JPH09143499A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition containing a specific silicon- containing compound, a cationic polymer and a specific surfactant, having low irritation, excellent in foaming power, having creamy foaming quality and excellent in combing property, conditioning effect and setting property after shampooing hair. SOLUTION: This detergent composition contains (A) 0.1-5wt.% compound of the formula, Z[O(AO)h (DO)i (GO)j R<1> ]k Z is a compound residue having 2-8 OH groups; R<1> is H, a 1-24C alkyl, a 7-24C aralkyl, a 6-24C aryl or a 2-24C acyl; A0 is a 2-22C oxyalkylene; DO is a group of formula I (R<2> is a 2-5C alkenyl); GO is group of formula II [X is a 2-5C alkylene; Y is a group of formula III (R<3> is a 1-24C hydrocarbon group; (u) is 0-3000); AO, DO and GO may be added in block-like or random-like state; (k) is 1-8; (hk) is 1-500; (ik) is 0-1000; (jk) is 1-100}, (B) 0.1-5wt.% cationic polymer and (C) 1-40wt.% synthetic anionic or ampholytic surfactant.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a cleaning composition. More specifically, the present invention is hypoallergenic, has excellent foaming properties, and has a creamy foam quality. In particular, when washing hair, it has good finger combability at the time of rinsing, combability after hair washing, and a conditioning effect. The present invention relates to a cleansing composition for hair, which has a good quality, is non-greasy, has a smooth and excellent setting property, and gives a natural luster to the hair, and has a small change in quality over time.

[0002]

2. Description of the Related Art Conventionally, in a detergent composition for hair, a cationic polymer such as cationic cellulose has been blended in order to improve the ability to pass through the fingers during washing and rinsing. However, in a detergent composition containing these cationic polymers, the cationic polymer forms a complex with a surfactant, which is a detergent component, and adheres to and remains on the hair at the time of washing the hair, resulting in hair fly and the like. The conditioning effect was inadequate due to swelling and stiffening. Therefore, in recent years, in order to impart a conditioning effect after washing hair, it has been used in combination with silicone compounds such as dimethylpolysiloxane, polyether-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, amino-modified silicone, and cation-modified silicone ( JP-A-56-72095 and JP-A-63
-307811, JP2-247113A, JP2-273612, JP3-188.
016, JP-A-3-184906, JP-A-4-36225, JP-A-4-234309). However, when these silicone compounds are used, the foamability is extremely deteriorated and the stability is adversely affected because the silicone compound is water-insoluble. Therefore, it is necessary to increase the viscosity of the system, which makes it difficult to take it out of the bottle when actually using it. Further, the cleaning composition using these silicone compounds has a good conditioning effect after drying, but has a problem that the hair setting property is deteriorated and permanent wave is less likely to be applied. Further, such a detergent composition is liable to change with time to cause thickening or coloring, and it is impossible to give the hair a natural luster.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and is low in irritation and excellent in foaming property, and also has excellent foam creaminess. In particular, when washing hair, fingers can be easily passed during rinsing. Good combability after washing hair, non-greasy, smooth and easy to set, and gives the hair a natural luster,
The purpose of the present invention is to provide a detergent composition for hair, which has a small change in quality over time.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that a polyoxyalkylene ether compound having a specific structure having a specific silicone pendant, a cationic polymer, and We have found that a synthetic anionic surfactant and / or amphoteric surfactant can be combined in a specific ratio to obtain a cleansing composition for hair with excellent feeling in use, and the present invention is based on this finding. Has been completed. That is,
The present invention includes (1) (A) a polyoxyalkylene ether compound having a silicone pendant represented by the general formula [1].
1 to 5% by weight, (B) cationic polymer 0.1 to 5% by weight, and (C) one or more synthetic anionic surfactants and / or amphoteric surfactants 1 to 40% by weight. detergent composition characterized by _{containing, Z [O (AO) h} (DO) i (GO) j R 1] k ... [1] [in the formula, Z is 2 to 8 hydroxyl groups The residue of the compound having, R ¹ is hydrogen, an alkyl group having 1 to 24 carbon atoms, an aralkyl group having 7 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms or an acyl group having 2 to 24 carbon atoms, and AO Is one or more oxyalkylene groups having 2 to 22 carbon atoms, and DO is one or more groups represented by general formula [2],

Embedded image (However, in the formula, R ² is an alkenyl group having 2 to 5 carbon atoms.) GO is one or more groups represented by the general formula [3],

Embedded image (In the formula, X is an alkylene group having 2 to 5 carbon atoms, and Y is a siloxyl group represented by the general formula [4].)

Embedded image (In the formula, R ³ is a hydrocarbon group having 1 to 24 carbon atoms and may be the same or different, and u is 0 to 3,000.
0. ) AO, DO, and GO may be added in blocks or randomly in any order. k
Is 1 to 8, hk is 1 to 1,500, ik is 0 to 1
00 and jk are 1 to 100. And (2) the synthetic anionic surfactant and / or amphoteric surfactant is an alkyl ether sulfate represented by the general formula [5], an acylmethyl taurate represented by the general formula [6],
Amido ether sulfate represented by the general formula [7], alkylamino acid type amphoteric surfactant represented by the general formula [8],
2. One or more selected from amidoamine-type amphoteric surfactants represented by general formula [9] or general formula [10] and amidobetaine-type surfactants represented by general formula [11]. of the detergent _{^{composition, [R 4 O (CH 2}} CH 2 O) m SO 3] n M 1 ... [5] ( in the formula, R ⁴ is an alkyl group or an alkenyl group of 7-21 carbon atoms , M ¹ is an alkali metal, alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, n is an integer equal to the valence of the atom or group represented by M ¹ , and m is 2 to 15. )

Embedded image (In the formula, R ⁵ is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, M ² is an alkali metal, an alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and o is M ² . It is an integer equal to the valence of the atom or group shown.) [R ⁶ CONH (CH ₂ CH ₂ O) _p SO ₃ ] _q M ³ ... [7] (wherein R ⁶ has 7 to 7 carbon atoms). 21 is an alkyl group or an alkenyl group, M ³ is an alkali metal, alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and q is an integer equal to the valence of the atom or group represented by M ³ . , P is 2 to 15.)

Embedded image (In the formula, R ⁷ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and r and s are the same or different 1 to
Is an integer of 3, M ⁴ and M ⁵ are hydrogen, an alkali metal, an alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and M ⁴ and M ⁵ may be the same or different. )

Embedded image [Wherein, R ⁸ and R ¹⁰ are an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and R ⁹ and R ¹¹ are —CH ₂
COOM ⁶ or -CH ₂ CH ₂ COOM ⁶ (wherein
M ⁶ is hydrogen, an alkali metal or an organic group-substituted ammonium group. ), R ¹² is hydrogen, —CH ₂ COOM ⁶ or —CH ₂ CH ₂ COOM ⁶ (wherein, M ⁶ is hydrogen,
It is an alkali metal or organic group-substituted ammonium group. )
It is. ]

Embedded image (However, in the formula, R ¹³ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and t is an integer of 2 to 4.),
Is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition of the present invention contains a polyoxyalkylene ether compound having a silicone pendant represented by the general formula [1]. In _{Z [O (AO) h (} DO) i (GO) j R 1] k ... [1] general formula [1], Z is the residue of a compound having 2-8 hydroxyl groups. Examples of the compound having 2 to 8 hydroxyl groups having Z as a residue include, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol, glycerin,
Diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbide, sorbitol-glycerin condensate, adonitol, arabitol, xylitol, Polyhydric alcohols such as mannitol; xylose, arabinose, repos,
Rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose,
Examples thereof include sugars such as raffinose, gentianose, and melezitose: and partial esterified products thereof; polyphenols such as catechol, resorcin, hydroquinone, and fluoroglucine; and aromatic alcohols such as styrene glycol.

The alkyl group having 1 to 24 carbon atoms represented by R ¹ in the general formula [1] includes, for example, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, isoheptyl group, 2-ethylhexyl group, octyl group, isononyl group, decyl group, dodecyl group, isotridecyl group Group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group, isostearyl group, octyldodecyl group, docosyl group, decyltetradecyl group and the like. Examples of the aralkyl group having 7 to 24 carbon atoms represented by R ¹ include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 24 carbon atoms represented by R ¹ include phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, dibutylphenyl group. , Octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group and the like. General formula [1]
In the acyl group having 2 to 24 carbon atoms represented by R ¹ , acetic acid, propionic acid, butyric acid, isobutyric acid, caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid Examples thereof include acyl groups derived from isopalmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, palmitoleic acid, benzoic acid, hydroxybenzoic acid, cinnamic acid and gallic acid.

Examples of the oxyalkylene group having 2 to 22 carbon atoms represented by AO in the general formula [1] include oxyethylene group, oxypropylene group, oxybutylene group, oxytrimethylene group, oxytetramethylene group and oxystyrene group. , Oxynonylene group, oxydecylene group, oxyundecylene group, oxidodecylene group, oxytridecylene group, oxytetradecylene group, oxypentadecylene group, oxyoctadecylene group, oxyicosylene group, oxidocosylene group, etc. be able to. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ² in the general formula [2] include vinyl group, allyl group, 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3-methyl-3. Examples thereof include an alkenyl group having an unsaturated bond such as a -butenyl group and a 1,1-dimethyl-2-propenyl group. Of these, an allyl group and a methallyl group are particularly preferable. Examples of the alkylene group having 2 to 5 carbon atoms represented by X in the general formula [3] include ethylene group, trimethylene group, tetramethylene group, 2-methyltrimethylene group, 2-methyltetramethylene group, and 1,1-dimethyl. A trimethylene group etc. can be mentioned. Among these,
Trimethylene and 2-methyltrimethylene are particularly preferred.

As the group represented by the general formula [3], the diorganohydropolysiloxane represented by the general formula [12] is added to the unsaturated bond of the alkenyl group represented by R ² of the general formula [2]. A group can be mentioned.

Embedded image However, in the general formula [12], R ³ has 1 to 2 carbon atoms.
4 hydrocarbon groups, which may be the same or different,
u is 0 to 3,000. Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R ³ in the general formula [4] and the general formula [12] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, and a pentyl group. , Isopentyl group, hexyl group, isoheptyl group, 2-ethylhexyl group, octyl group, isononyl group, decyl group,
Dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group, isostearyl group, octyldodecyl group, docosyl group, decyltetradecyl group, benzyl group, phenethyl group, phenyl group, methylphenyl group, dimethylphenyl group , Trimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, etc. it can. Among these, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and a methyl group is particularly preferable.

In the general formula [1], the carbon number of AO is 2
The hydrophilicity and lipophilicity of the compound represented by the general formula [1] can be adjusted by arbitrarily selecting it in the range of 22 to 22. In the general formula [1], A
O, DO and GO may each be a single group, or two or more different groups may be mixed. In the general formula [4], all of the plurality of R ³ may be the same or may be two or more different groups. U
Is 0 to 3,000, preferably 1 to 800, and more preferably 2 to 150. u is 3,000
When it exceeds, the viscosity of the compound represented by the general formula [1] becomes high, and the hydrophobicity may become too strong. In general formula [1], k is 1-8. If the value of k corresponds to the number of hydroxyl groups of the compound having a hydroxyl group having Z as a residue, in the compound represented by the general formula [1], all the hydroxyl groups of the compound having a residue of Z are oxyalkylene groups. Is added. When the value of k is smaller than the number of hydroxyl groups of the compound having a hydroxyl group having Z as a residue, the compound represented by the general formula [1] has a free hydroxyl group.

In the general formula [1], hk is AO added to 1 mol of a compound having a hydroxyl group having Z as a residue.
Is the number of moles of the oxyalkylene group represented by hk is 1 to 1,500, preferably 1 to 850,
More preferably, it is 2-220. If the value of hk is less than 1, it may be difficult to maintain the stability of the detergent composition due to insufficient hydrophilicity of the compound represented by the general formula [1]. When the value of hk exceeds 1,500, the viscosity of the compound represented by the general formula [1] increases,
Further, the water repellency, flexibility, and the like, which are characteristics of the silicone compound, may not be easily exhibited. In the general formula [1], jk is the number of moles of the oxyalkylene group having a silicone pendant represented by GO added to 1 mole of the compound having a hydroxyl group having Z as a residue, and jk is 1
To 100, preferably 1 to 50, and more preferably 2 to 25. When the value of jk is less than 1, the lipophilicity of the compound represented by the general formula [1] is insufficient, and thus it may be difficult to exhibit the finger combability during washing and the conditioning effect after washing. The value of jk is 1
If it exceeds 00, the viscosity of the compound represented by the general formula [1] may increase and the hydrophobicity may become too strong.
In the general formula [1], ik is the number of moles of an oxyalkylene group having a pendant alkenyloxymethyl group represented by DO added to 1 mole of a compound having a hydroxyl group having Z as a residue, and ik is It is 0 to 100, preferably 0 to 30, and more preferably 0 to 10. If the value of ik exceeds 100, the stability over time of the compound represented by the general formula [1] may decrease.

In the compound represented by the general formula [1],
The bonding state of the oxyalkylene groups represented by AO, DO and GO is not particularly limited, and for example, all of AO, DO and GO can be randomly added, and All of them can be added in a block shape, or a part of AO, DO or GO can be added in a block shape and the rest can be added in a random shape. When adding in blocks, the order of adding each block is not particularly limited,
Any addition order can be selected and added. The method for producing the compound represented by the general formula [1] used in the composition of the present invention is not particularly limited, and the compound can be produced by any known method. For example, by adding an alkylene oxide and an alkenyloxymethyl alkylene oxide to a compound having a hydroxyl group having Z as a residue in the presence of a catalyst such as an alkali, an oxyalkylene group represented by AO and an alkenyloxymethyl represented by DO. A compound having an oxyalkylene group having a pendant group is formed, and if necessary, the terminal hydroxyl group is etherified or esterified, and then an alkenyloxymethyl group is further converted to the general formula [1
2] and added with a diorganohydropolysiloxane to convert the oxyalkylene group pendant to an alkenyloxymethyl group represented by DO to a silicone pendant oxyalkylene group represented by GO. You can

In this reaction, the general formula [1
2] and the number of moles of the diorganohydropolysiloxane represented by [2] is the same as the number of moles of the oxyalkylene group pendant to the existing alkenyloxymethyl group represented by DO, whereby all the groups represented by DO are represented. Can be converted to a group represented by GO, and i can be 0 in the compound represented by the general formula [1]. When the number of moles of the diorganohydropolysiloxane represented by the general formula [12] used is less than the number of moles of the oxyalkylene group pendant to the existing alkenyloxymethyl group represented by DO, it is represented by DO. Leaving the group unreacted, represented by AO, DO and GO 3
It is possible to obtain a compound represented by the general formula [1] having certain oxyalkylene groups.

The composition of the present invention contains a cationic polymer. The cationic polymer to be used is not particularly limited, but for example, poly (dimethyldiallylammonium) represented by Mercoat 100, 280, 550 (Merck), Cellcoat H-100, L-200 (National Starch). Chloride) derivative, Gaffcoat # 7
Quaternary nitrogen-containing polyvinylpyrrolidone represented by 55 (manufactured by Gaff), polymers JR-125, JR-400,
Quaternary nitrogen-containing cellulose ether derivative represented by LR-400 and JR-30M (manufactured by Union Carbide Co.), polyethyleneimine represented by Epomin P-1000 (manufactured by Nippon Shokubai Kagaku Co., Ltd.), Nalco 600 (Narco Chemical Co., Ltd.) Water-soluble cationic polymer synthesized from tetraethylpentamine and epichlorohydrin typified by Sumitomo Chemical Co., Ltd., quaternary nitrogen-containing poly (trialkylaminoethyl methacrylate) derivative typified by Sumifloc (Sumitomo Chemical Co., Ltd.), Cosmedia C Examples include quaternary nitrogen-containing guar gum derivatives represented by -261 (manufactured by Henkel).

The detergent composition of the present invention contains a synthetic anionic surfactant and / or an amphoteric surfactant. The synthetic anionic surfactant and amphoteric surfactant to be used are not particularly limited, and synthetic anionic surfactant and amphoteric surfactant generally used as a cosmetic base can be used. Among these surfactants, the synthetic anionic surfactants include alkyl ether sulfate type anionic surfactants represented by the general formula [5] and acylmethyl taurate type anionic surfactants represented by the general formula [6]. An anionic surfactant, an amide ether sulfate type anionic surfactant represented by the general formula [7] and the like can be preferably used. As the amphoteric surfactant, an alkylamino acid salt type amphoteric surfactant represented by the general formula [8], an amidoamine type amphoteric surfactant represented by the general formula [9] or the general formula [10], and a general formula [11] ] Amidobetaine type amphoteric surfactants represented by the following formula can be preferably used.

In the alkyl ether sulfate type anionic surfactant [R ⁴ O (CH ₂ CH ₂ O) _m SO ₃ ] _n M ¹ ... [5] represented by the general formula [5], R ⁴ is a carbon number. 7 to 21 alkyl or alkenyl group, M ¹ is an alkali metal, alkaline earth metal or unsubstituted or organic group-substituted ammonium group, and n is an integer equal to the valence of the atom or group represented by M ^1. And m is the number of moles of ethylene oxide added of 2 to 15
It is. When m is less than 2, irritation to the skin of the detergent composition is strong, and when m is more than 15, foamability may be lowered. As M ¹ in the general formula [5],
For example, alkali metal such as sodium and potassium, alkaline earth metal such as magnesium and calcium, ammonium group, alkanolamine cationic residue such as triethanolamine, and basic amino acid cationic residue such as lysine and arginine. Can be mentioned. Examples of such an alkyl ether sulfate type anionic surfactant include polyoxyethylene (3 mol) sodium lauryl ether sulfate and polyoxyethylene (3 mol).
Sodium myristyl ether sulfate, polyoxyethylene (3 mol) sodium palmityl ether sulfate, polyoxyethylene (3 mol) magnesium lauryl ether sulfate, polyoxyethylene (3 mol) sodium coconut alkyl ether sulfate, polyoxyethylene (10 mol) Sodium lauryl ether sulfate, polyoxyethylene (10
Examples thereof include sodium (mole) myristyl ether sulfate, polyoxyethylene (10 mol) sodium coconut alkyl ether sulfate, and polyoxyethylene (3 mol) lauryl ether sulfate triethanolamine salt.

Acylmethyl taurate type anionic surfactant represented by the general formula [6]

Embedded image In, R ⁵ is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, M ² is an alkali metal, an alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and o is an atom represented by M ² or It is an integer equal to the valence of the group. As M ² in the general formula [6], for example,
Alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; ammonium groups; cationic residues of alkanolamines such as triethanolamine; cationic residues of basic amino acids such as lysine and arginine. be able to. Examples of such an acylmethyl taurate type anionic surfactant include N-lauroyl-N-methyl taurine sodium, N-lauroyl-N-methyl taurine potassium, N-lauroyl-N-methyl taurine magnesium, N- Lauroyl-N-methyltaurine calcium,
N-cocoyl-N-methyltaurine sodium, N-cocoyl-N-methyltaurine potassium, N-cocoyl-
N-methyltaurine magnesium, N-cocoyl-N-
Methyl taurine calcium, N-myristoyl-N-methyl taurine sodium, N-myristoyl-N-methyl taurine magnesium, N-palmitoyl-N-methyl taurine sodium, N-palmitoyl-N-methyl taurine magnesium, N-oleoyl-N -Methyl taurine sodium, N-oleoyl-N-methyl taurine potassium, N-oleoyl-N-methyl taurine magnesium, N-oleoyl-N-methyl taurine calcium, etc. can be mentioned.

In the amide ether sulfate type anionic surfactant [R ⁶ CONH (CH ₂ CH ₂ O) _p SO ₃ ] _q M ³ ... [7] represented by the general formula [7], R ⁶ is a carbon number. 7 to 21 is an alkyl group or an alkenyl group, M ³ is an alkali metal, alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and q is an integer equal to the valence of the atom or group represented by M ^3. And p is 2 to 15 in terms of the number of moles of ethylene oxide added.
It is. When p is less than 2, irritation to the skin of the detergent composition is strong, and when p is more than 15, foaming property may decrease. In the general formula [7], an acyl group R ⁶
The fatty acid that constitutes CO- is a linear or branched fatty acid having 8 to 22 carbon atoms, and such a fatty acid includes
Examples thereof include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. Examples of M ³ in the general formula [7] include alkali metals such as sodium and potassium,
Examples thereof include alkaline earth metals such as magnesium and calcium, ammonium groups, cationic residues of alkanolamines such as triethanolamine, and cationic residues of basic amino acids such as lysine and arginine. Examples of such an amide ether sulfate type anionic surfactant include polyoxyethylene (3 mol) coconut oil fatty acid amide ether sodium sulfate and the like.

Alkyl amino acid type amphoteric surfactant represented by the general formula [8]

Embedded image In, R ⁷ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, r and s are the same or different integers of 1 to 3, and M ⁴ and M ⁵ are hydrogen, an alkali metal, an alkaline earth metal or It is an unsubstituted or organic group-substituted ammonium group, and M ⁴ and M ⁵ may be the same or different. Examples of M ⁴ and M ⁵ in the general formula [8] include an alkali metal such as hydrogen, sodium and potassium, an alkaline earth metal such as magnesium and calcium, an ammonium group, and a cationic residue of an alkanolamine such as triethanolamine. Group, and cationic residues of basic amino acids such as lysine and arginine. Examples of such an alkylamino acid type amphoteric surfactant include sodium lauryliminodiacetic acid, potassium lauryliminodiacetic acid, sodium myristyliminodiacetic acid, potassium myristyliminodiacetic acid, sodium palmityliminodiacetic acid, and stearyliminodiacetic acid. Sodium, sodium lauryl imino dipropionate, potassium lauryl imino dipropionate, sodium myristyl imino dipropionate, potassium myristyl imino dipropionate, sodium palmityl imino dipropionate, sodium stearyl imino dipropionate and the like can be mentioned. .

Amidoamine type amphoteric surfactants represented by the general formula [9] or the general formula [10]

Embedded image In the above, R ⁸ and R ¹⁰ are an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and R ⁹ and R ¹¹ are —CH ₂ COO.
M ⁶ or —CH ₂ CH ₂ COOM ⁶ , R ¹² is hydrogen,
CH ₂ COOM ⁶ or —CH ₂ CH ₂ COOM ⁶ , M ⁶
Is hydrogen, an alkali metal or an organic group-substituted ammonium group. Examples of M ⁶ include hydrogen, an alkali metal such as sodium and potassium, a cationic residue of an alkanolamine such as triethanolamine, and a cationic residue of a basic amino acid such as lysine and arginine. Examples of such amidoamine-type amphoteric surfactants include N-lauroyl-N'-carboxymethyl-N '-(2-hydroxyethyl) ethylenediamine,
N-cocoyl-N'-carboxymethyl-N '-(2-hydroxyethyl) ethylenediamine, N-myristyl-
N'-carboxymethyl-N '-(2-hydroxyethyl)
Ethylenediamine and the like and salts thereof, N-lauroyl-N- (2-hydroxyethyl) -N'-carboxymethylethylenediamine, N-cocoyl-N- (2-hydroxyethyl) -N'-carboxymethylethylenediamine, N -Myristoyl-N- (2-hydroxyethyl)-
Examples thereof include N′-carboxymethylethylenediamine and salts thereof.

Amidobetaine-type amphoteric surfactant represented by the general formula [11]

Embedded image In, R ¹³ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and t is an integer of 2 to 4. Examples of such amidobetaine-type amphoteric surfactants include, for example, laurylamidopropyldimethylaminoacetic acid betaine, cocoamidopropyldimethylaminoacetic acid betaine, myristylamidopropyldimethylaminoacetic acid betaine, and palmitylamidopropyldimethylacetic acid betaine. You can

In the detergent composition of the present invention, the content of the polyoxyalkylene ether compound having a silicone pendant represented by the general formula [1], which is the component A, is 0.1 to 5% by weight, preferably 0. 0.2 to 3% by weight. The content of the compound represented by the general formula [1] is 0.1
If it is less than wt%, a sufficient conditioning effect may not be obtained. When the content of the compound represented by the general formula [1] exceeds 5% by weight, the foaming property may decrease. In the detergent composition of the present invention, the content of the cationic polymer which is the component B is 0.1 to 5% by weight, preferably 0.2 to 3% by weight. When the content of the cationic polymer is less than 0.1% by weight, not only the finger-passing property at the time of washing the hair is deteriorated, but also the hair may not be given a natural gloss. When the content of the cationic polymer exceeds 5% by weight, not only the stability of the detergent composition is deteriorated, but also the production may be difficult.
In the detergent composition of the present invention, the content of the synthetic anionic surfactant and / or the amphoteric surfactant is 1 to 40% by weight, preferably 5 to 30% by weight. If the content of the synthetic anionic surfactant and / or the amphoteric surfactant is less than 1% by weight, sufficient foaming property or detergency may not be obtained. When the content of the synthetic anionic surfactant and / or the amphoteric surfactant exceeds 40% by weight, the stability of the detergent composition may be problematic.

In the detergent composition of the present invention, known components and additives commonly used in detergents can be blended, if necessary. Such additives include, for example, nonionic surfactants such as alkanolamides for adjusting viscosity and improving foam quality, and cationic salts such as stearyltrimethylammonium chloride for improving conditioning effect after hair washing. A surfactant and the like can be mentioned. Other additives commonly used in detergents include, for example, higher alcohols, protein derivatives, squalane, jojoba oil, olive oil, castor oil, lanolin, lecithin, oily components such as fatty acid esters of polyethylene glycol, glycerin, ethylene. Moisturizers such as glycol and propylene glycol, semipolar surfactants such as alkylamine oxides, water-soluble polymers such as hydroxypropylmethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose, bactericides, chelating agents, UV absorbers, pH adjusters, animals and plants Examples include natural extracts, pigments, and fragrances.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The structural formulas of the compounds represented by the general formula [1] used in Examples and Comparative Examples are shown in Table 1.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

The shampoo was evaluated by the following method. However, the temporal stability was evaluated by (9) temporal stability a for the shampoos of Examples 1-14 and Comparative Examples 1-7, and by (10) temporal stability b of the shampoos of Examples 15-16. (1) Skin irritation Skin irritation was evaluated by the protein denaturation rate. That is, the height of the absorption peak at 220 nm when a sample was added to a sample concentration of 1% by weight using a pH 7 buffer solution with a concentration of 0.025% by weight of ovalbumin using aqueous high performance liquid chromatography. Was measured and the protein denaturation rate was determined by the following formula. Protein denaturation rate (%) = [(H 2 _O −H _S ) / H 2 _O ] × 100 where H 2 _O is the height of the absorption peak when the sample is not added, and H _S is the absorption when the sample is added. It is the height of the peak. Empirically, if the protein denaturation rate is less than 30%, the skin irritation is very weak, and the protein denaturation rate is 30% or more 6
If it is less than 0%, the skin irritation is weak and the protein denaturation rate is 60.
% To less than 80% has moderate skin irritation,
It has been known that those having a protein denaturation rate of 80% or more have strong skin irritation. (2) Foaming property An aqueous solution having a sample concentration of 1% by weight was prepared, and the foam height was measured at 25 ° C. immediately after the sample was put in and after 5 minutes by the Los Miles method. A cleaning agent having a foam height of 250 mm or more immediately after the introduction of the sample and a foam retention rate of 90% or more obtained by the following equation is a foaming agent with good foaming. Persistence of foam (%) = [(foam height after 5 minutes) / (foam height immediately after sample injection)] x 100 (3) Creamyness of foam 20 women are panelists and wash hair with 5 ml of shampoo. The creaminess of the foam was evaluated. The average value of 20 persons was calculated by setting 2 points when the foam was felt to be creamy, 1 point when it was felt to be slightly creamy, and 0 point when the foam was felt to be rough rather than creamy. If the average value is 1.5 points or more, the creaminess of the foam is considered to be good. (4) Finger combability at the time of washing hair Using 20 women as panelists, the finger combability at the time of washing hair with 5 ml of shampoo was evaluated. The average of 20 people who scored 2 points when they felt smooth and did not catch their hair, 1 point when they felt that their hair caught a finger, and 0 points when they felt that fingering was very bad. The value was determined. If the average value is 1.5 points or more, it is considered that the finger combability when washing hair is good. (5) Combability after washing hair With 20 women as panelists, wash hair with 5 ml of shampoo,
The combability after drying was evaluated. If the hair does not feel squeaky and the comb passage is smooth, it is 2 points, if the hair is slightly caught in the comb, 1 point, and if the comb passage is very bad, it is 0 points. The average value of 20 people was calculated. When the average value is 1.5 points or more, combability after washing hair is considered to be good. (6) Conditioning effect after washing hair With 20 women as panelists, wash hair with 5 ml of shampoo,
The conditioning effect after drying was evaluated. 2 points when you feel that the conditioning effect is excellent,
The average value of 20 persons was calculated by setting 1 point when it was felt that a conditioning effect was obtained, and 0 point when it was felt that the conditioning effect was not obtained. If the average value is 1.5 points or more, the conditioning effect after washing the hair is considered to be good. (7) Setting after drying 20 women are panelists, wash their hair with 5 ml of shampoo,
The settability of the hair after drying was evaluated. The average value of 20 persons was determined, with 2 points when the settability was felt excellent, 1 point when the settability was slightly better, and 0 point when the settability was poor. . When the average value is 1.5 points or more, it is considered that the settability is excellent. (8) Glossy hair after drying Twenty women were panelists and washed with 5 ml of shampoo,
The hair gloss after drying was evaluated. If you feel a natural luster, you get 2 points, if you feel a natural luster, you get 1 point, and if you feel it has no luster, you get 0 points.
The average value of 20 people was calculated. An average value of 1.5 or higher is considered to be a shampoo that gives hair a natural luster. (9) Stability over time a The sample was stored at -5 ° C, 25 ° C, and 45 ° C for 1 month, and its appearance was observed and evaluated according to the following three grades. ◯: Good stability (transparent or slightly turbid state, no change in appearance) Δ: Slightly poor stability (slightly cloudy or colored) ×: Poor stability (precipitation, solidification, or
After 1 month, samples with 3 points at -5 ° C., 25 ° C. and 45 ° C. are all ○, and samples with 1 or Δ are even.
Δ: A sample having x even at one point was evaluated as x. (10) Stability with time b The sample was stored at -5 ° C, 25 ° C and 45 ° C for 1 month, and its appearance was observed and evaluated according to the following three grades. ◯: Good stability (flowability without solidification, no change in appearance) Δ: Slightly poor stability (coloration occurs without solidification) ×: Poor stability (solidification or marked coloring)

Example 1 3 parts by weight of a compound represented by the formula [13] as component A, B
1 part by weight of Marcoat 100 (cationic polymer, trade name, manufactured by Merck) as a component, 6 parts by weight of polyoxyethylene (3 mol) lauryl ether sulfate triethanolamine salt as a component C, sodium N-cocoyl-N-methyltaurine. 3 parts by weight, 3 parts by weight of sodium lauryl iminodiacetic acid and 5 parts by weight of cocoamidopropyldimethylaminoacetic acid betaine, as other components 3 parts by weight of lauric acid diethanolamide, 0.3 parts by weight of behenyltrimethylammonium chloride, distearyldimethylammonium A shampoo was prepared by adding 0.5 part by weight of chloride and 75.2 parts by weight of purified water. The protein denaturation rate of this shampoo is 28%, and the foam height immediately after the sample is loaded is 2
It was 59 mm and the foam retention rate was 95%. The creaminess of the foam was 1.9 as evaluated by 20 female panelists.
1.9 points for finger combability after washing hair, 1.9 for combing after washing hair
The results were as follows: Conditioning effect after washing hair was 1.9 points, setting property after drying was 1.9 points, and gloss of hair after drying was 1.8 points. In the stability test with time, the three samples stored at -5 ° C, 25 ° C and 45 ° C for 1 month were all transparent and had no change in appearance. Examples 2 to 14 Shampoos having the compositions shown in Table 2 were prepared and evaluated in the same manner as in Example 1. Table 2 shows the obtained results.

[0030]

[Table 5]

[0031]

[Table 6]

[Note] 1) "Mercourt 10" manufactured by Merck Ltd.
0) 2) "Mercote 550" manufactured by Merck 3) "Gelner QH300" manufactured by Daicel Chemical Industries 4) "Gaff Cut 734" manufactured by Gaff 5) "KF-96-1000CS" manufactured by Shin-Etsu Chemical Co., Ltd. As a result, the shampoos of Examples 1 to 14, which are the detergent compositions of the present invention, have low irritation to the skin, excellent foaming and foam stability, the foam is creamy, and the fingers can be easily washed when washing hair. It can be seen that the combability after hair washing and the conditioning effect are good, the setting properties after drying are excellent, and the hair has a natural luster. In addition, stability over time is also good. Comparative Examples 1 to 7 Shampoos having the compositions shown in Table 3 were prepared and evaluated in the same manner as in Example 1. Table 3 shows the obtained results.

[0033]

[Table 7]

[Note] 1) "Merkot 10" manufactured by Merck & Co., Inc.
0) 2) "Mercote 550" manufactured by Merck Co., Ltd. 3) "Gelner QH300" manufactured by Daicel Chemical Industries, Ltd. 4) "Gafcut 734" manufactured by Gaff Co., Ltd. 5) "KF-96-1000CS" manufactured by Shin-Etsu Chemical Co., Ltd. Shampoo of Comparative Example 1 Contains no A component,
The combability after washing the hair, the combability after washing the hair, and the conditioning effect are inferior, and the shampoo of Comparative Example 2 has a large amount of the component A, so that the foaming is poor. Since the shampoo of Comparative Example 3 does not contain the B component, it is difficult for the dried hair to have natural gloss. In the shampoo of Comparative Example 4, the foaming was poor and the stability over time was poor because the content of the component B was too large. The shampoo of Comparative Example 5 had an extremely low content of the component C, so that foaming and foam persistence were extremely poor, and the creaminess of the foam was also poor. In the shampoo of Comparative Example 6, the content of the component C was too large, so that the foam creamy was inferior and the stability over time was poor. The shampoo of Comparative Example 7 was prepared by substituting the component A for dimethylpolysiloxane, but the settability after foaming and drying became poor, and it became difficult for the dried hair to have natural gloss and was stable over time. The sex is also poor.

Example 15 1.5 parts by weight of the compound represented by the formula [14] as the component A, 0.5 part by weight of Mercoat 100 (cationic polymer, trade name, manufactured by Merck & Co.) as the component B and Gelner QH300 (cation). Polymer, trade name, manufactured by Daicel Chemical Industries, Ltd.) 0.2 parts by weight, C component as N-cocoyl-N-methyltaurine magnesium 8 parts by weight, polyoxyethylene (10 mol) coconut oil fatty acid amide ether magnesium sulfate 2 parts by weight Parts, 6 parts by weight of N-cocoyl-N'-carboxymethyl-N '-(2-hydroxyethyl) ethylenediamine and 2 parts by weight of cocoamidopropyldimethylaminoacetic acid betaine, 3 parts by weight of lauric acid diethanolamide as other components, stearyl 0.3 parts by weight of trimethylammonium chloride, distearyl dimethyl acetate 0.6 parts by weight of monium chloride, 1.7 parts by weight of ethylene glycol distearate and 0.3 parts by weight of paraben and 73.9 parts by weight of purified water were added, and citric acid was added to adjust the pH to 6 to 7. Got shampoo. The rate of protein denaturation of this shampoo was 23%, the height of the foam immediately after the introduction of the sample was 254 mm, and the foam retention rate was 96%.
According to an evaluation by 20 female panelists, the creamyness of foam was 1.9 points, the finger combability when washing hair was 1.9 points, the combability after washing hair was 1.9 points, and the conditioning effect after washing hair was 1.9 points.
The setting property after drying was 1.8 points, and the gloss of the hair after drying was 1.8 points. In the aging stability test, -5 ° C, 25 ° C and 45 ° C were used.
All of the three samples stored at 1 ° C for 1 month did not solidify and maintained fluidity, and the appearance did not change.
From these results, this shampoo has low irritation to the skin, good foaming properties, creamy foam, good finger combability during hair wash, comb combability after hair wash and conditioning effect, and set after drying. It was found that the hair has excellent properties, gives a natural luster to the hair, and has good stability over time.

Example 16 1.5 parts by weight of the compound represented by the formula [14] as the component A, 0.3 parts by weight of Gelner QH300 (cationic polymer, trade name, manufactured by Daicel Chemical Industries, Ltd.) as the component B and gaff cut 734. (Cationic polymer, trade name,
Gaff) 0.3 part by weight, N-cocoyl as C component
5 parts by weight of sodium N-methyltaurine, 4 parts by weight of sodium N-lauroyl-L-glutamate, 1 part by weight of sodium polyoxyethylene (10 mol) coconut oil fatty acid amide ether sulfate, N-cocoyl-N'-carboxymethyl-N 6.5 parts by weight of '-(2-hydroxyethyl) ethylenediamine and 2.5 parts by weight of cocoamidopropyldimethylaminoacetic acid betaine, 3 parts by weight of coconut oil fatty acid diethanolamide and 0.3 parts by weight of behenyltrimethylammonium chloride as other components. , 0.5 parts by weight of distearyl dimethyl ammonium chloride, 1.7 parts by weight of ethylene glycol distearate and 0.5 parts of paraben.
3 parts by weight and 75.2 parts by weight of purified water were mixed, and citric acid was added to adjust the pH to 6 to 7 to obtain a shampoo. The protein denaturation rate of this shampoo was 20%, the foam height immediately after the sample was added was 258 mm, and the foam retention rate was 95%. According to an evaluation by 20 female panelists, the foamy creamy property was 1.9 points, the finger combing property when washing hair was 1.9 points, the combing property after washing hair was 1.8 points, and the conditioning effect after hair washing was 1.8 points.
Points, setting property after drying 1.8 points, gloss of hair after drying 1.9
Was a point. In the stability test with time, the three samples stored at -5 ° C, 25 ° C, and 45 ° C for 1 month each did not solidify, maintained fluidity, and had no change in appearance. From these results, this shampoo has low irritation to the skin, good foaming properties, creamy foam, good finger combability during hair wash, comb combability after hair wash and conditioning effect, and set after drying. It was found that the hair has excellent properties, gives a natural luster to the hair, and has good stability over time.

[0037]

The detergent composition of the present invention has very weak skin irritation, excellent foaming property, and creamy foam quality,
Excellent stability over time. When the cleaning composition of the present invention is used as a shampoo, it has a good feeling in use, has an excellent conditioning effect on hair, has excellent settability after drying, and gives the hair a natural luster after drying. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C11D 3:37)

Claims (2)

[Claims] 1. (A) 0.1 to 5% by weight of a polyoxyalkylene ether compound having a silicone pendant represented by the general formula [1], and (B) a cationic polymer 0.1 to
5% by weight, and (C) synthetic anionic surfactant and / or
Or 1 to 40% by weight of one or more amphoteric surfactants
A cleaning composition comprising: Residues of _{Z [O (AO) h (} DO) i (GO) j R 1] k ... [1] [In the formula, Z is a compound having 2 to 8 hydroxyl groups, R ¹ is hydrogen, carbon A C1-24 alkyl group, a C7-24 aralkyl group, a C6-24 aryl group or a C2-24 acyl group, and AO is one or two C2-22 The above is an oxyalkylene group, and DO is one or more groups represented by the general formula [2], and (In the formula, R ² is an alkenyl group having 2 to 5 carbon atoms.) GO is one or more groups represented by the general formula [3], and (In the formula, X is an alkylene group having 2 to 5 carbon atoms, and Y is a siloxyl group represented by the general formula [4].) (In the formula, R ³ is a hydrocarbon group having 1 to 24 carbon atoms and may be the same or different, and u is 0 to 3,000.
0. ) AO, DO, and GO may be added in blocks or randomly in any order. k
Is 1 to 8, hk is 1 to 1,500, ik is 0 to 1
00 and jk are 1 to 100. ] 2. A synthetic anionic surfactant and / or amphoteric surfactant is an alkyl ether sulfate represented by the general formula [5], an acylmethyl taurate represented by the general formula [6], or a general formula [7]. ] Amido ether sulfate represented by
Alkyl amino acid type amphoteric surfactant represented by the general formula [8], amidoamine type amphoteric surfactant represented by the general formula [9] or [10], and amidobetaine type surfactant represented by the general formula [11]. The cleaning composition according to claim 1, which is one kind or two or more kinds selected from the agents. _{^{[R 4 O (CH 2 CH}} 2 O) m SO 3] n M 1 ... [5] ( In the formula, R ⁴ is an alkyl or alkenyl group of 7 to 21 carbon atoms, M ¹ is an alkali metal , An alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, n is an integer equal to the valence of the atom or group represented by M ¹ , and m is 2 to 15.) (In the formula, R ⁵ is an alkyl group or an alkenyl group having 7 to 21 carbon atoms, M ² is an alkali metal, an alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and o is M ² . It is an integer equal to the valence of the atom or group shown.) [R ⁶ CONH (CH ₂ CH ₂ O) _p SO ₃ ] _q M ³ ... [7] (wherein R ⁶ has 7 to 7 carbon atoms). 21 is an alkyl group or an alkenyl group, M ³ is an alkali metal, alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and q is an integer equal to the valence of the atom or group represented by M ³ . , P is 2 to 15.) (In the formula, R ⁷ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and r and s are the same or different 1 to
Is an integer of 3, M ⁴ and M ⁵ are hydrogen, an alkali metal, an alkaline earth metal or an unsubstituted or organic group-substituted ammonium group, and M ⁴ and M ⁵ may be the same or different. ) [Wherein, R ⁸ and R ¹⁰ are an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and R ⁹ and R ¹¹ are —CH ₂
COOM ⁶ or -CH ₂ CH ₂ COOM ⁶ (wherein
M ⁶ is hydrogen, an alkali metal or an organic group-substituted ammonium group. ), R ¹² is hydrogen, —CH ₂ COOM ⁶ or —CH ₂ CH ₂ COOM ⁶ (wherein, M ⁶ is hydrogen,
It is an alkali metal or organic group-substituted ammonium group. )
It is. ] (However, in the formula, R ¹³ is an alkyl group or an alkenyl group having 7 to 19 carbon atoms, and t is an integer of 2 to 4.)