JP2005187767A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition excellent in low irritation, antibacterial property and use feeling. <P>SOLUTION: This detergent composition contains a glyceric acid salt expressed by general formula (1) [wherein, R is H or CH<SB>3</SB>; and M is a metal atom] and a surfactant. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a detergent composition containing glycerates.

  Conventionally, parabens, benzoic acid and their salts have been used as antibacterial agents (preservatives) for cleaning agents, and it is said that the antibacterial agents so far have relatively low skin irritation and high safety. ing. However, many rashes have been reported with detergents containing parabens. For example, according to Archives of Dermatology (108, P573, 1973) published by the North American Contact Dermatitis Group, sensitization of contact dermatitis due to parabens ranges from 2 to 3% of users. It is said. On the other hand, benzoic acid is easily affected by pH, so the stability of the effect is poor, and further, when used in combination with other compounding ingredients such as a surfactant, its antibacterial activity may be significantly reduced. doing. In recent years, the number of people who have an allergic reaction to these antibacterial agents has increased, so the direction for safety has increased, and there is a demand for a composition that does not contain any antibacterial agent or has reduced its amount. Is growing.

  Thus, various attempts have been made to overcome the drawbacks of conventional antibacterial agents and to reduce the amount of antibacterial agents used by searching for highly safe antibacterial substances and increasing the effectiveness of the antibacterial agents. For example, the use amount of an antibacterial agent is reduced by using a plurality of antibacterial agents and utilizing a synergistic effect thereof. Furthermore, the efficacy of conventional antibacterial agents depends on the amount present in the aqueous phase, but since many of them have low solubility in water, polyhydric alcohols such as 1,3-butylene glycol, dipropylene glycol and glycerin are used. By adding, the distribution of the antibacterial agent to the aqueous phase is increased, and the effect of the antibacterial agent is also increased.

However, the effect of increasing the antibacterial activity of the antibacterial agent by using a polyhydric alcohol such as 1,3-butylene glycol, dipropylene glycol and glycerin together with the conventional antibacterial agent is not remarkable, and these polyhydric alcohols The antibacterial action itself is exerted when a large amount is blended, for example, when 1,3-butylene glycol or dipropylene glycol is blended at 10% or more, and glycerin is blended at 30% or more. There was a problem that the feeling of use was impaired by the blending of. Further, Patent Document 1 describes an antibacterial / deodorant composition containing zinc glycerate / copper, but there is no description as a cleaning agent, and a solvent is often used at 80% by weight.
JP-A-10-236904

  The subject of this invention is providing the cleaning composition excellent in the hypoallergenicity, antibacterial property, and the usability | use_condition.

  The present invention provides a cleaning composition containing a glycerate represented by the general formula (1) and a surfactant:

(In the formula, R represents a hydrogen atom or a CH ₃ group, and M represents a metal atom).

  According to the present invention, a detergent composition having low irritation and excellent antibacterial properties and usability can be obtained.

  In general formula (1), from the viewpoint of antibacterial properties, M is preferably a metal atom of Group 11 or Group 12 of the periodic table, and more preferably a zinc atom or a copper atom.

  The glycerates of the general formula (1) can be prepared by reacting glyceric acid or methoxylactic acid with a metal hydroxide such as copper (II) hydroxide or zinc (II) hydroxide.

The glycerates of general formula (1) can be used alone or in combination of two or more.
The blending amount of the glycerates of the general formula (1) is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, from the viewpoint of antibacterial properties and hypoallergenicity. 0.1-3 weight% is still more preferable, and 0.3-1 weight% is especially preferable.

  As the surfactant, one or more selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

  As the anionic surfactant, those of sulfuric acid type, sulfonic acid type, carboxylic acid type, phosphoric acid type and amino acid type are preferable, for example, alkyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate. , Sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, polyoxyalkylene alkyl phenyl ether sulfate, alkane sulfonate, acyl isethionate, acylmethyl taurate, higher fatty acid salt, polyoxyalkylene alkyl ether acetic acid Examples thereof include salts, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, alanine derivatives, glycine derivatives, and arginine derivatives.

  Among these, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkenyl ether sulfate, alkyl sulfate, acyl isethionate, acyl methyl taurate, higher fatty acid salt, polyoxyalkylene alkyl ether acetate, alkyl phosphate Polyoxyalkylene alkyl ether phosphates, acyl glutamates, and alkylalanine derivatives are preferable, and polyoxyethylene alkyl ether sulfates are particularly preferable.

Nonionic surfactants include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl. Examples include phenyl ethers, polyoxyalkylene (cured) castor oils, sucrose fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, fatty acid alkanolamides, alkyl glycosides, and the like. Of these, alkylglycosides, polyoxyalkylene C ₈ -C ₂₀ fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamides are preferred. As the alkyl glycosides, those having 8 to 14 carbon atoms in the alkyl group and a sugar (glucose) condensation degree of 1 to 2 are preferable. As the fatty acid alkanolamide, those having an acyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms are preferable, and either a monoalkanolamide or a dialkanolamide may be used, but a hydroxyalkyl group having 2 to 3 carbon atoms may be used. What has is preferable. Specific examples of fatty acid alkanolamides include oleic acid diethanolamide, palm kernel oil fatty acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, coconut oil fatty acid monoethanolamide, laurin Examples include acid monoisopropanolamide, lauric acid monoethanolamide, palm kernel oil fatty acid methylethanolamide, and coconut oil fatty acid methylethanolamide.

  Examples of amphoteric surfactants include betaine surfactants. Of these, betaine surfactants such as imidazoline betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfobetaine are more preferred, and alkylcarboxymethylhydroxyethylimidazolium betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfone. Betaine is particularly preferred. Fatty acid amidopropyl betaine and alkylhydroxysulfobetaine preferably have an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly amide propyl betaine laurate, palm kernel fatty acid amidopropyl betaine, and coconut oil fatty acid. Amidopropyl betaine, lauryl hydroxysulfobetaine and the like are preferred.

  Cationic surfactants include quaternary ammonium salts such as mono long chain alkyltrimethylammonium chloride, dilong chain alkyldimethylammonium chloride, and the following general formula (2):

[Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ² and R ⁴ represent an alkyl group having 1 to 6 carbon atoms or — (AO) _n H (A represents an alkylene group having 2 to 4 carbon atoms, n represents a number of 1 to 6, n A may be the same or different, and the arrangement thereof is arbitrary), and R ³ represents , An alkyl group having 1 to 6 carbon atoms, a benzyl group or — (A′O) _m H (A ′ represents an alkylene group having 2 to 4 carbon atoms, m represents a number of 1 to 6; 'May be the same or different, and the arrangement thereof is arbitrary.) And X ⁻ represents an anion. An ether type cationic surfactant represented by the formula:

  From the viewpoint of detergency, preferred surfactants are anionic surfactants and nonionic surfactants. Particularly preferred surfactants are anionic surfactants such as polyoxyethylene alkyl ether sulfates and polyoxyalkylene alkyl ether acetates, and nonionic surfactants such as coconut oil fatty acid methylethanolamide.

  The blending amount of the surfactant is preferably 1 to 80% by weight, more preferably 3 to 30% by weight, and even more preferably 5 to 20% by weight of the cleaning composition from the viewpoints of detergency, antibacterial properties and irritation. preferable.

In the present invention, it is preferable to use a solvent. The solvent is used for the purpose of improving the stability of the cleaning composition and improving the antibacterial property synergistically with glycerates.
Any solvent can be used without particular limitation as long as it is excellent in compatibility with glycerates and surfactants and is used for a body cleanser. Specific examples of solvents that can be used include alcohols and glycol alkyl ethers. Examples of alcohols include aliphatic alcohols. Examples of the aliphatic alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol, and glycerin. Examples of glycol alkyl ethers include alkylene glycol alkyl ether solvents. Examples of alkylene glycol ether compounds include ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol monophenyl ether, and triethylene glycol. Examples thereof include monophenyl ether, triethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, and polyoxyethylene polyoxypropylene glycol monobutyl ether. These can be used alone or in combination of two or more.
The content of the solvent is 0.2 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight of the detergent composition from the viewpoint of antibacterial properties, feeling of use and irritation. is there.

  In addition to the above components, the cleaning composition of the present invention includes components used in ordinary cleaning agents, such as humectants such as sorbitol and panthenol; coloring agents such as dyes and pigments; hydroxyethyl cellulose, methyl cellulose, polyethylene glycol, Viscosity adjusting agents such as clay minerals and salts such as sodium chloride; pH adjusting agents such as citric acid and potassium hydroxide; other anti-dandruff agents, vitamin agents, anti-inflammatory agents, chelating agents, plant extracts, pearlizing agents, In addition to fragrances, pigments, ultraviolet absorbers, antioxidants, and the like, the components described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) can be appropriately blended.

  The cleaning composition of the present invention can be produced according to a conventional method. Also, the dosage form is not particularly limited, and can be any dosage form such as liquid, foam, paste, cream, solid, powder, etc., but liquid, paste or cream It is preferable to use a liquid. In the case of a liquid state, it is preferable to use water, polyethylene glycol or the like as the liquid medium, and the amount of water is preferably 10 to 80% by weight in the total composition.

  In the cleaning composition of the present invention, the pH of the aqueous solution when diluted 20 times by weight with water is preferably 4 to 10, and particularly preferably pH 5 to 8. If the cleaning composition is adjusted by adding acid or alkali, Good.

  The cleaning composition of the present invention can be produced according to a conventional method, and can be used as a body cleaning agent such as a hair cleaning agent, a whole body cleaning agent, a facial cleanser, and a hand cleaning agent.

Synthesis Example 1: Synthesis of copper (II) glycerate monohydrate (in formula (1), R = H, M = Cu)
A 200 mL four-necked flask was charged with 17.69 g of copper (II) hydroxide and 100.00 g of a 39.2% aqueous glyceric acid solution. The mixture was cooled in a water bath and stirred for 2 hours while keeping it at 40 ° C. or lower, and then heated to 50 ° C. and aged overnight. Distilled water was added to the resulting blue-white slurry to make about 500 g as a whole, heated to 70 ° C., and insolubles were removed by filtration. The filtrate was lyophilized, and the resulting powder was washed with acetone to obtain 27.28 g of a pale white powder of copper (II) glycerate monohydrate (yield 54%).
Analytical value: acid value 373.1 mgKOH / g, Cu content (ICP) 20%.

Synthesis Example 2: Synthesis of zinc glycerate (II) monohydrate (in formula (1), R = H, M = Zn) Copper hydroxide (II) was converted to zinc hydroxide (II) in Synthesis Example 1. Zinc glycerate monohydrate (II) was synthesized by the same procedure except that the change was made.

Synthesis Example 3: Synthesis of copper (II) methoxylactate monohydrate (in formula (1), R = CH ₃ , M = Cu)
A 500 mL four-necked flask was charged with 13.93 g of copper (II) hydroxide, 100.01 g of a 34.3% methoxylactic acid aqueous solution and 100.00 g of ion-exchanged water. The mixture was cooled in a water bath and stirred for 1 hour while keeping it at 40 ° C. or lower. 80 g of acetone was added to the resulting deep blue solution to precipitate the product. The precipitate was filtered off and washed with acetone to obtain 31.14 g of a pale white powder of methoxycopper lactate (II) monohydrate (yield 68%).
Analytical value: acid value 331.8 mgKOH / g, Cu content (ICP) 20%.

Synthesis Example 4 Synthesis of Zinc Methoxy Lactate (II) Monohydrate (R = CH ₃ , M = Zn in General Formula (1)) In Synthesis Example 3, copper hydroxide (II) was converted to zinc hydroxide (II) A methoxy zinc lactate (II) monohydrate was synthesized by the same procedure except that

Example 1
Using the glycerates produced in Synthesis Examples 1 to 4 and other antibacterial agents for comparison, detergents having the compositions shown in Table 1 (present invention products 1 to 5 and comparative products 1 to 3) were produced by a conventional method. .
About these cleaning agents, the cleaning property, antibacterial property, and irritation were evaluated by the following method.
<Evaluation method>
-Detergency Using the cleaning composition of the present invention and the comparative product whose composition is shown in Table 1, 10 panelists of 5 men and women each wash their bodies, and the sensory evaluation of the detergency at that time is based on the following criteria I went there.
5: I felt that the washability was good.
4: I felt that the washability was slightly better.
3: I felt the washability was normal.
2: I felt that the washability was not very good.
1: I felt that the washability was not good.
As a result, the average value of 10 panelists (rounded off to the nearest 0.1) was expressed as foaming power according to the following criteria.
A: Average value is 4.0 or more (good)
○: Average value is 3.2 to 3.9
Δ: Average value is 2.5 to 3.1
X: Average value is 2.4 or less (defect)
・ Antibacterial (Bacteria count)
The antibacterial properties against the test bacteria [ Escherichia coli and Staphylococcus aureus ] of the cleaning compositions of the present invention and comparative products having the compositions shown in Table 1 were evaluated as follows.
To 2 mL of the detergent composition diluted 1000-fold with sterilized water, add 50 μL of the test bacterial solution pre-cultured to about 10 ⁸ cfu / mL. After inoculation at 25 ° C./24 hours, 50 μL is taken, diluted arbitrarily, and 50 μL is put on SCDLP (SOYBEAN-CASEIN DIGEST BROTH with LECITHIN & POLYSORBATE 80) agar medium and cultured. The number of growing bacteria (number of colonies) is measured, multiplied by the dilution factor, the number of bacteria before dilution is calculated, and the difference from the initial number of bacteria (the number of bacteria in the test bacterial solution) is expressed in logarithm. The larger the value, the better the antibacterial properties of the cleaning composition.
・ Irritation (use test)
In the past, for the 20 panelists who complained of skin irritation when using a cleaning composition containing paraben, the cleaning composition of the product of the present invention and the comparative product were used twice a day in the morning and evening. Used for a week to report the presence or absence of skin irritation.
-Usability About the detergent composition which mix | blended this-invention product or the comparative product, the panel was made for five men and women, and the sensory evaluation of the usability in that case was performed on the following references | standards.
5: I felt that the feeling of use was good.
4: I felt that the feeling of use was slightly good.
3: I felt that the feeling of use was normal.
2: I felt that the feeling of use was not so good.
1: I felt that the feeling of use was not good.
As a result, the average value of 10 panelists was expressed as a feeling of use according to the following criteria.
A: Average value is 4.0 or more (good)
◯: Average value is 3.2 to 3.9
Δ: Average value is 2.5 to 3.1
X: Average value is 2.4 or less (defect)
The evaluation results are shown in Table 1.

Example 2
A shampoo having the following composition was produced.
(Composition) (wt%)
Copper (II) glycerate monohydrate 0.8
Polyoxyethylene (3) sodium lauryl ether sulfate 15.0
Palm oil fatty acid diethanolamide 3.0
Cationic polymer (Mercoat 550, ONDEO NALCO) 0.3
Propylene glycol 2.0
Perfume
Purified water balance
Total 100.0
This hair cleanser was mild and excellent in antibacterial and cleansing properties.

Example 3
A body shampoo having the following composition was produced.
(Composition) (wt%)
Zinc methoxylactate (II) monohydrate 1.2
Potassium laurate 10.0
Potassium myristate 4.0
Cocoamidopropylbetaine 1.0
Glycerin 3.0
Perfume
Purified water balance
Total 100.0
This body shampoo was mild and antibacterial and cleanable.

Claims (5)

A detergent composition containing the glycerates represented by the general formula (1) and a surfactant:

(In the formula, R represents a hydrogen atom or a CH ₃ group, and M represents a metal atom).   The cleaning composition according to claim 1, further comprising 0.2 to 10% by weight of a solvent.   The cleaning composition according to claim 1 or 2, wherein M in the general formula (1) is a zinc atom or a copper atom.   The detergent composition according to any one of claims 1 to 3, wherein the surfactant is at least one selected from an anionic surfactant and a nonionic surfactant. The cleaning composition according to any one of claims 1 to 4, comprising 0.01 to 10% by weight of the glycerate salt of the general formula (1).