HK1080876A - Silicones - Google Patents

Description

Siloxanes

Technical Field

In a first aspect, the present invention relates to functionalized siloxanes having defined structures. In another aspect, the present invention relates to topical compositions comprising these functionalized silicones. These compositions exhibit conditioning efficacy on polar and non-polar substrates that is higher than the conditioning efficacy of previously known silicone-based conditioners, especially when the substrate is hair that has been previously damaged by chemical treatment, such as occurs during permanent dyeing, bleaching and perming. In another aspect, the present invention relates to a hair treatment kit comprising a topical composition according to the present invention.

Background

Oxidative dyeing (also known as permanent dyeing) causes an irreversible physicochemical transformation to the hair. In this process, it is typical to mix the two components together prior to application to the hair. These components generally include an oxidizing agent such as hydrogen peroxide and include dyeing materials such as oxidative dye precursors and couplers (buffered at high pH, typically about 10). After contact with the hair, the mixture is left for a period of time suitable for the desired color transition to occur. Thereafter, the hair becomes more hydrophilic than the hair without dyeing due to irreversible chemical changes. Without being bound by theory, this change in hair hydrophilicity appears to be due, inter alia, to the oxidation of keratin-keratin cystine amino acids in the hair resulting in more hydrophilic cysteic acid amino acid residues and the removal of the natural hydrophobic F-layer by hydrolysis. This coloring process is typically repeated regularly by consumers in order to maintain their desired hair color and color intensity, and also to ensure that new hair growth has the same color as the previous hair. Thus, the polarity of the hair changes from a relatively hydrophobic surface near the scalp (undergoing a first dyeing) to a progressively more polar matrix at the tip of the hair (which may have undergone multiple dyeing treatments). A discussion of oxidative Hair staining can be found in Charles Zviak, "The Science of hairCare," Marcel Dekker, New York, 1986.

These irreversible physicochemical transformations can also be manifested by an increase in roughness, brittleness and dryness, resulting in hair that is not easily finished. The use of conditioning agents in dyeing processes is known. Conditioning materials may be added to the colorant product or, alternatively, these may be added as separate conditioning agents to the colorant kit and thus may be applied to the hair during the coloring process or after the colorant has been rinsed off. It is known to use aminosilicones for this purpose, as described in EP 0275707. However, it has now been determined that in the case of more polar hair, such as that obtained after continuous oxidative dyeing, aminosilicone deposition is greatly reduced and does not provide the same level of benefit in hair conditioning as non-oxidatively dyed hair, especially when the benefit is delivered in a harsh dyeing environment. Without being bound by theory, this may be due to the incompatibility of surface energy between the hair damaged by polar chemistry and the relatively non-polar aminosilicone, resulting in poor adsorption.

Improving deposition uniformity between more and less damaged hair provides a major improvement in being able to adequately deposit on more polar/more damaged tips where significant conditioning benefits are most needed, rather than over-depositing on the roots. Furthermore, this technical challenge represents an even greater problem in different consumer groups. For example, varying levels of damage present in different individuals can result in the same silicone yielding acceptable deposition in some cases, but excessive deposition in other cases, with negative sensory implications (e.g., first colored versus frequently colored, light black versus bleached blonde, etc.). Thus, there is a great need for a silicone active that can be deposited uniformly at all hairstyles and damage levels.

Improving hair feel immediately after dyeing is not the only desired property of a colorant conditioner. After the dyeing treatment, human hair is easily soiled due to contact with the surrounding environment and sebum secreted from the scalp. The soiling of hair gives it a dirty feel and an unattractive appearance and requires frequent regular shampooing. Shampooing cleans the hair by removing excess soil and sebum, but leaves the hair in a wet, tangled, and generally unmanageable state. Once the hair dries, it is often in a dry, rough, lusterless or frizzy condition due to the removal of its natural oils and other natural or deposited conditioning and moisturizing components. The hair also results in a higher level of static electricity after it dries, which can affect combing and can lead to a condition commonly referred to as "flyaway hair". This condition is more severe on hair that has previously been oxidatively dyed.

Various approaches have been developed to alleviate these post-shampoo problems. These methods range from post-shampoo application of hair conditioners such as leave-on or rinse-off products, to hair conditioning shampoos which attempt to both clean and condition the hair in one product. After shampooing, the hair conditioner is typically applied in a separate step. Hair conditioners are either rinse-off or leave-on, depending on the type of product used. In the application of shampoos and conditioners, Polydimethylsiloxane (PDMS) is commonly used as a conditioning material to improve hair feel. However, it is known that in the case of more hydrophilic hair obtained after oxidative dyeing, PDMS deposition is greatly reduced and does not provide the same benefits in hair conditioning as non-oxidative dyed hair.

It would be highly advantageous to invent a conditioner that does not require every application of the conditioner while shampooing, which is not currently possible with prior art compositions, including those defined in the art above. This is particularly a problem for hair damaged by hydrophilic oxidation, typically permanently coloured hair, which is more susceptible to damage during daily shampooing by subsequent further damage. Conditioners with durable deposition are capable of providing all-weather protection to hair. There is therefore a high need for a conditioning active that can be deposited during the dyeing process that remains on the hair during the wash cycle within days or weeks after dyeing to provide long lasting conditioning benefits.

Finally, to achieve improved conditioning it is also important to ensure that sufficient silicone fluid is deposited on each hair to meet the consumer's needs, i.e. that the absolute deposition of silicone fluid is sufficient to achieve this, both initially after subsequent shampooing and after prolonged shampooing.

Summarizing the needs of some consumers discussed above, the challenge faced by the present inventors is to create a conditioner that can be uniformly and durably deposited on hair in different damage states, ranging from undamaged virgin hair to hair that has been treated with multiple oxidative dyes.

Attempts have seemingly been made in the prior art to solve some of the problems discussed above. More specifically, highly hydrophobic PDMS-based siloxanes have been eliminated, but functionalized siloxanes have been used that include functional groups such as the amine and (especially) quaternary ammonium moieties discussed above. For example, US 6,136,304 discusses the problems associated with conditioning compounds that are very easily rinsed off from the hair. It also discusses the application of conditioning agents to virgin and damaged hair. Ethoxylated quaternary ammonium functionalized silicones, such as ABILQUAT 3272 (see Table 1 below) and ABIL-QUAT 3270(CTFA names Quaternary ammonium-80) from Goldschmidt Chemical Corporation, Hopewell, Va, which are proposed to achieve these objectives, are very hydrophilic, however, they are quickly washed away on the next shampooing. In other words, they do not achieve sufficient durability to meet the needs of the consumer. Depending on the polarity, these siloxanes are on the other end of the polarity spectrum from PDMS type materials, but they are also non-persistent and therefore not suitable.

In view of the above discussion, the present invention will ideally provide functionalized silicones that can be deposited uniformly on all types of hair present in the current population, ranging from undamaged virgin hair to hair that has been subjected to multiple oxidative dye treatments.

In addition, the present invention would desirably provide a functionalized silicone that can be uniformly deposited throughout the length of a hair strand, including both on undyed whole hair and on previously dyed whole hair with oxidative colorants.

Additionally, the present invention would ideally provide a long-lasting silicone conditioning agent for oxidatively dyed hair which is not quickly washed off and thus does not detract from the conditioning benefits to the consumer.

Additionally, in accordance with the present invention, it would be desirable to provide a fiber treatment composition comprising a functionalized silicone.

These and other features, aspects, and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.

Summary of The Invention

According to a first aspect of the present invention there is provided a functionalized silicone of the side-chain or graft type having a viscosity in the range 400 to 150,000mPa and incorporating one or more polar substituents selected from electron-withdrawing, charge-neutral or electron-donating groups having a Hammett sigma value between-1.0 and +1.5, wherein the one or more polar substituents comprise oxygen such that the sum of the oxygen content of the one or more polar substituents is from 1% to 10% by weight of the functionalized silicone and the silicone content is from 67% to 95% by weight of the functionalized silicone.

The term "fiber" as used herein includes a bundle of natural or synthetic substances. Non-limiting examples of natural substances are amino acid-based substances, including proteinaceous substances (such as wool, human hair (including vellus hair) and animal skins), cotton, cellulose and silk. Non-limiting examples of synthetic materials are polyester, nylon, and rayon.

The term "functionalized" siloxane as used herein includes Polydimethylsiloxane (PDMS), wherein at least one methyl group has been replaced by another group, which is preferably not hydrogen. The term "functional siloxane" is synonymous with the term "functionalized siloxane".

As used herein, the term "uniform" when used to describe deposition of functionalized silicone refers to relative deposition on damaged hair relative to undamaged hair, and refers to a deposition uniformity value of at least 50%, preferably at least 60%, and more preferably at least 70%, as determined by the operating convention herein below. Phrases such as "uniformly deposited" and "uniform deposition" must be interpreted as described above.

As used herein, the term "durable" when used to describe the deposition of functionalized silicones means that the durability index, as determined by the silicone durability index method operating convention herein below, is at least 0.20, preferably greater than 0.50, more preferably greater than 0.75, and most preferably greater than 1.0. Phrases such as "permanent deposit" and "permanent deposit" must be construed as described above.

The Hammett ∑ parameter values are discussed in R _ mpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart, New York, 9 th edition, 1995, "Hammett Gleichung".

The claimed functionalized siloxane structures enable their uniform and durable deposition on fibrous substrates. Without being bound by theory, this is believed to be due to the percentages of oxygen and siloxane defined above, which impart the polar character required to obtain sufficient durability while at the same time obtaining deposition uniformity.

The term HLB value is known to those skilled in the art-see, for example, R _ mppChemie Lexikon, Thieme Verlag, Stuttgart, 9 th edition, 1995, which is under the "HLB-Wert" bar.

Detailed Description

All cited references are incorporated herein by reference in their entirety.

All percentages given herein are by weight of the total composition, unless otherwise specifically indicated. All ratios given herein are weight ratios unless specifically indicated otherwise.

All molecular weights given herein are weight average molecular weights unless otherwise indicated.

Except where specific examples of actual measured values are set forth, the numerical values referred to herein should be construed as limited by the word "about".

In accordance with the present invention, the one or more polar substituents comprise oxygen, such that the sum of the oxygen content (percentage of oxygen) in the one or more polar substituents (excluding oxygen in the PDMS backbone) is from 1% to 10%, preferably from 2% to 9%, more preferably from 3% to 8%, by weight of the functionalized siloxane, and the siloxane content is from 67% to 95%, preferably from 70% to 90%, and more preferably from 75% to 85%, by weight of the functionalized siloxane. The siloxane content or calculated percent siloxane (percent siloxane) is defined as the average molecular weight of the PDMS backbone (consisting of silicon, oxygen, and any directly attached methyl groups) divided by the average molecular weight of the entire polymer. Similarly, the total oxygen content (percent oxygen) is defined as the molecular weight per oxygen atom multiplied by the average number of oxygen atoms present in the functionalized siloxane (excluding oxygen in the PDMS backbone) divided by the average molecular weight of the entire polymer.

The inventors have also determined that polysiloxane fluid viscosity has an effect on the absolute deposition level, degree of permanence and feel of the deposited siloxane. Advantageously, according to one embodiment of the invention, the viscosity of the silicone is in the range of 50 to 150,000mPa. More advantageously, the viscosity is in the range of 400 to 100,000 mPa. Still more advantageously, the viscosity is in the range 4000 to 25,000mPa.

If below 50mPa, the permanence of the functionalized silicone is too low to be acceptable.

The deposition and persistence of the functionalized silicones increases with increasing viscosity, up to a plateau viscosity, which was found to be higher than 400 mPa. Without being bound by theory, it is believed that at this plateau viscosity, the silicone provides sufficient shrink resistance, resistance to "roll-up" and subsequent removal to improve deposition over the time frame of the rinsing process.

We also determined that a viscosity above 4000mPa will improve the feel of the deposited functionalized silicone. Without being bound by theory, we believe that this is due to the formation of a deposited structural morphology that is smoother than fluid morphologies having viscosities between 400 and 4000 mPa.

Advantageously, according to the invention, the functionalized silicone is an organomodified silicone of the pendant or grafted type, in which the polar functional substituent is incorporated in or on a monovalent organic radicalA as used hereinbefore and hereinafter¹、A²、A³And A⁴As follows:

also included are block copolymer type organomodified siloxanes wherein these polar functional substituents are incorporated into or onto divalent organic groups, hereinafter A is used¹、A²、A³And A⁴：

Wherein Me is methyl, m is greater than or equal to 1, n is from about 50 to 2000, p is from about 0 to 50, q is from about 0 to 50, r is from about 0 to 50, s is from about 0 to 50, wherein p + q + r + s is greater than or equal to 1, B¹Is H, OH, alkyl or alkoxy and an organic radical A¹、A²、A³And A⁴Is a linear, branched or mono-or polycyclic aliphatic, mono-or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic, or heteroalkenyl moiety containing from 3 to 150 carbon atoms and from 0 to 50 heteroatoms.

More advantageously, the polar substituent may be nonionic, zwitterionic, cationic or anionic, comprising, for example, the group α as defined below¹、α²、α³And alpha⁴(ii) a S-linked radicals comprising S alpha¹、SCN、SO₂α¹、SO₃α¹、SSα1¹、SOα¹、SO₂Nα¹α²、SNα¹α²、S(Nα¹)α²、S(O)(Nα¹)α²、Sα¹(Nα²)、SONα¹α²(ii) a O-linked radicals, including O.alpha.¹、OOα¹、OCN、ONα¹α²(ii) a N-linked radicals, including N α¹α²、Nα¹α²α³+、NC、Nα¹Oα²、Nα¹Sα²、NCO、NCS、NO₂、N＝Nα¹、N＝NOα¹、Nα¹CN、N＝C＝Nα¹、Nα¹Nα²α³、Nα¹Nα²Nα³α⁴、Nα¹N＝Nα²(ii) a Other various groups, including COX, CON₃、CONα¹α²、CONα¹COα²、C(＝Nα¹)Nα¹α²CHO, CHS, CN, NC and X, wherein:

α¹、α²、α³and alpha⁴May be a linear, branched or mono-or polycyclic aliphatic, mono-or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic or heteroalkenyl moiety containing from 3 to 150 carbon atoms and from 0 to 50 heteroatoms, especially O, N, S, P.

X is F, Cl, Br or I.

H is hydrogen, O is oxygen, N is nitrogen, C is carbon, S is sulfur, Cl is chlorine, Br is bromine, I is iodine, and F is fluorine.

In accordance with the present invention, the above-described side-chain or block copolymer type organomodified siloxanes are also incorporated with branched siloxane groups, including MeSiO, which are referred to by those skilled in the art as silsesquioxanes or T groups_3/2And SiO known as the Q group_4/2。

The preferred polar functional substituents for use in the present invention include, but are not limited to, polyalkylene oxides (polyethers), primary and secondary amines, amides, quaternary amines, carboxyls, sulfonates, sulfates, carbohydrates, phosphates, and hydroxyls. More preferably, polar functional substituents of the present invention include, but are not limited to, polyoxyalkylenes, primary and secondary amines, amides, and carboxyl groups.

One highly preferred class of functionalized silicones useful in the compositions according to one embodiment of the present invention are those comprising polyoxyalkylene polar functional substituents.

The polyoxyalkylene content (polyether percentage) should be from 5% to 42%, preferably from 10% to 40%, and more preferably from 15% to 35%. Preferably, the sum of the siloxane percentage and the polyether percentage does not reach 100%, the other components such as amines and amides making up the balance. The siloxane content is as defined above and the polyether content (percent polyether) is defined as the molecular weight of each polyether side chain or block multiplied by the average number of side chains or blocks divided by the average molecular weight of the entire polymer. If the side chain or block polyether contains Ethylene Oxide (EO) and Propylene Oxide (PO) units, then this polyether percentage includes the sum of the EO percentage and the PO percentage. If the side chain or block polyethers consist of only EO units or only PO units, this polyether percentage corresponds to the respective EO percentage or PO percentage.

The functionalized silicones having polyoxyalkylene polar functional substituents defined above are capable of uniform and durable deposition on fibrous substrates. Without being limited by theory, the above defined percentages of polyether and silicone impart a polar character to the functionalized silicone, allowing it to obtain sufficient permanence and at the same time obtain deposition uniformity.

Still more preferably, the functionalized silicones of the invention are those of the side-chain type comprising an amino group and a polyoxyalkylene group, as represented by the general formula (1):

wherein Me is equal to methyl; r¹Is methyl or R²Or R³；R²Is- (CH)₂)_a-NH-[(CH₂)_a-NH]_b-H; and R is³Is- (CH)₂)_a-(OC₂H₄)_m-(OC₃H₆)_n-OZ; wherein x is from about 50 to 1500, y is from about 1 to 20, and z is from about 1 to 20; a is about 2 to 5, preferably 2 to 4; b is 0 to 3, preferably 1; m is about 1 to 30; n is about 1 to 30, and Z is H, alkyl having 1 to 4 carbon atoms, or acetyl, with the provisoProvided that when y is 0, R¹Is R²A group, and when z is 0, R¹Is R³A group.

In accordance with the present invention, the following exemplary structures can be prepared:

organomodified siloxanes example A

In example a, molecular weight 18738 and oxygen percentage 5.21% (provided by thirty-one oxygen atoms); and

the siloxane percentage is 81.42%

The polyether percentage is 16.33%

Other percentages ^* ＝2.25％

100.00％

^*From other side chains and from- (CH) s on polyether side chains₂)₃-and-OH moiety.

Organomodified siloxanes example B

Wherein Me is methyl.

According to a second aspect of the present invention there is provided a fibre treatment composition comprising a functionalized silicone as defined in the first aspect of the present invention. The fibre treatment composition according to the second aspect of the invention allows the functionalized silicone according to the first aspect of the invention to be deposited on the fibrous substrate in a durable and uniform manner which is not possible with existing fibre treatment compositions.

The fiber treatment composition according to the present invention may comprise from 0.1% to 20% by weight, preferably from 0.50% to 15% by weight, more preferably from 0.50% to 10% by weight, and still more preferably from 0.50% to 7.5% by weight of the functionalized silicone.

Further advantageous refinements of the first aspect of the invention are discussed below and are defined in the appended claims.

According to a third aspect of the present invention, there is provided a hair treatment kit comprising:

(a) oxidative bleaching compositions

(b) Dye composition

And a composition as defined in the second aspect of the invention, which is comprised in component (a) and/or comprised in component (b) and/or provided as a separate component.

For comparison with the functionalized siloxanes according to the present invention, the results of a number of commercially available siloxane nmr analyses are given in table 1 below, along with measured hydrophilicity index and performance data:

TABLE 1

	HI	Siloxane%	Polyether%	Oxygen%	Deposition uniformity (%)	Persistence index
							Wetsoft CTW1	100.0	41	58	18	70％	0.0
Abilsoft AF1003	99.7	56	43	14	110	0.0
							XS69-B54762	99.5	65	34	11	250	0.1
DC82115	73.4	95	0	0	5	1.2
							KF8626	60.2	97	0	0	5	1.4
KF-8616	55.8	96	0	0	6	1.5
							DC2-88225	45.7	97	0	0	5	1.4
Rhodorsil 216374	37.4	98	0	0	3	1.4
							ADM11001	**	99	0	0	3	4.2

^**Not measurable by hydrophilicity index measurement

¹Wacker Silicones

²GE-Bayer Silicones

³Goldschmidt

⁴Rhodia

⁵Dow Corning

⁶Shin-Etsu.

The side chain organomodified siloxanes of the general formula (1) above containing amino groups and polyoxyalkylene groups can be prepared by methods known to those skilled in the art, by steps involving known polymerization reactions (e.g., equilibration or polycondensation) and known methods of introducing organic substitutions into the siloxane backbone (e.g., hydrosilylation).

The fiber treatment composition according to the present invention may include a cosmetically acceptable vehicle to act as a diluent, dispersant or carrier for the silicone oil in the composition in order to facilitate distribution of the silicone oil when the composition is applied. The vehicle can be an aqueous emulsion, water, liquid or solid emollient, solvent, humectant, propellant, thickener, and powder.

Advantageously, the fiber treatment composition according to the invention may be in the form of an aqueous emulsion as the main component, although it may also comprise an aqueous organic solvent. The emulsion may be a water-in-oil emulsion, an oil-in-water emulsion, a water-in-oil-in-water multiple emulsion, or an oil-in-water-in-oil-in-water multiple emulsion, but preferably an oil-in-water emulsion (silicone-in-water emulsion). In the above case, the functionalized silicone particle size is preferably greater than 500nm, more preferably greater than 1 μm, and even more preferably greater than 2 μm.

The aqueous continuous phase of the emulsion treatment composition of the present invention may also include an emulsifier to promote the formation of an emulsion. The emulsifier used in the aqueous continuous phase of the present emulsion treatment composition may include anionic surfactants, cationic surfactants, amphoteric surfactants, water-soluble polymeric surfactants, water-soluble silicone-containing surfactants, nonionic surfactants having an HLB value greater than about 10, or surfactant systems capable of forming stable liquid crystals around the silicone droplets. The nonionic surfactant preferably has an HLB value of at least 12, and more preferably at least about 15. Surfactants belonging to this class are listed in McCutcheon "Emulsifiers and Detergents", North American and International edition, MCpublishing Co., Glen Rock NJ, pp.235 to 246 (1993).

The emulsifier used in the aqueous phase does not gel the aqueous phase. However, the emulsifier can form a stable lamellar liquid crystal layer around the silicone droplets. This barrier film prevents coalescence between the emulsion droplets. In this case, the surfactant system may be a single surfactant or a mixture of surfactants. In some cases, a particular surfactant alone cannot form a liquid crystal structure, but can participate in the formation of a liquid crystal in the presence of a second surfactant. The surfactant system described above forms a lamellar liquid crystal layer around the silicone to provide a barrier between the silicone and the aqueous phase. This type of emulsion differs from conventional emulsions which rely on the directional action of the hydrophilic and hydrophobic components of the surfactant at the silicone-water interface. The formation of a lamellar liquid crystal layer around the siloxane can be detected in the presence of a maltese cross, which can be seen by optical microscopy through crossed polarisers or by cryo-cut electron microscopy.

Exemplary classes of surfactants that can participate in the formation of liquid crystal structures around the silicone droplets include, but are not limited to, specific cationic surfactants, anionic surfactants, nonionic surfactants, quaternary ammonium surfactants, and lipid surfactants.

The surfactant which forms liquid crystals in the aqueous continuous phase is preferably non-ionic and comprises C_16-22And C comprising a C having 1 to 30 ethylene oxide groups_16-22The alcohol ethoxylate of (1). Specific examples include palmityl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, oleyl alcohol, palmitoylethylene ether ethoxylate with ethylene oxide groups from 10 to 30, ceteth ethoxylate with ethylene oxide groups from 10 to 30, steareth ethoxylate with ethylene oxide groups from 10 to 30, and combinations thereof. Preferably, C is_16-22Fatty alcohol of (2) and (C)_16-22The alcohol ethoxylates of (a) are used in combination in a ratio of from 10: 1 to 0.5: 1, more preferably from 6: 1 to 1: 1, most preferably from 5: 1 to 1.5: 1.

The aqueous continuous phase should ideally include an emulsifier in an amount sufficient to stabilize the silicone. In one embodiment, the aqueous continuous phase comprises emulsifier in an amount of from about 0.1% to about 15%, and more preferably from about 0.1% to about 10%, by weight of the aqueous continuous phase.

The compositions according to the present application find particular application in hair colouring compositions, especially oxidative hair colouring agents, in which the hair is subjected to a particularly aggressive environment.

A preferred hair coloring agent for use in the present invention is an oxidative hair coloring agent. In accordance with the present invention, the concentration of each oxidative hair coloring agent in the composition can range from about 0.0001% to about 5% by weight.

Any oxidative hair coloring agent can be used in the compositions of the present invention. Typically, oxidative hair dyes include at least two components, which are collectively referred to as dye-forming intermediates (or precursors). The dye-forming intermediate can be reacted with a suitable oxidizing agent to form a pigment molecule.

Dye-forming intermediates for oxidative hair dyes include: aromatic diamines, aminophenols, various heterocycles, phenols, naphthols, and various derivatives thereof. These dye-forming intermediates can be broadly divided into: primary intermediates and secondary intermediates. Primary intermediates (also known as oxidative dye precursors) are compounds that are activated by oxidation and then can react with each other and/or with couplers to form colored dye complexes. Secondary intermediates (also known as color modifiers or couplers) are generally colorless molecules that can form pigments in the presence of activated precursors/primary intermediates and can be used with other intermediates to produce specific color effects or to stabilize pigments.

Primary intermediates useful in the compositions and methods of the invention include: aromatic diamines, polyhydric phenols, aminophenols and derivatives of these aromatic compounds (e.g., N-substituted amine derivatives and ethers of phenols). The primary intermediates are generally colorless molecules prior to oxidation.

Without being bound by any particular theory, it is believed that the process of forming pigments from these primary intermediates and secondary coupling compounds generally involves a stepwise sequence according to which the primary intermediates can be activated (by oxidation) and then combined with a coupler to yield a dimeric conjugated chromonic material, which in turn is combined with another "activated" primary intermediate to yield a trimerized conjugated chromonic molecule.

In general, oxidative dye primary intermediates include those that undergo oxidation to form oligomers or polymers having an extended conjugated electron system in the molecular structure of the oligomer or polymer. Due to the new electronic structure, the electronic spectra of the resulting oligomers and copolymers appear to shift towards the visible range and produce color. For example, oxidative primary intermediates that can form colored polymers include those such as anilines, which have only one functional group and undergo oxidation to form a series of conjugated imine and quinoid dimers, trimers, and the like, ranging from green to black. Compounds having two functional groups, such as p-phenylenediamine, can be oxidatively polymerized to yield high molecular weight, colored materials having extended conjugated electron systems. Oxidative dyes known in the art may be used in the compositions of the present invention. A representative list of primary intermediates and secondary couplers suitable for use in the present invention is provided in Sagarin, "Cosmetic Science and Technology", Interscience, journal, Vol.2, p.308 to p.310.

The primary intermediates may be used alone or in combination with other primary intermediates, and one or more primary intermediates may be used in combination with one or more coupling agents. The choice of primary intermediate and coupler depends on the desired color, shade and intensity of color. There are nineteen preferred primary intermediates and couplers useful in the present invention, which may be used alone or in combination to provide dyes of various shades ranging from grey, linen to black; they are: pyrogallol, resorcinol, p-toluenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine, m-aminophenol, 2-amino-3-hydroxypyridine, 1-naphthol, N-bis (2-hydroxyethyl) p-phenylenediamine, resorcinol, diaminopyrazole, 4-amino-2-hydroxytoluene, 1, 5-dihydroxynaphthalene, 2-methylresorcinol, and 2, 4-diaminoanisole. These substances can be used in molecular form or in the form of salts compatible with peroxides.

In addition to, or instead of, oxidative hair coloring agents, the hair coloring compositions of the present invention may include non-oxidative dye materials and other dye materials. Optional non-oxidative and other dyes suitable for use in hair coloring compositions and methods according to the present invention include fugitive, temporary and other dyes. Non-oxidative dyes as defined herein include so-called "direct action dyes", metallic dyes, metal chelate dyes, fibre-reactive dyes and other synthetic or natural dyes. Various classes of non-oxidative dyes are detailed in: "chemical and Physical Behaviour of Human Hair" third edition, Clarence Robbins (pages 250 to 259); "The Chemistry and Manufacture of Cosmetics", volume IV, second edition, Main G.De Navarre, Chapter 45, G.S.Kass (pages 841 to 920); "cosmetics: science and Technology "second edition, volume II, Balsam bagarin, chapter 23, f.e. wall (pages 279 to 343); "The Science of Hair Care" c.zviak editions, chapter 7 (pages 235 to 261), and "Hair Dyes", j.c.johnson, noyes data company, Park Ridge, u.s.a. (1973), (pages 3 to 91, and pages 113 to 139).

The hair colouring composition of the present invention preferably comprises at least one oxidizing agent which may be an inorganic oxidizing agent or an organic oxidizing agent. Preferably, the oxidizing agent is present in the dyeing composition in an amount of from about 0.01% to about 10%, preferably from about 0.01% to about 6%, more preferably from about 1% to about 4%, by weight of the composition.

The oxidizing agent used in the present invention is preferably an inorganic peroxygen oxidizing agent. The inorganic peroxygen oxidizing agent used in the present compositions should be safe and effective. When the composition of the present invention is in liquid form or in a form intended for use, the inorganic peroxygen oxidising agent suitable for use in the present invention is preferably dissolved in the composition as described herein. The inorganic peroxygen oxidizing agents suitable for use in the present invention are preferably water soluble. A water-soluble oxidizing agent as defined herein refers to an agent that has a solubility in 1000ml of deionized water at 25 ℃ to the extent of about 10g ("Chemistry" c.e. mortimer, 5 th edition, page 277).

The inorganic peroxygen oxidizing agents useful in the present invention are generally inorganic peroxygen materials capable of generating peroxides in aqueous solutions. Inorganic peroxygen oxidizing agents are well known in the art and include hydrogen peroxide, inorganic alkali metal peroxides (e.g., sodium periodate, sodium perbromide, and sodium peroxide), and perhydrate inorganic salt oxides (e.g., alkali metal salts of perboric acid, percarbonic acid, perphosphoric acid, persilicate acid, persulfuric acid, and the like). These perhydrate inorganic salts may be incorporated as the monohydrate, tetrahydrate, and the like. Mixtures of two or more of the above inorganic peroxygen oxidizers may be used if desired. While alkali metal bromides and iodides are also suitable for use in the present invention, bromates are preferred. Highly preferred is the use of hydrogen peroxide in the composition according to the invention.

The compositions of the present invention may comprise one or more preformed organic peroxyacid oxidizing agents in place of, or in addition to, the inorganic peroxyacid oxidizing agent.

Organic peroxyacid oxidising agents suitable for use in the dyeing compositions according to the invention have the formula:

R-C(O)OOH

wherein R is selected from the group consisting of saturated or unsaturated, substituted or unsubstituted, straight or branched chain alkyl, aryl or alkaryl radicals having from 1 to 14 carbon atoms.

The organic peroxyacid oxidizing agents used in the compositions of the present invention should be safe and effective. The pre-formed organic peroxyacid oxidising agent suitable for use in the present invention should preferably be soluble in the composition used in accordance with the present invention when the composition is in liquid form and in the form intended for use. Organic peroxyacid oxidizing agents suitable for use in the present invention are preferably water soluble. A water soluble preformed organic peroxyacid oxidising agent as defined herein refers to a formulation having a solubility of around 10g in 1000ml of deionised water at 25 ℃ ("Chemistry" c.e. mortimer, 5 th edition, page 277).

The compositions of the present invention may optionally comprise a transition metal-containing catalyst for catalyzing the inorganic peroxygen oxidizer, and optionally a preformed peroxyacid oxidizer. Catalysts suitable for use in the present invention are disclosed in WO 98/27945.

The compositions of the present invention may comprise a heavy metal ion sequestrant as an optional component. In the present invention, the heavy metal ion chelating agent means a component acting on heavy metal ions of a chelating agent (chelate or scavenger). These components may also have a chelating capacity for calcium and magnesium, but preferably they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper. In the hair colouring compositions of the present invention, the above chelating agents help to deliver controlled oxidation and provide good storage stability of the hair colouring product.

The heavy metal ion sequestrant is present in an amount of from about 0.005% to about 20%, preferably from about 0.01% to about 10%, more preferably from about 0.05% to about 2%, by weight of the composition.

Suitable chelating agents are disclosed in WO 98/27945.

Treatment compositions according to embodiments of the present invention may be provided for use at a pH of about 3 to 11, preferably 4 to 10.5.

The present compositions find use not only in the treatment of fibers, such as hair, but also in the application to other substrates such as human skin, nails, and various animal body parts such as horns, hooves, and feathers.

Measurement method

Functionalized polysilazane fluid viscosity-determination protocol

The viscosity of the functionalized polysiloxane fluids used in the present invention can be determined using an AR 500 rotational rheometer (TA Instruments ltd., leitherhead, SurreyKT 227 UQ, UK). The measurements were performed at 30 ℃ with a 4cm 2 ° steel cone measuring system with a 49 μm (micrometer) gap inserted and by applying a shear stress of 0.5 to 590Pa during a 2 minute procedure. These data are used to generate a shear rate versus shear stress curve for the material. This rheological curve is then simulated to determine the viscosity of the material. These results are consistent with the following widely accepted newtonian model:

viscosity, μ ═ σ/γ

(where σ is shear stress; γ is shear rate)

Method for estimating the particle size of siloxane in product

The particle size of the siloxane in the final product was determined using a microscope (Nikon Eclipse E800). Typically, the image of the final product photographed (JVC color camera KY-F50) is magnified 100 times to 400 times in amplitude. Using the captured images, a scale (image software-Lucia version G4.51 (build 028), Laboratory Imaging) was added, which was calibrated in advance with a 100 μm graduated plate (gradules Ltd, TonbridgeWells, Kent, England) and compared to the average silicone particles in the sample to provide an estimate of particle size.

Functionalized siloxane deposition and deposition uniformity determination method

Hair matrix preparation method

Two different hair substrates of different polarity are required on which the silicone deposition is measured and from this, a value for the deposition uniformity is calculated from the two substrates. Hair was supplied by Hugo royer international Limited (10 Lakeside Business Park, Sandhurst, Berkshire, GU479DN, England) and was a confounding eastern european light brown human hair. Prior to use, the hair was evaluated and made to conform to low cuticle damage (< 20%) and error (< 5%) on a per bundle basis of at least 200 hairs. Any lesion on one hair is considered as one lesion point, and then the total is calculated as a percentage. This hair was made into 4 "(10 cm)2g circular knotted switches (where the length and weight of the hair corresponded to the knotted hair). To obtain a hair matrix with two different polarities, the hair is pretreated according to one of two different protocols.

Hair preparation

At a flow rate of 61L min^-1And a bath equipped with a shower, at a temperature of 372 ℃, the switches were washed using the following protocol: initially, the switch was allowed to wet for 30 seconds under the shower. The hair is then removed from the water stream,0.2g shampoo (Panten Classic careshampooo) was applied to each switch and then lathered by hand for 30 seconds, followed by rinsing under the shower for 60 seconds. The hair was removed from under the shower again and 0.2g shampoo was applied again and rubbed for lathering for 30 seconds followed by a final rinse under the shower for 60 seconds. Then, the switches were placed in a tempering oven set at 30 ℃ to dry. This wash regimen, comprising two shampoo applications and one drying step, is referred to as a single wash cycle. After this washing cycle is complete, the hair is then defined hereinafter as "virgin" hair and is used hereinafter as a hydrophobic hair substrate.

Chemically damaged hair preparation

Hair tresses were chemically damaged using the following two bleach formulation components:

peroxide matrices
		Composition (I)	Weight/weight percent
1. Emulsion matrix:
		deionized water	29.78
Cetyl alcohol (1)	2.24
		Stearyl alcohol (2)	2.24
Palm-based polyoxyethylene ether-25 (3)	1.50
		Phenoxyethanol (4)	0.11
Sodium benzoate (5)	0.09
		Ethylenediaminetetraacetic acid Tetrasodium salt (87%) (6)	0.04
		2. Chelant premix
Deionized water	35.72
		Pentetate (40%) (7)	0.24
Hydroxyethane diphosphonic acid (60%) (8)	0.16
		Phosphoric acid (75%) (9)	0.08
Sodium stannate (95%) (10)	0.04
3. Peroxide mixtures
		Hydrogen peroxide (35%) (11)	17.15
Deionized water	10.61

Carrier matrix for dye matrices
		Composition (I)	Weight/weight percent
1. Acetic acid premix
		Deionized water	46.49
Acetic acid (50%) (12)	3.91
2. Emulsion base
		Deionized water	29.78
Cetyl alcohol (1)	2.24
		Stearyl alcohol (2)	2.24
Palm-based polyoxyethylene ether-25 (3)	1.50
		Phenoxyethanol (4)	0.11
Sodium benzoate (5)	0.09
		Ethylenediaminetetraacetic acid Tetrasodium salt (87%) (6)	0.04

Ammonium hydroxide (13)

13.60

(1): commercially available from Surfachem, Leeds, UK under the trade name Surfac butyl alcohol (Surfac cetyl alcohol)

(2): from Surfachem, Leeds, UK under the trade name of surface stearyl alcohol

(3): available from Croda, North Chamberside, UK under the trade name Volpo CS25

(4): available under the trade name Phenoxythanol from Nipa-Hardwicke, Wilmington, Delaware

(5): available from Haltermann, Cumbria, UK under the trade name Sodium benzoate EP/USP

(6): available under the trade name Edeta B Powder from BASF, Chemale, Cheshire, UK

(7): available under the trade name Trilon C liquid from BASF, Cheadle, Cheshire, UK

(8): available from Solutia, Newport, South wales under the tradename Dequest 2010

(9): available under the trade name Phosphoric acid 750F (Phosphoric acid 750F) from Albright & Wilson, West Midlands, UK

(10): commercially available from Aldrich under the trade name Sodium stannate (Sodium stannate)

(11): available as Hydrogen peroxide 35% 171/4 from Ellis & Everard, Walsall, UK

(12): available as 50% acetic acid (50% acetic acid) from Hays, Greenwich, London, UK

(13): available under the trade name of Ammonium Solution BP grade from Brotherton Speciality Products, WestYorkshire, UK

These products were prepared using the following protocol:

peroxide matrix:

the first step is to prepare an emulsion matrix; this can be prepared as follows: deionized water was added to one vessel and stirring was started and then heated to 82 ℃. Then, tetrasodium ethylenediaminetetraacetate and sodium benzoate were added and dissolved, and then, palmitoylethylene ether-25, cetyl alcohol and stearyl alcohol were added. During the loading, the temperature was kept above 80 ℃, finally phenoxyethanol was added and the mixture was homogenized for 30 minutes. Cooling to give the emulsion structure while also high shear mixing the product below 50 ℃. The emulsion base was then allowed to stand for 60 minutes to thicken.

The chelant was added to deionized water with agitation to form a chelant premix. This premix is then added to the emulsion base prepared beforehand, with stirring. The complete peroxide base is prepared by adding the aqueous peroxide mixture followed by hydrogen peroxide to the emulsion base/chelant premix and stirring until homogeneous.

Dye carrier matrix

The dye carrier matrix can be prepared as follows: water was added to a vessel and stirring was initiated, followed by acetic acid, and an emulsion base (see emulsion base preparation described above, which was prepared for the preparation of peroxide base). When well mixed, ammonium hydroxide was added to the mixture and stirring was continued until the product was homogenous.

To use this bleaching system, equal weights of the two components, the peroxide base and the dye carrier base, are mixed together thoroughly. Then, 4g of the bleach system was applied to each dry untreated switch of hair and allowed to act sufficiently into the hair by hand to ensure even complete coverage. Then theThe switches were wrapped in a food film and incubated in a drying oven at 30 ℃ for 30 minutes, after which the product was rinsed with finger agitation for 2 minutes (at a set flow rate of 61 Lmin^-1And a 372 c bath with a shower). Finally, the switches (Babyliss light specialty 1015(1400W)) were dried with a hot air dryer for 3 minutes. Then, at a set flow rate of 61 Lmin^-1And washing the bleached switches in a 372 ℃ shower-equipped sink. Initially, the switch was allowed to wet for 30 seconds under the shower. The hair was then removed from the water stream, 0.2g Shampoo (Pantene Clarifying shampooo) was applied to each switch, and then lathered by hand for 30 seconds, followed by rinsing under the shower for 60 seconds. The hair was removed from under the shower again and 0.2g shampoo was applied again and rubbed for lathering for 30 seconds followed by a final rinse under the shower for 60 seconds. The switches (Babyliss light specialty 1015(1400W)) were then dried with a hot air dryer for 3 minutes. This wash regimen, comprising two shampoo applications and one drying step, is referred to as a single wash cycle. This washing process is then repeated again through another complete washing cycle. The switches are then bleached again in accordance with the method discussed above and then washed again through two complete wash cycles. Hereinafter, such hair is defined as "damaged" hair and is hereinafter used as a hydrophilic hair matrix.

Hair treatment

The functionalized siloxanes in the deposition and deposition uniformity studies were prepared and evaluated by the following methods. In a 100ml glass beaker, 28.8g of peroxide base (used in the preparation of damaged hair base described above) was weighed out; 1.2g of siloxane was then added to the vessel along with a 25mm magneton, and the vessel was placed on a magnetic stirrer (IKA RCTbasic) and stirred at 1000rpm for 30 minutes. The product was then removed from the magnetic stirrer and then 30g of the dye carrier base (used in the preparation of damaged hair base as described above) was added and mixed thoroughly by hand with a plastic spatula until homogeneous.Then, 16g of the bleaching system containing the silicone under study was applied simultaneously to two original starting switches and two damaged switches (equal to 4g applied to each individual switch), clamped together with the same clamp and worked sufficiently into the hair by hand to ensure uniform and complete coverage. The hair was then wrapped in a food film and incubated in a drying oven at 30 ℃ for 30 minutes, after which the product was rinsed with finger agitation for 2 minutes (at a set flow rate of 61 Lmin^-1And a 372 c bath with a shower). The switches (Babyliss light specialty 1015(1400W)) were dried with a hot air dryer for 3 minutes.

Deposition assay

An X-ray fluorescence wavelength analyzer (Phillips Electronics, PW2404 series "4000W" X-ray spectrometer system) was used to determine the deposition of silicone on hair. The luminometer is equipped with a rhodium tube and comprises InSb crystals to facilitate high sensitivity siloxane detection.

The inner shell electrons of the silicon atoms are excited and then the electrons jump from the higher energy state to the empty inner shell, thereby generating characteristic X-ray photons. The X-ray fluorescence of the siloxane in Polydimethylsiloxane (PDMS) is proportional to the amount of PDMS deposited on the hair. In the case of more functionalized silicones, this relationship can be biased, and any bias in this relationship is offset in the calculation of the deposit uniformity value (below). A key component that facilitates the use of XRF technology is its ability to present the sample consistently on the photometer. The switch was placed in a custom-made sample holder, which presented a continuous flat row of hair surfaces through an exposed sample face (16 mm diameter). The samples were analyzed under nitrogen atmosphere using a 32kV tube voltage and 125mA current with 60 second irradiation/acquisition time.

Drift in the analysis signal is regularly monitored and evaluated. The preferred method is to use a known standard that does not have to be prepared each time drift is assessed. The Ausmon sample is a monitoring sample suitable for a variety of applications, including the determination of silicon. Drift correction of silicon was performed with the Ausmon samples each day when the samples began to be analyzed. The calculated drift was below 3% between the groups analyzed.

Equation 1 is derived from the calculation of the silicon content on the hair in ppm.

X₂＝(I-b₁)/m₁(1)

Wherein m is₁And b₁Is calculated from a calibration curve made from the measurement of the XRF signal as a function of the amount of silicone deposited on the hair, as subsequently measured using atomic absorption on extracted silicone.

To convert the XRF silicone deposition data obtained as described above into a measure of deposition uniformity on the hair substrate (prepared with varying degrees of chemical damage), it is necessary to generate a deposition uniformity value. To generate the deposition uniformity value, the following formula is used:

where Dep (1) is equal to the XRF deposition value obtained on "damaged" hair (prepared as described above) and Dep (2) is equal to the XRF deposition value obtained on "virgin" hair (prepared as described above).

Siloxane durability index method

Hair matrix preparation

Durability was assessed on only one polarity of chemically damaged substrates. Hair was supplied by Hugo royer international Limited (10 Lakeside Business Park, Sandhurst, Berkshire, GU479DN, England) and was a confounding eastern european light brown human hair. Prior to use, the hair was evaluated and made to conform to low cuticle damage (< 20%) and error (< 5%) on a per bundle basis of at least 200 hairs. Any lesion on one hair is considered as one lesion point, and then the total is calculated as a percentage. The hair was made into 10cm (4 ") 2g circular knotted switches (where the length and weight of the hair corresponded to the knotted hair). To obtain a damaged polar hair matrix, the following protocol was used.

In the following method, the peroxide matrix, chelating agent premix and dye carrier matrix were used in the "functionalized siloxane deposition and deposition uniformity determination method" as above. In addition, the methods of making the "peroxide base" and the "dye carrier base" are also the same.

Hair treatment

The silicone is deposited on the hair via a solvent matrix. In delivering the functionalized polysiloxane fluids of the present invention, 2-propanol (available from Aldrich Chemicals, product number 15,479-2) was used as the solvent. The polysiloxane fluid was dissolved in 2-propanol at a concentration of 0.20% using a magnetic stirrer. The switches were applied flat on a food film and the resulting 2-propanol/silicone solution was applied using a syringe at a dose of 1g silicone solution per 1g hair (half on each side). The solution was then rubbed in the hair with the fingers for 30 seconds. The treated switches were allowed to dry naturally in ambient atmosphere. When the switches dried, they were divided into two groups, both groups containing the same number of damaged switches. The first set was used to measure the raw deposit after 2-propanol deposition. The second group was washed to assess silicone durability. At a set flow rate of 61 Lmin^-1And a 372 ℃ water bath equipped with a shower to wash the switches. Initially, the switch was allowed to wet for 30 seconds under the shower. The hair was removed from the water stream, and 0.2g Shampoo ("Panten Clarifying Clean shampooo") was applied to each switch, then lathered by hand for 30 seconds, and then rinsed under the shower for 60 seconds. The switch was then reapplied with 0.2g shampoo and massaged for 30 seconds followed by a final rinse under the shower for 60 seconds. The switches (Babyliss light specialty 1015(1400W)) were then dried with a hot air dryer for 3 minutes. This protocol, which includes two shampoo applications and one drying step, is referred to as a complete wash cycle. Then, through another eleven complete cyclesThe loop (twelve wash cycles in total) and this wash protocol was repeated again. The silicone deposition of these switches was then measured to assess the permanence properties.

Deposition assay

The deposition measurements used XRF values, as used in the "functionalized siloxane deposition and deposition uniformity determination methods" above.

To convert the XRF silicone deposition data obtained as described above into a measure of silicone durability, it is necessary to generate a silicone durability index value. To generate the silicone durability index value, the following formula is used:

where Dep (initial) equals the XRF deposition value obtained on the hair without wash cycles after silicone deposition, Dep (12 cycles) equals the XRF deposition value obtained on the hair after silicone deposition and 12 subsequent wash cycles.

Examples

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. The examples are for the purpose of illustration only and should not be construed as limiting the invention as many variations thereof are possible without departing from the scope thereof.

Examples 1 to 3 colorant compositions

Peroxide matrices	#1	#2	#3
				Composition (I)	Weight percent (%)	Weight percent (%)	Weight percent (%)
Emulsion matrix:
				deionized water	29.17	29.17	29.17
Cetyl alcohol (1)	2.20	2.20	2.20
				Stearyl alcohol (2)	2.20	2.20	2.20
Palm-based polyoxyethylene ether-25 (3)	1.47	1.47	1.47

Phenoxyethanol (4)	0.11	0.11	0.11
				Sodium benzoate (5)	0.09	0.09	0.09
Ethylenediaminetetraacetic acid Tetrasodium salt (87%) (6)	0.04	0.04	0.04
				Deionized water	35.00	35.00	35.00
Pentetate (40%) (7)	0.24	0.24	0.24
				Hydroxyethane diphosphonic acid (60%) (8)	0.16	0.16	0.16
Phosphoric acid (75%) (9)	0.08	0.08	0.08
				Sodium stannate (95%) (10)	0.04	0.04	0.04
				Hydrogen peroxide (35%) (11)	16.80	16.80	16.80
Deionized water	10.40	10.40	9.40
Siloxanes of the formula A	0	2.00	0
				Siloxanes of the formula B	2.00	0	3.00

Carrier matrix for dye matrices	#1	#2	#3
				Composition (I)	Weight percent (%)	Weight percent (%)	Weight percent (%)
				Deionized water	46.49	46.49	46.49
Acetic acid (50%) (12)	3.91	3.91	3.91
				Emulsion base (see above ingredients)	36.00	36.00	36.00
Ammonium hydroxide (13)	13.60	13.60	13.60

(1): commercially available from Surfachem, Leeds, UK under the trade name Surfac butyl alcohol (Surfac cetyl alcohol)

(2): from Surfachem, Leeds, UK under the trade name of surface stearyl alcohol

(3): commercially available from Croda, North Hunberside, UK under the trade name Volpo CS25

(4): available under the trade name Phenoxythanol from Nipa-Hardwicke, Wilmington, Delaware

(5): available from Haltermann, Cumbria, UK under the trade name Sodium benzoate EP/USP

(6): available under the trade name EdetaB Powder from BASF, Cheadle, Cheshire, UK

(7): available under the trade name Trilon C liquid from BASF, Cheadle, Cheshire, UK

(8): available from Solutia, Newport, South wales under the tradename Dequest 2010

(9): available under the trade name Phosphoric acid 750F (Phosphoric acid 750F) from Albright & Wilson, West Midlands, UK

(10): commercially available from Aldrich under the trade name Sodium stannate (Sodium stannate)

(11): available as Hydrogen peroxide 35% 171/4 from Ellis & Everard, Walsall, UK

(12): available as 50% acetic acid (50% acetic acid) from Hays, Greenwich, London, UK

(13): available under the trade name of Ammonium Solution BP grade from Brotherton Speciality Products, WestYorkshire, UK

EXAMPLES use of colorant preparations

Peroxide matrix:

the emulsion matrix can be prepared as follows: deionized water was added to the vessel and stirring was started while heating to 82 ℃. Then, a preservative (tetrasodium ethylenediaminetetraacetate, sodium benzoate) was added and dissolved. Then, palmitoylethylene oxide-25, cetyl alcohol and stearyl alcohol were added while maintaining the temperature above 80 ℃. Then, phenoxyethanol was added. The mixture is then heated through the return line to complete mixing and homogenization. The emulsion structure is obtained by cooling the product to below 50 ℃ and shearing while cooling. The product was allowed to sit for 60 minutes to allow thickening.

The chelant premix may be prepared as follows: the chelant was added to the water and mixed together in a vessel. This solution is then added to the emulsion base. Water is added to the previous mixture and then hydrogen peroxide is added with stirring to produce the final peroxide base.

The siloxane is then added to this peroxide matrix and stirred.

Support matrix for dye matrix:

the support matrix can be prepared as follows: water was added to the vessel and stirring was started, followed by addition of acetic acid. The emulsion base (see above for the preparation of the emulsion base) is then added. When fully homogenized, ammonium hydroxide was added to the mixture.

Examples 4 to 5-post-coloring Conditioning Agents

	#4	#5
			Composition (I)	Weight percent (%)	Weight percent (%)
			DeionizationWater (W)	61.95-proper amount	60.95-proper amount
			Emulsion matrix:
deionized water	29.76	29.76
			Cetyl alcohol (1)	2.25	2.25
Stearyl alcohol (2)	2.25	2.25
			Palm-based polyoxyethylene ether-25 (3)	1.50	1.50
Phenoxyethanol (4)	0.11	0.11
			Sodium benzoate (5)	0.09	0.09

Ethylenediaminetetraacetic acid Tetrasodium salt (87%) (6)	0.04	0.04
Anhydrous citric acid fine particle (14)	pH adjustment	pH adjustment
Siloxanes of the formula A	2.00	0
			Siloxanes of the formula B	0	3.00

(14): available from Aldrich under the trade name citric acid anhydrous fine

Preparation of the composition

The conditioner composition may be prepared as follows: deionized water and the emulsion base (see emulsion base preparation above) were added to the vessel with stirring. When homogenised, citric acid is added to the mixture until the pH of the emulsion is between 5 and 6.

Then, the single fluid is added to the emulsion and stirred.

Claims (22)

1. A side-chain or graft-type functionalized siloxane having a viscosity in the range of from 50 to 150,000mpa.s and incorporating one or more polar substituents selected from electron-withdrawing, charge-neutral or electron-donating groups having a Hammett sigma value between-1.0 and +1.5, wherein the one or more polar substituents comprise oxygen such that the sum of the oxygen content of the one or more polar substituents is from 1% to 10% by weight of the functionalized siloxane and the siloxane content is from 67% to 95% by weight of the functionalized siloxane.

2. A functionalized silicone according to claim 1, having a viscosity in the range of from 400 to 100,000mPa, preferably in the range of from 4000 to 25,000 mpa.s.

3. A functionalized siloxane according to claim 1 or 2, having the formula:

or a block copolymer type, represented by the following formula:

wherein Me is methyl, m is greater than or equal to 1, n is from about 50 to 2000, p is from about 0 to 50, q is from about 0 to 50, r is from about 0 to 50, s is from about 0 to 50, wherein p + q + r + s is greater than or equal to 1, B¹Is H, OH, alkyl or alkoxy and an organic radical A¹、A²、A³And A⁴Is a linear, branched or mono-or polycyclic aliphatic, mono-or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic, or heteroalkenyl moiety containing from 3 to 150 carbon atoms and from 0 to 50 heteroatoms incorporated with the one or more polar substituents.

4. A functionalised siloxane as claimed in claim 3 wherein said polar substituent comprises a group a as defined below¹、α²、α³And alpha⁴(ii) a S-linked radicals comprising S alpha¹、SCN、SO₂α¹、SO₃α¹、SSα1¹、SOα¹、SO₂Nα¹α²、SNα¹α²、S(Nα¹)α²、S(O)(Nα¹)α²、Sα¹(Nα²)、SONα¹α²(ii) a O-linked radicals, including O.alpha.¹、OOα¹、OCN、ONα¹α²(ii) a N-linked radicals, including N α¹α²、Nα¹α²α³+、NC、Nα^1Oα²、Nα¹Sα²、NCO、NCS、NO₂、N＝Nα¹、N＝NOα¹、Nα¹CN、N＝C＝Nα¹、Nα¹Nα²α³、Nα¹Nα²Nα³α⁴、Nα¹N＝Nα²；COX、CON₃、CONα¹α²、CONα¹COα²、C(＝Nα¹)Nα¹α²CHO, CHS, CN, NC and X, wherein:

α¹、α²、α³and alpha⁴Is a linear, branched or mono-or polycyclic aliphatic, mono-or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic or heteroalkenyl moiety containing from 3 to 150 carbon atoms and from 0 to 50 heteroatoms, especially O, N, S, P, and

x is F, Cl, Br or I, wherein

H is hydrogen, O is oxygen, N is nitrogen, C is carbon, S is sulfur, Cl is chlorine, Br is bromine, I is iodine, and F is fluorine.

5. A functionalized siloxane according to any preceding claim, incorporating a branched siloxane group comprising MeSiO_3/2Radicals or SiO_4/2A group.

6. A functionalized siloxane according to any preceding claim, comprising a polyoxyalkylene polar substituent.

7. The functionalized silicone of claim 6, wherein the polyoxyalkylene content is between 5% and 42% and the silicone content is 67% to 95%.

8. A functionalized siloxane according to claim 6 or 7, having the formula:

wherein Me is equal to methyl; r¹Is methyl or R²Or R³；R²Is- (CH)₂)_a-NH-[(CH₂)_a-NH]_b-H; and R is³Is- (CH)₂)_a-(OC₂H₄)_m-(OC₃H₆)_n-OZ; wherein x is from about 50 to 1500, y is from about 1 to 20, and z is from about 1 to 20; a is about 2 to 5, preferably 2 to 4; b is 0 to 3, preferably 1; m is about 1 to 30; n is about 1 to 30 and Z is H, alkyl having 1 to 4 carbon atoms or acetyl, with the proviso that when y is 0, R¹Is R²And when z is 0, R¹Is R³A group.

9. A functionalized siloxane having the formula:

10. a functionalized siloxane having the formula:

11. a fiber treatment composition comprising the functionalized silicone of any one of the preceding claims.

12. Fiber treatment composition according to claim 11, wherein the functionalized silicone deposits uniformly and durably on the fibers being treated.

13. Fiber treatment composition according to any one of claims 11 or 12, wherein the functionalized silicone is present in an amount ranging from 0.1% to 20% by weight, preferably from 0.50% to 10% by weight.

14. Fiber treatment composition according to any one of claims 11 to 13, in the form of an oil-in-water emulsion.

15. Fiber treatment composition according to claim 14, wherein the silicone droplets dispersed in the aqueous continuous phase have a particle size of more than 500nm, preferably more than 1 μm.

16. Fiber treatment composition according to claim 14 or 15, additionally comprising 0.1% to 15% of an emulsifier based on the weight of the aqueous continuous phase.

17. Fiber treatment composition according to claim 16, wherein the emulsifier comprises one or more of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a water-soluble polymeric surfactant, a water-soluble silicone-containing surfactant, and a nonionic surfactant.

18. Fiber treatment composition according to claim 17, wherein the surfactant comprises C₁₆-C₂₂And/or fatty alcohol ethoxylates having 1 to 30 ethylene oxide groups, preferably 10 to 30 ethylene oxide groups.

19. Fiber treatment composition according to claim 18, wherein the surfactant comprises C_16-22Fatty alcohol of (2) and C_16-22In a ratio of fatty alcohol to fatty alcohol ethoxylate of 10: toBetween 1 and 0.5: 1, more preferably between 6: 1 and 1: 1.

20. Fiber treatment composition according to any one of claims 11 to 19, wherein the fibers are hair.

21. A hair treatment composition according to claim 20, additionally comprising a hair bleaching composition or a hair coloring composition.

22. A hair treatment kit comprising:

(a) oxidative bleaching compositions

(b) A dye composition; and

a hair treatment composition according to claim 19, which is comprised in component (a) and/or comprised in component (b) and/or provided as a separate component.