.