CN1278717A

CN1278717A - Hair care compositions comprising optical brighteners and hair conditioning agents

Info

Publication number: CN1278717A
Application number: CN98811097A
Authority: CN
Inventors: 三松新; 罗晓春; 内山浩孝; 朱莉娅·L·塞瑟
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1997-09-17
Filing date: 1998-09-04
Publication date: 2001-01-03
Also published as: WO1999013846A1; AU4351497A; ZA988156B

Abstract

Disclosed are hair care compositions comprising: (a) an effective amount of a fluorescence brightener; (b) a hair conditioning agent, selected from siloxanes, cation compounds, refractory compound, perfume compounds, water-insoluble macromolecular oiliness compounds and mixture thereof.

Description

Hair care compositions comprising optical brighteners and hair conditioning agents

Technical Field

The present invention relates to a composition comprising an optical brightener that changes hair color while increasing the shine and protecting the hair from further damage. More particularly, the present invention relates to a hair care composition comprising an optical brightener and a hair conditioner.

Background

There is a continuing desire to restore the natural color and luster of damaged hair and to change the color of hair to make it more attractive. Consumers feel damaged hair does not look good and do not comb easily. This unsightly appearance includes changes and fading of the original hair color and a reduction in shine.

A common method of reducing the unpleasant appearance of damaged hair and achieving an attractive hair color is to dye the hair to the desired color. Dyeing the hair will provide the consumer with a stable hair color over a relatively long period of time. However, hair coloring is often a time consuming, cumbersome and messy task. Dyes can also cause chemical damage to hair, scalp and skin. The hair may be further damaged by the dyeing. Therefore, hair coloring products are not suitable for daily use. Furthermore, hair coloring can leave the hair with a dull appearance, making the hair appear lusterless.

Based on the foregoing, there is a continuing need for a hair composition that can be used on a daily basis and that can change the color of hair, while enhancing the shine and protection of the hair from further damage.

It is known in the art in the hair care field to use optical brighteners or other compounds known as fluorescent brighteners, fluorescent brighteners or fluorescent dyes, such as those described in the following documents: US3, 658, 985, US4, 312, 855, CA1, 255, 603, US3, 577, 528, british patent specification 1, 328, 108, south african application 676, 049, european patent publication 87, 060 and british patent specification 2, 307, 639.

However, the use of fluorescent whitening agents alone cannot provide sufficient conditioning benefits such as good combing, smoothness and static reduction. There is therefore a need for a hair care composition comprising an optical brightener and providing good conditioning efficacy.

The prior art does not provide all the advantages and effects of the present invention.

Summary of The Invention

The present invention relates to a hair care composition comprising: (a) an effective amount of a fluorescent whitening agent; and (b) a hair conditioning agent selected from the group consisting of silicone compounds, cationic compounds, high melting point compounds, perfume compounds, water-insoluble high molecular weight oily compounds, and mixtures thereof.

The foregoing and other features, aspects, and advantages of the present invention will become more apparent to those skilled in the art from the following detailed disclosure.

Detailed Description

While the claims at the end of this specification particularly point out and distinctly define the invention, it is believed that the invention will be better understood from the following description.

All percentages are by weight of the total composition unless otherwise indicated. All proportions are by weight unless otherwise indicated. All percentages, ratios, and levels of ingredients are based on the actual amount of the ingredient, and do not include solvents, fillers, or materials incorporated in commercially available products of the various ingredients, unless otherwise specified.

In the present invention, "comprising" means that other steps and other ingredients which do not affect the end result can be added. The term includes the terms "consisting" and "consisting essentially".

All cited documents are incorporated herein by reference in their entirety. None of the cited documents is intended to admit to the present claimed invention in an existing state of the art.

Fluorescent whitening agent

Optical brighteners are compounds that absorb ultraviolet light and release energy again in the form of visible light. Specifically, the optical brighteners employed in the present invention have an absorption, preferably a major absorption peak, in the wavelength range of about 1nm to 420nm and an emission, preferably a major emission peak, in the wavelength range of about 360nm to 830 nm; wherein the main absorption peak is shorter than the wavelength of the main emission peak. More preferably, the optical brighteners used in the present invention have a main absorption peak at a wavelength of about 200nm to 420nm and a main emission peak at a wavelength of about 400nm to 780 nm. Optical brighteners may or may not have a minor absorption peak in the visible range of wavelengths from about 360nm to 830 nm. Optical brighteners (Optical brighteners) may be described in the art and other industries by other names, such as fluorescent brighteners (fluorescent whitening agents), fluorescent brighteners (fluorescent brighteners), and fluorescent dyes (fluorescent dyes).

The optical brighteners of the present invention will be able to provide a beneficial effect to the hair in three respects when applied to the hair using a suitable carrier. First, the fluorescent whitening agents herein can change the color of hair by emitting light in the visible range. Second, the fluorescent whitening agents herein can enhance the shine of hair by emitting light in the visible range. Third, the optical brighteners herein also protect hair from ultraviolet light damage by absorbing ultraviolet light.

Optical brighteners are generally based on the structure of aromatic and heteroaromatic systems, which provide unique features. The fluorescent whitening agents used in the present invention can be classified into several classes as described below according to their basic structures. Preferred optical brighteners of the present invention include polystyrene based stilbenes (polystyrylstilbenes), triazinyl stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins and imidazoles, more preferably polystyrene based stilbenes and hydroxycoumarins.

Preferably, the optical brighteners are present in the hair care compositions of the present invention in an amount from about 0.001% to about 20% by weight, more preferably from about 0.01% to about 10% by weight.

Polystyrene based stilbene

Polystyrene-based stilbenes are a class of compounds having two or more of the following basic structures:

the polystyrene-based stilbene used in thepresent invention includes those having the following formulae (1), (2) and (3):

wherein R is¹⁰¹Is H, OH, SO₃M、COOM、OSO₃M, OPO (OH) OM where M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri-or tetra-C₁－C₃₀Alkylammonium, mono-, di-or tri-C₁－C₃₀Hydroxyalkylammonium or with C₁－C₃₀-alkyl and C₁－C₃₀-ammonium di-or tri-substituted with a mixture of hydroxyalkyl groups; or SO₂N(C₁－C₃₀-alkyl groups)₂、O－(－C₁－C₃₀Alkyl), CN, Cl, COO (C)₁－C₃₀Alkyl), CON (C)₁－C₃₀-alkyl groups)₂Or O (CH)₂)₃N⁺(CH₃)₂X-, wherein X-is the following anion: chloride, bromide, iodide, formate, acetate, propionate, glycolate, lactate, acrylate, methanephosphonate, phosphite, dimethyl or diethyl phosphite anion; CN or alkyl of 1 to 30 carbon atoms, R¹⁰²And R¹⁰³Independently of one another is H, SO₃M, wherein M is as previously defined; x is 0 or 1; wherein the compound hasTrans-coplanar or cis-coplanar orientation; preferably x is 1, R¹⁰¹Is SO₃Na，R¹⁰²And R¹⁰³Is H; wherein the compound has a trans-coplanar orientation;

wherein R is¹⁰⁴And R¹⁰⁵Independently of one another CN, COO (C)₁－C₃₀Alkyl), CONHC₁－C₄Alkyl or CON (C)₁－C₄-alkyl groups)₂Wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R¹⁰⁴And R¹⁰⁵Is 2-cyano, wherein the compound has a trans-coplanarorientation; and

wherein each R is¹⁰⁶Independently is H or alkyl of 1 to 30 carbon atoms; wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation.

Suitable polystyrene based stilbenes include: 1, 4' -bis (2-sulfostyryl) biphenyl disodium (c.i. fluorescent brightener 351), commercially available from Ciba specialty chemicals under the trade name Tinopal CBS-X; 1, 4-bis (2-cyanostyryl) benzene (c.i. fluorescent whitening agent 199) commercially available from BASF under the trade name Ultraphor RN.

Triazinyl stilbenes

The triazinyl stilbene is a compound which has triazine and styrene structures in the same molecule.

The triazinylstilbenes useful in the present invention include those having the following formula (4):

wherein R is¹⁰⁷And R¹⁰⁸Independently of one another, phenylamino, mono-or disulphonated phenylamino, morpholino, N (CH)₂CH₂OH)₂、N(CH₃)(CH₂CH₂OH)、NH₂、N(C₁－C₄-alkyl groups)₂、OCH₃、Cl、NH－(CH₂)_1－4SO₃H or NH- (CH)₂)_1－4OH; an-is the following anion: carboxylate, sulfate, sulfonate or phosphate, M being as previously defined, wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R¹⁰⁷Is 2, 5-disulfophenylamino, each R¹⁰⁸Is morpholino; or each R¹⁰⁷Is 2, 5-disulfophenylamino and each R¹⁰⁸Is N (C)₂H₅)₂(ii) a Or each R¹⁰⁷Is 3-sulfophenyl and each R¹⁰⁸Is NH (CH)₂CH₂OH) or N (CH)₂CH₂OH)₂(ii) a Or each R¹⁰⁷Is 4-sulfophenyl and each R¹⁰⁸Is N (CH)₂CH₂OH)₂(ii) a In each case, sulfurRadical being SO₃M, wherein M is sodium; wherein the compound has a trans-coplanar orientation.

Suitable triazinylstilbenes include: 4, 4 '-bis- [ (4-phenylamino-6-bis- (2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2' -disulfonic acid, commercially available from Ciba Specialty Chemicals under the trade name Tinopal UNPA-GX; disodium 4, 4 ' -bis [ (4-phenylamino-6-morpholin-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2 ' -sulfonate, commercially available under the name Tinopal AMS-GX, commercially available from Ciba Specialty Chemicals, disodium 4, 4 ' -bis- [ (4-phenylamino-6- (2-hydroxyethyl) methylamino-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2 ' -sulfonate, disodium Tinopal 5 BM-GX, commercially available from Ciba Specialty Chemicals, disodium 4 ', 4 ' -bis- [ (4, 6-diphenylamino-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2 ' -sulfonate, disodium 4, 4 ' -bis- [ (4-phenylamino-6-methylamino-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2 ' -sulfonate, disodium 4, 4 ' -bis- [ (4-ethylamino-6-methylamino-1, 3, 5-triazin-2-yl) amino]stilbene-2, 2 ' -sulfonate, 3, 5-triazin-2-yl) amino) stilbene-2, 2 ' -sulfonic acid disodium salt, and 4, 4 ' -bis- (4-phenyl-1, 2, 3-triazol-2-yl) stilbene-2, 2 ' -disulfonic acid.

Hydroxycoumarins

Hydroxycoumarins are a class of compounds having the following basic coumarin structure and having at least one hydroxyl group:

hydroxycoumarins useful in the present invention include those compounds having the following formula (5):

wherein R is²⁰¹Is H, OH, Cl, CH₃、CH₂COOH、CH₂SO₃H、CH₂OSO₃H or CH₂OPO(OH)OH，R²⁰²Is H, phenyl, COO-C₁－C₃₀-alkyl, glucose, or a group of formula (6):

R²⁰³is OH or O-C₁－C₃₀-alkyl, R²⁰⁴Is OH or O-C₁－C₃₀Alkyl, glucoside, or a group of the following formula (7):

wherein R is²⁰⁵And R²⁰⁶Independently of one another, phenylamino, mono-or disulphonated phenylamino, morpholino, N (CH)₂CH₂OH)₂、N(CH₃)(CH₂CH₂OH)、NH₂、N(C₁－C₃₀-alkyl groups)₂、OCH₃、Cl、NH－(CH₂)_1－4SO₃H or NH- (CH)₂)_1－4OH。

Suitable hydroxycoumarins include: 6, 7-dihydroxycoumarin, commercially available from Wako Chemicals, 4-methyl-7-hydroxycoumarin, commercially available from Wako Chemicals, 4-methyl-6, 7-dihydroxycoumarin, commercially available from Wako Chemicals, esculin, commercially available from Wako Chemicals, and 7-hydroxycoumarin (4-hydroxycoumarin), commercially available from Wako Chemicals.

Aminocoumarins

Aminocoumarins are a class of compounds having a basic coumarin structure and having at least one amino group.

Aminocoumarins useful in the invention include those compounds having formula (8):

wherein R²⁰⁷Is H, Cl, CH₃、CH₂COOH、CH₂SO₃H、CH₂OSO₃H or CH₂OPO(OH)OH、R²⁰⁸Is H, phenyl or COOC₁－C₃₀Alkyl radical, R²⁰⁹And R²¹⁰Independently of one another is H, NH₂、N(C₁－C₃₀Alkyl radical)₂、NHC₁－C₃₀Alkyl or NHCOC₁－C₃₀An alkyl group.

Suitable aminocoumarins include: 4-methyl-7, 7 '-diethylaminocoumarin, commercially available under the trade name Calcofluor-RWP, commercially available from BASF, 4-methyl-7, 7' -dimethylaminocoumarin, commercially available under the trade name Calcofluor-LD, commercially available from BASF.

Triazole compounds

Triazoles are a class of compounds having the following basic structure:

the triazole used in the present invention includes compounds having the following formulae (9) to (12) and (15) to (20):

wherein R is³⁰¹And R³⁰²Independently of one another is H, C₁－C₃₀Alkyl, phenyl or monosulfonated phenyl; an-and M are as previously defined, wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R³⁰¹Is phenyl, R³⁰²Is H and M is sodium; wherein the compound has a trans-coplanar orientation;

wherein R is³⁰³Is H or Cl; r³⁰⁴Is SO₃M、SO₂N(C₁－C₃₀-alkyl groups)₂、SO₂O-phenyl or CN; r³⁰⁵Is H, SO₃M、COOM、OSO₃M or OPO (OH) OM; and M is as previously defined, wherein the compound has a trans coplanar or cis coplanar orientation; preferably R³⁰³And R³⁰⁵Is H, R³⁰⁴Is SO₃M, wherein M is Na; wherein the compound has a trans-coplanar orientation;

wherein each R is³⁰⁶And R³¹²Independently of one another, H, a sulfonic acid group or a salt, ester or amide thereof, a carboxylic acid group or a salt, ester or amide thereof, a cyano group, a halogen atom, a substituted or unsubstituted alkylsulfonyl group, an arylsulfonyl group, an alkyl group, an alkoxy group, an aralkyl group, an aryl group, an aryloxy group, an aralkyloxy group or a cycloalkyl group, a substituted or unsubstituted 5-membered heterocyclic ring containing 2 to 3 nitrogen atoms or 1 oxygen atom and 1 or 2 nitrogen atoms; or with R³⁰⁷And R³¹³Together represent methylenedioxy, ethylenedioxy, methyleneoxymethyleneoxy, trimethylene, tetramethylene, propenylene, butenylene or butadienylene, each R³⁰⁷And R³¹³Independently of one another, H, a sulphonic acid group or a salt, ester or amide thereof,A carboxylic acid group or a salt, ester or amide thereof, a cyano group, a halogen atom, a substituted or unsubstituted alkyl or alkoxy group, or R³⁰⁶And R³¹²Together represent methylenedioxy, ethylenedioxy, methyleneoxymethyleneoxy, trimethylene, tetramethylene, propenylene, butenylene or butadienylene, each R³⁰⁸And R³¹⁴Independently of one another, H, a halogen atom or a substituted or unsubstituted alkyl radical, each R³⁰⁹And R³¹¹Independently of one another, represents H, a halogen atom, a cyano group, a sulphonic acid group or a salt, ester or amide thereof, a carboxylic acid group or a salt, ester or amide thereof, R³¹⁰Independently represents H, a halogen atom, a cyano group, a sulfonic acid group ora salt thereof, preferably an alkyl group substituted with a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a halogen atom, a carboxyl group, a sulfonic acid group, an alkoxy group having 1 to 30 carbon atoms in the alkoxy moietyCarbonyl, phenyl or phenoxy; alkoxy which may be substituted with hydroxy; alkoxy having 1 to 30 carbon atoms, cyano, halogen atom, carboxyl, alkoxycarbonyl having 1 to 30 carbon atoms in the alkoxy moiety, phenyl or phenoxy; phenyl, phenylalkyl or phenoxy which may be substituted by halogen atoms, cyano, carboxyl, alkoxycarbonyl having 1 to 30 carbon atoms in the alkoxy moiety, sulfo or alkyl or alkoxy having 1 to 30 carbon atoms respectively; wherein the compound has a trans-coplanar or cis-coplanar orientation; possible cycloalkyl groups are preferably cyclohexyl and cyclopentyl, which may be substituted by alkyl groups of 1 to 30 carbon atoms; the 5-membered heterocyclic ring which may be present is v-triazole, oxazole or 1, 3, 4-oxadiazolyl which may contain, as substituents, alkyl groups of 1 to 4 carbon atoms, halogen atoms, phenyl, carboxyl, alkoxycarbonyl groups whose alkoxy moiety has 1 to 30 carbon atoms, cyano, benzyl, alkoxy groups of 1 to 30 carbon atoms, phenoxy or sulfo, and two adjacent groups of the triazole and oxazole groups may together form a substituted or unsubstituted fused benzene ring; wherein the compound has a trans-coplanar orientation;

wherein Q is¹Represents one of the ring systems (13) or (14);

wherein R is³¹⁷Represents H, alkyl of 1 to 30 carbon atoms, cyclohexyl, phenylalkyl having 1 to 30 carbon atoms in the alkyl moiety, phenyl, alkoxy having 1 to 30 carbon atoms or Cl, or with R³¹⁸Together represent an alkylene group having 3 to 30 carbonatoms, R³¹⁸Represents H or alkyl of 1 to 30 carbon atoms, or with R³¹⁷Together represent an alkylene group having 3 to 30 carbon atoms, R³¹⁹Represents H or methyl, R³²⁰Represents H, alkyl of 1 to 30 carbon atoms, phenyl, alkoxy of 1 to 30 carbon atoms or Cl, or with R³²¹Together represent a fused benzene ring, R³²¹Represents H or Cl or with R³²⁰Together represent a fused benzene ring, R³¹⁵Represents H, alkyl of 1-30 carbon atoms, 1-30Alkoxy of carbon atoms or Cl, R³¹⁶Represents H or Cl, Q²Representing H, Cl, alkyl of 1-30 carbon atoms or phenyl, Q³Represents H or Cl; wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation;

wherein R is³²²Represents H, Cl, methyl, phenyl, benzyl, cyclohexyl or methoxy, R³²³Represents H or methyl, Z represents O or S; wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation; and

wherein R is³²⁴Denotes H, Cl, alkyl of 1 to 30 carbon atoms, phenylalkyl of 1 to 30 carbon atoms, phenyl or alkoxy of 1 to 30 carbon atoms, or R³²⁴And R³²⁵Together represent a fused phenyl group, R³²⁵Represents H or methyl or R³²⁵And R³²⁴Together represent a fused phenyl group, R³²⁶Represents H, alkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, Cl, alkoxycarbonyl of 1 to 30 carbon atoms or alkylsulfonyl of 1 to 30 carbon atoms, and R³²⁷Represents H, Cl, methyl or methoxy; wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation.

Suitable triazoles include:2- (4-styryl-3-sulfophenyl) -2H-naphtho [1, 2-d]triazole (C.I. fluorescent whitening agent 46), with the trade name Tinopal RBS, commercially available from Ciba Specialty Chemicals.

Pyrazolines

Pyrazolines are a class of compounds having the following basic structure:

pyrazolines used in the present invention include those having the following formulae (21) to (23):

wherein R is⁴⁰¹Is H, Cl or N (C)₁－C₃₀-alkyl groups)₂，R⁴⁰²Is H, Cl, SO₃M、SO₂NH₂、SO₂NH－(C₁－C₃₀Alkyl), COO-C₁－C₃₀Alkyl, SO₂－C₁－C₃₀Alkyl, SO₂NH(CH₂)_1－4N⁺(CH₃)₃Or SO₂(CH₂)_1－4N⁺H(C₁－C₃₀-alkyl groups)₂An－，R⁴⁰³And R⁴⁰⁴Which may be the same or different, are each H, C respectively₁－C₃₀Alkyl or phenyl, R⁴⁰⁵Is H or Cl; an-and M are as defined above, preferably R⁴⁰¹Is Cl, R⁴⁰²Is SO₂CH₂CH₂N⁺H(C₁－C₄-alkyl groups)₂An-, wherein An-is phosphite, R⁴⁰³、R⁴⁰⁴And R⁴⁰⁵Are each H; the formulae (22) and (23) are shown below:

suitable pyrazolines include: 1- (4-Acylaminosulfonylphenyl) -3- (4-chlorophenyl) -2-pyrazoline (C.I. optical brightener 121) is available under the trade name Blankophor DCB,commercially available from Bayer; 1- [ 4- (2-sulfoethylsulfonyl) phenyl]-3- (4-chlorophenyl) -2-pyrazoline; 1- [ 4- (2-sulfoethylsulfonyl) phenyl]-3- (3, 4-dichloro-6-methylphenyl) -2-pyrazoline; 1-<4- { N- [ 3- (N, N, N-trimethylammonio) propyl]-amidosulfonyl } phenyl>-3- (4-chlorophenyl) -2-pyrazoline methylsulfate and 1-<4- { 2- [ 1-methyl-2- (N, N-dimethylamino) ethoxy]ethylsulfonyl } phenyl>-3- (4-chlorophenyl) -2-pyrazoline methylsulfate.

Oxazole (oxazole)

Oxazoles are a class of compounds having the following basic structure:

oxazole useful in the present invention includes compounds having the formula (24), (25),(26) Those of (1) and (27):

wherein R is⁵⁰¹And R⁵⁰²Independently of one another are H, Cl, C₁－C₃₀Alkyl or SO₂－C₁－C₃₀An alkyl group, wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R⁵⁰¹Is 4-CH₃And R⁵⁰²Is 2-CH₃Wherein the compound has a trans-coplanar orientation;

wherein R is⁵⁰³Independently H, C (CH)₃)₃、C(CH₃)₂-phenyl, C₁－C₃₀Alkyl or COO-C₁－C₃₀Alkyl, preferably H and Q⁴is-CH ═ CH-;

preference is given to

Or, R on each ring⁵⁰³Is 2-methyl, another R⁵⁰³Then is H, and Q⁴is-CH ═ CH-; or one R on each ring⁵⁰³Is 2-C (CH)₃)₃And another R⁵⁰³Then is H;wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation.

Wherein R is⁵⁰⁴Is CN, Cl, COO-C₁－C₃₀Alkyl or phenyl; r⁵⁰⁵And R⁵⁰⁶Is an atom required to form a fused benzene ring, or R⁵⁰⁶And R⁵⁰⁸Independently of one another, H or C₁－C₃₀An alkyl group; r⁵⁰⁷Is H, C₁－C₃₀Alkyl or phenyl; wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R⁵⁰⁴Is 4-phenyl and R⁵⁰⁵To R⁵⁰⁸Each is H; wherein the compound has a trans-coplanar orientation; and

wherein R is⁵⁰⁹Denotes H, Cl, alkyl of 1 to 30 carbon atoms, cyclohexyl, phenylalkyl having 1 to 3 carbon atoms in the alkyl moiety, phenyl or alkoxy of 1 to 30 carbon atoms, R⁵¹⁰Represents H or alkyl of 1 to 30 carbon atoms, Q⁵Represents the following groups:

wherein R is⁵¹¹Represents H, alkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, Cl, alkoxycarbonyl of 1 to 30 carbon atoms, unsubstituted sulfamoyl or sulfamoyl which is mono-or disubstituted with alkyl or hydroxyalkyl of 1 to 30 carbon atoms or represents alkylsulfonyl of 1 to 30 carbon atoms; wherein the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation.

Suitable oxazoles include: 4, 4' -bis (5-methylbenzoxazol-2-yl) stilbene, and 2- (4-methoxycarbonylstyryl) benzoxazole.

Pyrene

Pyrene useful in the present invention includes those compounds having formulas (28) and (29):

wherein each R is⁶⁰¹Independently is C₁－C₃₀An alkoxy group; preferably a methoxy group; and

wherein each R is⁶⁰²Independently H, OH or SO₃M, wherein M is as defined above, a sulfonated phenylamino group or a phenylamino group.

Suitable pyrenes include: 2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine (c.i. fluorescent whitening agent 179) with the trade names fluolate XMF, 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid (D&C green No. 8) and 3-hydroxy-5, 8, 10-trissulfaminopyrene.

Porphyrins

Porphyrins useful in the present invention include those having the formulaThose of formulae (30), (31), and (32):

wherein R is⁷⁰¹Is CH₃Or CHO, R⁷⁰²Is H or COOC₁－C₃₀Alkyl and R⁷⁰³Is H or alkyl of 1 to 30 carbon atoms; and

wherein each R is⁷⁰⁴Independently is H, SO₃M、COOM、OSO₃M or OPO (OH) OM, wherein M is as defined above, a halide ion or an alkyl group of 1 to 30 carbon atoms; q⁶Is Cu, Mg, Fe, Cr, Co or a mixture thereof with cationic charge.

Suitable porphyrins include: porphyrins, commercially available from Wako Chemicals, and copper II phthalocyanine dye, commercially available from WakoChemicals.

Imidazole

Imidazoles are a class of compounds having the following basic structure:

the imidazole used in the present invention includes a compound having the following formula (33):

wherein X-is as defined above.

Suitable imidazoles include: those sold under the trade name c.i. fluorescent whitening agent 352, or Uvtex AT, are commercially available from Ciba Speciality Chemical.

Composition comprising a metal oxide and a metal oxide

The hair care compositions of the present invention may include components that characterize the form of the product. Product forms useful in the present invention include, but are not limited to: shampoo, conditioner, mousse, hair spray, lotion, gel and cream products, all of which can be designed for ease of rinsing or leave-on. The functions of the products for use in the present invention include, but are not limited to: cleansing and conditioning products. The selection of the components and their amounts can be made by one of ordinary skill in the art based on the desired characteristics of the product.

Hair conditioning agent

The compositions of the present invention comprise a hair conditioning agent selected from the group consisting of silicone compounds, cationic compounds, high melting compounds, fragrance compounds, water-insoluble high molecular weight oily compounds, and mixtures thereof. The hair conditioning compositions herein can provide good conditioning benefits such as ease of combing, smoothness and reduced static. Preferably, the hair conditioning agents are present in the present invention in an amount of from about 0.01% to about 20% by weight.

Siloxane compound

Silicone compounds are useful hair conditioning agents herein, preferably at levels of from about 0.01% to about 15%. The silicone compounds useful herein include volatile soluble or insoluble silicone conditioning agents, or nonvolatile soluble or insoluble silicone conditioning agents. By soluble, it is meant that the silicone compound is miscible with the carrier of the composition, thereby forming a partially identical phase. By insoluble, it is meant that the silicone forms a separate discontinuous phase with the carrier, such as in the form of an emulsion or suspension of silicone droplets. The silicone compounds of the present invention can be prepared by any suitable method known in the art, including emulsion polymerization. The silicone compound may also be incorporated into the present invention in the form of an emulsion, wherein the emulsion is prepared by mechanical mixing, or in the synthesis stage by emulsion polymerization, with or without the aid of a surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.

In one embodiment, the silicone compound used in the present invention is a high molecular weight silicone compound. The high molecular weight silicone compounds useful herein have a viscosity of from about 1000 to about 2000000 centistokes at 25 ℃, more preferably from about 10000 to about 1800000 centistokes, still more preferably from about 100000 to about 1500000 centistokes. The viscosity can be measured by a glass capillary viscometer as described in Dow Corning corporation Test Method CTM0004 (20/7 1970). The high molecular weight silicone compound can be prepared by emulsion polymerization. Suitable silicone fluids include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyether siloxane copolymers, and mixtures thereof. Other non-volatile silicone compounds having hair conditioning properties may also be used.

The silicone compounds herein are preferably used in an amount of from about 0.1% to about 60%, more preferably from about 0.1% to about 40%, by weight of the composition.

The silicone compounds herein include polyalkyl or polyaryl siloxanes having the following structure (I):

wherein R is⁹³Is an alkyl or aryl group and p is an integer from about 7 to about 8000. Z⁸Represents a group that blocks the end of the siloxane chain. Alkyl or aryl radicals (R) substituted on the siloxane chain⁹³) Alkyl or aryl radicals (Z) on or at the ends of the siloxane chain⁸) Can have any structure so long as the resulting silicone is fluid at room temperature, is dispersible, non-irritating, non-toxic, non-harmful when applied to the hair, is compatible with the other ingredients of the composition, is chemically stable under normal use and storage conditions, and is capable of being deposited on and conditions the hair. Suitable Z⁸Groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. Two R on a silicon atom⁹³The groups may be the same or different. Preferably two R⁹³The groups represent the same groups. Suitable R⁹³Groups include methyl, ethyl, propyl, phenyl, tolyl, and benzyl. Preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane and polymethylphenylsiloxane. Particular preference is given to polydimethylsiloxanes known as polydimethylsiloxanes (dimethicones). Polyalkylsiloxanes which may be used include, for example, polydimethylsiloxanes. These silicones are commercially available from General Electric Company as Viscasil (R) series and SF 96 series, and from Dow Corningas Dow Corning200 series.

Polyalkylarylsiloxane fluids, including, for example, polymethylphenylsiloxane, may also be used. These silicones are available, for example, from General Electric Company as SF 1075 methylphenyl fluid and from Dow Corning as 556 cosmetic grade fluid.

In order to enhance the shine characteristics of hair, it is also particularly preferred in the present invention to employ highly arylated silicone compounds, such as highly phenylated polyethyl silicone, having a refractive index of about 1.46 or greater than 1.46, and particularly about 1.52 or greater. When these high refractive index silicone compounds are used, they should be mixed with a spreading agent, such as a surfactant or a silicone resin, as described below, to reduce surface tension and enhance film formation of the material.

The silicone compounds which may be used include polypropylene oxide modified polydimethylsiloxanes, although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and propylene oxide content should be sufficiently low so that they do not interfere with the dispersing properties of the siloxane. These materials are also known as alkoxylated polydimethylsiloxanes.

Other silicone compounds include amino substituted materials. Suitable alkylamino substituted siloxane compounds include those having the structure of formula (II):

wherein R is⁹⁴Is H, CH₃Or OH, p¹、p²、q¹And q is²Is an integer depending on the molecular weight, and has an average molecular weight of about 5,000 to 10,000. This polymer is also known as "alkylaminated polydimethylsiloxane (amodificone)".

Suitable amino-substituted siliconefluids include silicones (R) having the following formula (III)⁹⁷)_aG_3－a－Si－(－OSiG₂)_p3－(－OSiG_b(R⁹⁷)_2－b)_p4－O－SiG_3－a(R⁹⁷)_a(Ⅲ)

Wherein G is selected from hydrogen, phenyl, hydroxy, C₁－C₈Alkyl, preferably methyl(ii) a a is 0 or an integer from 1 to 3, preferably 0; b is 0 or 1, preferably 1; p is a radical of³+p⁴Are 1 to 2,000, preferably 50 to 150, p³May represent a number from 0 to 1, 999, preferably from 49 to 149, p⁴May represent an integer of 1 to 2,000, preferably 1 to 10; r⁹⁷Is a monovalent group, satisfies the formula C_q3H_2q3L, wherein q³Is an integer from 2 to 8, L may be selected from the following groups:

－N(R⁹⁶)CH₂－CH₂－N(R⁹⁶)₂

－N(R⁹⁶)₂

－N(R⁹⁶)₃X′

－N(R⁹⁶)CH₂－CH₂－NR⁹⁶H₂X′

wherein R is⁹⁶Selected from hydrogen, phenyl, benzyl, saturated hydrocarbon radicals, preferably alkyl radicals having from 1 to 20 carbon atoms, X' is a halide ion.

A particularly preferred amino-substituted siloxane corresponding to formula (II) is known as "Trimethylsilylaminedimethylsiloxane", wherein R is⁹⁴Is CH₃。

Other amino-substituted siloxane polymers that can be used are represented by the following formula (V):

wherein R is⁹⁸Is a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably an alkyl or alkenyl group such as methyl; r⁹⁹Is a hydrocarbon radical, preferably C₁－C₁₈Alkylene or C₁－C₁₈More preferably C₁－C₈An alkyleneoxy group of (a); q^-Is a halide ion, preferably chlorine; p is a radical of⁵Is 2 to 20, preferably 2 to 8; p is a radical of⁶Is 20 to 200, preferably 20 to 50. Preferred polymers in this class are commercially available from Union Carbide under the designation "UCAR SILICONE ALE 56".

References disclosing suitable nonvolatile dispersed silicone compounds include: US2, 826, 551(Geen), US3, 964, 500 (Drakoff on day 22 of 6/1976), US4, 364, 837 (Pader); and GB 849, 433 (Woolston). A non-exclusive but more comprehensive list of suitable silicone compounds is listed by "Silicon Compound", Petrace System, Inc. (1984).

Another particularly useful non-volatile dispersed siloxane is a silicone gum. The term "silicone gums" as used herein means that these gums are polyorganosiloxane materials having a viscosity of greater than or equal to 1, 000, 000 centistokes at 25 ℃. It is understood that there may be some overlap of the silicone gums described herein with the silicone compounds described above. This overlap is not a limitation on any of these materials. Petrarch describes such silicone gums, and other references include: US4, 152, 416(Spitzer et al, granted 5/1 1979); noll, Walter, siloxane Chemistry and Technology (Chemistry and Technology of Silicones), New York: academic Press 1968. Also mentioned as Silicone gums are the general electric Silicone Rubber Product Data Sheets SE30, SE33, SE54 and SE76, all of which are incorporated herein by reference. The mass molecular weight of the silicone gum is generally greater than about 200,000, typically from about 200,000 to about 1,000,000. Specific examples are polydimethylsiloxane, poly (dimethylsiloxane) (methylvinylsiloxane) copolymer, poly (dimethylsiloxane) (diphenylsiloxane) (methylvinylsiloxane) copolymer, and mixtures thereof.

A silicone resin, which is a highly crosslinked polymeric siloxane system, may also be employed. During the production of silicone resins, trifunctional and tetrafunctional silanes with monofunctional or difunctional groups or both are added to introduce crosslinking. As is well known in the art, the degree of crosslinking required to form a silicone resin can vary depending on the particular silane units incorporated into the silicone resin. In general, silicone materials having sufficient trifunctional and tetrafunctional siloxane monomer units, and thus sufficient crosslinking, such that they dry into a rigid or hard film, are contemplated for use as the silicone resin. The ratio of oxygen atoms to silicon atoms indicates the level of crosslinking in a particular silicone material. Silicone materials having a ratio of oxygen atoms to silicon atoms of at least about 1.1 will generally be silicone resins of the present invention. Preferably, the ratio of oxygen atoms to silicon atoms is at least about 1.2: 1.0. Silanes used in the production of silicone resins include monomethyl, dimethyl, trimethyl, monophenyl, diphenyl, methylphenyl, monovinyl and methylvinyl chlorosilanes, and tetrachlorosilane, with methyl substituted silanes being most commonly employed. Preferred resins are supplied by General Electric as GE SS4230 and SS 4267. Commercially available silicone resins are typically low viscosity volatile or nonvolatile silicone fluids supplied in dissolved form. The silicone resin used in the present invention should be provided and incorporated into the compositions of the present invention in such dissolved form, as will be clear to those of ordinary skill in the art. Without being limited by theory, it is believed that the silicone resin enhances the deposition of other silicone polymers onto the hair and can improve the shine of the hair by using high refractive index silicones.

Other useful silicone resins are silicone resin powders, such as the CTFA material known under the name polymethylsilsesquioxane, Tospearl available from Toshiba Silicones^TM。

Methods for producing these siloxane polymers can be found in "encyclopedia of Polymer science and engineering" (fifteenth volume, second edition, p. 204-308, John Wiley&Sons, Inc., 1989), which is incorporated herein by reference.

Silicone materials, particularly silicone resins, are conveniently identified according to a convenient nomenclature system known to those skilled in the art as the "MDTQ" nomenclature. In this system, the siloxane is described in terms of the various siloxane monomer units present to make up the siloxane. In short, the symbol M represents a monofunctional unit (CH)₃)₃SiO_0．5(ii) a D represents a difunctional unit (CH)₃)₂SiO; t represents a trifunctional unit (CH)₃)SiO_1．5(ii) a Q represents a tetrafunctional unit SiO₂. The prime symbols of the unit symbols such as M ', D', T ', Q' represent substituents other than methyl, which are specifically defined at each occurrence. Typical alternativesAlternative substituents include, for example, vinyl, phenyl, amino, hydroxy, and the like. In the MDTQ system, the molar ratios of the various units, either in subscripts to the symbols indicating the total number (or average) of each type of unit in the siloxane, or in specific ratios and combinations of molecular weights, can complete the description of the siloxane material. In silicone resins, T, Q, T 'and/or Q' are present in relatively higher molar amounts than D, D ', M and/or M', indicating a high degree of crosslinking. However, as previously discussed, the overall level of crosslinking may also be expressedby the ratio of oxygen to silicon.

Preferred silicone resins of the present invention are MQ, MT, MTQ, MDT and MDTQ resins. Thus, the preferred siloxane substituent is methyl. MQ resins are particularly preferred, wherein the M: Q ratio is from about 0.5: 1.0 to 1.5: 1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.

Particularly suitable silicone compounds herein are nonvolatile silicone oils having a molecular weight of from about 200000 to about 600000, such as Dimethicone and Dimethiconol. These silicone compounds may be introduced into the composition in the form of a silicone oil solution; silicone oils are volatile or nonvolatile.

Commercially available silicone compounds useful herein include Dimethicone commercially available from Dow Corning Corporation under the trade designation DC345, Dimethicone colloidal solutions commercially available from General Electric under the trade designations SE30, SE33, SE54 and SE76, Dimethicone commercially available from Dow Corning Corporation under the trade designations DCQ 2-1403 and DCQ 2-1401, and emulsion polymerized Dimethicone commercially available from Toshiba as described in GB application 2303857.

Cationic compounds

The cationic compound used in the present invention includes a cationic polymer and a cationic surfactant. Preferably, the cationic compound has no fluorescent properties and is present in an amount of from about 0.01% to about 20%.

Cationic polymers

The term "polymer" as used herein includes materials whether polymerized from one type of monomer or two (i.e., copolymers) or more types of monomers.

Preferably, the cationic polymer is a water-soluble cationic polymer. By "water-soluble" cationic polymer is meanta polymer having sufficient solubility in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water (distilled or equivalent) at 25 ℃. The preferred polymer should dissolve sufficiently to form a substantially clear solution at a concentration of 0.5%, more preferably 1.0%.

The cationic polymers of the present invention generally have a weight average molecular weight of at least about 5,000, typically at least about 10,000, and less than about 10,000,000. The molecular weight is preferably from about 100,000 to about 2,000,000. Cationic polymers typically have cationic nitrogen-containing moieties, such as quaternary ammonium or cationic amino moieties and mixtures thereof.

The cationic charge density is preferably at least about 0.1 meq/g, more preferably at least about 1.5 meq/g, preferably at least about 1.1 meq/g, more preferably at least about 1.2 meq/g. The cationic charge density of the cationic polymer can be measured according to the Kjeldahl method. It will be appreciated by those skilled in the art that the charge density of the amino-containing polymer will vary depending on the pH and the isoelectric point of the amino groups. The charge density should meet the above range at the intended pH of use.

Any anionic counterion can be used in the cationic polymer, provided that the water solubility criteria is met. Suitable counterions include halide (e.g. chloride, bromide, iodide or fluoride, preferably chloride, bromide or iodide), sulfate and methylsulfate. Other ions may be used, and the above list of ions is non-exclusive.

The cationic nitrogen-containing moiety is typically present as a substituent on a portion of the total monomer units of the cationic hair conditioning polymer. Thus, cationic polymers include copolymers, terpolymers, etc. of quaternary ammonium or cationic amine substituted monomer units as well as other non-cationic units referred to herein as spacer monomer units. Such polymers are well known in the art and are described in the following references: CTFA Cosmetic ingredient dictionary (Cosmetic ingredient dictionary), 3 rd edition, edited by Estrin, cross and Haynes, (The Cosmetic, Toiletry, and france association, inc., Washington, d.c., 1982).

Examples of suitable cationic polymers include: copolymers of vinyl monomers having cationic amine or quaternary ammonium functionality with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone or vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C₁－C₇Alkyl radical, more preferably C₁－C₃An alkyl group. Other suitable spacer monomers include vinyl esters, vinyl alcohol (prepared by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol.

The cationic amine can be a primary, secondary, or tertiary amine, depending on the particular material and pH of the composition. In general, it is preferred to employ secondary and tertiary amines, especially tertiary amines.

Amine-substituted vinyl monomers can be polymerized in the amine form and then selectively converted to ammonium by quaternization. The amines may also be similarly quaternized subsequent to formation of the polymer. For example, the tertiary amine functionality may be quaternized by reaction with a salt of the formula R 'X, wherein R' is a short chain alkyl group, preferably C₁－C₇Alkyl, more preferably C₁－C₃Alkyl, X is an anion which forms a water-soluble salt with the quaternized ammonium.

Suitable cationic amino and quaternary ammonium monomers include: vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings, e.g. pyridinium, imidazolium, and quaternized pyrrolidone, e.g. alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidoneA radical pyrrolidone salt. The alkyl portion of these monomers is preferably lower alkyl, such as C₁－C₃Alkyl, more preferably C₁And C₂An alkyl group. Suitable amine-substituted vinyl monomers for use in the present invention include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides, and dialkylaminoalkyl methacrylamides. Among them, the alkyl group is preferably C₁－C₇Hydrocarbyl, more preferably C₁－C₃An alkyl group.

The cationic polymers of the present invention may comprise a mixture of monomer units derived from amine and/or quaternary ammonium substituted monomers and/or compatible spacer monomers.

Examples of suitable cationic polymers include: copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salts (e.g., chloride salts) (also known in the industry as polyquaternium-16 by "CTFA"), such as those commercially available from BASF Wyandotte Corp. (Parsippany, New Jersey, u.s.a.) under the trade name LUVIQUAT (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (also known in the industry as "CTFA" as polyquaternium-11), such as that commercially available from Gaf Corporation (Wayne, NJ, U.S. A.) under the trade name GAFQUAT (e.g., GAFQUAT 755N); cationic diallyl quaternary ammonium-containing polymers, including, for example: homopolymers of dimethyldiallylammonium chloride and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry as Polyquaternium-6 and Polyquaternium-7, respectively, by "CTFA"; and inorganic acid salts of amino-alkyl esters of homo-and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms as described in US patent 4,009,256, which is also incorporated herein by reference.

Other cationic polymers that may be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives.

Suitable cationic polysaccharide polymers include those having the formula:

wherein A is an anhydroglucose residue, such as a starch or cellulose anhydroglucose residue; r is an alkyleneoxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or a combination thereof; r¹、R²And R³Independently of each other, alkyl, aryl, alkaryl, aralkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, the total number of carbon atoms per cationic moiety (i.e., R)¹、R²And R³Total number of carbon atoms in) is preferably about 20 or less; x is an anionic counterion as previously described.

Preferred cationic cellulose polymers are those available from Amerchol Corp, (Edison, NJ, USA) as their Polymer JR-and LR-series polymers, such as salts reacted with epoxides substituted with trimethylammonium, also known in the industry as "CTFA" as Polyquaternium-10. Another type of preferred cationic cellulose comprises the polymeric quaternary ammonium salts of hydroxyethyl fibers reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry as Polyquaternium-24 by "CTFA". These materials are commercially available from Amerchol Corp (Edison, NJ, USA) under the trade name Polymer LM-200.

Other cationic polymers that may be used include cationic guar derivatives such as hydroxypropyl trimethyl ammonium chloride guar (guar), commercially available as the Jaguar R series from Celanese Corporation. Other materials include quaternary nitrogen-containing celloethers (as described in U.S. patent 3,962,418, which is incorporated herein by reference) and etherified cellulose and starch (as described in U.S. patent 3,958,581, which is incorporated herein by reference).

Cationic surfactant

The cationic surfactants employed in the present invention are well known to those skilled in the art.

The cationic surfactants useful in the present invention are those having the following formula (I):

wherein at least R¹、R²、R³And R⁴One of which is selected from an aliphatic group having from 8 to about 30 carbon atoms or an aryl group having up to about 22 carbon atoms, an alkoxy group, a polyoxyalkylene group, an alkylamido group, a hydroxyalkyl group, an aryl group or an alkaryl group; the rest of R¹、R²、R³And R⁴Independently of one another, from an aliphatic group having from 1 to about 22 carbon atoms or an aryl group having up to about 22 carbon atoms, an alkoxy group, a polyoxyalkylene group, an alkylamido group, a hydroxyalkyl group, an aryl group or an alkylaryl group; x is a salt-forming anion, such as selected from: halide (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkylsulfonate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The long chain aliphatic group, such as a group of about 12 carbon atoms or more, may be a saturated group or an unsaturated group. Preferably R¹、R²、R³And R⁴Independently selected from C₁－C₂₂An alkyl group. Non-limiting examples of cationic surfactants useful in the present invention include those having the following CTFA designation: quaternium-8, quaternium-24, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-43, quaternium-52, quaternium-53, quaternium-56, quaternium-60, quaternium-62, quaternium-70, quaternium-72, quaternium-75, quaternium-77, quaternium-78, quaternium-80, quaternium-81, quaternium-82, quaternium-83, quaternium-84, and mixtures thereof.

Another preferred class of cationic surfactants are hydrophilically substituted cationic surfactants, whichWherein at least one of the substituents contains one or more aromatic, ether, ester, amide or amino moieties, present as a substituent or as a bond in a free radical chain, wherein at least R¹－R⁴One of the radicals comprising one or more hydrophilic moieties selected from alkoxy (preferablyC selection₁－C₃Alkoxy), polyoxyalkylene (preferably C)₁－C₃Polyoxyalkylene), alkylamido, hydroxyalkyl, alkyl ester, and mixtures thereof. Preferably, the hydrophilically substituted cationic conditioning surfactant comprises from 2 to about 10 nonionic hydrophilic moieties within the above ranges. Preferred hydrophilically substituted cationic surfactants comprise the following surfactants of formula (II) to formula (VII):

wherein n is 8 to about 28, x + y is 2 to about 40, Z¹Is a short-chain alkyl radical, preferably C₁－C₃Alkyl, more preferably methyl, or- (CH)₂CH₂O)_zH, wherein X + y + z is at most 60 and X is a salt-forming anion as defined above;

wherein m is 1-5, R⁵、R⁶And R⁷Is independently C₁－C₃₀An alkyl group; the balance being-CH₂CH₂OH，R⁸And R⁹One or two of them and R¹⁰Independently is C₁－C₃₀Alkyl radical, the remainder being-CH₂CH₂OH, X is a salt-forming anion as defined above;

wherein Z is²Is alkyl, preferably C₁－C₃Alkyl, more preferably methyl; z³Is a short chain hydroxyalkyl group, preferably hydroxymethyl or hydroxyethyl; p and q are independently integers from 2 to 4 (including 2 and 4), preferably from 2 to 3 (including 2 and 3), more preferably 2; r¹¹And R¹²Independently a substituted or unsubstituted hydrocarbyl group, preferably C₁₂－C₂₀Alkyl or alkenyl, X is a salt-forming anion as described above;

wherein R is¹³Is a hydrocarbon radical, preferably C₁－C₃Alkyl, more preferably methyl; z⁴And Z⁵Independently a short chain hydrocarbyl group, preferably C₂－C₄Alkyl or alkenyl, more preferably ethyl; a is from 2 to about 40, preferably from about 7 to about 30, and X is a salt-forming anion as described above;

wherein R is¹⁴And R¹⁵Independently is C₁－C₃Alkyl, preferably methyl; z⁶Is C₁₂－C₂₂A hydrocarbyl, alkylcarboxyl or alkylamido group; a is a protein, preferably collagen, keratin, milk protein, silk protein (silk), soy protein, wheat protein or hydrolysed forms thereof; x is a salt-forming anion as described above;

wherein b is 2 or 3, R¹⁶And R¹⁷Independently is C₁－C₃A hydrocarbyl group, preferably methyl; x is a salt-forming anion as described above. Non-limiting examples of hydrophilically substituted cationic surfactants useful in the present invention include those having the following CTFA designation: quaternium-16, quaternium-61, quaternium-71, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk protein, quaternium-79 hydrolyzed soy protein, quaternium-79 hydrolyzed wheat protein. Particularly preferred compounds comprise the following commercially available materials: VARIQUAT K1215 and 638 (available from Witco Chemical); MACKPRO KLP, MACKPRO WLW, MACKPRO MLP, MACKPRO NSP, MACKPRONLW, MACKPRO WWP, MACKPRO NLP, MACKPRO SLP (available from Mclntyre); ETHOQUAD 18/25, ETHOQUAD O/12 PG, ETHOQUADC/25, ETHOQUAD S/25, and ETHODUOQUAD (available from Akzo); DEHYQUATSP (available from Henkel) and ATLAS G265 (available from ICI Americas).

Salts of primary, secondary and tertiary fatty amines are also suitable as cationic surfactants. The alkyl group of such amines preferably has from about 12 to about 22 carbon atoms, and it may be a substituted or unsubstituted group. Particularly useful are amido-substituted tertiary fatty amines. Such amines useful in the present invention include stearamidopropyl dimethylamine, stearamidopropyl diethylamine, stearamidoethyl dimethylamine, palmitamidopropyl diethylamine, palmitamidoethyl dimethylamine, behenamidopropyl diethylamine, behenamidoethyl dimethylamine, arachidopropyl diethylamine, arachidoethyl dimethylamine, diethylaminoethyl stearate. Dimethyl stearyl amine, dimethyl soyamine (soy amine), soyamine, myristyl amine, tridecyl amine, ethyl stearyl amine, N-tallow propane diamine, ethoxylated (with 5 moles of ethylene oxide) stearyl amine, dihydroxyethyl stearyl amine, and eicosyl docosyl amine may also be employed. These amines can also be used in combination with acids such as: l-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L-glutamic acid hydrochloride, and mixtures thereof; more preferred are L-glutamic acid, lactic acid and citric acid. Cationic amine surfactants useful in the present invention are disclosed in US4, 275, 055 (entitled Nachtigal et al, 6/23 1981), which is incorporated herein by reference.

The cationic surfactants useful in the present invention may also include a plurality of quaternary ammonium moieties or amino moieties, or mixtures thereof.

High melting point compound

The compositions of the present invention may comprise a high melting point compound having a melting point of at least about 25 ℃ selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, hydrocarbons, steroids, and mixtures thereof. While not being bound by any theory, it is believed that these high melting compounds can cover the surface of the hair and reduce friction, thereby providing the hair with a smooth hair feel and ease of combing. It will be appreciated by those skilled in the art that the compounds described in this section of the present specification may be classified in a variety of ways at certain times, for example, certain fatty alcohol derivatives may also be classified as fatty acid derivatives. However, the given classification is not intended to be a limitation on that particular compound, but is merely for convenience of classification and nomenclature. Further, it will be understood by those skilled in the art that certain compounds having certain desired numbers of carbon atoms may have melting points below about 25 ℃ depending on the number and position of double bonds, the length and position of the branches. These low melting compounds are not included in this section. Non-limiting examples of high melting point compounds are described in the following references: international Cosmetic Ingredient Dictionary, 5 th edition, 1993, and CTFA Cosmetic Ingredient Handbook, 2 nd edition, 1992, both of which are incorporated herein by reference.

The fatty alcohols useful herein are those having from about 14 to about 30 carbon atoms, preferably from about 16 to about 22 carbon atoms. These fatty alcohols may be straight or branched chain alcohols, and may be saturated or unsaturated alcohols. Non-limiting examples of fatty alcohols include: cetyl alcohol, stearyl alcohol, behenyl alcohol and mixtures thereof.

The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms. These fatty acids may be straight or branched chain acids, and may be saturated or unsaturated. Dibasic acids, tribasic acids, and other polybasic acids meeting the carbon number requirements of the present invention may also be included. The invention also includes salts of these fatty acids. Non-limiting examples of fatty acids include: lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof.

The fatty alcohol derivatives and fatty acid derivatives of the present invention include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds having esterifiable hydroxyl groups, hydroxyl-substituted fatty acids, and mixtures thereof. Non-limiting examples of fatty alcohol derivatives and fatty acid derivatives include: materials such as methyl stearyl ether; the ceteth series of compounds, such as ceteth-1 to ceteth-45, are glycol ethers of cetyl alcohol in which the numbers indicate the number of glycol moieties present; the octadecyl polyoxyethylene ether (steareth) series of compounds, such as steareth-1 to steareth-10, are glycol ethers of stearyl alcohol, wherein the numbers indicate the number of glycol moieties present; cetyl and stearyl polyoxyethylene ether (ceteareth) series of compounds, such as ceteareth-1 to ceteareth-10, which are glycol ethers comprising predominantly a mixture of fatty alcohols of cetyl and stearyl alcohols, wherein the numbers indicate the number of glycol moieties present; C1-C30 alkyl ethers of the previously described ceteth, steareth, ceteareth compounds; polyoxyethylene ethers of behenyl alcohol; ethyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethylene glycol monostearate, polyoxyethylene distearate, propylene glycol monostearate, propylene glycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, and mixtures thereof.

Hydrocarbons useful herein include compounds having at least about 20 carbon atoms.

Steroids useful in the present invention include compounds such as cholesterol.

High melting point compounds of a single compound of high purity are preferably employed. Particular preference is given to a single compound of pure fatty alcohol, selected from pure cetyl alcohol, stearyl alcohol and behenyl alcohol. By "pure" in the context of the present invention is meant that the compound is at least about 90% pure, preferably at least about 95% pure. These single compounds of high purity provide excellent rinsing ability from the hair when the consumer rinses the composition.

Commercially available high melting point compounds useful in the present invention include: cetyl alcohol, stearyl alcohol, and behenyl alcohol, available under the KONOL series from New Japan Chemical (Osaka, Japan); NAA series, commercially available from NOF (Tokyo, Japan); pure behenyl alcohol, trade name 1-DOCOSANOL, commercially available from WAKO (Osaka, Japan), various fatty acids, trade name NEO-FAT, commercially available from Akzo (Chicago Illinois, USA), HYSTRENE, commercially available from Witco Corp. (Dublin Ohio, USA), and DERMA, commercially available from Vevy (Genova, Italy); and cholesterol, available under the tradename NIKKOL agauasome LA, commercially available from Nikko. Preferably, the high melting point compound is present in the hair care compositions of the present invention in an amount of from about 0.01% to about 20%.

Fragrance compound

Perfume compounds are often a desirable ingredient in hair care compositions because they mask the unpleasant odor of other ingredients in the hair care composition and also provide a pleasing aesthetic perfume. The perfume compounds of the present invention can also provide conditioning benefits.

Various perfumes are known to those of ordinary skill in the art and are commercially available. The use of specific fragrances is a matter of choice. However, the amount of perfume used should be an amount effective to impart a perceivable fragrance to the composition or to mask an unpleasant odor of the composition.

Typically, the composition will contain a fragrance compound of carbonyl, ether or hydroxyl functionality or mixtures thereof in an amount of from about 0.01% to about 10%, preferably from about 0.05% to about 7%, more preferably from about 0.05% to about 3%. As used herein, a fragrance compound refers to a fragrance active ingredient, and "fragrance" or "fragrance ingredient" includes all fragrance compounds and any fragrance solvents associated therewith.

Fragrances can be made by those of ordinary skill in the art in a variety of flavors and intensities. Typical fragrances are available in Arctander Perfume and Flavour Chemicals (Aroma Chemicals), vols. i and ii (1969); and Arctander, Perfune and Flavour Materials of Natural Origin (1960).

The carbonyl-containing perfume compound comprises a functional group selected from the group consisting of: aldehydes, ketones, esters, carboxyl groups and mixtures thereof. These substances may be aliphatic (saturated or unsaturated), aromatic, heterocyclic or alicyclic. Typically they have from about 6 to about 18 carbon atoms.

Non-limiting examples of aliphatic aldehyde flavor compounds for use in the present invention include hexanal, heptanal, octanal, decanal, undecanal, undecyinic aldehyde, laurnal, methylnonyl (monol) acetaldehyde, myristyl aldehyde, and nonanal. Aromatic aldehydes include cinnamaldehyde such as amyl cinnamaldehyde and hexyl cinnamaldehyde, anisaldehyde, heliotropin, benzaldehyde, and vanillin. Heterocyclic aldehydes include piperonal and furan.

Non-limiting examples of fatty ketone fragrance compounds for use in the present invention include hexanone, heptanone, octanone, ionone, undecanolactone, nonanoate lactone (γ -nonyl lactone), camphor, α -methylindadone, (γ -undecyl lactone) γ -methylindadone, and β -methylnaphthyl ketone alicyclic ketones include β -naphthylmethyl ketone, p-hydroxyphenylbutazone, levo-carvone, and musk ketone heterocyclic ketones include thujonone, cedrenone, and cyclopentadecanolide.

Non-limiting examples of fatty ester fragrance compounds for use in thepresent invention are acetates, butyrates and formates, such as ethyl butyrate, ethyl formate, butyl acetate, isopropyl butyrate, ethyl formate, cis-3-hexenyl acetate, ethyl acetoacetate and phenyl ethyl acetate, carbonates such as methyl octene carbonate (octine) and phthalates such as diethyl phthalate. Heterocyclic esters include cedryl formate and cedryl acetate. Aromatic esters include benzyl acetate, benzyl salicylate, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, and methyl anthranilate. Other esters include cycloaliphatic esters and aliphatic/cycloaliphatic esters, such as 4-tert-butylcyclohexyl acetate. Ester flavors also include materials derived from flowers and fruits, as well as materials from animal flavors (e.g., natural isolates of civets, beavers, and musk deer).

Non-limiting examples of ether fragrance compounds useful in the present invention include ambrox, galaxolide, and rose oxide.

Non-limiting examples of the hydroxy perfume compound used in the present invention include 1-decanol, 1-nonanol, 1-octen-3-ol, 1-terpineol (β), 1-undecanol, 2, 4-decadien-1-ol, 2, 4-octadien-1-ol, 2, 6-dimethyl-6-hepten-1-ol, 2-hexen-1-ol, 2-octen-1-ol, 3, 7, 9-trimethyl-1, 6-decadien-3-ol, 3, 7-dimethyl-7-methoxyoct-2-ol, 3, 7-dimethyl-oct-1-ol, 3-methyl-oct-3-ol, 3-octanol, 9-decen-1-ol, α -terpineol, benzyl alcohol, (+) -cedrol, cinnamyl alcohol, cis-3-hexen-1-ol, citronellol, dihydrolinalool, dihydromyrcenol, dihydroterpineol, dimethylbenzyl alcohol, di-ethyl-1-enol, linalool type (3, linalool type), linalool type 3-3, linalool type 3-ethyl-7-1-2-ethyl-2-ethyl alcohol, linalool type, linaloo.

Non-limiting examples of ether fragrance compounds with hydroxyl groups for use in the present invention include 2-phenoxyethanol, carbitol (diethylene glycol monoethyl ether), dipropylene glycol, and triethyl citrate.

Non-limiting examples of ether fragrance compounds with a carbonyl group for use in the present invention include 2-phenoxyethyl-iso-butyrate, allylcyclohexanepropionate, allylphenoxyacetate, benzylacetate, benzylbutyrate, benzylcinnamate, benzylsalicylate, cinnamate, cis-3-hexenylacetate, cis-3-hexenylbutyrate, cis-3-hexenylsalicylate, citronellol acetate, citronellol formate, citronellol propionate, dimethylbenzylcarbyl (carbinyl) -isobutyrate, ethyl acetate, ethyl butyrate, ethyl octanoate, ethyl decanoate, ethyl-2-methylbutyrate, ethyl brassylate, cyclopentadecanolide, floretate, gamma-decanolactone, gamma-dodecanolactone, gamma-nonanolactone, gamma-undecanolactone, geranylacetate, Geranyl formate, helional, heliotropin, hexyl acetate, hexyl salicylate, isoamyl acetate, isoamyl salicylate, isopropyl myristate, linalyl acetate, menthyl acetate, methyl anthranilate, methyl benzoate, methylphenylcarbyl acetate, neryl acetate, phenylethyl acetate, isoamyl acetate, and trichloromethylphenylcarbyl acetate.

In addition, certain perfume compounds may be in one or more of these categories. As one of ordinary skill in the art will appreciate, the nomenclature for particular compounds does not affect their applicability in the present invention.

Perfume solvents are known in the art and conventional solvents such as dipropylene glycol, diethylene glycol, C may be used herein₁－C₆Alcohols, and the like.

The hydrophilicity of these raw perfume materials (herein referred to as PRMs) can be characterized by their octanol/water partition coefficient P. The octanol/water partition coefficient of an organic compound is the ratio of its equilibrium concentration in octanol and in water. Since the partition coefficients of organic compounds are generally large, they are more conveniently given in their logarithmic form with a base 10, logP.

logP has been reported for a number of compounds; such as the Pomona92 database, available from dailyght chemical Information Systems, Inc (dailyght CIS), contains a number of documents, as well as the original documents to which they are cited.

However, the most convenient way to calculate the logP value is to use the "CLOGP" program, also available from dayright CIS. The program lists empirical logP values when these values are available in the Pomona92 database. "calculated logP values" (CLOGP) were determined according to the fragment approach of Hansch and Leo (A.Leo, Comprehensive Medical Chemistry, Vol.4; C.Hansch, P.G.Sammens, J.B.Tayor and C.A.Ramden, eds., p295, Pergamon Press, 1990). The basis of the fragmentation method is the chemical structure of the compound, and the number and type of atoms, atomic connections, and chemical connections are considered. ClogP values are the most reliable and most widely used values to assess this physicochemical property and can be used in the selection of perfume compounds instead of experimental logP values. Preferably the perfume compounds of the present invention have a ClogP value between-1.0 and 8.0.

Without being bound by theory, it is believed that the addition of perfume compounds to the compositions of the present invention affects the stability of the compositions including tack and phase separation, as well as conditioning performance.

For shampoo compositions, the viscosity increase of the composition can be observed by the addition of PRMs. It is believed that the viscosity increase is due to dissolution of the PRMs into the lattice-like layer between the hydrocarbon core and the micelle surface. These molecules stretch in the regions between the surface molecules in the micelle, and the micelle size increases. The enlarged micelles increase the interaction between the micelles, such as entanglement of the cylindrical micelles, with the result that the volume proportion occupied by the micelles is increased.

Water-insoluble high molecular weight oily compound

The water-insoluble high molecular weight oily compounds of the present invention are those which provide excellent conditioning benefits such as smoothing hair and ease of combing. Without being bound by theory, it is believed that the water-insoluble high molecular weight oily compounds of the present invention are capable of depositing on and conditioning the hair. It is also believed that this water-insoluble high molecular weight oily compound coats the hair surface, resulting in reduced hair friction and smoothness. The water-insoluble high molecular weight oily compound is chemically stable under normal use and storage conditions.

The term "water-insoluble oily compound" as used herein refers to a compound that is not sufficiently soluble in water at room temperature. When these compounds are miscible with water at concentrations above 1.0%, preferably above 0.5%, the compounds disperse temporarily, form unstable colloids in water and then separate rapidly from the water in a very short time to form two phases.

The water-insoluble high molecular weight oily compound used in the present invention has a molecular weight of at least about 800, preferably at least about 1000, more preferably at least about 1200, as long as the specific gravity of such compound is at least about 0.9 and is in liquid form at 25 ℃.

The water-insoluble high-molecular weight oily compound used in the present invention includes those represented by the following formula (1):

wherein A is¹、A²、A³And A⁴Each independently of the others being an alkyl, alkenyl, aryl, alkylaryl, hydroxyalkyl, alkoxy, alkoxyalkyl, acyl, acylalkyl and alkanoyloxy group having from 1 to 30 carbon atoms or- (CH)₂) n-O-OCR, wherein R is C₁To about C₃₀N is an integer from 1 to about 30, preferably equal to 1.

Preferably, the water-insoluble high molecular weight oily compound of the present invention is wherein A¹、A²、A³And A⁴Are all ester groups or A¹、A²、A³And A⁴Three of which are ester groups and the remainder are esters of alkyl groups. More preferably, the water-insoluble high molecular weight oily compound of the present invention has about C₁₂To about C₂₂With pentaerythritol, having about C₁₂To about C₂₂Esters of fatty acids with trimethylolalkane, and mixtures thereof.

A preferred water-insoluble high molecular weight oily compound is A¹、A²、A³And A⁴Those having the same substituents and these substituents being ester groups.

Preferred water-insoluble high molecular weight oily compounds of the present invention are pentaerythritol tetraisostearate, trimethylolpropane triisostearate, pentaerythritol tetraoleate, trimethylolpropane trioleate and mixtures thereof.

Suitable ester compounds include, for example, pentaerythritol tetraisostearate and trimethylolpropane triisostearate available from Kokyo Alcohol under the trade names KAKPTI and KAKTTI, and pentaerythritol tetraoleate and trimethylolpropane trioleate available from ShinnihonRika under the trade names PTO and ENUJERUBU series, respectively.

The water-insoluble high molecular weight oily compound is used in an amount of from about 0.1% to about 20.0%, preferably from about 0.1% to about 10.0%, more preferably from about 0.2% to about 5.0% by weight of the composition.

Detersive surfactant

The compositions of the present invention may comprise a detersive surfactant. The detersive surfactants of the present invention are those suitable for cleansing hair. Detersive surfactants useful herein include anionic surfactants, amphoteric and zwitterionic surfactants, and nonionic surfactants.

When a detersive surfactant is employed, it is preferably present in an amount of from about 0.01 to about 75% by weight, based on the weight of the composition. Two or more surfactants may be used.

Anionic surfactants

Anionic surfactants useful in the present invention include alkyl and alkyl ether sulfates. These have the respective general formula ROSO₃M and RO (C)₂H₄O)_xSO₃M, wherein R is an alkyl or alkenyl group having from about 8 to about 30 carbon atoms, X is an integer from 1 to 10, and M is hydrogen or a cation such as ammonium, alkanolammonium (e.g., triethanolammonium), monovalent metal cations (e.g., sodium and potassium), or polyvalent metal cations (e.g., magnesium and calcium). The cation M should be selected so that the anionic surfactant component is water soluble. The anionic surfactant should be selected to have a Krafft temperature of about 15 ℃ or less, preferably about 10 ℃ or less, more preferably about 0 ℃ or less. It is also preferred that anionic surfactant is dissolved in the composition.

The Krafft temperature refers to the temperature at which the solubility of the ionic surfactant becomes determined by the lattice energy and the heat of hydration, and corresponds to the temperature at which the solubility increases sharply and discontinuously with increasing temperature. Each type of surfactant will have its own characteristic kraft temperature. The Krafft temperature of ionic surfactants is generally known and understood in the art. See, for example, the following documents: myers, Drew, surfactant science and technology, pp.82-85, VCH Publishers, Inc. (New York, USA), 1988(ISBN 0-89573-399-0), which is incorporated herein by reference.

In the above alkyl and alkyl ether sulfates, it is preferred that R in both have from about 8 to about 18 carbon atoms. Alkyl ether sulfates are generally prepared as condensation products of ethylene oxide and monohydric alcohols having from 8 to 24 carbon atoms. The alcohol may be derived from fats, such as coconut oil, palm kernel oil, tallow, etc., or it may be synthetic. Lauryl and straight chain alcohols derived from coconut or palm kernel oil are preferred. This alcohol is reacted with about 1 to 10, preferably about 3, molar proportions of ethylene oxide to form a mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per 1 mole of alcohol, and this mixture is sulfated and neutralized.

Specific examples of alkyl ether sulfates that can be used include: sodium and ammonium salts of cocoalkyltriethylene glycol ether sulfate, sodium and ammonium salts of tallow alkyltriethylene glycol ether sulfate, sodium and ammonium salts of tallow alkylhexaoxyethylene sulfate. Particularly preferred alkyl ether sulfates are mixtures of individual compounds wherein the compounds in the mixture have an average alkyl chain length of from about 8 to 16 carbon atoms and an average degree of ethoxylation of from about 1 to 4 moles of ethylene oxide. This mixture also contains 0 to 20 wt.% of C_12－13A compound; about 60 to 100 wt% of C_14－15－16A compound; 0-20 wt% of C_17－18－19A compound; about 3 to 30 weight percent of a compound having a degree of ethoxylation of 0; about 45 to 90 weight percent of a compound having a degree of ethoxylation of from 1 to 4; about 10 to 25 weight percent of a compound having a degree of ethoxylation of from about 4 to 8; and about 0.1 to 15 weight percent of a compound having a degree of ethoxylation greater than about 8.

Other suitable anionic surfactants are water-soluble salts of organic, sulfuric acid reaction products of the general formula [ R¹－SO₃－M]Wherein R is¹Is a straight or branched chain, saturated aliphatic hydrocarbon group having about 8 to 24 carbon atoms, preferably about 8 to 18 carbon atoms; m is a cation as described previously. Examples of such surfactants are the salts of the products obtained by reacting hydrocarbons of the methane series, including iso-, neo-, and n-paraffins, having from about 8 to 24 carbon atoms, preferably from about 8 to 18 carbon atoms, with organosulfuric acids of sulfonating agents, such asSuch as sulfur trioxide, sulfuric acid. Preference is given to sulfonated C₈－C₁₈Alkali metal and ammonium salts of n-paraffins.

Other suitable anionic surfactants are reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil or palm kernel oil; or sodium or potassium salts of fatty acid amides of methyl tauride, wherein the fatty acids are derived, for example, from coconut oil. Other similar anionic surfactants are described in the following patent documents: US2, 486, 921; US2, 486, 922; US2, 396, 278, all of which are incorporated herein by reference.

Another class of anionic surfactants suitable for use in shampoo compositions are the β -alkoxyalkanesulfonates, these surfactants having the formula

Wherein R is¹Is a straight chain alkyl group having about 6 to 20 carbon atoms, R²Is a lower alkyl group having from about 1 (preferred) to 3 carbon atoms, and M is a water-soluble cation as previously described. Many other anionic surfactants suitable for use in shampoo compositions are described in the following references: McCutcheon's, emulsifiers and detergents, 1989, published by m.c. publishing co; US3, 929, 678, which are incorporated herein by reference. Preferred anionic surfactants for use in the shampoo compositions include: ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine lauryl sulfate, diethanolamine lauryl sulfate, sodium laurTriethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.

Other anionic surfactants useful in the present invention include poly-hydrophilic anionic surfactants. By "hydrophilic" herein is meant that the surfactant has at least two hydrophilic groups that provide hydrophilic properties. The hydrophilic-rich surfactants used in the present invention are those compounds having at least two hydrophilic groups in the molecule, and do not include those compounds having only one hydrophilic group. One molecule of the multi-hydrophilic anionic surfactant of the present invention may comprise the same hydrophilic group or different hydrophilic groups. In particular, the polyhydrophilic anionic surfactant comprises at least one group selected from the group consisting of carboxyl, hydroxyl, sulfate, sulfonate, and phosphate.Suitable polyhydrophilic anionic surfactants are those compounds which contain at least one of a carboxyl, sulfate or sulfonate group, more preferably at least one carboxyl group.

Non-limiting examples of poly-hydrophilic anionic surfactants include: N-acyl-L-glutamates such as N-cocoyl-L-glutamate and N-lauroyl-L-glutamate, lauriminodipropionic acidSalts, N-acyl-L-aspartate, di- (N-lauroyl N-methyltaurate), polyoxyethylene lauryl sulfosuccinate, disodium N-octadecyl sulfosuccinate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N- (1, 2-dicarboxyethyl) -N-octadecyl sulfosuccinate; diamyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid and 2-cocoalkyl N-carboxyethyl N-carboxyethoxyethyl imidazolinium betaines, lauroyl amphoteric hydroxypropyl sulfonates, cocoglyceryl ether salts, cocoglyceride sulfates, lauroyl isethionates, lauroyl amphoacetates, and those of the formula:

the term "olefin sulfonate" as used herein means that the compound can be produced by sulfonating α -olefin with uncomplexed sulfur trioxide, followed by neutralizing the acidic reaction mixture under conditions such that the sulfone formed in the reaction is hydrolyzed to form the corresponding hydroxy-alkane sulfonate, the sulfur trioxide can be either a liquid or a gas, when used in liquid form, typically, but not necessarily, diluted with an inert diluent, such as liquid sulfur dioxide, chlorinated hydrocarbons, and the like, when used in gaseous form, diluted with air, nitrogen, gaseous sulfur dioxide, and the like, α -olefin used to form the olefin sulfonate is derived from a monoolefin, preferably a linear olefin, having from about 8 to 24 carbon atoms, preferably from about 10 to 16 carbon atoms, depending on the reaction conditions, the ratio of the reactants, and the properties of the linear olefin, in addition tothe true olefin sulfonate and a portion of the hydroxyalkane sulfonate, the olefin sulfonate can contain small amounts of other materials, such as olefin disulfonates, depending on the reaction conditions, the properties of the reactants, and the impurities in the 1967 and 1967 by-year processes of the olefin sulfonates, as disclosed in non-patented processes, e, by reference to the patent application, No. 5,332.

Another class of poly-hydrophilic anionic surfactants are amino acid surfactants, which have the basic chemical structure of an amino acid compound, i.e., a compound that comprises a structural component of one of the natural amino acids. It will be appreciated by those of ordinary skill in the art that certain surfactants can be considered to be either poly-hydrophilic anionic surfactants or amino acid surfactants. These surfactants are all suitable anionic surfactants.

Non-limiting examples of amino acid surfactants include N-cocoyl alanine salt, N-acyl-N-methyl- β -alanine salt, N-acyl sarcosinate, N-alkylaminopropionate and N-alkyliminodipropionate, specific examples of which include N-lauryl- β -aminopropionic acid or its salt, and N-lauryl- β -iminodipropionate, N-acyl-DL-alanine salt, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosinate, cocoyl sarcosinate, N-acyl-N-methyltaurate, lauroyl taurate and lauroyl lactate.

Suitable commercially available anionic surfactants are: N-acyl-L-glutamate with trade name AMISOFT CT-12S, sodium N-acyl glycinate with trade name AMILITE GCK-12, lauroyl glutamate with trade name amioft LS-11 and N-acyl-DL alanate with trade name AMILITE ACT12, supplied by Ajinomoto; acylaspartate, tradenames ASPARACK and AAS, supplied by Mitsubishi Chemical; acyl derivatives, trade name ED3A, supplied by Hampshire Chemical Corp.

Optionally, the counter ion of the anionic surfactant can be a multivalent cation. These anionic surfactants have been found to form coacervates in the compositions with cationic conditioning agents and polyvalent metal cations as described later. Cationic conditioning agents may be included in the compositions of the present invention to provide a single product shampoo having both cleansing and conditioning benefits.

Coacervate formation is dependent on various conditions such as molecular weight, ratio of component concentration and ionic strength of the interacting ionic components, charge density of the cationic and anionic components, pH and temperature. The coacervate system and the effects of these parameters are well known in the art.

It is believed that the presence of anionic surfactant and polyvalent metal cation at levels in the coacervate phase with the cationic conditioning agent is particularly beneficial. Coacervates formed in the composition are believed to tend to deposit on the hair upon dilution with large amounts of water, i.e., upon rinsing the shampoo.

While not being bound by any theory, it is believed that the coacervate provides two primary effects to the shampoo compositions of the invention. First, it lowers the critical micelle concentration (hereinafter "CMC") of the composition. The reduction in CMC correlates with a reduction in surface tension, thereby improving foam performance. Second, the presence of anionic surfactants with polyvalent metal cations enlarges the coacervate zone in the composition. Since the cationic conditioning agent is primarily transported through these coacervates in the composition, enlarging the area of coacervates will enable more cationic conditioning agent to be transported onto the hair. As a result, a single product form of a composition for both cleansing and conditioning hair is provided with improved overall conditioning and lather performance.

Techniques for analyzing complex coacervate formation are well known in the art. For example, microscopic analysis of the shampoo composition at any selected dilution stage can be used to identify whether a coacervate phase has formed. This coacervate phase can be identified as the other emulsified phase in the composition. The use of dyes can help to distinguish the coacervate phase from other insoluble phases dispersed in the shampoo composition.

Amphoteric and zwitterionic surfactants

Amphoteric surfactants useful in the present invention include derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be a straight or branched chain radical and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and the other contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Zwitterionic surfactants useful herein include aliphatic quaternary ammonium, quaternary phosphonium, and quaternary sulfonium compounds, in which the aliphatic radicals can be straight or branched chain radicals and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and the other contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. These compounds have the general formula:

wherein R is²An alkyl, alkenyl or hydroxyalkyl group having from about 8 to about 18 carbon atoms, containing from 0 to about 10 ethylene oxide units and from 0 to about 1 glyceryl unit; y is selected from nitrogen, phosphorus and sulfur atoms; r³Is an alkyl or monohydroxyalkyl group containing from 1 to about 3 carbon atoms; when Y is a sulfur atom, X is 1, and when Y is a nitrogen or phosphorus atom, X is 2; r⁴Is alkylene of 1 to about 4 carbon atoms orHydroxyalkylene, Z is aradical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate.

Examples of amphoteric and zwitterionic surfactants also include sulfobetaines and amidosulfobetaines. Examples of sulfobetaines, including amidosulfobetaines, are: coco dimethyl propyl sulfobetaine, stearyl dimethyl propyl sulfobetaine, lauryl bis- (2-hydroxyethyl) propyl sulfobetaine, etc.; and amidosulfobetaines, such as cocoamidodimethylpropyl sulfobetaine, stearyl amidodimethylpropyl sulfobetaine, lauryl amidobis- (2-hydroxyethyl) propyl sulfobetaine, and the like. Preferred are amidohydroxysultaines such as C₈－C₁₈Alkylamidopropyl hydroxysultaines, especially C₈－C₁₄Alkyl amidopropyl hydroxysultaines, such as lauryl amidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other sulfobetaines are described in US3, 950, 417, which is incorporated herein by reference.

Other suitable amphoteric surfactants are those of the formula R-NH (CH)₂)_nAmino alkanoate salts of COOM, formula R-N [ (CH)₂)_mCOOM]₂And mixtures thereof; wherein n and m are numbers from 1 to about 4, and R is C₈－C₂₂Alkyl or alkenyl, M is hydrogen, alkali metal, alkaline earth metal, ammonium or a chainAn alkanol ammonium.

Other suitable amphoteric surfactants include those represented by the formula:

wherein R is¹Is C₈－C₂₂Alkyl or alkenyl, preferably C₈－C₁₆；R²And R³Independently selected from hydrogen, -CH₂CO₂M、－CH₂CH₂OH、－CH₂CH₂OCH₂CH₂COOM or- (CH)₂CH₂O)_mH, wherein m is an integer from 1 to about 25, R⁴Is hydrogen, -CH₂CH₂OH or-CH₂CH₂OCH₂CH₂COOM, Z is-CO₂M or-CH₂CO₂M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as an alkali metal (e.g., lithium, sodium, potassium), an alkaline earth metal (beryllium, magnesium, calcium, strontium, barium) or ammonium. This type of surfactant is sometimes also classified as an imidazoline type amphoteric surfactant, it being understood that they are not necessarily obtained directly or indirectly via an imidazoline intermediate. Suitable such materials are commercially available under the trade name MIRANOL, and it will also be appreciated that complex mixtures of such materials may be included, for R²In the case of hydrogen, these may be present in protonated and unprotonated forms, depending on their pH. All such variations and species are meant to be encompassed by the above formula.

Examples of surfactants of the above formula are mono-and dicarboxylic acid salts. Specific examples thereof include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate), and cocoamphoacetate.

Commercially available amphoteric surfactants include those sold under the trade names: MIRANOL C2M conc.n.p., MIRANOL C2M conc.o.p., MIRANOL C2M SF, MIRANOL CM SPECIAL (MIRANOL, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo chemical group); SCHERCOTERIC MS-2 (Scher Chemicals).

Suitable betaine surfactants, i.e., zwitterionic surfactants, for use in the conditioning compositions of the present invention are those represented by the formula:

wherein R is¹Selected from COOM and CH (OH) CH₂SO₃M，R²Is lower alkyl or hydroxyalkyl; r³Is lower alkyl or hydroxyalkyl; r⁴Selected from hydrogen and lower alkyl; r⁵Is a higher alkyl or alkenyl group; y is lowerAlkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is an integer of 1 or 0; m is hydrogen or a cation as previously described, such as an alkali metal, alkaline earth metal or ammonium. The term "lower alkyl" or "hydroxyalkyl" refers to straight or branched chain saturated aliphatic and substituted hydrocarbon groups having from 1 to about 3 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or alkenyl" refers to straight or branched chain saturated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic hydrocarbon groups having from about 8 to about 20 carbon atoms, for example, lauryl, cetyl, stearyl, oleyl, and the like. It will be understood that the term "higher alkyl or alkenyl" includes mixtures of groups which may contain one or more intermediate chains such as ether or polyether chains or non-functional substituents such as hydroxyl or halogen radicals, wherein the radicals retain hydrophobic character.

Examples of the surfactant betaine of the above formula (when n is 0) used in the present invention include alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl- α -carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis- (2-hydroxyethyl) carboxymethyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl γ -carboxypropyl betaine, lauryl-bis- (2-hydroxypropyl) - α -carboxyethyl betaine, and the like.

Specific examples of amido betaines and amido sulfobetaines for use in the conditioning compositions of the present invention include amido carboxybetaines, such as cocoamidodimethylcarboxymethylbetaine, laurylamidedimethylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis- (2-hydroxyethyl) carboxymethylbetaine, cocoamido-bis- (2-hydroxyethyl) -carboxymethylbetaine, and the like. Representative of amidosulfobetaines are cocoamidodimethylsulfopropyl betaine, stearylamidogimethylsulfopropyl betaine, laurylamido-bis- (2-hydroxyethyl) -sulfopropyl betaine, and the like.

Nonionic surfactant

The compositions of the present invention may comprise a nonionic surfactant. Nonionic surfactants include those compounds produced by the condensation of hydrophilic oxyalkylene compounds with hydrophobic organic compounds, which may be aliphatic or alkyl aromatic in nature.

Non-limiting examples of preferred nonionic surfactants for use in shampoo compositions of the invention are:

(1) polyethylene oxide condensates of alkyl phenols, such as the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms and in either a straight or branched chain configuration, with ethylene oxide present in amounts of from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol;

(2) substances obtained by condensation of ethylene oxide with the product formed by the reaction of propylene oxide and ethylenediamine;

(3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms and in a linear or branched configuration with ethylene oxide, such as the cocol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of cocol, the cocol portion having from about 8 to about 14 carbon atoms;

(4) the term [ formula] ]Wherein R is¹Containing alkyl, alkenyl or monohydroxyalkyl groups having from about 8 to about 18 carbon atoms and having from 0 to about 10 ethylene oxide moieties, from 0 to about 1 glyceryl moiety, R²And R³Containing from about 1 to about 3 carbon atoms, and from 0 to about 1 hydroxyl group, such as methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl;

(5) the term [ formula] ]Wherein R comprises an alkyl, alkenyl or monohydroxyalkyl group having from about 8 to about 18 carbon atoms and has from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moietyR 'and R' comprise alkyl or monohydroxyalkyl groups of from about 1 to about 3 carbon atoms;

(6) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxyalkyl group (methyl is typically used) having from 1 to about 3 carbon atoms and also containing one long chain hydrophobic chain containing an alkyl, alkenyl, hydroxyalkyl or ketoalkyl group of from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties, from 0 to about 1 glyceryl moiety;

(7) alkyl Polysaccharide (APS) surfactants (e.g., alkyl polyglucosides), examples of which are described in US4, 565, 647, which is incorporated herein by reference; this document discloses APS surfactants having a hydrophobic group of from about 6 to about 30 carbon atoms and a polysaccharide group (e.g., a polyglucoside) as the hydrophilic group; optionally, there may be polyoxyalkylene groups linking the hydrophobic and hydrophilic groups; also, the alkyl group (i.e., hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, unsubstituted or substituted (e.g., with a hydroxyl group or a ring); preferred materials are alkyl polyglucosides, which are commercially available from Henkel, ICI Americas and Seppic; and

(8) such as RO (CH)₂CH₂)_nPolyoxyethylene alkyl ethers of H and polyethylene glycol (PEG) glycerol fatty acid esters, of formula R (O) OCH₂CH(OH)CH₂(OCH₂CH₂)_nThose of OH, wherein n is from 1 to about 200, preferably from about 20 to about 100, and R is an alkyl group having from about 8 to about 22 carbon atoms.

Carrier

The hair care compositions of the present invention may comprise a carrier. The amount and type of carrier may be selected based on compatibility with the other components and the desired characteristics of the product. For example, a high percentage of low boiling point volatile solvents and/or propellants are suitable for use in a product form that aids in staying on the hair. In another aspect, aqueous solutions of volatile and non-volatile solvents are suitable for use in product forms that aid in rinsing from the hair after washing or treatment with the product.

Carriers useful in the present invention include volatile solvents, non-volatile solvents, propellants and mixtures thereof.

Volatile solvents useful in the present invention include water, lower alkyl alcohols having 1-3 carbon atoms and hydrocarbons having about 5 to about 8 carbon atoms, with water, ethanol, isopropanol, pentane, hexane and heptane being preferred volatile solvents. Water for use in the present invention includes deionized water and water from natural sources and containing inorganic cations. Deionized water is preferably used.

The nonvolatile solvent used in the present invention includes an alkyl alcohol having a carbon number of more than 3 and a polyhydric alcohol. Polyols useful in the present invention include 1, 2-propanediol or propylene glycol, 1, 3-propanediol, hexylene glycol, glycerin, diethylene glycol, dipropylene glycol, 1, 2-butanediol, and 1, 4-butanediol.

Propellants may be used in mousse and hair spray products. When a propellant is employed in the present invention, it may be selected based on factors such as the residue of the ingredients, the packaging, and whether the product is designed for upright or inverted use.

Propellants useful in the present invention include fluorohydrocarbons such as difluoroethane 152a, commercially available from DuPont, dimethyl ether and hydrocarbons such as propane, isobutane, n-butane, mixtures of hydrocarbons such as LPG (liquid petroleum gas), carbon dioxide, nitric oxide, nitrogen and compressed air.

Additional Conditioning Agents

Additional conditioning agents for use in the present invention include oily compounds and nonionic polymers.

Oily compound

The oily compound used in the present invention has a melting point of no more than about 25 ℃ and is selected from the group consisting of a first oily compound, a second oily compound and mixtures thereof. The oily compound used in the present invention may be a volatile or nonvolatile compound. While not being bound by any theory, it is believed that the oily compound can penetrate the hair to improve the hydroxyl bonds of the hair, thereby making the hair soft and elastic. The oily compound may comprise a first oily compound or a second oily compound as described below. Preferably, a mixture of the first oily compound and the second oily compound is used. The oily compounds of this section are different from the high melting point compounds described above. Non-limiting examples of oily compounds are described in the following documents: international, Cosmetic Ingredient Dictionary, 5 th edition, 1993, and CTFA Cosmetic Ingredient Handbook, 2 nd edition, 1992, both of which are incorporated herein by reference.

A first oily compound

The fatty alcohols useful herein include those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty alcohols may be branched or straight chain alcohols and may be saturated or unsaturated alcohols, preferably unsaturated alcohols. Non-limiting examples of such compounds include oleyl alcohol, palmitoleic alcohol, isostearyl alcohol, isocetyl alcohol, undecanol, octyldodecanol, octyldecanol, octyl alcohol (octyl alcohol), octyl alcohol (caprylic alcohol), decyl alcohol, and lauryl alcohol.

Fatty acids useful herein include those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids may be branched or straight chain acids and may be saturated or unsaturated acids. Examples of suitable fatty acids include: oleic acid, linoleic acid, isostearic acid, linolenic acid, ethyl linolenic acid, arachidonic acid, and ricinoleic acid.

Examples of fatty acid derivatives and fatty alcohol derivatives defined in the present invention include: esters of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, and mixtures thereof. Non-limiting examples of fatty acid derivatives and fatty alcohol derivatives include: methyl linoleate, ethyl linoleate, isopropyl linoleate, isodecyl oleate, isopropyl oleate, ethyl oleate, octyldodecyl oleate, oleyl oleate, decyl oleate, butyl oleate, methyl oleate, octyldodecyl stearate, octyldodecyl isostearate, octyldodecyl isopalmitate, octyl isononanoate, octyl pelargonate, hexyl isostearate, isopropyl isostearate, isodecyl isononanoate, Oleth-2, pentaerythritol tetraoleate, pentaerythritol tetraisostearate, trimethylolpropane trioleate and trimethylolpropane triisostearate.

Commercially available first oily compounds useful in the present invention include: oleyl Alcohol, with the trade name UNJECOL90BHR, commercially available from New Japan Chemical, pentaerythritol tetraisostearate and trimethylolpropane triisostearate, with the trade names KAKPTI and KAKTTI, commercially available from Kokyu Alcohol (Chiba, Japan), pentaerythritol tetraoleate, with the same trade name as the compounds, commercially available from New Japan Chemical, trimethylolpropane trioleate, with the trade name ENUJERUBU TP3SO, commercially available from New Japan Chemical, various liquid esters, with the trade name schercomol series, commercially available from Scher, and hexyl isostearate, with the trade name HIS and isopropyl isostearate, with the trade name ZPIS, commercially available from Kokyu Alcohol.

A second oily Compound

The second oily compound used in the present invention is a linear, cyclic or branched hydrocarbon, which may be saturatedA hydrocarbon or unsaturated hydrocarbon, provided that its melting point does not exceed about 25 ℃. These hydrocarbons have from about 12 to about 40 carbon atoms, preferably from about 12 to about 30 carbon atoms, and more preferably from about 12 to about 22 carbon atoms. The invention also includes polymeric hydrocarbons of alkenyl monomers, such as C_2－6A polymer of an alkenyl monomer. These polymers may be linear or branched. Linear polymers generally have a relatively short chain length, with the total number of carbon atoms as previously described. Branched polymers have a significantly longer chain length. The number average molecular weight of such materials can be quite broad, but is generally up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350. Various grades of mineral oil may also be employed in the present invention. Mineral oil is a liquid mixture of various hydrocarbons obtained from petroleum. Specific examples of suitable hydrocarbon feedstocks include: paraffin oil, mineral oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene, isoeicosene, tridecane, tetradecane, polybutene, polyisobutene, and mixtures thereof. The hydrocarbons preferably used are selected from the group consisting of mineral oil, isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof.

Commercially available second oily compounds useful in the present invention include isododecane, isohexadecane and isoeicosene, under the trade names PERMETHYL 99A, PERMETHYL 101A and PERMETHYL 1082, commercially available from Presperse (South Plainfield New Jersey, USA), copolymers of isobutylene and n-butene, under the trade name INDOL H-100, commercially available from Amoco Chemicals (Chicago Illinois, USA), mineral oil, under the trade name BENOL, commercially available from Witco, isoparaffins, commercially available ISOPAR, commercially available from Exxon Chemical Co., Houston Texas, USA, α -olefin oligomers, under the trade name PURESYN6, commercially available from Mobil Chemical Co., and trimethylolpropane tricaprylate/tricarbate, commercially available MOBIL ESTER P43, commercially available from Mobil Co.

Nonionic polymers

Nonionic polymers useful in the present invention include cellulose derivatives, hydrophobically modified cellulose derivatives, ethylene oxide polymers and ethylene oxide/propylene oxide based polymers. Suitable nonionic polymers are cellulose derivatives including methylcellulose, trade name BENECEL, hydroxyethylcellulose, trade name NATROSOL, hydroxypropylcellulose, trade name KLUCEL, cetyl hydroxyethylcellulose, trade name POLYSURF67, all commercially available from Herculus. Other suitable nonionic polymers are ethylene oxide and/or propyleneoxide based polymers, commercially available from Amerchol under the trade names CARBOWAX PEGs, POLYOXWASRs and UCON FLUIDS.

Polyalkylene glycol

These compounds are particularly useful in the compositions of the present invention where it is desired to make the hair supple and moisturized. When these compounds are employed, the polyalkylene glycol is generally present in an amount of from about 0.025 to about 1.5 weight percent, preferably from about 0.05 to about 1 weight percent, more preferably from about 0.1 to about 0.5 weight percent, based on the weight of the composition.

The polyalkylene glycols are characterized by the general formula:

wherein R is selected from the group consisting of H, methyl, and mixtures thereof. When R is H, these materials are polymers of ethylene oxide, also known as polyethylene oxide, polyethylene oxide and polyethylene glycol. When R is methyl, these materials are polymers of propylene oxide, also known as polypropylene oxides, polypropylene oxides and polypropylene glycols. It will also be appreciated that when R is methyl, there are various positional isomers of the polymer formed.

In the above structures, n has an average value of from about 1500 to about 25,000, preferably from about 2500 to about 20,000, more preferably from about 3500 to about 15,000.

The polyethylene glycol polymer used in the present invention is PEG-2M, wherein R is H and n has an average value of about 2,000 (PEG-2M is also known as Polyox WSR)^_N-10, commercially available from Union Carbide, as PEG-2,000); PEG-5M wherein R is H and n has an average value of about 5,000 (PEG-5M is also known as Polyox WSR)^_N-35 and Polyox WSR^_N-80, both commercially available from Union Carbide as PEG-5,000 and polyethylene glycol 300,000); PEG-7M wherein R is H and n has an average value of about 7,000 (PEG-7M is also known as Polyox WSR)^_N-750, commercially available from Union Carbide); PEG-9M wherein R is H and n has an average value of about 9,000 (PEG 9-M, also known as PolyoxWSR)^_N-3333, commercially available from Union Carbide); and PEG-14M, wherein R is H and n has an average value of about 14,000 (PEG-14M is also known as Polyox WSR)^_N-3000, commercially available from Union carbide).

Other useful polymers include polypropylene glycol and mixed polyethylene/polypropylene glycols.

Additional Components

The compositions of the present invention may comprise various additional components, which may be selected by the skilled person depending on the characteristics of the final product. Additional ingredients include polyvalent metal cations, suspending agents, and other additional ingredients.

Polyvalent metal cation

Suitable polyvalent metal cations include divalent and trivalent metals, preferably divalent metals. Examples of metal cations include: alkaline earth metals such as magnesium, calcium, zinc and copper, trivalent metals such as aluminum and iron. Calcium and magnesium are preferred.

The polyvalent metal cation may be added in the form of an inorganic salt, an organic salt or a hydroxide. The polyvalent metal cation may also be added as a salt thereof with an anionic surfactant as described above, including the primary anionic surfactant mentioned above or the detersive surfactant mentioned below.

Preferably, the polyvalent metal cation is added in the form of an inorganic or organic salt. The inorganic salt includes: chloride, bromide, iodide, nitrate or sulfate, more preferably chloride or sulfate. The organic salts include: l-glutamate, lactate, malate, succinate, acetate, fumarate, L-glutamate hydrochloride and tartrate.

It will be clear to those skilled in the art that if anionic surfactants are used as a means of introducing polyvalent metal cations into the composition, then only a portion of the anionic surfactant is in polyvalent form and the remainder of the anionic surfactant is added in monovalent form as desired.

The hardness of the conditioning shampoo compositions can be measured by standard methods known in the art, such as by ethylenediaminetetraacetic acid (EDTA) titration. When the compositions of the present invention contain dyes or other coloring materials that interfere with the EDTA titration properties to produce a perceived color change, the hardness of the composition should be measured in the absence of the interfering dye or colorant.

Suspending agent

A preferred additional ingredient is a suspending agent, particularly for compositions containing high viscosity and/or large particle size silicone compounds. When a suspending agent is employed, the suspending agent is present in the composition in a dispersed form. Suspending agents are generally present in an amount of from about 0.1 to about 10 wt%, preferably from about 0.3 to about 5.0 wt%, based on the weight of the composition.

Preferred suspending agents include acyl derivatives, such as ethylene glycol stearate, including mono and distearate; long chain amine oxides such as alkyl (C)₁₆－C₂₂) Dimethyl amine oxides such as stearyl dimethyl amine oxide and mixtures thereof. When used in shampoo compositions, these preferred suspending agents are present in the composition in crystalline form. These suspending agents are described in U.S. 4, 741, 855.

Other suitable suspending agents include alkanolamides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably from about 16 to 18 carbon atoms, preferred examples of such suspending agents include: stearic acid monoethanolamide, coconut oil acid monoethanolamide, stearic acid diethanolamide, stearic acid monoisopropanolamide, and stearic acid monoethanolamide stearate.

Other suitable suspending agents include N, N-dihydrocarbylaminobenzoic acids and soluble salts thereof (e.g. sodium and potassium salts), especially the N, N-di (hydrogenated) C of the family₁₆、C₁₈And tallow amidobenzoic acid, which are commercially available from Stepan Company (Northfield, Illinois, USA).

Other suitable suspending agents include xanthan gum. The use of xanthan gum as a suspending agent for silicone-containing shampoo compositions is described, for example, in U.S. 4,788,006, which is incorporated herein by reference in its entirety. The combination of long chain acyl derivatives with xanthan gum may also be used as a suspending agent in shampoo compositions. Such combinations are described in U.S. 4,704,272, which is incorporated herein by reference in its entirety.

Other suitable suspending agents include carboxyvinyl polymers. Preferred among these polymers are copolymers of acrylic acid crosslinked with polyallyl sucrose as described in U.S. 2, 798, 053, which is incorporated herein by reference. Examples of such polymers include: carbomers, which are homopolymers of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose or an allyl ether of propylene. Neutralizing agents such as aminomethyl propanol, triethanolamine or sodium hydroxide may be required.

Other suitable suspending agents may be used in the compositions of the present invention, including those capable of imparting a gel-like viscosity to the composition, such as water-soluble or colloidally water-soluble polymers like cellulose ethers, such as hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, and such as guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch, and starch derivatives.

Other additional ingredients

Various other additional ingredients may be formulated in the compositions of the present invention. These ingredients include: other conditioning agents, such as hydrolyzed collagen, available under the trade name Peptein 2000, commercially available from Hormel, vitamin E, available under the trade name Emix-d, commercially available from Eisai, panthenol, commercially available from Roche, pantenyl (panthenyl) ethyl ether, commercially available from Roche, water keratin, proteins, plant extracts, and nutrients; hair styling polymers such as amphoteric styling polymers, cationic styling polymers, anionic styling polymers, nonionic styling polymers, and silicone graft copolymers; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolinyl urea; pH adjusters such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, typically such as potassium acetate and sodium chloride; colorants such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) agents such as hydrogen peroxide, perborates and persulfates; hair reducing agents such as thioglycolates; a fragrance; and chelating agents, such as disodium edetate; ultraviolet and infrared sunscreen and absorbing agents such as octyl salicylate and antidandruff agents such as zinc pyrithione. These optional ingredients are generally present in amounts of about 0.001 to 10.0 wt%, preferably about 0.01 to 5.0 wt%, respectively, based on the weight of the composition.

Examples

The following examples further describe and demonstrate embodiments within the scope of the present invention. These examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which may be variously modified without departing from the spirit and scope of the present invention. The ingredients are identified by chemical name or CTFA name or given according to the following definitions.

Preparation method

Hairsprays, mousses, emulsions and conditioners are suitably prepared by: if a polymeric material is included in the formulation, the polymer is dispersed in water at room temperature. If desired, polymers such as Carbomer and acrylate/Steareth-20 methacrylate copolymers may be neutralized after dispersion. The mixture is then heated to above 60 ℃, and if a fatty alcohol and an emulsifier are used in the formulation, the fatty alcohol and the emulsifier are added. After cooling to below 50 ℃, the remaining components were added with stirring and then cooled to about 30 ℃. If the formulation contains ethanol, ethanol is added. If it is desired to disperse these materials, a three-blade blender and mill can be used. The resulting mixture is packaged, where appropriate, into aerosol cans using a propellant.

The shampoo is suitably prepared by any conventional method known in the art. Suitable methods are as follows: the polymer and surfactant are dispersed in water to form a homogeneous mixture. Adding to the mixture other ingredients than the silicone emulsion (if such is included), fragrance and salt; the resulting mixture was stirred. If a silicone emulsion is used, the silicone emulsion is treated with Dimethicone or Dimethiconol, a minor amount of detersive surfactant and a portion of water. The resulting mixture was then cooled through a heat exchanger, and then the silicone emulsion, fragrance and salt were added. The resulting composition was poured into a bottle to obtain a hair shampoo composition.

Alternatively, water, surfactant and any other solid that requires melting are mixed at elevated temperatures, e.g., above about 70℃, to accelerate mixing into the shampoo. Additional ingredients are added to the hot premix or after it has cooled. The ingredients were thoroughly mixed at elevated temperature and then pumped through a high shear mill and then through a heat exchanger to cool to room temperature. If a silicone is used, the silicone emulsified in the concentrated surfactant at room temperature is added to the cooled mixture.

Composition comprising a metal oxide and a metal oxide

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Disodium 1, 4-bis (2-sulfostyryl) biphenyl ^*1	1．0	-	-	-	-	-
4, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) Amino-1, 3, 5-triazin-ethyl) amino]Diphenyl compound Ethylene-2, 2' -disulfonic acid^*2	-	0．8	-	-	-	-	Disodium 1, 4-bis (2-sulfostyryl) biphenyl ^*1	1．0	-	-	-	-	-
	-	0．8	-	-	-	-	4-methyl-6, 7-di-hydroxycoumarin^*3	-	-	1．0	-	-	-
4-methyl-7, 7' -dimethylaminocoumarin^*4	-	-	-	0．1	-	-	4-methyl-6, 7-di-hydroxycoumarin^*3	-	-	1．0	-	-	-
4-methyl-7, 7' -dimethylaminocoumarin^*4	-	-	-	0．1	-	-	2- (4-styryl-3-sulfophenyl) -2H-naphthalene And [1, 2-d ]]Triazole compounds	-	-	-	1．0	-	-
1- (4-Acylaminosulfonylphenyl) -3- (4-chloro) Phenyl) -2-pyrazolines^*5	-	-	-	-	0．5	-		-	-	-	1．0	-	-
	-	-	-	-	0．5	-	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-tri Oxazines^*6	-	-	-	-	-	1．0
Silicone emulsions^*15	3．0	2．0	2．0	3．0	1．6	2．0	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-tri Oxazines^*6	-	-	-	-	-	1．0
Silicone emulsions^*15	3．0	2．0	2．0	3．0	1．6	2．0	Lauryl polyoxyethylene ether-3 ammonium sulfate	21．0	12．0	12．0	15．0	10．0	10．0
Ammonium lauryl sulfate	2．0	2．0	2．0	2．0	-	-	Lauryl polyoxyethylene ether-3 ammonium sulfate	21．0	12．0	12．0	15．0	10．0	10．0
Ammonium lauryl sulfate	2．0	2．0	2．0	2．0	-	-	N-acyl-L-glutamic acid triethanolamine^*9	2．0	2．0	-	-	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	2．0	2．0	2．0	1．0	N-acyl-L-glutamic acid triethanolamine^*9	2．0	2．0	-	-	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	2．0	2．0	2．0	1．0	Cocoamidopropyl betaine^*11	2．0	4．0	4．0	4．0	2．0	2．0
Laureth-20^*12	-	0．5	-	0．5	0．5	-	Cocoamidopropyl betaine^*11	2．0	4．0	4．0	4．0	2．0	2．0
Laureth-20^*12	-	0．5	-	0．5	0．5	-	Alkyl polyglucosides^*13	1．0	-	1．0	-	-	-
Ethylene glycol distearate^*14	2．0	2．0	2．0	2．0	2．0	1．5	Alkyl polyglucosides^*13	1．0	-	1．0	-	-	-
Ethylene glycol distearate^*14	2．0	2．0	2．0	2．0	2．0	1．5	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	1．5	1．5
DMDM hydantoin	0．2	0．2	0．2	0．2	0．2	0．2	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	1．5	1．5
DMDM hydantoin	0．2	0．2	0．2	0．2	0．2	0．2	Magnesium chloride	0．5	-	0．5	-	-	-
Glycerol^*7	-	-	5．0	-	-	-	Magnesium chloride	0．5	-	0．5	-	-	-
Glycerol^*7	-	-	5．0	-	-	-	Propylene glycol^*8	1．0	3．0	-	10．0	5．0	10．0
Polyoxyethylene glycol^*16	-	0．2	-	0．1	0．5	-	Propylene glycol^*8	1．0	3．0	-	10．0	5．0	10．0
Polyoxyethylene glycol^*16	-	0．2	-	0．1	0．5	-	Hydroxyethyl cellulose^*17	0．1	-	0．1	-	-	0．5
Polyquaternium-10^*18	0．5	0．4	-	-	-	-	Hydroxyethyl cellulose^*17	0．1	-	0．1	-	-	0．5
Polyquaternium-10^*18	0．5	0．4	-	-	-	-	Monoalkyl trimethyl ammonium chloride	-	-	0．1	-	-	-
Cetyl alcohol^*19	0．2	0．1	-	0．1	0．1	-	Monoalkyl trimethyl ammonium chloride	-	-	0．1	-	-	-
Cetyl alcohol^*19	0．2	0．1	-	0．1	0．1	-	Stearyl alcohol^*20	-	-	-	0．1	0．2	-
Behenyl alcohol^*21	-	-	0．1	-	-	-	Stearyl alcohol^*20	-	-	-	0．1	0．2	-
Behenyl alcohol^*21	-	-	0．1	-	-	-	Perfume	0．5	0．5	0．5	0．5	0．5	0．5
Pentaerythritol tetraisostearate^*22	-	-	1．0	0．5	-	-	Perfume	0．5	0．5	0．5	0．5	0．5	0．5
Pentaerythritol tetraisostearate^*22	-	-	1．0	0．5	-	-	Trimethylol propane triisostearate^*23	0．5	-	-	-	0．3	-
Pentaerythritol tetraoleate	-	0．3	-	-	-	-	Trimethylol propane triisostearate^*23	0．5	-	-	-	0．3	-
Pentaerythritol tetraoleate	-	0．3	-	-	-	-	Trimethylolpropane trioleate^*24	-	-	-	-	-	0．5
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	Trimethylolpropane trioleate^*24	-	-	-	-	-	0．5
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5
Hydrolyzed collagen^*40	0．01	-	-	-	-	-	Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5	0－0．5
Hydrolyzed collagen^*40	0．01	-	-	-	-	-	Vitamin E^*41	0．01	-	-	-	-	-
Panthenol^*42	0．025	-	-	-	-	-	Vitamin E^*41	0．01	-	-	-	-	-
Panthenol^*42	0．025	-	-	-	-	-	Panthenyl ethyl ether^*43	0．225	-	-	-	-	-
Deionized water	To 100 percent						Panthenyl ethyl ether^*43	0．225	-	-	-	-	-

	Example 7	Example 8	Example 9	Example 10
	Example 7	Example 8	Example 9	Example 10	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．8	1．0	0．5	0．8
Silicone Dow Corning 200	2．0	-	-	-	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．8	1．0	0．5	0．8
Silicone Dow Corning 200	2．0	-	-	-	Silicone emulsions^*15	-	2．0	2．0	1．0
Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	15．0	10．0	Silicone emulsions^*15	-	2．0	2．0	1．0
Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	15．0	10．0	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	-	1．0	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	-	1．0	Cocoamidopropyl betaine^*11				2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	Cocoamidopropyl betaine^*11				2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5
Deionized water	An appropriate amount to 100%				Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5

	Example 11	Example 12	Example 13	Example 14	Example 15
	Example 11	Example 12	Example 13	Example 14	Example 15	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．80	-	-	0．10	-
4, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) amino- 1, 3, 5-triazin-ethyl) amino]Stilbene-2, 2' -bis Sulfonic acid^*2	-	-	-	-	0．80	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．80	-	-	0．10	-
	-	-	-	-	0．80	1- (4-Acylaminosulfonylphenyl) -3- (4-chlorophenyl) -substituted benzene 2-pyrazolines^*5	-	-	-	0．60	-
4, 4' -bis (5-methylbenzoxazol-2-yl) stilbene ^*25	-	-	0．50	-	-		-	-	-	0．60	-
4, 4' -bis (5-methylbenzoxazol-2-yl) stilbene ^*25	-	-	0．50	-	-	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	-	0．20	-	-	-
Silicone emulsions^*15	1．00	0．50	2．00	0．20	1．00	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	-	0．20	-	-	-
Silicone emulsions^*15	1．00	0．50	2．00	0．20	1．00	Cetyl alcohol^*19	2．00	0．50	0．60	0．20	0．60
Stearyl alcohol^*20	3．00	0．50	0．40	0．20	0．40	Cetyl alcohol^*19	2．00	0．50	0．60	0．20	0．60
Stearyl alcohol^*20	3．00	0．50	0．40	0．20	0．40	Behenyl alcohol^*21	-	-	-	0．20	-
Polysorbate 60^*26	1．00	-	-	-	-	Behenyl alcohol^*21	-	-	-	0．20	-
Polysorbate 60^*26	1．00	-	-	-	-	Lauryl methyl Gluceth-10 hydroxypropyl dimethyl chloride Dissolving ammonium^*27	-	1．00	-	0．50	-
Dihydrotallow amide ethyl hydroxyethyl methyl sulfate Ammonium salt^*28	-	-	0．10	-	0．10		-	1．00	-	0．50	-
	-	-	0．10	-	0．10	Citric acid^*29	0－0．2	0－0．2	0－0．2	0－0．2	-
Hydroxypropyl cellulose^*30	-	-	-	-	0．50	Citric acid^*29	0－0．2	0－0．2	0－0．2	0－0．2	-
Hydroxypropyl cellulose^*30	-	-	-	-	0．50	Polyoxyethylene glycol^*16	0．50	0．50	0．50	0．50	0．50
Aminomethylpropanol^*31	2．10	-	2．10	-	-	Polyoxyethylene glycol^*16	0．50	0．50	0．50	0．50	0．50
Aminomethylpropanol^*31	2．10	-	2．10	-	-	acrylate/Steareth-20 methacrylate co-polymer Polymer and method of producing the same^*32	1．75	-	1．75	-	-
Cetyl hydroxyethylcellulose^*33	-	0．75	-	0．75	-		1．75	-	1．75	-	-
Cetyl hydroxyethylcellulose^*33	-	0．75	-	0．75	-	Polyquaternium-10^*18	0．10	-	0．10	0．20	-
polyquaternium-7^*34	-	0．50	-	-	1．00	Polyquaternium-10^*18	0．10	-	0．10	0．20	-
polyquaternium-7^*34	-	0．50	-	-	1．00	Pentaerythritol tetraisostearate^*22	1．00	3．00	-	-	-
Trimethylolpropane trioleate^*24	-	-	0．50	-	0．10	Pentaerythritol tetraisostearate^*22	1．00	3．00	-	-	-
Trimethylolpropane trioleate^*24	-	-	0．50	-	0．10	Trimethylol propane triisostearate^*23	-	-	-	0．20	-
Preservative	0．90	0．90	0．90	0．90	-	Trimethylol propane triisostearate^*23	-	-	-	0．20	-
Preservative	0．90	0．90	0．90	0．90	-	Perfume	0．08	0．08	0．08	0．08	0．08
Glycerol^*7	-	-	5．00	-	-	Perfume	0．08	0．08	0．08	0．08	0．08
Glycerol^*7	-	-	5．00	-	-	Propylene glycol^*8	-	-	-	5．00	-
Denatured ethanol	-	-	-	-	18．98	Propylene glycol^*8	-	-	-	5．00	-
Denatured ethanol	-	-	-	-	18．98	Deionized water	An appropriate amount to 100%

	Example 16	Example 17	Example 18	Example 19
	Example 16	Example 17	Example 18	Example 19	4, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) amino-1, 3, 5-) Triazin-2-yl) amino]Stilbene-2, 2' -disulfonic acid^*2	0．80	-	-	-
4-methyl-6, 7-dihydroxycoumarin^*3	-	0．50	-	-		0．80	-	-	-
4-methyl-6, 7-dihydroxycoumarin^*3	-	0．50	-	-	4-methyl-7, 7' -dimethylaminocoumarin^*4	-	-	0．50	-
2- (4-styryl-3-sulfophenyl) -2H-naphtho [1, 2-d] Triazole compounds	-	-	-	0．40	4-methyl-7, 7' -dimethylaminocoumarin^*4	-	-	0．50	-
	-	-	-	0．40	15/85 Silicone blends^*35	-	-	-	4．20
Silicone emulsions^*15	0．20	0．50	1．00	-	15/85 Silicone blends^*35	-	-	-	4．20
Silicone emulsions^*15	0．20	0．50	1．00	-	Cetyl alcohol^*19	0．20	-	2．00	2．50
Stearyl alcohol^*20	0．20	-	-	4．50	Cetyl alcohol^*19	0．20	-	2．00	2．50
Stearyl alcohol^*20	0．20	-	-	4．50	Behenyl alcohol^*21	0．10	0．50	-	-
Stearamidopropyl dimethylamine^*36	0．20	-	-	2．00	Behenyl alcohol^*21	0．10	0．50	-	-
Stearamidopropyl dimethylamine^*36	0．20	-	-	2．00	L-glutamic acid^*37	0．08	-	-	0．64
Hydroxyethyl cellulose^*17	-	0．50	-	-	L-glutamic acid^*37	0．08	-	-	0．64
Hydroxyethyl cellulose^*17	-	0．50	-	-	Polyoxyethylene glycol^*16	0．50	0．50	0．50	0．20
Carbomer^*38	0．50	-	0．50	-	Polyoxyethylene glycol^*16	0．50	0．50	0．50	0．20
Carbomer^*38	0．50	-	0．50	-	Aminomethylpropanol^*31	0．60	-	0．60	-
Polyquaternium-10^*18	1．00	0．10	-	0．20	Aminomethylpropanol^*31	0．60	-	0．60	-
Polyquaternium-10^*18	1．00	0．10	-	0．20	Polyquaternium-7^*34	-	-	0．50	-
Pentaerythritol tetraisostearate^*22	0．10	0．10	0．20	-	Polyquaternium-7^*34	-	-	0．50	-
Pentaerythritol tetraisostearate^*22	0．10	0．10	0．20	-	Trimethylolpropane trioleate^*24	0．10	0．10	0．05	-
Trimethylol propane triisostearate^*23	-	-	-	0．25	Trimethylolpropane trioleate^*24	0．10	0．10	0．05	-
Trimethylol propane triisostearate^*23	-	-	-	0．25	Preservative	-	-	-	0．53
Perfume	0．08	0．08	0．08	0．20	Preservative	-	-	-	0．53
Perfume	0．08	0．08	0．08	0．20	Glycerol^*7	-	5．00	-	-
Propylene glycol^*8	-	-	5．00	-	Glycerol^*7	-	5．00	-	-
Propylene glycol^*8	-	-	5．00	-	Denatured ethanol	19．07	18．42	17．81	-
Deionized water	An appropriate amount to 100%				Denatured ethanol	19．07	18．42	17．81	-

	Examples 20	Examples 21	Examples 22	Examples 23	Examples 24	Examples 25
	Examples 20	Examples 21	Examples 22	Examples 23	Examples 24	Examples 25	1, 4-bis (2-sulfo) Styryl) biphenyl Disodium salt^*1	0．80	1．60	0．20	1．60	0．20	0．20
15/85 siloxane blend Mixture of^*35	-	-	-	-	4．20	4．20	1, 4-bis (2-sulfo) Styryl) biphenyl Disodium salt^*1	0．80	1．60	0．20	1．60	0．20	0．20
15/85 siloxane blend Mixture of^*35	-	-	-	-	4．20	4．20	Silicone emulsions^*15	1．00	1．00	1．00	0．50	-	-
Cetyl alcohol^*19	-	-	-	-	2．50	2．50	Silicone emulsions^*15	1．00	1．00	1．00	0．50	-	-
Cetyl alcohol^*19	-	-	-	-	2．50	2．50	Stearyl alcohol^*20	-	-	-	-	4．50	4．50
Alkyl trimethyl chloride Dissolving ammonium^*39	-	-	-	-	-	2．50	Stearyl alcohol^*20	-	-	-	-	4．50	4．50
Alkyl trimethyl chloride Dissolving ammonium^*39	-	-	-	-	-	2．50	Stearamidopropyl Dimethyl amine radical^*36	-	-	-	-	2．00	-
L-glutamic acid^*37	-	-	-	-	0．64	-	Stearamidopropyl Dimethyl amine radical^*36	-	-	-	-	2．00	-
L-glutamic acid^*37	-	-	-	-	0．64	-	Preservative	0．90	0．90	-	-	0．53	0．53
Perfume	0．08	0．08	0．08	0．08	0．20	0．20	Preservative	0．90	0．90	-	-	0．53	0．53
Perfume	0．08	0．08	0．08	0．08	0．20	0．20	Denatured ethanol	-	-	19．74	19．56	-	-
Deionized water	An appropriate amount to 100%						Denatured ethanol	-	-	19．74	19．56	-	-

Components	Example 26	Example 27	Example 28
Components	Example 26	Example 27	Example 28	4-methyl-7, 7' -dimethylaminocoumarin^*4	0．1	-	-
2- (4-styryl-3-sulfophenyl) -2H-naphtho [1, 2-d]Triazole compounds	1．0	-	-	4-methyl-7, 7' -dimethylaminocoumarin^*4	0．1	-	-
	1．0	-	-	1- (4-Acylaminosulfonylphenyl) -3- (4-chlorophenyl) -2-pyrazoline^*5	-	0．5	-
2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	-	-	1．0		-	0．5	-
2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	-	-	1．0	Polyquaternium-10^*18	-	0．35	0．35
Monoalkyl trimethyl ammonium	0．2	-	-	Polyquaternium-10^*18	-	0．35	0．35
Monoalkyl trimethyl ammonium	0．2	-	-	Lauryl polyoxyethylene ether-3 ammonium sulfate	15．0	10．0	10．0
Ammonium lauryl sulfate	2．0	-	-	Lauryl polyoxyethylene ether-3 ammonium sulfate	15．0	10．0	10．0
Ammonium lauryl sulfate	2．0	-	-	N-acyl-L-glutamic acid triethanolamine^*9	-	2．0	2．0
Sodium lauroyl sarcosinate^*10	2．0	2．0	1．0	N-acyl-L-glutamic acid triethanolamine^*9	-	2．0	2．0
Sodium lauroyl sarcosinate^*10	2．0	2．0	1．0	Cocoamidobetaine^*11	4．0	2．0	2．0
Laureth-20^*12	0．5	0．5	-	Cocoamidobetaine^*11	4．0	2．0	2．0
Laureth-20^*12	0．5	0．5	-	Ethylene glycol distearate^*14	2．0	2．0	1．5
Coconut oil monoethanolamide	1．5	1．5	1．5	Ethylene glycol distearate^*14	2．0	2．0	1．5
Coconut oil monoethanolamide	1．5	1．5	1．5	DMDM hydantoin	0．2	0．2	0．2
Propylene glycol^*8	10．0	5．0	10．0	DMDM hydantoin	0．2	0．2	0．2
Propylene glycol^*8	10．0	5．0	10．0	Siloxanes	3．0	1．6	2．0
Polyoxyethylene glycol^*16	0．1	0．5	-	Siloxanes	3．0	1．6	2．0
Polyoxyethylene glycol^*16	0．1	0．5	-	Hydroxyethyl cellulose^*17	-	-	0．5
Cetyl alcohol^*19	0．1	0．1	-	Hydroxyethyl cellulose^*17	-	-	0．5
Cetyl alcohol^*19	0．1	0．1	-	Stearyl alcohol^*20	0．1	0．2	-
Perfume	0．5	0．5	0．5	Stearyl alcohol^*20	0．1	0．2	-
Perfume	0．5	0．5	0．5	Pentaerythritol tetraisostearate^*22	0．5	-	-
Trimethylol propane triisostearate^*23	-	0．3	-	Pentaerythritol tetraisostearate^*22	0．5	-	-
Trimethylol propane triisostearate^*23	-	0．3	-	Trimethylolpropane trioleate^*24	-	-	0．5
Monosodium phosphate	0－0．5	0－0．5	0－0．5	Trimethylolpropane trioleate^*24	-	-	0．5
Monosodium phosphate	0－0．5	0－0．5	0－0．5	Disodium phosphate	0－0．5	0－0．5	0－0．5
Deionized water	An appropriate amount to 100%			Disodium phosphate	0－0．5	0－0．5	0－0．5

Components	Example 29	Example 30	Example 31	Example 32
Components	Example 29	Example 30	Example 31	Example 32	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．2	0．8	0．5	0．3
Polyquaternium-10^*18	0．4	0．5	-	-	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．2	0．8	0．5	0．3
Polyquaternium-10^*18	0．4	0．5	-	-	Monoalkyl trimethyl ammonium	-	-	0．1	0．2
Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	12．0	12．0	Monoalkyl trimethyl ammonium	-	-	0．1	0．2
Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	12．0	12．0	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5
Deionized water	An appropriate amount to 100%				Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5

Components	Example 33	Example 34	Example 35	Example 36	Example 37	Example 38
Components	Example 33	Example 34	Example 35	Example 36	Example 37	Example 38	1, 4-bis (2-sulfostyryl) Biphenyl disodium salt^*1	0．20	0．80	0．20	-	0．20	0．80
4-methyl-6, 7-dihydroxycoumarin ^*3	-	-	-	0．80	-	-	1, 4-bis (2-sulfostyryl) Biphenyl disodium salt^*1	0．20	0．80	0．20	-	0．20	0．80
4-methyl-6, 7-dihydroxycoumarin ^*3	-	-	-	0．80	-	-	1- (4-acyl)Aminosulfonylphenyl) - 3- (4-chlorophenyl) -2-pyrazoline^*5	-	-	0．40	-	-	-
Lauryl methyl Gluceth-10 hydroxy Propyl dimethyl ammonium chloride^*27	-	1．00	-	-	-	-		-	-	0．40	-	-	-
	-	1．00	-	-	-	-	Alkyl trimethyl ammonium chloride^*39	-	-	-	1．00	-	-
Dihydrotallow amide ethyl hydroxy Ammonium Ethyl methyl sulfate^*28	-	-	0．25	2．00	-	0．20	Alkyl trimethyl ammonium chloride^*39	-	-	-	1．00	-	-
	-	-	0．25	2．00	-	0．20	Stearamidopropyl dimethyl Amines as pesticides^*36	2．00	2．00	2．00	-	-	-
L-glutamic acid^*37	0．64	0．64	0．80	-	-	-	Stearamidopropyl dimethyl Amines as pesticides^*36	2．00	2．00	2．00	-	-	-
L-glutamic acid^*37	0．64	0．64	0．80	-	-	-	Polyquaternium-10^*18	0．40	-	-	0．40	0．40	0．40
Polyquaternium-7^*34	-	0．40	-	-	-	-	Polyquaternium-10^*18	0．40	-	-	0．40	0．40	0．40
Polyquaternium-7^*34	-	0．40	-	-	-	-	Preservative	0．53	0．53	0．53	0．53	-	-
Perfume	0．08	0．08	0．08	0．08	0．08	0．08	Preservative	0．53	0．53	0．53	0．53	-	-
Perfume	0．08	0．08	0．08	0．08	0．08	0．08	Denatured ethanol	-	-	-	-	19．86	19．70
Deionized water	An appropriate amount to 100%						Denatured ethanol	-	-	-	-	19．86	19．70

	Example 39
	Example 39	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	1．0
Stearyl alcohol^*20	0．2	2, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine^*6	1．0
Stearyl alcohol^*20	0．2	Lauryl polyoxyethylene ether-3 ammonium sulfate	10．0
N-acyl-L-glutamic acid triethanolamine^*9	2．0	Lauryl polyoxyethylene ether-3 ammonium sulfate	10．0
N-acyl-L-glutamic acid triethanolamine^*9	2．0	Sodium lauroyl sarcosinate^*10	1．0
Cocoamidopropyl betaine^*11	2．0	Sodium lauroyl sarcosinate^*10	1．0
Cocoamidopropyl betaine^*11	2．0	Ethylene glycol distearate^*14	1．5
Coconut oil monoethanolamide	1．5	Ethylene glycol distearate^*14	1．5
Coconut oil monoethanolamide	1．5	DMDM hydantoin	0．2
Propylene glycol^*8	10．0	DMDM hydantoin	0．2
Propylene glycol^*8	10．0	Siloxanes	2．0
Hydroxyethyl cellulose^*17	0．5	Siloxanes	2．0
Hydroxyethyl cellulose^*17	0．5	Perfume	0．5
Trimethylolpropane trioleate^*24	0．5	Perfume	0．5
Trimethylolpropane trioleate^*24	0．5	Monosodium phosphate	0－0．5
Disodium phosphate	0－0．5	Monosodium phosphate	0－0．5
Disodium phosphate	0－0．5	Deionized water	The proper amount is 100 percent

	Example 40	EXAMPLE 41	Example 42	Example 43
	Example 40	EXAMPLE 41	Example 42	Example 43	1, 4-bis (2-sulfostyryl) biphenylDisodium salt^*1	0．8	1．0	0．5	0．8
Cetyl alcohol^*19	0．1	0．1	-	-	1, 4-bis (2-sulfostyryl) biphenylDisodium salt^*1	0．8	1．0	0．5	0．8
Cetyl alcohol^*19	0．1	0．1	-	-	Stearyl alcohol^*20	0．1	-	0．1	-
Behenyl alcohol^*21	-	-	-	0．2	Stearyl alcohol^*20	0．1	-	0．1	-
Behenyl alcohol^*21	-	-	-	0．2	Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	15．0	10．0
Ammonium lauryl sulfate	2．0	2．0	2．0	2．0	Lauryl polyoxyethylene ether-3 ammonium sulfate	12．0	12．0	15．0	10．0
Ammonium lauryl sulfate	2．0	2．0	2．0	2．0	Sodium lauroyl sarcosinate	-	-	-	1．0
Cocoamidopropyl betaine	-	-	-	2．0	Sodium lauroyl sarcosinate	-	-	-	1．0
Cocoamidopropyl betaine	-	-	-	2．0	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5
DMDM hydantoin	0．2	0．2	0．2	0．2	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5
DMDM hydantoin	0．2	0．2	0．2	0．2	Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5
Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5
Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	Deionized water	An appropriate amount to 100%

	Example 44	Example 45	Example 46	Example 47
	Example 44	Example 45	Example 46	Example 47	1, 4-bis (2-sulfostyrene) Yl) Biphenyl disodium salt^*1	0．20	0．50	0．80	0．50
Cetyl alcohol^*19	0．40	-	1．00	0．50	1, 4-bis (2-sulfostyrene) Yl) Biphenyl disodium salt^*1	0．20	0．50	0．80	0．50
Cetyl alcohol^*19	0．40	-	1．00	0．50	Stearyl alcohol^*20	0．60	1．00	-	0．50
Polysorbate 60^*26	0．20	0．20	0．20	-	Stearyl alcohol^*20	0．60	1．00	-	0．50
Polysorbate 60^*26	0．20	0．20	0．20	-	Preservative	0．53	0．53	0．53	-
Perfume	0．08	0．08	0．08	0．08	Preservative	0．53	0．53	0．53	-
Perfume	0．08	0．08	0．08	0．08	Denatured ethanol	-	-	-	19．68
Deionized water	An appropriate amount to 100%				Denatured ethanol	-	-	-	19．68

	Example 48	Example 49	Example 50
	Example 48	Example 49	Example 50	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．80	-	-
4, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) amino group) -1, 3, 5-triazin-2-yl) amino]Stilbene-2, 2- Disulfonic acid^*2	-	0．50	1．00	Disodium 1, 4-bis (2-sulfostyryl) biphenyl^*1	0．80	-	-
	-	0．50	1．00	Cetyl alcohol^*19	2．00	2．50	2．50
Stearyl alcohol^*20	-	4．50	4．50	Cetyl alcohol^*19	2．00	2．50	2．50
Stearyl alcohol^*20	-	4．50	4．50	15/85 Silicone blends^*35	-	4．20	4．20
Polysorbate 60^*26	-	-	-	15/85 Silicone blends^*35	-	4．20	4．20
Polysorbate 60^*26	-	-	-	Alkyl trimethyl ammonium chloride^*39	-	-	2．50
Stearamidopropyl dimethylamine^*36	-	2．00	-	Alkyl trimethyl ammonium chloride^*39	-	-	2．50
Stearamidopropyl dimethylamine^*36	-	2．00	-	L-glutamic acid^*37	-	0．64	-
Preservative	-	0．53	0．53	L-glutamic acid^*37	-	0．64	-
Preservative	-	0．53	0．53	Perfume	0．08	0．20	0．20
Denatured ethanol	19．42	-	-	Perfume	0．08	0．20	0．20
Denatured ethanol	19．42	-	-	Deionized water	An appropriate amount to 100%

	Example 51	Example 52	Example 53	Example 54	Example 55
	Example 51	Example 52	Example 53	Example 54	Example 55	1, 4-bis (2-sulfostyryl) biphenyl Disodium salt^*1	1．0	-	-	-	-
4, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) ether) Radical) amino-1, 3, 5-triazin-2-yl) amino] Stilbene-2, 2' -disulfonic acid^*2	-	0．8	-	-	-	1, 4-bis (2-sulfostyryl) biphenyl Disodium salt^*1	1．0	-	-	-	-
	-	0．8	-	-	-	4-methyl-6, 7-dihydroxycoumarin^*3	-	-	1．0	-	-
4-methyl-7, 7' -dimethylamino tonka bean Vegetable extract^*4	-	-	-	0．1	-	4-methyl-6, 7-dihydroxycoumarin^*3	-	-	1．0	-	-
	-	-	-	0．1	-	2- (4-styryl-3-sulfophenyl) - 2H-naphtho [1, 2-d ]]Triazole compounds	-	-	-	1．0	-
2, 4-dimethoxy-6- (1' -pyrenyl) -one 1, 3, 5-triazines^*6	-	-	-	-	1．0		-	-	-	1．0	-
2, 4-dimethoxy-6- (1' -pyrenyl) -one 1, 3, 5-triazines^*6	-	-	-	-	1．0	Citronellol	0．2	-	-	-	0．05
α -ionones	-	0．2	-	-	-	Citronellol	0．2	-	-	-	0．05
α -ionones	-	0．2	-	-	-	Benzaldehyde	0．05	0．05	0．2	-	-
Geraniol	-	-	0．05	0．2	-	Benzaldehyde	0．05	0．05	0．2	-	-
Geraniol	-	-	0．05	0．2	-	Eugenol	-	-	-	0．05	0．2
Lauryl polyoxyethylene ether-3 ammonium sulfate	12	12	12	12	12	Eugenol	-	-	-	0．05	0．2
Lauryl polyoxyethylene ether-3 ammonium sulfate	12	12	12	12	12	Ammonium lauryl sulfate	2	2	2	2	2
N-acyl-L-glutamic acid triethanolamine^*9	2	2	2	2	2	Ammonium lauryl sulfate	2	2	2	2	2
N-acyl-L-glutamic acid triethanolamine^*9	2	2	2	2	2	Cocoamidopropyl betaine^*11	2	2	2	2	2
Ethylene glycol distearate^*14	2．0	2．0	2．0	2．0	2．0	Cocoamidopropyl betaine^*11	2	2	2	2	2
Ethylene glycol distearate^*14	2．0	2．0	2．0	2．0	2．0	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	1．5
DMDM acetolactam	0．2	0．2	0．2	0．2	0．2	Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	1．5
DMDM acetolactam	0．2	0．2	0．2	0．2	0．2	MgCl₂·6H₂O	0．5	0．5	0．5	0．5	0．5
Monosodium phosphate	0－1．0	0－1．0	0－1．0	0－1．0	0－1．0	MgCl₂·6H₂O	0．5	0．5	0．5	0．5	0．5
Monosodium phosphate	0－1．0	0－1．0	0－1．0	0－1．0	0－1．0	Disodium phosphate	0－1．0	0－1．0	0－1．0	0－1．0	0－1．0
Polyquaternium-10^*18	0．5	0．5	0．5	0．5	0．5	Disodium phosphate	0－1．0	0－1．0	0－1．0	0－1．0	0－1．0
Polyquaternium-10^*18	0．5	0．5	0．5	0．5	0．5	Siloxanes	2．0	2．0	2．0	2．0	2．0
Deionized water	An amount of up to 100-					Siloxanes	2．0	2．0	2．0	2．0	2．0
Deionized water	An amount of up to 100-					pH	4．0－6．5	4．0－6．5	4．0－6．5	4．0－6．5	4．0－6．5
Hydrolyzed collagen^*40	0．01	-	-	-	-	pH	4．0－6．5	4．0－6．5	4．0－6．5	4．0－6．5	4．0－6．5
Hydrolyzed collagen^*40	0．01	-	-	-	-	Vitamin E^*41	0．01	-	-	-	-
Panthenol^*42	0．025	-	-	-	-	Vitamin E^*41	0．01	-	-	-	-
Panthenol^*42	0．025	-	-	-	-	Panthenyl ethyl ether^*43	0．225	-	-	-	-

	Example 56	Example 57	Example 58	Example 59	Example 60
	Example 56	Example 57	Example 58	Example 59	Example 60	1, 4-bis (2-sulfostyryl) biphenyl Disodium salt^*1	-	1．50	-	-	1．50
6, 7-dihydroxycoumarin	-	-	0．20	-	-	1, 4-bis (2-sulfostyryl) biphenyl Disodium salt^*1	-	1．50	-	-	1．50
6, 7-dihydroxycoumarin	-	-	0．20	-	-	2- (4-styryl-3-sulfophenyl-2-) Naphthotriazole)	-	-	-	0．40	-
1, 3-diphenylpyrazoline	0．50	-	-	-	-	2- (4-styryl-3-sulfophenyl-2-) Naphthotriazole)	-	-	-	0．40	-
1, 3-diphenylpyrazoline	0．50	-	-	-	-	Citronellol	0．08	-	0．20	-	-
α -ionones	-	0．08	-	0．05	-	Citronellol	0．08	-	0．20	-	-
α -ionones	-	0．08	-	0．05	-	Benzaldehyde	-	-	0．10	-	1．00
Geraniol	-	-	-	0．2	-	Benzaldehyde	-	-	0．10	-	1．00
Geraniol	-	-	-	0．2	-	Eugenol	-	-	-	-	0．1
Cetyl alcohol^*19	2．00	-	-	2．50	-	Eugenol	-	-	-	-	0．1
Cetyl alcohol^*19	2．00	-	-	2．50	-	Stearyl alcohol^*20	3．00	-	-	4．50	-
Behenyl alcohol^*21	-	-	0．50	-	-	Stearyl alcohol^*20	3．00	-	-	4．50	-
Behenyl alcohol^*21	-	-	0．50	-	-	15/85 Silicone blends^*35	-	-	-	4．20	-
Silicone emulsions^*15	1．00	1．00	0．50	-	-	15/85 Silicone blends^*35	-	-	-	4．20	-
Silicone emulsions^*15	1．00	1．00	0．50	-	-	P0lysorbate60^*26	1．00	-	-	-	-
Stearamidopropyl dimethylamine^*36	-	-	-	2．00	-	P0lysorbate60^*26	1．00	-	-	-	-
Stearamidopropyl dimethylamine^*36	-	-	-	2．00	-	L-glutamic acid^*37	-	-	-	0．64	-
Citric acid^*29	0－0．2	0－0．2	-	-	-	L-glutamic acid^*37	-	-	-	0．64	-
Citric acid^*29	0－0．2	0－0．2	-	-	-	Hydroxyethyl cellulose^*17	-	-	0．50	-	-
Polyoxyethylene glycol^*16	0．50	-	0．50	0．20	-	Hydroxyethyl cellulose^*17	-	-	0．50	-	-
Polyoxyethylene glycol^*16	0．50	-	0．50	0．20	-	Aminomethylpropanol^*31	2．10	-	-	-	-
acrylate/Steareth-20 methyl propane Alkenoic acid ester copolymer^*32	1．75	-	-	-	-	Aminomethylpropanol^*31	2．10	-	-	-	-
	1．75	-	-	-	-	Cetyl hydroxyethylcellulose^*33	-	0．80	-	-	-
Polyquaternium-10^*18	0．10	-	0．10	0．20	-	Cetyl hydroxyethylcellulose^*33	-	0．80	-	-	-
Polyquaternium-10^*18	0．10	-	0．10	0．20	-	Pentaerythritol tetraisostearate^*22	1．00	-	-	-	-
Preservative	0．90	0．53	0．90	0．53	0．53	Pentaerythritol tetraisostearate^*22	1．00	-	-	-	-
Preservative	0．90	0．53	0．90	0．53	0．53	Glycerol^*7	-	-	5．00	-	-
Propylene glycol^*8	-	5．00	-	-	-	Glycerol^*7	-	-	5．00	-	-
Propylene glycol^*8	-	5．00	-	-	-	Denatured ethanol	-	-	18．34	-	-
Deionized water	----100％----					Denatured ethanol	-	-	18．34	-	-

	Example 61	Example 62	Example 63	Example 64
	Example 61	Example 62	Example 63	Example 64	1, 4-bis (2-sulfostyryl) bis Disodium benzene^*1	0．8	1．0	0．5	0．8
Pentaerythritol tetraisostearate^*22	0．3	-	-	-	1, 4-bis (2-sulfostyryl) bis Disodium benzene^*1	0．8	1．0	0．5	0．8
Pentaerythritol tetraisostearate^*22	0．3	-	-	-	Trimethylolpropane triisostearic acid Esters^*23	-	0．5	-	-
Pentaerythritol tetraoleate	-	-	0．3	-	Trimethylolpropane triisostearic acid Esters^*23	-	0．5	-	-
Pentaerythritol tetraoleate	-	-	0．3	-	Trimethylolpropane trioleate^*24	-	-	-	0．8
Lauryl polyoxyethylene ether-3 sulfuric acid Ammonium salt	12．0	12．0	15．0	10．0	Trimethylolpropane trioleate^*24	-	-	-	0．8
Lauryl polyoxyethylene ether-3 sulfuric acid Ammonium salt	12．0	12．0	15．0	10．0	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	-	1．0	Ammonium lauryl sulfate	2．0	2．0	2．0	2．0
Sodium lauroyl sarcosinate^*10	-	-	-	1．0	Cocoamidopropyl betaine^*11	-	-	-	2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	Cocoamidopropyl betaine^*11	-	-	-	2．0
Coconut oil monoethanolamide	1．5	1．5	1．5	1．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	DMDM hydantoin	0．2	0．2	0．2	0．2
Monosodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5	Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5
Deionized water	An appropriate amount to 100%				Disodium phosphate	0－0．5	0－0．5	0－0．5	0－0．5

	Example 65	Example 66	Example 67	Example 68
	Example 65	Example 66	Example 67	Example 68	1, 4-bis (2-sulfostyryl) bis Disodium benzene^*1	0．80	0．80	1．60	0．20
Pentaerythritol tetraisostearate^*22	1．00	0．50	-	-	1, 4-bis (2-sulfostyryl) bis Disodium benzene^*1	0．80	0．80	1．60	0．20
Pentaerythritol tetraisostearate^*22	1．00	0．50	-	-	Trimethylolpropane trioleate^*24	-	-	0．50	-
Trimethylolpropane triisostearic acid Esters^*23	-	-	-	0．50	Trimethylolpropane trioleate^*24	-	-	0．50	-
Trimethylolpropane triisostearic acid Esters^*23	-	-	-	0．50	Preservative	0．53	0．53	0．53	0．53
Perfume	0．08	0．08	0．08	0．08	Preservative	0．53	0．53	0．53	0．53
Perfume	0．08	0．08	0．08	0．08	Deionized water	An appropriate amount to 100%

Definition of

^*Disodium 11, 4-bis (2-sulfostyryl) biphenyl: TINOPAL CBX from Ciba Geigy.

^*24, 4-bis [ (4-anilino-6-bis (2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) amino group]Stilbene-

2, 2' -disulfonic acid: tinopal UNPA-GX from Ciba Geigy.

^*34-methyl-6, 7-dihydroxycoumarin: from Wako.

^*44-methyl-7, 7' -dimethylaminocoumarin: from Wako.

^*51- (4-Acylaminosulfonylphenyl) -3- (4-chlorophenyl) -2-pyrazoline: blankophor DCB to obtain

From Bayer.

^*62, 4-dimethoxy-6- (1' -pyrenyl) -1, 3, 5-triazine: from Ciba Geigy.

^*7, glycerin: glycerin USP from Nihon Yushi.

^*8, propylene glycol: lexol PG-865 from Inolex.

^*9N-acyl-L-glutamic acid triethanolamine: CT12S, from Ajinomoto.

^*10 sodium lauroyl sarcosinate: soypon is available from Kawaken Fine Chem.

^*11 cocamidopropyl betaine: tegobetaine is available from th.

^*12 Laureth-20: BL-20 is available from Nikko.

^*13 alkyl polyglucoside: plantare 2000UP, available from Henkel.

^*14 ethylene glycol distearate: EGDS, from th.

^*15 silicone emulsion: x65-4829, obtained from Tosil/GE.

^*16 polyoxyethylene glycol: WSR N-10 from Amerchol.

^*17 hydroxyethyl cellulose: from Aqualon.

^*18 Polyquaternium-10: UCARE Polymer LR 400 from Amerchol.

^*19, cetyl alcohol: konol series, from Shinihon Rika.

^*20 stearyl alcohol: konol series, from Shinihon Rika.

^*21 behenyl alcohol: 1-Docosanol (97%) from Wako.

^*22 pentaerythritol tetraisostearate: KAK PTI from Kokyu alcohol.

^*23 trimethylolpropane triisostearate: KAK TTI from Kokyu alcohol.

^*24 trimethylolpropane trioleate: enujerubu TP3SO from Shinihon Rika.

^*254, 4' -bis (5-methylbenzoxazol-2-yl) stilbene: from the TCI.

^*26 Polysorbate 60: tween 60, derived from ICI.

^*27 lauryl methyl Gluceth-10 hydroxypropyl dimethyl ammonium chloride: glucquat 125 from

Amerchol．

^*28 Dihydrotallow amidoethyl hydroxyethyl ammonium methyl sulfate: varisoft 110 from Witco.

^*29, citric acid: anhydrous citric acid from Haarman&Reimer．

^*30 hydroxypropyl cellulose: metlose, available from Shinetsu.

^*31 aminomethyl propanol: AMP-conventional, from Angus.

^*32 acrylate/Steareth-20 methacrylate copolymer: aculyn from Rohm&

Haas．

^*33 cetyl hydroxyethylcellulose: polysurf67 from Aqualon.

^*34 Polyquaternium-7: merquat S, from Calgon.

^*3515/85 Silicone blend: from Shinetsu.

^*36 stearamidopropyl dimethylamine: amidoamine MPS from Nikko.

^*37L-glutamic acid: L-Glutamic acid (cosmetic grade), from Ajinomoto.

^*38 Carbomer: carbopol 980, available from BF Goodrich.

^*39 alkyl trimethyl ammonium chloride: from TOHO.

^*40 hydrolysis of collagen: PEPTEIN 2000 from Hormel.

^*41, vitamin E: EMIX-d from Eisai.

^*42 panthenol: from Roche.

^*43 panthenyl ethyl ether: from Roche.

The embodiments disclosed and represented by the foregoing examples have many advantages. For example, they can provide the benefits associated with fluorescent whitening agents (e.g., shine, UV protection, color change) while also providing desirable conditioning benefits.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.

Claims

1. A hair care composition comprising:

(a) an effective amount of a fluorescent whitening agent; and

(b) a hair conditioning agent selected from the group consisting of silicone compounds, cationic compounds, high melting point compounds, fragrance compounds, water insoluble high molecular weight oily compounds, and mixtures thereof.

2. A hair care composition comprising

(a) An effective amount of a fluorescent whitening agent selected from the group consisting of polystyrylbenzenes, hydroxycoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles, and mixtures thereof; and

(b) a siloxane compound.

3. The hair care composition of claim 2, further comprising a carrier suitable for application to hair.

4. The hair care composition of claim 2, wherein the optical brightener is a polystyrene based stilbene.

5. The hair care composition of claim 2, wherein the optical brightener is hydroxycoumarin.

6. A hair care composition comprising

(a) An effective amount of a fluorescent whitening agent; and

(b) a siloxane compound selected from the group consisting of high molecular weight polydimethylsiloxanes.

7. The hair care composition of claim 6, further comprising a carrier suitable for application to hair.

8. The hair care composition of claim 7, wherein the optical brightener is a polystyrene based stilbene.

9. The hair care composition of claim 7, wherein the optical brightener is hydroxycoumarin.

10. The hair care composition of claim 7, wherein the optical brightener is a triazine stilbene.

11. The hair care composition of claim 2 or claim 6 comprising from about 0.001% to about 20% by weight of the optical brightener.

12. The hair care composition of claim 11, comprising from about 0.01% to about 15% by weight of the silicone compound.

13. The hair care composition of any of claims 2 to 12 further comprising another conditioning agent.

14. A shampoo composition comprises

(a) An effective amount of a fluorescent whitening agent;

(b) a detersive surfactant suitable for cleansing hair; and

(c) a siloxane compound.

15. The shampoo composition of claim 14 further comprising a carrier suitable for application to hair.

16. The shampoo composition of claim 15, wherein the optical brightener is selected from the group consisting of polystyrenedistyrene, hydroxycoumarin, aminocoumarin, triazole, pyrazoline, oxazole, pyrene, porphyrin, imidazole, and mixtures thereof.

17. The shampoo composition of claim 16, comprising from about 0.001% to about 20% by weight of the optical brightener.

18. The shampoo composition of claim 17, comprising from about 0.01% to about 15% by weight of the silicone compound.

19. The shampoo composition of any one of claims 2 to 18, further comprising another conditioning agent.

20. A hair care composition comprising

(a) An effective amount of a fluorescent whitening agent;

(b) a cationic compound; and

(c) a carrier suitable for application to hair.

21. The composition of claim 20 further comprising a detersive surfactant suitable for cleansing hair.

22. The composition of claim 21, further comprising another conditioning agent.

23. The composition of claim 20, further comprising another conditioning agent.

24. The composition of any of claims 20-23, wherein the fluorescent whitening agent is selected from the group consisting of: polystyrene based stilbenes, triazine stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles and mixtures thereof.

25. The composition of claim 24 comprising from about 0.001% to about 20% by weight of the optical brightener.

26. The composition of claim 25, comprising from about 0.01% to about 15% by weight of the cationic compound.

27. A hair care composition comprising

(a) An effective amount of a fluorescent whitening agent;

(b) a high melting point compound; and

(c) a carrier suitable for application to hair.

28. The hair care composition of claim 27, further comprising a detersive surfactant suitable for cleansing hair.

29. The composition of claim 28, further comprising another conditioning agent.

30. The composition of claim 27, further comprising another conditioning agent.

31. The composition of any of claims 27-30, wherein the fluorescent whitening agent is selected from the group consisting of: polystyrene based stilbenes, triazine stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles and mixtures thereof.

32. The composition of claim 31 comprising from about 0.001% to about 20% by weight of the optical brightener.

33. The composition of claim 32 comprising from about 0.01% to about 20% by weight of the high melting point compound.

34. The composition of claim 33 wherein the high melting point compound is selected from the group consisting of: cetyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, and mixtures thereof.

35. A hair care composition comprising

(a) An effective amount of a fluorescent whitening agent;

(b) a perfume compound having a CLogP ester between about-1.0 to about 8.0; and

(c) a carrier suitable for application to hair.

36. The composition of claim 35, further comprising a detersive surfactant suitable for cleansing hair.

37. The composition of claim 36, further comprising another conditioning agent.

38. The composition of claim 35, further comprising another conditioning agent.

39. The composition of any of claims 35-38, wherein the fluorescent whitening agent is selected from the group consisting of: polystyrene based stilbenes, triazine stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles and mixtures thereof.

40. The composition of claim 39, comprising from about 0.001% to about 20% by weight of the optical brightener.

41. The composition of claim 40, comprising about 0.05% by weight of the perfume compound.

42. The composition of claim 41, wherein the fragrance compound is selected from the group consisting of carbonyl-containing fragrance compounds, ether-containing fragrance compounds, hydroxyl-containing fragrance compounds, and mixtures thereof.

43. A hair care composition comprising

(a) An effectiveamount of a fluorescent whitening agent; and

(b) a water-insoluble oily compound with high molecular weight.

44. The hair care composition of claim 43, further comprising a carrier suitable for application to hair.

45. The composition of claim 44 further comprising a detersive surfactant suitable for cleansing hair.

46. The composition of claim 45, further comprising another conditioning agent.

47. The composition of any of claims 43-46, wherein the fluorescent whitening agent is selected from the group consisting of: polystyrene based stilbenes, triazine stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, imidazoles and mixtures thereof.

48. The composition of claim 47 comprising from about 0.001% to about 20% by weight of the optical brightener.

49. The composition of claim 48, comprising from about 0.1% to about 10% by weight of the water-insoluble high molecular weight oily compound.