JP2001131583A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having low irritation to the skin (including scalp), excellent in foaming performances and imparting a good feeling of use which is smooth and lubricous while imparting quick rinsing and a freshened feeling without imparting a stiff feeling after use and becoming sticky. SOLUTION: This detergent composition is characterized by comprising (A) an amidecarboxylic acid or a salt thereof represented by general formula (I) [wherein, R is an 8-22C straight-chain or branched alkyl, alkenyl or hydroxyalkyl; A is H or a 1-6C straight-chain or branched alkyl or hydroxyalkyl; X is CH(OH)CH2, CH2CH(OH), mixture of them or CH(OH)CH (OH); and M denotes H, an alkali metal ion, alkaline earth metal ion, ammonium ion or an alkanolamine] and (B) a water-insoluble solid particle. Furthermore, a water-soluble polymer can be included as the ingredient (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-greasy, non-greasy, and non-greasy feeling after use, while giving a low irritation to the skin (including the scalp), an excellent foaming power, and a quick rinsing feeling. The present invention relates to a detergent composition which gives a smooth and good feeling of use.

[0002]

2. Description of the Related Art Hitherto, higher fatty acid salts have been widely formulated as a detergent composition for skin and the like, and are known to give a refreshing feel at the time of rinsing and after washing. There is a problem of giving a dry feeling.

On the other hand, Japanese Patent Application Laid-Open No. 62-109897 discloses a liquid detergent composition containing a sulfosuccinic acid monoester salt and an N-acylamino acid salt as mild surfactants having low skin irritation. JP-A 1-2870
Japanese Unexamined Patent Publication No. 17-153798 discloses a hypoallergenic detergent composition containing an N-acylglutamic acid-based, isethionate-based, and sulfosuccinic acid-based surfactant, and JP-A-3-153798 discloses an N-acylamino acid-based and sulfosuccinic surfactant. A hypoallergenic detergent composition containing an acid surfactant is disclosed. However, the surfactants disclosed in these publications have a problem that they still have a slimy feeling when rinsed and lack a smooth and smooth feel even after use.

[0004] Further, in order to improve the feeling of use, water-insoluble solid particles such as clay mineral montmorillonite and spherical fine particle pigments have been incorporated into a detergent composition (Japanese Patent Application Laid-Open No. 1-190622; JP-A-4-372700
No.). However, in the water-insoluble solid particles disclosed in these publications, a satisfactory effect of improving the slimy feeling at the time of rinsing cannot be secured yet, and there is a problem that the smooth and smooth feel is lacking even after use. is there.

[0005] Therefore, any of the above-mentioned conventional cleaning compositions is not sufficient in rinsing performance (freshness) at the time of use and its improving effect, and imparts a smooth and smooth feeling after use. There is a problem that cannot be done.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has been made to solve the problem, and has a low irritation to the skin (including the scalp) and an excellent foaming power. It is an object of the present invention to provide a detergent composition which gives a feeling of quick and fresh rinsing, has no feeling of being flat after use, is non-greasy, and gives a smooth and smooth feeling of use.

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned conventional problems and the like, the present inventor has found that the above-mentioned cleaning by adding a specific amide carboxylic acid or a salt thereof and water-insoluble solid particles is carried out. The present invention has been completed by finding that an agent composition can be obtained. That is, the present invention resides in the following (1) to (3). (1) A cleaning composition comprising the following components (A) and (B). (A) Amidocarboxylic acid represented by the following general formula (I) or a salt thereof (B) Water-insoluble solid particles

Embedded image (2) The cleaning composition according to the above (1), further comprising a water-soluble polymer as the component (C). (3) The cleaning composition according to the above (1) or (2), wherein the water-insoluble solid particles of the component (B) are water-swellable clay minerals.

[0008]

Embodiments of the present invention will be described below in detail. The cleaning composition of the present invention is characterized by containing an amide carboxylic acid represented by the following general formula (I) or a salt thereof as the component (A), and water-insoluble solid particles as the component (B). Things.

Embedded image

In the present invention, the amide carboxylic acid represented by the general formula (I) or a salt thereof as the component (A) is
It has low irritation, excellent foaming power (foaming property), is refreshing at the time of rinsing, and does not have a feeling of tightness after use, and its synthesis method is not particularly limited. For example, dicarboxylic anhydride Amidation using a product and an amine as a raw material, and dehydration amidation using a dicarboxylic acid and an amine as a raw material (including a method via an imide as an intermediate). Synthetic methods are preferred. In a preferred production method, first, malic acid, acetic anhydride and a catalyst are mixed and stirred to obtain acetylated malic anhydride. The method of mixing and stirring is not particularly limited, and usually, malic acid is dispersed in acetic anhydride,
A method of gradually adding a catalyst to the dispersion or dispersing or dissolving the catalyst in acetic anhydride and gradually adding malic acid to the catalyst dispersion or the catalyst solution is employed.
Malic acid may be a D-form or L-form optical isomer alone, or may be a racemic form. The reaction is preferably carried out at a temperature of 100 ° C. or lower, more preferably 80 ° C. or lower. When the reaction temperature exceeds 100 ° C., malic acid dehydration reaction occurs in competition and causes maleic anhydride, fumaric acid, and polymer by-products. Reaction time is 0.5-3
About an hour.

The catalyst may be any one which does not react with malic acid and acetic anhydride and activates the carbonyl group, and is usually an acid or base catalyst, preferably sulfuric acid, toluenesulfone, methanesulfonic acid, phosphoric acid, chloride, or the like. Acid catalysts such as hydrogen,
More preferably, sulfuric acid is used. Also, the reaction
An organic solvent can be used if necessary, and hexane, benzene, chloroform, ethyl acetate and acetic acid which dissolve the product and do not react are suitable. The reaction molar ratio is
Malic acid / acetic anhydride is preferably in the range of 1/2 to 1/5, more preferably in the range of 1/2 to 1 / 2.5. When the molar ratio is larger than 1/2 and the amount of malic acid is excessive, unreacted malic acid remains and the viscosity during the reaction increases, so that the reaction cannot proceed smoothly. When the molar ratio is less than 1/5 and the amount of acetic anhydride is excessive, removal of by-product acetic acid and unreacted acetic anhydride after the reaction requires a great deal of effort, which is not preferable. Further, the amount of the catalyst is 0.01 to 5% by mass (hereinafter, simply referred to as "%") based on the mass of malic acid. Further, when an organic solvent is used, the amount of the organic solvent used is 0 to 5 times the amount of malic acid.

In the above-mentioned ring-opening amidation method and dehydration amidation method, malic acid contains a large amount of impurities caused by having a hydroxyl group, so that malic anhydride as a raw material is produced with high purity. Despite the difficulties, this method results in high purity acetylated malic anhydride. Next, the obtained acetylated malic anhydride is reacted with a primary amine or a secondary amine. The primary amine to be used is preferably a primary amine having a hydrocarbon group having 6 to 24 carbon atoms, and the secondary amine is preferably a primary hydrocarbon group having 6 to 24 carbon atoms and a secondary amine having 1 to 18 carbon atoms. Secondary amines having a hydrocarbon group are preferred.

Specific examples of the primary amine include, for example, those whose hydrocarbon group is hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl). ), Amines such as alkyl or alkenyl groups such as octadecenyl (oleyl), nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,
Examples of such a mixture include plant extracts and amines derived from animal oils. Among these, from the viewpoint of solubility, carbon number 8
Preferred are amines having from 18 to 18 alkyl or alkenyl groups. As specific examples of the secondary amine, for example, the first hydrocarbon group is hexyl, heptyl, octyl, nonyl,
Alkyl or alkenyl groups such as decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), octadecenyl (oleyl), nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, etc. Wherein the second hydrocarbon group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl) ), Octadecenyl (oleyl)
And amines such as an alkyl group or an alkenyl group, and amines derived from plant extracts and animal oils, which are mixtures thereof. Among these, from the viewpoint of solubility, amines in which the first hydrocarbon group is an alkyl group or alkenyl group having 8 to 18 carbon atoms and the second hydrocarbon group is an alkyl group having 1 to 6 carbon atoms are preferable.

The reaction molar ratio of the primary amine or the secondary amine to the acetylated malic anhydride is preferably in the range of amine / acetylated malic anhydride = 0.5 / 1.0 to 1.0 / 1.0. , More preferably amine / acetylated malic anhydride = 0.8 / 1.0 to 1.0 / 1.0. When the amine is excessive, diamide is by-produced, and the molar ratio is 0.5 / 1.
If it is less than 0, the production amount of the amide compound will be small, which is not economical. The reaction temperature is preferably 100 ° C. or lower, more preferably 70 ° C. or lower. When the temperature exceeds 100 ° C., by-products such as maleic amide and fumaric amide increase due to the deacetic acid reaction. The reaction time is about 0 to 2 hours after the addition of the entire amount of the amine.

In the reaction, if necessary, an organic solvent,
For example, hexane, benzene, chloroform, ethyl acetate, acetic acid, and the like can be used. Acetic acid is suitable because it dissolves the product and does not react. The amount of the organic solvent used is 0 to 5 times, preferably 0 to 1 times the mass of the acetylated malic anhydride.

In this way, acetylmalic acid monoamide or the like is obtained as the amide carboxylic acid, which is further reacted for 1 to 5 hours by adding a base such as potassium hydroxide at 40 to 90 ° C. Thereafter, an acid such as hydrochloric acid is added under the condition of 20 to 50 ° C. and reacted for 3 to 6 hours.
Malic acid monoamide, which is an amide carboxylic acid, is obtained. When used in the form of a salt, the neutralizing salt is preferably an alkaline earth metal such as potassium or sodium, or an alkanolamine such as diethanolamine (DEA) or triethanolamine (TEA).

Specific examples of the amide carboxylic acids or salts thereof thus obtained include mono-N-lauryl malamide, potassium mono-N-lauryl malate,
Sodium mono-N-lauryl malate, Mono-N-
Lauryl malic acid amide diethanolamine, mono-N-
Lauryl malate amide triethanolamine, mono-
Potassium N-methyl-N-urilylmalate, mono-
N-myristyl malamide, potassium mono-N-myristyl malamide, sodium mono-N-myristyl malate, mono-N-myristyl malamide diethanolamine, mono-N-myristyl malamide triethanolamine, mono -N-palmityl malamide, sodium mono-N-palmityl malate,
Mono-N-decylmalamide, potassium mono-N-decylmalamide, mono-N-decyltartaramide, mono
Ammonium-N-decyl tartrate, mono-N-oleylmalate, monosodium mono-N-oleylmalate and the like can be used alone or in combination of two or more. The compounding amount of the amide carboxylic acid or a salt thereof as the component (A) is preferably 2 to 50%, more preferably 2 to 50% based on the total amount of the composition.
30%. If the blending amount of the component (A) is less than 2%, the foaming power is not sufficient, and moreover, a refreshing feeling upon rinsing,
Low effect of giving a firm feeling after use, and 50%
When the amount exceeds the above range, there is no remarkable effect of improving the foaming power, and there is no further effect of giving a refreshing feeling upon rinsing and a refreshing feeling after use.

In the present invention, a group consisting of an anionic surfactant, an amphoteric surfactant, a semipolar surfactant and a nonionic surfactant is preferably used together with the amide carboxylic acid or the salt thereof as the component (A). At least one surfactant selected from the following can be used. As the anionic surfactant, for example, carboxylate, sulfonate, sulfate, alkyl phosphate, and the like can be used. Examples of the carboxylate include, in addition to saturated and unsaturated fatty acids having carbon atoms of C12 to C18, coconut oil fatty acids, hydrogenated coconut fatty acids, and mixtures thereof.
Fatty acid soaps such as potassium salt, sodium salt, triethanolamine salt and ammonium salt of palm oil fatty acid, hardened palm oil fatty acid, tallow fatty acid, hardened tallow fatty acid, etc., alkyl ether carboxylate, N-acyl sarcosine salt, N-acyl Glutamates and the like, for example, potassium laurate, sodium laurate, triethanolamine myristate, N-lauroyl sarcosine sodium, N-lauroyl glutamate sodium, N-lauroyl-N-methyl-β-alanine potassium and the like Can be The fatty acid soap may be used as it is, or may be used after neutralizing the fatty acid and the alkali separately in the detergent composition. Examples of the sulfonate include N-acylaminosulfonate, polyoxyethylene sulfosuccinate and the like, N-cocoylmethyltaurine sodium, N-lauroylmethyltaurine sodium, N-myristoylmethyltaurine triethanolamine, And sodium polyoxyethylene alkyl sulfosuccinate. Examples of the sulfates include higher alkyl sulfates and polyoxyethylene alkyl ether sulfates. Examples of the alkyl phosphate salt include triethanolamine monolauryl phosphate, sodium monolauryl phosphate, triethanolamine monomyristyl phosphate, triethanolamine dimonomyristyl phosphate, and the like. Among the above-mentioned anionic surfactants, use of a carboxylate is preferred from the viewpoint of feeling of use. Further, the above-mentioned various anionic surfactants can be used alone or in combination of two or more.

Examples of the amphoteric surfactant and semipolar surfactant include imidazoline type, amide amino acid salt, carbobetaine type, alkylbetaine type, alkylamidobetaine type, alkylsulfobetaine type, alkylhydroxysulfobetaine type and acyl acylate. Tertiary amine oxides, acyl tertiary phosphine oxides and the like can be used. Examples of the imidazoline type include, for example, coconut oil alkyl-N-hydroxyethylimidazolinium betaine. Examples of the alkylbetaine type include, for example, lauryl dimethylaminoacetate betaine, and examples of the alkylamide betaine type include coconut oil fatty acid amide propyl. As alkylsulfobetaine type such as betaine,
For example, acyl tertiary amine oxides such as coconut oil fatty acid dimethylsulfopropyl betaine include, for example, lauryl dimethylamine oxide, and acyl tertiary phosphonates include, for example, lauryl dimethyl phosphine oxide. Among the amphoteric surfactants and semipolar surfactants described above, alkyl betaine type and acyl tertiary amine oxides are preferable from the viewpoint of foaming properties, and desalted ones are preferable from the viewpoint of stability. The amphoteric surfactants and semipolar surfactants described above can be used alone or in combination of two or more.

Examples of the nonionic surfactant include, for example,
Polyoxyalkylene addition type, polyoxypropylene
Polyoxyethylene addition type, mono- or diethanolamide type, sorbitan fatty acid ester, glycerin fatty acid ester, sucrose fatty acid ester, alkyl saccharide type, N-polyhydroxyalkyl fatty acid amide and the like can be used. As polyoxyalkylene addition type, for example, polyoxyethylene alkyl ether, polyoxypropylene polyoxyethylene addition type, such as polyoxypropylene polyoxyethylene glycerin ether, mono- or diethanolamide-based, for example, Examples of sorbitan fatty acid esters such as coconut oil fatty acid diethanolamide include sorbitan monoisostearate, and examples of glycerin fatty acid esters include glycerin sesquioleate. The above nonionic surfactants can be used alone or in combination of two or more.

These surfactants can be used alone or
It can be used in combination of more than one kind, the compounding amount of the above (A) component amide carboxylic acid or a salt thereof,
It is desirable that the mixing ratio of the component (A) / other surfactant is 1/20 or more, preferably 1/10 or more, by mass ratio with the above other surfactant. 1/20
If it is less than 1, there is an effect of preventing a feeling of tension after use,
The smooth feeling after use cannot be sufficiently exhibited.

The water-insoluble solid particles of the component (B) used in the present invention are not particularly limited, as long as they give a smooth feel after use. And water-insoluble solid particles processed by the above method. As the inorganic powder, for example, bentonite, talc, mica, mica, sericite, silica, titanium oxide, barium sulfate, calcium carbonate and the like, and as the organic powder, for example, natural polymer powder such as cellulose, Hydrocarbon polymers such as polyethylene, polypropylene, polystyrene, etc., polyamide polymers such as nylon, vinyl polymers such as polyvinyl chloride, polyacrylonitrile, polyvinyl acetate, polyvinylidene fluoride, polyester polymers, polyurethane polymers And polymer powders such as copolymers thereof, and further processed are distearyl dimethyl ammonium chloride-treated bentonite and distearyl dimethyl ammonium chloride-treated hectonite obtained by treating an inorganic substance with an organic reactant. Such as modified organic Things and the like. The average particle diameter of these water-insoluble solid particles is 0.01 to 100 μm, particularly preferably 0.01 to 10 μm in the case of an inorganic powder or an organic inorganic substance, and 0.01 to 1 mm, particularly in the case of an organic powder. 10 μm to 1 mm is preferred.

Further, the water-insoluble solid particles of the component (B) are preferably water-swellable clay minerals. By using a water-swellable clay mineral in the water-insoluble solid particles of the component (B), the smoothness after use is further improved. As water-swellable clay minerals, for example,
Natural products, purified products of natural products, natural swelling modified or synthetic, and the like, these alone,
Alternatively, two or more kinds can be used in combination. Specifically, natural or synthetic montmorillonite, beidellite, nontronite, saponite, sauconite,
Smectite group clay minerals such as hectorite and stevensite, vermiculite, swellable synthetic fluoromica (Na-type, Li-type synthetic mica) and the like can be used. In addition, a high metal ion-substituted clay mineral having an improved swelling property obtained by subjecting the clay mineral to an ion exchange reaction can also be used. The water-swellable clay mineral that can be used in the present invention contains exchangeable ions that hydrate and take in water molecules between layers, and have swelling, adsorptive, binding, suspending, and thickening properties. Having different properties from other clay minerals. Among the water-swellable clay minerals, a smectite group, bentonite mainly composed of smectite group montmorillonii, and the like are preferable. Water-swellable clay minerals that can be used in the present invention include Polargel (manufactured by American Colloids), Laponite (manufactured by Nippon Silica Kogyo Co., Ltd.), Wenger (manufactured by Toyoshun Mining Co., Ltd.), Lucentite (manufactured by Corp Chemical), Kunipia Commercially available products such as (Kunimine Industries), Benclay (Mizusawa Chemical Industries) and Vegum (Vanderbilt) can be used. The water-swellable clay minerals can be used alone or in combination of two or more.

In addition, those collected from nature contain non-swelling impurities such as calcite, tridymite, cristobalite, quartz, and various inorganic substances, which are contained in the emulsion composition or the detergent composition. It may cause sedimentation or dissolve and release the electrolyte, thereby impairing the appearance of the detergent and the dispersibility of the clay mineral. Therefore, when using a water-swellable clay mineral having the above properties collected from nature, the water-swellable component is 90% or more (non-swellable impurities are 10% or more).
), Particularly 95% or more (less than 5% of non-swellable impurities).

In the present invention, the compounding amount of the water-insoluble solid particles containing the water-swellable clay mineral (B) is preferably 0.1 to 20%, more preferably 0.1 to 20%, based on the total amount of the composition. Desirably, it is 1 to 10%. If the amount of the water-insoluble solid particles of the component (B) is less than 0.1%, the effect of imparting a smooth feel after use is not sufficient.
Even if the content exceeds 0%, there is no remarkable effect by increasing the amount.

The detergent composition of the present invention contains the above-mentioned components (A) and (B), so that it is less irritating to the skin (including the scalp), has excellent foaming power, and can be rinsed quickly. While giving a refreshing feel, there is no feeling of being tight after use, and it gives a smooth and smooth good feeling of use, but it is preferable to further include a water-soluble polymer as the component (C). By including this water-soluble polymer, a smooth feel after use can be further provided.

The water-soluble nonionic polymer compound (C) which can be used in the present invention includes, for example, anionic polymers, cationic polymers, nonionic polymers and the like. As the anionic polymer, for example,
Carrageenan, xanthan gum, sodium alginate, potassium alginate, propylene glycol alginate, hyaluronic acid, etc. as natural polymer compounds, carboxyvinyl polymer, polyacrylic acid, maleic acid copolymer, maleic acid / diisobutylene copolymer as synthetic polymer compounds And methacrylic acid / acrylic acid ester copolymer. Examples of methacrylic acid / acrylate copolymers include, for example, methacrylic acid / methyl acrylate copolymer, methacrylic acid / ethyl acrylate copolymer, methacrylic acid / propyl acrylate copolymer, methacrylic acid / butyl acrylate Copolymer, methacrylic acid / methyl acrylate / ethyl acrylate copolymer, methacrylic acid / methyl acrylate / propyl acrylate copolymer, methacrylic acid / methyl acrylate / butyl acrylate copolymer, methacrylic acid / acrylic Ethyl acrylate / propyl acrylate copolymer, methacrylic acid / ethyl acrylate / butyl acrylate copolymer, methacrylic acid / propyl acrylate / butyl acrylate copolymer,
Methacrylic acid, methyl acrylate, ethyl acrylate
Propyl acrylate copolymer, methacrylic acid / methyl acrylate / ethyl acrylate / butyl acrylate copolymer, methacrylic acid / methyl acrylate / propyl acrylate / butyl acrylate copolymer, methacrylic acid / methyl acrylate Examples include ethyl acrylate / propyl acrylate copolymer / butyl acrylate copolymer. Among these anionic polymers, methacrylic acid / acrylic ester copolymers are preferable from the viewpoint of improving dispersion stability, and in particular, a water-soluble vinyl polymer having a carboxylic acid group such as acrylic acid or methacrylic acid and carbon It is composed of two or more acrylates or methacrylates having different chain lengths and has an average molecular weight of 5,000.
In the range of 、 2,000,000, and the molar% ratio between the hydrophilic group and the hydrophobic group is 1.
A copolymer having a ratio of 5 to 0.25 is preferred.

Examples of the cationic polymer include cationized cellulose derivatives, cationic starch, cationized guar gum derivatives, diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and quaternized Polyvinylpyrrolidone derivative, polyglycolpolyamine condensate, adipic acid / dimethylaminohydroxypropylethylenetriamine copolymer, cationized dextran, xanthan gum, carboxyvinyl polymer, methylcellulose and JP-A-53-13
9734 and JP-A-60-36407. Furthermore, examples of the nonionic polymer include polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose.

These water-soluble polymers of the component (C) may be used alone or in combination of two or more. The amount of the water-soluble polymer is preferably based on the total amount of the detergent composition. , 0.1 to 5%, more preferably 0.1 to 3%
It is. (C) The content of the water-soluble polymer of the component is 0.1%.
If it is less than 5, the further effect of imparting a smooth feel after use is not sufficient, and even if it is more than 5%, stickiness occurs at the time of rinsing and after use, which is not preferable.

The cleaning composition containing the above-mentioned components (A) and (B) or the cleaning composition containing the above-mentioned components (A) to (C) of the present invention can be applied to the skin (including the scalp). On the other hand, it has a low irritation, excellent foaming power, and gives a feeling that rinsing is quick and refreshing, but it has a smooth feeling without stickiness after use, giving a good feeling of smoothness, By blending, the moist feeling and the like can be further improved. Examples of the oil component include mineral oils such as wax, petrolatum, liquid paraffin, and petrolactam; synthetic oils such as fatty acid triglyceride and higher fatty acid ester; higher fatty acids such as isostearic acid, stearic acid, behenic acid, lauryl alcohol, and cetostearyl. Alcohols, higher alcohols such as behenyl alcohol (particularly 16 to 22 carbon atoms); animal oils such as squalane, whale oil, seal oil, cod liver, tallow, beeswax; vegetable squalane, almond oil, arakin, malt oil, palm oil, palm kernel oil And vegetable oils such as coconut oil, olive oil, jojoba oil, castor oil, soybean oil, and carnauba wax. The amount of the oil component is preferably 0.01 to 20% with respect to the total amount of the detergent composition,
More preferably, it is blended to be 0.5 to 10%.

The properties of the cleaning composition of the present invention are not particularly limited, and examples thereof include a liquid, a paste, a solid, and a gel. Further, the cleaning composition of the present invention can be contained in a normal container,
For example, it can be housed in a pump container, tube, former container, or the like. When a former container is used, the viscosity of the detergent composition is 100 mP at 5 ° C.
It is preferable from the viewpoint of foam formation that the composition be adjusted to not more than a · s, more preferably not more than 50 mPa · s. Further, the former container is not particularly limited to a pump type or a squeeze type, but a porous body that allows the contents to pass therethrough to form a foam has a mesh size of 100 or more, preferably 200 meshes, and the number of the foams is 2 or more. It is preferable from the viewpoint of foam formation.

[0031] In the cleaning composition of the present invention, optional components can be further appropriately blended as long as the effects of the present invention are not hindered. Optional components include, for example, lanolin derivatives, protein derivatives, acrylic resin dispersions, drugs such as vitamins, bactericides, preservatives, pH adjusters, antioxidants, sequestering agents, ultraviolet absorbers, animal and plant extracts or their extracts. Derivatives,
Dyes, fragrances, pigments, hydroxylated compounds (humectants), water (conditioning water: ion-exchanged water, purified water) and the like can be mentioned. In addition,
The mixing amount of these optional components can be appropriately set as long as the effects of the present invention are not hindered. Further, as an apparatus for preparing the cleaning composition of the present invention, a stirring apparatus having a plurality of stirring blades capable of mixing with the shearing force, for example, a propeller, a turbine, a disper, and the like are desirable, and particularly preferably an azihomomixer. , A backflow mixer, a hybrid mixer and the like are desirable.

In the above optional components, examples of the flavor include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, and aliphatics. Ethers such as ethers and aromatic ethers, oxides such as aliphatic oxides and terpenes, aldehydes such as aliphatic aldehydes, terpene aldehydes, aliphatic cyclic aldehydes, thioaldehydes, aromatic aldehydes, and aliphatic ketones , Terpene ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids,
Acids such as aliphatic cyclic carboxylic acids and aromatic carboxylic acids, acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, lactones such as aliphatic cyclic lactones, aromatic lactones, aliphatic esters, furan carboxylic acids Acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acid esters, and other esters; nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, and the like. One or two or more kinds of synthetic fragrances such as nitrogen compounds and natural fragrances from animals and plants, and mixed fragrances containing natural fragrances and / or synthetic fragrances can be used.

As synthetic fragrances, “Synthetic fragrance chemistry and product knowledge”, written by Motoichi Indo, published by Kagaku Kogyo Nippo, 1996, 19
1969 MONTCLAIR, N.M. J. Published by Stefan Arctander
Written by Perfume and Flavor Chemicals (P
erfume and Flavor Chemica
ls) "and the like. As the natural fragrance, the fragrance described in “Encyclopedia of Fragrance” edited by the Japan Fragrance Association can be used. The specific names of the main fragrances are aldehyde C
6 to C12, anisaldehyde, acetal R, acetophenone, acetylsedrene, adoxal, allyl amyl glycolate, allyl cyclohexanepropionate, α-damascon, β-damascon, δ-damascon, ambroxane, amylcinamic aldehyde,
Amylcinnamic aldehyde dimethyl acetal, amyl valerinate, amyl salicylate, isoamyl acetate, isoamyl salicylate, ouranciol, acetyl eugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, p -T-butylcyclohexanol,
pt-butylcyclohexyl acetate, ot-butylcyclohexanol, ot-butylcyclohexyl acetate, benzaldehyde, benzylformate, caryophyllene, cashmeren, carvone, sedroambar, cetyl acetate, cedrol, celestrid, cinamic Alcohol, cinnamic aldehyde, cis jasmon, citral, citral dimethyl acetal, citrasal, citronellal, citronellol, citronellyl acetate, citronellyl formate, citronellyl nitrile, cyclaset, cyclamenaldehyde, cyclaprop, caron, coumarin, cinnamyl acetate , Δ-C6-C13 lactone,
Dimethylbenzylcarbinol, dihydrojasmon,
Dihydrolinalool, dihydromyrcenol, dimethol, dimyrcetol, diphenyl oxide, ethyl wanilin, eugenol, fluitate, phentyl alcohol, phenylethylphenyl acetate, galaxolide, γ-C6-C13 lactone, α-pinene, β-pinene, limonene, myrcene , Β-caryophyllene, geraniol, geranyl acetate, geranyl formate,
Geranyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinnamic aldehyde, hexyl salicylate, hyacinthium dimethyl acetal, hydrotropic alcohol, Hydroxycitronellal,
Indole, ionone, isobornyl acetate, isocyclocitral, iso-E super, isoeugenol, isononyl acetate, isobutylquinoline, jasmar, jasmolactone, jasmophylan, coabon, rigstral, lilial, lime oxide, linalool, linalool oxide , Linalyl acetate, lilal, manzanate, mayol, menthanyl acetate, menthone, methyl anthranilate, methyl eugenol, menthol, α-methyl ionone, β-methyl ionone, γ-methyl ionone, methyl iso eugenol, methyl lavender ketone, methyl salicylate, muguet Aldehyde, mugol, musk TM-II, musk 781, musk C14, muscone, civetone, cyclopentadeca Non, cyclohexadecenone, cyclopentadecanolide, ambledride, cyclohexadecanolide, 10-oxahexadecanolide,
11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brassate, ethylene dodecandioate, oxahexadecen-2-one, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musktivetine, nopyr Alcohol, nopyr acetate, neryl acetate, nerol,
Methyl phenyl acetate, mirac aldehyde, neobergamate, oakmoss no. 1, Oribund, oxyphenylone, p-cresyl methyl ether, pentalid, phenylethyl alcohol, phenylethyl acetate, lubafuran, damacenone, raspberry ketone,
Dimethylbenzylcarbyl acetate, jasmacyclene, methyl naphthyl ketone, rosephenone, rose oxide, sandaroa, sandella, santalex, styryl acetate, styraryl propionate, terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydro Linalyl acetate,
Tetrahydrogeraniol, tetrahydrogeranyl acetate, tonalid, traseolide, tripral,
Thymol, crocodile, veldox, yarayara, anise oil, bay oil, boad rose oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil , Coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil, geranium oil,
Hiba oil, cypress oil, jasmine oil, lavandin oil, lavender oil tA, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, patchouli oil, peppermint oil, perilla oil, petitgren oil, pine oil, Rose oil, rosemary oil, camphor oil, fragrance oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, crocodile bean tincture, vetiver oil, ylang ylang Oil, grapefruit oil, citron oil, benzoin,
Peruvian sam, true balsam, tuberose oil, absolute oak moss, fabal sam, musk tincture, castorium tincture, civet tincture, ambergris tincture and the like. In addition, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene, or the like can be used as a solvent or a retaining agent for the fragrance.

In the detergent composition of the present invention thus constituted, the above-mentioned component (A) of the amide carboxylic acid represented by the general formula (I) or a salt thereof, and the component (B) of the water-insoluble solid particles Contains, for the first time, low irritation to the skin (including the scalp), excellent foaming power, and gives a quick and crisp feel while rinsing. It gives a good feeling of use, and by adding a water-soluble polymer as the component (C), it becomes possible to give a smooth feeling after use (these points will be further described later). Examples will be described below. Therefore, the cleansing composition of the present invention can be suitably used as a hair cleansing composition such as shampoo and a skin cleansing composition such as body shampoo.

[0035]

EXAMPLES Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, “%” is “mass%”.

[Examples 1 to 16 and Comparative Examples 1 to 4] The following Table 1 and Table 2 (Examples 1 to 10) which are continuations of Table 1 and the following Tables 3 and 4 which are continuations of Table 3 (Table 4) Examples 11 to
16 and Comparative Examples 1 to 4) by a common method using the composition shown in
A detergent composition was prepared, and its foaming property (foaming power), a refreshing feeling upon rinsing, a refreshing feeling after use, and a smooth feeling were evaluated by the following methods. These results are shown in Tables 1 to 4 below.
Shown in

(1) Method of Evaluating Foaming After 10 women (specialized panelists) used the product of the present invention and the comparative product on skin and / or hair, the amount of foam was sensory evaluated according to the following criteria. Evaluation criteria: ◎: very good ○: good △: slightly bad ×: bad

(2) Evaluation method of refreshing feeling at the time of rinsing Ten women (specialized panelists) evaluated the product of the present invention (Example),
After using the comparative product (Comparative Example) on the skin and / or hair, the refreshing feeling was sensuously evaluated according to the following criteria. Evaluation criteria: ◎: very good ○: good △: slightly bad ×: bad

(3) Evaluation method of lack of tightness after use Ten women (specialized panelists) evaluated the lack of tightness according to the following criteria after using the product of the present invention and the comparative product on the skin and / or hair. Was evaluated. Evaluation criteria: ◎: very good ○: good △: slightly bad ×: bad

(4) Evaluation Method for Smoothness after Use Ten women (specialized panelists) were asked to use the product of the present invention (Example),
After using the comparative product (comparative example) on the skin and / or hair, the smoothness was organoleptically evaluated according to the following criteria. Evaluation criteria: ◎: very good ○: good △: slightly bad ×: bad

Examples 1 to 16 and Comparative Example 1 in Tables 1 to 4
The composition of the fragrances A to C used in Nos. 4 to 4 and Examples 17 to 22 described below is as follows. (Fragrance A) Lemon oil 5% Sweet orange oil 10% Geranium oil 3% Lavender oil 6% Sandalwood oil 1% Liliar 5% Nopyr acetate 1% Linalool 2% Benzyl benzoate 2% Benzyl salicylate 3% β-ionone 2% Methylionone 3% Helional 2% Hedion 8% Iso-E Super 3% cis-3-hexenol 0.3% Ligantral 0.3% Tripral 0.4% Cyclamenaldehyde 1.5% Hexylcinnamic aldehyde 6% Belfix 3% Galaxolide 5% Tonalid 6% Pentalid 1% Bakudanol 0.5% Kashmeran 2% Musk T 1% Fruit base 3% Rose base 3% Jasmine base 1% Mugue base 3% Amber base 1% Nonana 10% dipropylene glycol solution 2% decanal 10% dipropylene glycol solution 1% methylnonyl aldehyde 10% dipropylene glycol solution 2% dipropylene glycol 1%

(Fragrance B) Undecanal 0.1% Allyl amyl glycolate 0.5% Ambroxane 1% Dipropylene glycol solution 0.5% Bergamot oil 10% cis-3-hexenol 0.2% Citronellol 10% Dihydro Myrsenol 3% Eucalyptus oil 0.5% Galaxolide 50% Dipropylene glycol solution 5% Geranyl nitrile 1% Grapefruit oil 10% Methyl dihydrojasmonate 5% Helional 2% Ionone 1% Lemon oil 14.9% Lilial 2% Lime oil 2% Lillal 2% Orange oil 8% ot-butylcyclohexyl acetate 5% Rose absolute 0.2% Phenylethyl acetate 1% Santalinol 1% Tarpineol 1% Tonalid 7% Vanillin 10% Zip Propylene glycol solution 1% pentalide 2% ethylene brush rate 2% oxahexadecen-2-one 1% 14-methylhexadecenolide 1%

(Fragrance C) Decanal 0.1% Bakudanol 1% Benzoin Resinoid 0.5% Benzyl Acetate 1% Phenylethyl Alcohol 4.5% Bergamot Oil 5% Citronellol 3% Geranyl Acetate 2% Dihydromyrcenol 1% Eugenol 0.5% linalool 5% galaxolide 50% dipropylene glycol solution 6% geraniol 3% geranium oil 0.5% heliotropin 1% α-hexylcinnamic aldehyde 3% ionone 3% iso-E super 7% jasmine absolute 0.3 % Lilyal 7.9% Lillal 4.5% Methyl dihydrojasmonate 4% Methyl ionone 8% Absolute oak moss 0.1% pt-butylcyclohexyl acetate 2% Phenylethyl ace Tate 3% Rose Absolute 0.1% Styrilal acetate 0.5% Terpineol 2% Tetrahydromugol 6% Tonalid 5% γ-Undecalactone 0.3% Acetyl Cedrene 3% Ylang Ylang Oil 0.2% Pentalid 3% Ethylene brush rate 1% 14-Methylhexadecanolide 1% Oxahexadecene-2-one 1%

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

* 1 to * 15 in the above Tables 1 to 4 are as follows. * 1: Polagel NF (manufactured by American Colloids) * 2: Wenger FW (manufactured by Toyoshun Industries) * 3: Kunipia F (manufactured by Kunimine Industries) * 4: Vegum R (manufactured by Vanderbilt) * 5: Lucentite SWN (manufactured by Corp Chemical) * 6: Laponite XLG (manufactured by Nippon Silica Co., Ltd.) * 7: Gohsenol EG-25 (manufactured by Nippon Synthetic Chemical Industry) * 8: HE Daicel SP550 (manufactured by Daicel Chemical Industry) * 9: Nisso HPC (manufactured by Nippon Soda Co., Ltd.) * 10: Metrolose HPMC 60SH 4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) * 11: Carrageenin CSK-1 (San-Ei Gen F.F.
* 12: Neosoft G-11 (manufactured by Taiyo Kagaku) * 13: Carbopol 941 (manufactured by BF Goodrich) * 14: Average molecular weight 1,000,000 * 15: Average molecular weight 2,000,000

As is evident from the results of Tables 1 to 4, Examples 1 to 16, which fall within the scope of the present invention, have lower irritation to the skin than Comparative Examples 1 to 4, which fall outside the scope of the present invention. It was found to be excellent in foaming power (foaming property), giving a quick and refreshing feel during rinsing, and giving a good feeling of smoothness without stickiness after use after use. Furthermore, it has been found that the composition containing a water-soluble polymer as the component (C) can give a smooth feel after use. On the other hand, it was found that the effects of the present invention could not be achieved in Comparative Examples 1 to 4, which did not contain any of the (A) component amide carboxylic acid or its salt and the (B) component water-insoluble solid particles. .

In Examples 17 to 22 below, specific examples of the cleaning composition (liquid cleaning composition, deodorant and dandruff-preventing shampoo composition, creamy cleaning composition, cleansing gel composition, solid The soap composition and the liquid detergent composition for filling the former container will be further described. When these cleaning compositions were evaluated by the above-described evaluation methods, they were excellent in standing (◎), refreshing feeling during rinsing (◎), moist feeling after use (◎) and smooth feeling (◎). I found out.

Example 17: Liquid detergent composition (1) potassium mono-N-lauryl malate amide 8% (2) potassium laurate 5% (3) potassium myristate 5% (4) potassium palmitate 3% (5) Potassium stearate 1% (6) Lauryl dimethylamine oxide 2% (7) Polar gel NF (manufactured by American Colloids) 0.5% (8) Hydroxyethyl cellulose 0.3% (HEC Daicel SP550, Daicel Chemical) (9) Carboxy vinyl polymer 1% (Carbopol 941, BF Goodrich) (10) Propylene glycol 10% (11) 1,3-butylene glycol 5% (12) Squalane 2% (13) Silicone emulsion 2% (BY22-055, manufactured by Dow Corning Toray Silicone Co., Ltd.) (14) Potassium chloride 0.3% (15) Tetrasodium edetate Tetrahydrate 0.2% (16) Dibutylhydroxytoluene 0.1% (17) Melissa extract 1% (18) Dipotassium glycyrrhizinate 0.1% (19) Flavor A 1% (20) Blue 403 suitable amount (21 ) Yellow No. 4 qs (22) Remaining purified water

(Example 18: Shampoo composition for deodorant and anti-dandruff) (1) Mono-N-lauryl malamide triethanolamine 10% (2) POE (3) Sodium lauryl ether sulfate 10% (3) Lauryl Betaine dimethylaminoacetate 3% (4) Diethanolamide rallic acid 2% (5) Wenger FW (manufactured by Toyoshun Mining Co., Ltd.) 0.5% (6) Cationized cellulose (Leoguard GP, manufactured by Lion Chemical) 0.5% ( 7) Lauryl dimethylamine oxide 2% (8) Hexylene glycol 7% (9) Ethanol 1% (10) Methyl paraben 0.2% (11) Propyl paraben 0.1% (12) Oil-soluble licorice extract 2% (13 ) Triclosan 0.2% (14) Pyroctone Oramine 0.1% (Octopirox, manufactured by Clariant Japan) (15) l-Menthol 0.3% (16) Silicone Emulsion 2% (BY22-020, Dow Corning Toray Silicone Co., Ltd.) (17) 1,3-butylene glycol 5% (18) Ethylene glycol distearate 1% (19) Fragrance B 1% (20) Blue 403 No. Appropriate amount (21) Remaining purified water

(Example 19: Creamy detergent composition) (1) Mono-N-lauryl malamide 10% (2) Mono-N-myristyl malamide 10% (3) Mono-N-palmityl Malic amide 5% (4) Monopotassium N-lauroylglutamate 2% (5) Potassium hydroxide 3.9% (6) Glycerin 15% (7) PEG 4000 5% (8) Sorbitol 6% (9) Purification Lanolin 0.5% (10) Orange oil 1% (11) Sorbitan monoisostearate 1% (12) POE triisostearate (4) Sorbitan 1% (13) POE triisostearate (3) Glyceryl 1% (14) Highly polymerized polyethylene glycol 0.5% (Polyox WSR-N750, manufactured by Union Carbide Co., Ltd.) (15) Darbilia extract 1% (16) Birch extract 1% (17) Kunipia F (Kunimine Industries) 0 3% (18) Titanium oxide (average particle size 0.25 μm, rutile type) 1% (19) Gunjo (average particle size 0.3-2 μm) 0.05% (20) Bengala (average particle size 0.03 μm) 0.05% (21) Nylon powder (average particle size 100 μm) 0.05% (22) Tetrasodium edetate tetrahydrate 0.3% (23) Fragrance C 1% (24) Purified water balance

(Example 20: Cleansing gel composition) (1) Mono-N-lauryl malic acid amide triethanolamine 5% (2) Mono-N-myristyl malic acid amide triethanolamine 2% (3) Mono- N-decyl malic acid amide triethanolamine 1% (4) mono-N-decyl tartaramide amide triethanolamine 2% (5) lauryl dimethylamine oxide 1% (6) N-lauroyl-N-methyl-β-alanine triethanol Amine 1% (7) Coconut oil fatty acid diethanolamide 3% (8) POE (6) Glyceryl isostearate 1% (9) Dimethylpolysiloxane 2% (SH200-30cs, manufactured by Dow Corning Toray Silicone Co., Ltd.) (10) Hydroxypropyl methylcellulose 0.7% (Metroze HPMC 60SH4000, Shin-Etsu Chemical Co., Ltd. (11) Methacrylic acid / butyl acrylate / methyl methacrylate copolymer 0.2% (average molecular weight: 2,000,000) (12) Isopropyl methyl phenol 0.1% (13) Ellagic acid 0.2% (14) Laponite XLG (manufactured by Nippon Silica Co., Ltd.) 0.3% (15) Polyethylene powder (average particle size 100 μm) 0.3% (16) Perfume A 1% (17) Purified water balance

(Example 21: Bar soap composition) (1) 15% potassium mono-N-lauryl malate amide (2) 15% sodium coconut fatty acid isethionate (3) Palm / sodium coconut fatty acid (palm / (Coconut oil fatty acid = 65/35) 50% (4) Palmitic acid 3% (5) Sunflower oil 1% (6) Dimethylpolysiloxane 1% (SH200-30cs, manufactured by Dow Corning Silicone Toray) (7) High Polymerized polyethylene glycol 0.3% (Polyox WSR-N750, manufactured by Union Carbide Co.) (8) Dibutylhydroxytoluene 0.1% (9) Tetrasodium edetate tetrahydrate 0.1% (10) Hydroxyethane Phosphonic acid 0.1% (11) Sodium chloride 0.5% (12) Isopropyl methyl phenol 0.1% (13) Titanium dioxide 0.2% (14) Ellagic acid 0.5% (15) Wenger F (Hojun Mining Co., Ltd.) 0.5% (16) Perfume B 1% (17) Purified water Balance

(Example 22: Liquid detergent composition for filling a former container) (1) Mono-N-lauryl malamide triethanolamine 5% (2) Arginine laurate 5% (3) Amidopropyl betaine laurate 3% (4) Hydroxypropyl methylcellulose 0.2% (Shin-Etsu Chemical Co., Ltd. Metroose HPMC 60SH15) (5) Polyoxyalkylene-modified methylpolysiloxane 0.5% (SH3775M, Dow Corning Toray Silicone) ( 6) Kunipia F (manufactured by Kunimine Industries) 0.1% (7) Propylene glycol 15% (8) Rosemary extract (rosemary water, manufactured by Maruzen Pharmaceutical Co., Ltd.) 1% (9) Tetrasodium edetate tetrahydrate 0. 1% (10) Hydroxyethanediphosphonic acid 0.1% (11) Fragrance C 1% (12) Purified water balance

[0057]

According to the first aspect of the present invention, the skin (including the scalp) is used with low irritation, excellent foaming power (foaming property), and a quick and refreshing feel when rinsing. There is provided a detergent composition which does not have a feeling of being tight, is non-greasy, and gives a smooth and good feeling of use.
According to the second aspect of the present invention, there is provided a cleaning composition excellent in giving a smooth feel after use. According to the third aspect of the present invention, there is provided a detergent composition which is superior to the second aspect of the invention in that it provides a smooth feel after use.

Continued on front page F-term (reference) 4C083 AA112 AB032 AB232 AB242 AB332 AB432 AB441 AB442 AC022 AC102 AC122 AC132 AC242 AC312 AC422 AC442 AC472 AC482 AC532 AC552 AC562 AC641 AC642 AC662 AC712 AC782 AC792 AC812 AC852 AC892 AD022 AD042 AD072 AD092 AD132 AD152 AD152 BB21 BB36 CC01 CC23 CC38 DD08 DD21 DD23 DD31 DD41 EE06 EE07 EE10 EE23 4H003 AB03 AB06 AB44 AB46 AC15 BA01 BA12 DA02 EA19 EA25 EA27 EB03 EB04 EB16 EB29 EB30 EB33 EB37 EB42 EB43 EB46 FA02 FA18 FA18 FA21

Claims (3)

[Claims] 1. A cleaning composition comprising the following components (A) and (B). (A) Amidocarboxylic acid represented by the following general formula (I) or a salt thereof (B) Water-insoluble solid particles 2. The cleaning composition according to claim 1, further comprising a water-soluble polymer as the component (C). 3. The cleaning composition according to claim 1, wherein the water-insoluble solid particles of the component (B) are water-swellable clay minerals.