WO2011129034A1 - 濃縮液状洗浄剤組成物及びその製造方法 - Google Patents
濃縮液状洗浄剤組成物及びその製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
Definitions
- the present invention relates to a concentrated liquid detergent composition, and more particularly to a concentrated liquid detergent composition containing a high concentration of an ionic surfactant and suitable for diluting with water, and a method for producing the same.
- cleaning agents that use ionic surfactants include hair or skin cleaning compositions.
- the solid or cream cleaning agent is mainly composed of an anionic surfactant whose hydrophilic group is carboxylic acid, but it feels good when applied to hair and skin, or it is foamed and washed with hard water. The power was not good.
- a solid or creamy cleaning material mainly composed of an anionic surfactant whose hydrophilic group portion is not a carboxylic acid has been known, the usability and ease of use are not good. Therefore, from the viewpoint of ease of use, the dosage form of the hair or skin cleaning composition is often liquid.
- Such a liquid detergent composition is generally a composition containing 60 to 80% of water while blending 10 to 20% of an ionic surfactant.
- the raw material of the ionic surfactant is widely distributed in the form of a 25-35% aqueous solution of the surfactant. It is done. Therefore, in order to reduce the water content of the cleaning composition, it is necessary to increase the concentration of the surfactant aqueous solution. However, as the surfactant concentration increases, the viscosity of the solution usually increases significantly, making product preparation very difficult. In addition, some anionic surfactants were distributed in the form of 65-75% aqueous solution, but when mixed with other water-containing components or water, a significant increase in viscosity occurs. A mixing device was required. Therefore, the following technical development has been carried out in order to facilitate the utilization of the surfactant in a high concentration state.
- Patent Document 1 discloses that an amount of a surfactant selected from anionic, amphoteric, and nonionic is large (from 30% by mass) to a hair cleanser that contains both an ethylene glycol long-chain ester and a specific polyhydric alcohol. It is disclosed that foaming and moisturizing properties are imparted by blending. However, since the technique of Patent Document 1 is not intended to reduce the water content of the composition, there is no mention of gelation of the composition by polyhydric alcohol and its suppression when water is reduced.
- Patent Documents 2 and 3 disclose surfactant compositions that facilitate the use of high-concentration polyoxyethylene alkyl ether sulfates or alkyl sulfates.
- the composition is prepared by combining a water-soluble salt with a glyceryl ether or diglyceryl ether having an alkyl group or an alkenyl group (Patent Document 2) or an alkylene oxide adduct of an alcohol having a specific structure (Patent Document 3). This solves the problem of viscosity increase and gelation under the condition of high surfactant concentration.
- Patent Document 4 describes a compact liquid laundry detergent composition containing 5 to 45% by weight of water and a non-amino functional solvent in total. When measured at 20 s ⁇ 1 , the composition has a pure viscosity Vn of 1 Pa ⁇ s to 10 Pa ⁇ s and a diluted viscosity Vd of 0.5 Vn or less, and preferably dilutes upon dilution. That is, the composition described in Patent Document 4 is a laundry detergent composition that exhibits a significant decrease in viscosity before and after dilution.
- monovalent or divalent alcohol and a specific nonionic surfactant are used as a medium for anionic surfactants and amphoteric surfactants that are cleaning components. It has been found that a composition containing an agent has a small viscosity change due to dilution with water, is easy to dilute, and has a viscosity that is easy to handle before and after dilution, and has completed the present invention.
- the concentrated detergent composition according to the present invention comprises (A) an anionic surfactant, (B) an amphoteric surfactant, (C) 5 to 15% by mass of a monovalent or divalent alcohol, (D) 8 to 18% by weight of IOB 0.8 to 1.1 and a nonionic surfactant having a molecular weight of 500 or less, (E) 45% by weight or less of water, and the total of (A) and (B) is 40 to A liquid detergent composition having a mass ratio of 60% by mass and a blending ratio (C) :( D) of 3.5: 1 to 1: 2.5, wherein the composition has a concentration of (A) and (B).
- the viscosity when diluted to 15% by mass is 300 mPa ⁇ s or more at 30 ° C.
- the nonionic surfactant is a long-chain fatty acid N-methylethanolamide and / or a long-chain fatty acid diethylene glycol having an average carbon number of 10 to 14.
- the anionic surfactant contains polyoxyethylene alkyl ether sulfate.
- the concentrated liquid detergent composition preferably further contains an organic or inorganic salt.
- the method of using the concentrated liquid detergent composition according to the present invention is characterized by mixing with water.
- the method for producing the concentrated liquid detergent composition according to the present invention comprises (A) an aqueous solution of an anionic surfactant containing (C) a monovalent or divalent alcohol and (D) a nonionic surfactant. And (B) adding an aqueous solution of an amphoteric surfactant to the mixture and mixing the mixture.
- the manufacturing method of the liquid cleaning composition concerning this invention mixes the said concentrated liquid cleaning composition and water, It is characterized by the above-mentioned.
- the present invention it is possible to obtain a concentrated liquid detergent composition that can be easily diluted with water while maintaining an appropriate viscosity.
- the composition makes it possible to reduce energy during production and transportation without degrading the quality as a liquid detergent.
- the concentrated liquid detergent composition according to the present invention is compact because of its low water content, can be used in an easy-to-handle form, and is very advantageous for being brought into an airplane or used outdoors.
- the concentrated cleaning composition according to the present invention does not contain a large amount of water, it can be produced in a shorter time and with lower energy than before.
- the present invention includes (A) an anionic surfactant, (B) an amphoteric surfactant, (C) a monovalent or divalent alcohol, (D) IOB 0.8 to 1.1, and a molecular weight of 500 or less.
- the composition of the present invention has a very small change in viscosity when diluted with water until the components (A) + (B) reach a specific concentration, so that it can be easily diluted to a desired concentration while maintaining an appropriate viscosity. can do.
- the viscosity of the LES 70% aqueous solution rapidly increases from the start of dilution, and reaches a peak (about 1 million mPa ⁇ s) when the dilution factor is 1.5 times. Furthermore, when the dilution rate exceeds 2 times, the viscosity rapidly decreases, and when the dilution rate is 2.5 times, the viscosity drops to about 100 mPa ⁇ s.
- a concentrated liquid detergent containing an anionic surfactant at a concentration three times the normal concentration as a cleaning component is unstable when first trying to dilute, becoming harder to mix and then suddenly loosening. Shows behavior.
- Test Example 2 in FIG. 1 contains POE sodium lauryl ether sulfate, coconut oil fatty acid amidopropyl betaine solution, alkyl (8-16) glucoside, and the concentration of anionic surfactant is about 45%.
- the viscosity change due to dilution of a detergent base mixture (Plantapon 611C, manufactured by Cognis Co., Ltd.) in which the total amount of the surfactant is about 64% is shown.
- the composition of Test Example 2 has a viscosity that rapidly increases and decreases with the dilution factor, and is very difficult to handle as a concentrate to be used after dilution.
- Such a viscosity change due to dilution of the cleaning component is considered to be due to a change in the association structure of the active agent.
- cmc critical micelle concentration
- a string-like micelle is formed, and when the concentration is further increased, an aggregate structure is formed into a lamellar liquid crystal through a hexagonal liquid crystal. It is known to change. Therefore, when a high-concentration surfactant is simply diluted with water, the aggregate structure changes from lamellar liquid crystal ⁇ hexagonal liquid crystal ⁇ string-like micelle.
- lamellar liquid crystal and hexagonal liquid crystal are gel-like structures having high viscosity, and particularly hexagonal liquid crystal is a very hard gel. That is, the high-viscosity region shown by Test Examples 1 and 2 in FIG. 1 is considered to be a region where the aggregate structure of the surfactant is a lamellar liquid crystal or hexagonal liquid crystal.
- a nonionic surfactant is further used as a cosurfactant.
- Cosurfactants exert an effect of strengthening hydrophobic interaction while alcohol gradually weakens the packing of hydrophilic groups, while gradually entering into the aggregate. Therefore, as shown in Test Example 4 in which the nonionic surfactant coconut oil fatty acid N-methylethanolamide (Aminone C11, manufactured by Kao Corporation) is added to Test Example 3 in FIG. 1, the string-like micelle is diluted with water. However, the fluidity does not increase, and an appropriate viscosity is maintained.
- anionic surfactant As the anionic surfactant to be blended in the present invention, those usually used in cosmetics and pharmaceuticals can be used. Examples of the anionic surfactant suitable for the present invention include polyoxyethylene alkyl ether sulfates represented by the following general formula (I).
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- N represents an integer of 1 to 3.
- Examples of X include a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, and a basic amino acid cation.
- polyoxyethylene alkyl ether sulfate examples include POE (1-3) alkyl ether sodium sulfate, POE (1-3) alkyl ether sulfate triethanolamine, POE (1-3) ammonium lauryl ether sulfate, POE (1-3) sodium lauryl ether sulfate and the like.
- the alkyl sulfate represented by the following general formula (II) is mentioned.
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- Examples of X include a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, and a basic amino acid cation.
- alkyl sulfate examples include ammonium lauryl sulfate, potassium myristyl sulfate, sodium lauryl sulfate, triethanolamine cocoyl sulfate, and the like.
- anionic surfactant suitable for the present invention includes an N-acyl taurine salt represented by the following general formula (III).
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- X 1 represents a hydrogen atom or a methyl group.
- X 2 include a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, and a basic amino acid cation.
- the N-acyl taurine salt include N-cocoyl methyl taurine sodium, N-lauroyl methyl taurine sodium, N-myristoyl methyl taurine sodium, N-stearoyl methyl taurine sodium, coconut oil fatty acid methyl taurine sodium and the like. Can be mentioned.
- anionic surfactants suitable for the present invention include N-acyl amino acid salts represented by the following general formulas (IV) and (V).
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- X include a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, and a basic amino acid cation.
- N-acyl amino acid salt as described above include sodium lauroylmethylalanine, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, lauroyl sarcosine sodium, lauroyl sarcosine potassium and the like.
- anionic surfactant suitable for the present invention includes hydroxy ether carboxylates represented by the following general formula (VI).
- R represents a linear or branched alkyl group or alkenyl group, and the carbon number thereof is preferably 4 to 34, more preferably 8 to 25. When the number of carbon atoms of the alkyl group or alkenyl group is less than 4 or more than 34, sufficient foamability and feeling of use may not be obtained.
- At least one of X 1 and X 2 may be —CH 2 COOM or —CH 2 CH 2 COOM, and the other may be a hydrogen atom.
- M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation.
- anionic surfactant suitable for the present invention includes a polyoxyethylene alkyl ether carboxylate represented by the following general formula (VII).
- R represents a linear or branched alkyl group or alkenyl group, and the carbon number thereof is preferably 4 to 34, more preferably 8 to 25.
- N is 0 or an integer of 1 or more.
- M represents a salt-forming cation such as alkali metal, alkaline earth metal, ammonium or alkanolamine.
- polyoxyethylene alkyl ether sulfate or polyoxyethylene alkyl ether carboxylate is preferable, more preferably polyoxyethylene alkyl ether sulfate, particularly preferably.
- commercially available products such as Texapon N70 (manufactured by Cognis) and Sinoline SPE-1250 (manufactured by Shin Nippon Chemical Co., Ltd.) can be used.
- the blending amount of the (A) anionic surfactant is 20 to 40%, preferably 25 to 30% by mass, more preferably 26 to 28, in a pure amount with respect to the composition. % By mass.
- the blending amount of the component (A) is less than 20% by mass or exceeds 40% by mass with respect to the composition, the viscosity of the composition before dilution becomes high and the preparation becomes difficult. In some cases, the viscosity of the composition increases remarkably, making it difficult to dilute, or the viscosity of the diluted composition becomes remarkably low and difficult to handle.
- anionic surfactant raw materials are supplied to the market as 25-35, 65-75% fluid aqueous solutions, or 85-100% solids containing no water.
- a raw material in an aqueous solution having a concentration of 25 to 35% is used.
- a raw material having a higher concentration of anionic surfactant preferably 50% or more.
- a raw material dissolved in a liquid form is preferable from the viewpoint of ease of production, rather than a dried and powdered raw material as an anionic surfactant.
- the higher the concentration of the active agent in the raw material is, the higher the concentration of the anionic surfactant can be obtained.
- amphoteric surfactant With respect to the amphoteric surfactant to be blended in the present invention, those that are usually used in cosmetics, pharmaceuticals and the like can be used.
- amphoteric surfactants suitable for the present invention include betaine acetate type amphoteric surfactants represented by the following general formulas (VIII) and (IX).
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- betaine acetate type amphoteric surfactant as described above include lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, and palm kernel oil amidopropyldimethylaminoacetic acid betaine.
- amphoteric surfactants suitable for the present invention include imidazoline type amphoteric surfactants represented by the following general formula (X).
- R represents a linear or branched alkyl group, and the carbon number thereof is preferably 10 to 16, more preferably 12 to 14.
- Examples of the imidazoline type amphoteric surfactant as described above include N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium, 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2. -Imidazoline sodium and the like.
- amphoteric surfactants suitable for the present invention include tertiary amine oxides represented by the following general formula (XI).
- R 1 represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms
- R 2 and R 3 each represent a methyl group or an ethyl group.
- the tertiary amine oxide include coconut oil fatty acid dimethylamine oxide, lauric acid dimethylamine oxide, tetradecyldimethylamine oxide, and dodecyldimethylamine oxide.
- amphoteric surfactants particularly suitable in the present invention are lauryl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, palm kernel oil amidopropyldimethylaminoacetic acid betaine, 2-undecyl-N. , N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium.
- Examples of the substance include Anon BL-SF (manufactured by NOF Corporation), Levon 2000-SF (manufactured by Sanyo Chemical Co., Ltd.), Genegen Cab 818J (manufactured by Clariant Japan), TEGO Betain C60 (manufactured by Degussa), Dehyton PK45 ( Commercially available products such as Cognis Co., Ltd., Nissan Anon BDC-SF (manufactured by Nippon Oil & Fats), and ovazoline 662N (manufactured by Toho Chemical Co., Ltd.) can be used.
- the blending amount of the (B) amphoteric surfactant in the present invention is 10 to 20% by mass, preferably 11 to 17% by mass, more preferably 14 to 16% by mass with respect to the composition.
- the blending amount of the component (B) is less than 10% by mass with respect to the composition, the viscosity of the diluted solution may be remarkably lowered. Further, if the blending amount exceeds 20% by mass, the viscosity of the composition before dilution becomes high and preparation becomes difficult, or the viscosity of the composition increases significantly during dilution, which may make dilution difficult.
- the commercially available amphoteric surfactant raw material as described above is usually supplied to the market as a 25-40% aqueous solution.
- a raw material having a higher concentration of the amphoteric surfactant preferably 35% or more.
- concentration of the active agent in the raw material the higher the concentration of the amphoteric surfactant can be obtained.
- the total blending amount of the component (A) and the component (B), which are cleaning components is 40 to 60% by mass with respect to the composition. If the total blending amount of these surfactants is less than 40% by mass, the merit as a concentrated composition is diluted and unattractive. On the other hand, if it exceeds 60% by mass, a composition that is easily diluted with water cannot be obtained.
- the concentrated detergent composition according to the present invention is a monovalent or divalent alcohol and a nonionic surfactant, respectively, as a medium for the components (A) and (B). Or it contains 2 or more types.
- the monohydric or dihydric alcohol blended in the present invention is not particularly limited. However, in view of storage stability as a concentrated detergent composition and ease of handling during dilution, the composition can be stored and used. Those exhibiting a liquid state at less than 50 ° C. are assumed.
- ethanol for example, ethanol, isostearyl alcohol, jojoba alcohol as monohydric alcohol, dipropylene glycol, 1,3-butylene glycol, propylene glycol, 1,2-pentanediol, isoprene glycol as dihydric alcohol. Hexylene glycol, 1,2-octanediol and the like. Particularly preferred in the present invention are ethanol, dipropylene glycol, butylene glycol, propylene glycol and isoprene glycol.
- the blending amount of the (C) monovalent or divalent alcohol is 5 to 15% by mass, more preferably 10 to 13% by mass, based on the composition. If the blending amount of the component (C) is less than 5% by mass with respect to the composition, the viscosity of the composition before dilution becomes high and preparation becomes difficult, or the viscosity of the composition significantly increases during dilution. Dilution may be difficult. On the other hand, if the blending amount exceeds 15% by mass, the viscosity of the diluted solution may be extremely low and difficult to handle.
- Nonionic surfactant having an IOB of 0.8 to 1.1 and a molecular weight of 500 or less
- the nonionic surfactant used in the concentrated detergent composition according to the present invention has an IOB of 0.8 in the organic conceptual diagram. It is a compound having a molecular weight of 500 or less at ⁇ 1.1.
- nonionic surfactants include long chain fatty acid diethylene glycol, long chain fatty acid propylene glycol, long chain fatty acid fatty acid diethanolamide, long chain fatty acid fatty acid N-methylethanolamide, long chain fatty acid (POE) 2 monoethanol.
- amides and the like those satisfying the IOB range and the molecular weight range can be mentioned.
- fatty acid diethylene glycol having an average carbon number of 10 to 14 and fatty acid N-methylethanolamide having an average carbon number of 10 to 14 are particularly preferable.
- nonionic surfactants for example, genapol DEL (manufactured by Clariant Japan) as diethylene glycol laurate, and aminone C-11 (manufactured by Kao Corporation) as coconut oil fatty acid N-methylethanolamide are suitable.
- genapol DEL manufactured by Clariant Japan
- aminone C-11 manufactured by Kao Corporation
- coconut oil fatty acid N-methylethanolamide are suitable.
- the blending amount of the (D) nonionic surfactant is 8 to 18% by mass, more preferably 10 to 15% by mass, based on the composition.
- the blending amount of the component (D) is less than 8% by mass with respect to the composition, the viscosity of the diluted solution may be remarkably lowered. Further, if the blending amount exceeds 18% by mass, the viscosity of the composition before dilution becomes high and preparation becomes difficult, or the viscosity of the composition increases significantly during dilution, which may make dilution difficult.
- the total blending amount of the component (C) and the component (D) is preferably 20 to 30 with respect to the composition containing the component (A) and the component (B) in a pure content of 40% by mass or more. % By mass, more preferably 22 to 24% by mass.
- the diluted detergent composition is easily diluted in water, but the solution after dilution May become too low in viscosity.
- (E) concentrated detergent composition according to the water present invention containing 45 wt% water.
- water can be appropriately added as a single component, but it is usually sufficient to add water as a solvent for the surfactant raw material.
- anionic surfactants, amphoteric surfactants and the like are commercially available as high-concentration aqueous solutions of about 25 to 40%. Therefore, the use of these surfactants in the state of the aqueous solution can also serve as a blend of water in the present invention.
- the presence of water exceeding 45% by mass is not preferable from the viewpoint of reducing energy required for production and transportation of products.
- the concentrated detergent composition according to the present invention comprises (A) an anionic surfactant aqueous solution mixed with (C) a monovalent or divalent alcohol (D) a nonionic surfactant, and (B) an amphoteric interface.
- an aqueous solution of a monovalent or divalent alcohol and a nonionic surfactant is added to an aqueous solution of an anionic surfactant at room temperature and mixed until uniform. At this time, if the viscosity increases and bubbles are likely to be entrained by mixing, heating may be performed.
- the composition of this invention can be obtained by adding the aqueous solution of an amphoteric surfactant and stirring.
- a conventional liquid detergent composition having a high water content is produced, the order of mixing the components does not have a great influence on the production of the composition.
- the order of addition is different from the above, the viscosity is remarkably increased and the production of the composition may be difficult.
- the concentrated detergent composition of the present invention comprising such components and production method can be used as a hair shampoo precursor composition before being applied to hair as a hair shampoo, for example. That is, the concentrated detergent composition according to the present invention can be used in the same manner as a conventional hair shampoo by mixing and diluting an appropriate amount with water or the like at the time of use.
- the specific dilution ratio of the present invention can be appropriately adjusted according to the blending amount of the essential components and the blending ratio thereof, but the total concentration of the component (A) and the component (B) is usually pure. By diluting to 15% by mass, a cleaning effect comparable to that of a conventional liquid hair shampoo can be obtained. Therefore, for example, when the blending amount of (A) + (B) is 40% by mass with respect to the composition, an appropriate dilution ratio is about 2.6.
- the dilution rate increases as the temperature of the water to be diluted increases, water at room temperature (20 to 30 ° C.) can be sufficiently diluted.
- the hardness of the water to be diluted has little influence on the dilution rate, and depending on the dilution method, it can be sufficiently diluted even if the hardness is high.
- the concentrated liquid detergent composition according to the present invention may be used by diluting the necessary amount on the palm each time it is used, or may be diluted and used in a suitable size container before use. Good.
- the concentrated liquid detergent composition of the present invention does not have a high-viscosity region depending on the water content, and thus maintains a viscosity that is easy to handle before dilution—during dilution—after dilution.
- a liquid composition can be easily mixed when the viscosity at 30 ° C. is 20000 mPa ⁇ s or less, and mixing is difficult when the viscosity exceeds 50000 mPa ⁇ s.
- liquid viscosity of the composition (stock solution) of the present invention described above and the composition is diluted with water until the total concentration of the component (A) and the component (B) is 15% by mass in pure content
- the liquid viscosity is 50000 mPa ⁇ s or less, preferably 20000 mPa ⁇ s or less at 30 ° C. and normal pressure.
- the liquid viscosity after dilution of the concentrated liquid detergent composition of the present invention is set to 300 mPa ⁇ s or more at 30 ° C. and normal pressure. If the viscosity of the composition at the time of dilution, that is, when used is less than 300 mPa ⁇ s, the viscosity is too low to be handled, and it is difficult to apply the composition to the entire hair.
- the liquid viscosity after dilution is preferably adjusted to 300 to 20000 mPa ⁇ s (30 ° C.) in consideration of ease of handling during use as a cleaning agent. When the viscosity at the time of use exceeds 20000 mPa ⁇ s, the viscosity is too high, and it becomes difficult to apply to the object to be cleaned and put it in and out of the container.
- the composition “easy to handle before and after dilution” means that the viscosity increase (viscosity change) during the dilution due to the influence of the aggregate structure of the surfactant is 50000 mPa ⁇ s, preferably 20000 mPa ⁇ s.
- the viscosity after dilution (when used) is 300 mPa ⁇ s or more, preferably 300 to 20000 mPa ⁇ s.
- the phase state of the composition of the present invention and the diluted product thereof is preferably one phase. It is not preferable that the composition is separated into two phases in terms of stability as well as ease of handling of the composition.
- an organic or inorganic salt in order to reduce the viscosity of the composition in the high viscosity region and to facilitate dilution into water.
- the salt include organic acid salts, amino acid salts, and inorganic salts.
- the organic acid salt include hydrochlorides such as citric acid, lactic acid, oxalic acid, succinic acid, malic acid, tartaric acid, and sulfonic acid, metal salts (sodium salt, potassium salt), amine salts, and the like.
- amino acid salts include hydrochlorides such as glycine, alanine, proline, lysine, aspartic acid, and glutamic acid, metal salts (sodium salt, potassium salt), amine salts, and the like.
- Inorganic salts include carbonates such as sodium, potassium, magnesium, calcium, and ammonium, phosphates, nitrates, borates, sulfates, sulfites, and halogen compounds (sodium chloride, potassium chloride, ammonium chloride, etc.). Can be mentioned.
- the amount of the salt is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 2.0% by mass with respect to the composition, and sodium chloride, ammonium chloride, or citric acid. It is preferable to add sodium.
- the concentrated detergent composition according to the present invention in addition to the above components, other components that are usually used in cosmetics and pharmaceuticals can be blended within a range not impairing the effects of the present invention.
- Other ingredients include, for example, oils, cationic surfactants, powder components, natural polymers, synthetic polymers, thickeners, UV absorbers, sequestering agents, pH adjusters, skin nutrients, vitamins, Antioxidants, antioxidant assistants, fragrances and the like can be mentioned.
- oils include liquid oils, solid oils, hydrocarbon oils, and silicone oils.
- liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
- solid fat examples include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.
- hydrocarbon oil examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
- silicone oil examples include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl).
- linear polysiloxanes for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
- cyclic polysiloxanes for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl.
- Silicone resin silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, polyether-alkyl co-modified polysiloxane, Fluorine-modified polysiloxane, polyoxyethylene / polyoxypropylene copolymer-modified polysiloxane, linear amino polyether-modified polysiloxane, amide alkyl-modified polysiloxane, Roh glycol modified polysiloxane, aminophenyl modified polysiloxane, carbinol modified polysiloxane, polyglycerin modified polysiloxane, polyglycerin-alkyl co-modified polysiloxane), dimethiconol, and acrylic silicones, or the like.
- the blending conditions of the silicone oil may be solubilized or emulsified in the composition, and the particle diameter when emul
- Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, behenyltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylchloride Ammonium dialkyldimethylammonium salt; poly (N, N′-dimethyl-3,5-methylenepiperidinium); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; POE alkylamine; alkylamine salt; polyamine fatty acid derivative; amyl alcohol fatty acid derivative; benzalkonium chloride; benzethonium chloride and the like.
- alkyltrimethylammonium salts eg, stearyltrimethylammonium chloride, lauryltrimethylammonium
- the powder component examples include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
- inorganic powders for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
- natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned. Further, derivatives thereof (POE / POP modification, alkyl modification, cationization, anionization, silylation) are also included.
- plant-based polymers for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malm
- Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) , Dialkyldimethylammonium sulfate cellulose, hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and hydrophobically modified compounds of these polymers ⁇ Example: partly stearoxy-modified> and cationically modified compounds of these polymers, etc.) Alginate-based polymers (eg, sodium alginate, propylene glycol alginate, etc.); sodium pectate, etc. And the like.
- starch polymers eg, carboxymethyl starch, methylhydroxypropyl starch, etc.
- cellulose polymers methylcellulose, ethylcellulose, methyl
- Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40).
- vinyl polymers eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer
- polyoxyethylene polymers eg, polyethylene glycol 20,000, 40.
- poly (dimethyldiallylammonium halide) type cationic polymer for example, Mercat 100 (Merquat 100) manufactured by Merck & Co., USA); dimethyldiallylammonium halide And acrylamide copolymer type cationic polymer (for example, Merquat 550 manufactured by Merck USA); acrylic polymer (for example, sodium polyacrylate, polyethylacrylate) Over DOO, polyacrylamide), polyethylene imine; cationic polymers; silicate AlMg (Veegum); polyquaternium -39, polyquaternium -47, polyquaternium -74; (trimonium chloride acrylamide / dimethyl acrylamide) copolymer, and the like.
- poly (dimethyldiallylammonium halide) type cationic polymer for example, Mercat 100 (Merquat 100) manufactured by Merck & Co., USA
- thickeners examples include gum arabic, carrageenan, caraya gum, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, AlMg silicate (Beegum), Examples thereof include laponite and silicic anhydride.
- ultraviolet absorber examples include benzoic acid-based ultraviolet absorbers (for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester.
- PABA paraaminobenzoic acid
- PABA monoglycerin ester N, N-dipropoxy PABA ethyl ester
- N, N-diethoxy PABA ethyl ester examples include benzoic acid-based ultraviolet absorbers (for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester.
- PABA paraaminobenzoic acid
- sequestering agent examples include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate.
- Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
- Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
- Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
- ingredients that can be blended include, for example, preservatives (ethyl paraben, butyl paraben, 1,2-alkanediol (carbon chain length 6-14) and derivatives thereof, phenoxyethanol, methylchloroisothiozoline, etc.); (Eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (eg, cypress extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, Sembli, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokuinin, loofah, lily, saffron, senkyu, ginger, hypericum, onionis, garlic, capsicum, chimpi, cypress,
- the concentrated cleaning composition of the present invention is applied to shampoos for hair, body cleaning agents, facial cleansers, infant shampoos, infant body cleaning agents, kitchen cleaning agents, medical detergents, and other various cleaning compositions. It can utilize for a use and each usage form is not specifically limited.
- a predetermined amount of concentrated detergent composition and water are mixed in a screw test tube, and judged from the number of times of lightly shaking, as “evaluation during dilution" "A” means that no significant increase in viscosity is observed during dilution and dilution is very easy. “B” means that no significant increase in viscosity is observed during dilution, and dilution can be easily performed. Dilution is possible, but “C” indicates a significant increase in viscosity during dilution. As shown. In addition, as “evaluation of the appearance of the diluted solution”, the diluted detergent composition (diluted product) was visually observed to evaluate the phase state of the diluted solution.
- Test Example 1-2 in which an anionic surfactant and an amphoteric surfactant are combined in a pure amount of 40% by mass or more is excellent in ease of dilution, and the viscosity after dilution is also washed. The material was moderate (300 to 20000 mPa ⁇ s).
- Test Example 1-1 in which the concentrations of the anionic surfactant and the amphoteric surfactant were lowered, and Test Examples 1-3 and 1-4 in which only one of the anionic surfactant and the amphoteric surfactant was blended. Markedly increased the viscosity during dilution and lowered the viscosity of the composition after dilution. From the above, in the present invention, it is preferable that the total amount of the anionic surfactant and the amphoteric surfactant is 40% by mass or more as a pure component.
- the blending amount of alcohol is in the range of 5 to 15% by weight
- the blending amount of the nonionic surfactant is 8 to 18% by weight
- the blending ratio of both components (alcohol: nonionic property) It was found that when the surfactant was 3.5: 1 to 1: 2.5, a concentrated liquid detergent composition excellent in all of the above evaluations was obtained.
- Test Examples 3-1 and 3-2 containing dipropylene glycol (dihydric alcohol) and ethanol (monohydric alcohol) were excellent in dilution, and the viscosity after dilution was also washed. The material was moderate (300 to 20000 mPa ⁇ s).
- Test Example 3-3 using glycerin (trihydric alcohol) the viscosity after dilution was high, and it was difficult to handle at the time of use. From the above, in the present invention, it is preferable to use a monovalent or divalent alcohol.
- Test Examples 4-1 and 4-2 in which a nonionic surfactant having an IOB value of 0.8 to 1.1 was blended, the viscosity change during dilution was low and after dilution A concentrated detergent composition having an excellent viscosity was obtained.
- Test Examples 4-3 and 4-7 in which a nonionic surfactant having an IOB value of less than 0.8 was blended, the diluted solution was in a two-phase state.
- Test Examples 4-4 and 4-8 containing a nonionic surfactant having an IOB value exceeding 1.1 were concentrated detergent compositions having excellent low viscosity change during dilution and excellent viscosity after dilution. It did not become.
- test Example 4-5 in which a nonionic surfactant having an IOB value of 0.8 to 1.1 and other IOB values were used in combination, the appearance of the diluted solution was improved. Furthermore, even when the IOB is in the range of 0.8 to 1.1, in Test Example 4-6 in which a long-chain nonionic surfactant having a high molecular weight was blended, the viscosity of the composition after dilution was extremely low. became. From the above, in the present invention, a nonionic surfactant having an IOB value of 0.8 to 1.1 and having both a hydrophobic group and a hydrophilic group having no long chain may be blended. Is preferred. Further, as a result of further investigation, it was found that the nonionic surfactant preferably has a molecular weight of 500 or less.
- Test Example 5-7 in which salt was blended was smaller in viscosity difference before and after dilution due to the blending of salt and easier to dilute than Test Example 5-1 in which salt was not blended. It was excellent. Moreover, although the viscosity before dilution and during dilution became low due to the blending of the salt, a composition having a reasonably high viscosity after dilution was obtained. From the above, it is preferable to further add a salt in the present invention.
- a coconut oil fatty acid N-methylethanolamide, a coconut oil fatty acid monoethanolamide, and dipropylene glycol are mixed with stirring in a polyoxyethylene (2) sodium lauryl sulfate solution and an ammonium lauryl sulfate solution. Furthermore, other components are mixed to obtain a composition.
- the resulting composition can be easily diluted in water, and can be suitably used as a hair shampoo by diluting it with water by a factor of 2.71.
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Abstract
Description
エネルギー削減の手段としては、前記のような物流面における努力の他、液状洗浄剤組成物の製造の際にかかるエネルギー使用量を抑えることが考えられる。しかしながら、含水量の多い液状洗浄剤組成物では、多大なエネルギーを消費する昇温・冷却の工程を必要とする一方で、そのエネルギー削減効果には製造上の限界があり、十分な効果を得るには至っていない。
さらに、使用者の視点においても、アウトドアでの使用にも対応可能な軽量且つコンパクトなヘアシャンプーの要求は年々高まっている。
よって、ヘアシャンプーの含水量の低減は、製造や運搬における多大なエネルギーの低下、ひいては地球環境向上に貢献が期待される上、市場要求にも合致する。
したがって、洗浄剤組成物の含水量を低減するにあたっては、界面活性剤水溶液の高濃度化が必要となる。しかしながら、界面活性剤濃度が高くなると、通常、溶液の粘度が著しく増大してしまい、製品調製は非常に困難となる。また、一部のアニオン性界面活性剤では、65~75%水溶液の形態で流通していたが、他の含水成分や水と混合すると、著しい粘度上昇を生じるため、その使用にあたっては、特殊な混合装置が必要であった。そこで、界面活性剤を高濃度の状態で利用し易くするため、次のような技術開発が行われている。
しかしながら、特許文献1の技術は、組成物の含水量を低減することを意図したものではないため、減水した場合の多価アルコールによる組成物のゲル化やその抑制に関する言及はない。
しかし、このようなゲル化抑制剤の配合によって、界面活性剤を高濃度に含む系、つまり含水量を低減した毛髪洗浄剤組成物を取り扱い易い粘性のものとすることは可能であるものの、界面活性剤を高濃度のままで使用することは、皮膚への刺激性・安全性の観点や、少量の洗浄剤で髪全体を洗うという煩雑さ・使いにくさから好ましくない。そこで、毛髪洗浄剤組成物としての安全性や使用性を考慮すれば、界面活性剤が高濃縮された組成物を輸送・提供した後に、使用時又は使用前に水で希釈し、通常濃度の液状組成物の状態にして用いることが好ましいと考えられる。
本発明は上記課題に鑑みてなされたものであり、水による希釈前後において扱い易い濃縮液状洗浄剤組成物及びその製造方法を提供することを目的とする。
また、前記濃縮液状洗浄剤組成物において、(A)アニオン性界面活性剤が、ポリオキシエチレンアルキルエーテル硫酸塩を含むものであることが好適である。
また、前記濃縮液状洗浄剤組成物において、さらに、有機性又は無機性の塩を含むことが好適である。
さらに、本発明にかかる前記濃縮液状洗浄剤組成物の製造方法は、(A)アニオン性界面活性剤の水溶液に、(C)1価又は2価のアルコール及び(D)ノニオン性界面活性剤を混合する工程と、前記混合物に(B)両性界面活性剤の水溶液を加えて混合する工程とを含むことを特徴とする。
さらに、本発明にかかる液状洗浄剤組成物の製造方法は、前記濃縮液状洗浄剤組成物と、水とを混合することを特徴とする。
また、本発明にかかる濃縮洗浄剤組成物は多量の水を含まないため、従来よりも短時間且つ低エネルギーでの製造を可能とする。
一般に、界面活性剤は溶媒(水)中での臨界ミセル濃度(以下cmc)を超えると紐状ミセルを形成し、さらに濃度を上げていくと、ヘキサゴナル液晶を経てラメラ液晶へと会合体構造が変化することが知られている。したがって、高濃度の界面活性剤を単に水で希釈する場合、その会合体構造はラメラ液晶→ヘキサゴナル液晶→紐状ミセルと変化することになる。この内、ラメラ液晶及びヘキサゴナル液晶は粘度の高いゲル状構造物であり、特にヘキサゴナル液晶は非常に硬いゲルである。つまり、図1の試験例1、2によって示される高粘度領域は、界面活性剤の会合体構造がラメラ液晶またはヘキサゴナル液晶となる領域であると考えられる。
(A)アニオン性界面活性剤
本発明に配合されるアニオン性界面活性剤は、通常化粧品や医薬品等に使用されるものを用いることができる。本発明に適したアニオン性界面活性剤としては、例えば、下記一般式(I)で表されるポリオキシエチレンアルキルエーテル硫酸塩が挙げられる。
上記のようなポリオキシエチレンアルキルエーテル硫酸塩としては、例えば、POE(1~3)アルキルエーテル硫酸ナトリウム、POE(1~3)アルキルエーテル硫酸トリエタノールアミン、POE(1~3)ラウリルエーテル硫酸アンモニウム、POE(1~3)ラウリルエーテル硫酸ナトリウム等が挙げられる。
上記のようなアルキル硫酸塩としては、例えば、ラウリル硫酸アンモニウム、ミリスチル硫酸カリウム、ラウリル硫酸ナトリウム、ココイル硫酸トリエタノールアミン等が挙げられる。
上記のようなN-アシルタウリン塩としては、例えば、N-ココイルメチルタウリンナトリウム、N-ラウロイルメチルタウリンナトリウム、N-ミリストイルメチルタウリンナトリウム、N-ステアロイルメチルタウリンナトリウム、ヤシ油脂肪酸メチルタウリンナトリウム等が挙げられる。
上記のようなN-アシルアミノ酸塩としては、例えば、ラウロイルメチルアラニンナトリウム、ヤシ油脂肪酸サルコシンナトリウム、ヤシ油脂肪酸サルコシントリエタノールアミン、ラウロイルサルコシンナトリウム、ラウロイルサルコシンカリウム等が挙げられる。
X1、X2の少なくとも一方は -CH2COOM、または -CH2CH2COOMであり、他方は水素原子であってもよい。Mは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、低級アルカノールアミンカチオン、低級アルキルアミンカチオン、または塩基性アミノ酸カチオンである。
本発明に配合される両性界面活性剤に関しても、通常化粧品や医薬品等に使用されるものを用いることができる。本発明に適した両性界面活性剤としては、例えば、下記一般式(VIII)及び(IX)で表される酢酸ベタイン型両性界面活性剤が挙げられる。
上記のような酢酸ベタイン型両性界面活性剤としては、例えば、ラウリルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、パーム核油アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられる。
上記のようなイミダゾリン型両性界面活性剤としては、例えば、N-ヤシ油脂肪酸アシル-N-カルボキシメチル-N-ヒドロキシエチルエチレンジアミンナトリウム、2-ウンデシル-N,N-(ヒドロキシエチルカルボキシメチル)-2-イミダゾリンナトリウム等が挙げられる。
上記のような第三級アミンオキシドとしては、例えばヤシ油脂肪酸ジメチルアミンオキシド、ラウリン酸ジメチルアミンオキシド、テトラデシルジメチルアミンオキシド、ドデシルジメチルアミンオキシドなどが挙げられる。
なお、前述のような市販の両性界面活性剤原料は、通常、25~40%水溶液として市場へ供給されている。本発明においては、濃縮された組成物を得るという観点から、両性界面活性剤がより高濃度、好適には35%以上の原料を用いることが好ましい。前記原料中の活性剤濃度純分が高濃度であるほど、両性界面活性剤を濃厚に含む濃縮洗浄剤組成物を得ることができる。
本発明にかかる濃縮洗浄剤組成物は、上記(A)及び(B)成分の媒質として1価又は2価のアルコール及びノニオン性界面活性剤をそれぞれ1種又は2種以上含有する。
本発明に配合される1価又は2価のアルコールは特に限定されないが、濃縮洗浄剤組成物としての保存安定性や、希釈時の取り扱い易さを考慮すれば、該組成物の保存・使用が想定される50℃未満において液状を呈するものが好ましい。
このようなものしては、例えば、一価アルコールとしてエタノール、イソステアリルアルコール、ホホバアルコール、二価アルコールとしてジプロピレングリコール、1,3-ブチレングリコール、プロピレングリコール、1,2-ペンタンジオール、イソプレングリコール、ヘキシレングリコール、1,2-オクタンジオール等が挙げられる。本発明おいて特に好ましくは、エタノール、ジプロピレングリコール、ブチレングリコール、プロピレングリコール、イソプレングリコールである。
本発明にかかる濃縮洗浄剤組成物に使用されるノニオン性界面活性剤は、有機概念図におけるIOBが0.8~1.1で分子量が500以下となる化合物である。
このようなノニオン性界面活性剤としては、例えば、長鎖脂肪酸ジエチレングリコール、長鎖脂肪酸プロピレングリコール、長鎖脂肪酸脂肪酸ジエタノールアミド、長鎖脂肪酸脂肪酸N-メチルエタノールアミド、長鎖脂肪酸(POE)2モノエタノールアミド等のうち、前記IOB範囲と前記分子量範囲を満たすものが挙げられる。IOBが0.8を下回る、またはIOBが1.1を上回ると、希釈中に著しい粘度上昇を生じる、希釈後の粘度が著しく小さくなる、または希釈後の溶液組成物が1相ではなくなるといった問題が生じる。また、分子量が500を超えると希釈後の組成物の粘度が著しく低くなる。本発明において特に好ましくは、平均炭素数10~14の脂肪酸ジエチレングリコール、平均炭素数10~14の脂肪酸N-メチルエタノールアミドである。
また、市販のノニオン性界面活性剤としては、例えば、ラウリン酸ジエチレングリコールとして、ゲナポールDEL(クラリアントジャパン社製)を、ヤシ油脂肪酸N-メチルエタノールアミドとして、アミノーンC-11(花王社製)を好適に使用することができる。
本発明にかかる濃縮洗浄剤組成物は、45質量%以下の水を含む。本発明において、水は単独の成分として適宜添加することも可能であるが、通常は、界面活性剤原料の溶媒として含まれる水としての配合で足る。一般的に、アニオン性界面活性剤や両性界面活性剤等は、25~40%程度の高濃度水溶液として市販されている。したがって、これらの界面活性剤を前記水溶液の状態で用いることで、本発明における水の配合を兼ねることができる。
45質量%を超える水の存在は、製品の製造や運搬にかかるエネルギー削減観点から好ましくない。
具体的には、例えば、室温においてアニオン性界面活性剤の水溶液に1価又は2価のアルコール及びノニオン性界面活性剤の水溶液を加えて均一になるまで混合する。この際、粘度が増大し、混合による泡を巻き込みやすい状態となった場合は加熱してもよい。その後、両性界面活性剤の水溶液を加えて撹拌することにより本発明の組成物を得ることができる。
従来の含水量の多い液状洗浄剤組成物を製造する際は、構成成分を混合する順序が組成物の製造に大きな影響を与えることはない。しかし、本発明にかかる濃縮洗浄剤組成物の製造においては、添加順が上記と異なると、著しく粘度が上昇し、組成物の製造が困難になることがある。
また、希釈する水の温度は、高温になるほど希釈速度が速まるが、室温(20~30℃)の水でも十分に希釈することができる。また、希釈する水の硬度は、希釈速度にほとんど影響を与えず、希釈方法によっては硬度が高くても十分に希釈することができる。
また、本発明にかかる濃縮液状洗浄剤組成物は、使用する毎に必要量を掌上で希釈して用いても、使用前に予め適当な大きさの容器にまとめて希釈し、使用してもよい。
一般に、液状の組成物は、30℃における粘度が20000mPa・s以下であると容易に混合することができ、50000mPa・sを超えると混合が困難になると考えられる。したがって、上記した本発明の組成物(原液)の液粘度、及び、該組成物を前記(A)成分及び(B)成分の合計濃度が純分で15質量%となるまで水で希釈する間の液粘度は、30℃、常圧下において50000mPa・s以下、好ましくは20000mPa・s以下である。
さらに、本発明の組成物及びその希釈物の相状態は、1相であることが好ましい。2相に分離した状態であると、組成物の取り扱い易さだけでなく、安定性の点においても好ましくない。
塩としては、有機酸塩、アミノ酸塩、無機塩などが挙げられる。有機酸塩としては、例えば、クエン酸、乳酸、シュウ酸、コハク酸、リンゴ酸、酒石酸、スルホン酸等の塩酸塩、金属塩(ナトリウム塩、カリウム塩)、アミン塩などが挙げられる。アミノ酸塩としては、グリシン、アラニン、プロリン、リジン、アスパラギン酸、グルタミン酸等の塩酸塩、金属塩(ナトリウム塩、カリウム塩)、アミン塩などが挙げられる。無機塩としては、ナトリウム、カリウム、マグネシウム、カルシウム、アンモニウム等の炭酸塩、リン酸塩、硝酸塩、ホウ酸塩、硫酸塩、亜硫酸塩、ハロゲン化合物(塩化ナトリウム、塩化カリウム、塩化アンモニウム等)などが挙げられる。
本発明において、塩の配合量は、組成物に対し0.1~5.0質量%が好ましく、より好ましくは1.0~2.0質量%であり、塩化ナトリウム、塩化アンモニウム、又はクエン酸ナトリウムを配合することが好ましい。
他の成分としては、例えば、油分、カチオン性界面活性剤、粉末成分、天然高分子、合成高分子、増粘剤、紫外線吸収剤、金属イオン封鎖剤、pH調整剤、皮膚栄養剤、ビタミン、酸化防止剤、酸化防止助剤、香料等が挙げられる。
液体油脂としては、例えば、アボガド油、ツバキ油、タートル油、マカデミアナッツ油、トウモロコシ油、ミンク油、オリーブ油、ナタネ油、卵黄油、ゴマ油、パーシック油、小麦胚芽油、サザンカ油、ヒマシ油、アマニ油、サフラワー油、綿実油、エノ油、大豆油、落花生油、茶実油、カヤ油、コメヌカ油、シナギリ油、日本キリ油、ホホバ油、胚芽油、トリグリセリン等が挙げられる。
; ジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料(例えば、赤色201号、赤色202 号、赤色204号、赤色205号、赤色220号、赤色226号、赤色228号、赤色405号、橙色203号、橙色204号、黄色205号、黄色401号、及び青色404号などの有機顔料、赤色3号、赤色104号、赤色106号、赤色227号、赤色230号、赤色401号、赤色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、緑色3
号及び青色1号等);天然色素(例えば、クロロフィル、β-カロチン等)等が挙げられる。
ビタミン類としては、例えば、ビタミンA、B1、B2、B6、C、E及びその誘導体、パントテン酸及びその誘導体、ビオチン等が挙げられる。
酸化防止剤としては、例えば、トコフェロール類、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、没食子酸エステル類等が挙げられる。
まず、本実施例で用いた濃縮洗浄剤組成物(及びその希釈物)の評価方法を説明する。
濃縮洗浄剤組成物(及びその希釈物)の評価方法
濃縮洗浄剤組成物(及びその希釈物)の粘度は、それぞれB型粘度計を用いて、1分間回転した後の数値として測定した。
また、水への希釈のし易さは、濃縮洗浄剤組成物に水を加え、アニオン性及び両性界面活性剤の混合濃度が15質量%となるように希釈した際の撹拌混合のし易さから評価を行った。具体的には、ネジ口試験管に所定量の濃縮洗浄剤組成物と水とを混合し、軽く振った回数から判断し、「希釈中の評価」として、
希釈中に大幅な粘度増加が認められず、希釈が非常に容易にできるものを「A」、
希釈中に大幅な粘度増加が認められず、希釈が容易にできるものを「B」、
希釈は可能であるが、希釈中に大幅な粘度増加が認められるものを「C」、
として示した。
また、「希釈後溶液の外観の評価」として、上記希釈後の洗浄剤組成物(希釈物)を目視で観察し、希釈後の溶液の相状態を評価した。
アニオン性界面活性剤溶液にジプロピレングリコール及びノニオン性界面活性剤を撹拌混合した後、両性界面活性剤溶液を加えて混合し、濃縮液状洗浄剤組成物を得た。
一方、アニオン性界面活性剤と両性界面活性剤の濃度を低くした試験例1-1、アニオン性界面活性剤と両性界面活性剤の一方のみしか配合しなかった試験例1-3及び1-4は、希釈中の粘度増加や希釈後組成物の低粘度化が著しかった。
以上のことから、本発明においては、アニオン性界面活性剤及び両性界面活性剤を合計で、純分として40質量%以上含むことが好適である。
アニオン性界面活性剤溶液にアルコール及びノニオン性界面活性剤溶液を撹拌混合した後、両性界面活性剤を加えて混合し、濃縮液状洗浄剤組成物を得た。
一方、ジプロピレングリコールおよびラウリン酸ジエチレングリコールが適量配合された試験例2-3~2-5においては、全ての評価項目が良好な結果を示した。
以上のことから、本発明においては、アルコールとノニオン性界面活性剤を適量で組み合わせ、配合することが好適である。
また、さらなる試験の結果、本発明において、アルコールの配合量を5~15質量%の範囲、ノニオン性界面活性剤の配合量を8~18質量%、さらに両成分の配合比(アルコール:ノニオン性界面活性剤)を3.5:1~1:2.5とすると、上記全て評価に優れた濃縮液状洗浄剤組成物が得られることが分かった。
アニオン性界面活性剤溶液にアルコール及びノニオン性界面活性剤を撹拌混合した後、両性界面活性剤溶液を加えて混合し、濃縮液状洗浄剤組成物を得た。
一方、グリセリン(3価アルコール)を用いた試験例3-3では希釈後の粘度が高くなり、使用時の取り扱い易さに難があった。
以上のことから、本発明においては、1価又は2価のアルコールを使用することが好適である。
(製造方法)
アニオン性界面活性剤溶液にアルコール及びノニオン性界面活性剤溶液を撹拌混合した後、両性界面活性剤を加えて混合し、濃縮液状洗浄剤組成物を得た。
一方、IOB値が0.8未満のノニオン性界面活性剤を配合した試験例4-3、4-7では、希釈後溶液が2相状態となった。IOB値が1.1を超えるノニオン性界面活性剤を配合した試験例4-4、4-8は、希釈中の粘度変化の低さ及び希釈後の粘度の程度が優れた濃縮洗浄剤組成物とはならなかった。
また、IOB値0.8~1.1のノニオン性界面活性剤と、それ以外のIOB値のものを併用した試験例4-5においては、希釈後溶液の外観が良くなる結果となった。
さらに、IOBが0.8~1.1の範囲であっても、分子量の高い長鎖のノニオン性界面活性剤を配合した試験例4-6では、希釈後の組成物粘度が著しく低いものとなった。
以上のことから、本発明においては、IOB値が0.8~1.1のノニオン性界面活性剤で疎水基・親水基が共に長鎖を有さないノニオン性界面活性剤を配合することが好適である。また、さらに検討した結果、前記ノニオン性界面活性剤は、分子量が500以下ものが好適であることが分かった。
下記表6において、試験例5-1の組成物を1.5倍、2.0倍、2.5倍、2.82倍、3倍に水で希釈したものが、それぞれ試験例5-2、5-3、5-4、5-5、5-6である。
同様に、下記表7において、試験例5-7の組成物を1.5倍、2.0倍、2.5倍、2.82倍、3倍に水で希釈したものを、それぞれ試験例5-8、5-9、5-10、5-11、5-12とした。
アニオン性界面活性剤溶液にアルコール及びノニオン性界面活性剤を撹拌混合した後、塩及び両性界面活性剤溶液を加えて混合し、濃縮液状洗浄剤組成物を得た。
以上のことから、本発明において、さらに塩を配合することが好適である。
<処方例1 濃縮ヘアシャンプー>
(製造方法)
ポリオキシエチレン(2)ラウリル硫酸ナトリウム溶液及びラウリル硫酸アンモニウム溶液に、ヤシ油脂肪酸N-メチルエタノールアミド及びヤシ油脂肪酸モノエタノールアミドとジプロピレングリコールを撹拌混合する。さらに、その他の成分を混合し、組成物を得る。
得られる組成物は、水に容易に希釈することができ、水で2.71倍に希釈することによってヘアシャンプーとして好適に使用することができる。
(製造方法)
ポリオキシエチレン(1)ラウリル硫酸ナトリウム、90%ラウレス-4カルボン酸、アンモニア水を撹拌混合する。この溶液に、ラウリン酸ジエチレングリコール、POE(1)-1,2-ドデカンジオールとジプロピレングリコールを撹拌混合する。さらに、その他の成分を混合し、組成物を得る。
得られる組成物は、水に容易に希釈することができ、水で3.03倍に希釈することによってシャワージェルとして好適に使用することができる。
(製造方法)
ラウレス-4カルボン酸、アンモニア水にラウリン酸ジエチレングリコールとジプロピレングリコール、エタノールを撹拌混合する。さらに、その他成分を混合し、組成物を得る。
得られる組成物は、水に容易に希釈することができ、水で2.8倍に希釈することによってヘアシャンプーとして好適に使用することができる。
(製造方法)
ポリオキシエチレン(1)ラウリル硫酸ナトリウム、ポリオキシエチレン(3)ラウリル硫酸ナトリウム、90%ラウレス-4カルボン酸、アンモニア水を撹拌混合する。この溶液に、ラウリン酸ジエチレングリコール、ヤシ油脂肪酸N-メチルエタノールアミドとジプロピレングリコールを撹拌混合する。さらに、その他の成分を混合し、組成物を得る。
得られる組成物は、水に容易に希釈することができ、水で3.36倍に希釈することによってシャワージェルとして好適に使用することができる。
Claims (7)
- (A)アニオン性界面活性剤、
(B)両性界面活性剤、
(C)5~15質量%の1価又は2価のアルコール、
(D)8~18質量%のIOB0.8~1.1で分子量が500以下のノニオン性界面活性剤、
(E)45質量%以下の水、
を含み、(A)及び(B)の合計が40~60質量%、配合比(C):(D)が3.5:1~1:2.5である液状洗浄剤組成物であって、前記組成物を(A)及び(B)の濃度が15質量%となるまで希釈した際の粘度が30℃において300mPa・s以上であることを特徴とする濃縮液状洗浄剤組成物。 - (D)ノニオン性界面活性剤が、平均炭素数10~14の長鎖脂肪酸N-メチルエタノールアミド及び/又は長鎖脂肪酸ジエチレングリコールであることを特徴とする請求項1に記載の濃縮液状洗浄剤組成物。
- (A)アニオン性界面活性剤が、ポリオキシエチレンアルキルエーテル硫酸塩を含むものであることを特徴とする請求項1又は2に記載の濃縮液状洗浄剤組成物。
- さらに、有機性または無機性の塩を含むことを特徴とする請求項1~3のいずれかに記載の濃縮液状洗浄剤組成物。
- 水と混合することを特徴とする請求項1~4のいずれかに記載の濃縮液状洗浄剤組成物の使用方法。
- (A)アニオン性界面活性剤の水溶液に(C)1価又は2価のアルコール及び(D)ノニオン性界面活性剤を混合し、その後、(B)両性界面活性剤の水溶液を混合する工程を含むことを特徴とする請求項1~4のいずれかに記載の濃縮液状洗浄剤組成物の製造方法。
- 請求項1~4のいずれかに記載の濃縮液状洗浄剤組成物と、水とを混合することを特徴とする液状洗浄剤組成物の製造方法。
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10849870.0A EP2559749A4 (en) | 2010-04-12 | 2010-12-28 | Concentrated liquid detergent composition and method of making same |
| RU2012145779/04A RU2517692C1 (ru) | 2010-04-12 | 2010-12-28 | Концентрированная жидкая композиция моющего средства и способ ее получения |
| US13/640,347 US20130053295A1 (en) | 2010-04-12 | 2010-12-28 | Concentrated Liquid Detergent Composition And Process For Production Thereof |
| HK13105183.1A HK1178198B (en) | 2010-04-12 | 2010-12-28 | Concentrated liquid detergent composition and process for production thereof |
| KR1020127025850A KR20130040802A (ko) | 2010-04-12 | 2010-12-28 | 농축액상 세정제 조성물 및 이의 제조방법 |
| BR112012025881A BR112012025881A2 (pt) | 2010-04-12 | 2010-12-28 | composição de limpeza líquida concentrada e método de produção da mesma. |
| CN201080066149.XA CN102947436B (zh) | 2010-04-12 | 2010-12-28 | 浓缩液状洗净剂组合物及其制造方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-091799 | 2010-04-12 | ||
| JP2010091799A JP4912483B2 (ja) | 2010-04-12 | 2010-04-12 | 濃縮液状洗浄剤組成物及びその製造方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011129034A1 true WO2011129034A1 (ja) | 2011-10-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/073771 Ceased WO2011129034A1 (ja) | 2010-04-12 | 2010-12-28 | 濃縮液状洗浄剤組成物及びその製造方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130053295A1 (ja) |
| EP (1) | EP2559749A4 (ja) |
| JP (1) | JP4912483B2 (ja) |
| KR (1) | KR20130040802A (ja) |
| CN (1) | CN102947436B (ja) |
| BR (1) | BR112012025881A2 (ja) |
| RU (1) | RU2517692C1 (ja) |
| TW (1) | TWI406936B (ja) |
| WO (1) | WO2011129034A1 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012124766A1 (ja) * | 2011-03-16 | 2012-09-20 | 株式会社 資生堂 | 濃縮液状毛髪洗浄剤組成物 |
| JP2017525805A (ja) * | 2014-08-20 | 2017-09-07 | イノスペック パフォーマンス ケミカルズ ヨーロッパ リミテッドInnospec Performance Chemicals Europe Limited | 洗浄用洗剤のための組成物 |
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- 2010-12-28 KR KR1020127025850A patent/KR20130040802A/ko not_active Ceased
- 2010-12-28 BR BR112012025881A patent/BR112012025881A2/pt not_active Application Discontinuation
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| JP2017525805A (ja) * | 2014-08-20 | 2017-09-07 | イノスペック パフォーマンス ケミカルズ ヨーロッパ リミテッドInnospec Performance Chemicals Europe Limited | 洗浄用洗剤のための組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201134939A (en) | 2011-10-16 |
| HK1178198A1 (en) | 2013-09-06 |
| JP4912483B2 (ja) | 2012-04-11 |
| RU2517692C1 (ru) | 2014-05-27 |
| EP2559749A1 (en) | 2013-02-20 |
| US20130053295A1 (en) | 2013-02-28 |
| BR112012025881A2 (pt) | 2016-06-28 |
| KR20130040802A (ko) | 2013-04-24 |
| CN102947436A (zh) | 2013-02-27 |
| TWI406936B (zh) | 2013-09-01 |
| CN102947436B (zh) | 2015-01-07 |
| JP2011219663A (ja) | 2011-11-04 |
| EP2559749A4 (en) | 2013-12-25 |
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