JP3018158B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a detergent composition, and more particularly, to a detergent composition which has excellent detergency and feel after washing, can stably contain a cationic germicide, and has a high bactericidal and antibacterial effect. The present invention relates to a detergent composition that is excellent in preventing scalp and body swelling and deodorizing and can prevent dandruff on the scalp.

[0002]

2. Description of the Related Art Conventionally, cleaning agents, particularly hair cleaning agents, include:
In many cases, an anionic surfactant such as polyoxyethylene alkyl ether sulfate or alkenyl ether sulfate was used as a main base for the purpose of obtaining excellent detergency and foaming power.

On the other hand, detergents, especially for hair and body, are required to have a bactericidal and antibacterial effect in addition to the washing effect. The use of a cationic disinfectant as a disinfectant is known.

[0004] However, when an anionic surfactant and a cationic germicide are used in combination, these complexes are formed, resulting in a problem that not only the detergency is reduced but also the bactericidal effect is not sufficiently exhibited.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a detergent composition which is excellent in detergency, feel after washing, and stably blends a cationic germicide to exhibit a high bactericidal effect and a high antibacterial effect. Another object of the present invention is to provide a detergent composition having anti-dandruff property, anti-itch property and deodorant effect.

[0006]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and have found that a specific sulfate ester-based surfactant, a specific cationic bactericide, a zwitterionic surfactant, etc. If a specific amount of the reactive polymer is combined and formulated, it has high detergency, excellent feel after cleaning, and has sufficient bactericidal and antibacterial properties. As a result, it has excellent effects such as anti-dandruff, anti-kayumi, and deodorant The present inventors have found that a detergent composition can be obtained and completed the present invention.

That is, the present invention provides the following component (A):
(B), (C) and (D); (A) General formula (1) R ¹ O— (CH ₂ CH ₂ O) _n —SO ₃ M ¹ (1) [wherein, R ¹ has 8 carbon atoms. represents a linear or branched alkyl or alkenyl group to 20, n is a number average of 0, M ¹ is an alkali metal atom, an alkaline earth metal atom, ammonium group, alkylammonium group or alkanol en Moni Sulfate ester surfactant represented by the following formula: (B) a cationic germicide represented by the following general formula (2), (3), (4) or (5) One or more selected from polyhexamethylene biguanides and 0.2 to 5% by weight;

[0008]

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[R ² and R ³ each represent a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group having 6 to 14 carbon atoms and a total of 16 to 26 carbon atoms. May be. R ⁴ and R ⁵ have 1 carbon atom
Represents an alkyl group, a hydroxyalkyl group or a polyoxyethylene group having an average number of moles of 10 or less, which may be the same or different. Z ¹ is a halogen atom, an amino acid, a fatty acid, an anionic residue of a phosphate ester, a phosphonate ester, a sulfonate ester or a sulfate ester having a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, or polymerization Degree 3
An anionic oligomer or polymer containing a formalin condensate of a sulfonated polycyclic aromatic compound having styrene sulfonic acid or having a hydrocarbon group as a substituent is described. ]

[0010]

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Wherein R ⁶ is a hydrocarbon group having 8 to 14 carbon atoms or

[0012]

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Wherein Z ¹ is a halogen atom, an amino acid, a fatty acid, a phosphoric ester, a phosphonic ester or a sulfonic acid having a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms. An anion residue of an ester or a sulfate ester, or an anion containing a formalin condensate of a sulfonated polycyclic aromatic compound having styrenesulfonic acid having a degree of polymerization of 3 or more or having a hydrocarbon group as a substituent Shows a functional oligomer or polymer. ]

[0014]

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[Z ² represents gluconic acid, acetic acid or hydrochloric acid. ]

[0016]

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Wherein R ⁷ represents a straight-chain or branched-chain alkyl group having 6 to 18 carbon atoms, and Z ³ represents a halogen atom, an amino acid, a fatty acid, a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms. May have an anionic residue of a phosphoric acid ester, a phosphonic acid ester, a sulfonic acid ester or a sulfuric acid ester having a carboxylic acid group or an alkenyl group, or a styrenesulfonic acid having a degree of polymerization of 3 or more, or may have a hydrocarbon group as a substituent. An anionic oligomer or polymer containing a formalin condensate of a sulfonated cyclic aromatic compound is shown. (C) one or more selected from amphoteric surfactants, amine oxide surfactants, alkanolamide surfactants and amide amino acid surfactants, 0.1 to 10% by weight, D) a cationic polymer; and a component (A) a sulfate ester-based surfactant as a main cleaning base.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula (1) showing (A) a sulfate ester surfactant used in the present invention, R ¹ is a linear or branched alkyl or alkenyl group having 10 to 16 carbon atoms. And n is preferably 0 to 6 on average from the viewpoint of detergency and foaming property, more preferably 0 to 4, and particularly preferably 1 to 4. Also particularly preferred is a sodium atom, ammonium and triethanol ammonium as M ^1.

The sulfate ester-based surfactant of the component (A) serves as a main cleaning base of the cleaning composition of the present invention, and is used in an amount of 50% by weight or more of the total detersive surfactant. is there. In addition, from the viewpoints of detergency, foaming properties, and incorporation of other components, 5 to 50% by weight (hereinafter simply referred to as%), preferably 7 to 30%, particularly preferably 8 to 25% by weight in the whole composition. %.

The cationic bactericide of the component (B) used in the present invention includes a quaternary ammonium salt represented by the general formula (2), a benzalkonium salt represented by the general formula (3), and benzethonium. At least one selected from a salt, a chlorhexidine salt represented by the general formula (4), a pyridinium salt represented by the general formula (5), and polyhexamethylene biguanide. Polyhexamethylene biguanide is available from CTFA's International Cosmetic Ingredlent Di
ctionary 5th edition, POLYAMINOPROPYL BIGUANIDE
"Cosmocil",
Known under the trademark “Mikrokill”. As Z ¹ in the general formulas (2) and (3), a halogen atom is particularly preferable.

Specific examples of preferred component (B) include benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, chlorhexidine acetate, chlorhexidine hydrochloride, and the like, with benzalkonium chloride and benzethonium chloride being particularly preferred. . Furthermore, the general formula (3a)

[0022]

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Wherein R ^6a represents a linear or branched alkyl or alkenyl group having 8 to 14 carbon atoms.

Benzalkonium chloride represented by the following formula is preferred.

The cationic bactericide of the component (B) can be used singly or in combination of two or more. From the viewpoint of the antibacterial effect, 0.2 to 5%, preferably 0.3 to 4% in the total composition. %,
Particularly preferably, the content is 0.5 to 2%.

The amphoteric surfactant of the component (C) used in the present invention is represented by the following general formula (6):

[0027]

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(Wherein, R ⁸ represents a linear or branched alkyl or alkenyl group having 7 to 22 carbon atoms, a represents an integer of 1 to 4, b represents a number of 0 or 1, R ⁹ and R ¹⁰ are each an alkyl group having 1 to 4 carbon atoms or — (CH ₂ C
H ₂ O) _d H (d represents an average of 1 to 3), and R ¹¹ is
_{-CH 2 CH (OH) CH 2} SO 3 -, - (CH 2) e SO 3 - or ^{_{- (CH 2) f COO -}} (e
Represents an integer of 2 to 5, and f represents an integer of 1 to 3)).

Of these, the general formula (6a)

[0030]

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(Wherein R ¹² is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms or R ¹³ C
ONH (CH ₂ ) _y- (R ¹³ represents a linear or branched alkyl or alkenyl group having 7 to 19 carbon atoms, and y represents an integer of 1 to 5), and x Represents an integer of 1 to 5), and a carbobetaine-type surfactant represented by the following general formula (6b) or (6c):

[0032]

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(Wherein, R ¹⁴ represents a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, and x has the same meaning as described above) or hydroxysulfobetaine Type surfactants are preferred. In the general formula (6a), R ¹² is a straight-chain or branched-chain alkyl or alkenyl group having 8 to 16 carbon atoms or R ¹³ CONH (CH ₂ ) ₃ (R ¹³ is a straight-chain having 7 to 15 carbon atoms). A chain or branched alkyl group or alkenyl group) is preferable, and x is preferably 1.
In the general formula (6b) or (6c), R ¹⁴ is
A straight-chain or branched-chain alkyl group or alkenyl group having 8 to 16 carbon atoms is preferable, and in the general formula (6a), R ¹² is
Fatty acid amidopropyl betaine which is R ¹³ CONH (CH ₂ ) _y — (R ¹³ represents a linear or branched alkyl or alkenyl group having 7 to 15 carbon atoms, and y represents 3) is particularly preferred.

The amine oxide surfactant of the component (C) used in the present invention is represented by the following general formula (7):

[0035]

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(Wherein, R ¹⁵ represents a linear or branched alkyl or alkenyl group having 7 to 18 carbon atoms, R ¹⁶ and R ¹⁷ each represent a methyl, ethyl or hydroxyethyl group, and g represents 0 Or 1 and h represent an integer of 0 to 3), of which the following general formula (7
a)

[0037]

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(Wherein R ¹⁵ is the same as described above) is preferred.

The alkanolamide surfactant of the component (C) used in the present invention is represented by the general formula (8):

[0040]

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(Where R¹⁸Is a straight chain having 7 to 19 carbon atoms or
A branched alkyl or alkenyl group, i and j
Represents an integer of 0 to 10, and at least i and j
Is preferably 1 or more).
And i + j is 1 to 5, especially 1 or 2, and R ¹⁸But charcoal
A straight-chain or branched-chain alkyl group or alk
Those which are a nyl group are more preferred.

The amide amino acid surfactant of the component (C) used in the present invention is represented by the following general formula (9) or (10):

[0043]

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(Where R¹⁹And R²⁰Each have 7 carbon atoms
To 19 linear or branched alkyl or alkenyl groups
And s and t each represent an integer of 2 to 4;
And L are each -CH_TwoCH (OH) CH_TwoSO_Three,-(CH_Two)_uSO_ThreeOr-(C
H_Two)_vCOO (u is an integer of 2 to 5, v is an integer of 1 to 3)
E) is a hydrogen atom or -L-M^ThreeAnd M^Twoas well as
M ^ThreeAre hydrogen atom, alkali metal, alkaline earth
Metal, ammonium, organic ammonium or a mixture thereof
Which shows a compound). Where M^Two
And M^ThreeSpecific examples of hydrogen, lithium, sodium
, Potassium, 1/2 calcium, 1/2 magnesium
Ammonium, monoethanol ammonium, die
Tananol ammonium, triethanol ammonium,
Monoisopropanol ammonium, diisopropanol
Ammonium, triisopropanol ammonium, etc.
Is mentioned. This amide amino acid surfactant is an example
For example, 1 mol of imidazoline derivative may be added to monochloroacetic acid or
With a surfactant obtained by reacting 1 to 2 mol of crylic acid
Once, imidazoline-type zwitterionic surfactants
Or it was called imidazolinium betaine
So, in the 5th edition of CTFA Dictionary SOD
IUM COCOAMPHOACETATE, SODIUM COCOAMPHOPROPIONATE,
SODIUM COCOAMPHOHYDROXYPROPYLSULFONATE, SODIUM LAU
ROAMPHOACETATE, SODIUM LAUROAMPHOPROPIONATE, DISOD
To those listed as IUM COCOAMPHODIACETATE
Correspondingly, it is widely known under the trademark "Miranol".

Component (C), selected from amphoteric surfactants, amine oxide surfactants, alkanolamide surfactants and amidoamino acid surfactants
Species or two or more surfactants are contained in the total composition in an amount of 0.1 to 1 from the viewpoints of detergency, foaming property, bactericidal / antibacterial effect and irritation.
0%, preferably 1 to 8%, particularly preferably 2 to 7%.

In the cleaning composition of the present invention, (A)
The weight ratio of / (C) is preferably from 1 to 50, more preferably from 2 to 30, and even more preferably from 2 to 15, from the viewpoint of the sterilization / antibacterial effect.

The cationic polymer of component (D) used in the present invention includes cationic cellulose derivatives, cationic starch, copolymers of diallyl quaternary ammonium salts and acrylamide, quaternized polyvinylpyrrolidone derivatives, Graded vinylpyrrolidone vinylimidazole polymer [eg, Rubicoat (LUVIQ, manufactured by BASF)
UAT), polyglycolamine condensate, quaternized collagen polypeptide, polyethyleneimine, cationic silicone polymer [for example, AMO described in CTFA]
DIMETHICONE, a cationic silicone polymer sold by Dow Chemical Company under the name Dow Corning 929 (cationic emulsion) as a mixture with other components], a copolymer of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (for example, Santos, USA, caltaretin), polyaminopolyamide (for example, the polymer described in French Patent No. 2,252,840 and its cross-linked water-soluble polymer), cationic chitin, and cationized guar gum derivative (for example, manufactured by Celanese Corporation) Jaguar C-13 · S, Jaguar C-17,
Jaguar C-16), quaternary ammonium salt polymer (for example, Miraball A-15, Miraball AD-1, Miraball AZ-1 manufactured by Milanol, USA) and U.S. Pat. Nos. 2,261,002 and 2 No. 2,271,378, No. 2,273,780, No. 2,388,614,
Nos. 2,454,547 and 3,206,462) and cationic polymers selected from the following (a), (b) and (c). Can be

(A) selected from polyalkylene-polyamines having two primary amino groups and at least one secondary amino group, diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms. And the resulting polyaminopolyamide and epichlorohydrin are reacted at a molar ratio of polyalkylene-polyamine to dicarboxylic acid of 0.8: 1 to 1.4: 1. A polymer obtained by reacting at a molar ratio of epichlorohydrin to tertiary amino group of 0.5: 1 to 1.8: 1. This polymer is disclosed in U.S. Pat.
7,615 and 2,961,347.

A polymer of this type is sold in particular by Hercules under the name Hercoset 57, a 10% aqueous solution having a viscosity of 30 cps at 25 ° C. and a copolymer of epoxypropyl adipate-diethylenetriamine copolymer. The case is sold by the company under the name PD170 or Dellset 101. (B) Next unit

[0050]

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(Wherein R ²³ represents a hydrogen atom or a methyl group; A ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms;
R ²⁴ , R ²⁵ and R ²⁶ are the same or different and have 1 to 1 carbon atoms.
8 represents an alkyl group or a benzyl group, R ²¹ and R ²² represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X is a methosulfate anion or a halide such as chloride or bromide. A homopolymer or copolymer introduced from acrylic acid or methacrylic acid.

The copolymer or copolymer mixture that can be used includes acrylamide, methacrylamide,
Examples include diacetone-acrylamide, acrylamide and methacrylamide in which a lower alkyl group is substituted on the nitrogen, alkyl esters of acrylic acid and methacrylic acid, vinylpyrrolidone and vinyl esters. The following may be mentioned as examples: Cosmetic Ingredient Di
ctionary, the product listed under QUATERNIUM 38, 37, 49 and 42 by Hercules, Inc.
n an acrylamide / beta methacryloyloxyethyltrimethylammonium methosulfate copolymer sold under the names 205, 210, 220 and 240, sold under the name Catrex by the National Starch,
An 8% aqueous solution of an aminoethyl acrylate / acrylate copolymer having a viscosity of 700 cps at 25 ° C. and a molecular weight of 10,000 to 1,000,000, preferably 15,000 to 500,000; A crosslinked cationic graft copolymer obtained from the copolymerization of one cosmetic monomer, b) dimethylaminoethyl methacrylate, c) polyethylene glycol, and d) a polyunsaturated crosslinker. These copolymers are described in French Patent No. 2,189,
No. 434. Crosslinking agents include ethylene glycol dimethacrylate, diallyl phthalate, divinylbenzene, tetraallyloxyethane and sucrose 1
It is selected from the group consisting of polyallyl sucrose having 2 to 5 allyl groups per mole.

The cosmetic monomers can be of a very wide variety, for example vinyl esters of carboxylic acids having 2 to 18 carbon atoms, allyl or methallyl esters of carboxylic acids having 2 to 18 carbon atoms, 1 to 1 Acrylates or methacrylates of saturated alcohols having 18 carbon atoms, alkyl vinyl ethers whose alkyl groups have 2 to 18 carbon atoms, 4 to 18
Olefins having 3 carbon atoms, vinylic heterocyclic derivatives, dialkyl or N, N-dialkylaminoalkyl maleates in which the alkyl group has 1 to 3 carbon atoms or anhydrides of unsaturated acids. .

[0054] (c) the following formula ^{-A 2 -Z 4 -A 2 -Z 4} - (I) wherein, A ² is two amino groups, preferably a group having a piperazinyl group, Z ⁴ Represents the symbol B or B ^′ ,
B and B ^′ are the same or different and are unsubstituted or substituted by a hydroxyl group, and can also have oxygen, nitrogen and sulfur atoms and also have 1 to 3 aromatic and / or heterocyclic rings. Having a unit represented by the following formula:

-A ² -Z ⁵ -A ² -Z ^5- (II)

[Wherein A ² is as defined above;
⁵ is the symbol B ¹ or B ^{1 ′} , at least one of which is B ^{1 ′}
Wherein B ¹ is a linear or branched alkylene or hydroxyalkylene group, B ^{1 ′} is unsubstituted or substituted with one or more hydroxyl groups, and has one or more nitrogen atoms in the chain. A straight-chain or branched-chain alkylene group sandwiched therebetween, the nitrogen atom optionally being interposed by an oxygen atom in the chain and substituted by an alkyl group optionally having one or more hydroxyl groups] And cationic polymers selected from quaternary ammonium salts and oxidation products of the polymers of formulas (I) and (II). Among the various cationic polymers as described above, in particular, a cationic cellulose derivative, a cationic starch, a cationized guar gum derivative, a copolymer of diallyl quaternary ammonium salt and acrylamide,
Quaternized polyvinylpyrrolidone derivatives and polyglycolamine condensates are preferred. As the cationic cellulose derivative, for example, a compound represented by the following general formula (III) is preferable.

[0057]

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In the formula (III), A ³ represents a residue of an anhydroglucose unit, 1 is an integer of 50 to 20,000, and each R ²⁷ is represented by the following general formula (IV) Shows a substituent.

[0059]

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(R in the formula (IV)²⁸, R²⁹Is 2 or 3 carbon atoms
And m represents an integer of 0 to 10.
M ′ represents an integer of 0 to 3, and p represents 0 to 10
R represents an integer³⁰Is an alkylene group having 1 to 3 carbon atoms
Or a hydroxyalkylene group;³¹, R³², R³³
Are the same or different and each have an alkyl group having up to 10 carbon atoms,
Reel group, aralkyl group or compound containing nitrogen atom in formula
X may form a ring. ¹Is an anion (chlorine, bromine,
Iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid
Etc.)]] The degree of cation substitution of the cationic cellulose derivative is 0.
01 to 1, ie per anhydroglucose unit
The average value of m 'is 0.01 to 1, especially 0.02 to 0.5.
Is preferred. The sum of m + p is 1 to 3 on average. Place
If the degree of conversion is less than 0.01, it is not sufficient, and
Although it does not matter, it is preferably 1 or less from the viewpoint of the reaction yield. This
The molecular weight of the cationic cellulose derivative used here is about 1
It is between 00,000 and 3,000,000. Katio
As the functional starch, those represented by the following general formula (V) are preferred.
Good.

[0061]

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[In the formula (V), A ⁴ represents a starch residue;
³⁴ represents an alkylene group or a hydroxyalkylene group,
R ³⁵ , R ³⁶ and R ³⁷ are the same or different, and may form a heterocyclic ring containing an alkyl group having 10 or less carbon atoms, an aryl group, an aralkyl group or a nitrogen atom in the formula. X '
Is chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate,
Represents an anion such as phosphoric acid or nitric acid, and l ′ represents a positive integer)

The cationic starch has a degree of cation substitution of 0.0
1-1, that is, 0.01-1 per anhydroglucose unit
And particularly preferably those having 0.02 to 0.5 cationic groups introduced. A degree of substitution of 0.01 or less is not sufficient, and may be more than 1.
The following is preferred. As the copolymer of cationic diallyl quaternary ammonium salt and acrylamide, those represented by the following general formula (VI) or (VII) are preferable.

[0064]

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[In the formulas (VI) and (VII), R ³⁸ and R ³⁹ are the same or different and each represents a hydrogen atom, an alkyl group (1-18 carbon atoms), a phenyl group, an aryl group, a hydroxyalkyl group, An alkyl group, a cyanoalkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group, wherein R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are the same or different and are a hydrogen atom, a lower alkyl group (1 to 3 carbon atoms) or X ″ represents a phenyl group, X ″ represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, nitric acid, etc.), l ¹ represents an integer of ¹ to 50, and m ¹ represents an integer of ¹ to 50. an integer, n ¹ is the molecular weight of the copolymer of which] diallyl quaternary ammonium salt and acrylamide represents an integer of 150～8,000 30,000 2,000,000 is particularly 100,000 to 1,000,000 range preferable. As the quaternized polyvinylpyrrolidone derivative, those represented by the following general formula (VIII) are preferable.

[0066]

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[In the formula (VIII), R ⁴⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴⁵ , R ⁴⁶ and R
⁴⁷ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group, and Y represents an oxygen atom or an amide bond. X '''represents chlorine, bromine, iodine, sulfuric acid,
Represents an anion such as sulfonic acid, alkylsulfuric acid having 1 to 4 carbon atoms, phosphoric acid, nitric acid, etc., q represents an integer of 1 to 10, and m ² and n ² are m ² + n ² = 20 to 8,000.
The molecular weight of the quaternized polyvinylpyrrolidone derivative is 1
It is preferably from 10,000 to 2,000,000, particularly preferably from 50,000 to 1.5,000,000. The content of cationic nitrogen derived from the cationic polymer contained in the vinyl polymer is 0.0
It is from 0.4 to 0.2%, preferably from 0.01 to 0.15%. Less than 0.004% has no sufficient effect, 0.2%
If it exceeds, the performance is good, but it causes coloring of the vinyl polymer, and is economically disadvantageous. As the polyglycolpolyamine condensate, those represented by the following general formula (IX) are preferable.

[0068]

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[In the formula (IX), R ⁴⁹ , R ⁵¹ , R ⁵² and R ⁵⁴ represent a hydroxyalkylene group having 2 to 4 carbon atoms, and R ⁵⁰ and R ⁵³ represent an alkylene group having 2 to 3 carbon atoms. , X ¹ and y ¹ each represent an integer of 10 to 20, and m ³
Represents an integer of 2 to 4, n ³ represents an integer of 2 to 6, r represents an integer of 1 to 50, and R ⁴⁸ has 6 carbon atoms.
And 20 or more linear or branched alkyl groups.] The component (D) is one or more of the above-mentioned cationic polymers.
More than one kind is used as a mixture, and 0.01 to 5
%, Especially 0.1 to 1.5 in the case of a hair cleaner.
%, Especially 0.1 to 2% for a skin cleanser.

The detergent composition of the present invention can further enhance the sterilizing and antibacterial effects by adding a chelating agent.
The metal chelating agent used in the present invention is not particularly limited as long as it has the ability to chelate metal ions, but aminopolycarboxylic acid chelating agents, aromatic and aliphatic carboxylic acid chelating agents, amino acid chelating agents Agents, ether polycarboxylic acid chelating agents, phosphonic acid chelating agents such as iminodimethylphosphonic acid (IDP), alkyl diphosphonic acid (ADPA), 1-hydroxyethane-1,1-diphosphonic acid (DEQUEST ^™ 2010), Hydroxycarboxylic acid chelating agent, phosphoric acid chelating agent, polymer electrolyte (including oligomer electrolyte) chelating agent, and dimethylglyoxime (DG)
Is mentioned. Each of these chelating agents may be in a free acid form or in a salt form such as a sodium salt, a potassium salt, and an ammonium salt. In addition, they may be in the form of their hydrolyzable ester derivatives.

Specific examples of the aminopolycarboxylic acid chelating agent include: a) a compound represented by the chemical formula R ⁵⁵ N (Y ¹ ) ₂ , b) a compound represented by the chemical formula N (Y ¹ ) ₃ , c) A compound represented by the chemical formula R ⁵⁵ -N (Y ¹ ) -CH ₂ CH ₂ -N (Y ¹ ) -R ⁵⁵ ; d) the chemical formula R ⁵⁵ -N (Y ¹ ) -CH ₂ CH ₂ -N (Y ¹ ) compounds represented by _2, e) the chemical formula _{^{(Y 1) 2 NR 56 -N}} (Y 1) compounds represented by _2,
And f) a compound similar to the compound of e), wherein the compound contains 4 or more Y ¹ , for example, a compound of the formula

[0072]

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And the like.

In the above formula, Y ¹ is —CH ₂ COOH or —CH ₂ CH ₂ COO
H, R ⁵⁵ represents a hydrogen atom, an alkyl group, a hydroxyl group, a group constituting a known chelating agent such as a hydroxyalkyl group, and R ⁵⁶ represents an alkylene group, a known chelating agent such as a cycloalkylene group. Shows the constituent groups.

A typical example of the aminopolycarboxylic acid chelating agent is ethylenediaminetetraacetic acid (EDT).
A), cyclohexanediaminetetraacetic acid (CDT
A), nitrilotriacetic acid (NTA), iminodiacetic acid (I
DA), N- (2-hydroxyethyl) iminodiacetic acid (HIMDA), diethylenetriaminepentaacetic acid (D
TPA), N- (2-hydroxyethyl) ethylenediaminetriacetic acid (EDTA-OH) and glycol etherdiaminetetraacetic acid (GEDTA), and salts thereof.

Examples of the aromatic or aliphatic carboxylic acid chelating agents used in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, aconitic acid, pyruvic acid, salicylic acid, Examples include acetylsalicylic acid, hydroxybenzoic acid, aminobenzoic acid (including anthranilic acid), phthalic acid, trimellitic acid and gallic acid, and salts, methyl esters and ethyl esters thereof. Examples of the amino acid chelating agent used in the present invention include glycine, serine, alanine, lysine, cystine, cysteine, ethionine, tyrosine, methionine, and salts and derivatives thereof.

Further, examples of the ether polycarboxylic acid-based chelating agent used in the present invention include diglycolic acid, compounds represented by the following formula, analogous compounds thereof and salts thereof (for example, sodium salts). .

[0078]

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Examples of the hydroxycarboxylic acid chelating agent used in the present invention include malic acid, citric acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, lactic acid and salts thereof. Examples of the phosphate chelating agent used in the present invention include orthophosphoric acid, pyrophosphoric acid, triphosphoric acid and polyphosphoric acid. Examples of the polymer electrolyte (including oligomer electrolyte) chelating agent used in the present invention include acrylic acid polymer, maleic anhydride polymer, α-hydroxyacrylic acid polymer, itaconic acid polymer, Copolymers composed of two or more kinds of constituent monomers of the union and epoxy succinic acid polymers are exemplified. Furthermore, in the present invention, ascorbic acid, thioglycolic acid, phytic acid, glyoxylic acid and glyoxalic acid, and salts thereof can also be suitably used as a chelating agent.

Among the above-mentioned chelating agents, particularly preferred are ethylenediaminetetraacetic acid (EDTA), succinic acid, salicylic acid, oxalic acid, lactic acid, fumaric acid, tartaric acid, 1-hydroxyethane-1,1-diphosphonic acid and the like. Salts.

The metal chelating agent is preferably contained in an amount of 0.1 to 8%, more preferably 0.2 to 5%, particularly preferably 0.2 to 3% in the whole composition.

Further, the cleaning composition of the present invention may contain an anionic surfactant which is usually used for a cleaning agent, as long as the effect of the present invention is not impaired. Such anionic surfactants include alkyl sulfonates,
Sulfosuccinates, α-sulfofatty acid ester salts, α-olefin sulfonates, saturated or unsaturated higher fatty acid salts, monoester phosphate surfactants, acylated amino acids, acylated isethionates, and the like.

Further, by adding 0.1 to 5% of a silicone derivative to the cleaning composition of the present invention, a good sliding feeling and a smooth feeling can be obtained. The silicone derivative is not particularly limited as long as it is generally used in detergents and cosmetics. Examples thereof include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, epoxy-modified silicone, alkoxy-modified silicone, and fatty-acid-modified silicone. And fluorine-modified silicone.

The cleaning composition of the present invention may contain 0.1 to 5% of an anti-dandruff agent. Here, examples of the anti-dandruff agent include zinc pyrithione, pyrocton auramine, selenium disulfide and the like.

Further, in addition to the above-mentioned components, the detergent composition of the present invention may further contain, if necessary, components usually incorporated in cosmetics, pharmaceuticals, foods, etc., for example, non-cationic fungicides,
Anti-inflammatory agents such as glycyrrhizic acid, dihydrocholesterin and allantoin, medicinal agents and preservatives; humectants such as propylene glycol, glycerin, diethylene glycol monoethyl ether, sorbitol and panthenol; dyes;
Coloring agents such as pigments; pearling agents, chitosan derivatives such as hydroxypropyl chitosan; various compounded fragrances; and other encyclopedias of shampoos and ingredients [ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELL
E PRESS 1985)] can be appropriately blended as long as the effects of the present invention are not impaired.

The cleaning composition of the present invention can be produced according to a usual method, and can be in the form of paste, gel, liquid or the like. It is also suitable as a hair, body, and finger cleaner.

[0087]

The cleaning composition of the present invention has excellent detergency and feeling after cleaning, and can stably contain a cationic germicide, and has a high germicidal / antibacterial effect and a broad germicidal / antibacterial spectrum. Sufficient anti-dandruff properties on the scalp,
Itching and anti-odor effects can be imparted to the body and scalp.

[0088]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the compounding amount of each component in the following examples was shown on the basis of the effective component.

Examples 1 to 8 and Comparative Examples A to D A cleaning composition having the composition shown in Table 1 was produced by a conventional method, and its cleaning power, feeling after cleaning, antibacterial effect, antidandruff effect and deodorant effect were evaluated. evaluated. Table 1 shows the results.

<Evaluation Method and Evaluation Criteria for Detergency> Five healthy men and women were used to cleanse their hair once a day with each cleaning composition.
1 week, and the cleaning power was evaluated according to the following criteria.

(Evaluation criteria) 5: Detergency was good 4: Detergency was good 3: Detergency was normal 2: Detergency was not so good 1: Detergency Felt bad

The results were expressed as an average of 10 panelists as detergency according to the following criteria. ◎: Good for 4.0 or more ○: Somewhat good for 3.2 to 3.9 △: Normal for 2.5 to 3.1 ×: Poor for 2.4 or less

<Method for evaluating moist feeling after washing and evaluation criteria> Ten healthy women were allowed to wash their hair for one week with each of the detergent compositions, and the sensory evaluation of the washed hair was evaluated according to the following criteria. evaluated.

4: After washing, hair felt moist 3: After washing, hair felt slightly moist 2: After washing, hair felt slightly moist 1: After washing, hair felt soft Was

The results were expressed as an average value of 10 panelists as a moist feeling according to the following criteria. ◎: Good for 4.0 or more ○: Somewhat good for 3.2 to 3.9 △: Normal for 2.5 to 3.1 ×: Poor for 2.4 or less

<Anti-dandruff evaluation method and evaluation criteria> The hair was treated with the cleaning composition of the present invention for 1 month on 5 male monitors.
Washed once a day. After the last shampoo, the shampoo was stopped for about 48 hours, and the hair was washed once again with 3 g of the detergent composition twice to collect the entire shampoo. The entire amount of the collected hair washing liquid was filtered through a 50 nylon mesh to remove unnecessary dust and hair. The total amount of the filtrate was filtered through a 255 nylon mesh (100 × 100 μm) whose weight was measured in advance. After the nylon mesh was air-dried for about 48 hours at room temperature, the dandruff weight was determined by the weight of the stratum corneum captured by the 255 nylon mesh. The average value of the dandruff weights of six persons was expressed as anti-dandruff property according to the following criteria.

：: dandruff weight ≦ 30 mg ○: 30 mg <dandruff weight ≦ 40 mg Δ: 40 mg <dandruff weight ≦ 50 mg ×: 50 mg <dandruff weight

<Evaluation Method and Evaluation Criteria of Deodorant Effect> Each detergent composition was subjected to a use test by panelists of five men and women once a day for two weeks. With respect to the deodorant effect, a body odor 24 hours after the final washing was evaluated by a professional evaluator according to the following evaluation criteria.

(Evaluation criteria) 5: No smell 4: Slight smell 3: Smell 2: Very smell 1: Very strong smell

The results were expressed as an average of 10 panelists as a deodorant effect according to the following criteria. ◎: Good for 4.0 or more ○: Somewhat good for 3.2 to 3.9 △: Normal for 2.5 to 3.1 ×: Poor for 2.4 or less

<Test method for antibacterial activity> Test bacterium Staphylococcus
aureus (St. aureus) IFO 12732
CD medium (manufactured by Nippon Pharmaceutical Co., Ltd.), test strain Malass ezia fu
For rfur (M. furfur) IFO 658, preculture is Malt-Yeast
Medium (Casitone (Difco) 0.5%, Yeast-extract (Difc
o) 0.67%, Yeast-Nitrogen-base (Difco) 0.5
%, Glucose 2%, Reodol TW-S120 (Kao Corporation)
0.1%) at 35 ° C.

For the pre-cultured bacterial solution, SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) for St. aureus and Malt agar medium (Malt-extract (manufactured by Difco)) for M. furfur 2
%, Leo Doll TW-S120 (manufactured by Kao Corporation) 0.1% agar 1.5
%). After injecting 50 μl of the detergent composition, a water-washed paper disc (diameter 8 mm) is placed on an agar medium smeared with a bacterial solution, and the diameter (mm) of the inhibition circle after 24 hours at 35 ° C. is determined. did.

[0103]

[Table 1]

Example 9 A systemic detergent having the following composition was produced by a conventional method.

Polyoxyethylene coco ether sulfate sodium salt (EO = 3) 16% coconut oil fatty acid diethanolamide 1% lauric acid amide propyl betaine 1% sodium coco amphoacetate 2% cetylpyridinium chloride 1% cationic starch 0.5 % Disodium ethylenediaminetetraacetate 1% Methyl paraben 0.2% Pearling agent (ethylene glycol distearate) 1% Fragrance 0.1% Water balance meter 100.0%

The obtained whole body detergent was excellent in detergency and feeling after washing, and had a deodorant effect and an antidandruff effect.

Example 10 A hand cleanser having the following composition was produced by a conventional method.

Polyoxyethylene lauryl ether sulfate sodium salt (EO = 2) 18% sodium cocoamphoacetate 3% lauric acid diethanolamide 1% benzalkonium chloride ^{* 1} 0.8% cationized cellulose 0.2% succinic acid Disodium 0.6% 1-hydroxyethane-1,1-diphosphonic acid liquid (60%) 0.2% Butyl paraben 0.2% Pearling agent (ethylene glycol distearate) 2% Fragrance 0.2% Water Balance total 100.0%

The resulting detergent was excellent in detergency and feel after washing, and had a bactericidal and antibacterial effect.

Example 11 A hair cleansing composition having the following composition was produced by a conventional method.

Polyoxyethylene Lauryl Ether Sulfate Ammonium (EO = 3) 20% Amidopropyl Betaine Laurate 2% Sodium Lauroamphoacetate 2% Benzalkonium Chloride ^{* 1} 1% Cationized Cellulose 0.5% Disodium Succinate 0.8% Propylene glycol 0.5% Glycerin 1% Butyl paraben 0.2% Fragrance 0.3% Water balance meter 100.0%

The obtained hair cleansing agent was excellent in detergency, hair feel after washing, and had an anti-dandruff effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C11D 1/83 C11D 1/83 3/20 3/20 3/30 3/30 3/32 3/32 3/48 3/48 (72) Inventor Yasuhiro Doi 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-8-109394 (JP, A) JP-A-7-109204 (JP, A) JP-A 7-109 53995 (JP, A) JP-A-6-1222893 (JP, A) JP-A-6-506938 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/12 C11D 1 / 65 C11D 1/75 C11D 1/83 C11D 3/20 C11D 3/30 C11D 3/32 C11D 3/48 A61K 7/075 A61K 7/50

Claims (3)

(57) [Claims] 1. The following components (A), (B), (C) and (D): (A) General formula (1) R ¹ O— (CH ₂ CH ₂ O) _n —SO ₃ M ¹ ( 1] [wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, n represents an average of 0 to 10, M ¹ represents an alkali metal atom, an alkaline earth A metal atom, an ammonium group, an alkylammonium group or an alkanol ammonium group] 5 to 50% by weight of a sulfate ester surfactant represented by the following general formulas (2), (3) and (4) One or more selected from the group consisting of a cationic fungicide represented by formula (5) and polyhexamethylene biguanide: 0.2 to 5% by weight; [R ² and R ³ each have 6 to 14 carbon atoms and a total of 16 to
26 represents a long-chain alkyl group, a long-chain alkenyl group, or a long-chain hydroxyalkyl group, which may be the same or different. R ⁴ and R ⁵ are alkyl groups having 1 to 3 carbon atoms, shows a hydroxyalkyl group or an average addition mole number of 10 or less polyoxyethylene groups, or different phases the same as each other. Z ¹ is a halogen atom, an amino acid, a fatty acid, an anionic residue of a phosphate ester, a phosphonate ester, a sulfonate ester or a sulfate ester having a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, or polymerization An anionic oligomer or polymer containing a formalin condensate of a sulfonated polycyclic aromatic compound having styrene sulfonic acid having a degree of 3 or more or having a hydrocarbon group as a substituent is shown. [Chemical formula 2] [Wherein R ⁶ is a hydrocarbon group having 8 to 14 carbon atoms or And Z ¹ represents a halogen atom, an amino acid,
Fatty acids, phosphoric acid esters having a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, phosphonic acid esters, sulfonic acid esters or sulfuric acid ester anionic residues, or styrene sulfonic acid having a polymerization degree of 3 or more. An anionic oligomer or polymer containing a formalin condensate of a sulfonated polycyclic aromatic compound which may have or have a hydrocarbon group as a substituent is shown. [Formula 4] [Z ² represents gluconic acid, acetic acid or hydrochloric acid. [Chemical formula 5] [Wherein, R ⁷ represents a linear or branched alkyl group having 6 to 18 carbon atoms, and Z ³ represents a halogen atom, an amino acid, a fatty acid, a linear or branched alkyl group or alkenyl having 1 to 30 carbon atoms. Anionic residue of a phosphoric acid ester, a phosphonic acid ester, a sulfonic acid ester or a sulfuric acid ester, or a polycyclic aromatic compound having styrenesulfonic acid having a degree of polymerization of 3 or more or having a hydrocarbon group as a substituent An anionic oligomer or polymer containing a formalin condensate of a sulfonated group compound is shown. (C) one or more selected from amphoteric surfactants, amine oxide surfactants, alkanolamide surfactants and amide amino acid surfactants, in an amount of 0.1 to 10% by weight, D) A cleaning composition comprising a cationic polymer and comprising, as a main cleaning base, a component (A) a sulfate ester surfactant. 2. The cleaning composition according to claim 1, wherein the content of the cationic polymer (D) is 0.01 to 5% by weight. 3. The cleaning composition according to claim 1, further comprising one or more metal chelating agents.