CN1275904A - Hair care compositions comprising optical brighteners which alter hair colors - Google Patents

Abstract

The present invention discloses a hair care composition comprising: (a) an optical brightener in an amount such that the color of the hair to which the composition is applied changes one or both of the a value and the b value by about 0.2 units to about 15 units; and (b) a hair care active selected from the group consisting of detersive surfactants, conditioning agents, styling polymers and mixtures thereof. The invention also discloses a method for changing hair color by applying fluorescent whitening agent to hair.

Description

Hair care composition comprising optical brightener for changing hair color

field of invention

The present invention relates to hair care compositions comprising optical brighteners which alter the color of the hair.

Background of the invention

There is a constant desire to restore the natural color and shine of damaged hair, as well as to change the color of the hair to make it more appealing. Consumers perceive damaged hair to be unattractive and difficult to comb. This unsightly appearance includes a change and fading of the original hair color, loss of luster, and loss of brightness.

A conventional way of reducing the unsightly appearance of damaged hair and making it attractive is to dye the hair the desired color. Coloring the hair will allow the consumer to have a consistent hair color over a relatively long period of time. However, staining is often a time-consuming, cumbersome and labor-intensive affair. Dyes can also cause chemical damage to the hair, scalp, and skin. Hair can be further damaged by coloring. Therefore, hair coloring products are not suitable for daily use. Furthermore, coloring the hair may also give the hair a dull appearance, making the hair look less lustrous.

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

The use of optical brighteners or compounds known as optical brighteners or fluorescent dyes is known in the prior art in the field of hair care, as described in the following documents, US 3,658,985, US 4,312,855, CA 1,255,603 , US 3,577,528, GB 1,328,108, South African application 676,049, European publication 87,060 and GB 2,307,639.

Changes in hair color can technically be measured using L, a, b color parameters. When one or both of the a and b values are changed to a certain extent, people feel that the appearance of the hair has changed. In this way, the unsightly appearance of damaged hair can be alleviated, or the hair's Colors become more attractive. Thus, there is a need to find a hair composition that can be used on a daily basis and that provides a perceived color change.

All the advantages and effects of the present invention cannot be provided in the prior art.

Summary of the invention

The present invention relates to a hair care composition comprising: (a) an optical brightener in an amount to change the color of the hair to which the composition is applied by changing either or both of the a value and the b value by about 0.2 units to about 15 units; and (b) a hair care active selected from the group consisting of detersive surfactants, conditioners, styling polymers and mixtures thereof.

The invention also relates to a method of changing the color of hair by applying a fluorescer to the hair.

The above and other features, aspects and advantages of the present invention will be more apparent upon reading the following detailed disclosure.

Brief description of the drawings

While the description and claims specifically point out and clearly define the present invention, it is believed that the present invention can be better understood through the following description in conjunction with the accompanying drawing 1, in which the "L, a, b, Color coordinates".

Detailed description of the invention

While the specification and claims 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 calculated by weight of the total composition and all ratios are by weight unless otherwise indicated. All percentages, ratios and ingredient levels are based on the actual level of the ingredients and do not include solvents, fillers or other incorporated materials in various commercially available products.

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

All cited documents are incorporated herein by reference. The incorporation of these references does not imply that prior art is equally capable of accessing the subject matter claimed in the present invention.

Fluorescent whitening agent

Optical brighteners are compounds that absorb UV light and re-emit the energy in the form of visible light. Specifically, the fluorescent whitening agent used in the present invention has absorption between about 1 nm to about 420 nm wavelength, preferably a main absorption peak, and emits between about 360 nm to about 830 nm wavelength, preferably a main emission peak; wherein, The wavelength of 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 major absorption peak between about 200 nm to about 420 nm wavelength and a major emission peak between about 400 nm to about 780 nm wavelength. Optical brighteners may or may not have a secondary absorption peak in the visible wavelength range of about 360 nm to about 830 nm. Optical brighteners can be described by some other names in the prior art and other industrial fields, such as fluorescent whitening agents, fluorescent brighteners and fluorescent dyes.

When the fluorescent whitening agent of the present invention is applied to the hair with a suitable carrier, the fluorescent whitening agent of the present invention can bring three beneficial effects to the hair. First, optical brighteners can change the color of hair by emitting light in the visible range. Second, optical brighteners can enhance the shine of hair by emitting light in the visible range. Third, optical brighteners can also protect hair from UV damage by absorbing UV rays.

Optical brighteners are often based on the structure of aromatic and heteroaromatic systems, which provide unique characteristics. The fluorescent whitening agents used in the present invention can be classified according to their basic structures into the following categories. Preferred optical brighteners of the present invention include polystyryl stilbenes, triazinyl stilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins and imidazoles .

polystyrene toluene

用于本发明中的聚苯乙烯基二苯乙烯包括具有下述式(1)、(2)和(3)的那些：

其中，R¹⁰¹是H、OH、SO₃M、COOM、OSO₃M、OPO(OH)OM，其中M是H、Na、K、Ca、Mg，铵，单-、二-、三-或四-C₁-C₃₀烷基铵，单-、二-或三-C₁-C₃₀羟基烷基铵或用C₁-C₃₀-烷基和C₁-C₃₀-羟烷基的混合物二或三取代的铵；或者SO₂N(C₁-C₃₀-烷基)₂、O-(-C₁-C₃₀-烷基)、CN、Cl、COO(C₁-C₃₀-烷基)、CON(C₁-C₃₀-烷基)₂或O(CH₂)₃N⁺(CH₃)₂X^-，其中，X^-是氯离子、溴离子、碘离子、甲酸根、乙酸根、丙酸根、羟乙酸根、乳酸根、丙烯酸根、甲烷膦酸根、亚磷酸根、二甲基或二乙基亚磷酸根阴离子；CN或具有1-30个碳原子的烷基，R¹⁰²和R¹⁰³彼此独立地是H、SO₃M，其中M如前定义；x是0或1；其中，该化合物具有反式共面或顺式共面取向；优选x是1，R¹⁰¹是SO₃Na，R¹⁰²和R¹⁰³是H；其中该化合物具有反式共面取向；

其中，R¹⁰⁴和R¹⁰⁵彼此独立地为CN、COO(C₁-C₃₀-烷基)、CONHC₁-C₄-烷基或CON(C₁-C₄-烷基)₂，其中，该化合物具有反式共面或顺式共面取向；优选R¹⁰⁴和R¹⁰⁵是2-氰基，其中，该化合物具有反式共面取向；和其中，每个R¹⁰⁶独立地是H或具有1-30个碳原子的烷基；其中，该化合物具有反式共面或顺式共面取向，优选反式共面取向。Polystyryl stilbenes are a class of compounds with two or more of the following basic structures:

Polystyryl stilbenes useful in the present invention include those having the following formulas (1), (2) and (3):

Wherein, R ¹⁰¹ is H, OH, SO ₃ M, COOM, OSO ₃ M, OPO(OH)OM, wherein M is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra -C ₁ -C ₃₀ alkylammonium, mono-, di- or tri-C ₁ -C ₃₀ hydroxyalkylammonium or a mixture of C ₁ -C ₃₀ -alkyl and C ₁ -C ₃₀ -hydroxyalkylammonium or trisubstituted ammonium; or SO ₂ N(C ₁ -C ₃₀ -alkyl) ₂ , O-(-C ₁ -C ₃₀ -alkyl), CN, Cl, COO(C ₁ -C ₃₀ -alkyl ), CON(C ₁ -C ₃₀ -alkyl) ₂ or O(CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ X ^- , where X ^- is chloride, bromide, iodide, formate, acetate , propionate, glycolate, lactate, acrylate, methanephosphonate, phosphite, dimethyl or diethylphosphite anion; CN or an alkyl group with 1-30 carbon atoms, R ¹⁰² and R ¹⁰³ are independently H, SO ₃ M, wherein M is as defined above; x is 0 or 1; wherein, the compound has a trans-coplanar or cis-coplanar orientation; preferably x is 1, and R ¹⁰¹ is SO ₃ Na, R ¹⁰² and R ¹⁰³ are H; wherein the compound has a trans-coplanar orientation;

Wherein, R ¹⁰⁴ and R ¹⁰⁵ are independently CN, COO(C ₁ -C ₃₀ -alkyl), CONHC ₁ -C ₄ -alkyl or CON(C ₁ -C ₄ -alkyl) ₂ , wherein, the The compound has a trans-coplanar or cis-coplanar orientation; preferably R and R are 2 ^{- cyano} , wherein the compound has a trans-coplanar orientation; and Wherein, each R ¹⁰⁶ is independently H or an alkyl group having 1-30 carbon atoms; wherein, the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation.

Suitable polystyryl stilbenes include: disodium-1,4'-bis(2-sulfostyryl)biphenyl (C.I. Optical brightener 351), trade name Tinopal CBS-X, commercially available from Ciba Specialty Chemicals; 1,4-bis(2-cyanostyryl)benzene (C.I. Optical brightener 199), trade name Ultraphor RN, commercially available from BASF.

Triazinyl stilbene

Triazinyl stilbenes are a class of compounds that have both triazine and styrene structures in the same molecule.

其中，R¹⁰⁷和R¹⁰⁸彼此独立地是苯基氨基、单或二磺化苯基氨基、吗啉代、N(CH₂CH₂OH)₂、N(CH₃)(CH₂CH₂OH)、NH₂、N(C₁-C₄-烷基)₂、OCH₃、Cl、NH-(CH₂)_1-4SO₃H或NH-(CH₂)_1-4OH；An^-是阴离子羧酸根、硫酸根、磺酸根或磷酸根，M如前定义，其中，该化合物具有反式共面或顺式共面取向；优选R¹⁰⁷是2，5-二磺基苯基氨基，每一个R¹⁰⁸是吗啉代；或每一个R¹⁰⁷是2，5-二磺基苯基氨基二磺基苯基氨基和每一个R¹⁰⁸是N(C2H5)₂；或每一个R¹⁰⁷是3-磺基苯基和每一个R¹⁰⁸是NH(CH₂CH₂OH)或N(CH₂CH₂OH)₂；或每一个R¹⁰⁷是4-磺基苯基和每一个R¹⁰⁸是N(CH₂CH₂OH)₂；在任何情形下，磺基都是其中M是钠的SO₃M；其中，该化合物具有反式共面取向。Triazinyl stilbenes useful in the present invention include those compounds having the following formula (4):

Wherein, R ¹⁰⁷ and R ¹⁰⁸ are independently phenylamino, mono- or disulfonated phenylamino, morpholino, N(CH ₂ CH ₂ OH) ₂ , N(CH ₃ )(CH ₂ CH ₂ OH) , NH ₂ , N(C ₁ -C ₄ -alkyl) ₂ , OCH ₃ , Cl, NH-(CH ₂ ) _1-4 SO ₃ H or NH-(CH ₂ ) _1-4 OH; An ^- is an anion Carboxylate, sulfate, sulfonate or phosphate, M as defined above, wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R ¹⁰⁷ is 2,5-disulfophenylamino, each R ¹⁰⁸ is morpholino; or each R ¹⁰⁷ is 2,5-disulfophenylaminodisulfophenylamino and each R ¹⁰⁸ is N(C2H5) ₂ ; or each R ¹⁰⁷ is 3-sulfo ^or _each R ¹⁰⁷ _is 4 _- sulfophenyl and _each R ₁₀₈ ^is N(CH ₂ CH ₂ OH) ₂ ; in any case the sulfo group is SO ₃ M wherein M is sodium; wherein the compound has a trans coplanar orientation.

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

Hydroxycoumarin

用于本发明中的羟基香豆素包括具有下式(5)的那些化合物：

其中，R²⁰¹是H、OH、Cl、CH₃、CH₂COOH、CH₂SO₃H、CH₂OSO₃H或CH₂OPO(OH)OH，R²⁰²是H、苯基、COO-C₁-C₃₀-烷基、葡萄糖基或式(6)的基团： Hydroxycoumarins are a class of compounds with the basic coumarin structure and at least one hydroxyl group:

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

Wherein, R ²⁰¹ is H, OH, Cl, CH ₃ , CH ₂ COOH, CH ₂ SO ₃ H, CH ₂ OSO ₃ H or CH ₂ OPO(OH)OH, R ²⁰² is H, phenyl, COO-C ₁ -C ₃₀ -alkyl, glucosyl or a group of formula (6):

R ²⁰³ is OH or OC ₁ -C ₃₀ -alkyl, R ²⁰⁴ is OH or OC ₁ -C ₃₀ alkyl, glucoside or the group of the following formula (7): Wherein, R ²⁰⁵ and R ²⁰⁶ are independently phenylamino, mono- or disulfonated phenylamino, morpholino, N(CH ₂ CH ₂ OH) ₂ , N(CH ₃ )(CH ₂ CH ₂ OH) , NH ₂ , N(C ₁ -C ₃₀ -alkyl) ₂ , OCH ₃ , Cl, NH—(CH ₂ ) _1-4 SO ₃ H or NH—(CH ₂ ) _1-4 OH.

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, escin, commercially available from Wako Chemicals, and 7-hydroxycoumarin (4-hydroxycoumarin), commercially available from Wako Chemicals.

aminocoumarin

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

其中、R²⁰⁷是H、Cl、CH₃、CH₂COOH、CH₂SO₃H、CH₂OSO₃H或CH₂OPO(OH)OH、R²⁰⁸是H、苯基或COOC₁-C₃₀烷基，R²⁰⁹和R²¹⁰彼此独立地是H、NH₂、N(C₁-C₃₀烷基)₂、NHC₁-C₃₀烷基或NHCOC₁-C₃₀烷基。Aminocoumarins for use in the present invention include those compounds having the formula (8):

Wherein, R ²⁰⁷ is H, Cl, CH ₃ , CH ₂ COOH, CH ₂ SO ₃ H, CH ₂ OSO ₃ H or CH ₂ OPO(OH)OH, R ²⁰⁸ is H, phenyl or COOC ₁ -C ₃₀ alkane R ²⁰⁹ and R ²¹⁰ are independently H, NH ₂ , N(C ₁ -C ₃₀ alkyl) ₂ , NHC ₁ -C ₃₀ alkyl or NHCOC ₁ -C ₃₀ alkyl.

Suitable aminocoumarins include: 4-methyl-7,7'-diethylaminocoumarin, trade name Calcofluor-RWP, commercially available from BASF, 4-methyl-7,7'-di Methylaminocoumarin, tradename Calcofluor-LD, is commercially available from BASF.

Triazole

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

其中R³⁰³是H或Cl；R³⁰⁴是SO₃M、SO₂N(C₁-C₃₀-烷基)₂、SO₂O-苯基或CN；R³⁰⁵是H、SO₃M、COOM、OSO₃M或OPO(OH)OM；M如前述定义，其中，该化合物具有反式共面或顺式共面取向；优选R³⁰³和R³⁰⁵为H，R³⁰⁴是SO₃M，其中M是Na；其中，该化合物具有反式共面取向；

其中每一个R³⁰⁶和R³¹²彼此独立地是H、磺酸基团或其盐、酯或酰胺、羧酸基团或其盐、酯或酰胺、氰基、卤原子、取代或未取代的烷基磺酰基、芳基磺酰基、烷基、烷氧基、芳烷基、芳基、芳氧基、芳烷氧基或环烷基、包含2至3个氮原子或1个氧原子和1或2个氮原子的取代或未取代的5-元杂环；或与R³⁰⁷和R³¹³一起表示亚甲二氧基、亚乙二氧基、亚甲氧基亚甲氧基、三亚甲基、四亚甲基、亚丙烯基、亚丁烯基或亚丁二烯基，每一个R³⁰⁷和R³¹³彼此独立地表示H、磺酸基团或其盐、酯或酰胺、羧酸基团或其盐、酯或酰胺、氰基、卤原子、取代或未取代的烷基或烷氧基，或与R³⁰⁶和R³¹²一起表示亚甲二氧基、亚乙二氧基、亚甲氧基亚甲氧基、三亚甲基、四亚甲基、亚丙烯基、亚丁烯基或亚丁二烯基，每一个R³⁰⁸和R³¹⁴彼此独立地表示H、卤原子或取代或未取代的烷基，每一个R³⁰⁹和R³¹¹彼此独立地表示H、卤原子、氰基、磺酸基团或其盐、酯或酰胺、羧酸基团或其盐、酯或酰胺，R³¹⁰独立地表示H、卤原子、氰基、磺酸基团或其盐、烷基(优选被羟基取代)、具有1-30个碳原子的烷氧基、氰基、卤原子、羧基、磺酸基、烷氧基部分具有1-30个碳原子的烷氧羰基、苯基或苯氧基；可被羟基取代的烷氧基；具有1-30个碳原子的烷氧基、氰基、卤原子、羧基、在烷氧基部分具有1-30个碳原子的烷氧羰基、苯基或苯氧基；可被卤原子、氰基、羧基取代的苯基、苯基烷基或苯氧基、烷氧基部分具有1-30个碳原子的烷氧羰基、磺基或分别具有1-30个碳原子的烷基或烷氧基；其中，该化合物具有反式共面或顺式共面取向；可能的环烷基优选环己基和环戊基，其可被具有1-30个碳原子的烷基取代；可有的5元杂环为v-三唑、噁唑或1，3，4-噁二唑基，其可包含作为取代基的具有1-4个碳原子的烷基、卤原子、苯基、羧基、烷氧基部分具有1-30个碳原子的烷氧羰基、氰基、苄基、具有1-30个碳原子的烷氧基、苯氧基或磺基，三唑和噁唑基团的两个相邻的基团可一起形成取代或未取代的稠合苯环；其中，该化合物具有反式共面取向；

其中，Q¹表示环体系(13)或(14)之一；其中、R³¹⁷表示H、具有1-30个碳原子的烷基、环己基、烷基部分具有1-30个碳原子的苯基烷基、苯基、具有1-30个碳原子的烷氧基或Cl，或者，与R³¹⁸一起代表具有3-30个碳原子的亚烷基，R³¹⁸表示H或具有1-30个碳原子的烷基，或者与R³¹⁷一起表示具有3-30个碳原子的亚烷基，R³¹⁹表示H或甲基，R³²⁰表示H、具有1-30个碳原子的烷基、苯基、具有1-30个碳原子的烷氧基或Cl，或与R³²¹一起表示稠合苯环，R³²¹表示H或Cl或与R³²⁰一起表示稠合苯环，R³¹⁵表示H、具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基或Cl，R³¹⁶表示H或Cl，Q²表示H、Cl、具有1-30个碳原子的烷基或苯基，Q³表示H或Cl；其中，该化合物具有反式共面或顺式共面取向，优选反式共面取向；其中，R³²²表示H、Cl、甲基、苯基、苄基、环己基或甲氧基，R³²³表示H或甲基，Z表示O或S；其中，该化合物具有反式共面或顺式共面取向，优选反式共面取向；

其中，R³²⁴表示H、Cl、具有1-30个碳原子的烷基、具有1-30个碳原子的苯基烷基、苯基或具有1-30个碳原子的烷氧基，或R³²⁴与R³²⁵一起表示稠合苯基，R³²⁵表示H或甲基或R³²⁵与R³²⁴一起表示稠合苯基，R³²⁶表示H、具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、C1、具有1-30个碳原子的烷氧羰基或具有1-30个碳原子的烷基磺酰基，和R³²⁷表示H、Cl、甲基或甲氧基；其中，该化合物具有反式共面或顺式共面取向，优选反式共面取向。Triazoles useful in the present invention include compounds having the following formulas (9) to (12) and (15) to (20): Wherein, R ³⁰¹ and R ³⁰² are independently H, C ₁ -C ₃₀ alkyl, phenyl or monosulfonated phenyl; An ^- and M are as defined above, wherein, the compound has trans coplanar or cis Coplanar orientation; preferably R ³⁰¹ is phenyl, R ³⁰² is H and M is sodium; wherein, the compound has a trans coplanar orientation;

wherein R ³⁰³ is H or Cl; R ³⁰⁴ is SO ₃ M, SO ₂ N(C ₁ -C ₃₀ -alkyl) ₂ , SO ₂ O-phenyl or CN; R ³⁰⁵ is H, SO ₃ M, COOM, OSO ₃ M or OPO(OH)OM; M is as defined above, wherein the compound has a trans-coplanar or cis-coplanar orientation; preferably R ³⁰³ and R ³⁰⁵ are H, R ³⁰⁴ is SO ₃ M, wherein M is Na; Wherein, the compound has trans coplanar orientation;

wherein each of R ³⁰⁶ and R ³¹² is independently H, a sulfonic acid group or a salt thereof, an ester or amide, a carboxylic acid group or a salt thereof, an ester or an amide, a cyano group, a halogen atom, a substituted or unsubstituted alkane Sulfonyl, arylsulfonyl, alkyl, alkoxy, aralkyl, aryl, aryloxy, aralkoxy or cycloalkyl containing 2 to 3 nitrogen atoms or 1 oxygen atom and 1 Or a substituted or unsubstituted 5-membered heterocyclic ring with 2 nitrogen atoms; or together with R ³⁰⁷ and R ³¹³ represent methylenedioxy, ethylenedioxy, methyleneoxymethyleneoxy, trimethylene , tetramethylene, propenylene, butenylene or butadienylene, each of R ³⁰⁷ and R ³¹³ independently represents H, a sulfonic acid group or its salt, ester or amide, a carboxylic acid group or its Salt, ester or amide, cyano group, halogen atom, substituted or unsubstituted alkyl or alkoxy group, or together with R ³⁰⁶ and R ³¹² represent methylenedioxy, ethylenedioxy, methyleneoxyethylene Methoxy, trimethylene, tetramethylene, propenylene, butenylene or butadienylene, each of R ³⁰⁸ and R ³¹⁴ independently represents H, a halogen atom or a substituted or unsubstituted alkyl group, Each of R ³⁰⁹ and R ³¹¹ independently represents H, a halogen atom, a cyano group, a sulfonic acid group or a salt thereof, an ester or amide, a carboxylic acid group or a salt thereof, an ester or an amide, and R ³¹⁰ independently represents H, Halogen atom, cyano group, sulfonic acid group or salt thereof, alkyl group (preferably substituted by hydroxyl group), alkoxy group having 1 to 30 carbon atoms, cyano group, halogen atom, carboxyl group, sulfonic acid group, alkoxy group An alkoxycarbonyl group, phenyl or phenoxy group having 1-30 carbon atoms in part; an alkoxy group which may be substituted by a hydroxyl group; an alkoxy group having 1-30 carbon atoms, a cyano group, a halogen atom, a carboxyl group, a Alkoxycarbonyl, phenyl or phenoxy groups having 1 to 30 carbon atoms in the alkoxy moiety; phenyl, phenylalkyl or phenoxy groups which may be substituted by halogen atoms, cyano groups, carboxyl groups, alkoxy moieties Alkoxycarbonyl, sulfo, or alkyl or alkoxy having 1-30 carbon atoms, respectively; wherein, the compound has a trans-coplanar or cis-coplanar orientation; possible ring Alkyl is preferably cyclohexyl and cyclopentyl, which may be substituted by alkyl having 1-30 carbon atoms; possible 5-membered heterocycles are v-triazole, oxazole or 1,3,4-oxadiazole group, which may contain, as a substituent, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a carboxyl group, an alkoxycarbonyl group having 1 to 30 carbon atoms in an alkoxy group, a cyano group, a benzyl group, Alkoxy, phenoxy or sulfo groups with 1-30 carbon atoms, two adjacent groups of triazole and oxazole groups can form together a substituted or unsubstituted condensed benzene ring; wherein, the The compound has a trans-coplanar orientation;

Wherein, ^Q represents one of the ring systems (13) or (14); Wherein, R ³¹⁷ represents H, alkyl having 1-30 carbon atoms, cyclohexyl, phenylalkyl having 1-30 carbon atoms in the alkyl part, phenyl, alkoxy having 1-30 carbon atoms or Cl, or together with R ³¹⁸ represents an alkylene group with 3-30 carbon atoms, R ³¹⁸ represents H or an alkyl group with 1-30 carbon atoms, or together with R ³¹⁷ represents an alkylene group with 3-30 carbon atoms The alkylene group of carbon atoms, R ³¹⁹ represents H or methyl, R ³²⁰ represents H, an alkyl group with 1-30 carbon atoms, phenyl, an alkoxy group with 1-30 carbon atoms or Cl, or with R ³²¹ together represents a fused benzene ring, R ³²¹ represents H or Cl or together with R ³²⁰ represents a fused benzene ring, R ³¹⁵ represents H, an alkyl group having 1-30 carbon atoms, an alkyl group having 1-30 carbon atoms Alkoxy or Cl, R ³¹⁶ represents H or Cl, Q ² represents H, Cl, an alkyl or phenyl group with 1-30 carbon atoms, Q ³ represents H or Cl; wherein, the compound has trans coplanar Or cis-coplanar orientation, preferably trans-coplanar orientation; Wherein, R ³²² represents H, Cl, methyl, phenyl, benzyl, cyclohexyl or methoxy, R ³²³ represents H or methyl, Z represents O or S; wherein, the compound has trans coplanar or cis Type coplanar orientation, preferably trans coplanar orientation;

Wherein, ^R represents H, Cl, an alkyl group having 1-30 carbon atoms, a phenylalkyl group having 1-30 carbon atoms, a phenyl group or an alkoxy group having 1-30 carbon atoms, or R ³²⁴ and R ³²⁵ together represent fused phenyl, R ³²⁵ represents H or methyl or R ³²⁵ and R ³²⁴ represent fused phenyl together, R ³²⁶ represents H, an alkyl group with 1-30 carbon atoms, an alkyl group with 1- Alkoxy with 30 carbon atoms, C, alkoxycarbonyl with 1 to 30 carbon atoms or alkylsulfonyl with 1 to 30 carbon atoms, and ^R represents 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. Optical brightener 46), trade name Tinopal RBS, Commercially available from Ciba Specialty Chemicals.

pyrazoline

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

其中，R⁴⁰¹是H、Cl或N(C₁-C₃₀-烷基)₂，R⁴⁰²是H、Cl、SO₃M、SO₂NH₂、SO₂NH-(C₁-C₃₀烷基)、COO-C₁-C₃₀烷基、SO₂-C₁-C₃₀烷基、SO₂NH(CH₂)_1-4N⁺(CH₃)₃或SO₂(CH₂)_1-4N⁺H(C₁-C₃₀-烷基)₂An^-，R⁴⁰³与R⁴⁰⁴可相同或不同，每一个分别是H、C₁-C₃₀烷基或苯基，R⁴⁰⁵为H或Cl；An^-和M如前述定义，优选R⁴⁰¹是Cl，R⁴⁰²为SO₂CH₂CH₂N⁺H(C₁-C₄-烷基)₂An^-，其中An^-是亚磷酸根，R⁴⁰³、R⁴⁰⁴和R⁴⁰⁵分别是H；如下所示的式(22)和(23)：

Pyrazolines useful in the present invention include those having the following formulas (21) to (23):

Wherein, R ⁴⁰¹ is H, Cl or N(C ₁ -C ₃₀ -alkyl) ₂ , R ⁴⁰² is H, Cl, SO ₃ M, SO ₂ NH ₂ , SO ₂ NH-(C ₁ -C ₃₀ -alkyl ), COO-C ₁ -C ₃₀ alkyl, SO ₂ -C ₁ -C ₃₀ alkyl, SO ₂ NH(CH ₂ ) _1-4 N ⁺ (CH ₃ ) ₃ or SO ₂ (CH ₂ ) _1-4 N ⁺ H(C ₁ -C ₃₀ -alkyl) ₂ An ^- , R ⁴⁰³ and R ⁴⁰⁴ may be the same or different, each is H, C ₁ -C ₃₀ alkyl or phenyl, R ⁴⁰⁵ is H or Cl ; An ^- and M are as defined above, preferably R ⁴⁰¹ is Cl, R ⁴⁰² is SO ₂ CH ₂ CH ₂ N ⁺ H(C ₁ -C ₄ -alkyl) ₂ An ^- , wherein An ^- is phosphite, R ⁴⁰³ , R ⁴⁰⁴ and R ⁴⁰⁵ are H respectively; formulas (22) and (23) as shown below:

Suitable pyrazolines include: 1-(4-amidosulfonylphenyl)-3-(4-chlorophenyl)-2-pyrazoline (C.I. Optical brightener 121) trade name Blankophor DCB, available Commercially available from Bayer; 1-[4-(2-sulfoethylsulfonyl)phenyl]-3-(4-chlorophenyl)-2-pyrazoline; 1-[4-(2-sulfo Ethylsulfonyl)phenyl]-3-(3,4-dichlorophenyl)-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

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

其中，R⁵⁰³独立地是H、C(CH₃)₃、C(CH₃)₂-苯基、C₁-C₃₀烷基或COO-C₁-C₃₀烷基，优选H和Q⁴是-CH＝CH-；

Oxazoles useful in the present invention include those compounds having the formulas (24), (25), (26) and (27): Wherein, R ⁵⁰¹ and R ⁵⁰² are independently H, Cl, C ₁ -C ₃₀ alkyl or SO ₂ -C ₁ -C ₃₀ alkyl, wherein the compound has a trans-coplanar or cis-coplanar orientation; Preferably R ⁵⁰¹ is 4-CH ₃ and R ⁵⁰² is 2-CH ₃ , wherein the compound has a trans coplanar orientation;

Wherein, R ⁵⁰³ is independently H, C(CH ₃ ) ₃ , C(CH ₃ ) ₂ -phenyl, C ₁ -C ₃₀ alkyl or COO-C ₁ -C ₃₀ alkyl, preferably H and Q ⁴ are -CH=CH-;

preferred

其中，R⁵¹¹表示H、具有1-30个碳原子的烷基、具有1-30个碳原子的烷氧基、Cl、具有1-30个碳原子的烷氧羰基、未取代的氨磺酰基或用1-30个碳原子的烷基或羟烷基单或二取代的氨磺酰基或表示具有1-30个碳原子的烷基磺酰基；其中，该化合物具有反式共面或顺式共面取向，优选反式共面取向。Alternatively, R ⁵⁰³ on each ring is 2-methyl, the other R ⁵⁰³ is H, and Q ⁴ is -CH=CH-; or one R ⁵⁰³ on each ring is 2-C(CH ₃ ) ₃ , another R ⁵⁰³ is H; wherein, the compound has a trans-coplanar or cis-coplanar orientation, preferably a trans-coplanar orientation. Wherein, R ⁵⁰⁴ is CN, Cl, COO-C ₁ -C ₃₀ alkyl or phenyl; R ⁵⁰⁵ and R ⁵⁰⁶ are atoms required to form a fused benzene ring, or R ⁵⁰⁶ and R ⁵⁰⁸ are independently H or C ₁ -C ₃₀ alkyl; R ⁵⁰⁷ is H, C ₁ -C ₃₀ alkyl or phenyl; wherein, the compound has a trans-coplanar or cis-coplanar orientation; preferably R ⁵⁰⁴ is 4-phenyl and R ⁵⁰⁵ Each of R to ^R is H; wherein the compound has a trans-coplanar orientation; and Wherein, R ⁵⁰⁹ represents H, Cl, alkyl having 1-30 carbon atoms, cyclohexyl, phenylalkyl having 1-3 carbon atoms in the alkyl part, phenyl or phenyl having 1-30 carbon atoms Alkoxy group, R ⁵¹⁰ represents H or has the alkyl group of 1-30 carbon atom, Q ⁵ represents following group:

Wherein, ^R represents H, an alkyl group having 1-30 carbon atoms, an alkoxy group having 1-30 carbon atoms, Cl, an alkoxycarbonyl group having 1-30 carbon atoms, an unsubstituted sulfamoyl group Or a sulfamoyl group mono- or disubstituted with an alkyl or hydroxyalkyl group of 1-30 carbon atoms or an alkylsulfonyl group with 1-30 carbon atoms; wherein, the compound has a trans coplanar or cis Coplanar orientation, preferably trans coplanar orientation.

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

Pyrene

其中，每一个R⁶⁰¹独立地是C₁-C₃₀烷氧基；优选甲氧基；和

其中，每一个R⁶⁰²独立地是H、OH或SO₃M，其中，M是如前述定义，磺化苯基氨基或苯氨基。Pyrene useful in the present invention includes those compounds having formulas (28) and (29):

Wherein, each R ⁶⁰¹ is independently C ₁ -C ₃₀ alkoxy; preferably methoxy; and

Wherein, each R ⁶⁰² is independently H, OH or SO ₃ M, wherein M is sulfonated phenylamino or phenylamino as defined above.

Suitable pyrenes include: 2,4-dimethoxy-6-(11-pyrenyl)-1,3,5-triazine (C.I. Fluorescent Brightener 179), trade name Fluolite XMF, 8-hydroxy- 1,3,6-pyrenetrisulfonic acid (D&C Green No. 8) and 3-hydroxy-5,8,10-trisulphanilic pyrene.

porphyrin

其中，R⁷⁰¹是CH₃或CHO，R⁷⁰²是H或COOC₁-C₃₀烷基和R⁷⁰³是H或1-30个碳原子的烷基；和

其中，每一个R⁷⁰⁴独立地是H、SO₃M、COOM、OSO₃M或OPO(OH)OM，其中M是如前述定义，卤离子或具有1-30个碳原子的烷基；Q⁶是Cu、Mg、Fe、Cr、Co或带有阳离子电荷的混合物。Porphyrins useful in the present invention include those compounds having the following formulas (30), (31 ) and (32):

Wherein, R ⁷⁰¹ is CH ₃ or CHO, R ⁷⁰² is H or COOC ₁ -C ₃₀ alkyl and R ⁷⁰³ is H or alkyl of 1-30 carbon atoms; and

Wherein, each R ⁷⁰⁴ is independently H, SO ₃ M, COOM, OSO ₃ M or OPO(OH)OM, wherein M is as defined above, a halide ion or an alkyl group with 1-30 carbon atoms; Q ⁶ It is Cu, Mg, Fe, Cr, Co or a mixture with cationic charges.

Suitable porphyrins include: porphyrin commercially available from Wako Chemicals and the phthalocyanine copper II commercially available from Wako Chemicals.

imidazole

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

其中，X^-如前述定义。Imidazoles useful in the present invention include compounds having the following formula (33):

Wherein, X ^- as defined above.

Suitable imidazoles include those commercially available from Ciba Specialty Chemical under the tradename C.I. Optical Brightener 352 or UvtexAT.

Optical brighteners are present in the present invention in amounts that alter the color of the hair to which the composition is applied. Color can be described using three independent variables, namely lightness (lightness), hue (hue) and saturation (saturation). In the present invention, the degree of color change is determined by units of color parameters using colorimetric data obtained from either a Macbeth 1500 Reflective Color Meter (supplied by Kollmorgen Corporation) or a MiniScan XE spectrophotometer (provided by Hunter Associates Laboratory) calculated from the measured spectral data. The color parameters are suitably described by "L, a, b, color coordinates" shown in FIG. 1 . "L, a, b, color coordinates" describes the color of any material based on the three parameters L, a, and b. The parameter "L" is a measure of lightness, ranging from 0 (full black) to 100 (full white). The parameters "a" and "b" represent hue and saturation by degrees of red (positive a), green (negative a), and yellow (positive b), blue (negative b). For achromatic colors such as white, gray, and black, the parameters "a" and "b" are both 0; that is, colors that have no tint. The larger the absolute value of a and b, the more saturated or colorful the color is. The a value varies from -50 for pure green to +50 for pure red. The b value varies from -50 for pure blue to +50 for pure yellow.

The optical brightener is present in an amount that changes the color of the hair to which the composition is applied by about 0.2 to 15 units of a color parameter selected from the group consisting of a value and b value and both. When the degree of color change is from about 0.2 units to about 15 units with respect to a value, b value, or both, we perceive a change in the color of the hair in such a way that the unsightly appearance of damaged hair is lessened, or Makes hair color more infectious. The amount of fluorescer to alter the hair color of the applied composition for a noticeable, pleasing change is from about 0.5 units to 10 units for the a value, the b value, or both.

Hair color can change towards a more achromatic color, or towards a more saturated or pigmented color. As the color changes toward decreasing the absolute value of the a-value and/or the b-value, the color of the hair becomes darker. This change may be more practical for consumers who think the perfect brunette is contagious and/or undamaged. On the other hand, when the color changes towards increasing the absolute value of the a value and/or the b value, the hair becomes more saturated or more colored. This change is more practical for consumers who find saturated or more colored hair attractive. The type and amount of optical brighteners can be selected based on their absorption/emission spectra to provide the desired degree and type of color change. Two or more optical brighteners can be included in the composition to provide the desired degree and type of color change. It will be clear to those of ordinary skill in the art that such changes in hair color can also be accomplished by applying dyes to the hair. In the present invention, the degree and type of color change can be achieved without the aid of dyes of any kind. Of course, dyes may optionally be included in the compositions of the present invention in amounts which do not cause damage to the hair or make it dull. However, dye is not an essential ingredient.

Hair color can be described by L, a, b color parameters. The compositions of the present invention can change the color of hair having any color parameter. Preferably, the color change occurs within 20 units from the 0 point of the a-value axis and the b-value axis. The change in color is particularly noticeable when the change occurs within 10 units, preferably within 5 units, from the 0 point of the a-value axis and the b-value axis.

The specific amount of fluorescer used in the hair care compositions of the present invention will vary depending on the nature of the fluorescer, the form of the product containing the fluorescer, and the other components contained in the composition. For example, fluorescers with relatively stronger emissions will change color in lesser amounts than those with relatively weaker emissions. In another example, a product form that is intended to be left on the hair can be formulated with a lower amount of optical brightener than a product form that is intended to be rinsed from the hair. In another example, a composition comprising a component that provides strong deposition to hair may have a lesser amount of optical brightener than a composition not comprising said component. The compositions of the present invention are preferably formulated so that the optical brightener is applied to the hair at a level of from about 1 ppm to 2%, preferably from 10 ppm to 1%, more preferably from about 100 ppm to 0.3%, by weight of the hair. Preferably, optical brighteners are present in the hair care compositions of the present invention at a level of from about 0.001 to 20% by weight, more preferably from about 0.01 to 10% by weight.

The hair care compositions of the present invention comprising optical brighteners provide beneficial effects to the hair in three respects. First, optical brighteners can change the color of hair by emitting light in the visible range, as explained in detail above. Second, optical brighteners can enhance the shine of hair by emitting light in the visible range. Third, optical brighteners can also protect hair from damage caused by UV light by absorbing it.

The hair care compositions of the present invention are intended for daily use. The hair color changing effect can be enhanced by daily repeated use of the composition of the present invention. On the other hand, hair color altered by the compositions of the present invention can be restored to its original color after one or about several washes of the hair with conventional shampoos.

hair care actives

The hair care compositions of the present invention comprise an ingredient characterized by product form and function. Product forms for use in the present invention include, but are not limited to: shampoos, conditioners, treatments, mousses, sprays, lotions, gels and creams, all of which can be designed for ease of use. Rinse off or don't wash off. Product functions for use in the present invention include, but are not limited to: cleansing, conditioning and styling. To prepare these products, hair care actives may be included which are selected from detersive surfactants, conditioning agents, styling polymers and mixtures thereof. The hair care actives and their levels can be selected by those skilled in the art according to the desired properties of the product.

detersive surfactant

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

When employed, detersive surfactants are preferably present at levels from about 0.01 to about 75% by weight of the composition. Two or more surfactants may be used.

anionic surfactant

Anionic surfactants useful in the present invention include alkyl and alkyl ether sulfates. These _materials have the general formulas _ROSO3M and RO( _C2H4O ) _xSO3M , respectively, where _R is an alkyl or alkenyl group having from about 8 to about 30 carbon atoms and x is from 1 to about 10 M is an integer of hydrogen or a cation, such as ammonium, alkanolammonium (such as triethanolammonium), monovalent metal cations (such as sodium and potassium), or multivalent metal cations (such as magnesium and calcium). Preferably M should be chosen such that the anionic detersive surfactant ingredient is water soluble. Anionic surfactants should be selected to have a Krafft temperature of about 15°C or less, preferably about 10°C or less, more preferably about 0°C or less. It is also preferred that the anionic surfactant is dissolved in the composition.

The Krafft temperature is the temperature at which the solubility of an ionic surfactant becomes determined by the lattice energy and heat of hydration, and corresponds to the temperature at which a sharp and discontinuous increase in solubility occurs with increasing temperature. Each type of surfactant will have its own characteristic Krafft temperature. The Krafft temperatures of ionic surfactants are generally well known. See, for example, the following: Myers, Drew, Surfactant Science and Technology, pp. 82-85, VCH Publishers, Inc. (New York, USA), 1988 (ISBN 0-89573-399-0), incorporated in This article is for reference.

In the above alkyl and alkyl ether sulfates, it is preferred that R has 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 about 8 to about 24 carbon atoms. Alcohols may be synthetic, or they may be derived from fats such as coconut oil, palm kernel oil, tallow. Lauryl alcohol and straight chain alcohols derived from coconut or palm kernel oil are preferred. This alcohol is reacted with ethylene oxide in a molar ratio of from 1 to about 10, preferably about 3, to form a mixture having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, and this mixture is then sulfated and neutralized .

Specific examples of alkyl ether sulfates that may be used include: sodium and ammonium coco alkyl triethylene glycol ether sulfates, sodium and ammonium tallow alkyl triethylene glycol ether sulfates, tallow alkyl triethylene glycol ether sulfates, Sodium and ammonium salts of oxyethylene sulfate. Particularly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, wherein the compounds in the mixture have an average alkyl chain length of from about 8 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to About 4 moles of ethylene oxide. This mixture also contains 0 to about 20% by weight of C _12-13 compounds; about 60 to about 100% by weight of C _14-15-16 compounds; 0 to about 20% by weight of C _17-18-19 compounds; 3 to about 30% by weight of compounds with a degree of ethoxylation of 0; about 45 to about 90% by weight of compounds with a degree of ethoxylation of 1 to about 4; about 10 to about 25% by weight of ethoxylated and about 0.1 to about 15% by weight of compounds having a degree of ethoxylation greater than about 8.

Other suitable anionic surfactants are organic, water-soluble salts of sulfuric acid reaction products having the general formula [ ^R1 - _SO3 -M], wherein ^R1 is carbon atoms, linear or branched, saturated aliphatic hydrocarbon group; M is a cation as mentioned above. Examples of such surfactants are salts of products obtained from the organic sulfuric acid reaction of methane series hydrocarbons and sulfonating agents according to known sulfonation methods (including bleaching and hydrolysis), and said hydrocarbons include iso, neo, normal Paraffins have about 8-24 carbon atoms, preferably about 8-18 carbon atoms, and the sulfonating agent is, for example, sulfur trioxide and sulfuric acid. Preference is given to alkali metal and ammonium salts of sulfonated C ₈ -C ₁₈ n-paraffins.

Other suitable anionic surfactants are the reaction products of fatty acids obtained, for example, from coconut oil or palm kernel oil, with isethionic acid and neutralized with sodium hydroxide; Sodium or potassium salts of fatty acid amides, wherein the fatty acid is obtained, for example, from coconut oil. Other similar anionic surfactants are described in the following patent documents: US 2,486,921; US 2,486,922; US 2,396,278, all of which are incorporated herein by reference.

其中，R¹为具有约6至约20个碳原子的直链烷基，R²为具有约1，优选至约3个碳原子的低级烷基，M如前所述。许多其它适用于香波组合物中的阴离子表面活性剂在下述文献中有述：McCutcheon′s，乳化剂和洗涤剂，1989年报，由M.C.Publishing Co.出版；US 3,929,678，这些文献引入本文作为参考。优选的用于香波组合物中的阴离子表面活性剂包括：月桂基硫酸铵、月桂基聚氧乙烯醚硫酸铵、月桂基硫酸三乙胺、月桂基聚氧乙烯醚硫酸三乙胺、月桂基硫酸三乙醇胺、月桂基聚氧乙烯醚硫酸三乙醇胺、月桂基硫酸单乙醇胺、月桂基聚氧乙烯醚硫酸单乙醇胺、月桂基硫酸二乙醇胺、月桂基聚氧乙烯醚硫酸二乙醇胺、月桂单甘油酯硫酸钠、月桂基硫酸钠、月桂基聚氧乙烯醚硫酸钠、月桂基硫酸钾、月桂基聚氧乙烯醚硫酸钾、椰油酰基硫酸铵、月桂酰基硫酸铵、椰油酰基硫酸钠、月桂酰基硫酸钠、椰油酰基硫酸钾、月桂基硫酸钾、月桂基硫酸三乙醇胺、月桂酰基硫酸三乙醇胺、椰油酰基硫酸单乙醇胺、月桂基硫酸单乙醇胺、十三烷基苯磺酸钠、十二烷基苯磺酸钠以及它们的混合物。Another class of anionic surfactants suitable for use in shampoo compositions are the beta-alkoxyalkanesulfonates. The general formula of these surfactants is

Wherein, R ¹ is a linear alkyl group with about 6 to about 20 carbon atoms, R ² is a lower alkyl group with about 1, preferably to about 3 carbon atoms, and M is as previously described. Many other anionic surfactants suitable for use in shampoo compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989, published by MC Publishing Co.; US 3,929,678, which are incorporated herein by reference. Preferred anionic surfactants for use in shampoo compositions include: Ammonium Lauryl Sulfate, Ammonium Laureth Sulfate, Triethylamine Lauryl Sulfate, Triethylamine Laureth Sulfate, Lauryl Sulfate Triethanolamine, Triethanolamine Laureth Sulfate, Monoethanolamine Lauryl Sulfate, Monoethanolamine Laureth Sulfate, Diethanolamine Lauryl Sulfate, Diethanolamine Laureth Sulfate, Lauryl Monoglyceride Sulfate Sodium, Sodium Laureth Sulfate, Sodium Laureth Sulfate, Potassium Laureth Sulfate, Potassium Laureth Sulfate, Ammonium Cocoyl Sulfate, Ammonium Laureth Sulfate, Sodium Cocoyl Sulfate, Lauroyl Sulfate Sodium, Potassium Cocoyl Sulfate, Potassium Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Monoethanolamine Cocoyl Sulfate, Monoethanolamine Lauryl Sulfate, Sodium Tridecylbenzene Sulfate, Lauryl Sulfate Sodium phenyl sulfonate and their mixtures.

Other anionic surfactants useful in the present invention include polyhydrophilic anionic surfactants. The so-called "multi-hydrophilic" herein means that the surfactant has at least two kinds of hydrophilic groups that provide hydrophilic properties. The polyhydrophilic 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 polyhydrophilic anionic surfactant of the present invention may contain the same hydrophilic group or different hydrophilic groups. In particular, the polyhydrophilic anionic surfactant comprises at least one group selected from 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 those compounds which contain at least one carboxyl group.

其中，R为8-18个碳原子的烷基。其它多亲水性阴离子表面活性剂包括具有约10至约24个碳原子的烯烃磺酸盐。本文中所用术语“烯烃磺酸盐”是指所述化合物可通过用未配合的三氧化硫磺化α-烯烃，随后中和酸性反应混合物，这样反应中形成的任何磺内酯被水解而形成相应的羟基-烷磺酸盐，得到所述化合物。三氧化硫可为液体或气体，当以液体形式使用时，通常但并非必要地，用惰性稀释剂进行稀释，例如用液体二氧化硫，氯代烃等；当以气体形式使用时，用空气、氮气、气体二氧化硫等进行稀释。用于形成烯烃磺酸盐的α-烯烃是具有约8至约24个碳原子、优选约10至约16个碳原子的单烯烃。优选它们是直链烯烃。除了真的烯烃磺酸盐和一部分羟基烷磺酸盐外，烯烃磺酸盐可包含少量的其它物质，如烯烃二磺酸盐，这取决于反应条件、反应物的比例、原料烯烃的性质及烯烃中的杂质和磺化过程中的副反应等。这种α-烯烃磺酸盐混合物的非限定性实例在US 3,332,880(Pflaumer和Kessler，1967年7月25日授权)中有述，该文献引入本文作为参考。Non-limiting examples of polyhydrophilic anionic surfactants include: N-acyl-L-glutamate such as N-cocoyl-L-glutamate and N-lauroyl-L-glutamate , lauryl iminodipropionate, N-acetyl-L-aspartate, di-(N-lauroyl N-methyl taurate), polyoxyethylene lauryl sulfosuccinate, Disodium N-octadecylsulfosuccinate; Disodium Laurylsulfosuccinate; Diammonium Laurylsulfosuccinate; N-(1,2-dicarboxyethyl)-N-octadecyl Tetrasodium sulfosuccinate; Dipentyl ester of sodium sulfosuccinate; Dihexyl ester of sodium sulfosuccinate; Dioctyl ester of sodium sulfosuccinate and 2-cocoalkyl N-carboxyethyl N- Carboxyethoxyethylimidazolinium Betaine, Lauroyl Amphohydroxypropyl Sulfonate, Coco Glyceryl Ether Salt, Coco Glyceryl Sulfate, Lauroyl Isethionate, Lauroamphoacetic Acid salt, and those of the formula:

Wherein, R is an alkyl group of 8-18 carbon atoms. Other polyhydrophilic anionic surfactants include olefin sulfonates having from about 10 to about 24 carbon atoms. The term "olefin sulfonate" as used herein means that the compound can be formed by sulfonating an alpha-olefin with uncomplexed sulfur trioxide followed by neutralization of the acidic reaction mixture so that any sultones formed in the reaction are hydrolyzed to form the corresponding Hydroxy-alkane sulfonates to give the compound. Sulfur trioxide may be liquid or gas. When used in liquid form, it is usually, but not necessarily, diluted with an inert diluent, such as liquid sulfur dioxide, chlorinated hydrocarbons, etc.; when used in gaseous form, it is diluted with air, nitrogen, etc. , gas sulfur dioxide, etc. for dilution. The alpha-olefins used to form the olefin sulfonates are monoolefins having from about 8 to about 24 carbon atoms, preferably from about 10 to about 16 carbon atoms. Preferably they are linear olefins. In addition to true olefin sulfonates and a portion of hydroxyalkane sulfonates, olefin sulfonates may contain small amounts of other substances, such as olefin disulfonates, depending on the reaction conditions, the ratio of reactants, the nature of the starting olefin and Impurities in olefins and side reactions during sulfonation, etc. Nonlimiting examples of such alpha-olefin sulfonate mixtures are described in US 3,332,880, Pflaumer and Kessler, issued Jul. 25, 1967, which is incorporated herein by reference.

Another class of polyhydrophilic anionic surfactants are amino acid surfactants which have the basic chemical structure of an amino acid compound, ie, the compound contains structural components of one of the natural amino acids. It will be appreciated that certain surfactants can be considered both as polyhydrophilic anionic surfactants and as amino acid surfactants. These surfactants are all suitable anionic surfactants.

Non-limiting examples of amino acid surfactants include: N-cocoyl alaninate, N-acyl-N-methyl-β-alaninate, N-acyl sarcosinate; N-alkylamino Propionates and N-alkyliminodipropionates, specific examples of which include N-lauryl-β-alanine or salts thereof, and N-lauryl-β-iminodipropionates, N- Acyl-DL-alanine, sodium lauryl sarcosinate, sodium lauryl sarcosinate, lauryl sarcosine, cocoyl sarcosine, N-acyl-N-methyl taurate, lauryl Acyl taurate and lauroyl lactylate.

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

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

Coacervate formation depends on various conditions such as molecular weight, component concentrations and ratios of interacting ionic components, ionic strength, charge density of cationic and anionic components, pH, and temperature. Coacervate systems and the effect of these parameters are well known in the art.

It is believed that the presence of anionic surfactants and multivalent metal cations in levels in the coacervate phase together with cationic conditioning agents is particularly beneficial. It is believed that the coacervate formed in the composition tends to deposit on the hair when the coacervate is diluted with large amounts of water, ie when the shampoo is rinsed off.

While not being bound by any theory, it is believed that the coacervate provides two main functions to the shampoo composition. First, it reduces the critical micelle concentration (hereinafter "CMC") of the composition. Reducing CMC means reducing surface tension, which improves foam performance. Second, the presence of anionic surfactants and multivalent metal cations expands the area of the coacervate in the composition. Since the cationic conditioning agent in the composition is primarily delivered through these coacervates, enlarging the area of the coacervate will allow more cationic conditioning agent to be delivered to the hair. As a result, compositions that simultaneously cleanse and condition hair in a single product form with improved overall conditioning and foam performance are provided.

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

Amphoteric and Zwitterionic Surfactants

Amphoteric surfactants useful in the present invention include aliphatic secondary and tertiary amine derivatives, wherein the aliphatic group may be straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, while the other contains an anionic water solubilizing group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate.

其中，R²包含烷基、链烯基或羟基烷基，具有约8至约18个碳原子、0至约10个氧化乙烯单元和0至约1个甘油基单元；Y选自氮、磷和硫原子；R³为包含1至约3个碳原子的单羟基烷基；当Y为硫原子时，X为1，当Y为氮或磷原子时，X为2；R⁴为具有1至约4个碳原子的亚烷基或羟基亚烷基，Z为选自羧酸根、磺酸根、硫酸根、膦酰根和磷酸根的基团。Zwitterionic surfactants useful in the present invention include aliphatic quaternary ammonium, quaternary phosphonium, and quaternary sulfonium compounds, wherein the aliphatic group can be straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, while the other contains an anionic group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. The general formula of these compounds is as follows:

Wherein, R ² comprises an alkyl, alkenyl or hydroxyalkyl group having from about 8 to about 18 carbon atoms, from 0 to about 10 oxyethylene units and from 0 to about 1 glyceryl unit; Y is selected from nitrogen, phosphorus and a sulfur atom; R ³ is a monohydroxyalkyl group containing 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; R ⁴ is a An alkylene or hydroxyalkylene group of up to about 4 carbon atoms, Z is a group selected from carboxylate, sulfonate, sulfate, phosphono and phosphate.

Examples of amphoteric surfactants and zwitterionic surfactants also include sultaines and amido sultaines. Examples of sultaines including amido sultaines are: coco dimethyl propyl sultaine, stearyl dimethyl propyl sultaine, lauryl bis-(2- Hydroxyethyl)propyl sultaine, etc.; and amido sultaines such as cocoamidodimethylpropyl sultaine, stearyl amidodimethylpropyl sultaine , Laurylamidobis-(2-hydroxyethyl)propyl sulfobetaine, etc. Preference is given to amido hydroxy sultaines such as C ₈ -C ₁₈ hydrocarbyl amidopropyl hydroxy sultaines, especially C ₈ -C ₁₄ hydrocarbyl amidopropyl hydroxy sultaines, e.g. lauryl amido Propyl Hydroxysultaine and Cocamidopropyl Hydroxysultaine. Other sultaines are described in US 3,950,417, which is incorporated herein by reference.

Other suitable amphoteric surfactants are aminoalkanoates of formula R—NH(CH _{2 ) n} COOM, iminodialkanoates of RN[(CH ₂ ) _m COOM] and mixtures thereof; wherein, n and m is a number from 1 to about 4, R is C ₈ -C ₂₂ alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.

其中，R¹为C₈-C₂₂烷基或链烯基，优选C₈-C₁₆；R²和R³独立地选自氢、CH₂CO₂M、CH₂CH₂OH、CH₂CH₂OCH₂CH₂COOM或(CH₂CH₂O)_mH，其中，m为1至约25的整数，R⁴为氢、CH₂CH₂OH或CH₂CH₂OCH₂CH₂COOM，Z为CO₂M或CH₂CO₂M，n为2或3，优选2，M为氢或阳离子，如碱金属(如锂、钠、钾)、碱土金属(铍、镁、钙、锶、钡)或铵。这一类型的表面活性剂有时也分类为咪唑啉型两性表面活性剂，可以理解，它们并非必须由咪唑啉中间体直接或间接得到。适宜的此类物质可以商品名MIRANOL商购，还应理解，可以包含此类物质的复合混合物，对于R²为氢型时的物质而言，根据其pH值，它们可以质子化和非质子化形式存在。所有这种变化和种类均指包含于上式中。Other suitable amphoteric surfactants include those represented by the formula:

Wherein, R ¹ is C ₈ -C ₂₂ alkyl or alkenyl, preferably C ₈ -C ₁₆ ; R ² and R ³ are independently selected from hydrogen, CH ₂ CO ₂ M, CH ₂ CH ₂ OH, CH ₂ CH ₂ OCH ₂ CH ₂ COOM or (CH ₂ CH ₂ O) _m H, wherein m is an integer from 1 to about 25, R ⁴ is hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ COOM, Z It is CO ₂ M or CH ₂ CO ₂ M, n is 2 or 3, preferably 2, M is hydrogen or cations, such as alkali metals (such as lithium, sodium, potassium), alkaline earth metals (beryllium, magnesium, calcium, strontium, barium ) or ammonium. Surfactants of this type are sometimes classified as imidazoline-type amphoteric surfactants, and it is understood that they are not necessarily obtained directly or indirectly from imidazoline intermediates. A suitable such material is commercially available under the tradename MIRANOL, and it is also understood that complex mixtures of such materials may be included, which may be protonated and unprotonated depending on their pH for species where ^R is in the hydrogen form form exists. All such variations and species are meant to be encompassed by the above formulae.

Examples of surfactants of the above formula are monocarboxylates and dicarboxylates. Specific examples thereof include cocoamphopropionate, cocoamphopropionate, cocoamphocarboxyglycinate (also known as cocoamphodiacetate), and cocoamphoacetate.

Commercially available amphoteric surfactants include those sold under the following tradenames: MIRANOLC 2M 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).

其中，R¹选自COOM和CH(OH)CH₂SO₃M，R²为低级烷基或羟烷基；R³为低级烷基或羟烷基；R⁴选自氢和低级烷基；R⁵为高级烷基或链烯基；Y为低级烷基，优选甲基；m为2-7的整数，优选2-3；n为整数1或0；M为氢或如前所述的阳离子，如碱金属、碱土金属或铵。术语“低级烷基”或“羟烷基”是指具有1至约3个碳原子的直链或支链的饱和脂族烃基和取代烃基，例如甲基、乙基、丙基、异丙基、羟丙基、羟乙基等。术语“高级烷基或链烯基”是指具有约8-约20个碳原子的直链或支链饱和(即“高级烷基”)和不饱和(即“高级链烯基”)脂族烃基，例如月桂基、鲸蜡基、硬脂基、油基等。可以理解，术语“高级烷基或链烯基”包括可包含一个或多个中间连接键如醚或多醚键或非官能取代基如羟基或卤素的基团混合物，其中，所述基团保留了疏水特性。Betaine surfactants, i.e., zwitterionic surfactants suitable for use in conditioning compositions of the present invention are those represented by the formula:

Wherein, R ¹ is selected from COOM and CH(OH)CH ₂ SO ₃ M, R ² is lower alkyl or hydroxyalkyl; R ³ is lower alkyl or hydroxyalkyl; R ⁴ is selected from hydrogen and lower alkyl; ^R is higher alkyl or alkenyl; Y is lower alkyl, preferably methyl; m is an integer of 2-7, preferably 2-3; n is an integer 1 or 0; M is hydrogen or as previously described Cations such as alkali metals, alkaline earth metals 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, such as methyl, ethyl, propyl, isopropyl , Hydroxypropyl, Hydroxyethyl etc. The term "higher alkyl or alkenyl" refers to straight or branched chain saturated (ie "higher alkyl") and unsaturated (ie "higher alkenyl") aliphatic compounds having from about 8 to about 20 carbon atoms. Hydrocarbon groups, such as lauryl, cetyl, stearyl, oleyl, etc. It will be understood that the term "higher alkyl or alkenyl" includes mixtures of groups which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substituents such as hydroxyl or halogen, wherein the groups retain hydrophobic properties.

Examples of the surfactant betaine (when n is 0) of the above formula used in the present invention include alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl 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. Representatives of sultaines are coco dimethyl sulphopropyl betaine, stearyl dimethyl sulphopropyl betaine, lauryl bis-(2-hydroxyethyl)-sulphopropyl betaine wait.

Specific examples of amidobetaines and amidosulfobetaines for use in the conditioning compositions of the present invention include amidocarboxybetaines such as cocoamidodimethylcarboxymethylbetaine, laurylamidodimethyl Cetyl carboxymethyl betaine, cetyl amido dimethyl carboxymethyl betaine, lauryl amido bis-(2-hydroxyethyl) carboxymethyl betaine, cocoamido-bis-(2- Hydroxyethyl)-carboxymethyl betaine, etc. Representative amido sulfobetaines are cocoamido dimethyl sulfopropyl betaine, stearyl amido dimethyl sulfopropyl betaine, lauryl amido-bis-(2-hydroxyethyl base)-sulfopropyl betaine, etc.

nonionic surfactant

The compositions of the present invention may contain a nonionic surfactant. Nonionic surfactants include those compounds produced by condensation of alkylene oxide compounds which are hydrophilic in nature with hydrophobic organic compounds, which may be aliphatic or alkylaromatic in nature.

Examples of preferred nonionic surfactants for use in the shampoo compositions of the present invention are:

(1) Polyoxyalkylene condensates of alkylphenols, such as condensation products of alkylphenols with ethylene oxide in which the alkyl group contains from about 6 to about 20 carbon atoms and is in a linear or branched configuration, so The amount of ethylene oxide is from about 10 to about 60 moles of ethylene oxide per mole of alkylphenol;

(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 about 10 to about 30 moles of ethylene oxide per mole of coconut oil alcohol Cocoalcohol ethylene oxide condensates of alkanes, the cocoalcohol moiety having from about 8 to about 14 carbon atoms;

(4) long chain tertiary amine oxides of the formula [R ¹ R ² R ³ N→O], wherein R ¹ comprises an alkyl, alkenyl or monohydroxyalkyl group having from about 8 to about 18 carbon atoms, and Having 0 to about 10 ethylene oxide moieties, 0 to about 1 glyceryl moiety, ^R2 and ^R3 containing about 1 to about 3 carbon atoms and 0 to about 1 hydroxyl group, such as methyl, ethyl, propyl , hydroxyethyl or hydroxypropyl;

(5) Long-chain tertiary phosphine oxides of the formula [RR'R"P→O], wherein R comprises an alkyl, alkenyl or monohydroxyalkyl group having from about 8 to about 18 carbon atoms, and having 0 to about 10 ethylene oxide moieties and 0 to about 1 glyceryl moiety, R' and R" are each an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms;

(6) Long-chain dialkylsulfoxides comprising a short-chain alkyl or hydroxyalkyl group (usually methyl) having 1 to about 3 carbon atoms, and also comprising a long-chain hydrophobic chain, including alkyl , alkenyl, hydroxyalkyl or ketoalkyl comprising about 8 to about 20 carbon atoms, 0 to about 10 ethylene oxide moieties and 0 to about 1 glyceryl moiety;

(7) Alkyl polysaccharide (APS) surfactant (as alkyl polyglucoside), its example is described in US4,565,647, and this document is incorporated herein as a reference; This document discloses APS surfactant, and it has about Hydrophobic groups of 6 to about 30 carbon atoms and polysaccharide groups (such as polyglucosides) as hydrophilic groups; optionally, polyoxyalkylene groups are present to link the hydrophobic and hydrophilic groups; Also, the alkyl group (i.e. the hydrophobic group) may be saturated or unsaturated, branched or straight chained, unsubstituted or substituted (e.g. substituted with hydroxyl or ring); preferred species are alkylpolyglucose Glycosides, which are commercially available from Henkel, ICI Americas and Seppic; and

(8) Polyoxyethylene alkyl ethers of the formula RO(CH ₂ CH ₂ ) _n H and those polyethylene glycols of the formula R(O)OCH ₂ CH ₂ (OH)CH ₂ (OCH ₂ CH ₂ ) _n OH Alcohol (PEG) fatty acid esters of glycerol, wherein n is 1 to about 200, preferably about 20 to about 100, and R is an alkyl group having about 8 to about 22 carbon atoms.

conditioner

Conditioners for use in the present invention include conditioners. Conditioners for use herein are those suitable for conditioning and caring for hair. Conditioning agents useful herein include cationic surfactants, high melting point compounds, oily compounds, cationic polymers, silicone compounds and nonionic polymers.

When used, conditioning agents are preferably present at a level of from about 0.01% to about 30% by weight of the composition. When two or more conditioning agents are used, it is preferred that the amount of each conditioner does not exceed about 20% by weight of the composition.

cationic surfactant

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

其中，至少R¹、R²、R³和R⁴之一选自具有8至约30个碳原子的脂族基团或具有至多约22个碳原子的芳族基团、烷氧基、聚氧化烯基、烷基酰氨基、羟基烷基、芳基或烷芳基；其余的R¹、R²、R³和R⁴彼此独立地选自具有1-约22个碳原子的脂族基团或具有至多约22个碳原子的芳族基团、烷氧基、聚氧化烯基、烷基酰氨基、羟基烷基、芳基或烷芳基；X为成盐阴离子，如卤离子(如氯离子、溴离子)、乙酸根、柠檬酸根、乳酸根、羟乙酸根、磷酸根、硝酸根、磺酸根、硫酸根、烷基硫酸根和烷基磺酸根。脂族基团除碳和氢原子外还可包含醚键及其它基团如氨基。长链脂族基团如具有约12个碳原子或更多个碳原子的基团可为饱和基团或不饱和基团。优选R¹、R²、R³和R⁴独立地选自C₁至约C₂₂烷基。用于本发明的阳离子表面活性剂的非限定性实例包括具有下述CTFA命名的物质：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和其混合物。Cationic surfactants useful in the present invention are those cationic surfactants having the following formula (I):

wherein at least one of R ¹ , R ² , R ³ and R ⁴ is selected from aliphatic groups having 8 to about 30 carbon atoms or aromatic groups having up to about 22 carbon atoms, alkoxy, poly Oxyalkylene, alkylamido, hydroxyalkyl, aryl or alkaryl; the remaining R ¹ , R ² , R ³ and R ⁴ are independently selected from aliphatic groups having 1 to about 22 carbon atoms or an aromatic group having up to about 22 carbon atoms, alkoxyl group, polyoxyalkylene group, alkylamido group, hydroxyalkyl group, aryl group or alkaryl group; X is a salt-forming anion, such as a halide ion ( such as 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. Long-chain aliphatic groups, such as groups having about 12 carbon atoms or more, can be saturated or unsaturated. Preferably R ¹ , R ² , R ³ and R ⁴ are independently selected from C ₁ to about C ₂₂ alkyl groups. Non-limiting examples of cationic surfactants useful in the present invention include materials having the following CTFA designations: 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.

其中，n为8至约28，x+y为2至约40，Z¹为短链烷基，优选C₁-C₃烷基，更优选甲基，或(CH₂CH₂O)_zH，其中，x+y+z至多为60，X为如上定义的成盐阴离子；

其中，m为1-5，R⁵、R⁶和R⁷中的一个或多个独立地为C₁-C₃₀烷基；其余为CH₂CH₂OH，R⁸和R⁹中的一个或两个及R¹⁰独立地为C₁-C₃₀烷基，其余为CH₂CH₂OH，X为如上定义的成盐阴离子；

其中，Z²为烷基，优选C₁-C₃烷基，更优选甲基；Z³为短链羟基烷基，优选羟甲基或羟乙基；p和q独立地为2-4的整数，优选2-3，更优选2；R¹¹和R¹²独立地为取代或未取代的烃基优选C₁₂-C₂₀烷基或链烯基，X为如上所述的成盐阴离子；

其中，R¹³为烃基，优选C₁-C₃烷基，更优选甲基；Z⁴和Z⁵独立地为短链烃基，优选C₂-C₄烷基或链烯基，更优选乙基；a为2-约40，优选约7-约30，X为如上所述的成盐阴离子；其中，R¹⁴和R¹⁵独立地为C₁-C₃烷基，优选甲基；Z⁶为C₁₂-C₂₂烃基、烷基羧基或烷基酰氨基；A为蛋白质，优选胶原、角蛋白、乳蛋白、丝蛋白(silk)、大豆蛋白、小麦蛋白或其水解形式；X为如上所述的成盐阴离子；

其中，b为2或3，R¹⁶和R¹⁷独立地为C₁-C₃烃基，优选甲基；X为如上所述的成盐阴离子。用于本发明的亲水取代的阳离子表面活性剂的非限定性实例包括具有下述CTFA命名的物质：quaternium-16、quaternium-61、quaternium-71、quaternium-79水解胶原、quaternium-79水解角蛋白、quaternium-79水解乳蛋白、quaternium-79水解丝蛋白、quaternium-79水解大豆蛋白、quaternium-79水解小麦蛋白。特别优选的化合物包含下述商购物质：VARIQUAT K1215和638(购自Witco Chemical)；MACKPRO KLP、MACKPRO WLW、MACKPRO MLP、MACKPRO NSP、MACKPRONLW、MACKPRO WWP、MACKPRO NLP、MACKPRO SLP(购自Mclntyre；ETHOQUAD 18/25、ETHOQUAD O/12PG、ETHOQUADC/25、ETHOQUAD S/25和ETHODUOQUAD(购自Akzo)；DEHYQUATSP(购自Henkel)和ATLAS G265(购自ICI Americas)。Another preferred class of cationic surfactants are hydrophilic substituted cationic surfactants wherein at least one of the substituents contains one or more aromatic, ether, ester, amide or amino moieties as substituents or as A bond exists in a residue wherein at least one of the R ¹ -R ⁴ groups contains one or more hydrophilic moieties selected from alkoxy (preferably C ₁ -C ₃ alkoxy), Polyoxyalkylene groups (preferably C ₁ -C ₃ polyoxymethylene groups), alkylamido groups, hydroxyalkyl groups, alkyl esters and mixtures thereof. Preferred hydrophilic substituted cationic conditioning surfactants contain from 2 to about 10 non-hydrophilic moieties within the above range. Preferred hydrophilic substituted cationic surfactants comprise surfactants of the following formulas (II)-(VII):

Wherein, n is 8 to about 28, x+y is 2 to about 40, Z ¹ is a short chain alkyl, preferably C ₁ -C ₃ alkyl, more preferably methyl, or (CH ₂ CH ₂ O) _z H , wherein, x+y+z is at most 60, and X is a salt-forming anion as defined above;

Among them, m is 1-5, one or more of R ⁵ , R ⁶ and R ⁷ are independently C ₁ -C ₃₀ alkyl; the rest are CH ₂ CH ₂ OH, one of R ⁸ and R ⁹ or Two and R ¹⁰ are independently C ₁ -C ₃₀ alkyl, the rest are CH ₂ CH ₂ OH, and X is a salt-forming anion as defined above;

Wherein, Z ² is an alkyl group, preferably a C ₁ -C ₃ alkyl group, more preferably a methyl group; Z ³ is a short-chain hydroxyalkyl group, preferably a hydroxymethyl group or a hydroxyethyl group; p and q are independently 2-4 Integer, preferably 2-3, more preferably 2; R ¹¹ and R ¹² are independently substituted or unsubstituted hydrocarbon groups, preferably C ₁₂ -C ₂₀ alkyl or alkenyl, and X is a salt-forming anion as described above;

Wherein, R ¹³ is a hydrocarbon group, preferably C ₁ -C ₃ alkyl, more preferably methyl; Z ⁴ and Z ⁵ are independently short-chain hydrocarbon groups, preferably C ₂ -C ₄ alkyl or alkenyl, more preferably ethyl ; a is 2-about 40, preferably about 7-about 30, and X is a salt-forming anion as described above; Wherein, R ¹⁴ and R ¹⁵ are independently C ₁ -C ₃ alkyl, preferably methyl; Z ⁶ is C ₁₂ -C ₂₂ hydrocarbon group, alkyl carboxyl or alkylamido; A is protein, preferably collagen, keratin , milk protein, silk protein (silk), soybean protein, wheat protein or hydrolyzed forms thereof; X is a salt-forming anion as described above;

Wherein, b is 2 or 3, R ¹⁶ and R ¹⁷ are independently a C ₁ -C ₃ hydrocarbon group, preferably a methyl group; X is a salt-forming anion as described above. Non-limiting examples of hydrophilically substituted cationic surfactants useful in the present invention include materials having the following CTFA designations: quaternium-16, quaternium-61, quaternium-71, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed horn Protein, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk protein, quaternium-79 hydrolyzed soybean protein, quaternium-79 hydrolyzed wheat protein. Particularly preferred compounds comprise the following commercially available substances: 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 McIntyre; ETHOQUAD 18/25, ETHOQUAD O/12PG, ETHOQUADC/25, ETHOQUAD S/25 and ETHODUOQUAD (from Akzo); DEHYQUATSP (from Henkel) and ATLAS G265 (from ICI Americas).

Salts of primary, secondary and tertiary fatty amines are also suitable as cationic surfactants. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms and can be substituted or unsubstituted. Particularly useful are amido-substituted tertiary fatty amines. Such amines useful in the present invention include stearamidopropyl dimethylamine, stearamidopropyl diethylamine, stearamidoethyl diethylamine, stearamidoethyl dimethyl Palmitoylamine, Palmitoamidopropyl Dimethylamine, Palmitoamidopropyl Diethylamine, Palmitoamidoethyl Diethylamine, Palmitoamidoethyl Dimethylamine, Behenamidopropyl behenyl dimethylamine, behenyl amidopropyl diethylamine, behenyl amidoethyl diethylamine, behenyl amidoethyl dimethylamine, arachidamide Dimethylamine, Arachimidopropyldiethylamine, Arachimidoethyldiethylamine, Arachimidoethyldimethylamine, Diethylaminoethylstearamide. Dimethylstearylamine, dimethylsoyamine (soyamine), soyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallow propylenediamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine and eicosylbehenylamine. 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 preferably L-glutamic acid, lactic acid, citric acid. Cationic amine surfactants useful herein are those disclosed in US 4,275,055, issued June 23, 1981 to Nachtigal et al., which is incorporated herein by reference.

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

high melting point compound

The compositions of the present invention may comprise high melting compounds having a melting point of at least about 25°C selected from the group consisting of fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, hydrocarbons, steroids and mixtures thereof. While not wishing to be bound by any theory, it is believed that these high melting point compounds coat the surface of the hair and reduce friction, thereby providing the hair with a smooth feel and easy combing. Those skilled in the art can understand that the compounds disclosed in this section of the present invention sometimes have multiple classification methods, for example, some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification does not limit a particular compound, but is for ease of classification and nomenclature. Furthermore, those skilled in the art will appreciate that certain compounds having a certain number of carbon atoms may have a melting point below about 25°C, depending on the number and location of double bonds and the length and location of branches. These low melting point compounds are not included in this section. Non-limiting examples of high melting point compounds are described in the International Cosmetic Ingredient Dictionary, 5th Edition, 1993, and the CTFA Cosmetic Ingredient Handbook, 2nd 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 chain 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 used in the present invention are fatty acids 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 acids. It can also include dibasic acid, tribasic acid and other polybasic acid meeting the requirements of the present invention. The present 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, hydroxy-substituted fatty acids and mixtures thereof. Non-limiting examples of fatty alcohol derivatives and fatty acid derivatives include: substances such as methyl stearyl ether; ceteth series compounds such as ceteth-1 to ceteth-45, which are Glycol ethers of cetyl alcohol, where the number indicates the number of ethylene glycol moieties; octadecyl polyoxyethylene ether (steareth) series compounds, such as steareth-1 to steareth-10, which are ethylene glycol ethers of stearyl alcohol Glycol ethers, where the number indicates the number of ethylene glycol moieties; cetearyl/stearyl polyoxyethylene ether (ceteareth) series compounds, such as ceteareth-1 to ceteareth-10, which mainly contain cetearyl alcohol Glycol ethers of mixtures with fatty alcohols of stearyl alcohol, where the numbers indicate the number of glycol moieties; C ₁ -C ₃₀ alkyl ethers of alkyl polyoxyethylene ether compounds; polyoxyethylene ethers of behenyl alcohol; ethyl stearate, cetyl stearate, cetyl palmitate, stearic acid Stearyl ester, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethylene glycol Alcohol monostearate, polyoxyethylene 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 in the present invention include compounds having at least about 20 carbon atoms.

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

It is preferred to use high-purity single-compound refractory compounds. Particular preference is given to single compounds of pure fatty alcohols selected from the group consisting of pure cetyl alcohol, stearyl alcohol and behenyl alcohol. "Pure" as used herein means that the compound is at least about 90% pure, preferably at least about 95% pure. These single compounds of high purity provide excellent rinse power when the consumer rinses the composition.

Commercially available high melting point compounds used in the present invention include: cetyl alcohol, stearyl alcohol and behenyl alcohol, trade name KONOL series, commercially available from New Japan Chemical (Osaka, Japan); NAA series, available Commercially available from NOF (Tokyo Japan); pure docosanol, 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); DERMA, commercially available from Vevy (Genova, Italy); and Cholesterol, available under the trade name NIKKOL AGUASOME LA, commercially available from Nikko purchase.

oily compound

The compositions of the present invention comprise an oily compound having a melting point of not more than about 25°C selected from the first oily compound, the second oily compound, and mixtures thereof. The oily compounds used in the present invention may be volatile or non-volatile compounds. While not being bound by any theory, it is believed that the oily compounds penetrate the hair and improve the hair's hydroxyl bonds, thereby making the hair soft. The oily compound may comprise the first oily compound or the second oily compound as described below. Preferably a mixture of the first oily compound and the second oily compound is used. The oily compounds in this section are distinguished from the high melting point compounds described above. Non-limiting examples of oily compounds are described in the International Cosmetic Ingredient Dictionary, 5th Edition, 1993, and the CTFA Cosmetic Ingredient Handbook, 2nd Edition, 1992, both of which are incorporated herein by reference.

first oily compound

Fatty alcohols useful in the present invention include those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, more preferably from about 16 to about 22 carbon atoms. These fatty alcohols may be branched or linear and may be saturated or unsaturated, preferably unsaturated. Non-limiting examples of these compounds include oleyl alcohol, palm oil alcohol, isostearyl alcohol, isocetyl alcohol, undecyl alcohol, octyldodecanol, octyldecanol, octyl alcohol, Caprylic alcohol, decyl alcohol and lauryl alcohol.

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

Examples of fatty acid derivatives and fatty alcohol derivatives as defined in the present invention include esters of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of 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 Esters, Octyldodecyl Isononanoate, Octyl Isononanoate, Octyl Nonanoate, Hexyl Isostearate, Isopropyl Isostearate, Isodecyl Isonononanoate, Oleth-2, Pentaerythritol Tetraoil pentaerythritol tetraisostearate, trimethylolpropane trioleate and trimethylolpropane triisostearate.

The first commercially available oily compounds for use in the present invention include: oleyl alcohol, commercially available as UNJECOL 90BHR from New Japan Chemical; pentaerythritol tetraisostearate and trimethylolpropane triisostearate , trade names KAKPTI and KAKTTI, commercially available from KokyuAlcohol (Chiba, Japan); pentaerythritol tetraoleate, having the same trade name as the compound, commercially available from New Japan Chemical; trimethylolpropane trioleate, commercially available from Named ENUJERUBU TP3SO, commercially available from New Japan Chemical; various liquid esters, trade name SCHERCEMOL series, commercially available from Scher and hexyl isostearate, trade name HIS and isopropyl isostearate, trade name is ZPIS, commercially available from Kokyu Alcohol.

second oily compound

The second oily compound used in the present invention is straight chain, cyclic and branched chain hydrocarbons, which may be saturated or unsaturated hydrocarbons as long as their melting point does not exceed about 25°C. These hydrocarbons have from about 12 to about 40 carbon atoms, preferably from about 12 to about 30 carbon atoms, more preferably from about 12 to about 22 carbon atoms. The invention also encompasses polymerized hydrocarbons of alkenyl monomers, such as polymers of _C2-6 alkenyl monomers. These polymers may be linear or branched. Linear polymers generally have relatively short chain lengths with a total number of carbon atoms as previously stated. Branched polymers have significantly longer chain lengths. The number average molecular weight of such materials can vary widely, but generally is up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350. Various grades of mineral oils can also be used in the present invention. Mineral oil is a mixture of various hydrocarbons obtained from petroleum. Specific examples of suitable hydrocarbon materials include: paraffin oil, mineral oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene, isoeicosene, tridecane, tetradecane alkanes, polybutenes, polyisobutenes and mixtures thereof. The hydrocarbons preferably employed are selected from mineral oil, isododecane, isohexadecane, polybutene, polyisobutene and mixtures thereof.

Commercially available second oily compounds useful in the present invention include: isododecane, isohexadecane and isoeicosene, available under the tradenames PERMETHYL 99A, PERMETHYL 101A and PERMETHYL 1082 from Presperse (South Plainfield New Jersey, USA); Copolymer of isobutene and n-butene, commercially available under the tradename INDOPOL H-100 from AmocoChemicals (Chicago Illinois, USA); Mineral oil, commercially available under the tradename BENOL from Wltco; Isoparaffins , trade name ISOPAR, commercially available from Exxon Chemical Co. (HoustonTexas, USA); olefin oligomer, trade name PURESYN 6, commercially available from Mobil Chemical Co. and trimethylolpropane tricaprylate/tricaprate Esters, available under the trade name MOBIL ESTER P43 from Mobil Chemical Co.

cationic polymer

As used herein, the term "polymer" shall include a substance whether it is prepared from one type of monomer or from two or more types of monomers.

Preferably, the cationic polymer is a water-soluble cationic polymer. By "water soluble" cationic polymer is meant a 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°C. Preferred polymers are sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably at a concentration of 1.0%.

The cationic polymers of the present invention generally have a weight average molecular weight of at least about 5,000, generally 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 generally 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 meg/g, still more preferably at least about 1.1 meq/g, still more preferably at least about 1.2 meq/g. The cationic charge density of cationic polymers can be measured according to the Kjeldahl method, which is well known to those skilled in the art. Those skilled in the art will appreciate that the charge density of amino-containing polymers will vary depending on the pH and isoelectric point of the amino groups. The charge density should fall within the above range at the intended pH.

Any type of anionic counterion can be used in the water-soluble cationic polymer as long as the water-solubility criteria are met. Suitable counterions include halides (such as chlorine, bromine, iodine or fluorine, preferably chlorine, bromine or iodine), sulfate and methylsulfate. Other ions may also be used, the above listed ions are not exclusive.

The cationic nitrogen-containing moiety is usually present as a substituent on a portion of the overall monomer unit of the cationic hair conditioning polymer. Thus, cationic polymers include copolymers, terpolymers, etc. of quaternary ammonium or cationic amine substituted monomer units and other non-cationic units known as spacer monomer units. Such polymers are well known in the art and such polymers are described in: CTFA Cosmetic Ingredient. Dictionary, 3rd Edition, edited by Estrin, Crosley and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982).

Examples of suitable cationic polymers include: vinyl monomers with cationic amine or quaternary ammonium functionality with water soluble spacer monomers such as acrylamides, methacrylamides, alkyl and dialkyl acrylamides, alkyl and dioxane Copolymers of methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone or vinyl pyrrolidone. Alkyl and dialkyl substituted monomers preferably have C ₁ -C ₇ alkyl groups, more preferably C ₁ -C ₃ alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (prepared by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol.

Cationic amines can be primary, secondary or tertiary, depending on the particular species and pH of the composition. In general, secondary and tertiary amines are preferred, especially tertiary amines.

Amine substituted vinyl monomers can be polymerized in the amine form and then selectively converted to ammonium by quaternization. Amines can also be similarly quaternized, followed by polymer formation. For example, tertiary amine functionality can be quaternized by reaction with a salt of formula R'X, wherein R' is a short chain alkyl, preferably C ₁ -C ₇ alkyl, more preferably C ₁ -C ₃ alkane group, X is an anion that forms a water-soluble salt with quaternized ammonium.

Suitable cationic amino and quaternary ammonium monomers include, for example, dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, monoalkylaminoalkyl acrylates, monoalkylaminoalkyl methacrylates alkyl esters, trialkylmethacryloyloxyalkylammonium salts, trialkylacryloyloxyalkylammonium salts, diallyl quaternary ammonium salts substituted vinyl compounds, and cyclic nitrogen-containing cationic rings Vinyl quaternary ammonium monomers such as pyridinium, imidazolium and quaternized pyrrolidones, eg alkylvinylimidazolium, alkylvinylpyridinium, alkylvinylpyrrolidone salts. The alkyl portion of these monomers is preferably a lower alkyl such as C ₁ -C ₃ alkyl, more preferably C ₁ and C ₂ alkyl. Amine substituted vinyl monomers suitable for use in the present invention include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkylacrylamides and dialkylaminoalkylmethacrylates. Acrylamide. Among them, the alkyl group is preferably a C ₁ -C ₇ hydrocarbon group, more preferably a C ₁ -C ₃ alkyl group.

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

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

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

其中，A为葡糖酐残基，如淀粉或纤维素葡糖酐残基；R为亚烷基氧基亚烷基、多亚氧烷基或羟基亚烷基基团，或其组合；R¹、R²和R³彼此独立地为烷基、芳基、烷芳基、芳烷基、烷氧基烷基或烷氧基芳基，每一个基团包含至多约18个碳原子，每一阳离子部分的总碳原子数(即R¹、R²和R³中的碳原子总数)优选为约20或更少；X为如前所述的阴离子抗衡离子。Cationic polysaccharide polymer materials suitable for use in the present invention include those polymers having the formula:

Wherein, A is anhydroglucose residue, such as starch or cellulose anhydroglucose residue; R is an alkyleneoxyalkylene group, a polyoxyalkylene group or a hydroxyalkylene group, or a combination thereof; R ^{1. R2} and ^R3 are independently of each other alkyl, aryl, alkaryl, aralkyl, alkoxyalkyl or alkoxyaryl, each group containing up to about 18 carbon atoms, each The total number of carbon atoms in a cationic moiety (ie, the total number of carbon atoms in ^R1 , ^R2 and ^R3 ) is preferably about 20 or less; X is an anionic counterion as previously described.

Cationic celluloses are those polymers available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR and LR series of polymers, such as hydroxyethyl cellulose reacted with trimethylammonium substituted epoxides The salt of the element is also called polyquaternium-10 by "CTFA" in the industry. Another class of cationic cellulose includes the polymeric quaternium salt of hydroxyethyl cellulose reacted with a lauryldimethylammonium substituted epoxide, known commercially by "CTFA" as polyquaternium-24. These materials are commercially available from Amerchol Corp. (Edison, NJ, USA) under the tradename Polymer LM-200(R).

Other cationic polymers that can be used include cationic guar derivatives such as guar hydroxypropyltrimonium chloride, commercially available from Celanese Corporation in the Jaguar R series. Other materials include quaternary nitrogen-containing cellulose ethers (eg, as described in US 3,962,418, incorporated herein by reference) and copolymers of esterified cellulose and starch (eg, as described in US 3,958,581, incorporated herein by reference).

Silicone compound

Conditioning agents useful herein include silicone compounds. The silicone compounds of the present invention include volatile soluble or insoluble silicone conditioning agents, or nonvolatile soluble or insoluble silicone conditioning agents. By soluble is meant that the silicone compound is miscible with the carrier of the composition so as to form part of the same 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.

Suitable silicone fluids include polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, polyethersiloxane copolymers, and mixtures thereof. Other nonvolatile silicone compounds having hair conditioning properties can also be used.

其中，R为烷基或芳基，x为约7-约8,000的整数。“A”代表硅氧烷链的封端基团。在硅氧烷链上(R)或在硅氧烷链的末端处(A)取代的烷基或芳基基团可具有任何结构，只要形成的硅氧烷在室温下为流体，当其涂敷至头发上时可分散、无刺激、无毒、无害，并且与组合物的其它成分相容，在常规使用和贮藏条件下化学性质稳定，并且能够沉积于头发上并调理头发。适宜的A基团包括羟基、甲基、甲氧基、乙氧基、丙氧基和芳氧基。在硅原子上的两个R基团可表示相同的基团或不同的基团。优选两个R表示相同的基团。适宜的R基团包括甲基、乙基、丙基、苯基、甲苯基和苯甲基。优选的硅氧烷化合物为聚二甲基硅氧烷、聚二乙基硅氧烷和聚甲基苯基硅氧烷。特别优选被称之为聚二甲基硅氧烷(dimethicone)的聚二甲基硅氧烷。可采用的聚烷基硅氧烷例如包括聚二甲基硅氧烷。这些硅氧烷可商购自GeneralElectric Company，为ViscasilR系列及SF 96系列，以及商购自Dow Corning的Dow Corning200系列。The siloxane compounds used in the present invention also include polyalkyl or polyaryl siloxanes having the following structural formula (I):

Wherein, R is an alkyl group or an aryl group, and x is an integer ranging from about 7 to about 8,000. "A" represents a capping group for the siloxane chain. Alkyl or aryl groups substituted on the siloxane chain (R) or at the end of the siloxane chain (A) can have any structure as long as the siloxane formed is fluid at room temperature and when coated with Dispersible, non-irritating, non-toxic, non-hazardous when applied to the hair, compatible with the other ingredients of the composition, chemically stable under normal conditions of use and storage, and capable of depositing on and conditioning the hair. Suitable A groups include hydroxy, methyl, methoxy, ethoxy, propoxy and aryloxy. The two R groups on the silicon atom may represent the same group or different groups. Preferably both R represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, tolyl and benzyl. Preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane and polymethylphenylsiloxane. Particular preference is given to polydimethylsiloxanes known as dimethicones. Useful polyalkylsiloxanes include, for example, polydimethylsiloxanes. These siloxanes are commercially available from the General Electric Company as the Viscasil R series and the SF 96 series, and from Dow Corning as the Dow Corning 200 series.

Polyalkylaryl siloxane fluids may also be used, including, for example, polymethylphenyl siloxanes. These siloxanes are commercially available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid, and as 556 Cosmetic Grade Fluid from Dow Corning.

It is also particularly preferred herein to employ highly arylated silicone compounds, such as highly phenylated polyethylsiloxane, having a refractive index of about 1.46 or greater, especially about 1.52 or greater, in order to enhance the shine properties of the hair big. When these high refractive index silicones are used, they should be mixed with a spreading agent, such as a surfactant or silicone resin, as described below, to lower the surface tension and enhance the film-forming properties of the material.

Silicone compounds which may be used include, for example, polypropylene oxide modified polydimethylsiloxane, although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The levels of ethylene oxide and propylene oxide should be low enough that they do not interfere with the dispersion properties of the silicone. These materials are also known as alkoxylated dimethicone copolyols.

Other silicone compounds include amino substituted materials. Suitable alkylamino substituted silicone compounds include those having the structure of formula (II): Wherein, R is _CH3 or OH, x and y are integers depending on molecular weight, and the average molecular weight is approximately 5,000 to 10,000. This polymer is also known as "amodimethicone".

Suitable amino-substituted silicone fluids include silicones having the following formula (III):

(R ¹ ) _a G _3-a -Si-(-OSiG ₂ ) _n -(-OSiG _b (R ¹ ) _2-b ) _m -O-SiG _3-a (R ¹ ) _a (III) where G is selected From hydrogen, phenyl, hydroxyl, C ₁ -C ₈ alkyl, preferably methyl; a is an integer of 0 or 1-3, preferably 0; b is 0 or 1, preferably 1; the sum of n+m is 1 -2,000, preferably 50-150, n can represent a number of 0-1,999, preferably 49-149, m can represent an integer of 1-2,000, preferably 1-10; R ¹ is a monovalent group such as formula C _q H _2q L Group, wherein q is an integer of 2-8, and L can be selected from the following groups:

-N(R ₂ )CH ₂ -CH ₂ -N(R ₂ ) ₂

-N(R ₂ ) ₂

-N(R ₂ ) ₃ A ^-

-N(R ₂ )CH ₂ -CH ₂ -NR ₂ H ₂ ^A -Wherein, R ₂ is selected from hydrogen, phenyl, benzyl, saturated hydrocarbon group, preferably an alkyl group with 1-20 carbon atoms, A ^-is halide ion.

Particularly preferred amino-substituted siloxanes corresponding to formula (III) are polymers of formula (IV), which are also known as "trimethylsilyl aminated polydimethylsiloxanes" , where n and m are chosen according to the exact molecular weight desired for the compound.

Other useful amino-substituted siloxanes are represented by the following formula (V): Among them, R ₃ is a monovalent hydrocarbon group with 1-18 carbon atoms, preferably an alkyl or alkenyl group, such as methyl; R ₄ is a hydrocarbon group, preferably a C ₁ -C ₁₈ alkylene group or a C ₁ -C ₁₈ , preferably C ₁ -C ₈ alkyleneoxy group; Q ^- is a halide ion, preferably chlorine; the average statistical value of r is 2-20, preferably 2-8; the average statistical value of s is 20-200, preferably 20- 50. A preferred polymer of this type is commercially available from Union Carbide under the trade designation "UCARSILICONE ALE 56".

Documents disclosing suitable non-volatile dispersed silicone compounds include: US 2,826,551 (Geen), US 3,964,500 (granted to Drakoff on June 22, 1976), US 4,364,837 (Pader); and GB 849,433 (woolston). "Silicon Compounds" published by Petrarch Systems, Inc. (1984) provides a broad and non-exclusive list of suitable silicone compounds.

Another particularly suitable non-volatile dispersion silicone is an insoluble silicone gum. As used herein, the term "silicone gum" refers to a polyorganosiloxane material having a viscosity at 25°C of greater than or equal to 1,000,000 centistokes. It will be appreciated that the silicone gums described herein may also have some overlap with the silicone compounds described above. This overlap is not a limitation on these materials. Such silicone gums are described by Petrarch, among others: US 4,152,416 (Spitzer et al., issued May 1, 1979); Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Also mentioning silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE76. The weight average molecular weight of the silicone gum is generally greater than about 200,000, typically about 200,000-1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenylsiloxane) ( Methylvinylsiloxane) copolymers and mixtures thereof.

Also useful are silicone resins, which are highly crosslinked polymeric silicone systems. Crosslinking is introduced by incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional or both silanes during the production of silicone resins. As is known in the art, the degree of crosslinking required to obtain a silicone resin can vary depending on the specific silane units incorporated into the silicone resin. In general, silicone materials that contain sufficient amounts of trifunctional and tetrafunctional siloxane monomer units and are therefore sufficiently crosslinked to form a rigid or hard film when dried are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms reflects the degree of crosslinking in a particular silicone material. Silicone materials having at least about 1.1 oxygen atoms per silicon atom are typically 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, tetrachlorosilanes, most commonly methyl-substituted silanes. Preferred resins are GE SS 4230 and SS 4267 supplied by General Electric. Commercially available silicone resins are typically low viscosity volatile or non-volatile silicone fluids supplied in dissolved form. It will be clear to those of ordinary skill in the art that the silicone resins for use in the present invention should be provided in such dissolved form and incorporated into the compositions of the present invention. Without being bound by theory, it is believed that the silicone resins enhance the deposition of other silicone polymers on the hair and can improve the shine of the hair through the use of high refractive index silicones.

Other useful silicone resins are silicone resin powders, such as polysilsequioxane by CTFA nomenclature, commercially available as Tospearl ^™ from Toshiba Silicones.

Methods for producing such siloxane compounds can be found in the following literature: "Encyclopedia of Polymer Science and Engineering", Vol. 15, Second Edition, pp. 204-308, John Wiley & Sons. Inc., 1989".

Silicone materials, particularly silicone resins, are conveniently identified by the "MDTQ" nomenclature, a system of shorthand nomenclature well known to those skilled in the art. In this system, siloxanes are described in terms of the presence of the various siloxane monomer units that make up the siloxane. In short, the symbol M represents the monofunctional unit (CH ₃ ) ₃ SiO _0.5 ; D represents the difunctional unit (CH ₃ ) ₂ SiO; T represents the trifunctional unit (CH ₃ ) SiO _1.5 ; Q represents the tetrafunctional unit SiO ₂ . The apostrophe of the unit symbol such as M', D', T', Q' represents a substituent other than methyl, which needs to be defined each time. Typical substitutable substituents are vinyl, phenyl, amino, hydroxyl, and the like. In the MDTQ system, the description of the siloxane species is completed either by subscripting the symbol to indicate the total number (or average) of each type of unit in the siloxane, or by specifying the ratio and stating the molecular weight. A relatively high molar amount of T, Q, T' and/or Q' compared to D, D', M and/or M' in a silicone resin indicates a high degree of crosslinking. However, as previously discussed, the overall level of crosslinking can also be expressed by the ratio of oxygen to silicon.

The silicone resins of the present invention are preferably MQ, MT, MTQ, MDT and MDTQ resins. Thus, the preferred siloxane substituent is methyl. Particularly preferred are MQ resins 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.

Commercially available silicone compounds useful in the present invention include: Dimethicone with the trade name D-130, Cetyl Dimethicone with the trade name DC2502, Dimethicone with the trade name DC2503 Stearyl Dimethicone, Emulsified Dimethicone with the tradename DC1664 and DC1784, Alkyl Graft Copolymer Silicone Emulsion with the tradename DC2-2845; all commercially available from CowCorning Corporation; and emulsion polymerized Dimethiconol commercially available from Toshiba Silicone as described in GB 2,303,857.

nonionic polymer

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 with the tradename BENECEL, hydroxyethylcellulose with the tradename NATROSOL, hydroxypropylcellulose with the tradename KLUCEL, POLYSURF 67 cetyl hydroxyethylcellulose, both commercially available from Herculus. Other suitable nonionic polymers are ethylene oxide and/or propylene oxide based polymers available under the tradenames CARBOWAXPEGs, POLYOX WASRs and UCON FLUIDS, all commercially available from Amerchol.

polyalkylene glycol

These compounds are particularly useful in compositions of the present invention designed to leave the hair soft and moisturized. When employed, the polyalkylene glycols generally comprise from about 0.025% to about 1.5%, preferably from about 0.05% to about 1%, more preferably from about 0.1% to about 0.5%, by weight of the composition.

其中，R选自H、甲基和其混合物。当R为H时，这些物质为环氧乙烷的聚合物，也被称之为聚环氧乙烷、聚氧化乙烯和聚乙二醇。当R为甲基时，这些物质为环氧丙烷的聚合物，也被称之为聚环氧丙烷、聚氧化丙烯和聚丙二醇。还可以理解，当R为H时，所形成的聚合物存在各种位置异构体。Polyalkylene glycols have the general formula:

Wherein, R is selected from 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 oxide, polypropylene oxide and polypropylene glycol. It is also understood that when R is H, the resulting polymer exists in various positional isomers.

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

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

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

Styling Polymer

The compositions of the present invention may comprise a styling polymer. The styling polymers useful herein are those polymers which provide styling or fixative benefits to the hair, including amphoteric styling polymers, anionic styling polymers, cationic styling polymers, nonionic styling polymers and silicone graft copolymers . The styling polymers in this section can be distinguished from the conditioning polymers mentioned above and the suspending agent polymers mentioned below, which are film-forming and which are provided by a 3% aqueous solution of the styling polymers of the present invention. The viscosity should not exceed about 2,000 cps.

Styling polymers, when employed, comprise from about 0.01% to about 10% by weight of the composition. When two or more styling polymers are employed, each styling polymer should not comprise more than about 5% by weight of the composition.

amphoteric polymer

Amphoteric polymers useful in the present invention include betainized amphoteric polymers described in the following formulas (1) and (2), and non-betained amphoteric polymers described in the following formulas (3) and (4). Styling polymers.

Betainized Amphoteric Polymers

其中，R¹表示氢原子或甲基，R²表示具有1-4个碳原子的亚烷基，Y表示O或-NH-，R³和R⁴彼此独立地表示氢或具有1-4个碳原子的烷基，和阳离子衍生物，该阳离子衍生物由包含至少一个与一个或多个脂肪链连接的氮原子并选择性地被季铵化的阳离子表面活性剂组成，或由多胺、聚氨基聚酰胺或聚-(季铵)型的阳离子聚合物组成，其中胺或铵基团构成聚合物链的一部分或与之相连接。这些聚合物的分子量通常为500至2,000,000。(1) Used in the present invention are betainized dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl (meth)acrylamides comprising at least units of the formula:

Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1-4 carbon atoms, Y represents O or -NH-, R ³ and R ⁴ independently represent hydrogen or have 1-4 Alkyl groups of carbon atoms, and cationic derivatives consisting of cationic surfactants comprising at least one nitrogen atom bonded to one or more fatty chains and optionally quaternized, or consisting of polyamines, Composition of cationic polymers of the polyaminopolyamide or poly-(quaternary ammonium) type in which amine or ammonium groups form part of or are attached to the polymer chain. These polymers typically have a molecular weight of 500 to 2,000,000.

其中，R¹如前述定义，R⁵表示具有4-24个碳原子的烷基或链烯基，或具有4-24个碳原子的环烷基。Amphoteric polymers comprising units corresponding to the above formula (I) are generally in the form of copolymers which, in addition to comprising units of the above formula (I), also comprise at least units of the following formula:

Wherein, R ¹ is as defined above, and R ⁵ represents an alkyl or alkenyl group with 4-24 carbon atoms, or a cycloalkyl group with 4-24 carbon atoms.

It is also possible to use terpolymers, tetrapolymers or pentpolymers which, in addition to the units (I) and (II), also contain units of the formula: Among them, R ⁶ is preferably an alkyl or alkenyl group with 1-3 carbon atoms; R ¹ is as defined above.

Based on the total weight of the polymer, the amount of units of formula (1) is preferably 25-45% by weight, the amount of units of formula (II) is preferably 5-65% by weight, and the amount of units of formula (III) is preferably 50% by weight.

Particularly preferred polymers are copolymers comprising formulas (I), (II) and (III), wherein Y represents an oxygen atom, R ² represents the group -C ₂ H ₄ -, R ¹ , R ³ and R ⁴ Represents a methyl group, R ⁵ represents an alkyl group with 4-18 carbon atoms, and R ⁶ represents an alkyl group with 1-3 carbon atoms. The average molecular weight of the polymer is preferably 50,000 to 100,000. This polymer is supplied by Mitsubishi Chemical Corporation under the trade name "Yukaformer" or "Diaformer".

其中，R¹表示可聚合的不饱和基团，如丙烯酸、甲基丙烯酸、丙烯酰胺或甲基丙烯酰胺基团，x和y彼此独立地表示1至3的整数，R²和R³彼此独立地表示氢、甲基、乙基或丙基，R⁴和R⁵彼此独立地表示氢或烷基且R⁴和R⁵中的总碳原子数不超过10。(2) Useful in the present invention are betained polymers containing zwitterionic units derived from the formula:

Wherein, R ¹ represents a polymerizable unsaturated group, such as acrylic acid, methacrylic acid, acrylamide or methacrylamide group, x and y independently represent an integer from 1 to 3, R ² and R ³ are independent of each other represents hydrogen, methyl, ethyl or propyl, ^R4 and ^R5 independently represent hydrogen or an alkyl group and the total number of carbon atoms in ^R4 and ^R5 does not exceed 10.

Particularly preferred betainized amphoteric polymers include the following commercially available materials: for example, YUKAFORMER SM, YUKAFORMER FH, YUKAFORMER 301, YUKAFORMER 204WL, YUKAFORMER 510, YUKAFORMER M-75, YUKAFORMER R250S, Diaformer Z-SM and Diaformer Z-W, all Commercially available from Mitsubishi Chemical Corporation.

Non-betainized amphoteric polymer

(3) Useful in the present invention are non-betainized amphoteric polymers formed by copolymerizing a vinyl monomer bearing at least one carboxyl group with a basic monomer, said vinyl monomer A monomer such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid or α-chloroacrylic acid, the basic monomer being a substituted vinyl compound containing at least one basic nitrogen atom , such as dialkylaminoalkyl esters of methacrylic acid and acrylic acid and dialkylaminoalkylmethacrylamides and acrylamides.

(4) Used in the present invention are non-betainized amphoteric polymers comprising units derived from:

i) at least one monomer selected from acrylamide or methacrylamide, wherein the nitrogen atom is substituted by an alkyl group,

ii) at least one acidic comonomer comprising one or more active carboxyl groups, and

iii) At least one basic comonomer of acrylic acid and methacrylic acid, such as an ester, bearing primary, secondary and tertiary amine substituents and quaternary ammonium substituents, the product derived from dimethylaminoethyl methacrylate and Quaternization of Dimethyl Sulfate or Diethyl Sulfate.

The most preferred N-substituted acrylamides or methacrylamides are those in which the alkyl group contains 2-12 carbon atoms, especially N-ethylacrylamide, N-tert-butylacrylamide, N-tert-butyl Octylacrylamide, N-octylacrylamide, N-decylacrylamide and N-dodecylacrylamide and the corresponding methacrylamide. Acidic comonomers are mainly selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, and alkyl monomers of maleic acid or fumaric acid whose alkyl group has 1 to 4 carbon atoms. ester.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl and N-tert-butylaminoethyl methacrylate.

Particularly preferred non-betainized amphoteric polymers include the following commercially available materials, e.g., octylacrylamine/acrylates/butylaminoethyl methacrylate copolymers available under the tradenames AMPHOMER, AMPHOMER SH701, AMPHOMER 28-4910, AMPHOMER LV71 and AMPHOMER LV47, even commercially available from National Starch & Chemical.

cationic styling polymer

The cationic styling polymer used in the present invention is:

(1) Vinylpyrrolidone/quaternized dialkylaminoalkyl acrylate or methacrylate copolymers such as those sold by Gaf Corp. under the tradenames Gafquat 734 and 755N.

(2) Cellulose ether derivatives containing quaternary ammonium groups.

(3) Cationic polysaccharides.

(4) Cationic polymers selected from the group consisting of:

i) polymers comprising units of the formula:

-AZ ¹ -AZ ² - (I) wherein, A represents a group containing two amino groups, preferably piperazinyl, and Z ¹ and Z ² independently represent divalent groups, which are linear or branched chain alkylene A group comprising up to about 7 carbon atoms in its backbone, which may be substituted or unsubstituted by one or more hydroxyl groups, may also contain one or more oxygen, nitrogen and sulfur atoms and 1-3 aromatic rings and/ Or heterocycle, oxygen, nitrogen and sulfur atoms are usually ether or thioether, sulfoxide, sulfone, sulfonium, amine, alkylamine, alkenylamine, benzylamine, amine oxide, quaternary ammonium, amide, imide in the form of amines, alcohols, esters and/or urethanes;

ii) polymers comprising units of the formula:

-AZ'-AZ'- (II) wherein, A represents a group containing two amino groups, preferably piperazinyl, Z' represents the symbols Z ³ and Z ⁴ , and simultaneously represents the symbol Z ⁴ at least once; Z ³ represents two A valent group which is a straight or branched chain alkylene or hydroxyalkylene group comprising up to about 7 carbon atoms in its main chain, and ^Z4 is also a divalent group which is a straight or branched chain alkylene Alkyl groups containing up to about 7 carbon atoms in their main chain, which are unsubstituted or substituted by one or more hydroxyl groups and separated by one or more nitrogen atoms separated by 1 to 4 carbon atoms Alkyl chain substitution of atoms, preferably 4 carbon atoms, optionally separated by oxygen atoms and optionally containing one or more hydroxyl groups; and

iii) Polymers of the formulas (I) and (II) described in i) and ii) above with alkyl and benzyl halides, alkyl tosylate or alkyl methanesulfonate having 1 to 6 carbon atoms Alkylation and oxidation products.

(5) Polyamino-polyamides prepared by polycondensation reaction of acidic compounds and polyamines. Acidic compounds may be organic dibasic acids containing double bonds, aliphatic monobasic acids and dibasic acids, esters of the aforementioned acids, preferably with lower alkanols having 1 to 6 carbon atoms, and mixtures thereof. The polyamine is a di-primary or mono- or di-secondary polyalkylene-polyamine, wherein up to 40 mol % of the polyamine can be a bis-primary amine, preferably ethylenediamine, or a bis-secondary amine, preferably piperazine, and up to 20 mol% can be hexamethylenediamine.

(6) The above polyamino-polyamide may be alkylated and/or crosslinked. Alkylation can be carried out with glycidol, ethylene oxide, propylene oxide or acrylamide. The crosslinking reaction can be carried out using a crosslinking agent as described below:

i) epihalohydrins, diepoxides, dianhydrides, unsaturated anhydrides and disaturated derivatives in a ratio of 0.025-0.35 mol of crosslinking agent per amino group of the polyamino-polyamide;

ii) epihalohydrins, bis-azetidine compounds, bishaloacyldiamines and bis-(alkyl halides);

iii) derived from the group consisting of bis-halohydrins, bis-azetidine compounds, bishaloacyldiamines and bis-(alkyl halides), epihalohydrins, diepoxides and diunsaturated an oligomer obtained by reacting a compound with another difunctional compound with which it reacts; and

iv) quaternization products of compounds selected from compounds of ii) and oligomers of iii), said compounds comprising one or more tertiary amine groups, which may be used in whole or in part with methyl or ethyl chloride Alkylating reagents for alkylation of compounds, bromides, iodides, sulfates, mesylate and tosylate, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, by Polyamino-amino groups of polyamides, crosslinked with 0.025 to 0.35 mol, preferably 0.025 to 0.2 mol, more preferably 0.025 to 0.1 mol of a crosslinking agent.

(7) Polyamino-polyamide derivatives, which are obtained by condensation reaction of polyalkylene polyamines and polycarboxylic acids, and then alkylated with difunctional agents, such as adipic acid/dimethylaminohydroxyalkane Alkyl-dialkylenetriamine copolymers wherein the alkyl group contains 1 to 4 carbon atoms and preferably represents a methyl, ethyl or propyl group.

A useful polymer is adipic acid/dimethylaminohydroxypropyl-diethyltriamine copolymer, available as Cartaretine F, F4 or F8 from SANDOZ.

(8) A polymer prepared by reacting a polyalkylenepolyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from the group consisting of Glycolic acid and a saturated aliphatic dibasic carboxylic acid with 3-8 carbon atoms, the molar ratio of polyalkylene polyamine and dibasic carboxylic acid is 0.8:1 to 1.4:1, and the polyamide formed is then mixed with the table Halohydrin reaction, the molar ratio of epihalohydrin to secondary amino groups of polyamide is 0.5:1 to 1.8:1.

Useful such polymers are those sold by Hercules Incorporated under the tradename HERCOSETT 57, and those sold by Hercules under the tradename PD 170 or DELSETTE 101.

其中，p和t为0或1，p+t＝1，R″表示氢或甲基，R和R′彼此独立地表示1-22个碳原子的烷基，烷基部分优选具有1-5个碳原子的羟基烷基，或低级酰氨基烷基，R和R′及与其相连的氮原子合在一起表示杂环基团，如哌啶基或吗啉基，Y为溴、氯、乙酸根、硼酸根、柠檬酸根、酒石酸根、硫酸氢根、亚硫酸氢根、硫酸根或磷酸根。包含式III和III′单元的共聚物也可包含由丙烯酰胺或由双丙酮丙烯酰胺得到的单元。(9) Cyclic polymers, generally having a molecular weight of 20,000 to 3,000,000, such as homopolymers comprising units corresponding to formula (III) or (III') as the main constituent of the chain:

Wherein, p and t are 0 or 1, p+t=1, R "represents hydrogen or a methyl group, R and R' independently represent an alkyl group of 1-22 carbon atoms, and the alkyl part preferably has 1-5 A hydroxyalkyl group of carbon atoms, or a lower amidoalkyl group, R and R' and the nitrogen atom connected to it together represent a heterocyclic group, such as piperidinyl or morpholinyl, Y is bromine, chlorine, acetic acid , borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate. Copolymers comprising units of formula III and III' may also contain acrylamide or diacetone acrylamide unit.

Among the quaternary ammonium polymers as defined above, those homopolymers of dimethyldiallylammonium chloride, sold under the trade name MERQUAT 100, having a molecular weight of less than 100,000; dimethyldiallylammonium chloride/acrylamide Copolymer, molecular weight over 500,000, sold under the tradename MERQUAT 550 by CALGON Corporation.

(10) Poly-(quaternary ammonium) compounds of the following formula wherein R ¹ , R ² , R ³ and R ⁴ are independently aliphatic, cycloaliphatic or arylaliphatic groups with a maximum number of carbon atoms of 20, or lower hydroxy aliphatic groups, or, and The connected nitrogen atoms together form a heterocyclic ring optionally containing a second heteroatom in addition to the nitrogen atom, or R ¹ , R ² , R ³ and R ⁴ represent the group CH ₂ CHR' ³ R' ⁴ , wherein, R' ³ represents hydrogen or lower alkyl, R' ⁴ represents SO, CN, CON(R' ⁶ ) ₂ , COOR' ⁵ , COR' ⁵ , COOR' ⁷ D or CONHR' ⁷ D; R' ⁵ represents lower alkyl , R' ⁶ represents hydrogen or a lower alkyl group, R' ⁷ represents an alkylene group and D represents a quaternary ammonium group; A and B independently represent a polymethylene group comprising 2-20 carbon atoms, which can be straight Chain or branched chain, saturated or unsaturated group, and one or more groups -CH ₂ -y-CH ₂ - can be inserted in the main chain, where Y represents benzene, O, S, SO, SO ₂ , SS , NR′ ⁸ , N ⁺ (R′ ⁹ ) ₂ X ¹ -, CHOH, NHCONH, CONR′ ⁸ or COO; X ^1- represents an anion obtained from an inorganic acid or an organic acid, and R′ ⁸ represents hydrogen or a lower alkyl group and ^R'9 represent lower alkyl, or A and ^R1 and ^R3 form a piperazine ring together with the two nitrogen atoms attached to it. If A represents a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene group, B can also represent a group: -(CH ₂ ) _n -CO-D-OC-(CH ₂ ) _n -; where n should be chosen so that the molecular weight is typically from 1,000 to 100,000; and D means:

i) a diol group of the formula -O-Z-O-, wherein Z represents a linear or branched hydrocarbon group or a group corresponding to the following formula:

-[CH ₂ -CH ₂ -O-]x-CH ₂ -CH ₂ -or-[CH ₂ -C(CH ₃ )HO-]y-CH ₂ -C(CH ₃ )H, wherein, x and y Represents an integer 1-4, representing a clear and unique degree of aggregation;

ii) bis-secondary diamine groups, such as piperazine derivatives;

iii) a bis-primary diamine group of the following formula: -NHY-NH-, wherein Y represents a linear or branched hydrocarbon group or a divalent group -CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -; or

iv) 1,3-ureidenes of the formula -NH-CO-NH-.

其中，R¹是H或CH₃，A是直链或支链的具有1-6个碳原子的烷基或具有1-4个碳原子的羟烷基，R²、R³和R⁴独立地表示具有1-18个碳原子的烷基或苄基，R⁵和R⁶表示H或具有1-6个碳原子的烷基，X表示甲基硫酸根或卤离子，如氯离子或溴离子。(11) Homopolymers or copolymers derived from acrylic acid or methacrylic acid and containing at least one of the following units:

Wherein, R ¹ is H or CH ₃ , A is a linear or branched alkyl group with 1-6 carbon atoms or a hydroxyalkyl group with 1-4 carbon atoms, R ² , R ³ and R ⁴ are independent ground represents an alkyl or benzyl group with 1-18 carbon atoms, R ^{and R} represent H or an alkyl group with 1-6 carbon atoms, X represents methylsulfate or a halide such as chloride or bromide ion.

Comonomers which may be employed generally belong to the group comprising acrylamide, methacrylamide, diacetone-acrylamide, acrylamide and methacrylamide substituted at the nitrogen by one or more lower alkyl groups, acrylic acid and methacrylamide Alkyl, vinylpyrrolidone and vinyl esters of acrylates.

Useful polymers are Quaternium 38, 37, 49, and 42 (CTFA designations); acrylamide/β-methacryloxyethyl-trimethylammonium methyl sulfate copolymers, trade names Teten 205, 210, 220 and 240 are sold by Hercules; amino ethyl acrylate phosphate/acrylate copolymers sold under the tradename Catrex by National Starch &Chemicals; crosslinked graft cationic copolymers having a molecular weight of 10,000 to 1,000,000, preferably 15,000 to 500,000 , obtained by copolymerization of at least one cosmetic monomer, dimethylaminoethyl methacrylate, polyethylene glycol and a polyunsaturated crosslinking agent, such as those mentioned in the CTFA dictionary under the name AMODIMETHICONE, as in Products sold under the trade name DOW CORNING 929 Cationic Emulsion are mixtures with other ingredients.

(12) Other usable are polyalkyleneimines, especially polyethyleneimines, polymers containing vinylpyridine units or vinylpyridinium units in the chain, condensates of polyamines and epihalides Condensates of substituted alcohols, poly-(quaternized 1,3-ureidene) and chitin derivatives.

Particularly preferred cationic styling polymers include commercially available materials such as Polyquaternium 4, available under the tradenames CELQUAT H100 and CELQUAT L200, available from National Starch &Chemicals; Polyquaternium 11, available under the tradename GAFQUAT 755N, available from ISP.

Anionic Styling Polymers

Anionic styling polymers useful herein include those containing units derived from carboxylic, sulfonic or phosphoric acids and generally having a molecular weight of from 500 to 5,000,000. These polymers are water-soluble polymers whose solubility can be obtained by neutralization.

其中，n是0或1至10的整数，A表示选择性地连接至饱和基团的碳原子上的亚甲基，或者在n大于1时，经杂原子如氧或硫与相邻的亚甲基基团相连，R¹表示氢原子或苯基或苄基，R²表示氢原子、低级烷基或羧基，R³表示氢原子、低级烷基、CH₂COOH或苯基或苄基。按照本发明，包含羧酸基团的优选的聚合物是：Carboxylic acid groups may be provided by unsaturated monocarboxylic or dicarboxylic acids, such as those corresponding to the formula:

Wherein, n is 0 or an integer from 1 to 10, and A represents a methylene group selectively connected to a carbon atom of a saturated group, or when n is greater than 1, a heteroatom such as oxygen or sulfur and an adjacent methylene group The methyl groups are connected, ^R1 represents a hydrogen atom or a phenyl or benzyl group, ^R2 represents a hydrogen atom, a lower alkyl group or a carboxyl group, ^R3 represents a hydrogen atom, a lower alkyl group, _CH2COOH or a phenyl group or a benzyl group. According to the invention, preferred polymers comprising carboxylic acid groups are:

(1) Homopolymers or copolymers of acrylic acid or methacrylic acid or their salts, especially the following commercially available products from BASF under the names VERSICOLE or K and ULTRAHOLD; from Vander Bilt under the name DARVAN No. 7; acrylic acid/acrylamide copolymers named RETEN 421, 423 or 425 in sodium salt form from HERCULES; and sodium salts of polyhydroxycarboxylic acids under the tradename HYDAGENF available from HENKEL.

(2) Copolymers of acrylic acid or methacrylic acid and monovinyl monomers such as ethylene, styrene, vinyl or allyl esters or acrylates or methacrylates, selectively grafted to polyalkylene di Alcohols such as polyethylene glycol and optionally cross-linked. Other such copolymers contain an optionally N-alkylated and/or N-hydroxylated acrylamide unit in their chain, such as those sold by American Cyanamid under the tradename QUADRAMER 5.

(3) Copolymers derived from crotonic acid, such as those containing vinyl acetate or vinyl propionate units in their chains and optionally other monomers such as allyl or methyl groups of saturated linear or branched carboxylic acids Allyl esters, vinyl ethers or vinyl esters, carboxylic acids having a carbon chain length of at least 5 carbon atoms, grafted and crosslinked of these polymers as appropriate, also containing alpha- or beta-cyclic carboxylic acids vinyl, allyl or methallyl esters. Copolymers included in this class include those sold by National Starch & Chemicals under the trade designations RESYN 28-2930, 28-2913 and 28-1310.

(4) Polymers obtained from maleic acid, fumaric acid and itaconic acid or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and their esters, such as commercially available Those sold by ISPs under the names GANTREZ A, SP and ES. Other polymers included in this class are copolymers of maleic, citraconic and itaconic anhydrides with allyl or methallyl esters optionally containing acrylamido or methacrylamido groups, or Copolymers with alpha-olefin, acrylate or methacrylate, acrylic or methacrylic acid or vinylpyrrolidone units in their chains; the anhydride groups may be monoesterified or monoamidated.

(5) Polyacrylamides containing carboxylate groups. Polymers containing sulfonic acid groups include polymers containing vinylsulfonic, styrylsulfonic, lignosulfonic, or naphthalenesulfonic units. These polymers are selected in particular from:

i) Polyvinylsulfonates with a molecular weight of 1,000 to 100,000, and copolymers with unsaturated comonomers, such as acrylic or methacrylic acid or their esters and substituted or unsubstituted acrylamides or methacrylamides, ethylene esters, vinyl ethers and vinylpyrrolidones.

ii) Polystyrene sulfonates such as the sodium salts sold under the trade names Flexan 500 and 130 by National Starch & Chemicals.

iii) Alkali or alkaline earth metal salts of sulfonic acids derived from lignin, especially calcium or sodium lignosulfonate, such as the product sold by American Can Co. under the trade name Marasperse C-21 and _C10 by Avebene to C ₁₄ products.

iv) Polymers comprising salified alkylnaphthalenesulfonic acid units, such as the sodium salt sold under the tradename Darvan No. 1 by Van der Bilt.

To aid the shampoo removal properties of liquid hair cosmetic compositions, the anionic hair styling polymers according to the invention comprising anionic monomers are preferably used in at least partially neutralized form. In this composition, the neutralization of the polymer may be carried out with an inorganic base, preferably potassium hydroxide. However, organic bases, preferably AMP (aminomethylpropanol), and mixtures of inorganic and organic bases can also be used to achieve the desired degree of neutralization of the hair styling composition. In general, from about 50% to about 100%, preferably from about 70% to about 100%, more preferably from about 80% to 100%, of the acidic monomers of the polymer employed should be neutralized with a base.

Any of the conventionally employed bases, organic or inorganic, can be used to neutralize the acidic polymer provided they are used in accordance with the teachings of the present invention. Alkali metal, alkaline earth metal hydroxides and aminoalcohols are suitable neutralizing agents.

Examples of suitable organic neutralizing agents for inclusion in the compositions of the present invention include: amines, especially aminoalcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amine-2-ethane 1,3-propanediol (AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB), monoethanolamine (MEA), diethanolamine (DEA ), triethanolamine (TEA), monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine (TIPA), dimethylstearylamine (DMS) and aminomethylpropanol (AMP) and mixtures thereof.

Preferred neutralizing agents for use in the hair care compositions of the present invention are potassium hydroxide and sodium hydroxide.

Particularly preferred anionic styling polymers include commercially available materials such as vinyl acetate/crotonic acid/vinyl neodecanoate copolymers available under the tradenames RESYN 28-2930, RESYN 28-2913 and RESYN 28-1310 from National Starch & Chemicals, and acrylate copolymers and acrylate/acrylamide copolymers under the trade names LUVIMER 100P, ULTRAHOLD 8 and ULTRAHOLD STRONG are commercially available from BASF Corporation.

nonionic styling polymers

Nonionic styling polymers useful herein are homopolymers of vinylpyrrolidone or vinylcaprolactam or copolymers of vinylpyrrolidone and vinyl acetate, such as those offered by BASF under the tradenames LUVISKOLK grades and LUVISKOLVA grades.

siloxane graft copolymer

Silicone graft copolymers useful in the present invention include those polydimethylenes having a vinyl polymeric backbone (A and B monomers) and grafted to said backbone with a weight average molecular weight of from about 1,000 to about 50,000. Those copolymers of siloxane-based macromers (C-macromonomers). Preferably, these copolymers comprise from about 50.0% to about 99.9% of a combination of A and B monomers, from about 0.1% to about 50.0% of a C macromonomer, where A is a lipophilic, low polar, free radically polymerizable ethylene base monomers, such as methacrylate or acrylate; B is a hydrophilic polar monomer, which can be copolymerized with A, such as acrylic acid, N,N-dimethylacrylamide, dimethylaminomethacrylate ethyl ester, diallyldimethylammonium chloride, vinylpyrrolidone or quaternized dimethylaminoethyl methacrylate; C is a silicone-containing macromolecular unit based on polydimethylsiloxane body having a weight average molecular weight of from about 1,000 to about 50,000. Preferred silicone-grafted copolymers are those having a Tg value greater than about -20°C and a molecular weight of from about 10,000 to about 1,000,000.

Silicone graft copolymers suitable for use in the present invention include those listed below: where the numerical values represent the ratio of the various monomers to the macromonomer in the copolymer, and the silicone macromonomer S1 has a molecular weight of about 20,000 polydimethylsiloxane, the silicone macromer S2 is a polydimethylsiloxane with a molecular weight of about 10,000.

1) 20/63/17 Acrylic/tert-Butyl Methacrylate/Siloxane Macromer S2, the molecular weight of the copolymer is about 100,000

2) 10/70/20 Dimethacrylamide/Isobutyl Methacrylate/Siloxane Macromer S2, the molecular weight of the copolymer is about 400,000

3) 60/20/20 diallyldimethylammonium methacrylate/isobutyl methacrylate/siloxane macromer S2, the molecular weight of the copolymer is about 500,000

4) 40/40/20 Acrylic/Methyl Methacrylate/Siloxane Macromer S1, the molecular weight of the copolymer is about 400,000

5) 10/70/20 acrylic acid/tert-butyl methacrylate/silicone macromer S1, the molecular weight of the copolymer is about 300,000

6) 25/65/10 Acrylic/Isopropyl Methacrylate/Siloxane Macromer S2, the molecular weight of the copolymer is about 200,000

7) 60/25/15 N,N'-dimethylacrylamide/methoxyethyl methacrylate/siloxane macromer 51, the molecular weight of the copolymer is about 200,000

8) 12/64/4/20 N,N'-dimethylacrylamide/isobutyl methacrylate/2-ethylhexyl methacrylate/siloxane macromer S1, the molecular weight of the copolymer about 300,000

9) 30/40/10/20 N,N'-dimethylacrylamide/isobutyl methacrylate/2-ethylhexyl methacrylate/siloxane macromer S1, the molecular weight of the copolymer about 300,000

10) 80/20 tert-butyl acrylate/siloxane macromer S2, the molecular weight of the copolymer is about 150,000

carrier

The compositions of the present invention may comprise a carrier. The amount and type of carrier can be selected based on compatibility with other ingredients and desired product properties. For example, high percentages of low boiling point volatile solvents and/or propellants are suitable for product forms that aid in staying on the hair. On the other hand, aqueous solutions of volatile and non-volatile solvents are suitable for use in product forms which are rinsed 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 to 3 carbon atoms, and hydrocarbons having from about 5 to about 8 carbon atoms. Preferred volatile solvents are water, ethanol, isopropanol, ammonium alkanes, hexanes and heptanes. Water useful in the present invention includes deionized water and water from natural sources containing inorganic cations. Deionized water is preferably used.

Non-volatile solvents used in the present invention include alkyl alcohols having more than 3 carbon atoms and polyhydric alcohols. Polyhydric alcohols useful in the present invention include 1,2-propanediol or propylene glycol, 1,3-propanediol, hexanediol, glycerin, diethylene glycol, dipropylene glycol, 1,2-butanediol and 1,4 - butanediol.

Propellants are used in mousse and hairspray products. When a propellant is used in the present invention, it can be selected based on factors such as residues of components, packaging, and whether the product is designed for static or inverted use.

Propellants useful in the present invention include fluorocarbons 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 components

The compositions of the present invention may contain various additive components, which may be selected by those skilled in the art according to the characteristics of the final product. Additive ingredients include, for example, polyvalent metal cations, suspending agents, and other additive ingredients.

polyvalent metal cation

Suitable multivalent 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.

Multivalent metal cations can be added in the form of inorganic salts, organic salts or hydroxides. The polyvalent metal cations may also be added as their salts with anionic surfactants as described above.

Preferably the polyvalent metal cations are added as inorganic or organic salts. Inorganic salts include: chloride, bromide, iodide, nitrate or sulfate, more preferably chloride or sulfate. 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 polyvalent salts of anionic surfactants are used as a means of introducing polyvalent metal cations into the compositions of the present invention, only a portion of the anionic surfactants may have polyvalent forms, the rest Anionic surfactants must be added in monovalent form.

The hardness of a conditioning shampoo composition can be measured by methods well known in the art, such as ethylenediaminetetraacetic acid (EDTA) titration. When the composition of the present invention contains dyes or other coloring materials that interfere with the titration performance of EDTA, a perceptible color change will occur, and the hardness of the composition should be measured in the absence of interference from dyes or colorants.

Suspending agent

A preferred additional ingredient is a suspending agent, especially for compositions containing highly viscous and/or large particle size silicone compounds. When used, the suspending agent is present in the composition in dispersed form. Suspending agents generally comprise from about 0.1% to about 10%, preferably from about 0.3% to about 5.0%, by weight of the composition.

Preferred suspending agents include acyl derivatives such as ethylene glycol stearates, including mono- and distearates; long-chain amine oxides such as alkyl (C ₁₆ -C ₂₂ ) dimethyl amine oxides, such as stearate; Aliphatic dimethylamine oxide and mixtures thereof. When used in shampoo compositions, these preferred suspending agents are present in the composition in crystalline form. Such suspending agents are described in US 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: stearyl monoethanolamide, coconut Oil monoethanolamide, stearyl diethanolamide, stearyl monoisopropanolamide and stearyl monoethanolamide stearate.

Other suitable suspending agents include N,N-dihydrocarbylamidobenzoic acids and soluble salts thereof (such as sodium and potassium salts), especially N,N-di(hydrogenated) _C16 , _C18 and tallowamidobenzoic acids , 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 in US 4,788,006, which is incorporated herein by reference. Long chain acyl derivatives in combination with xanthan gum can also be used as suspending agents in shampoo compositions. This combination is described in US 4,704,272, which is incorporated herein by reference.

Other suitable suspending agents include carboxyvinyl polymers. A preferred polymer of this type is a copolymer of acrylic acid crosslinked with polyallyl sucrose as described in US 2,798,053, which is incorporated herein by reference. Examples of such polymers include carbomers, which are homopolymers of acrylic acid crosslinked with alkyl ethers of pentaerythritol, allyl ethers of sucrose or allyl ethers of propylene. Neutralizing agents such as aminomethylpropanol, 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 colloidal water-soluble polymers like cellulose ethers, such as hydroxyethyl Cellulose, hydroxymethylcellulose, hydroxypropylcellulose and substances such as guar gum, polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, starch and starch derivatives.

other additives

Various other additive ingredients may be formulated in the compositions of the present invention. These ingredients include: other conditioning agents such as Cape Collagen, commercially available from Hormel under the tradename Peptein 2000; vitamin E, commercially available from Eisai under the tradename Emix-d; panthenol, commercially available from Roche; Panthenyl ethyl ether, commercially available from Roche; hydrolyzed keratin, proteins, plant extracts and nutrients; emulsifying surfactants for dispersing water-insoluble components in carriers; preservatives such as benzyl alcohol , methylparaben, propylparaben, and imidazolinyl urea; pH adjusters such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, usually such as potassium acetate and sodium chloride; coloring agents, 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; fragrances; chelating agents and anti-dandruff agents such as zinc pyrithione. These optional ingredients generally comprise from about 0.001% to about 10.0%, preferably from about 0.01% to about 5.0%, respectively, by weight of the composition.

Example

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 invention, and various changes may be made thereto without departing from the spirit and scope of the invention. Components are identified by chemical name or CTFA name or given as defined below.

Example IV Non-rinsing Spray Example I Example II Example III Example IV Example V components weight% 1,4-bis(2-cyanostyrene)benzene ^*1 0.50 - - - - Disodium-1,4-bis(2-sulfostyrene)biphenyl ^*2 - 0.50 - - - 4,4'-bis[(4-phenylamino-6-bis(2-hydroxyethyl)amino-1,3,5-triazin-2-yl)amino]stilbene-2,2'-di Sulfonic acid ^*3 - - 1.00 - - 4-Methyl-6,7-dihydroxycoumarin - - - 0.25 - 4-Methyl 7,7′-Dimethylaminocoumarin - - - 0.25 - 4,4′-bis(5-methylbenzoxazol-2-yl)stilbene ^*4 - - - - 0.50 Carbomer 956 ^*5 0.26 0.26 - - - Citric acid ^*6 0.10 0.10 - - - L-glutamic acid ^*7 - - 0.10 0.10 0.10 Octyl Methoxycinnamate ^*8 0.01 0.01 - - - Stearamidopropyl dimethylamine ^*9 - - 0.50 0.50 0.50 Silicone emulsifier ^*10 5.80 5.80 - - - preservative 0.65 0.65 0.65 0.65 0.65 spices 0.15 0.15 0.08 0.08 0.08 Hydrolyzed Collagen ^*37 0.01 - - - - Vitamin E ^*38 0.01 - - - - Panthenol ^*39 0.025 - - - - Panthenyl ethyl ether ^*40 0.025 - - - - Deionized water Balance to 100 Color changes average value a value processing side 0.63 2.51 2.90 2.27 0.44 control side 0.81 2.05 2.79 2.88 1.16 Change 0.18 0.46 0.11 0.61 0.72 b value processing side 0.11 1.11 1.61 1.70 0.77 control side 0.58 2.60 2.98 2.67 1.16 Change 0.47 1.49 1.37 0.97 0.39

Examples VI-IX Non-rinsing Sprays Example VI Example VII Example VIII Example IX components weight% Disodium-1,4-bis(2-sulfostyrene)biphenyl ^*2 1.00 0.20 - - 2-(4-Styryl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole ^*11 - 0.20 - - 1-(4-amidosulfonylphenyl)-3-(4-chlorophenyl)-2-pyrazoline ^*12 - - 1.00 - 2,4-Dimethoxy-6-(1′pyrenyl)-1,3,5-triazine ^*13 - - - 0.50 Acrylate/Steareth-20 Methacrylate Copolymer ^*14 1.75 - - - Aminomethylpropanol ^*15 2.10 - - - Cetyl Alcohol ^*16 2.00 0.50 0.50 0.50 Cetyl hydroxyethyl cellulose ^*17 - 0.75 0.75 0.75 Citric acid ^*6 0-0.2 0-0.2 0-0.2 0-0.2 Lauryl Methyl Gluceth-10 ^*18 Hydroxypropyl Dimethyl Ammonium Chloride ^*19 - 1.00 1.00 1.00 Pentaerythritol Tetraisostearate ^*20 1.00 3.00 3.00 3.00 Polyoxyethylene glycol ^*21 0.50 0.50 0.50 0.50 Polyquaternium-10 ^*22 0.10 - - - Polyquaternium-7 ^*23 - 0.50 0.50 0.50 Polysorbate 60 ^*24 1.00 - - - Silicone emulsion ^*25 1.00 0.50 0.50 0.50 Stearyl alcohol ^*26 3.00 0.50 0.50 0.50 preservative 0.90 0.90 0.90 0.90 spices 0.08 0.08 0.08 0.08 Deionized water Appropriate amount to 100 color measurement average value a value processing side 1.20 1.57 2.55 0.18 control side 1.80 1.64 2.68 0.74 Change 0.60 0.07 0.13 0.56 b value processing side 0.20 0.12 1.31 0.45 control side 1.80 1.28 2.89 0.55 Change 2.00 1.40 1.58 1.00

Examples X-XIII Shampoos and conditioners Example X Example XI Example XII Example XIII components weight% Disodium-1,4-bis(2-sulfostyrene)biphenyl ^*2 0.50 - 0.50 1.00 4,4'-bis[(4-phenylamino-6-bis(2-hydroxyethyl)amino-1,3,5-triazin-2-yl)amino]stilbene-2,2'-di Sulfonic acid ^*3 - 1.00 - - Cetyl Alcohol ^*16 - - 2.50 2.50 L-glutamic acid ^*7 - - 0.64 0.64 Polyoxyethylene stearyl ether ^*27 - - - 0.50 Polyquaternium-10 ^*22 0.50 0.50 - - Stearamidopropyl dimethylamine ^*9 - - 2.00 2.00 Stearyl alcohol ^*26 - - 4.50 4.50 preservative - - 0.53 0.53 spices 0.50 0.50 0.20 0.20 Ammonium Laureth-3 Sulfate 10.00 10.00 - - N-acyl-L-glutamate ^*28 Triethanolamine 4.00 4.00 - - Cocamidopropyl Betaine ^*29 4.00 4.00 - - Cocamide MEA 1.50 1.50 - - Ethylene glycol distearate ^*30 2.00 2.00 - - DMDM hydantoin 0.20 0.20 - - 15/85 silicone blend ^*31 - - 4.20 4.20 40/60 silicone blend ^*32 2.00 2.00 - - monosodium phosphate 0-1.0 0-1.0 - - disodium phosphate 0-1.0 0-1.0 - - Deionized water Appropriate amount to 100 color measurement average value a value processing side 1.80 0.37 0.76 0.85 control side 2.03 0.59 1.10 0.92 Change 0.23 0.22 0.34 0.07 b value processing side 0.83 0.13 0.04 0.12 control side 1.66 0.47 0.64 0.63 Change 0.83 0.60 0.60 0.51

Examples XIV-XVI Styling Hair Sprays and Mousses Example X Example XI Example XII components weight% Disodium-1,4-bis(2-sulfostyrene)biphenyl ^*2 0.20 0.25 - Porphyrin ^*33 - - 0.20 denatured ethanol 73.25 7.50 7.50 spices 0.20 0.10 0.10 Polyacrylic acid-co-ethyl acrylate-co-tert-butylacrylamide ^*34 6.00 - - Polyoctylacrylamide-co-Alkyl Acrylate-Co-Butylaminoethyl Methacrylate ^*35 - 4.00 4.00 Aminomethylpropanol ^*15 0.15 0.70 0.70 Dimethicone Copolyol ^*36 0.10 - - Lauramide DEA 0.10 - - Laureth-23 - 0.20 0.20 Laureth-7 - 0.10 0.10 Propylene Glycol - 0.10 0.10 preservative - 0.10 0.10 Isobutane/Propane - 7.00 7.00 Deionized water Appropriate amount to 100 color measurement average value a value processing side 1.31 1.30 1.10 control side 1.66 1.14 1.25 Change 0.35 0.16 0.15 b value processing side 4.25 0.38 0.32 control side 5.30 1.16 1.23 Change 1.05 0.78 0.91

definition

^*1 1,4-bis(2-cyanostyryl)benzene: Ultraphor RN, commercially available from BASF

^*2 Disodium-1,4-bis(2-sulfostyryl)biphenyl: Tinopal CBX, commercially available from CibaGeigy

^*3 4,4'-bis[(4-phenylamino-6-bis(2-hydroxyethyl)amino-1,3,5-triazin-2-yl)amino]stilbene-2,2' - Disulfonic acid: Tinopal UNPA-GX, commercially available from Ciba Geigy

^*4 4,4'-bis(5-methylbenzoxazol-2-yl)stilbene: commercially available from TCI

^*5 Carbomer 956: Carbopol 980, commercially available from BF Goodrich

^*6 Citric acid: anhydrous citric acid, commercially available from Haarman & Reimer

^*7 L-glutamic acid: cosmetic grade, commercially available from Ajinomoto

^*8 Octyl Methoxycinnamate: Commercially available from ISP

^*9 Stearamidopropyldimethylamine: Amidoamine MPS, commercially available from Nikko

^*10 Silicone emulsifier: SM-2169, commercially available from GE

^*11 2-(4-Styryl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole: Tinopal RBS, commercially available from Ciba Specialty Chemicals

^*12 1-(4-amidosulfonylphenyl)-3-(4-chlorophenyl)-2-pyrazoline: Blankophor DCB, commercially available from Sayer

^*13 2,4-Dimethoxy-6-(1'pyrenyl)-1,3,5-triazine: commercially available from Ciba Geigy

^*14 Acrylate/Steareth-20 Methacrylate Copolymer: Aculyn, commercially available from Rohm & Haas

^*15 Aminomethylpropanol: AMP-conventional, commercially available from Angus

^*16 Cetyl alcohol: Konol series, commercially available from Shinihon Rika

^*17 Cetyl hydroxyethylcellulose: Polysurf 67, commercially available from Aqualon

^*18 Laurylmethyl Gluceth-10: Glucquat 125, commercially available from Amerchol

^*20 Pentaerythritol tetraisostearate: KAK PTI, commercially available from Kokyu alcohol

^*21 Polyoxyethylene glycol: WSR N-10, commercially available from Amerchol

^*22 Polyquaternium-10: UCARE polymer LR 400, commercially available from Amerchol

^*23 Polyquaternium-7: MerquatS, commercially available from Calgon

^*24 Polysorbate 60: Tween 60, commercially available from ICI

^*25 Silicone Emulsion: X65-4829, commercially available from Tosil/GE

^*26 Stearyl alcohol: Konol series, commercially available from Shinihon Rika

^*27 Polyoxyethylene stearyl ether: Brij-721, commercially available from ICI

^*28 N-acyl-L-glutamate triethanolamine: CT12S, commercially available from Ajinomoto

^*29 Cocamidopropyl Betaine: Tegobetain, commercially available from Th. Goldschmidt AG

^*30 Ethylene Glycol Distearate: EGDS, commercially available from Th. Goldschmidt AG

^*31 15/85 silicone blend: commercially available from Shinetsu

^*32 40/60 silicone blend: SE76, commercially available from GE

^*33 Porphyrin: commercially available from Wako

^*34 Polyacrylic acid-co-ethyl acrylate-co-tert-butyl acrylamide: Ultrahold-8, commercially available from BASF

^*35 Polyoctylacrylamide-co-alkyl acrylate-co-butylaminoethyl methacrylate: Amphomer 28-4910, commercially available from National Starch

^*36 Dimethicone copolyol: SH3746, commercially available from Dow Corning

^*37 Hydrolyzed collagen: Peptein 2000, commercially available from Hormel

^*38 Vitamin E: Emix-d, commercially available from Eisai

^*39 Panthenol: commercially available from Roche

^*40 Panthenyl ethyl ether: commercially available from Roche

Preparation

The above compositions of Examples I to XVI can be prepared according to conventional methods well known in the art. Suitable methods are described below.

For the hairsprays of Examples I and II, the following preparation procedure was applied: water, Carbomer 956, optical brightener Ultraphor RN or Tinopal CBS-X were mixed at room temperature. Add polydimethylsiloxane emulsion SM2169. The materials were properly dispersed using a triblender and mill. Subsequently, the other components are added with stirring.

The hair sprays of Examples III, IV and V are prepared by heating water, stearamidopropyldimethylamine, glutamic acid, cetyl alcohol and stearyl alcohol at a temperature higher than 70° C., and then Gradually cool to room temperature. Add silicone emulsion. The materials are properly dispersed using a triple mixer and a mill. Subsequently, the other components are added with stirring.

The hair lotion of Example VI is suitable for the following preparation process: acrylate/stearyl polyoxyethylene ether-20 methacrylic acid copolymer is neutralized with an aqueous solution of aminomethylpropanol in water at room temperature . Subsequently, Polyquaternium-10 and polyoxyethylene glycol were added. The mixture is heated to above 60°C and cetyl alcohol, stearyl alcohol and Polysorbate 60 are added. Upon cooling to below 50°C, the remaining ingredients were added with stirring, then cooled to about 30°C.

The hair lotions of Examples VII, VIII and IX were prepared by the following procedure: Cetyl hydroxyethyl cellulose and Polyquaternium-10 or Polyquatemium-7 were dispersed in water at room temperature. Polyoxyethylene glycol is then added. The mixture was heated above 60°C and cetyl alcohol, stearyl alcohol and lauryl methyl Gluceth-10 hydroxypropyl dimethyl ammonium chloride were added. Upon cooling to below 50°C, the remaining ingredients were added with stirring, then cooled to about 30°C.

The shampoos of Examples X and XI were prepared using the following procedure: Water, Laureth-3 Ammonium Sulfate, Cetyl Alcohol, Stearyl Alcohol, Cocamide MEA, and Ethylene Glycol Distearate were heated above 75°C, and then Gradually cool to room temperature. Polyquatemium-10 was dispersed alone in water at 35°C. Mix the above two together and add the remaining ingredients with stirring.

The conditioner of Example XII was prepared by heating water, stearamidopropyldimethylamine, glutamic acid, cetyl alcohol, stearyl alcohol to a temperature above 70°C and then gradually cooling to room temperature. Add disodium-1,4'-bis(2-sulfostyryl)biphenyl, silicone blend. Subsequently, the remaining ingredients are added with stirring.

The conditioner of Example XIII is prepared according to the following procedure: water, stearamidopropyldimethylamine, glutamic acid, disodium-1,4'-bis(2-sulfostyrene)biphenyl Mix and heat above 70°C. In addition, water, stearamidopropyl dimethylamine, glutamic acid, cetyl alcohol and stearyl alcohol were mixed and heated to higher than 70°C. The above two mixtures were mixed together and cooled to room temperature. The remaining ingredients were added with stirring.

The hair styling spray of Example XIV was prepared by dissolving the hair styling polymer in a portion of water and ethanol. To this was added the remaining components except the isobutane/propane blend. The obtained mixture was mixed until homogeneous. Finally, the obtained concentrate is filled into aerosol cans containing isobutane/propane.

The hair mousses of Examples XV and XVI were prepared by dissolving the hair styling polymer in a portion of the water. To this was added the remaining components except the isobutane/propane blend. The obtained mixture was mixed until homogeneous. Finally, the obtained concentrate is filled into aerosol cans containing isobutane/propane.

Color Change Measurement Method

Color alterations as indicated above were measured according to the procedure described below.

Hair color measurements are made on 20 cm long hair switches made from 15 g of straight Asian human hair. The same hair switch was divided into two parts, one part was treated with the product of the example (treatment side), and the other part was treated with the control product, which had the same formula as the product of the example, except that the optical brightener was replaced with water ( control side). Apply an equal amount of product to both sides of the hair switches following the process detailed below. The a and b values were measured using a Macbeth 1500 Reflective ColorMeter (supplied by Kollmorgen Corporation) or a MiniScan XE Spectrophotometer (supplied by Hunter Associates Laboratory Inc). Each measurement was repeated at least three times, and the average value was taken.

For Examples I-V, the product of the Examples was sprayed onto a portion of the hair switch. Instead, the control product was sprayed onto another section of the hair switch. After drying, measure the color of the hair.

For Examples VI-IX, the products of the Examples were applied to a portion of a hair switch that had been cleaned with ALS twice and dried overnight before use. Apply the control product to another section of the hair switch. After drying, measure the color of the hair.

For Examples X-XIII, the product of the Examples was applied to a portion of the hair switch for 30 seconds, followed by rinsing with water for 30 seconds. The control product was applied to another section of the hair switch for 30 seconds, followed by rinsing with water for 30 seconds. After drying, measure the color of the hair.

For Example XIV, the Example product was sprayed onto a portion of the hair switches. Instead, the control product was sprayed onto another portion of the hair switch. After drying, measure the color of the hair.

For Examples XV and XVI, the Example products were applied to a portion of the hair switch. Apply the control product to another section of the hair switch. After drying, measure the color of the hair.

The products of Examples I to XVI have many advantages. For example, they can be used on a daily basis and provide color change, impart shine and protect hair from UV damage.

It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various changes may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (25)

1, a kind of Haircare composition, it comprises:

(a) a kind of fluorescent whitening agent, the hair color that its amount for a change applies said composition makes one of a value and b value or both change about 0.2 unit to about 15 units; With

(b) a kind of hair care active substance, it is selected from detersive surfactant, conditioner, styling polymer and its mixture.

2, according to the Haircare composition of claim 1, also comprise a kind of carrier.

3, according to the Haircare composition of claim 1, wherein one of a value and b value or both absolute values reduce.

4, according to the Haircare composition of claim 1, wherein one of a value and b value or both absolute values increase.

5, according to the Haircare composition of claim 3, wherein the b value changes.

6, according to the Haircare composition of claim 5, wherein the b value changes about 0.5 unit to about 5 units.

7, according to the Haircare composition of claim 4, wherein the b value changes.

8, according to the Haircare composition of claim 7, wherein the b value changes about 0.5 unit to about 5 units.

9, according to the Haircare composition of claim 3, wherein a value changes.

10, according to the Haircare composition of claim 9, wherein a value changes about 0.5 unit to about 5 units.

11, according to the Haircare composition of claim 4, wherein a value changes.

12, according to the Haircare composition of claim 11, wherein a value changes about 0.5 unit to about 5 units.

13, according to each Haircare composition of claim 1 to 12, wherein the variation of a value from 0 of a value axle within about 5 units, and wherein the variation of b value from 0 of b value spool within about 5 units.

14, according to each Haircare composition of claim 1 to 12, wherein Haircare composition is substantially free of dyestuff.

15, according to each Haircare composition of claim 1 to 12, wherein fluorescent whitening agent is selected from polystyrene-based stilbene, triazine radical stilbene, Hydroxycoumarin, aminocoumarin, triazole, pyrazoline, oxazole, pyrene, porphyrin, imidazoles and its mixture.

16, a kind of Haircare composition, it comprises:

(a) a kind of fluorescent whitening agent, its amount is for when it is coated on the hair, and about 1ppm of hair weight is to about 2%; With

(b) a kind of hair care active substance, it is selected from detersive surfactant, conditioner, styling polymer and its mixture; Wherein the color of the hair of Haircare composition change coating said composition makes one of a value and b value or both change about 0.2 unit to about 15 units.

17, according to the Haircare composition of claim 16, also comprise a kind of carrier.

18, according to the Haircare composition of claim 16, wherein the content of fluorescent whitening agent is for when it is coated on the hair, and about 10ppm of hair weight is to about 1%.

19, according to the Haircare composition of claim 18, wherein the content of fluorescent whitening agent is that about 100ppm of hair weight is to about 0.3% when it applies on hair.

20, according to each Haircare composition of claim 16 to 19, wherein Haircare composition is substantially free of dyestuff.

21, according to each Haircare composition of claim 16 to 19, wherein fluorescent whitening agent is selected from polystyrene-based stilbene, triazine radical stilbene, Hydroxycoumarin, aminocoumarin, triazole, pyrazoline, oxazole, pyrene, porphyrin, imidazoles and its mixture.

22, a kind of method that changes hair color by coating fluorescent whitening agent on hair.

23, according to the method for the change hair color of claim 22, the coating amount of fluorescent whitening agent on hair is that about 1ppm of hair weight is to about 2%.

24, according to the method for the change hair color of claim 22, wherein fluorescent whitening agent is selected from polystyrene-based stilbene, triazine radical stilbene, Hydroxycoumarin, aminocoumarin, triazole, pyrazoline, oxazole, pyrene, porphyrin, imidazoles and its mixture.

25, a kind of by following compositions is coated on the method that changes hair color on the hair, described compositions comprises:

(a) a kind of fluorescent whitening agent, the hair color that its amount for a change applies said composition makes one of a value and b value or both change about 0.2 unit to about 15 units; With

(b) a kind of hair care active substance, it is selected from detersive surfactant, conditioner, styling polymer and its mixture.