TWI247797B - Cleanser composition - Google Patents

Abstract

The present invention provides a cleanser composition having a high foaming ability with a low stimulus to the skin. The cleanser composition of the present invention is weakly acidic and comprises (a) a phosphate monoester represented by the general formula (1) and (b) a phosphate diester represented by the general formula (2) wherein the ratio of the component (a) to the component (b), i.e. the (a)/(b) ratio, is from 65/35 to 90/10 by weight: wherein R1 represents an alkyl or alkenyl group containing 9 to 15 carbon atoms on average with a branching degree of 10% or more, X1 and X2 and X3 each represent a hydrogen atom or an alkali metal, and n is a number of 0 to 5.

Description

1247797 发明Invention Description: The present invention relates to a detergent composition having low skin irritation and high foaming property. [Prior Art] As a surfactant for a conventional skin cleansing agent, there are anionic interfaces such as higher fatty acid salts, alkane sulfates, polyoxyethylene alkyl sulfates, alkylbenzenesulfonates, and α-olefin sulfonates. Active agents are widely used. However, when such a detergent containing an anionic surfactant is used, there is a tendency that skin problems such as cracking of the hand are likely to occur. On the other hand, although nonionic surfactants are hardly known to cause skin cracking, the basic performance of detergents such as foaming power and detergency is inferior to that of anionic surfactants. A phosphate ester surfactant which is one of the anionic surfactants is known to have a low irritation to the skin and the like, and is a mild surfactant. This is produced, for example, by reacting an aliphatic alcohol with a phosphorus oxide such as phosphoric anhydride or a phosphorus oxychloride oxide, but usually a mixture of a monoester and a diester or a mixture of mono-, di- and tri-esters is obtained. Especially in the case of an alkyl ester having a high linear chain rate, if the content of the diester or the triester is large, the solubility in water or the foaming power is not good, so a complicated purification step must be performed to increase the monoester. Purity. On the other hand, in order to improve the water solubility, a phthalocyanate compound in which an oxyethylene group is introduced is known, but the foaming power of the compound is small, and the performance as a cleaning base is insufficient. In order to improve the problem of the foaming property, a detergent composition has been proposed in Japanese Patent No. 6 312 / Invention Specification (Supplement) / 92127287 1247797 JP - A - 2 Ο Ο 1 - 1 8 1 6 7 7 It contains a phosphate ester surfactant having a branched alkyl group, but it still does not fully satisfy the above requirements. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a detergent composition having low skin irritation and high foaming property. The present invention provides a detergent composition comprising the following components (a) and (b), wherein the weight ratio of the component (a) to the component (b) is (a) / (b) = 6 5 / 3 5 ~9 0 / 1 0, and it is weakly acidic. U) a monoester of phosphoric acid or a salt thereof as shown in the general formula (1)

Rx〇-(CH2CH20)n - P - OX1 (1) OX2 (wherein R1 represents an alkyl group or an alkenyl group having an average carbon number of 9 to 15 and a branching ratio of 10% or more, and X1 and X2 represent a hydrogen atom or a base, respectively. The metal, η is the number of 0 to 5 representing the average addition weight of the epoxy oxime. (b) The phosphodiester or its salt represented by the general formula (2)

Rb—(CH2CH20)n 3 XP-0X3 (2) R10-(CH2CH20)n// 7 312/Invention Manual (Supplement)/92127287 1247797 (wherein, the meanings represented by R1 and η are the same as above, and X3 represents Hydrogen or metal test.) Further, the present invention provides a detergent composition which further comprises a self-ethoxylated alkyl sulfate, a betaine type surfactant fatty acid or a salt thereof, an amine oxide, and a hydroxyl group in the above composition. At least selected from the group consisting of ethanesulfonic acid surfactant, sugar surfactant, alkanolamine, hydrazine-hydrazinoamine acid salt, and strontium-S&-anthracene-germanium sulfonate An auxiliary interface activity (hereinafter referred to as component (c)). The present invention further provides a detergent composition, which may also contain a diol having 5 to 6 carbons as the component (d), which has high foaming property and less viscosity due to viscosity at a low temperature relative to normal temperature. It can also be used for ease of use at low temperatures. Further, the present invention provides a weakly acidic detergent composition, which may also contain a carboxyl group-containing tackifying polymer as the component (e), which has a refreshing feeling of use and has a detergent suitable for use in the body and a face wash. Sticky. (Detailed Description of the Invention) In the components (a) and (b) of the present invention, R1 is an alkyl group or an alkenyl group having an average carbon number of 9 to 15 from the point of foaming property and water solubility. The number is preferably 1 0 to 1 4, and 1 1 to 1 3 is more preferable; the branching rate is 10% or more, preferably 10% to 60%. The branching ratio herein refers to the ratio (% by weight) of the branched alkyl group or the branched chain alkenyl group in all the alkyl groups or alkenyl groups represented by R1, and the actual branching is analyzed by gas chromatography. The sample sample was calculated from the respective peak areas of the corresponding linear esters and branched esters by the following formula. 312/Invention Manual (Supplement)/92127287 Number of Substrate Boundary Bases Make Carbon and Fractional Chains 8 1247797 Branching Rate % = Peak Area of _Σ Branch Chain _ Peak Area of Σ Straight Chain + Peak Area of Σ Branch Chain Further, X1, X2 and X3 each represent a hydrogen atom or an alkali metal, and the alkali metal may, for example, be lithium, sodium or potassium, and preferably sodium or potassium. The η system represents the number of 0 to 5 of the average weight of the ethylene oxide, preferably 0 to 3. The ratio of the component (a) to the component (b) in the detergent composition of the present invention is (a)/(b)=65/35 to 90 in terms of water solubility, foaming property, and the like. /10, preferably 65/35~85/15. Further, the total content of the component (a) and the component (b) in the detergent composition of the present invention is preferably 3 to 50% by weight, more preferably 5 to 5% by weight. The component (a) and the component (b) of the present invention are, for example, a phosphorus oxidizing agent such as a corresponding aliphatic alcohol and a phosphoric acid anhydride or a phosphorus oxychloride oxide, and the component (a) and the component (b) can be obtained. The above reaction is carried out under the conditions of a weight ratio, and further, by neutralizing with a base such as sodium hydroxide or potassium hydroxide, a mixture of the component (a) and the component (b) can be obtained. In the present invention, the content of the triester body in the mixture is preferably 1% by weight or less, that is, the total amount of the component (a) and the component (b). It is preferably 99% by weight or more. The phosphate compound having the component (a) and the component (b) as a main component has an excellent branched structure and has an oxyethylene group, and has excellent foaming properties even if it is not purified. As the aliphatic alcohol to be used herein, a mixture having an aliphatic group and having an average carbon number and a branching ratio as described above, or a commercially available aliphatic alcohol having an average carbon number and a branching ratio as described above can be used. The detergent composition of the present invention contains the above-mentioned (a) 9 312 / invention specification (supplement) / 92127287 1247797 component and (b) component in the proportions as described above, and exhibits weak acidity. Here, the weakly acidic means that when the composition is diluted with water, the p Η at 25 ° C is 4 · 5 to 6. 5 . In particular, when the detergent composition of the present invention is diluted with ion-exchanged water to a concentration of 5% by weight, ρ Η is preferably 4.5 to 6.5. The pH of the composition is adjusted to the above range with an acid or a base to adjust to p Η 4. 5 to 6. 0 is preferred. The organic acid may, for example, be citric acid, succinic acid, lactic acid, malic acid, glutamic acid, aspartic acid, porphyrin carbonate, tartaric acid, glycolic acid or ascorbic acid. Further, examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and particularly preferably phosphoric acid. Further, the base is preferably sodium hydroxide or potassium hydroxide. The detergent composition of the present invention further comprises at least one self-ethoxylated alkyl sulfate, a betaine-type surfactant, a fatty acid or a salt thereof, an amine oxide, an ethyl sulphate-based surfactant, and a sugar-based interface. The auxiliary surfactant selected from the group consisting of the active agent, the decylamine, the hydrazine-mercaptoamine, and the fluorenyl-fluorenyl-methyl-taurine salt is preferably the component (c). In the detergent composition of the present invention, the content of the component (c) is 0 · 5 to 2 0 by weight! Preferably, 1 to 10% by weight is better. The auxiliary surfactant of the component (c) is preferably at least one selected from the group consisting of the following (c-1) to (c-9). (c - 1 ) ethoxylated alkyl sulfate represented by general formula (3) 0 〇-(CH2CH2〇)m-S-Οχ4 ( 3 )

II ο 10 312/Invention Manual (supplement)/92127287 1247797 Number of carbons are shown in Table 2 R Formula of formula ο Chain of olefins

m is a gold base shown in Table 4 X or the ear molybdenum plus the average chain of the diene or the chain of oxygen is shown to be 8

C - agent - type live - type sauerkraut sweets show N1/ 4 / (\

CINIC H3

5 X 4 3 Η [wherein R3 represents an alkyl or alkenyl group having an average carbon number of 8 to 18, or a mercaptoamine alkyl group represented by the formula: R4CONH(CH2)a-; R4CO represents an average carbon number of 8~ A thiol group of 18, a represents an integer of 2 to 4; and X5 represents a CH2CH(OH) ch2s〇3_ group or a CH2C001T group. (c - 3 ) - a fatty acid or a salt thereof of the formula (5)

0 II —c—oxc (5) (wherein R5 represents an alkyl or alkenyl group of a straight or branched chain having an average carbon number of 9 to 17; and X6 represents a hydrogen atom, an alkali metal, NH4 or an alkanolammonium.) (c-4) Amine oxide CH3 L-N-CH3 11 312 as shown in general formula (6) / invention specification (supplement) / 92127287 (6) 1247797 (alkenyl, average carbon (c-5) - (in the formula: (c - 6 ) R6 represents a linear or branched chain having an average carbon number of 8 to 18 or a mercaptoamine alkyl group represented by the formula: R7CONH(CH2)b; b represents an integer of 2 to 4.) • The trans-acid surfactant R8-C-〇CH2CH2S03Z (7) 0 R8 represented by the general formula (7) represents a linear or branched chain having an average carbon number of 9 to 17. The chain Z represents a hydrogen atom, an alkali metal, NH4 or an alkanolammonium.) - a sugar-based surfactant R9-〇-(RI0〇) plant represented by the general formula (8) (G)fl (8) alkyl or The chain R7CO represents an alkyl group or a chain (wherein, the number 2 to 4 is a non-orthosaccharide (c-7) - R9 represents an alkyl group or an alkenyl group having an average carbon number of 8 to 18; 0 to 1 0 of the average molar amount of the reduced oxime olefinene having a carbon number of 5 to 6; q 1 to 1 of the average degree of condensation The number of 0.) - The alkanolamine 1 () represented by the general formula (9') represents a carbon 0 residue; P is a value of 〇 π II R - c - nh - ch2

(9) 312 / invention specification (supplement) / 92127287 12 1247797 (wherein R11 represents an alkyl or alkenyl group of a straight or branched chain having an average carbon number of 7 to 17; R12 represents a hydrogen atom or a methyl group; R13 Represents a hydroxyl group or a hydrogen atom; r represents a number from 1 to 5; r R12 and r R13 may be the same or different, wherein at least one of r R13 is a hydroxyl group.) (c - 8 ) has an average carbon number 8 to 18 fluorenyl N-nonylamino acid salt (c-9) having an average carbon number of 8 to 18, N-8&-N-mercapto ergic acid salt, the above ethoxylated alkyl group In the sulfate compound (c-1), from the viewpoint of foaming property, R 2 is an average carbon number of 10 to 18, preferably 10 to 14, and more preferably 1 to 1 3 A chain or branched alkyl or alkenyl group. Further, X4 represents an alkali metal, and the alkali metal may, for example, be lithium, sodium or potassium, and preferably sodium or potassium. m is a number of 0 to 1 0 indicating the average number of moles of cyclooxyethylene, preferably 0 to 3. In the above-mentioned betaine type surfactant (c-2), R 3 is an alkyl group having an average carbon number of 8 to 18, preferably 10 to 14 from the viewpoint of viscosity increasing property and foaming property. Or alkenyl, or the formula R4CONH(CH2)a - (R4CO is an average carbon number of 8 to 18, preferably 10 to 14 fluorenyl; a is an integer of 2 to 4, preferably 3) Shows a mercaptoalkyl group. Further, R3 or R4 may be an animal oil such as tallow or lard or a natural or synthetic oil of a plant such as soybean oil, coconut oil or palm kernel oil, and an alkyl or alkenyl group derived from such a mixed oil. Or 醯基. In particular, a mixed alkyl group derived from coconut oil or coix seed oil is preferred. X5 represents a CH2CH(OH)CH2S〇3_ group or a -CH2COO_ group. In the betaine type surfactant (c-2), the hydroxy sulfobetaine having R3 is an alkyl or alkenyl group having an average carbon number of 8 to 18, and X5 is a CH2CH(OH)CH2S〇3_ group. (hydroxysulfobetaine); R3 is R4CONHC3H6- (R4CO Table 13 312 / invention specification (supplement) / 92127287 1247797 shows the meaning of the above), amidoxime propyl, X5 is a CH2C0CT amidoxime carboxybetaine is preferred . Specific examples of the betaine-type surfactants include dodecane dimethyl hydroxysulfonyl betaine represented by formula (10) and dodecylamine propyl dimethyl ester represented by formula (1 1 ). A carboxybetaine, a coconut oil fatty acid guanamine dimethyl carboxybetaine represented by the formula (12), and the like.

C12H25—N—CH.2—C ΗCH—S 0 3 ch3 oh (10) Η CH3 C11H23—C—N—(CH2)3-N-CH2—COO 〇ch3 (ii) R14—C-II 0

H ch3 N—(CH2)3-N—CH2-CO 0 CH3 (12) (R14: from coconut oil fatty acid) In the above fatty acid or its salt (c-3), from the viewpoint of foaming, R5 is The linear or branched alkyl group or alkenyl group having an average carbon number of 9 to 17 , preferably 1 1 to 1 5 , more preferably 1 1 to 1 3 . Further, as the fatty acid or the salt thereof (c-3), a mixed fatty acid derived from a fat or oil raw material may be used, and examples of the fat or oil include coconut oil, palm kernel oil, and rape oil. The fatty acid derived from fats and oils may be used singly or in combination with a plurality of different fatty acids derived from fats and oils. In the case of combination use, it is preferred that the ratio of the average carbon number of R 5 falls between 1 1 and 1 3 . 14 312 / invention specification (supplement) / 92127287 1247797 Further, X6 represents a hydrogen atom, an alkali metal, nh4 or an alkanolammonium; examples of the alkali metal include lithium, sodium, potassium, etc.; and an alkanol which forms an alkanolammonium ion Examples of the amine include mono-, di- or triethanolamine, mono-, di- or tripropanolamine and the like. X6 is preferably sodium or potassium. In the above amine oxide (C-4), from the viewpoints of detergency and foaming property, R6 is an alkyl group or alkenyl group having an average carbon number of 8 to 18, preferably 10 to 14 or R7CONH(CH2)b - (R7CO represents a mercaptoamine alkyl group having an average carbon number of 8 to 18, preferably 10 to 14 fluorenyl groups, and b is 2 to 4, preferably 3). Further, R6 or R7CO may be animal or natural oils or synthetic oils such as butter, lard, or soybean oil, coconut oil, palm kernel oil, and mixed alkyl or alkene derived from such mixed oils. Base or thiol. In particular, it is preferred to use a mixed alkyl or sulfhydryl group derived from coconut oil or palm kernel oil. Preferred examples of the amine oxide include dodecyl dimethyl amine oxide represented by the formula (13), and dodecylaminopropyl dimethyl amine oxide represented by the formula (14), which are represented by the formula (15). The coconut oil fatty acid is amidoxime dimethylamine oxide and the like. Ch3 (13)

I C12H25—N —►〇 CH3 Η CH3 (14) C11H23—C—N—(CH2)3—N- 〇 ch3

H R15—CN-(CH2)3- 〇CH3I -N—ch3 15 312/Invention Manual (Supplement)/92127287 (15) 1247797 (R 15 : Fatty acid from coconut oil) The above-mentioned isethionate surfactant In (c - 5 ), R8 in the general formula (7) is preferably an alkyl group or an alkenyl group having an average carbon number of from 1 to 1 3 . Further, the alkali metal represented by Z may, for example, be lithium, sodium or potassium; and the alkanolamine which forms an alkanolammonium ion may be mono-, di- or triethanolamine, mono-, di- or tripropanolamine or the like. Preferred examples of the isethionate-based surfactant (c-5) include sodium dodecyl hydroxyethanesulfonate, sodium tetradecyl hydroxyethanesulfonate, potassium dodecyl hydroxyethanesulfonate, and fourteen. Potassium carboxyhydrocarbonate, triethanol of dodecyl hydroxyethanesulfonate, sodium hydroxyethanesulfonate of coconut oil, potassium potassium isethionate, etc. In the above-mentioned saccharide-based surfactant (c-6), R9 in the general formula (8) is an alkyl group having an average carbon number of 8 to 18, particularly 10 to 14 (an alkyl group, a dodecyl group, Tetradecyl groups, etc. are preferred. R 1G is preferably an alkylene group having 2 to 3 carbon atoms. p is preferably 0 to 2, and 0 is more preferred. G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, and a reducing sugar having 5 to 6 carbon atoms is preferably glucose, galactose, fructose or the like. The average condensation degree q of the reducing sugar is from 1 to 10, particularly preferably from 1 to 4. It is preferable to select q considering the physical properties of the carbon number of the alkyl group or the alkenyl group represented by R9, for example, when R9 is an alkyl group or an alkenyl group having a carbon number of 8 to 11, and q is preferably selected from 1 to 4. When R9 is an alkyl group or an alkenyl group having a carbon number of 12 to 14, it is preferred that q is selected from 1.5 to 4.0. Further, q can be obtained by a proton NMR method. In the above-mentioned alkanolamine (c-7), R 11 is a linear or branched alkyl group or alkenyl group having an average carbon number of 7 to 17 , preferably 10 to 14. R12 is a hydrogen atom or a methyl group. R13 represents a hydroxyl group or a hydrogen atom, and at least one of r R13 is a hydroxyl group. r is a number from 1 to 5, preferably 1 to 2. Specific examples of the alkanolamine (C-7) include lauric acid monoethanolamine, coconut 16 3^/invention specification (supplement)/92127287 1247797 fruit oil fatty acid monoethanol decylamine, palm eucalyptus oil fatty acid single Ethanol amide, lauric acid melamine, coconut oil fatty acid melamine, lauric acid glycerol decylamine and the like. In the above N-nonylamino acid salt (c-8), the fluorenyl group is a saturated or unsaturated fluorenyl group having an average carbon number of 8 to 18, preferably 10 to 14, and examples thereof include a octyl group and a fluorenyl group. A single fluorenyl group such as a tetradecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group or an oleic acid group. Further, a mixed base of a coconut oil fatty acid sulfhydryl group, a palm kernel oil fatty acid sulfhydryl group or the like is also preferred. Examples of the amino acid include glutamic acid, aspartic acid, aminic acetic acid, uronic acid, alanine, ?-alanine, and N-methyl-?-alanine. The salt is not particularly limited, and examples thereof include an alkali metal salt, an alkaline earth metal salt, and an alkanolamine salt. However, an alkali metal salt such as a sodium salt or a potassium salt is preferred. In the above fluorenyl-fluorenyl-fluorenyl sulfonate (c-9), the fluorenyl group is a saturated or unsaturated fluorenyl group having an average carbon number of 8 to 18, preferably 10 to 14. Such as octyl, fluorenyl, fluorenyl, tetradecyl, hexadecanyl, octadecyl, oleic acid and the like. Further, a mixed base of a coconut oil fatty acid sulfhydryl group, a palm kernel fat, a fatty acid sulfhydryl group or the like is also preferred. The salt is not particularly limited, and examples thereof include an alkali metal salt, an alkaline earth metal salt, and an alkanolamine salt. However, it is preferred to use a metal salt such as a sodium salt or a potassium salt. The component (d) used in the present invention has a carbon number of 5 to 6, and examples thereof include dipropylene glycol and isopropyl glycol. These may be used in two or more kinds, and in the total composition, it is preferably 0.1 to 30% by weight, particularly preferably 0.5 to 5% by weight, more preferably 1 to 10% by weight. Further, the weight ratio of the component (d) to the components (a) and (b) is 17 312 / invention specification (supplement) / 92127287 1247797 (d) / [(a) + (b)] = 95/5~5 /95' is preferably 80/20 to 20/80. If it falls within this range, the foamability and the ease of handling at low temperatures can be maintained at the same time. Further, the total content of the components (a), (b), and (c) is 3 to 60% by weight, preferably 5 to 40% by weight, and if less than 3% by weight, 'foaming property is insufficient' 60% by weight, it is detrimental to the viscosity stability at low temperatures. The tackifier polymer compound containing a component (e) carboxyl group used in the present invention preferably has a carboxyl group in its molecule and has a crosslinked structure, and examples thereof include polyacrylic acid as a main chain and an allyl group. A sucrose structure or a carboxyvinyl polymer of a pentyl erythritol structure (commercial products Carbopol 940, Carbopol 941, Carbopol 980, Carbopol 981 (all of which are manufactured by BF GOODRICH)), acrylic acid alkyl methacrylate (C10) -C30) a copolymer (commercial products such as Peiwu Lian TR1, Pemba Union TR2, Carbopol 1342, Carbopol ETD2020 (all of which are manufactured by BF GOODRICH Co., Ltd.)). These may be used in two or more kinds, and contain 0. 0 0 5 to 5 wt% in the total composition, and contain 0 · 1 to 2 by weight! Kq is better. In the above range, the detergent composition obtained by combining the components (a) and (b) is preferable because it can simultaneously satisfy the feeling of refreshing use and the moderate viscosity-increasing effect. Here, the preferred viscosity as a body and a cleansing agent means a viscosity of about 100 to 500,000 mPa*s at 25 ° C, particularly 200 to 300,000 mPa*s, more preferably 500~ 100,000 mPa*s is preferred. When the detergent composition of the present invention is made into a liquid form such as a shower gel (sh 〇werge 1 ) or a shower gel, the viscosity at 25 ° C is 2 0 0 4 , 0 0 0 m P a · s, especially 5 0 0~2 , 0 0 0 m P a · s is preferred. Moreover, in the case of a paste material such as a face washing material 18 312 / invention specification (supplement) / 92127287 1247797, the viscosity at 25 ° C is 1 Ο, Ο Ο Ο ~ 300, 00011? 3 *3, especially 20,000~100,000 111?3*5 is preferred. The detergent composition of the present invention does not freeze at a low temperature of 5 ° C or lower, and has a low viscosity increase compared with the viscosity at normal temperature. In the detergent composition of the present invention, other surfactants used in general detergents, such as alkylbenzenesulfonate, α-olefinsulfonate, alkanesulfonate, α-, may also be formulated as needed. An anionic surfactant such as a sulfo fatty acid ester salt or a polyoxyalkylene alkyl carbonate; a nonionic surfactant such as a polyoxyalkylene alkyl ester or a Pluronic surfactant; A cationic surfactant such as a grade 4 money salt. Further, in the cleaning composition of the present invention, the components used in the general detergent may be formulated as needed, for example, humectants such as propylene glycol, glycerin, and sorbitol; thiol cellulose and polyethylene oxide glycol. Viscosity modifiers such as stearate and ethanol; fungicides such as Triclosan and Triclorocarban; glycyrrhizic acid moss, tocopherol such as tocopherol; thiopentate Anti-dandruff agents such as zinc and hydroxymethyl ketone ketone (0 ct 〇pir ο X ); methylparaben, butylparaben, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate Preservatives; other oily ingredients, chelating agents, perfumes, pigments, touch modifiers, salts, pearlizing agents, anti-dandruff agents, cooling agents, UV absorbers, plant extracts, antioxidants, etc. The detergent composition of the present invention has low skin irritation and high foaming property, and is suitable for washing skin or hair, and can be used as a face washing material, a bath gel, a shampoo, a shower gel, and the like. Also, it can be used as a kitchen cleaner, etc. 19 312 / invention manual (supplement) / 92127287 1247797 Grounding detergent for long-term contact with the skin. [Embodiment] (Example 1) Using the mixture of the component (a) shown in Table 1 and the component (b), ab-1 to ab-3, and the component (c) shown in Table 2, Table 3 was produced by a usual method. And the detergent composition of each composition shown in Table 4.重量重量。 The content of each of the mixture of the sulphate is 0. 5 wt%. Further, p oxime is adjusted by phosphoric acid or an aqueous solution of sodium hydroxide. With respect to the obtained detergent composition, the pH was measured by the following method, and the foaming property was evaluated. The results are shown in Tables 3 and 4. <Measurement of pH> 2 g of the detergent composition was weighed, and 3 8 g of ion-exchanged water was added and stirred for 5 minutes, and measured by p Η (Η 0 RIBA ρ Η Μ ETERF _ 2 2 ) 2 5 The pH of the aqueous solution which has reached a uniform state at °C. <Foamability evaluation method> The aqueous solution 4 m 1 obtained by diluting the detergent composition by 10 times with ion-exchanged water was respectively charged into three 10 m 1 scale-containing centrifugal sedimentation tubes. It is placed in a side-by-side manner in a commercially available handless shaker (simple vibration machine SHK-COCK; Asahi TECHNOGLASS system). The vibration was carried out under the conditions of a temperature of 25 ° C in a vibration period of 180 cycles/minute, a vibration angle of 45 degrees, and a vibration time of 15 seconds. The amount of bubble of each sample was measured, and the average of three samples was determined, and the judgment was made based on the following criteria. ◎......foam volume 4. 5 m 1 or more 泡...foam volume 3 · 5 m 1 or more, less than 4 · 5 in 1 20 312 / invention manual (supplement) / 92127287 1247797 Δ ...... 泡量 2. 5 m 1 or more, less than 3. 5 m 1 χ ... the amount of foam is less than 2. 5 m 1 Table 1 Raw material alcohol (R ^ OH) R 丨 average Branch rate of carbon number R1 (3⁄4) Average E0 plus moles (η) (a)/(b) Weight ratio % 卜 ^ V X2 X3 ab- 1 蓬巴诺尔ο 〇*1 0 80/20 K Η κ ab- 2 12. 5 25 2 75/25 Na Η Na ab-3 u 0 2 60/40 Na Η Na * 1 : Mitsubishi Chemical (stock) Table 2 c - 1 - 1 ethoxydodecyl ( 2) Sulfate salt (in general formula (3), R2 = dodecacarbyl, m = 2, X4 = Na) c-2-1 dodecyl dimethyl hydroxy sulfobetaine (formula (10) Compound shown) c-2-2 c - 2-3 dodecylaminopropylcarboxybetaine (compound represented by formula (1 1 )) coconut oil fatty acid guanamine carboxycarboxybetaine (formula 1 2 ) compound) c-3-1 sodium laurate c - 4 - 1 , dodecyl dimethyl amine oxide c - 5 - 1 , sodium dodecyl decyl isethionate c - 5 - 2 Coconut oil fatty acid Sodium c - 6 - 1 decyl glucoside c - 7-1 lauric acid monoethanol decyl c-8-1 sodium dodecyl glutamate c - 9 - 1 dodecyl decyl methyl tauro Sodium 21 312 / invention specification (supplement) / 92127287 1247797 Table 3 Inventive product 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Detergent composition (% by weight) (a) Ingredient and (b) Mixture of ingredients ab - 1 15 20 ab-2 20 15 15 15 15 15 15 15 15 15 15 15 ab - 3 (c) Ingredient c-b 1 5 5 c-2- 1 5 c-2-2 5 c- 2-3 5 c-3-1 5 c-4 - 1 5 c- 5 - 1 5 c - 6 - 1 5 c-7- 1 5 c-8-l 5 c-9~ 1 5 pH adjuster ( Phosphoric acid, aqueous sodium hydroxide solution) The amount of the appropriate amount of ion exchange water (total amount of 100% by weight) Evaluation results pH 5.5 5. 5 5. 5 5.5 5. 5 5.5 5.5 5. 5 5.5 5. 5 5. 5 5.5 5 5 5.5 Foaming 〇〇〇〇 ◎ 〇 ◎ 〇〇 ◎ ◎ 〇〇〇 4 Table comparison product 1 2 3 4 5 6 7 8 9 10 11 12 13 Detergent composition (% by weight) (a) a mixture of the component and the component (b) ab - 1 15 ab-2 15 15 15 15 15 15 15 15 15 15 15 ab-3 15 (C) component c - 1 - 1 5 5 5 c-2- 1 5 c-2 - 2 5 c-2-3 5 c-3 - 1 5 c - 4 - 1 5 c-5- 1 5 c - 6 - 1 5 c-7- 1 5 c-8-1 5 c - 9 - 1 5 pH adjuster (phosphoric acid, sodium hydroxide solution) The amount of ion exchange water (the total amount becomes 1 C 0 ί fc! Quantity) Evaluation Results pH 5.5 7. 0 7.0 7. 0 7. 0 7. 0 7. 0 7. 0 7.0 7. 0 7.0 7.0 7. 0 Foaming Δ Δ Δ Δ Δ Δ Δ X Δ Δ X Δ Δ 312 / invention specification (supplement) / 92127287 22 1247797 (Example 2) Using the phosphate ester mixture shown in Table 5, the detergent composition of the composition shown in Table 6 was produced by a usual method. The resulting detergent composition was evaluated for viscosity at 0 ° C and 25 ° C and foaming at 40 ° C. The reason why the foaming property is evaluated at 40 °C is to assume that the face or body is cleaned with warm water. The results are shown in Table 6. (Evaluation method), (1) Viscosity: After each detergent composition was stored at 0 ° C and 25 ° C for 24 hours, a B Μ type viscosity meter (Τ Ο KI Μ ECINC ·) was used. The viscosity at each temperature was measured. (2) Foaming property: In a 10-fold diluted aqueous solution of each detergent composition of 100 m L, 2 g of lanolin was added as an artificial stain, and the inner diameter of 6.5 cm was attached with a scale. In a glass cylindrical tube, the condition was set to a number of revolutions of 10 rpm, and a reverse rotation of 10 rpm at 40 ° C, and the mixture was stirred for 1 minute with a flat screw. After the completion of the stirring, the amount of foaming after 5 minutes was measured and judged by the following criteria.

〇: The amount of foam is more than 1 5 5 m L. △: The amount of foam is more than 1 4 5 m L, less than 1 5 5 m L x : The amount of foam is less than 1 4 5 m L 23 312 / invention manual (supplement) / 92127287 1247797 Table raw material alcohol (R^OH) R1 average carbon number R1 branching rate (%) Average E0 plus moles (η) (a) / (b) Weight ratio f; f ion X1 X2 X3 ab - 4 Diya Dol 1 1" 11.0 50 0 80/20 KHK ab-3 Pocket Barnol 2 3 M 12. 5 25 2 60/40 Na H Na ab- 2 Pocket Barnol 23" 12. 5 25 2 75/25 Na H Na ab- 5 Pocket Barnol 23” 12. 5 25 2 95/5 Na H Na ab- 6 Carumel 2 0 98*2 12. 0 0 2 75/25 Na H Na * 1 : Mitsubishi Chemical (share) system*2: Kao company tabulation

Ingredient (% by weight) Comparative product of the present invention 21 22 23 24 21 22 23 24 25 26 27 28 29 A · B Filling ester (ab-4) 30 30 30 30 Phosphate (ab - 3 ) 30 30 Phosphate ( Ab - 2 ) 30 30 30 phosphate (ab - 5 ) 30 30 phosphate (ab - 6 ) 30 30 C dipropylene glycol 5 5 5 5 5 isopropyl glycol 5 5 1 , 3_ butanediol 5 ion exchange water balance Viscosity (mPa*s): 0 °C 606 590 1260 1110 2 53 0 3180 2 0 6 0 778 3 24 0 2 600 5160 58 00 5880 Viscosity (m P a · s ) ·· 2 5 °C 292 230 718 690 254 908 996 202 366 870 1220 1180 334 Foaming 〇〇〇〇Δ XXX Δ XXXX (Example 3 (washing material)) A paste-like washing material of the composition shown below was produced by a usual method. The obtained face wash material has a viscosity of 4 5,0 0 m P a · s at 25 ° C and a viscosity of 48,000 mPa*s at 0 ° C. The viscosity at low temperature is low and has a high rise. Foaming. (Component) phthalate mixture (ab - 2 ) 2 0 (% by weight) 12-acid acid 5 24 312 / invention specification (supplement) / 92127287 1247797 12-carbon hydroxy sulfonyl betaine (c-2- 1) 3 lauric acid 2 dipropylene glycol 3 ethylene glycol distearate 1.5 dibutyl hydroxytoluene 0.02 ethylene tetraamine tetraacetic acid tetrasodium hydrate 0.02 gasification sodium 3 fragrance 0.5 48% sodium hydroxide to PH5. Amount of water of 5 (Example 4) Using the phosphate ester mixture shown in Table 5, the detergent composition of the composition shown in Table 7 was produced by a usual method. The resulting detergent composition was evaluated for its washability and viscosity. The results are shown in Table 7. (Evaluation method) (1) Flushing property: 10 males and 10 female assessors, taking 5 g of each detergent composition in one hand palm, diluted with tap water, and washed with two palms, The following criteria were used to evaluate the ease of rinsing during rinsing and were judged by the average score. (Evaluation Criteria) Score 0: Not easy to rinse. Score 1: Slightly difficult to rinse. Score 2: Easy to rinse. Score 3: Very easy to rinse. 25 312/Invention Manual (Supplement)/92127287 1247797 (Criteria for Judgment) 〇: The average score is 2 or more and 3 or less. △: The average score is 1 or more and less than 2. X ·· The average score is above 、, less than 1. (2) Viscosity: The viscosity of each detergent composition at 25 ° C was measured by a BM type viscosity meter (TOKIMEC INC ). 26 3 U/Invention Manual (Supplement)/92127287 1247797 Comparison Product 3 LO becomes the specified amount of pH LO LO < 44.2 LO LO L0 < 62. 8 * CO LO Inch LO < 80.6 〇〇CO LO LO LO X ο ai CO CO LO r—H LO LO Ο οα ai CO CO CO LO cz> tH inch LO < 3130 LO CO LO C=> rH LO LO < 4060 inch CO LO ◦ rH CO LO < 2220 CO CO LO ◦ rH LO LO < 36101 C<I CO LO CD rH LO LO < 2060 LO CD rH LQ LO < 5500 The present invention CO CO LTD ◦ rH LO LO 〇3970 in CO LO 〇tH LO LO 〇7030 CO LO CD t-H inch LO 〇6680 CO CO LO τ-Ή ◦ rH LO LO 〇3600! Cvl CO LO rH o rH inch LO 〇5930 > i CO LO rH o rH CO LO 〇6090 Ingredients (weight %) Phosphate (ab-4) Phosphate (ab-3) Phosphate (ab-2) Phosphate (ab - 5) Scalate S (ab-6) CARBOPOL940 CARBOPOL ETD2020 Pembiu with TR1 Malate Exchange water α rinsing viscosity (mPa*s) io , LZ Z, 8S § (·) Li Yee / s 1247797 (Example 5 (Body Wash)) in a usual manner for manufacturing the shower gel composition of FIG. The obtained shower gel has a viscosity of 3 00 mPa*s at 25 ° C, is easy to rinse, and has a refreshing feeling of use. (Ingredient) Phytate mixture (ab - 2 ) 1 5 (% by weight) pemiculide TR 1 0.2 sodium lauryl sulfate 3 12-carbon-based basal acid-based beet test (c-2-1) 3 Lauric acid 1 glycerol 10 2 0.02 0.02 is the amount of pH 5.5 0. 8 ethylene glycol distearate dibutyl hydroxy benzene benzene ethylene tetraamine tetraacetic acid tetrasodium 4 hydrate 8 5 % phosphoric acid perfume water The balance (Example 6 (washing material)) A paste-like washing material having the composition shown below was produced by a usual method. The obtained face-washing material has a viscosity of 8 3,0 0 mPa*s at 25 ° C, is easy to wash, and has a refreshing feeling of use. (Component) Phosphate mixture (ab - 2 ) 1 5 (% by weight) CARBOPOL ETD2020 0. 6 28 312 / invention specification (supplement) / 92127287 1247797 Dodecylphosphoric acid dodecyl sulphate (c-2-l) lauric acid glycerol ethylene glycol distearate dibutylhydroxytoluene ethylenediaminetetraacetic acid tetrasodium tetrahydrate 4 hydrate 8 5 % continuous acid flavor 5 5 1 10 0.020.02 Η5.5 The amount of water is 0. 8 Water balance (Example 7) Combine the component ab-2 of Table 1 with the auxiliary surfactant component (c) of Table 2, and make the detergent composition by the composition of Table 8, and The same test was carried out as in Example 1. The amount of foaming (m 1 ) is shown in Table 8. It is understood that the composition obtained by combining the phosphate ester mixture of the present invention and the auxiliary surfactant has a markedly improved foaming property. 29 312/Invention specification (supplement)/92127287 1247797 8 Table of the Invention 4 1 4 2 4 3 4 4 4 5 4 6 4 7 4 8 4 9 5 0 5 1 5 2 5 3 5 4 5 5 5 6 ( a) Mixture of ingredients and (b) ingredients ab-2 1.6 1. 6 1 . 6 1. 6 1.6 2.0 2.0 4.0 4.0 4.0 6.0 6.0 7.07.09.09.0 (c) Component c-1 -1 c-2-1 C-2-2 c-3-1 c - 4 - 1 c-5-2 c - 6 - 1 c-7-1 c-8-1 c - 9 - 1 0.4 0. 4 0. 4 0. 4 0. 4 2.0 2.0 2.0 2.0 2. 0 pH adjuster The amount of ion exchange water (total amount of 100% by weight) pH 5.5 5.5 5.5 5.5 5.5 5.5 7.0 5.5 5.5 5.5 5.5 7.0 5.0 5.0 5.5 7.0 Foaming amount (m 1) 3.7 4.5 5.7 4.7 4.9 3.8 3.5 4.5 4.3 4.8 3.6 3.5 4.4 4.5 3.8 3.7 (Example 8) Where the pasty wash material is, for example, (component) Phosphoric acid S mixture (ab - 2 ) CARBOPOL ETD2020 Dodecyl decylamine Carboxyl sulfonate (c-2-2) Sorbitol Dibutylhydroxytoluene Ethylenediaminetetraacetic acid tetrasodium 4 hydrate 85% acid-supplemented perfume shown underwater. 1 5 (wt%) 0.6 betaine 15 14 0.02 substance 0 · 0 2 becomes the amount of ρΗ5·5 0. 4 balance 30 312/invention specification (supplement)/92127287

Claims (1)

1247797 |;':ΐ. ! Pickup, patent application scope: 1 · A detergent composition containing the following components (a), (b) and (c), (a) component and (b) component The weight ratio is (a) / (b) = 65/35 to 90/10, (a) the total content of the component and the component (b) is 3 to 50% by weight, and the content of the component (c) is 0.5. 〜2 0重量%, the p Η at a concentration of 5% by weight diluted with ion-exchanged water is 4. 5~6 . 5, and the detergent composition is weakly acidic; (a) General (1) Carbonate monoester or salt thereof Ο (CH2CH20)n — P — OX1 OX" (wherein R 1 represents an alkyl group or an alkenyl group having an average carbon number of 9 to 15 and a branching ratio of 10% or more, and X1 and X2 each represent a hydrogen atom or an alkali metal, η is the number of 0 to 5 of the average molar amount of the ethylene oxide; (b) the phosphodiester or the salt thereof represented by the general formula (2) R'O-^CHiO),, 〇Xp-ox3 R10-(CH2CH20)n// (2) (wherein R1 and η have the same meanings as above, and X3 represents a hydrogen atom or an alkali metal) (c) at least 1 From ethoxylated alkyl sulfate, betaine type surfactant, lipid 326\general file\92\92127287\92127287 (replacement)-1 31 1247797 fatty acid or its salt, amine oxide, isethionate interface activity Auxiliary surfactant selected from the group consisting of an active agent, an alkanolamine, an N-mercaptoamine, and an N-mercapto-acid salt. 2. A detergent according to claim 1 a composition selected from the group consisting of the following groups (c-1) to (c-9); (c-1) an ethoxylated alkyl sulfate represented by the general formula (3): Interface N-methyl taurosulfonate, which contains one species as (C) R20-(CH2CH2〇)r 〇-S-ΌΧ4IIο (3 (wherein R2 represents a linear or branched chain with an average carbon number of 10 to 18) Base, X4 represents the metal, m is the number of 0 to 1 0 of the ethylene oxide); (c - 2) the beet test surfactant of the general formula (4): CH3 R3 - N -——X5 (4) I ch3 chain of alkyl or even plus [In the formula, R3 represents an alkyl group having an average carbon number of 8 to 18 or an alkylene group represented by an alkene R4C0NH(CH2)a-; R4C0 is a fluorenyl group of Tables 8 to 18, and a represents an integer of 2 to 4; ; X5 represents a CH2S〇3~ group or a CHzCOOIT group]; (c-3) a fatty acid or a salt thereof of the formula (5): a group, or a formula and an average carbon number-CH2CH(0H) 326\ total File\92\92127287\92127287 (replace)-1 32 1247797 ό R5—c—ΟΧ6 (wherein R5 represents an alkyl or alkenyl group having an average carbon number of 9 to 17 in a straight or branched chain; X6 represents a hydrogen atom, an alkali metal, N Η 4 or an alkanolammonium); (c-4) a general formula (6) The amine oxide shown: ch3 r6—(6) CH3 (wherein R6 represents an alkyl or alkenyl group having a linear or branched chain having an average carbon number of 8 to 18, or the formula R7C0NH(CH2)b - a mercaptoalkylamine group as shown; R7C0 represents an fluorenyl group having an average carbon number of 8 to 18, and b represents an integer of 2 to 4; (c - 5 ) - a carboxylic acid represented by the formula (7) Is a surfactant R8-C-0CH2CH2S03Z (7) 〇 (wherein R8 represents a linear or branched alkyl or alkenyl group having an average carbon number of 9 to 17; Z represents a hydrogen atom, an alkali metal, NH4 or an alkane Alcohol ammonium); (c - 6 ) The sugar-based surfactant of the general formula (8): R9 - 〇 - (R10 〇) p - (G) q (8) 33 326 \ total file \92\92127287 \92127287(substituted)-1 1247797 (wherein R9 represents an alkyl or alkenyl group having an average carbon number of 8 to 18; R1G represents an alkylene group having a carbon number of 2 to 4; and G represents a reduction of from 5 to 6 carbon atoms; The residue of the sugar; the number of 0 to 1 0 indicating the average molar amount of the epoxy olefin; Q is Also the number average degree of condensation of the sugar of 0 1~1 shown); (c-7) - as shown in general formula (9) an amine of burning alcohol XI: (wherein R11 represents an alkyl or alkenyl group having an average carbon number of 7 to 17 in a straight or branched chain; R12 represents a hydrogen atom or a fluorenyl group; R13 represents a hydroxyl group or a hydrogen atom; and r represents a number of 1 to 5; R12 and r R13 may be the same or different; wherein, at least one of r R13 is a hydroxyl group; (c-8) an N-fluorene amino acid salt having an average carbon number of 8 to 18 fluorenyl groups; c - 9 ) N-fluorenyl _ N - fluorenyl taurine β malang 34 326 \ total file \92\92127287\92127287 (replacement)-1 having an average carbon number of 8 to 18 fluorenyl groups